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diff --git a/old/68224-0.txt b/old/68224-0.txt deleted file mode 100644 index 6635bb5..0000000 --- a/old/68224-0.txt +++ /dev/null @@ -1,12941 +0,0 @@ -The Project Gutenberg eBook of Synthetic resins and their raw -materials, report no. 131, second series, by United States Tariff -Commission - -This eBook is for the use of anyone anywhere in the United States and -most other parts of the world at no cost and with almost no restrictions -whatsoever. You may copy it, give it away or re-use it under the terms -of the Project Gutenberg License included with this eBook or online at -www.gutenberg.org. If you are not located in the United States, you -will have to check the laws of the country where you are located before -using this eBook. - -Title: Synthetic resins and their raw materials, report no. 131, second - series - A survey of the types and uses of synthetic resins, the - organization of the industry, and the trade in resins and raw - materials, with particular references to factors essential to - tariff consideration - -Author: United States Tariff Commission - -Release Date: June 2, 2022 [eBook #68224] - -Language: English - -Produced by: Juliet Sutherland and the Online Distributed Proofreading - Team at https://www.pgdp.net - -*** START OF THE PROJECT GUTENBERG EBOOK SYNTHETIC RESINS AND THEIR -RAW MATERIALS, REPORT NO. 131, SECOND SERIES *** - - - - - - - UNITED STATES TARIFF COMMISSION - - SYNTHETIC RESINS - AND THEIR RAW MATERIALS - - REPORT No. 131 - - SECOND SERIES - -[Illustration] - - - - -RECENT REPORTS OF THE UNITED STATES TARIFF COMMISSION - - - REPORTS TO THE PRESIDENT - - _Under the Rate Adjustment Provisions (Sec. 336) of the - Tariff Act of 1930_ - - Dressed or Dyed Furs, Report No. 122, Second Series, 1937 $0.05 - Slide Fasteners (Zippers), Report No. 113, Second Series, 1936 .10 - - _Under the Unfair Practices Provisions (Sec. 337) of the - Tariff Act of 1930_ - - Coilable Metal Rules, Report No. 106, Second Series, 1936 .05 - - REPORTS TO THE UNITED STATES SENATE - - _Under the General Powers Provision (Sec. 332) of the - Tariff Act of 1930_ - - Nets and Netting and Other Fishing Gear, Report No. 117, Second - Series, 1937 .10 - Salmon and Other Fish, Report No. 121, Second Series, 1937 .15 - Subsidies and Bounties to Fisheries Enterprises by Foreign - Countries, Report No. 116, Second Series, 1936 .15 - Tuna Fish, Report No. 109, Second Series, 1936 .10 - Wood Pulp and Pulpwood, Report No. 126, Second Series, 1938 .30 - - OTHER REPORTS UNDER THE GENERAL POWERS PROVISION OF THE - TARIFF ACT OF 1930 - - Dominion and Colonial Statistics, Report No. 127, Second - Series, 1938 .10 - Dyes and Other Synthetic Organic Chemicals in the United - States, 1937, Report No. 132, Second Series, 1938 .10 - Extent of Equal Tariff Treatment in Foreign Countries, - Report No. 119, Second Series, 1937 .15 - The Mica Industry, Report No. 130, Second Series, 1938 .25 - Chemical Nitrogen, Report No. 114, Second Series, 1937 .25 - Flat Glass and Related Glass Products, Report No. 123, - Second Series, 1937 .35 - Iron and Steel, Report No. 128, Second Series, 1938 .60 - Cutlery Products, Report No. 129, Second Series, 1937 .15 - - TRADE AGREEMENTS INFORMATION - - Trade Agreement With Canada (a summary of the provisions of - this agreement), Report No. 111, Second Series, 1936 .15 - - _Miscellaneous Reports_ - - Changes in Import Duties Since the Passage of the Tariff Act - of 1930, Miscellaneous Series, 1937 .10 - Rules of Practice and Procedure (Sixth Revision) and Laws - Relating to the United States Tariff Commission, Miscellaneous - Series, 1938 .10 - -For sale by the Superintendent of Documents, Government Printing Office, -Washington, D. C., at the prices indicated - - - - -UNITED STATES TARIFF COMMISSION - -Washington - - - - -ERRATA - - -Since publication of the report on Synthetic Resins the Commission’s -attention has been called to certain necessary corrections. - -Page 37—2d line under heading “Production in the United States” - -_Strike out_ “The Resinous Products and Chemical Co., Inc.,” and -_insert_ “Rohm and Haas,” - -Page 154—Last item under “Vinyl Resins” - -_Transfer_ the name of E. I. du Pont de Nemours and Co., Wilmington, -Del. to line below so that it will not be opposite a trade name. This -company manufactures Vinyl Resins but not “Koroseal”. - -December 1938 - -Transcriber’s Note: The errata have been corrected for this e-text, -together with a number of sundry typos. - - - - - UNITED STATES TARIFF COMMISSION - - SYNTHETIC RESINS - AND THEIR RAW MATERIALS - - A SURVEY OF THE TYPES AND USES OF SYNTHETIC - RESINS, THE ORGANIZATION OF THE INDUSTRY, - AND THE TRADE IN RESINS AND RAW - MATERIALS, WITH PARTICULAR - REFERENCE TO FACTORS - ESSENTIAL TO TARIFF - CONSIDERATION - - UNDER THE GENERAL PROVISIONS OF SECTION 332, TITLE III, - PART II, TARIFF ACT OF 1930 - - REPORT No. 131 - SECOND SERIES - - [Illustration] - - UNITED STATES - GOVERNMENT PRINTING OFFICE - WASHINGTON: 1938 - - For sale by the Superintendent of Documents, Washington, D. C. - Price 25 cents - - - - -UNITED STATES TARIFF COMMISSION - - - _RAYMOND B. STEVENS, Chairman_ - _HENRY F. GRADY, Vice Chairman_ - _EDGAR B. BROSSARD_ - _OSCAR B. RYDER_ - _E. DANA DURAND_ - _A. MANUEL FOX_ - _SIDNEY MORGAN, Secretary_ - -Address All Communications - -UNITED STATES TARIFF COMMISSION - -WASHINGTON, D. C. - - - - -TABLE OF CONTENTS - - - Page - - Acknowledgment XI - - 1. Introduction 1 - - Scope and purpose 2 - - Fundamental definitions 2 - - Tariff history 3 - - Broadening use of synthetic resins 4 - - Relation of synthetic resins to their raw materials 5 - - Sources of information 7 - - 2. Summary: - - Growth of the industry 7 - - Raw materials 8 - - Resins 9 - - The industry abroad 10 - - International trade 10 - - 3. Tar-acid resins 11 - - The three stages of a tar-acid resin 13 - - Classification of tar-acid resins 13 - - Processes of resin manufacture 14 - - Production in the United States 15 - - Imports into the United States 16 - - Exports from the United States 17 - - Tar-acid resins for molding: - - Molding powders and pellets 18 - - The molding of tar-acid resins 19 - - Production of tar-acid molding resins 19 - - Cast phenolic resins: - - Process of manufacture 20 - - Uses 20 - - Patents and licensing 21 - - Production of cast phenolic resins 21 - - Imports and exports 21 - - Tar-acid resins for laminating 21 - - Uses of tar-acid resin laminated products 22 - - Production of tar-acid resins for laminating 23 - - Imports into the United States 24 - - Exports from the United States 24 - - Tar-acid resins for surface coatings: - - Types of resin used and the resultant coatings 24 - - Production in the United States 25 - - Imports into and exports from the United States 25 - - Tar-acid resins in adhesives 25 - - Tar-acid resins for other uses 26 - - 4. Alkyd resins: - - Description and uses 26 - - Development and patents 27 - - Classification of alkyd resins: - - Unmodified drying alkyd resins 28 - - Drying alkyd resins, modified with natural materials 29 - - Drying alkyd resins, modified with other synthetic resins 29 - - Drying alkyd resins, modified with other synthetic resins - and oil extended 29 - - Semidrying alkyd resins 29 - - Nondrying alkyd resins 30 - - Miscellaneous modified alkyd resins 30 - - Alkyd resins in water dispersion 30 - - Alkyd resins in molding compositions and other uses 30 - - Pigments and solvents in alkyd resins 31 - - Production in the United States 31 - - Imports into and exports from the United States 32 - - 5. Urea resins: - - Description and uses 32 - - Production in the United States 34 - - United States imports and exports 35 - - 6. Acrylate resins: - - Properties and uses 35 - - Production in the United States 37 - - Imports into and exports from the United States 38 - - 7. Coumarone and indene resins: - - Description and uses 38 - - Production in the United States 39 - - Imports into and exports from the United States 39 - - 8. Petroleum resins: - - Properties and uses 39 - - Production 41 - - Imports and exports 41 - - 9. Polystyrene resins: - - Properties and uses 41 - - Production in the United States 42 - - Imports into and exports from the United States 42 - - 10. Vinyl resins 43 - - Description and uses: - - Polyvinyl acetate resins 44 - - Copolymers of vinyl acetate and vinyl chloride 46 - - Polyvinyl chloride resins 47 - - Polyvinyl chloroacetate resins 47 - - Divinyl acetylene and synthetic rubber 47 - - Production in the United States 48 - - Imports into the United States 48 - - Exports from the United States 50 - - 11. Other synthetic resins: - - Adipic acid resins 50 - - Aniline resins 50 - - Citric acid resins 50 - - Diphenyl resins 51 - - Furfural resins 51 - - Resins from sugar 51 - - Sulphonamide resins 51 - - 12. The organization of the synthetic resin industry: - - Horizontal relationships between resin producers 52 - - Vertical relationships between resin producers: - - Tar-acid resins for molding 53 - - Tar-acid resins for laminating 54 - - Cast phenolic resins 54 - - Tar-acid resins for coatings 55 - - Tar-acid resins for miscellaneous uses 55 - - Alkyd resins made from phthalic anhydride 55 - - Alkyd resins made from maleic anhydride 55 - - Urea resins for molding 56 - - Urea resins for other uses 56 - - Coumarone and indene resins 56 - - Other resins 56 - - Relationship of the resin industry to other industries: - - The chemical industry 56 - - The surface-coating industry 57 - - The electric industry 57 - - The auto industry 57 - - 13. The United States tariff and international trade in synthetic - resins 58 - - Rapid expansion in home markets 59 - - The effect of patents on international trade 59 - - The United States tariff on resins and resin products: - - Synthetic resins 60 - - Articles made of synthetic resin 61 - - 14. Synthetic resin prices, properties, and uses: - - Synthetic resins as substitutes 62 - - Motives for substitution 63 - - Materials displaced by synthetic resins 63 - - Competition between synthetic resins 63 - - Resins classified by cost 64 - - The physical properties of a resin and its uses 65 - - 15. Synthetic resins in other countries: - - Germany: - - Production 75 - - Tar-acid resins 75 - - Alkyd resins 76 - - Urea resins 76 - - Polystyrene and vinyl resins 76 - - Uses of synthetic resins 76 - - Organization 77 - - Foreign trade 77 - - Great Britain: - - Production 78 - - Tar-acid resins 79 - - Urea resins 79 - - Acrylate resins 79 - - Aniline resin 79 - - Organization 79 - - Foreign trade 80 - - France: - - Producers 80 - - Foreign trade 81 - - Czechoslovakia 82 - - Italy 82 - - Japan 83 - - Production 83 - - Canada 84 - - Union of Soviet Socialist Republics 85 - - Netherlands 85 - - Denmark 86 - - Poland 86 - - 16. Raw materials for alkyd resins 86 - - Naphthalene: - - Recovery of naphthalene 87 - - Description and uses 87 - - United States production 88 - - Organization of the industry 89 - - Trend of production 89 - - World production 90 - - Germany 91 - - Great Britain 92 - - Belgium 93 - - Czechoslovakia 93 - - France 94 - - Poland 94 - - Netherlands 94 - - Canada 94 - - Union of Soviet Socialist Republics 94 - - Japan 94 - - United States imports: - - Rates of duty 95 - - Import statistics 96 - - United States exports 98 - - Competitive conditions 98 - - Phthalic anhydride: - - Description and uses 98 - - United States production 100 - - Production in other countries 101 - - United States foreign trade 101 - - Competitive conditions 101 - - Polybasic acids other than phthalic anhydride: - - Maleic acid and anhydride 102 - - Malic acid and malomalic acid 102 - - Adipic acid 102 - - Succinic acid and anhydride 102 - - Fumaric acid 102 - - Glycerin: - - Description and uses 103 - - United States production 103 - - Production in other countries 104 - - International trade 104 - - United States imports 105 - - United States exports 107 - - Competitive conditions 108 - - 17. Raw materials for tar-acid resins: - - The tar acids 109 - - Phenol: - - Description and uses 110 - - United States production 111 - - Grades produced for resins 112 - - Producers 112 - - World production 113 - - United States imports: - - Rates of duty 114 - - Import statistics 114 - - United States exports 116 - - Competitive conditions 116 - - The cresols, xylenols, and cresylic acid: - - Description and uses: - - The cresols 117 - - Metacresol 118 - - Orthocresol 118 - - Paracresol 118 - - Metaparacresol 118 - - Cresol 118 - - The xylenols 118 - - Other high-boiling tar acids 119 - - Cresylic acid 119 - - United States production: - - The cresols 120 - - The xylenols 120 - - Other high-boiling tar acids 120 - - Cresylic acid 120 - - Foreign production 122 - - United States imports: - - Rates of duty 124 - - Import statistics 125 - - United States exports 131 - - Competitive conditions 131 - - Synthetic tar acids other than phenol 132 - - Para tertiary amyl phenol 133 - - Para tertiary butyl phenol 133 - - Phenyl phenols 133 - - Resorcinol 133 - - Formaldehyde: - - Description and uses 133 - - United States production 134 - - Production in other countries 134 - - United States imports and exports 134 - - Competitive conditions 135 - - Hexamethylenetetramine: - - Description and uses 136 - - United States production 136 - - Production in other countries 136 - - United States imports and exports 136 - - Competitive conditions 137 - - Furfural 137 - - 18. Raw materials for urea resins: - - Urea 138 - - Thiourea 139 - - 19. Raw materials for vinyl resins: - - Description and uses 140 - - United States production 140 - - United States imports 141 - - Competitive conditions 141 - - APPENDIXES - - Appendix A. Statistical tables on foreign trade in raw material - for synthetic resins 144 - - Appendix B. Trade names for synthetic resins made in the United - States 153 - - Appendix C. Trade names for synthetic resins made in Great Britain 155 - - Appendix D. Trade names for synthetic resins made in Germany 156 - - Appendix E. List of United States manufacturers of raw materials - for synthetic resins 158 - - Appendix F. Glossary 160 - - TABLES - - No. - - 1. Synthetic resins: United States production and sales, 1921-37 8 - - 2. Tar-acid resins: United States production and sales, by type - of raw material, 1933-37 14 - - 3. Tar-acid resins: United States production and sales, 1927-37 15 - - 4. Synthetic resins of coal-tar origin: United States imports for - consumption, 1919-37 16 - - 5. Synthetic resins of coal-tar origin: United States imports for - consumption, by principal sources, in specified years 1929-37 17 - - 6. Cast phenolic resins: United States production and sales, - 1934-37 21 - - 7. Alkyd resins from phthalic and maleic anhydride: United States - production and sales, 1933-37 31 - - 8. Urea resins: United States production and sales, 1933-37 35 - - 9. Resoglas and Trolitul: United States imports for consumption, - 1933-37 43 - - 10. Synthetic resins classified under paragraph 11: United States - imports for consumption, 1931-37 49 - - 11. Vinyl acetate resins: United States imports for consumption, - 1934-37 49 - - 12. Mowilith resins: United States imports for consumption, 1932-37 49 - - 13. Synthetic resins: United States production and imports, 1934-37 58 - - 14. Comparison of the international trade of the United States in - synthetic resins and in certain raw materials for resins, - 1934-37 58 - - 15. Tariff classification and rates of duty in Tariff act of 1930 - upon certain articles made of synthetic resin 61 - - 16. Manufactured articles n. s. p. f. in which synthetic resin - is the chief binding agent: United States imports for - consumption, 1931-37 62 - - 17. Synthetic resins and other plastics: Properties that affect - appearance 66 - - 18. Synthetic resins and other plastics: Molding properties 68 - - 19. Synthetic resins and other plastics: Strength properties 70 - - 20. Synthetic resins and other plastics: Heat properties 71 - - 21. Synthetic resins and other plastics: Electrical properties 72 - - 22. Synthetic resins and other plastics: Specific gravity, - specific volume, and resistance to other substances 73 - - 23. Synthetic resins: German exports, 1930-37 77 - - 24. Synthetic resins: German exports, by countries, 1934-37 78 - - 25. Synthetic resins: Production in Great Britain, 1934 and 35 78 - - 26. Synthetic resins: Imports into the United Kingdom, 1930-36 80 - - 27. Synthetic resins: Exports from the United Kingdom, 1930-36 80 - - 28. Synthetic resins: French imports, by types, and countries, - 1931 and 1933-37 81 - - 29. Synthetic resins: French exports, 1931 and 1933-37 82 - - 30. Manufactures of tar-acid resins: Production in Japan, 1929-35 84 - - 31. Prices of gums and resins in the Netherlands, 1936 86 - - 32. Synthetic resins: Netherland imports by countries 1931 - and 1933-37 86 - - 33. Crude naphthalene: United States production, 1918-37 88 - - 34. Refined naphthalene: United States production and sales, 1917-37 89 - - 35. Naphthalene (all grades): World production, by countries, - 1933 and 1935 90 - - 36. Naphthalene: German production, imports, exports, and apparent - consumption, 1928-37 92 - - 37. Naphthalene: Production in Great Britain, in specified years 92 - - 38. Naphthalene: Exports from the United Kingdom, 1928-36 93 - - 39. Naphthalene: Belgian production, 1928-35 93 - - 40. Naphthalene: Czechoslovak production, 1928-35 93 - - 41. Crude naphthalene: Polish production, 1928-36 94 - - 42. Naphthalene: Rates of duty upon imports into the United - States, 1916-38 95 - - 43. Crude naphthalene (solidifying at less than 79° C.): United - States imports for consumption, 1919-37 96 - - 44. Refined naphthalene (solidifying at or above 79° C.): United - States imports for consumption, 1919-37 96 - - 45. Crude naphthalene (solidifying under 79° C.): United States - imports for consumption from principal sources, in specified - years 97 - - 46. Crude naphthalene: United States production, imports, and - apparent consumption, in specified years 98 - - 47. Phthalic anhydride: United States production and sales, 1917-37 100 - - 48. Glycerin: United States production, 1919-37 103 - - 49. Glycerin: United States production for sale, 1919-35 104 - - 50. Glycerin: Imports and exports of principal countries, 1931 - and 1933-37 105 - - 51. Glycerin: United States imports for consumption, 1919-20 - and 1923-37 106 - - 52. Crude glycerin: United States imports for consumption from - Cuba, 1919-37 107 - - 53. Crude glycerin: United States imports for consumption from - Philippine Islands, 1925-37 107 - - 54. Glycerin: United States exports, 1919-37 108 - - 55. Refined glycerin: United States production, imports, exports, - and apparent consumption, in specified years 108 - - 56. Tar acids: Commercial and chemical names, boiling points, and - average percent in coal tar 109 - - 57. Tar acids available in coal tar produced and distilled in 1936 110 - - 58. Phenol: Estimated consumption by industries, 1936-37 111 - - 59. Phenol: United States production and sales, in specified - years, 1918-37 112 - - 60. Phenol: Estimated annual production, by countries, 1933-35 113 - - 61. Phenol: Rates of duty upon imports into the United States, - 1916-37 114 - - 62. Phenol: United States imports for consumption, 1910-37 115 - - 63. All distillates of tar yielding below 190° C., an amount of - tar acids equal to or more than 5 percent: United States - imports for consumption, 1918-37 115 - - 64. Phenol: United States exports, 1918-24 116 - - 65. Phenol: United States exports, 1934-36 116 - - 66. Phenol: United States production, imports, exports, and - apparent consumption, in specified years, 1918-37 117 - - 67. Meta, ortho, and para cresols: United States production and - sales, 1934 120 - - 68. Refined cresylic acid: United States production and sales, - 1929-37 121 - - 69. Cresol: German production, in specified years 122 - - 70. Cresol: German imports and exports in specified years 122 - - 71. Cresol: Production in Czechoslovakia in specified years 123 - - 72. Cresylic acid: British exports, by countries, 1933-37 123 - - 73. The cresols: Rates of duty upon United States imports, 1916-37 124 - - 74. Cresylic acid: Rates of duty upon United States imports, - 1916-37 125 - - 75. Metacresol, orthocresol, and paracresol, 90 percent or - more pure: United States imports for consumption, 1920 - and 1923-37 125 - - 76. Metacresol: United States imports for consumption by principal - sources, in specified years 126 - - 77. Orthocresol: United States imports for consumption by principal - sources, in specified years 127 - - 78. Paracresol: United States imports for consumption by principal - sources, in specified years 128 - - 79. Crude cresylic acid: United States imports for consumption, - 1924-37 129 - - 80. Refined cresylic acid: United States imports for consumption, - in specified years, 1919-37 129 - - 81. Crude cresylic acid: United States imports for consumption by - principal sources, in specified years, 1929-37 130 - - 82. Refined cresylic acid: United States imports for consumption - by principal countries, in specified years 130 - - 83. The cresols: Comparison of production and imports, 1934 132 - - 84. Formaldehyde: United States production and sales, in specified - years 134 - - 85. Formaldehyde: United States exports to principal markets, in - specified years 135 - - 86. Hexamethylenetetramine: United States production and sales, - 1923 and 1925-37 136 - - 87. Hexamethylenetetramine: United States imports for consumption, - 1923-37 137 - - 88. Urea: United States imports for consumption, 1919-20 and - 1923-37 138 - - 89. Urea: United States imports for consumption, by countries, - 1931 and 1933-37 139 - - 90. Thiourea: United States imports through the New York customs - district, 1931-37 140 - - 91. Vinyl acetate, unpolymerized: United States imports for - consumption, 1931-37 141 - - 92. Naphthalene: German imports and exports, by countries, 1929 - and 1932-37 144 - - 93. Crude naphthalene: Belgian imports and exports, 1932-37 146 - - 94. Refined naphthalene: Belgian imports and exports, 1932-37 147 - - 95. Crude and refined naphthalene: Netherland imports and exports, - by countries, 1929 and 1932-37 148 - - 96. Refined naphthalene: Canadian imports, by countries, 1928-29 - and 1932-37 150 - - 97. Naphthalene: Japanese imports by countries, 1928-29 and 1932-36 150 - - 98. Crude glycerin: United States imports for consumption, by - countries, 1929 and 1931-37 151 - - 99. Refined glycerin: United States imports for consumption, - by countries, 1929 and 1931-37 152 - - ILLUSTRATIONS - - Chart. Derivation of certain synthetic resins 6 - - Preform press making pellets for use in molding 18 - - Vacuum cleaner parts of tar-acid resin illustrating the intricate - molded shapes possible 19 - - Radio cabinet and telephone sets of molded tar-acid resin 19 - - Cast phenolic resins. Standard shapes and small articles fabricated - from them 20 - - Laminating sheet press 22 - - Gears made of laminated tar-acid resin 22 - - Cocktail lounge using tar-acid laminated decorative materials 23 - - Thermostat case of molded urea resin 33 - - Scales case of molded urea resin 33 - - Airplane cockpit enclosures of cast acrylate resin 36 - - Spectacle lenses molded to optical prescription from acrylate resin 37 - - Molded polystyrene resins 42 - - - - -ACKNOWLEDGMENT - - -In the preparation of this report, the Commission had the services of -Paul K. Lawrence, Prentice N. Dean, and others of the Commission’s -staff. - - - - -1. INTRODUCTION - - -This survey deals with the several commercially important types of -synthetic resins covered by paragraphs 2, 11, and 28 of the Tariff Act -of 1930 and with the raw materials necessary for their production. It is -made under the general investigatory powers of the Tariff Commission as -provided in section 332 of that act. - -The field of synthetic resins is a comparatively new one, most of its -commercial development having occurred within the past 10 years. In 1937 -the domestic output was more than 160 million pounds as compared with -slightly more than 10 million pounds in 1927. - -The first important patents on synthetic resins were granted about 25 -years ago. These patents covered phenolic resins probably intended for -use as substitutes for certain natural resins. It was soon found that -these synthetics offered possibilities of application vastly greater -than the natural materials. At first progress in their application was -slow as is usually the case with new products. During the World War the -shortage of phenol promoted interest in the use of the other tar acids -as raw materials for synthetic resins and intensive research developed -resins from the cresols and higher boiling tar acids. These resins -possessed properties sufficiently different from those made from phenol -to establish them permanently. - -In the meantime research on other types of resins was carried on in the -United States and in Europe. The tar-acid resins for molding were the -only commercially important ones on the market until about 1929. About -that time, however, new commercial products began to appear rapidly. Cast -phenolic resins became available as material for novelties of unusual -brilliancy and beauty, the urea resins to meet the requirements for light -colored thermosetting resins in molded articles, and the alkyd resins for -use in new surface coatings which replaced conventional paint materials. - -Later there followed a number of thermoplastic materials offering new and -unusual properties. Vinyl resins found application in molded products -and in safety glass. The acrylate resins became the nearest approach to -organic glass yet developed. The polystyrene resins, long in the research -stage, made their commercial appearance in 1937. Resins from petroleum, -from furfural, from adipic acid, and from aniline are on the market. Many -others are under investigation and some of them will undoubtedly become -important. - -The versatility of synthetic resins is most unusual. In various uses they -have successfully displaced glass, wood, metal, hard rubber, bone, glue, -cellulose plastics, protein plastics, and conventional paint materials. -They compete with glass in shades and reflectors and offer properties -which will increase their use for this purpose. Cases for scales, radios, -and clocks, formerly of wood and metal, are now made of these synthetic -resins. - - -Scope and purpose. - -This survey deals with the synthetic resins, the nature and trade in the -raw materials necessary for their production, the processes by which they -are made, trade in them in the United States and between nations, and -the nature of the competition which they meet. It does not go into the -details of manufacture of and trade in the multitude of articles made of -synthetic resins but stops at the point where these materials are turned -over to the resin fabricator. The synthetic resins are but one of four -broad groups of organic plastics. The others—natural resins, cellulose -ethers and esters, and protein plastics—are discussed herein only as they -relate to or compete with the synthetic resins. - -The purpose of the survey is to bring together in one publication the -available information on synthetic resins so as to provide a basis -for consideration of future tariff problems. Because the industries -involved are comparatively young and are expanding rapidly, their present -day importance is not generally realized. The rapidity with which -the synthetic resin industry is developing causes any comprehensive -report on the subject to be practically out of date before it can be -published. Notwithstanding the progress made each year in the quantity of -production, new applications, and new commercial products, the industry -may be said to be still in the industrial nursery. This circumstance -necessarily limits the period during which any treatment of the subject -will be representative. - - -Fundamental definitions. - -The scope of this report has been stated to include synthetic resins up -to the point where they are further manufactured, and the raw materials -used in producing them. It was also stated that natural resins and -synthetic plastics other than resins, such as the cellulose compounds -and modified rubber compounds, are excluded. The boundaries of these -categories are therefore important.[1] - -The term “resin” was formerly applied exclusively to a group of natural -products, principally of vegetable origin, although at least one -important resin, shellac, is of animal origin.[2] These natural resins -are widely used in paints, varnishes, and lacquers for decorative and -protective surface coatings. They also have extensive use in textile -impregnation, adhesives, soap, paper, and in cold-molded articles. In -recent years the natural resins have had to compete with synthetic -products, and each gravitates toward uses which demand the quality or -combination of qualities which it can most completely supply. - -A resin may be defined as a semisolid or solid, complex, amorphous -mixture of organic compounds with no definite melting point and no -tendency to crystallize. The resins are characterized by a typical luster -and a conchoidal fracture rather than by definite chemical composition. -The term includes natural resins, such as colophony (ordinary rosin), -copal, damar, lac, mastic, sandarac, shellac, etc., sometimes called gums -or gum resins although none of them are true gums. - -A synthetic resin is a resin made by synthesis from nonresinous organic -compounds. The term includes materials ranging from viscous liquids to -hard, infusible, amorphous solids. As a rule synthetic resins possess -properties distinct from those of natural resins. The term “plastics,” -sometimes applied to synthetic resins, also includes many materials which -are not resins. - -A plastic is anything possessing plasticity; that is, anything which -can be deformed under mechanical stress without losing its coherence -or its ability to keep its new form. According to this definition the -term includes such materials as putty, cement, clay, glass, and metals, -as well as certain modified natural or semisynthetic products, such -as cellulose acetate, cellulose nitrate, and casein more commonly so -designated. To speak of the plastics industries is almost meaningless -because of their enormous scope, including as they do those producing -cement, ceramics, confectionery and rubber, as well as those producing -the semisynthetic products mentioned. - -The resin industry embraces two main types of materials, thermoplastic -and thermosetting. Thermoplastic materials are those which, although -rigid at normal temperatures, may be deformed and molded under heat -and pressure. Among such materials are the cellulose esters, acrylate -resins, vinyl resins, polystyrene resins, etc. The recent development of -injection molding has given thermoplastics a new significance. - -Thermosetting substances are thermoplastic at some stage of their -existence, but become hard, rigid, and permanently infusible upon the -application of the proper heat and pressure. They are then irreversible -whereas the thermoplastics are reversible. Outstanding among the -thermosetting resins are tar-acid resins, urea resins, and the alkyd -resins. - - -Tariff history. - -The earliest mention of synthetic resins in the tariff laws of the -United States was the provision in group III of the Emergency Tariff Act -of 1916 for a duty of 30 percent ad valorem and 5 cents per pound on -synthetic phenolic resins. None of the non-coal-tar synthetic resins were -specifically mentioned prior to the Tariff Act of 1930. - -The Tariff Act of 1922 (par. 28) provided for synthetic phenolic resin -and all resinlike products, solid, semisolid or liquid, prepared from -phenol, cresol, phthalic anhydride, coumarone, indene, or from any other -article or material provided for in paragraph 27 or 1549. The rate of -duty was 60 percent ad valorem based on American selling price or United -States value and 7 cents per pound, with a provision that the ad valorem -rate should be reduced to 45 percent 2 years after the passage of the act. - -The Tariff Commission made two investigations of synthetic resins under -section 316 of the act of 1922. The first was undertaken April 16, 1926, -upon complaints of several domestic manufacturers, of unfair methods of -competition and unfair acts in the importation and sale of synthetic -phenolic resin, Form C, and articles made wholly or in part therefrom, in -infringement of the patent rights of the Bakelite Corporation. Following -the investigation, the Commission recommended on May 25, 1927, that -this material (as described under United States Patents No. 942,809 and -1,424,738) be excluded from entry into the United States. Importers -appealed from the findings of the Commission to the Court of Customs -Appeals, and the judicial proceedings were ended on October 13, 1930, by -denial of a writ of certiorari for the Supreme Court of the United States -to review the judgment of the Court of Customs and Patent Appeals. The -latter court had held, among other things, that there was substantial -evidence in support of each finding of the Commission. On November 26, -1930, the Treasury Department issued an order prohibiting the importation -of synthetic phenolic resin, Form C, with certain exceptions. (T. D. -44411.) - -The second investigation by the Tariff Commission was instituted -on December 23, 1927, also under section 316 of the act of 1922. -It concerned unfair methods of competition and unfair acts in the -importation into the United States of laminated products of paper or -other materials and insoluble, infusible condensation products of phenols -and formaldehyde. The Commission recommended to the President that, until -March 4, 1929, inclusive, certain products covered by United States -Letters Patent Nos. 1,018,385, 1,019,406, and 1,037,719 be excluded from -entry into the United States. These products were laminated cloth, paper -or the like, combined with insoluble, infusible condensation products -of phenols and formaldehyde. The order of the President prohibiting the -importation was contained in T. D. 42801 issued June 11, 1928. - -Under the Tariff Act of 1930, practically no changes were made in the -provisions of paragraph 28 that concern coal-tar synthetic resins. -Paragraph 2 was extended to include, among other things, the resins -(polymers) of certain organic compounds. The only commercial products -covered by this provision are the vinyl resins. The rate of duty was 30 -percent ad valorem on foreign value and 6 cents per pound. Under the -trade agreement with Canada, the duty on vinyl acetate, polymerized or -unpolymerized, and on synthetic resins made in chief value therefrom was -reduced to 15 percent ad valorem and 3 cents per pound (effective Jan. 1, -1936). - -The Tariff Act of 1930 contains a provision, in paragraph 11, for -synthetic gums and resins not specially provided for, 4 cents per pound -and 30 percent ad valorem on foreign value. - - -Broadening use of synthetic resins. - -The application of synthetic resins has extended into practically every -branch of industry. This marked expansion is not surprising when the -adaptability of these products is considered. Their uses range from -jewelry and bottle closures to building materials; from adhesives and new -types of surface coatings to light reflectors and shades. They are being -substituted for natural materials, such as wood, metal, and glass at an -increasing rate. They have provided new uses for raw materials formerly -used in antiseptics, disinfectants, explosives, embalming fluids, -fertilizers, moth repellants, and as solvents. The speed of expansion -of their use in resin manufacture has been such as to create a serious -shortage of some of these raw materials. - -New applications for synthetic resins appear almost daily. They are used -in furniture, wall panels, builders’ hardware, electrical fixtures, and -in thousands of small appliances. The automobile industry is probably -the largest single user. An interesting application here is in silent -gears and shaft bearings where the use of synthetic resins makes water -lubrication possible. Other automotive uses are in distributor heads, -horn buttons, gear shift knobs, dome light reflectors, control knobs and -the finishing lacquers. Additional uses contemplated for the near future -are in accelerator pedals and instrument panels. A new type of safety -glass in which vinyl resins are used was introduced in 1936. - -In decorative uses remarkable progress has been made. Panels of laminated -resins are widely used in store fronts, lobbies of office buildings, -and hotels; doors faced with this material are in use. The liner _Queen -Mary_ is paneled, in part, with laminated resins, as is the annex to the -Library of Congress. Lamp shades of urea resin are used in many Pullman -cars and are available for home and office use. - -Other things being equal, the cheaper a synthetic resin, the more widely -it may be applied as a substitute for other materials. As a result many -an apparently useless byproduct, such as oat hulls which yield furfural, -is either already used or being tested as a source of raw material. Other -materials which have already found a place or may do so, are soybean -meal, sugar, and certain petroleum distillates. - -Each of the important groups of synthetic resins has been sponsored by -one or more manufacturers of established reputation and large capital -resources. When a product reaches the commercial stage, after heavy -research cost, its future importance is therefore usually assured. - - -Relation of synthetic resins to their raw materials. - -Most of the commercially important synthetic resins are derived directly -or indirectly from coal. The chart (p. 6) shows the derivation of -certain synthetic resins from the principal raw materials used in their -manufacture and the intermediate products back to the original source of -the material. - -The polystyrene resins, for example, are made by polymerizing styrene -or vinyl benzene. Although basically from ethylene and benzene, vinyl -benzene may be formed in several ways. Ethylene is found in the gases -from the destructive distillation of coal but is obtained commercially by -cracking natural gas or petroleum. Styrene, found already formed in the -light oil fractions from coal tar, causes gum-forming in motor benzol and -certain industrial gases. - -When coke and lime are mixed and heated in an electric furnace to 2,000° -C., calcium carbide is formed. This compound with water yields acetylene, -the starting point for a long list of important products, including -several types of synthetic resins. When acetylene gas is passed through -acetic acid (itself obtained from acetylene) vinyl acetate is obtained. -If hydrochloric acid is used instead of acetic acid, vinyl chloride is -obtained. These compounds, when polymerized, yield the vinyl resins. -The acrylate resins may be obtained from the same basic raw material -by an entirely different procedure. Synthetic rubber is also derived -from acetylene, as are acetic anhydride and acetic acid (used in making -cellulose acetate plastics) and many other chemicals of commercial -importance. - -[Illustration: Derivation of certain synthetic resins.] - -When naphthalene (from coal tar) is treated with air at elevated -temperatures, phthalic anhydride is formed. Substituting benzene for -naphthalene yields maleic anhydride. Both of these substances when -condensed with glycerin, a byproduct of the soap industry, yield alkyd -resins. - -The tar acids from coal tar, either separated or mixed, when condensed -with formaldehyde give the highly important tar-acid resins. Or if -formaldehyde is condensed with urea, obtained from carbon dioxide and -ammonia, the urea resins are formed. - -The chart indicates the synthetic resins which are thermoplastic, -that is, which become plastic again upon reheating, and those which -are thermosetting, that is, pass into an infusible stage at a certain -critical temperature and pressure and do not again become plastic upon -subsequent reheating. - - -Sources of information. - -The data used in this report were obtained from a great variety of -sources. The several American and British trade journals were freely -consulted as were the various text books on this subject. Much of the -information on the domestic industry was obtained by personal contact -with producers and by correspondence. Field work included visits to -most of the domestic producers of resins and a representative group -of fabricators. Information of this type which was nonconfidential or -which could be combined so as not to reveal individual operations was -invaluable. Even where it was such that it could not be published it -became part of the general background. - -The data pertaining to the industry in foreign countries were, for the -most part, furnished the Tariff Commission by Department of Commerce -representatives stationed abroad, in response to inquiries by the -Commission. - - - - -2. SUMMARY - - -Growth of the industry. - -The coal-tar synthetic resin industry in the United States began on a -small scale some years before the World War. The output then was confined -to a few types of tar-acid resins and the applications were quite limited -until 1927, when certain of the basic patents expired. The output of -about 1.5 million pounds in 1921 had increased to more than 13 million -pounds in 1927 and the average unit value of sales had dropped from -81 cents per pound to 47 cents. Production continued to increase and -the unit value to decrease annually until 1932 when general economic -conditions forced a slight curtailment for 1 year. Since then the annual -increase in volume and variety has been rapid. Production of non-coal-tar -synthetic resins was started on a small scale in 1929 when both urea and -vinyl resins entered the picture. Commercial production of the petroleum -resins began in 1936 and of the acrylate resins in 1937. Table 1 shows -the production and sales of coal-tar resins and of non-coal-tar resins, -from 1921 through 1937. - -TABLE 1.—_Synthetic resins: United States production and sales, 1921-37_ - - ---------------------+------------+-------------------------------------- - | | Sales - Year | Production +------------+------------+------------ - | | Quantity | Value | Unit value - ---------------------+------------+------------+------------+------------ - | _Pounds_ | _Pounds_ | | - Coal-tar resins:[1] | | | | - 1921 | 1,643,796 | 1,674,456 | $1,352,166 | $0.81 - 1922 | 5,944,133 | 6,415,931 | 4,315,196 | .67 - 1923-26 | ([2]) | | | - 1927 | 13,452,230 | 13,084,313 | 6,094,656 | .47 - 1928 | 20,411,465 | 20,778,856 | 7,211,958 | .35 - 1929 | 33,036,490 | 30,660,513 | 10,393,397 | .33 - 1930 | 30,867,752 | 24,014,093 | 7,323,656 | .30 - 1931 | 34,179,000 | 29,343,000 | 7,862,000 | .27 - 1932 | 29,039,000 | 23,891,000 | 5,001,000 | .21 - 1933 | 41,628,485 | 31,657,653 | 7,238,560 | .23 - 1934 | 56,059,489 | 43,350,876 | 10,126,849 | .23 - 1935 | 90,913,162 | 65,923,334 | 12,777,195 | .19 - 1936 |117,301,780 | 86,213,735 | 17,056,099 | .20 - 1937 |141,098,844 |108,284,175 | 20,165,064 | .19 - | | | | - Non-coal-tar resins: | | | | - 1932 | 1,898,000 | 1,787,000 | 796,000 | .45 - 1933 | 3,571,717 | 3,256,411 | 1,745,102 | .54 - 1934 | ([2]) | 3,500,829 | 1,491,145 | .43 - 1935 | ([2]) | ([2]) | ([2]) | - 1936 | 15,611,041 | 14,766,640 | 3,591,467 | .24 - 1937 | 21,005,869 | 18,891,277 | 5,680,600 | .30 - ---------------------+------------+------------+------------+------------ - - [1] Does not include resins from adipic acid, coumarone and - indene, hydrocarbon, polystyrene, succinic acid and sulfonamides. - With the exception of coumarone and indene resins in recent years - production of the resins not included was small. - - [2] Not publishable. Figures would reveal operations of - individual producers. - - Source: Compiled from annual reports of the Tariff Commission on - dyes and other synthetic organic chemicals in the United States. - -Many factors have contributed to the growth of the synthetic resin -industry. Among these are the intensive research and development work -carried on by many individuals and firms; their widespread application in -many fields competing with wood, metal, and glass; and the development -of processes for raw materials which have greatly reduced their cost and -made their wider use possible. - -_Raw materials._—Although the chief raw materials consumed in the -synthetic resin industry are coal-tar derivatives and formaldehyde, many -others are utilized. The rapid expansion of the industry has created new -demands for materials in increasing quantities and has not only increased -the markets for well-known materials but has resulted in the production -on a huge scale of materials entirely new to commerce. Practically all -the raw materials now used can be derived from a few natural substances, -such as air, water, coal, petroleum crudes, salt, sulphur, and limestone. -The air yields nitrogen which may be converted to ammonia, a raw -material for urea, one of the components of the urea resins. Coal, as -is well known, yields a great variety of substances, many of which are -essential to synthetic resin manufacture. Benzene is the starting point -for synthetic phenol; naphthalene is used to make phthalic anhydride -and maleic anhydride; coke is converted to calcium carbide, which in -turn yields acetylene, acetic acid, and many other synthetics; carbon -monoxide which is converted to methanol and formaldehyde; and the natural -tar acids such as phenol, the cresols, and the xylenols. Limestone is a -component of calcium carbide, and salt yields needed alkalies and acids. -Water is broken down, and the hydrogen is converted to ammonia, methanol, -formaldehyde, and ethylene. - -Some idea of the expansion in production of these raw materials whose -principal use is in synthetic resins may be had by comparing the output -in 1923 of tar acids, formaldehyde, phthalic anhydride, maleic anhydride, -urea, vinyl acetate, and vinyl chloride, which amounted to 35 million -pounds, with the output of 270 million pounds in 1936. The manufacture of -these materials is largely by coal-tar distilling companies and makers of -chemicals. - -_Resins._—The coal-tar resins are the most important in quantity, value, -and variety of application. This class includes four groups: (_a_) tar -acid, (_b_) alkyd, (_c_) coumarone and indene, and (_d_) polystyrene. Of -these, resins from tar acids (phenol, cresols, and xylenols) are produced -in the largest quantity, the output having increased from about 15 -million pounds in 1932 to about 80 million pounds in 1937. In the latter -year about 40 percent of the consumption of tar acid resins was in molded -articles, 25 percent in paint and varnishes, 20 percent in laminated -products, and 15 percent in miscellaneous uses. - -The alkyd resins have shown a remarkable increase in output. Production -totaled slightly less than 10 million pounds in 1933; in 1937 it amounted -to about 61 million pounds. Practically all of the alkyds have been -consumed in paints and varnishes. - -The coumarone and indene resins have increased steadily over a number of -years and are now one of the most important groups. - -The polystyrene resins have been in an experimental stage for a long -time, with the volume of production small. In 1937, however, commercial -production of a water-white product was announced, and it is believed -that the output of these resins will increase sharply in the near future. - -The non-coal-tar resins were of little importance prior to 1930 and -production amounted to less than 2 million pounds in 1932. Since then, -however, progress has been rapid, both in types and output. Resins from -urea constitute an important part of this class and the output has -increased practically every year since 1929 when production was started. -Most of the output is used in molded articles where light and pastel -shades are required. In 1936, for the first time, appreciable quantities -were consumed in laminating and in surface coatings. - -The vinyl resins have been produced in increasing quantities for the past -8 years. Production reached a new high in 1937, and with the acceptance -of this type of resin for safety glass laminations it is expected that -the output will increase materially in the near future. In 1937 the -application in surface coatings, molded articles, and laminations were of -approximately equal importance. - -The acrylate resins are among the newest commercial developments in this -industry. Of the several types now manufactured, one appears valuable in -surface coatings and adhesives and another, in the form of its cast or -molded polymer, in airplane windows, machined articles, and lenses. - -Petroleum resins were first produced in commercial quantities in 1936, -but the output in that year was appreciable. These low-priced synthetics -are used in surface coatings, laminations, and miscellaneous uses. - - -The industry abroad. - -World production of synthetic resins at this time is estimated at 300 -million pounds annually, of which the United States accounts for 45 -percent. Germany produces about 27 percent and Great Britain about 20 -percent of the total and a number of countries including France, Italy, -Czechoslovakia, Canada, and Japan produce the remainder. Practically all -types are made in Germany and Great Britain although in lesser quantities -than here. The urea resins originated abroad, as did the acrylates and -polystyrenes. - -Commercial development of the synthetic resins abroad has been somewhat -behind that in the United States, although in recent years the increase -there has been so rapid as to seriously affect the international raw -material market. Germany, formerly one of our principal sources of crude -naphthalene, for a time restricted exports of that commodity in order -to conserve the available supply for home consumption, presumably in -alkyd resins. Great Britain, formerly the principal exporter of phenol, -has found it necessary to supplement production of natural phenol with -synthetic phenol. It is possible that in the future similar conditions -may arise in world markets for cresylic acid. - - -International trade. - -International trade in the synthetic resins has been small. Germany has -been the principal exporting country. There are a number of reasons -for the negligible movement of these materials in international trade, -the chief of which are active home markets in the principal producing -countries; the existence of patents of a basic nature which limited -trade to the owners and licencees under them; affiliation of producing -companies in different countries with allocation of the world market; and -high tariff barriers in many countries. - -The principal domestic producer of tar-acid resins is affiliated with -firms in Germany, the United Kingdom, France, Italy, Canada, and Japan. -The two principal American makers of urea resins have or have had -agreements as to patents, exchange of technical information, and probably -markets, with producers in Great Britain. Similar conditions exist with -other types of resins. - -In 1937 production of all synthetic resins in the United States amounted -to 162 million pounds and imports to less than 674,000 pounds (see table -13, p. 58). Production of tar-acid resins in that year amounted to 79.8 -million pounds; alkyd resins to 61.2 million pounds and all coal-tar -resins to 141 million pounds. Imports of all coal-tar synthetic resins -(which would include both tar acid and alkyd as well as others) amounted -to only 19,000 pounds. Coal-tar resins are dutiable at 7 cents per pound -and 45 percent ad valorem based on American selling price. On the small -imports in 1937 the duty collected averaged 54 percent ad valorem on -American selling price and would have averaged much higher had it been -calculated upon foreign value as are most duties. - -In 1937 the production of non-coal-tar resins totaled about 21 million -pounds. In that year imports of non-coal-tar resins totaled 65,000 -pounds. Imports of non-coal-tar resins, other than vinyl resins, amounted -to less than 2,000 pounds. These were dutiable at 4 cents per pound and -30 percent ad valorem on foreign value, equivalent on the average to 48 -percent ad valorem. The vinyl resins have been imported into the United -States in increasing quantities in recent years. The principal foreign -producer, in Canada, developed markets in the United States, but is a -joint owner of a plant now under construction in this country. Imports of -vinyl resins in 1937 were 653,000 pounds. These were dutiable at 3 cents -per pound and 15 percent ad valorem on foreign value, equivalent to 25 -percent ad valorem. - -It is apparent that foreign competition with United States producers -in the home market has been and is likely to continue insignificant -under existing duties. With a large home market and generally favorable -conditions with respect to the necessary raw materials and the technical -skills, this situation would probably continue even under lower duties. -Moreover, as international trade develops in these materials, this -country is more likely to be a net exporter than a net importer. - - - - -3. TAR-ACID RESINS - - -The tar-acid resins were the first true synthetic resins to appear in -commerce, but they were preceded by two plastics, celluloid and casein. -Probably the first successful attempt to make a semisynthetic or modified -natural product as a substitute for natural materials was the discovery -of celluloid in 1868 by John Wesley Hyatt. By treating cotton with nitric -acid he obtained a material which could be substituted for ivory in -billiard balls. The Celluloid Corporation grew out of this discovery and -the product was widely used to replace amber, ivory, mother-of-pearl, -tortoise shell and other materials. - -The discovery of casein plastic took place in 1890. Adolph Spitteler of -Hamburg, Germany, in trying to make a white blackboard, found that casein -(from milk) could be hardened by treating it with formaldehyde. Casein -plastics are now widely used in buttons, buckles, and other ornaments. - -As early as 1872 the reactions between coal-tar acids and aldehydes were -being studied, and by 1900 many research workers were investigating -phenol-formaldehyde condensation products. During the period 1900-1910, -the study of these products increased greatly, both with regard to -process of production and to applications, such as its substitution for -shellac and other natural resins. United States Patents Nos. 942,699 and -942,809 issued December 7, 1909, to Dr. L. H. Baekeland and commonly -known as the heat and pressure patents were probably the basic patents on -phenol-formaldehyde resins. Baekeland so modified these resins by methods -of hardening under heat and pressure that rigid molded articles could be -made. The range of uses of tar-acid-formaldehyde molding compositions -has steadily widened. Molded articles such as pencil and pen barrels, -ash trays, bottle closures, parts for automobiles, cameras, precision -instruments, dynamos, motors, and other electrical equipment, cafeteria -trays, table and counter tops are well known to the public. - -During the life of these and other basic patents issued about 1909 the -domestic production of phenol-formaldehyde molding compositions was -practically restricted to one company. Since the expiration of these -patents in 1926 a number of other producers have been established. In -1937 there were 36 domestic makers of tar-acid-formaldehyde resins for -molding, laminating, and surface coating applications. - -The early work done on phenol-formaldehyde resins gave dark-colored -products which were too hard and brittle to be machined or worked on -a lathe. Investigations by F. Pollak and A. Ostersetzer, in Vienna, -resulted in a process for the manufacture of cast phenolic resin with -a range of color possibilities from water-white transparency through -all shades and degrees of translucency and opaqueness. This product is -cast into sheets, rods, tubes, and special castings, all of which may -be turned or milled on automatic machines. United States Patent No. -1,854,600, issued April 19, 1932, to F. Pollak and A. Ostersetzer and -assigned to Pollopas, Ltd., London, is considered the basic patent for -cast phenolic resins. American rights under this and related patents -are owned by the Catalin Corporation of America who have licensed other -domestic makers. The German equivalent of rights under this patent is -owned by a subsidiary of I. G. Farbenindustrie Aktiengesellschaft and -rights under the French equivalent by Établissements Kuhlmann. - -In the early days of the phenol-formaldehyde resin industry (1909-16) -there was considerable uneasiness about the supply of phenol. World -production was not large and Germany and England controlled most of -it. The output of the United States was almost entirely for medicinal -use, although our potential production was large (see p. 111). This -situation caused many research workers to study the resins made from -other tar acids, principally meta and para cresols and the xylenols. The -investigations resulted in many new types of resins and in modifications -of the phenol-formaldehyde type. The World War changed conditions -materially. Imports of phenol were shut off and prices soared. Production -of synthetic phenol was begun, and, although the wartime production -went into explosives, its development had an important bearing on the -synthetic resin industry. Unusual demand for phenol, toluene, and other -coal-tar crudes resulted in a great expansion of production. With the -cessation of hostilities there was an ample supply of cheap phenol and -the expansion of the coal-tar industry continued so that the supply of -tar acids kept pace with the new demand for use in the production of -synthetic resin. - -In 1926, the early patents on resins from tar acids began to expire -and the second era of the industry began. Since that year most of -the research work has been for materials that would give different -properties to the resultant resins. The past 10 years have seen a -greater diversification in the manufacture of resins from tar acids and -substantial reductions in their prices. Tar-acid resins averaged $1.29 -per pound in 1920, 23 cents per pound in 1934, and 19 cents per pound in -1937. The production of certain resins of this class which are soluble in -drying oils has been an important achievement. They yield varnishes of -improved type that are quick-drying. - - -The three stages of a tar-acid resin. - -About 28 years ago the Journal of Industrial and Engineering Chemistry -published the original paper of Dr. Leo H. Baekeland on the Synthesis, -Constitution, and Uses of Bakelite. According to Baekeland’s theory, the -reaction between phenol and formaldehyde consists of condensation and -polymerization taking place in three stages. The first product formed, -called “initial condensation product A” is usually a liquid or semisolid -which on continued heating is converted to “intermediate condensation -product B.” B is an insoluble solid which can be softened by heat, and is -the material used by molders, laminators, and other fabricators. - -The final stage, known as “final condensation product C,” is probably -the result of polymerization of B, by heat and pressure. C product is -infusible, indifferent to all solvents, and cannot be distilled or -melted; hence the tar-acid resins belong to the thermosetting group. -The conversion to C takes place in the presses of the molder or final -fabricator of the resin. This theory is generally accepted and the -designations of the several stages are in universal use in the trade. - - -Classification of tar-acid resins. - -All the synthetic resins obtained by the condensation of a tar acid, or -a mixture of tar acids, with an aldehyde are popularly called phenolic -resins, regardless of whether they are made from phenol, the isomeric -cresols, xylenols, other high boiling tar acids, or any mixture of these -materials. A more accurate designation and that used in this survey is -tar-acid resins, reserving the term phenolic resins for those made from -pure phenol. - -The tar-acid resins might be classified in a number of ways; for example, -by composition, physical form, or general application. Each of these has -its shortcomings. To classify them by composition, that is, by the kind -of tar acid used, is not satisfactory because of the vast number of types -made from mixed tar acids. For the purpose of this discussion it seems -best to classify the tar-acid resins by their general application into -six groups: for molding, for casting, for laminating, for surface coating -(paints, varnishes, and lacquers), for adhesives, and for miscellaneous -uses. - -In 1937 approximately 66 percent of the United States production of -tar-acid resins was made from phenol; 18 percent from phenol-cresol -mixtures; 13 percent from cresol-cresylic acid mixtures; and 3 percent -from cresol-xylenol mixtures. Table 2 shows for recent years production -and sales of tar-acid resins by type of raw material. Pure phenol is used -for cast resins. Molding resins are usually made from pure phenol or from -tar-acid mixtures, chiefly phenol. Laminating and coating resins are -usually made from mixtures containing substantial amounts of the cresols -and xylenols (frequently spoken of by the trade as cresylic acid). - -TABLE 2.—_Tar-acid resins: United States production and sales, by type of -raw material, 1933-37_ - - ----+--------------------------------+--------------------------------- - | Phenol | Tar-acid mixtures[1] - +----------+----------+----------+----------+---------------------- - | | Sales | | Sales - Year|Production+----------+----------+Production+----------+----------- - |(net resin| Quantity | |(net resin| Quantity | - | content) |(net resin| Value | content) |(net resin| Value - | | content) | | | content) | - ----+----------+----------+----------+----------+----------+----------- - | _1,000 | _1,000 | _1,000 | _1,000 | _1,000 | _1,000 - | pounds_ | pounds_ | dollars_ | pounds_ | pounds_ | dollars_ - | | | | | | - 1933| 25,163 | 21,851 | 5,383 | 6,535 | 6,152 | 1,182 - 1934| 29,777 | 27,995 | 7,332 | 10,887 | 8,091 | 1,705 - 1935| 36,323 | 34,597 | 6,568 | 16,654 | 12,371 | 2,200 - 1936| 51,603 | 49,053 | 9,419 | 18,747 | 12,908 | 2,325 - 1937| 52,472 | 50,209 | 8,616 | 27,373 | 23,337 | 4,685 - +----------+----------+----------+----------+----------+----------- - | Phenol-cresol | Cresol-cresylic | Cresol-xylenol - | mixtures | acid mixtures | mixtures - +----------+----------+----------+----------+----------+----------- - | | | | | | - |Production|Sales (net|Production|Sales (net|Production|Sales (net - |(net resin| resin |(net resin| resin |(net resin| resin - | content) | content) | content) | content) | content) | content) - +----------+----------+----------+----------+----------+----------- - | _1,000 | _1,000 | _1,000 | _1,000 | _1,000 | _1,000 - | pounds_ | pounds_ | pounds_ | pounds_ | pounds_ | pounds_ - 1937| 14,046 | 13,238 | 10,702 | 8,467 | 2,625 | 1,632 - ----+----------+----------+----------+----------+----------+----------- - - [1] Includes phenol-cresol mixtures, cresol-cresylic acid - mixtures, and cresol-xylenol mixtures. For 1937, where it is - possible, the totals of tar-acid mixtures are broken down into - these three groups. - - Source: Dyes and Other Synthetic Organic Chemicals in the United - States, U. S. Tariff Commission. - - -Processes of resin manufacture. - -The processes of and patents for the manufacture of tar-acid-formaldehyde -resins are numerous. No attempt is made here to describe in detail the -several processes of manufacture or the endless number of variations and -modifications. In general the processes in operation may be designated -(_a_) one stage wet, (_b_) two stage wet, and (_c_) dry. - -The one-stage wet process consists in heating molecular proportions of -tar acid and formaldehyde (40-percent solution) in the presence of an -acid or alkaline catalyst. The formaldehyde is added all at once and the -reaction proceeds with the elimination of water. The difficulty with -this process is that of obtaining uniform batches because it cannot be -controlled exactly. - -The two-stage process is probably the one most widely used today and -consists in introducing formaldehyde in two or more stages as the -reaction progresses. Much better process control and more uniform results -are so obtained. A soluble, fusible resin is formed from which the water -is easily removed. Fillers and pigments may be added during the latter -part of the operation. - -The dry process is the least important and is used only where cast resins -are being made. Light-colored, transparent resins are obtained and the -operation is carried on to the final stage (C resin). In this process the -aldehyde used is solid paraformaldehyde or hexamethylenetetramine. These -materials are more costly than formaldehyde solution. - -Proportions of raw materials used vary widely—Baekeland suggested 7 -mols of formaldehyde and 6 mols of phenol (210 parts of 100-percent -formaldehyde to 564 parts of phenol), with a yield of resin equivalent -to 118 percent of the phenol. Larger proportions of formaldehyde are said -to increase the yield to as much as 140 percent of the phenol. - -Catalysts used to aid in the condensation of the reacting bodies may be -acids or bases. Certain properties of the resins may be varied by the -kind and quantity of catalyst used. Large proportions of basic or acidic -catalysts may affect the filler or metal inserts. Basic catalysts used -include caustic soda, caustic potash, ammonia, carbonates, and alkali -sulphites. Acid catalysts are usually one of the mineral acids such as -hydrochloric acid or sulphuric acid. - -While formaldehyde in the form of a 40-percent solution is the principal -aldehyde used with the tar acids, certain other aldehydes are used in -small amounts. Among these are acetaldehyde, butyraldehyde, benzaldehyde, -and others. Resins from furfural and phenol are discussed as “Furfural -Resins,” page 51. - - -Production in the United States. - -The production of tar-acid resins in the United States has increased -markedly in the last 10 years. Table 3 shows the production and sales -of all coal-tar resins in 1927 and 1928 (when there was no further -break-down available but when this classification was made up chiefly of -tar-acid resins) and of tar-acid resins from 1929 to 1937. The figures -given are in net resin content and do not include fillers, modifiers, or -pigments. From 1929 to 1937 production increased from 26 million pounds -to 80 million pounds; sales from 25 million pounds valued at 9.9 million -dollars to 74 million pounds valued at 13.3 million dollars; the value -per pound dropped from 39 cents to 19 cents. - -In 1937 the production of tar-acid resins for molding accounted for about -40 percent of the total; those for surface coatings, about 25 percent; -those for lamination, about 20 percent; and those for miscellaneous uses, -about 15 percent. - -TABLE 3. _Tar-acid resins: United States production and sales 1927-37_ - - --------+-------------+---------------------------------------- - | | Sales - | Production +------------+--------------+------------ - Year | (net resin | Quantity | | - | content) | (net resin | Value | Unit value - | | content) | | - --------+-------------+------------+--------------+------------ - | _Pounds_ | _Pounds_ | | - 1927[1] | 13,452,230 | 13,084,313 | $6,094,656 | $0.47 - 1928[1] | 20,411,465 | 20,778,856 | 7,211,958 | .35 - 1929[2] | 26,235,792 | 25,129,701 | 9,869,274 | .39 - 1930[2] | 18,338,389 | 17,428,687 | 6,576,023 | .38 - 1931[2] | 22,647,000 | 21,496,000 | 6,646,000 | .31 - 1932[2] | 17,163,000 | 15,042,000 | 3,946,000 | .26 - 1933[2] | 31,697,780 | 28,002,799 | 6,564,670 | .23 - 1934[2] | 40,663,565 | 36,086,008 | 9,037,861 | .25 - 1935[2] | 52,731,728 | 46,733,378 | 8,730,438 | .19 - 1936[2] | 70,349,328 | 61,961,200 | 11,743,978 | .19 - 1937[2] | 79,844,825 | 73,545,880 | 13,300,870 | .19 - --------+-------------+------------+--------------+---------- - - [1] All coal-tar resins. - - [2] Resins from tar acids only. - - Source: Compiled from annual reports of the Tariff Commission on - dyes and other synthetic organic chemicals in the United States. - - -Imports into the United States. - -Imports of tar-acid resins into the United States are dutiable under -paragraph 28 at 7 cents per pound and 45 percent ad valorem based upon -American selling price. Discussion of this rate, other restrictions upon -imports in the earlier years, and of the rates upon articles made of -these resins will be found on pages 59 to 61. - -Imports of tar-acid resins are not shown separately in official -statistics; the classification under which such imports are entered -includes all synthetic resins of coal-tar origin. Table 4 shows the -quantity and value of imports of all coal-tar resins since 1918, and -table 5 shows the principal sources of imports for certain years. - -Invoice analyses of imports in the last 3 years show only very small -quantities of phenolic resins being imported. In 1934 there was an -importation of 950 pounds of Bakelite molding compound; in 1935 imports -of 100 pounds of molding compound and 22 pounds of aminophenol resin are -recorded, and in 1936 imports of Bakelite filament compound totaled 250 -pounds and other resins 8,851 pounds. - -Even if in the years up to 1933 all of the imports of resins of coal-tar -origin were tar-acid resins, imports of tar-acid resins have been -negligible when compared with production. The smallness of imports may -be accounted for by a combination of factors, (1) the prohibition of -imports of certain types, which conflicted with patent rights; (2) the -rate of duty upon imports; (3) the fact that the manufacture of tar-acid -resins developed more rapidly in the United States than in most foreign -countries; and (4) the allocation of markets through agreements between -affiliated producers in different countries. (See p. 58.) - -TABLE 4.—_Synthetic resins of coal-tar origin: United States imports for -consumption, 1919-37_ - - --------+----------+----------+-----------+------------+--------------- - | | | | Computed | Computed - Year | Quantity | Dutiable | Value per | ad valorem | specific - | | value | pound | rate | rate - --------+----------+----------+-----------+------------+--------------- - | _Pounds_ | | | _Percent_ | _Per pound_ - 1919 | 1,114 | $2,860 | $2.57 | 32.0 | $0.82 - 1920 | 2,479 | 2,681 | 1.08 | 34.6 | .37 - 1921 | 1,420 | 2,366 | 1.67 | 33.0 | .55 - 1922 | 2,518 | 3,498 | 1.39 | 52.3 | .73 - 1923 | 3,183 | 10,512 | 3.30 | 62.1 | .20 - 1924 | 8,756 | 4,183 | .48 | 68.9 | .33 - 1925 | 1,537 | 889 | .58 | 57.1 | .33 - 1926 | 1,649 | 1,298 | .79 | 53.9 | .42 - 1927 | 11,359 | 4,266 | .38 | 63.6 | .24 - 1928 | 60,547 | 10,984 | .18 | 83.6 | .15 - 1929 | 67,529 | 17,503 | .26 | 72.0 | .19 - 1930 | 46,464 | 10,417 | .22 | 76.2 | .17 - 1931 | 6,074 | 6,180 | 1.02 | 51.9 | .53 - 1932 | 6,403 | 3,905 | .61 | 56.5 | .34 - 1933 | 3,776 | 2,508 | .66 | 55.5 | .37 - 1934 | 15,711 | 8,680 | .55 | 57.7 | .32 - 1935 | 18,015 | 6,075 | .34 | 65.8 | .22 - 1936 | 18,598 | 13,643 | .73 | 54.5 | .40 - 1937[1] | 18,977 | 14,278 | .75 | 54.3 | .41 - --------+----------+----------+-----------+------------+--------------- - - [1] Preliminary. - - Source: Foreign Commerce and Navigation of the United States. - -TABLE 5.—_Synthetic resins of coal-tar origin: United States imports for -consumption, by principal sources, in specified years, 1929-37_ - - ---------------+--------+-------+-------+-------+-------+-------+------- - Imported from— | 1929 | 1931 | 1933 | 1934 | 1935 | 1936 |1937[1] - +--------+-------+-------+-------+-------+-------+------- - | Quantity (pounds) - +-------+-------+-------+-------+-------+-------+------- - Germany | 50,770 | 3,166 | 2,724 | 9,801 | 2,220 |10,750 | 13,950 - France | 20 | 2,331 | 740 | | 297 | 168 | - United Kingdom | 336 | | | 1,065 |13,242 | 1,979 | 2,215 - Switzerland | 3,473 | 1,781 | 4,384 | 1,716 | | | - Canada | 1,372 | 135 | 1,266 | 594 | | | - All other | | | | | | | - countries | 16,403 | 577 | 312 | | 340 | 51 | 502 - +--------+-------+-------+-------+-------+-------+------- - Total | 67,529 | 6,074 | 3,776 |15,711 |18,015 |18,598 | 18,977 - +--------+-------+-------+-------+-------+-------+------- - | Value - +-------+-------+-------+-------+-------+-------+------- - Germany |$11,771 |$4,053 |$1,913 |$5,303 |$1,959 |$9,700 |$11,960 - France | 21 | 1,760 | 465 | | 236 | 177 | - United Kingdom | 2,235 | | | 255 | 2,476 | 1,090 | 659 - Switzerland | | | | 2,621 | 1,308 | 2,154 | 1,197 - Canada | | | | 501 | 46 | 486 | 214 - All other | | | | | | | - countries | 3,476 | 367 | 130 | | 50 | 36 | 248 - +--------+-------+-------+-------+-------+-------+------- - Total | 17,503 | 6,180 | 2,508 | 8,680 | 6,075 |13,643 | 14,278 - +--------+-------+-------+-------+---------------+------- - | Unit value - +--------+-------+-------+-------+-------+-------+------- - Germany | $0.23 | $1.28 | $0.70 | $0.54 | $0.88 | $0.90 | $0.86 - France | 1.05 | .76 | .63 | | .79 | 1.05 | - United Kingdom | 6.65 | | | .24 | .19 | .55 | .30 - Switzerland | | | | .75 | .73 | .49 | .70 - Canada | | | | .37 | .34 | .38 | .36 - All other | | | | | | | - countries | .21 | .64 | .42 | | .15 | .71 | .49 - +--------+-------+-------+-------+-------+-------+------- - Average | .26 | 1.02 | .66 | .55 | .34 | .73 | .75 - +--------+-------+-------+-------+-------+-------+------- - | Percent of total quantity - +--------+-------+-------+-------+-------+-------+------- - Germany | 75.2 | 52.1 | 72.1 | 62.4 | 12.3 | 57.8 | 73.5 - France | .1 | 38.4 | 19.6 | | 1.6 | .9 | - United Kingdom | .5 | | | 6.8 | 73.5 | 10.6 | 11.7 - Switzerland | | | | 22.1 | 9.9 | 23.6 | 9.1 - Canada | | | | 8.7 | .8 | 6.8 | 3.1 - All other | | | | | | | - countries | 24.2 | 9.5 | 8.3 | | 1.9 | .3 | 2.6 - ---------------+--------+-------+-------+-------+-------+-------+------- - - [1] Preliminary. - - Source: Foreign Commerce and Navigation of the United States. - - -Exports from the United States. - -Appreciable quantities of phenolic resins are exported annually in the -form of molding compounds and as finished articles of wide variety. -Statistics of these exports are not compiled separately by the Department -of Commerce. - -Exportation is limited by a number of factors, such as licensing -agreements, patents, allocation of markets, and high tariffs or embargoes -in certain countries. The largest domestic maker is affiliated with -producers in Great Britain, Germany, France, Italy, Canada, and Japan. -Other domestic firms have agreements as to patents and markets with -producers in England, Germany, and other countries. - - -TAR-ACID RESINS FOR MOLDING - -The tar-acid resins were first developed for molding and they are still -used in large volume in this way. An article produced in large quantity -is more likely to be made of molded resin. The cost of the mold, which -may amount to several thousand dollars, then becomes very small per unit -produced. If the article is of such a shape that it would require a great -deal of labor to produce in metal or wood, it may be produced in quantity -much more cheaply from resin, since it will come from the mold almost in -finished form. - -A few of the large molders find it economical to make their own -resins when they use one type in large volume or desire some special -modification. Most of the molders buy resins for molding in the form of -either powder or pre-formed pellets ready for use. - - -Molding powders and pellets. - -Molding powder is made from B-stage resin (see p. 13), a filler, a -pigment, a lubricant, and a plasticizer. These materials are mixed and -put through rolls at a moderate heat and pressure. The resin softens -and amalgamates with the other materials. It hardens upon cooling and -is ground to powder. A pre-formed pellet may be made from the powder by -pressure; use in this form saves the time of the molder when filling the -mold, since he is not required to measure the powder. - -The proper selection of the filler in a molding powder is important in -influencing the quality of the molded article. Fibrous fillers improve -the mechanical strength and shock resistance of the finished article. -Wood flour is the most widely used filler in tar-acid resins as well as -in other thermosetting resins. Pine, spruce, and fir are the principal -kinds used, and consideration must be given to the bulk, gum content, -color, and the size and shape of the wood particles. Color is the least -important since most of the tar-acid resins give brown or black moldings. -When the molding must withstand high temperatures, asbestos fiber is -used as a filler. In articles requiring high shock resistance, such as -golf club heads, a filler of paper pulp is used. Where high electrical -insulation and dielectric properties are required, ground mica is used -as the filler. Certain inorganic fillers such as powdered slate, gypsum, -barium sulphate, calcium sulphate, china clay, zinc oxide, and infusorial -earths, are sometimes used. Large proportions of these may be used where -hardness is more important than strength, as in phonograph records. Other -materials used include rubber, graphite, horn, bone, starch, pumice, and -cork. - -Coloring matter used may be coal-tar dyes or pigments such as bone black, -carbon black, and iron oxides. Pigments are usually more satisfactory, -although dyes are sometimes preferred in articles for insulation. - -A lubricant is added to the molding mixture to overcome the tendency to -stick in the mold. Metallic soaps, stearates, and stearic acid are those -most commonly used. - -Sometimes a plasticizer is included, its function being to act as a -solvent for the resin, thus increasing the flow of the material in the -mold. The plasticizer should be one which will become infusible or at -least remain solid in the molded article. - -[Illustration: PREFORM PRESS MAKING PELLETS FOR USE IN MOLDING. - -Source: Bakelite Corporation, 247 Park Avenue, New York, N. Y.] - -[Illustration: VACUUM CLEANER PARTS OF TAR-ACID RESIN ILLUSTRATING THE -INTRICATE MOLDED SHAPES POSSIBLE. - -Source: Bakelite Corporation, 247 Park Avenue, New York, N. Y.] - -[Illustration: RADIO CABINET AND TELEPHONE SET OF MOLDED TAR-ACID RESIN. - -Source: Bakelite Corporation, 217 Park Avenue, New York, N. Y.] - -A typical molding powder or pre-form pellet will contain by weight: - - Resin 40 to 50 percent - Filler 35 to 50 percent - Plasticizer 5 percent - Lubricant 1 percent - Pigment 1 percent - - -The molding of tar-acid resins. - -Ordinarily the molds used are made of hardened steel, highly polished. -They must stand working pressures of several thousand pounds per -square inch. The mold is placed in a hydraulic press, heated by steam, -electricity, or gas, and the molding material is placed in the mold. The -press is closed and heat and pressure are applied. The temperatures used -range between 250° F. and 365° F., and the pressures between 1,000 and -8,000 pounds per square inch. The molding time depends on the shape and -size of the article and on the composition of the molding material. As -little as one-half minute is required for small objects and as long as 10 -minutes for large objects. Average molding time is about 3 minutes. The -article is removed from the mold, allowed to cool, and is then trimmed, -sanded, filed, or polished. Since the mold is highly polished, the -finishing operation is usually needed only to remove the flash. Inserts, -such as metal parts (binding posts, electrical contacts, etc.), or inlays -of polished metal in name plates, and signs, are often molded in; gear -shift knobs are molded over a hollow metal core; rubber inserts are used -in castors, electrical plugs, and similar objects. - -The molding operation is an art, and has made remarkable progress in -recent years. Many articles molded of tar-acid resins are well-known to -the public. The automotive industry is the best customer, using such -molded parts as gear shift knobs, horn buttons, accelerator pedals, -light switches, ignition parts, and distributor heads. Other well-known -applications are builders’ hardware, electrical switch plates, switches -and fixtures, fountain pens, radio parts, telephone parts, handles for -stoves, vacuum cleaners, and other appliances, buttons, buckles, costume -jewelry, camera cases, radio cabinets, small containers, and hundreds of -others. - -The importance of tar-acid resins in molded articles is shown by the fact -that more than 75 percent of all synthetic resin molded articles made in -1937 used this type of resin as a binder. - - -Production of tar-acid molding resins. - -Domestic production of tar-acid molding powders and pellets was reported -to the Tariff Commission by 15 makers in 1937. Most of these firms have -specialized in resin development and manufacture. Among the well-known -brands are Bakelite, Durez, Durite, Resinox, Indur, and others (see p. -153 for list of trade names). - -Statistics of production and sales of tar-acid resins used in molding -were collected separately for the first time in 1935. They show a net -resin output of about 21,000,000 pounds, with sales of 18,000,000 pounds -or about 40 percent of the total tar-acid resins. The average unit value -was 17 cents per pound. In 1937 the production of tar-acid resins for -molding exceeded 32,000,000 pounds, again about 40 percent of the total. -These statistics are based on net resin and do not include fillers, -modifiers, pigments, or inert material of any kind. - - -CAST PHENOLIC RESINS - - -Process of manufacture. - -The production of cast phenolic resins requires pure materials, expensive -equipment, and extreme care in the control of the operation. A mixture -of phenol and formaldehyde and a catalyst (usually sodium or potassium -hydroxide) is charged into a nickel-lined reaction kettle and heated -until the water separates and is removed. The reaction is then allowed -to proceed to the desired point. Glycerin is added to aid in forming a -transparent product. All equipment, including pipe lines, valves, and -pumps, is nickel or nickel lined except that used for formaldehyde, which -is made of aluminum. - -The resin is usually made in 1,000 pound batches, and the reaction cycle -ranges from 6 to 18 hours. It is colored with soluble coal-tar dyes and -cast into lead molds. These are placed in a heated room and allowed -to cure for 3 to 6 days. The resin is removed from the mold with air -hammers, and the lead molds are melted. - -The appearance of the resin may be changed by varying its water content, -by the addition of dyes and fillers, and by the addition of other -substances to produce some desired effect, such as imitation ivory or -marble. The clarity of the resin depends upon its water content—the -greater the degree of dehydration the clearer the product. Range of -colors is complete, from crystal clear to the darker shades, with any -degree of transparency, translucency, or opaqueness. - -Casting is in the form of sheets, rods, tubes, or special forms suitable -for the production of buckles, jewelry, and other small products. Molds -of complicated shape cannot be used, which means that most articles -if produced of cast resin must be produced from standard shapes by -subsequent working. Recently small radio cabinets have been cast. - - -Uses. - -Cast phenolic resin can be machined in the same manner as hard wood. It -must be polished after machining, usually by tumbling with shoe pegs and -pumice or with muslin wheels. The smooth finish and low degree of heat -conduction give the material a pleasant feel, not cold to the touch as -is metal. The coloring is not superficial and therefore does not chip -or wear off. Electrical properties are excellent. A slow polymerization -continues for some time after fabrication, resulting in slight shrinkage. - -Cast phenolic resins are marketed by the producers as rods, sheets, -cylinders, and special castings. Standard round rods range from ⅜ inch to -more than 5 inches in diameter. Special rods are available in such forms -as square, hexagon, octagon, and fluted. Standard sheets are in sizes -from 12 by 24 inches to 36 by 72 inches, and from ⅛ to 1 inch thick. -Stock cylinders are available in a wide range of inside and outside -diameters. - -[Illustration: CAST PHENOLIC RESINS, STANDARD SHAPES AND SMALL ARTICLES -FABRICATED FROM THEM. - -Source: Bakelite Corporation, 247 Park Avenue, New York, N. Y.] - -Stock material is fabricated by a number of firms into an endless variety -of articles. Among these are toilet articles such as combs, backs for -brushes, cosmetic containers, and trinkets; fittings for automobiles, -electrical appliances, furniture, and display fixtures; jewelry, dress -ornaments, clock cases, handbag frames, vanity cases, smokers’ articles, -signs and advertising specialties, picture frames, handles for cutlery, -chessmen, pens, desk penholders, pencils, and many others. Probably the -largest consumption is in the making of buttons and buckles. - -The cast phenolic resins are odorless, tasteless, nonflammable, resistant -to oils and greases, and practically nonbreakable. - - -Patents and licensing. - -The basic patent covering the manufacture of cast phenolic resins is -United States Patent No. 1,854,600, issued April 19, 1932, to F. Poliak -and A. Ostersetzer, of Vienna, and assigned to Pollopas, Ltd., of London. -Many other patents have been granted on variations and modifications of -this one. The basic process is also patented in England, France, Germany, -and other countries. - -United States and Canadian patent rights were purchased by the American -Catalin Corporation; German rights by the Interessen Gemeinschaft -Industrie A. G. (German I. G.); French rights by Kuhlmann Co., and -British rights by the Imperial Chemical Industries. These licensing -arrangements limited the licensee to sales in his own and, in some -instances, nearby countries. - -The American Catalin Corporation has successfully defended the validity -of this patent and has licensed a number of domestic manufacturers to -produce cast phenolic resins on a royalty basis. - -In 1937 there were seven domestic makers of cast phenolic resins located -in New Jersey, New York, Massachusetts, and Pennsylvania. These firms -produce and market resins under the following trade names: Catalin, -Prystal, Joanite, Fiberlon, Phenolin, and Marblette. - - -Production of cast phenolic resins. - -Production was initiated about 1929 by the American Catalin Corporation. -The output increased substantially every year from that year through -1933. Statistics of production and sales are not publishable for -the years prior to 1934 because they would reveal the operations of -individual firms; they are given in table 6 for subsequent years. - -TABLE 6.—_Cast phenolic resins: United States production and sales, -1934-37_ - - ------+-------------+--------------------------------------- - | | Sales - Year | Production +------------+-------------+------------ - | | Quantity | Value | Unit value - ------+-------------+------------+-------------+------------ - | _Pounds_ | _Pounds_ | | - 1934 | 4,968,445 | 4,793,658 | $2,099,035 | $0.44 - 1935 | 5,566,621 | 5,454,490 | 2,205,879 | .40 - 1936 | 6,111,632 | 6,013,855 | 2,476,619 | .41 - 1937 | 5,459,654 | 5,335,746 | 2,180,620 | .41 - ------+-------------+------------+-------------+------------ - - Source: Dyes and Other Synthetic Organic Chemicals in the - United States, U. S. Tariff Commission. - - -Imports and exports. - -The licensing agreements, as outlined above, provide for the allocation -of markets for cast phenolic resins. Because of this arrangement there -are little or no imports and exports of this material. - - -TAR-ACID RESINS FOR LAMINATING - -By laminating is meant the impregnation of sheets of paper, fiber, or -cloth with a solution of synthetic resin and the building up of these -layers into sheets of reinforced synthetic resin of various thicknesses. -When a tar-acid resin is used the paper or cloth is immersed in or coated -with a solution of the B-stage resin, dried, and layers of the material -are compressed and consolidated, under heat and pressure to form sheets, -rods, tubes, blocks, and other forms, in the infusible C-stage. - -The coating of sheets of paper with solutions of natural resin and the -compacting of these sheets by heat and pressure is an old practice, -especially for electrical uses. Shellac and copal have been widely used -and yield a laminated board of good electrical and mechanical properties -when used at temperatures under 70° C. Above 70° C. the resin softens and -the desirable properties are lost. Since temperatures above 70° C. are -not uncommon in electrical equipment, the limitations of these natural -resins in this use can readily be seen. The use of tar-acid resins to -impregnate insulation material removes the temperature limitation and -otherwise improves the product; insulators so made are widely used in all -sorts of electrical and radio equipment. - - -Uses of tar-acid resin laminated products. - -Laminated sheets of tar-acid resin are made with paper, canvas, duck, -linen, pulpboard, vulcanized fiber, plywood, and other materials. Paper -is the material generally used for electrical insulation, although cloth -is sometimes used when greater strength is needed. Canvas is used where -maximum strength is required, as in gears for automobiles and industrial -machinery. Impregnated linen is adapted to punched parts and small gears. - -These laminated materials are uniformly dense, tough, resilient and light -in weight. They are nonabsorptive, have low thermal conductivity, and a -low coefficient of expansion. Their dielectric strength is excellent and -chemically they are inert to oils, brine, most acids, weak alkalies, and -many solvents. Structurally they are strong under tension, compression, -flexion, or impact; they are easy to machine and are sound absorbing. - -Gears made of laminated canvas are widely used; they are silent and -outwear those made of metal. The development of such gears was brought -about by the demand for a positive drive without the clash and clatter -resulting from metal to metal contact. The laminated gear absorbs -vibrations, eliminates noise, and reduces wear. The laminated material is -one-seventh the weight of brass, one-sixth the weight of steel, one-fifth -the weight of cast iron and one-half the weight of aluminum. Laminated -gear blanks may be cut on automatic machines into helical, spur, bevel, -or worm gears. - -Timing gears in automobiles are frequently of this type; they require no -adjustment and seldom need replacement during the life of the motor. The -light weight of the material reduces to a minimum flywheel effect on the -camshaft. Where lubrication is difficult a graphite impregnated blank may -be used. - -Bearings made from laminated fabric are successfully used in heavy -rolling mills where they reduce replacement costs and decrease power -consumption. The laminated material possesses strength, smooth surface, -density, good load carrying capacity, high impact resistance, nonscoring -properties, and is practically frictionless. Power consumption is said to -be reduced as much as 40 to 60 percent of that of metal bearings and the -life of the laminated bearing has been as much as 10 times that of the -metal ones. It replaces Babbitt metal, brass, bronze, white metal, gun -metal, or lignum vitae in this application. - -[Illustration: LAMINATING SHEET PRESS. - -Source: Bakelite Corporation, 247 Park Avenue, New York, N. Y.] - -[Illustration: GEARS MADE OF LAMINATED TAR-ACID RESIN. - -Source: Bakelite Corporation, 247 Park Avenue, New York, N. Y.] - -[Illustration: COCKTAIL LOUNGE USING TAR-ACID LAMINATED DECORATIVE -MATERIAL. - -Source: Bakelite Corporation, 247 Park Avenue, New York, N. Y.] - -In decorative uses, laminated materials have made remarkable progress -in recent years. In this application the material made from laminated -paper is veneered on wood or fiber board, and the surface is so durable -that refinishing is probably not necessary during the life of the -equipment. Table tops for public rooms such as restaurants, cafeterias, -and bars are widely used because of the beautiful designs obtainable and -because the material is not discolored by lighted cigarettes, alcohol -or other liquids, and does not chip or crack. Laminated sheets are used -for bathroom and kitchen walls, doors, window sills, store and theater -fronts, lobby walls in hotel and office buildings, and counter tops in -banks and post offices. The liner _Queen Mary_ is equipped with panels -of this material as is also the new Library of Congress Annex. Most of -the leading hotels have installed bar and cocktail lounges of laminated -materials because of the range of color and the ease with which novel -designs may be carried out. - -Almost any solid color, design, or imitation of another material may be -given the laminated sheet simply by printing it upon the top sheet of -paper used in the impregnated assembly. Thus a beautiful piece of walnut -or mahogany may be photographed, inexpensively reproduced upon paper, and -the finished laminated sheet will closely imitate the polished wood. The -combination of beauty with long life should permit the widespread use of -this type of material in all sorts of building and equipment. It has been -suggested as a possibility in automobile body construction. - -Other important uses are in trim and door strips for mechanical -refrigerators, in cafeteria trays, buckets and special containers, tires -for factory trucks, textile spools, miners’ safety helmets, gaskets, -valve discs and rings for pumps, pulleys, besides many others. - - -Production of tar-acid resins for laminating. - -Statistics of production and sales of synthetic resins for laminating -were not separately compiled prior to 1935. Since that year the resins -made from cresylic acid have been used to the greatest extent in -laminating, followed by those made from phenol. Tar-acid resins reported -as “used in paints, varnishes, and lacquers” may include appreciable -quantities of resin varnishes used for laminating. The total production -and sale in 1937 of tar-acid resins used in laminating, therefore, would -be the sum of the 20 percent of the total (see table 3) reported for -laminating plus some part of the 25 percent reported for surface coatings. - -Domestic producers of tar-acid resins for laminating are located -in Delaware, New Jersey, New York, Illinois, Massachusetts, and -Pennsylvania. The makers of the laminated materials are located in -Delaware, New Jersey, New York, Ohio, Illinois, Pennsylvania, Indiana, -and Connecticut. Their products are marketed under a number of trade -names, including Micarta, Dilecto, Celoron, Formica, Textolite, -Phenolite, Insurok, Spauldite, Synthane and Phenol Fibre. - - -Imports into the United States. - -There has been practically no importation of synthetic resins for -laminating. Imports of laminated products (rods, tubes, blocks, strips, -blanks, or other forms) of which synthetic resin is the chief binding -agent totaled only 215 pounds, valued at $612 in 1931 (principally from -the United Kingdom); 13 pounds, valued at $71 in 1932; none in 1933 and -1934; 609 pounds, valued at $579 in 1935 from Canada, Germany, and the -Netherlands; and 3,260 pounds, valued at $9,468 in 1936 from Austria, -Germany, and the United Kingdom. - - -Exports from the United States. - -Exports of phenolic or other synthetic resins for laminating and of -laminated articles are not separately recorded in official statistics. It -is known that appreciable quantities of laminated articles are exported -to Canada, England, and other countries. - - -TAR-ACID RESINS FOR SURFACE COATINGS - -Synthetic resins are widely used for surface coatings, chiefly because -of the ease with which new types can be produced to meet special -requirements and because of their uniformity. Tar-acid resin coatings may -be varied in composition and properties to meet a particular purpose. -Possible variations depend on the type or mixture of tar acid used -(phenol, cresols, xylenols, tertiary amyl phenol, tertiary butyl phenol, -phenyl phenol), whether the condensation takes place in the presence of -an acid or an alkali, and on the proportion of formaldehyde used. The -resin so formed may be modified with natural resins, synthetic resins -of the alkyd type, fatty acids, or other materials. The almost endless -opportunities for different types can, therefore, readily be appreciated. - - -Types of resin used and the resultant coatings. - -The tar-acid resins used in varnishes and other surface coatings are -usually oil-soluble types. They may be divided into three general -classes: (1) Phenol-formaldehyde condensation products rendered -oil-soluble by chemical combination or physical dispersion in other -materials, such as rosin and copal; (2) condensation products made -from tar acids other than simple phenol, which are themselves soluble -in drying oils and thinners; and (3) products from the condensation -of the substituted phenols and formaldehyde. These three classes of -oil-soluble tar-acid resins differ widely in their chemical and physical -properties and in their functions. The first group are usually called -modified phenolic resins, the second group are referred to as unmodified -or 100-percent soluble, and the third group are known as substituted -phenolic resins. - -The unmodified resins are extensively used in long-oil tung varnishes, -to which they impart greater drying speed, durability, and resistance -to alkalis and gases. The modified types impart the same properties to -tung oil varnishes but to a lesser extent. In addition the modified -types possess considerable hardness so that greater gloss and fullness -are obtained. Modifiers are either drying oils or natural resins; tung -oil is the most widely used oil and rosin the principal natural resin. -Substituted phenols such as para tertiary amyl phenol and para tertiary -butyl phenol may be used in place of simple phenol; while these are -relatively high priced components, the resins made therefrom have -increased in recent years to an appreciable volume because of their -improved properties. - -Other synthetic resins, such as those of the alkyd, petroleum, urea, -and vinyl types, are sometimes incorporated with the phenolics in the -same surface coating to obtain some desired property. The addition of a -plasticizer, such as tricresyl phosphate or dibutyl phthalate, improves -the flexibility of the film. - -Spirit varnishes, in which the synthetic resin is dissolved in a solvent, -are also available. In this type the soluble fusible resin (form A) is -dissolved in an organic solvent such as acetone or the various alcohols, -and conversion of the resin to the insoluble, infusible state (form C) is -effected by baking the film. - -Coatings made from tar-acid resins are widely used in so-called 4-hour -enamels and varnishes, for both interior and exterior application. -They are also used in the manufacture of linoleum, artificial leather, -adhesives, and printing inks. When incorporated with nitrocellulose -or cellulose acetate lacquers they improve the adhesion, luster, and -resistance to alkalies. - - -Production in the United States. - -In 1937 the output of tar-acid resins for surface coatings exceeded 20 -million pounds (net resin). Those from phenol and the substituted phenols -accounted for a very large part of the total. They were followed by -resins from cresylic acids and the xylenols in that order. - -In 1937 there were about 20 domestic makers of this type of synthetic -resin, with factories located in California, Connecticut, Illinois, -Indiana, New Jersey, New York, Massachusetts, Michigan, Missouri, Ohio, -Pennsylvania, and Rhode Island. - - -Imports into and exports from the United States. - -Imports of oil-soluble phenolic resins have been negligible. This is due, -in part, to licenses and agreements between certain domestic and foreign -makers, to the remarkable advancement and pioneering work done in this -country, to the holding of many basic patents by Americans, and to the -relatively high duty on imports. - -Exports of these products, usually in the form of enamels, varnishes, and -lacquers, have been appreciable and are probably increasing each year. -Official statistics are not reported separately. - - -TAR-ACID RESINS IN ADHESIVES - -A comparatively new use for tar-acid resins is in the manufacture of -wood adhesives. Ordinary vegetable and animal glues have long been used, -although their deficiencies in certain characteristics are well known. -These include (a) their inability to produce uniform products, (b) the -tendency of most alkaline glues to stain wood, (c) the bad effects -of moisture on them, and of bacteria and fungi in the case of animal -glues. The tar-acid resins have none of these objectionable qualities. -Being chemically inert they are free from attack by fungi and bacteria. -Moisture does not affect them, and they do not stain wood. - -Three types of resins are used as wood adhesives, principally in bonding -plywoods and veneers: (1) Hot press liquid, (2) cold press liquid, and -(3) resin film. Furniture, radio cabinets, games, and building products -constructed from plywoods bonded with resins can be shipped to tropical -countries, the bond not being affected by extreme climatic conditions. - -These resin adhesives are more expensive than the usual animal and -vegetable glues, a factor which has limited their application. Their -advantages may, however, open up to resin bonded plywoods uses in which -the more ordinary types are not satisfactory. - - -TAR-ACID RESINS FOR OTHER USES - -The application of tar-acid resins in casting, molding, laminating, -surface coatings, and adhesives has been described. There are many other -uses, but most of them approach the types of application dealt with. - -Impregnation of all sorts of materials with tar-acid resins is an -increasing use; such applications are in fabrics for aircraft, crease -resistant textiles, wood, asbestos, concrete, and electrical coils. Wood -with resin forced into the fiber under pressure is used for furniture, -flooring, heads for golf clubs, and handles for utensils. Resin is used -as a binder in the manufacture of brake linings for automobiles, as well -as in the manufacture of abrasive and grinding wheels. - -An interesting application is in the construction of corrosion-resistant -chemical plant equipment. In 1922 the German firm of Saureschutz -Gesellschaft was incorporated to fabricate equipment composed of a -special acid-resisting type of phenolic resin and asbestos. Sometime -later its manufacture was started in the United States. All sorts of -industrial plant equipment is now available, including cylindrical and -rectangular tanks up to 9 feet in diameter and 12 feet high, piping for -corrosive liquids and gases, valves, pumps, fans and ventilators, filter -press plates and frames, buckets, dippers, etc. - -Another new use is for making matrices in which to mold rubber printing -plates. Such plates are used at present chiefly in printing cotton and -paper bags but extensive experimentation promises to broaden their use. -The matrix is made of fiber board of very open structure impregnated with -tar-acid resin in the process of manufacture. - - - - -4. ALKYD RESINS - - -Description and uses. - -The alkyd resins, used principally in paints, varnishes, and lacquers, -are a group of condensation products synthesized by reacting polyhydric -alcohols, such as glycerin and the glycols, with dibasic organic acids, -such as phthalic, maleic, succinic, and sebacic. The condensation product -is almost always modified to give properties to the resin desirable or -essential to the specific application contemplated. The modifying agent -may be a drying, semidrying, or nondrying oil; the fatty acid of an oil; -a natural resin, such as rosin; a synthetic resin of the tar-acid group -or of the urea-formaldehyde type; or other substance. Up to the present -time unmodified alkyd resins have not been commercially important. - -A wide variety of types is obtained by the use of different materials -and different modifiers. The variations begin with the dibasic acid -used, and with the polyhydric alcohol used. The modifications possible -are practically endless, and almost any fixed oil or the corresponding -fatty acid, and most of the natural or synthetic resins may be used. The -importance of the modifier is shown by the proportion used in most alkyd -resins. On the average, approximately 50 percent of the total weight of -the drying and semidrying alkyd resin products is modifier, 30 percent -dibasic acid, and 20 percent polyhydric alcohol. The proportions will, of -course, vary with individual types. Certain types on the market contain -only 25 percent modifier while others have as much as 75 percent. - -In a new industry such as this, rapid changes in types and applications -must be expected. Extensive research is being carried on by various -groups. The raw material makers are seeking cheaper products or those -with special properties; the resin makers are investigating an endless -number of modifications, and the makers of surface coatings are testing -most of the new types offered. - - -Development and patents. - -Probably the earliest record of research leading to the development of -the alkyds was that of van Bemmelen, who reported in a German technical -journal in 1856 the sirupy products obtained by heating together succinic -acid and glycerin or citric acid and glycerin. The first investigation -of the phthalic anhydride-glycerin resins was recorded in 1901.[3] -Watson Smith, while engaged in research on phthalein dyes, obtained a -transparent, highly refractive resinlike substance when glycerin and -phthalic anhydride were heated together. Smith recommended the product as -a cement for ceramic wares. - -During the period 1910-16 the research laboratories of the General -Electric Co., engaged in research on a synthetic resin from glycerin -and phthalic anhydride. As a result of these studies numerous patents -were granted for this type of resin to which the trade name Glyptal -was applied. Intensive research was carried on by several firms, many -variations were developed, and literally hundreds of patents were granted. - -The paint and varnish industry has been undergoing radical readjustment. -Methods and natural products, which for decades or centuries had changed -very little, are giving way to synthetic creations of our laboratories. -The first important departure from the traditional practices was the -development of nitrocellulose lacquers. The commercial application of -the alkyd resins followed, and their use is increasing rapidly. Because -this development is still comparatively young, the large number of -modifications offered has confused the coating manufacturer. It is -probable that many of the synthetic products now being marketed have no -special technical or economic justification and that they will in time -lose out in competition with better products known at present, or still -to be developed. - -United States Patent No. 1,893,873, dated January 10, 1933, granted to R. -H. Kienle and assigned to the General Electric Co., was considered one of -the basic patents in this field. Early in 1936 it was declared invalid -in a suit claiming infringement brought against the Paramet Chemical Co. -of Brooklyn, N. Y. The decision in this case seems to have opened the -glycerin-phthalic anhydride resins to a large number of manufacturers. - -Among the principal brands of alkyd resins now on the domestic market are -Beckosol, Dulux, Esterol, Glyptal, Rezyl, and Teglac. Each of these trade -names identifies a series of products. - - -Classification of alkyd resins. - -A number of classifications of the alkyd resins are possible and -practical. Since by far the most important applications are in -surface coatings, and their use in molding compositions is relatively -unimportant, it seems advisable at this time to emphasize the -more important use. For the purpose of this survey the following -classification is used: - - (1) Drying alkyd resins. - (a) Unmodified. - (b) Modified with natural materials. - (c) Modified with other synthetic resins. - (d) Modified with other synthetic resins and oil extended. - (2) Semidrying alkyd resins. - (3) Nondrying alkyd resins. - (4) Miscellaneous modified alkyd resins. - (5) Alkyd resins in water dispersion. - (6) Alkyd resins in molding compositions. - -At least 75 percent of the alkyd resin finishes used at present are of -the drying type and about 15 percent of the nondrying type. - -_Unmodified drying alkyd resins._—This class of alkyd resins consists of -a series of compounds made from polyhydric alcohols, polybasic acids, and -fatty acids in chemical combination. The alcohol is usually glycerin, and -the polybasic acid largely phthalic anhydride or acid, although others, -such as maleic anhydride (acid) are increasing rapidly in importance. The -fatty acid or oil used may be linseed, tung, perilla, hempseed, soybean, -sunflower, safflower, or other drying oil. It is believed that tung oil -and perilla oil are the most important at this time. - -Unmodified drying alkyd resins are characterized by excellent durability -but limited resistance to water in air-dried finishes. Both in air-dried -and in baked finishes they are outstanding as to flexibility, quick -drying, long luster life, and permanent adhesion. Their principal uses -are in finishes for interior walls and woodwork, automobiles, coatings on -steel such as for refrigerators, railway equipment, bridges, advertising -signs, and lithographed containers. In these applications the products -of this type compete with nitrocellulose lacquers and the older types -of varnishes and paints. While the initial cost is higher, greater -durability is obtained together with faster drying, flexibility, and -hardness. - -Probably the largest field for surface coatings is outdoor wood finishes. -Several attempts have been made to adapt pure alkyd finishes to this -use but with limited success because the hard and non-porous finish -does not permit the escape of moisture contained in the wood and the -pressure developed from vaporization of the moisture by the sun’s rays -tends to lift the coating from the wood surface. Recently it has been -found practicable to incorporate from 15 to 20 percent alkyd resins in -conventional types of outdoor paints for wood. Here the use of alkyds has -contributed greater durability and retention of fresh appearance over a -longer period. Paints of this type are now on the retail market. - -_Drying alkyd resins modified with natural materials._—This type of -alkyd resin is modified principally with natural resins, such as rosin, -damar, mastic, shellac, or copal. The use of these natural resins imparts -hardness to the resin but shortens its durability. They make the product -less expensive, permit easier incorporation of the drying oil, and in -some instances increase the water resistance. - -Their principal application is to modify nitrocellulose lacquers and -lacquer sealers, in order to impart gloss, hardness, and easy sanding. It -has been said that the commercial production of drying alkyds modified -with natural resins was as important a development in the surface coating -industry as the discovery of the alkyds themselves. - -_Drying alkyd resins modified with other synthetic resins._—Drying alkyd -resins may be modified with tar-acid formaldehyde resins, tar-acid -furfural resins, urea-formaldehyde resins, petroleum resins, and the -coumarone and indene resins. - -Modification with tar-acid resins gives a quicker setting, harder drying -finish with a higher gloss. Alkyd resins so modified are adapted to both -air-drying and baked undercoats and finishes; they have good durability -and adhesion and good resistance to grease, oils, alcohol and abrasion. -For some uses the tar-acid resin modification gives better qualities -than either component possesses alone, but in light colored finishes it -has a tendency to cause the finish to yellow. Coatings made of drying -alkyd resins modified with tar acid resins are widely used on automobile -chassis, fenders, and bodies, machinery coatings, steel fixtures and -toys; they are especially suitable for primers, undercoats, and finishes -on metal. - -Modification with urea resins produces baked-finish coatings. As much as -40 percent of the urea resin is incorporated. It makes possible coatings -with a full range of permanent colors and improves their hardness and -mar-proofness, whereas without the ureas the combination of color range -with hardness had been difficult to obtain. The urea resin modified -alkyds find use on metal surfaces of articles which must stand rough -handling, such as toys, furniture, and motors. - -Modification with petroleum resins produces air-dried finishes. For -industrial use on metal they give coatings with better adhesion, -dispersion of pigments, and resistance to acids, alkalies, and moisture -at a lower cost than is obtained by ester gum or tar-acid resin -modification. The petroleum resin modification minimizes skinning and -improves the luster and the flow. - -_Drying alkyd resins modified with other synthetic resins and oil -extended._—Excellent water resistance and versatility are the -characteristics of finishes made of alkyd resins modified with other -synthetic resins (usually tar-acid) and oil extended. The incorporation -of drying oils gives a low cost finish with better compatibility and -brushing and with the combined properties of a quick-setting varnish -and an alkyd resin. Although not so durable or quick setting as the -unmodified finishes, they have better water resistance. These finishes -may be brushed or sprayed, air-dried or baked. They have wide industrial -and architectural uses. - -_Semidrying alkyd resins._—Cottonseed oil is the principal modifier in -semidrying alkyd resins. Alkyd resins of this type are used in finishes -requiring maximum gloss and color retention. When baked on metal at -high temperatures they show no tendency to wrinkle. They are used as -reinforcing agents to increase flexibility and durability, and to -plasticize other finishes. - -_Nondrying alkyd resins._—The nondrying or nonoxidizing alkyd resins -are those containing a nondrying oil, such as castor oil or coconut -oil, or the fatty acid of a nondrying oil, such as stearic, palmitic, -or oleic acid. Nondrying oils make the resin less sensitive to heat -hardening and impart greater flexibility. These resins are used -principally as plasticizers in nitrocellulose lacquers. In this use they -have the advantage of better retention of plasticizing efficiency than -other plasticizers, many of which are lost by evaporation, migration, -absorption, or oxidation. These modified nitrocellulose lacquers, either -clear or pigmented, are used for coating wood, composition board, cloth, -paper, rubber, leather, and similar surfaces. - -_Miscellaneous modified alkyd resins._—This group includes alkyd resins -modified with materials other than those already discussed. To date -(1938) there has been little, if any, commercial production of such -resins. There are many modifiers which have been suggested and which -might be used but for the fact that they are too expensive. Among these -are butyl alcohol and benzoic acid. - -_Alkyd resins in water dispersion._—Emulsions of alkyd resins in water -are now available for use in clear and pigmented coatings. These are sold -in the form of paste containing 40 to 50 percent solids and are diluted -with water at the time of application. They are especially suitable for -coating porous surfaces, such as brick, concrete, plaster, stucco, and -masonry of all kinds. They are applied by brushing or spraying and they -combine the ease of application of water paints with the durability, -washability, and hardness of oil paints. They dry quickly, and the dried -film cannot again be dissolved or suspended in water; the coating can -therefore be washed or, after several weeks, scrubbed with cleansers. -Compared with oil paints, they give better coverage, are easier to apply, -and cost appreciably less. Compared with other types of water paints, -such as kalsomine, they give a glossier coating of greater durability and -superior appearance; they seal porous surfaces better; their covering -capacity is greater; and their applied cost is slightly less per square -yard of surface. - -Coatings of this type may be applied directly over fresh plaster without -a sizing coat, since they allow the curing of the plaster to continue. -The usual paint pigments may be incorporated. - -A special use of the water dispersed alkyds is on asphalt or tar since -they are nonbleeding in the solvents of these materials. This quality -permits their use for traffic and zone markers on streets. - -_Alkyd resins in molding compositions and other uses._—The alkyd resins -are much less important as binders in molded articles than in coatings -and finishes. Conversion of the resin to the insoluble infusible form is -extremely slow, requiring days as compared with minutes for the tar-acid -and urea resins. - -The alkyds are used as binders for flake, powder, and split mica to -produce insulation material of high electrical strength. Other uses are -in the production of linoleums; gaskets; brake linings; laminated fabric, -paper, and cardboard sheets; printing inks; and coated paper, textiles, -and leathers. - - -Pigments and solvents in alkyd finishes. - -Since the alkyd resins are largely used in surface coatings and finishes -and since this application in this field is producing great changes in -the industry, it is appropriate to consider the effect of their use on -other materials. - -The average alkyd resin consists of 50 percent glycerol phthalate -modified with 50 percent oil, fatty acid, natural resin, or synthetic -resin. The alkyd and modifier are dissolved in a solvent, usually a -coal-tar light oil such as toluol, or xylol, or a petroleum solvent, and -pigmented with titanium dioxide or other pigment. Highly basic pigments -such as zinc oxide, carbonate white lead, whiting and aluminum hydrate -(all important pigments in the conventional types of finishes) are not -used in alkyd finishes. - - -Production in the United States. - -Prior to 1929, the domestic production of resins from phthalic anhydride -was confined largely to one maker. The quantities produced were -relatively small. In 1929 there were three producers, the volume of whose -production exceeded one million pounds for the first time. Beginning with -1933 the Tariff Commission collected and compiled production and sales -statistics for these resins. They are shown in table 7. - -TABLE 7.—_Alkyd resins from phthalic and maleic anhydride: United States -production and sales, 1933-37_ - - --------+-----------+------------+------------------------------------ - | | | Sales - Year | Number of | Production +------------+-----------+----------- - | makers | | | | - | | | Quantity | Value | Unit value - --------+-----------+------------+------------+-----------+----------- - | | _Pounds_ | _Pounds_ | | - 1933 | 6| 9,930,705| 3,654,854 | $673,890 | $0.18 - 1934 | 10| 15,219,247 | 7,084,602 | 1,022,436 | .14 - 1935 | 15| 34,312,713 | 15,836,942 | 3,482,078 | .22 - 1936[1] | 31| 46,952,452 | 24,252,535 | 5,312,121 | .22 - 1937[1] | 39| 61,254,019 | 34,738,295 | 6,864,194 | .20 - --------+-----------+------------+------------+-----------+----------- - - [1] Includes resins from maleic anhydride. - - Source: Dyes and Other Synthetic Organic Chemicals in the United - States, U. S. Tariff Commission. - -In 1933 there were 6 makers of resins from phthalic anhydride, in 1935 -there were 15, and in 1937 there were 35. The 1937 output of alkyd resins -from phthalic anhydride was 58,450,032 pounds net resin, with sales -of 32,583,307 pounds valued at $6,446,011. Producing plants are well -scattered through northern and eastern United States. In 1936 fewer than -one-third of the makers accounted for about 90 percent of the output. - -The domestic production of resins from maleic anhydride was reported for -the first time in 1933. The output in that year consisted of experimental -quantities produced by two firms. A small increase in production occurred -in 1934 when another maker began operation. In 1936 there were eight -producers and the output was many times that of 1934. In 1937 there were -12 makers of these resins with an output of 2,803,987 pounds and sales of -2,154,988 pounds, valued at $418,183. It is the opinion of some persons -in the industry that in volume of production and sales the resins from -maleic anhydride will in the near future approach that obtained from -phthalic anhydride. - - -Imports into and exports from the United States. - -No imports of alkyd resins have been recorded in official statistics. - -Exports of alkyd resin coatings and finishes are not separately shown, -but data collected from the several producers show that appreciable -quantities were exported in recent years, principally to Central and -South American countries. - - - - -5. UREA RESINS - - -One of the most important series of thermosetting resins is the group -made by condensing urea and formaldehyde. As early as 1897 it was -discovered that an amorphous condensation product was obtained from the -reaction of urea and formaldehyde. The clear glass-like mass obtained led -to considerable research work toward the development of a substitute for -glass. It was found, however, that the resin obtained absorbed moisture, -resulting in a dimming of its luster, and that on standing for a time, -the condensation continued producing cracks, fissures, and disfigurements -in the molded article. In 1926 a successful commercial product was -developed in England by the use of thiourea. Cost of production, however, -was high. The addition of thiourea gave the product greater strength -and water resistance than that obtained with urea alone but retarded -the rate of cure. Also the sulphur present attacked steel molds, which -necessitated the use of expensive chromium plated or stainless steel -molds. - -About 1929 the first successful straight urea product was perfected in -the United States. It was found that a filler, such as highly refined -alpha cellulose, minimized the stresses. The filler (as much as 30 to 40 -percent is usually incorporated), destroys the transparency but permits -the manufacture of translucent articles in a wide range of color. Many of -the colors possible with the urea resins, particularly the light shades, -cannot at present be obtained in molded tar-acid resins. - -An interesting fact concerning these resins is that they are produced -indirectly from four gases: Ammonia, carbon dioxide, hydrogen, and carbon -monoxide. Ammonia and carbon dioxide react to form urea, and hydrogen and -carbon monoxide yield methyl alcohol which is converted to formaldehyde. - - -Description and uses. - -The urea resins are outstanding largely because of their brilliancy and -depth of color, properties not readily obtained in other thermosetting -resins. Being odorless and tasteless and completely resistant to oils -and greases, they are adapted to use in the manufacture of cosmetic -containers. Concentrated acids and alkalies attack the resin. The -electrical properties of the urea resins compare favorably with those of -the tar-acid resins. They have a lower power factor at high-frequencies -than the tar-acid resins, and are replacing, to some extent, established -materials in heavy duty electrical equipment where “tracking” causes -trouble. Molded articles made from urea resins are resilient but not -unbreakable. - -[Illustration: THERMOSTAT CASE OF MOLDED UREA RESIN. - -Source: Plaskon Company, Inc., 2112 Sylvan Avenue, Toledo, Ohio.] - -[Illustration: SCALES CASE OF MOLDED UREA RESIN. - -Source: Plaskon Company, Inc., 2112 Sylvan Avenue, Toledo, Ohio.] - -The important uses of the urea resins are dictated by their pleasing -color and appearance. In 1935 the largest outlets were in buttons and -buckles, in bottle closures, and in such premium items as biscuit cutters -and cereal bowls distributed by a large food manufacturer. Tableware, -bathroom fixtures, all sorts of containers and closures, housings for -radios, clocks, scales, and other machines for retail stores, and -light-colored wall plates and switches, knobs, handles, and trim on dash -panels of automobiles, and handles and trimming on gas and electric -ranges were among the widespread applications of the urea resins. In -1938 probably the fastest growing outlet for urea resins is in lighting -equipment. Use in packaging, in closures, and in housings, is also -increasing. Tableware, the principal outlet for a number of years, is -declining markedly. - -A comparatively new use is in shades and reflectors, replacing opal -glass. The unpigmented resin is highly translucent and gives high -light transmission and an exceptional degree of light diffusion. These -properties, together with low unit manufacturing costs, reduced shipping -costs, and resistance to breakage make the urea resins an ideal material -for all sorts of shades and reflectors for direct and indirect lighting -fixtures. Many of the shades used in railway cars are of this material. -The resin is available in degrees of denseness and opacity to give -particular ratios of reflection and transmission. Reflectors as large as -28 inches in diameter are on the market. - -Although molded articles are the large outlets for the urea resins, other -applications are of increasing importance. Sirups used to impregnate -paper and cloth are used in laminating and the resulting materials have -unusual decorative possibilities. The surface is hard and durable and the -wide range of colors possible permits very attractive applications. The -urea resins are used both as the principal binding material for laminated -sheets or on the surface laminae of sheets where tar-acid resins are used -as the chief binder. The latter practice permits a wide color range in -decorative materials without loss of strength or other characteristics -of the tar-acid resins. In 1937 there were seven makers, and their -production of urea resins for laminating accounted for slightly less than -10 percent of the total of all urea resins. - -Another application of urea resins which has grown rapidly in the past 2 -years is in combination with alkyd resins in surface coatings. In 1937 -there were three makers, and their output of urea resins for coatings -amounted to more than 10 percent of the total production of urea. Until -recently the use of urea resins in paints and varnishes was discouraged -by their insolubility in organic solvents and their instability. On the -other hand, their lack of color, their high transparency, their hardness, -and their freedom from after-yellowing were desirable characteristics. -The development of methods for preparing condensates, which overcome the -undesirable properties, has made available resins for this use. They -are marketed as water-white viscous solutions in a mixture of organic -solvents and are intended for use in baking finishes. They cannot be -used alone because the cured resin is extremely hard and brittle and -lacks adhesion. When combined with more elastic film-forming materials -such as drying or nondrying oil alkyd resins, they produce coatings that -are mar-proof, resistant to alcohol, grease, oil, and fruit acids, and -available in a full range of colors. Applications are in metal furniture -finishes, toys, refrigerators, can, and drum coatings. - -The value of urea resins as adhesives has been known for many years and -one of the first patents issued for such use was United States Patent -No. 1,355,834 granted in 1920. Commercial development and application, -however, did not take place until the last 2 years. Several brands of -urea adhesives are now on the market. These meet the need for a hot-press -adhesive which is applied in liquid form, cures rapidly at moderate -temperatures, and is economical. For greater economy, the urea adhesive -may be mixed with various proportions of flour (up to 50 percent) without -affecting its water resistance. Diluted thus it comes within the cost -range of animal and vegetable glues and is more durable. At present, it -sells for 18 to 20 cents per pound; mixing it with 50 percent flour gives -an adhesive for plywood, costing about 10 cents per pound. In 1937 three -producers made urea resins for this use. - -Other uses are in the treatment of textiles to obtain crease-proof -properties and in the impregnation of wood. United States Patent No. -1,951,994 issued on March 20, 1934, reports the preparation of artificial -silk from urea resins. - - -Production in the United States. - -Commercial production of urea resins in the United States was reported -for the first time in 1929. Early in that year the American Cyanamid Co. -concluded an arrangement with the British Cyanides Co. of England for -the American rights to manufacture and sell in the United States a resin -made from urea, thiourea, and formaldehyde and marketed as Beetle molding -powder. A manufacturing unit was built at Bound Brook, N. J., and in 1930 -the output was substantial. - -In 1931 another producer, the Toledo Synthetic Products Co., began -manufacture of urea resins. Several years prior to that time the Toledo -Scale Co. started a search for a material light in weight to replace the -heavy porcelain-on-steel used in cases for scales. The search led to the -urea resins and to commercial production by their subsidiary. In 1935 the -Toledo Synthetic Products Company reached an agreement with the Imperial -Chemical Industries of England for the interchange of technical and -commercial information and of free patent licenses on urea molding and -laminating resins. The name of the domestic firm was later changed to the -Plaskon Co. - -In 1932 the Unyte Corporation started commercial production of urea -resins at Grasselli, N. J. This firm was affiliated with the American -I. G. Corporation. Late in 1936 the Plaskon Co. took over the Unyte -Corporation. - -The output of urea resins increased markedly in 1936 and 1937. Statistics -for those years cannot be published without disclosing operations of -individual firms. It may be stated, however, that the increase in both -years over the previous year was considerably greater than for any -earlier period. Most of the production was used in molded articles -although appreciable quantities were consumed in laminated articles, in -surface coatings, in the impregnation of fabric, and in adhesives. - -There were 10 domestic makers of these resins in 1937. - -Domestic production and sales of urea resins are shown in table 8. - -TABLE 8.—_Urea resins: United States production and sales, 1933-37_ - - --------+------------+------------------------------------ - | | Sales - Year | Production +-----------+------------+----------- - | | Quantity | Value | Unit value - --------+------------+-----------+------------+----------- - | _Pounds_ | _Pounds_ | | - 1933 | 3,234,356 | 2,977,791 | $1,422,671 | $0.48 - 1934 | 3,470,916 | 3,115,608 | 1,290,802 | .41 - 1935 | 4,202,536 | 4,005,083 | 1,828,565 | .46 - 1936-37 | ([1]) | ([1]) | ([1]) | - - [1] Not publishable; figures would reveal operations of - individual firms. - - Source: Dyes and Other Synthetic Organic Chemicals in the United - States, U. S. Tariff Commission. - - -United States imports and exports. - -Resins obtained from urea and thiourea, if imported, would probably be -classified under paragraph 11 of the Tariff Act of 1930. The present rate -of duty under this classification is 4 cents per pound and 30 percent ad -valorem. - -There has been no importation of these resins. This is due principally -to the international licensing arrangements which usually include the -allocation of markets. - -Exports are not shown separately in official statistics. - - - - -6. ACRYLATE RESINS - - -A new development of widespread importance in the synthetic resin -industry is the commercial production of the polymers of certain -derivatives of acrylic acid. The commercial exploitation of the acrylates -is another example of the belated realization of the value of substances -known for many years. Acrylic acid has been known for about a hundred -years, and the polymer of methyl acrylate was first described in 1880. It -was not until 1927, however, that a suitable method for their commercial -production was developed. The study of the many derivatives of acrylic -and methacrylic acids leads to the conclusion that those of greatest -practical application in the resin field are the lower esters, such as -methyl and ethyl, polymerized separately or together. - -Colorless transparency, stability against aging, thermoplasticity, and -chemical resistance to many reagents are the general characteristics -of the acrylate resins. In consistency they range from soft, sticky, -semiliquids to hard, tough, thermoplastic solids. Since these widely -varying properties are obtained by control of manufacturing conditions, -rather than by the use of plasticizers, the resins retain their initial -properties indefinitely. Aging and weathering have no effect as they -are stable under exposure to heat, light, and oxidizing agents. The -methacrylates are harder and tougher but less elastic than the acrylates. - - -Properties and uses. - -The acrylate resins are marketed in a number of forms, such as solutions -in organic solvents, dispersions in water, solid cast sheets, rods and -tubes, and molding powders. All of these are distinguishable from many -other resins by their colorless transparency, adhesive qualities, -great elasticity, and chemical resistance. The brilliant water-white -color makes it possible to secure masses having a high degree of light -transmission and great optical clarity. - -The earliest commercial use of the acrylate resins was in laminated -safety glass marketed as Plexigum in the United States and as Luglas and -Sigla in Europe. The extensibility and elasticity of the resin film gives -the laminated glass a flexible or yielding type of break when subjected -to a hard impact. Having excellent adhesion to glass there is no need of -an auxiliary cement to bond the resin to the glass, nor is it necessary -to seal the edges since the resin has good resistance to moisture. The -acrylate resin used for this purpose is in the form of a viscous solution -in an organic solvent. A film is applied to each sheet of glass, the -solvent removed by drying, and the sheets are pressed together. - -The harder acrylic resins are used in the form of solid thermoplastics. -Methyl methacrylate is of special interest. As the monomer is a mobile -liquid it can be cast-polymerized to a solid of any desired shape in -predesigned molds or produced in finely divided form for use as molding -powder. The cast resin is marketed in this country as Crystalite, -Plexiglas and Lucite, and in England as Diakon. - -The solid acrylate resins are clearer than cast phenolic resins, not as -brittle as the polystyrene resins, and not as tough as cellulose acetate -or nitrocellulose plastics. Their transparency and resistance to aging -and weather permit their use in applications not previously considered -for synthetic resins. Sheets of this resin may be formed or molded -into many useful shapes. The aircraft industry has found them suitable -for windshields and cockpit enclosures to effect streamlining and thus -greatly reduce wind resistance. - -Methyl methacrylate is probably the nearest approach to organic glass -thus far developed. Its optical properties make it suitable for spectacle -lenses, camera lenses, magnifying glasses, and protective goggles. -Spectacle lenses are now being made to prescription by molding. It is -estimated that 900 molds will supply the requirements of about 98 percent -of the prescriptions. The excellent light transmitting quality of methyl -methacrylate permits its use in edge lighting, advertising displays, and -instrument dials. It is also used in inspection windows in various types -of machinery where curved sections are necessary and where glass might be -broken. - -A synthetic resin combining the properties mentioned, together with high -tensile and impact strength, good dielectric properties, ultraviolet -transmission, and resistance to water, oil, acids, and alkalies is an -important contribution. The acrylates may be colored or have fillers -added to give any desired translucency or opaqueness. They can be sawed, -cut, blanked, turned, drilled, ground, polished, and sanded much the same -as are nitrocellulose plastics. - -[Illustration: AIRPLANE COCKPIT ENCLOSURES OF CAST ACRYLATE RESIN. - -Source: Rohm & Haas Company, 222 W. Washington Square, Philadelphia, Pa.] - -[Illustration: SPECTACLE LENSES MOLDED TO OPTICAL PRESCRIPTION FROM -ACRYLATE RESIN. - -Source: Rohm & Haas Company, 222 W. Washington Square, Philadelphia, Pa.] - -A new and interesting application of the acrylate resins is as molded -reflectors in a system of indirect highway lighting. The reflectors are -pressed from colorless, transparent methyl methacrylate resin and are -1⅝ inches in diameter. They are assembled in a pressed metal housing to -form a double facing marker which is snap-locked to the top of an angle -iron post. The posts are so located that the reflectors are accurately -aligned 3 feet above the pavement edge. An installation has been made -on U. S. Highway No. 16 between Detroit and Lansing, Mich., at a cost -of about $340 per mile. The motorist provides his own light from his -headlights which strikes the reflectors and is returned as a narrow beam -of brilliant illumination. The chief of the United States Bureau of -Public Roads states that this is a definite contribution to the safety -and utility of the highways at night. The reflector is a group of tiny -cube corners, over 300 in each disk. Each cube corner is a complete -retrodirective optical system; a light ray entering the front surface -is reflected from surface to surface of the cube and after the third -reflection is directed back toward the headlight regardless of the -entrance angle. If the cubes are made with a high degree of dimensional -accuracy, the reflected light has a high candlepower, strong enough to be -seen for a mile. - -Other uses for these resins are in sound recording records, dentures, -telephone and radio transmitter diaphragms, novelties, and lighting -fixtures. - -The monomer (unpolymerized methyl methacrylate) may be used to impregnate -wood, cloth, wallboard, cork, paper, electrical coils, tile, or stone, -and then polymerized to form the resin. Paper and cloth so treated have -many uses, such as in the electrical and food-packaging industries. -Laminated sheets find wide possibilities for use in the aircraft field, -and for lamp shades. Wood may be impregnated with as much as 60 percent -of the monomer. Solutions of these resins in organic solvents, such as -ethylene dichloride, ethyl acetate, and toluol, are used in surface -coatings, undercoats on difficult adhesion jobs, to impregnate paper and -textiles, and in insulation. These coating solutions are marketed in the -United States under the trade name Acryloids and in Europe under the -trade names, Borron, Plexigum, and Acronol. They may be brushed, sprayed, -dipped, and baked. Baking is recommended to give a higher gloss, better -adhesion, and a harder film. The dried film has an elasticity of 1,000 -percent at ordinary room temperature and the light transmission of clear -films is intermediate between ordinary window glass and quartz. - -Acrysol is an adhesive consisting of a dispersion of the resin in water -and is recommended for use where adhesion is difficult, as on rubber or -rubberized surfaces. - - -Production in the United States. - -Commercial production of acrylate resins in the United States was started -in 1931 by Rohm and Haas, Philadelphia, Pa., under United States Patents -Nos. 1,388,016 of August 16, 1921, and 1,829,208 of October 27, 1931. - -Commercial production of methyl methacrylate resins was started in 1937 -by E. I. du Pont de Nemours & Co. This development is under United States -Patent No. 1,980,483, issued in 1934. The liquid monomer is produced at -Belle, W. Va., and shipped to Arlington, N. J., where it is polymerized -by heat to the solid resin. - -The output of acrylate resins was hardly more than experimental in 1935 -but increased somewhat in 1936 and very appreciably in 1937. Although -statistics of production are not publishable, it can be stated that -in 1937 the output approached that of other synthetic resins made in -commercial quantities. The properties of these resins indicate very -large commercial production in the near future. Prices of the several -types are still high as compared with other resins but should eventually -be somewhat lower than those of cellulose acetate and nitrocellulose -plastics and slightly higher than those of cast phenolic resins. - - -Imports into and exports from the United States. - -There have been no recorded imports of acrylate resins. The two domestic -producers have agreements, licenses, or affiliations with the principal -foreign makers of these products, one in England and one in Germany. Such -arrangements would account for the absence of imports, except for sample -or experimental lots, and might also limit export markets. - - - - -7. COUMARONE AND INDENE RESINS - - -Coumarone and indene are present in appreciable quantities in certain -coal-tar fractions, especially in the solvent naphtha fractions -distilling between 160° and 190° C. No attempt is made to isolate -them from the solvent naphtha. Such a procedure would be difficult -and expensive and, since polymerization readily takes place in dilute -solutions, it is more economical to use fractions of solvent naphtha rich -in these substances. The resins obtained are mixtures of polymerized -coumarone and polymerized indene. - -The solvent naphtha must be refined by fractional distillation and -the polymerization very carefully controlled. The polymerizing agent -is usually sulphuric acid although metallic salts, such as aluminum -chloride, are sometimes used. The yield and color of the resin are -affected by temperature and amount of acid used. Light colored resins -are the most desirable. After polymerization the acid or metallic salt -is removed, the product washed and neutralized and finally distilled. -Several byproducts, such as naphtha, paracoumarone soap, and high boiling -oils, are also obtained. - - -Description and uses. - -Coumarone and indene resins are produced and marketed in the United -States under the trade names Cumar and Neville. A number of grades are -available, including the following: - - Designation: _Melting point_ - Rubber grade, soft 50°- 65° C. - Medium soft 65°- 85° C. - Rubber grade, hard 85°-100° C. - Medium hard 100°-135° C. - Varnish grade 135°-160° C. - -In addition to these, certain types are produced for special purposes. - -The coumarone and indene resins are used to a large extent in varnishes -for metal and wood. In this application they may be used to replace -all or part of the higher priced natural resins and, to some extent, -ester gum. Their application is somewhat limited by their rather -short durability and elasticity. They are neutral, nonoxidizing and -nonsaponifiable and impart to varnishes greater inertness and adhesion, -fair dielectric strength, and shorter drying time than many of the -natural resins. They cannot be used in nitrocellulose lacquer since they -are not compatible with that plastic. - -Another important use of these resins is as an ingredient in mastic -floor tile, in the production of which a thermoplastic binder is -used. Originally, asphalt was used, but demand for light colored tile -necessitated some other binder, the requirements for which were met by -the coumarone and indene resins. - -The next largest application of these resins is in rubber compounding, -their effect being to soften the rubber during milling and to facilitate -its handling on rolls. They do not affect the aging qualities of rubber -and are used as a softener for reclaimed as well as for new rubber. - -Coumarone and indene resins are used, to some extent, in linoleum, for -impregnating roofing felt, in electrical and friction tapes, paper -and cloth sizing, printing inks, brake linings, adhesives, artificial -leather, oil cloth, and shoe polishes. As a substitute for chicle as -much as 10 percent may be incorporated in the chewing gum mixture. -Their application in molded articles is very limited because of their -brittleness and low tensile strength. - - -Production in the United States. - -There are three domestic makers of these resins. Statistics of production -and sales cannot be published without disclosing the operations of -individual companies. The output, however, has increased appreciably -in recent years and this type of synthetic resin is now among the most -important produced. - - -Imports into and exports from the United States. - -There have been no recorded imports of coumarone and indene resins in -recent years. This is understandable because the duty alone would usually -be more than the domestic price.[4] - -Official export statistics do not separately record these resins, -although quantities are exported to nearby countries, including Canada. - - - - -8. PETROLEUM RESINS - - -Considerable research work has been done on the synthesis of resins from -petroleum. It has long been known that cracked petroleum distillates, -when stored for a time, have a tendency to form gums. This tendency is -so pronounced that inhibitors are added to arrest such formation. These -gums are of little value as resins, but it is possible to obtain good -varnish resins by oxidation or controlled polymerization of certain -distillates of petroleum cracking. By carefully controlling operations, -resins of varied properties are obtained and several of them have become -commercially important. The unsaturated compounds, largely olefins -and diolefins, present in highly cracked petroleum distillates can be -polymerized, with certain catalysts. The resin produced depends upon the -types of unsaturated hydrocarbons present and upon the conditions of -polymerization. - - -Properties and uses. - -Several types of petroleum resins are on the market, one made from the -“polymer slop” obtained in the high temperature, vapor-phase cracking -operation, and the other prepared primarily for the production of resin. -The former is marketed under the trade name Petropol and the latter as -Santoresin. - -The “Petropol” resins are marketed in two grades, No. 1158 and No. 2138. -The specifications for these are as follows: - - -----------------+--------------------------+------------------------- - | Petropol No. 1158 liquid | Petropol No. 2138 liquid - -----------------+--------------------------+------------------------- - Gravity | 15.5-18.5 | 10-11 A. P. I. - Flash | 175° F. minimum. | 230° F. minimum. - Fire | 215° F. minimum. | 280° F. minimum. - Viscosity | 200-225 at 212° F. | 225-300 at 210° F. - Pour | 0° F. maximum. | 45° F. approximate. - Iodine No. | 195 minimum. | 200 minimum. - Molecular weight | 300 approximate. | 425 approximate. - Percent solids | 60-65. | 80-85. - -----------------+--------------------------+------------------------- - - Miscible in all proportions with petroleum solvents. - -Petropol No. 1158 is used by core oil makers to replace such vegetable -oils as linseed, tung, and perilla. It is used also as a binder and -waterproofing agent on rock wool insulation, replacing rosin and mineral -oil. For spraying coal to minimize dusting, it has the advantage over -calcium chloride of increasing the B. t. u. content of the fuel. - -Petropol No. 2138 is a surface coating material which dries by -polymerization. A low cost paint is obtained by combining a pigment and -a plasticizer with the resin. Such paint dries in about one-fourth the -time of linseed oil paints, adheres better to metal, and has greater -resistance to water, acids, and alkalies. In varnishes and enamels it -replaces 12 to 15 percent of tar-acid resin, minimizes skinning, and -gives a higher luster and better flow. Another use of this Petropol is as -a binder in brake linings, replacing certain tar-acid resins. - -These two Petropol resins are among the lowest priced synthetics, selling -at present (1938), in tank carlots, for 2 to 5 cents per pound. - -The Santoresins are clear, hard, neutral products, melting at 100° C. -They are soluble in drying oils, accelerate the gelatination of tung -oil, are nonreactive with pigments, do not yellow on outdoor exposure, -and are resistant to alkalies, acids, alcohol, and water. Applications -are in protective coatings for wood, metal, paper, leather, cement, -plaster, and other materials, in printing inks, plastic tile, linoleum, -and fiber packages. Being odorless and tasteless they may be used to line -food containers. Their high resiliency and purity recommend their use -as a base for chewing gum. Other uses are as an agent for wetting and -dispersing pigments in rubber and in surface coatings, to replace ester -gum or modified tar-acid resins. - -At present the Santoresins are offered at 15 cents per pound in lots of -20,000 pounds or more. Their approximate specifications are: - - Appearance A clear hard resin. - Melting point 110° to 120° C. A. S. T. M. (Ring & Ball). - Acid value 0 to 1. - Iodine value 125 to 135. - Specific gravity (at 20° C.) 1.02 or 8.5 lbs. per gallon. - Color (50 percent solution - by weight in toluol) 13 to 15 Gardner Holt standard. - -Odor slight when cold, sweet and aromatic when melted. Soluble in -aromatic hydrocarbons, petroleum thinners, turpentine, and varnish oils. -Insoluble in alcohols, esters, ketones, and not completely compatible -with nitrocellulose. - - -Production. - -In the United States two makers of petroleum resins are producing in -commercial quantities and several others are carrying on extensive -research. Production was small in 1935, but increased in 1936 and in -1937. The development and expansion of these resins over the past 2 years -indicate that they will become important. - - -Imports into and exports from the United States. - -There has been no importation of petroleum resins into the United States. -Exports have been confined to samples and experimental quantities. - - - - -9. POLYSTYRENE RESINS - - -The polystyrene resins are thermoplastic products discovered about -100 years ago and are therefore the oldest synthetic resins known. -Their practical application has been greatly retarded by the lack -of inexpensive raw materials of high purity and by the difficulties -experienced in their manufacture. - -Ethylene, from petroleum or natural gas, is combined with benzene, from -byproduct coke-oven operations, to form ethyl benzene, which is cracked -to vinyl benzene or styrene. This monomer is polymerized by heat at -100°-150° C. The resin may be extremely tough or very brittle, depending -on the conditions of polymerization. Products having different properties -are obtained by (_a_) low temperature polymerization, (_b_) high -temperature polymerization, and (_c_) catalytic polymerization. - -The low-temperature polymers, sometimes designated as alpha-metastyrol, -are produced by polymerizations of vinyl benzene at temperatures under -175° C. A transparent resin, colorless to light yellow, is produced which -is remarkably tough, has excellent tensile strength, unusually good -dielectric properties, and is resistant to most chemicals. - -Polymerization at high temperatures (above 175° C.) yields a brittle -resin designated as beta-metastyrol. This type is transparent but usually -dark in color, has low tensile strength and shock resistance. - -When vinyl benzene is polymerized in the presence of catalysts, the -resulting resin is similar to resins obtained at high temperatures, -except that it is lighter in color. It is sometimes designated as -gamma-metastyrol. Oxidizing agents are usually the catalysts. Clear, -colorless, vitreous resins are obtained by excluding air during -polymerization. - - -Properties and uses. - -Polystyrene resin is a clear, colorless, highly thermoplastic molding -material with high insulating property, moisture resistance, inertness, -dimensional stability, and impact strength. It can be molded directly -by heat and pressure, and the molded articles are remarkably resistant -to discoloration by light. Polystyrene has a dielectric constant of -2.6, a power factor of 0.02 percent, and is equivalent to fused quartz -as an electrical insulator of low dielectric loss. Films of 0.002 inch -thickness have a dielectric strength of more than 2,000 volts per mil -thickness, which is better than that of any other available synthetic -resin and even better than that of shellac. The tensile strength of -the resin is 5,500 to 7,000 pounds per square inch, and its impact -resistance remains unchanged at temperatures as low as minus 70° C. It -transmits all wave lengths of light down to 3,000 Angstrom units. - -Polystyrene is adapted to large scale production of transparent, -translucent, and opaque moldings in a wide variety of colors. It is -easily molded by injection processes, softening at about 150° F. and is -molded at 300° to 375° F., under 3,000 to 30,000 pounds pressure per -square inch. As much as 40 percent filler may be used without seriously -affecting the tensile strength, although the filler does affect the -dielectric properties. Since the resin is thermoplastic there is no waste -in the molding operation; scrap material may be reground and used again. - -The unusual properties of these polystyrene resins should give them -widespread applications when the cost is low enough to make them -competitive with other materials. Potentially large volume outlets are -in radio frequency insulation; in dentures because of the strength, low -specific gravity, ease of coloring, and absence of odor and taste of the -material; in electrical parts for submarine and aircraft storage battery -cases and separators; and for the manufacture of glass eyes. - -Other possible applications of polystyrene resins are in metal lacquers -and in light colored enamels. Their toughness and light color, together -with their solubility in cheap solvents, suggest their use for these -purposes. Such lacquers are said to be quick-drying, resistant to water, -and moderately so to acids and alkalies. - - -Production in the United States. - -For a number of years, the Naugatuck Chemical Division of the United -States Rubber Co. produced small quantities of polystyrene resins, which -were marketed under the trade name Victron when for general purposes and -under the trade name Marvelyn when for use in dentures. Little progress -was made because of high costs and failure to produce a water-white -product. The sales price was between $1.50 and $2 per pound. Early -in 1937 the Naugatuck Chemical Division transferred its patents on -polystyrene resins to the Carbide and Carbon Chemicals Corporation. - -The Dow Chemical Co., Midland, Mich., late in 1937 announced commercial -production of clear, colorless polystyrene in several forms. Styron -is the trade name for the resin from this source. In January 1938, -the Bakelite Corporation announced Bakelite Polystyrene. The plants -manufacturing polystyrene have a capacity in excess of 2,000,000 pounds a -year, and the resin is currently offered at 72 cents per pound. - -At least one other domestic firm is doing research on the polystyrenes -and expects to produce commercially in the near future. - - -Imports into and exports from the United States. - -At least two commercial types of polystyrene resins are produced abroad. -Both are made in Germany and marketed under the trade names Resoglas -and Trolitul. Resoglas is a water-white, transparent thermoplastic -resin softening at about 150° C. Its water absorption is low, it is -nonoxidizing, and does not discolor on weathering and baking. Appreciable -quantities are produced in Germany and the sales price there was reported -to have been 40 cents per pound during 1936. - -[Illustration: MOLDED POLYSTYRENE RESINS. - -Source: Bakelite Corporation, 247 Park Avenue, New York, N. Y.] - -Small quantities of Resoglas and Trolitul have been imported from Germany -in recent years. Table 9 shows the quantities imported in recent years. - -TABLE 9.—_Resoglas and Trolitul: United States imports for consumption, -1933-37_ - - --------+-----------------------------+--------------------------- - | Resoglas (polystyrol) | Trolitul - Year +----------+-------+----------+--------+-------+---------- - | Quantity | Value |Unit value|Quantity| Value |Unit value - --------+----------+-------+----------+--------+-------+---------- - | _Pounds_ | | |_Pounds_| | - 1933 | 771 | ([1]) | | 672 | ([1]) | - 1934 | 991 | ([1]) | | 200 | ([1]) | - 1935 | 110 | $97 | $0.88 | 4,608 |$3,782 | $0.82 - 1936 | 2,220 | 1,901 | .86 | 4,671 | 3,641 | .78 - 1937[2] | None | None | | 6,788 | 4,077 | .60 - --------+----------+-------+----------+--------+-------+---------- - - [1] Not available. - - [2] Preliminary. - - Source: Analyses of invoices of paragraph 28, act of 1930—U. S. - Tariff Commission. - -With the more advanced development of polystyrol resins in Germany prior -to 1938, evidenced by larger commercial production, by wider application, -by the marketing of a water-white product at a considerably lower price, -it might be expected that imports into the United States would have been -in considerably larger amount than shown in table 9. That they were small -was probably due to the high rate of duty which made them expensive -as compared with other synthetic resins in the United States and thus -limited their market to uses in which the others were less satisfactory. -Resoglas was reported to have been selling for 40 cents per pound in -Germany. The imported resin is assessed for duty under the provisions of -paragraph 28 of the Tariff Act of 1930 at 45 percent ad valorem based -on American selling price (as a competitive product) and 7 cents per -pound. The American selling price of the resin made in the United States -until late in 1937, as determined by the Bureau of Customs, Treasury -Department, was $1.85 per pound. The duty was therefore 90 cents per -pound. Imports of Trolitul were valued at 75 cents per pound, giving a -cost of $1.75 per pound laid down, duty paid, in domestic markets. With -the present American selling price of 72 cents per pound, the duty would -be approximately 36 cents per pound. - - - - -10. VINYL RESINS - - -Vinyl acetate, vinyl chloride, and to a lesser extent vinyl -chloroacetate, are the raw materials (monomers) for the several vinyl -resins commercially produced in the United States, Canada, and Germany. -These are all esters of the hypothetical vinyl alcohol and are made by -the action of acetic and hydrochloric acids on acetylene. - -The spontaneous polymerization of vinyl derivatives has been known for -many years, although its significance and industrial application have -been realized only recently. Vinyl acetate, probably the most important -of the vinyl esters, was discovered in 1912 and first made in Canada in -1917. - -Vinyl resins may be classified into (_a_) polyvinyl acetate, (_b_) -copolymers of vinyl acetate and vinyl chloride, (_c_) polyvinyl chloride, -and (_d_) polyvinyl chloroacetate. - - -Description and uses. - -_Polyvinyl acetate resins._—The several commercial types of vinyl acetate -resins are marketed under the trade names Vinyloid A, Alvar, Gelva, -Formvar, and Mowilith. The first of these is a product of Carbide and -Carbon Chemicals Co., New York, the next three are products of Shawinigan -Chemicals Limited, Shawinigan Falls, Canada, and the last is made by -the Interessen Gemeinschaft Industrie A. G., Germany. Vinyloid A and -Gelva represent the simplest series of vinyl acetate resins and are -made by polymerizing the monomer. The softening point and viscosity of -the polyvinyl acetate resins increase with higher polymerization. Such -resins are colorless, tasteless, odorless, thermoplastic products. They -are soluble in coal-tar solvents and are compatible with certain alkyd -resins, tar-acid resins, and natural resins. Films of polyvinyl acetate -resin are not discolored by exposure, and after irradiation they become -opaque to ultraviolet light, are hard and tough, and have good adherence -and endurance. Their dielectric strength is good and they do not show a -carbon track after the passage of an electric arc. Various grades having -softening points from 80° to 200° C. are available. - -Polyvinyl acetate resins are used in making transparent papers, -paper to metal laminations, glassine papers for food packaging, as a -substitute for chicle in chewing gum, and as a component of paints, -varnishes, and lacquers. They have the desirable properties of -compatibility, durability, resistance to abrasion, and rust inhibition -in the surface-coating use. Having the same refractive index as pyrex -glass, they leave no line of demarcation when used as a cement for that -material. They have been used to stiffen toe-caps in shoes and articles -made from paper pulp suspensions. Gelvas are not molded as such because -of their tendency to cold flow. They are used, however, as a binder for -ground mineral fillers in advertising signs and for wood flour in molded -artificial wood carvings. In nitrocellulose lacquers they improve the -adhesion, luster, and toughness. - -Alvars are made by replacing part or all of the acetate groups in -Gelva with acetaldehyde. Their viscosity varies with the degree of -polymerization and their properties vary according to the extent of -replacement of the acetate groups. The Alvar types do not cold flow -when molded, are tougher, harder, and have better adhesion but are less -resistant to weathering than the Gelva types. Other properties are about -the same as those of the Gelvas. Alvars having 70 to 80 percent acetate -group replacement are used chiefly in spirit type varnishes, lacquers, -and enamels that must stand exposure to weather. Another Alvar type -is used in injection and press molding. The high binding power of the -resin permits the use of large percentages of filler without loss of -desirable properties. Such moldings may be machined and polished, and -take inserts, such as the wood core in shoe heels. Flexible phonograph -and transcription records made from the Alvars have gained wide approval. -An 85 percent (acetate replacement) type has better impact strength and -is used in toilet articles. Sheets, rods, and tubes of this resin may be -machined in much the same way as nitrocellulose plastic and used where -noninflammability is an asset. - -Formvars are made by replacing part or all of the acetate groups in Gelva -with formaldehyde. These resins are colorless, odorless, tasteless, and -thermoplastic. They have higher softening points and greater tensile and -impact strength than the Alvars. They are resistant to alcohols, coal-tar -solvents, fats, oils, or water. Moisture transmission rate through a film -of this resin is about one-tenth that through regenerated cellulose and -one-fourth that through cellulose acetate. - -The grades of the Formvars available are designated by the extent of -replacement of the acetate group. The 75-percent replacement type has -excellent mechanical strength and flexibility and is unaffected by -sunlight. Formvars of 95 percent acetate displacement have a tensile -strength as high as 10,000 pounds per square inch and offer possibilities -in the manufacture of artificial silk and photographic film. - -The vinyl resins have made possible a new type of safety glass superior -to any heretofore marketed. By condensing butylaldehyde with vinyl -acetate, a polymer is obtained which is used as the inner layer between -two sheets of glass. Heat and pressure secure complete adhesion and yield -a sheet with greater resistance to breakage at low temperatures than the -types now in general use. - -Although safety glass was invented in 1905, and many substitutes for the -original nitrocellulose inner layer have been proposed, only two reached -commercial importance before the development of the vinyl resins. These -are cellulose acetate and the acrylate resins. Safety glass used in -automobile windshields up to about 1930 discolored after a year or two -of service. This discoloration was due to the action of the actinic rays -of the sun on the nitrocellulose layer. Since 1930 this difficulty has -been largely overcome by using an actinic ray filter glass (a special -glass with a high iron content) in front of the nitrocellulose sheet, or -by using cellulose acetate, which is not discolored to the same extent -by light, as a substitute for nitrocellulose. Both cellulose nitrate -and cellulose acetate, however, have a tendency to lose toughness and -strength at low temperatures, to absorb moisture, and to separate from -the glass around the edge unless sealed, and to lose their plasticizer -and shrink. - -Although a vast improvement over ordinary plate glass, laminated glass -made with cellulose nitrate or acetate has the serious defect of being -brittle at low temperatures, such as prevail in the winters of northern -States. It is easily shattered at zero Fahrenheit, while at 60° F. -and above it is quite strong. This shortcoming led to the development -of the vinyl resin sheet for safety glass with a remarkable degree of -toughness. At normal temperatures it has rubberlike toughness which, -although decreased at low temperatures, is not punctured by the impact -of a half-pound steel ball falling from a 30-foot height at minus 10° -F., whereas nitrocellulose or acetate laminated glass withstands the -impact of a fall from not greater than one-tenth this height. A further -advantage of the vinyl sheet is that it is water resistant, making the -sealing of the edges of the glass unnecessary and thus reducing costs. -Exposure to ultraviolet light in Florida sunlight for more than 2 years -did not discolor it. - -The many desirable properties of the vinyl resins, as outlined above, -indicate their widespread use in laminated safety glass when it is -available in sufficient quantities. It is estimated that our annual -output of safety glass interlayer sheets exceeds 17,000,000 pounds, of -which 25 to 30 percent are for windshields, and 70 to 75 percent for side -and back windows of automobiles. - -At least one of the series of Mowiliths made in Germany is polymerized -vinyl acetate. It is recommended as an ingredient of water-white -lacquers. It is compatible with nitrocellulose and is extremely durable -and not disintegrated or discolored on exposure to weather. - -_Copolymers of vinyl acetate and vinyl chloride._—The simultaneous -polymerization of mixtures of vinyl acetate and vinyl chloride yields -resins with the desirable properties of the two reactants. The extent -of plasticity is largely controlled by varying the ratio of the vinyl -derivatives. Resins high in vinyl chloride content are better suited to -molding, and those high in vinyl acetate are better lacquer ingredients. -These resins are marketed as Vinylites by the Carbide and Carbon -Chemicals Co., New York. They are thermoplastic, odorless, tasteless, and -practically nonflammable. Their outstanding properties are resistance -to water, soap, acids, alkalies, and alcohol, and their strength and -good dielectric properties. Their stability to light is improved by -the addition of ultraviolet absorbing compounds and their stability to -heat by the addition of lead oleate, calcium stearate, or other bases. -Water absorption and compatibility with other resins is increased as the -chloride content increases. - -The principal types of copolymers are: - -Vinylite VYN, high molecular weight. This resin is used in dentures -where good fatigue resistance, impact strength, and tensile strength are -required. It contains 85 to 88 percent vinyl chloride. - -Vinylite VYN, medium molecular weight. This resin is used in general -molding and extending applications including sheets, rods, and tubes. Its -vinyl chloride content averages 85 to 88 percent. - -Vinylite VYN, low molecular weight. This resin is used in moldings, -coated paper, lacquers, floor tile, phonograph records, and felt -impregnation. It contains 85 to 88 percent vinyl chloride. - -Vinylite VYC. This resin of low molecular weight is compatible with -nitrocellulose and is used in lacquers and finishes for industrial -applications. Lacquers from the Vinylites are called Vinyloids. - -The Vinylites for molding are thermoplastic and shrink very little, -making them applicable to large moldings. They may be used in extension -processes such as tooth-brush preforms, pipe lining, and wall trim. -Fillers and pigments may be added, although pigments containing iron and -zinc have harmful effects on the stability of the resin. The fillers -used are wood flour, mica, talc, and alpha cellulose. Fillers reduce the -mechanical strength of the resin and lessen its resistance to water. -Plasticizers, such as dibutyl phthalate or tricresyl phosphate, give a -softer, more flexible resin. Resins from the copolymers resemble the -cellulose derivatives in their molding characteristics, mechanical -strength, and appearance. - -In lacquers the Vinylites offer high resistance to water, oils, and -chemicals. The drying of such lacquers is by evaporation rather than -by oxidation. They are suitable for lining food containers, coating -concrete, coating paper for bottle cap liners, and as a stiffener for -box toes of shoes. Their most successful application at present is as an -inside coating for beer cans. Floor tile containing these resins mixed -with slate flour or other filler has good possibilities. - -_Polyvinyl chloride resins._—Vinyl chloride may be polymerized to give -nonflammable resins of varying solubilities. The completely polymerized -resin is practically insoluble at ordinary temperatures and is used as a -rubber substitute. It is marketed as Koroseal by B. F. Goodrich Rubber -Co., Akron, O. Compared with natural rubber, it has greater resistance to -acids, alkalies, oils, and alcohol, more flexing life, better resistance -to sunlight, water, and oxidation. Solutions of this resin marketed as -Korolac are used in special types of varnishes. - -_Polyvinyl chloroacetate resins._—These resins known as Mowiliths are -made in Germany. Application is largely for surface coating. Practically -no information on this type is available. - -_Divinyl acetylene and synthetic rubber._—Two products closely related -to those described above but probably not synthetic resins as defined -for this discussion are divinyl acetylene, a synthetic drying oil, and -Neoprene, a synthetic rubber. - -Acetylene, when passed into a solution of copper chloride and ammonium -chloride, combines with itself. When two molecules of acetylene react -monovinyl acetylene is formed, and when three molecules of acetylene -react divinyl acetylene is formed. Monovinyl acetylene reacts with -hydrochloric acid to give chloroprene, which is polymerized to synthetic -rubber or Neoprene. - -Divinyl acetylene is a colorless liquid which darkens on exposure to -light and which has an onionlike odor. When polymerized liquids are -formed, then as the reaction progresses viscous products and finally -insoluble, infusible, inert resins. By arresting the reaction before the -gel point is reached, an amber colored heavy liquid, soluble in aromatic -hydrocarbons, is obtained. Since divinyl acetylene will continue to -polymerize at ordinary temperatures, this property is taken advantage of -in using it as a basis for paints, under the name “synthetic drying oil.” -Clear, amber films are obtained from solutions of this oil in solvent -naphtha. Divinyl acetylene is quick drying, is many times more impervious -to moisture than linseed oil, and is thermosetting. It is not attacked -by solvents but is attacked by strong oxidizing agents, and the gelled -material may ignite spontaneously. - -Although not classified as a resin, synthetic rubber is discussed here -because of its close chemical relationship to the vinyl resins. It is -made commercially by E. I. du Pont de Nemours & Co., Wilmington, Del., -and is marketed as Neoprene. It is sold as a plastic polymer which is -vulcanized and processed much the same as natural rubber except that -sulphur is not essential to vulcanization. Synthetic rubber is higher in -price than natural rubber, but it has certain properties which make it -suitable for service conditions where natural rubber is unsatisfactory. -Among these properties are its resistance to gasoline, oils, and greases, -and to elevated temperatures. It does not check or crack on exposure to -sunlight, nor does it oxidize as rapidly as natural rubber. Its principal -applications are in special gaskets, printing rolls, jackets for high -tension cable, linings for gasoline or oil hose lines, balloon fabrics, -diaphragms for regulators, and packing for compressors. Its existence -acts as a limit to the increase in the price of natural rubber and -assures a supply in emergencies. - - -Production in the United States. - -Some of the products described are commercially produced in the United -States; others in Canada or in Germany. Those made in the United States -are usually not made by more than one firm, so that statistics of -production and sales are not publishable. The vinyl acetate resins have -been produced principally in Canada; the copolymers of vinyl chloride and -vinyl acetate are domestic products. In 1935 the United States output of -all vinyl resins exceeded 1,000,000 pounds, a figure that was increased -in 1936 and 1937. - -The Canadian output of Gelva and Alvar has reached commercial quantities; -that of Formvar is still confined to experimental plant lots. - -The acceptance of vinyl resin sheets for safety glass will greatly -increase the output in 1938. The basic patent, known as the -Morrison-Blaike patent, United States No. 2,036,092 issued on March 31, -1936, is owned by Shawinigan Chemicals, Ltd., Montreal, Canada, who have -licensed several domestic producers. The monomer (vinyl acetate) is now -produced at Niagara Falls, N. Y., by the Niacet Chemicals Corp., which -is jointly owned by this Canadian firm, Carbide and Carbon Chemicals -Corporation, and E. I. du Pont de Nemours & Co. It is also produced by -du Pont at Belle, W. Va. It is shipped, in tank cars, to polymerization -and sheet-forming plants at Indian Orchard, Mass., Arlington, N. J., and -Charleston, W. Va. The Indian Orchard plant, known as the Shawinigan -Resin Products Co., and jointly owned by the Canadian firm and the -Fiberloid Corporation, is now in operation. The plant of the du Pont -Company at Arlington, N. J., began production in May 1938, and that -of Carbide and Carbon Chemicals Corp, at Charleston, W. Va., is in -production. These plants have a combined annual capacity of about 10 -million pounds of vinyl resin sheets. According to present plans this -new safety glass will be available for 1939 model automobiles. The resin -sheet to be used is 0.0015 inch thick as compared with the 0.0025 inch -thickness of the present cellulose acetate and nitrocellulose sheet. -Several trade names have been adopted for the vinyl resin sheets, among -which are Vinylite X, and Butvar. The licenses granted to domestic makers -under the Morrison-Blaike patent also permit them to make vinyl acetate -resins for purposes other than safety-glass sheets. Considerable progress -has been made in adapting these resins to injection molding operations -for the production of tooth-brush handles, combs, closures, and other -parts. - - -Imports into the United States. - -The official statistics of imports of vinyl resins prior to 1936 are not -satisfactory for purposes of comparison. Imports could be entered under -either paragraph 2 or paragraph 11 and could be included either with the -statistics of imports of vinyl acetate (see table 91, page 141) or be -thrown into a general group of non-coal-tar synthetic gums and resins, n. -s. p. f., which in addition to vinyl resins would include the acrylates -and ureas. Table 10 gives imports of synthetic resins under paragraph 11 -of the Tariff Act of 1930. - -TABLE 10.—_Synthetic resins classified under paragraph 11:[1] United -States imports for consumption 1931-37_ - - --------+----------+-------+----------- - Year | Quantity | Value | Unit value - --------+----------+-------+----------- - | _Pounds_ | | - 1931 | 453 | $173 | $0.38 - 1932 | 454 | 29 | .06 - 1933 | 1,120 | 496 | .44 - 1934 | 4,084 | 1,576 | .39 - 1935 | 3,105 | 1,804 | .58 - 1936 | 146 | 65 | .45 - 1937[2] | 1,963 | 439 | .22 - --------+----------+-------+----------- - - [1] Statistical classification 838.914, synthetic gums and - resins, n. s. p. f. (not coal tar) 1931-35; 838.939 same, other - than those in chief value of vinyl acetate, 1936 and 1937. - - [2] Preliminary. - - Source: Compiled by the U. S. Tariff Commission from official - statistics of the U. S. Department of Commerce. - -A better idea of the imports of vinyl resins prior to 1936 is obtained -by an invoice analysis of imports through the Port of New York under -paragraphs 2 and 11. Table 11 shows imports of vinyl acetate resins based -on such an analysis for 1934 and 1935 and on official statistics for the -years 1936 and 1937. - -Similarly table 12 shows imports of Mowilith resins based upon import -analysis for the period 1932-1935, and upon official statistics for 1936 -and 1937. - -TABLE 11.—_Vinyl acetate resins: United States imports for consumption, -1934-37_ - - ----------+----------+--------+----------- - Year | Quantity | Value | Unit value - ----------+----------+--------+----------- - | _Pounds_ | | - ----------+----------+--------+----------- - 1934[1] | 42,000 | | - 1935[1] | 240,000 | | - 1936[2] | 600,808 |$144,782| $0.24 - 1937[2][3]| 652,730 | 201,213| .31 - ----------+----------+--------+----------- - - [1] Invoice analysis of imports entered through the New York - customs district. - - [2] Statistical classification 817.58 (par. 2), vinyl acetate, - polymerized, and synthetic resins made in chief value from vinyl - acetate, n. s. p. f. (excluding imports from Germany) and 838.938 - (par. 11), synthetic resins made in chief value from vinyl - acetate, n. e. s. - - [3] Preliminary. - - Source: Compiled by the U. S. Tariff Commission from official - statistics of the U. S. Department of Commerce. - -TABLE 12.—_Mowilith resins: United States imports for consumption, -1932-37_ - - ----------+----------+--------+----------- - Year | Quantity | Value | Unit value - ----------+----------+--------+----------- - | _Pounds_ | | - ----------+----------+--------+----------- - 1932[1] | 555 | $229 | $0.41 - 1933[1] | 741 | 247 | .33 - 1934[1] | 2,950 | 1,668 | .57 - 1935[1] | 3,372 | 3,175 | .94 - 1936[2] | 7,056 | 2,410 | .34 - 1937[2][3]| 220 | 308 | 1.40 - ----------+----------+--------+----------- - - [1] Analysis of invoices of imports entered through the New York - customs district. - - [2] Imports from Germany under statistical classification 817.58 - (par. 2), vinyl acetate, polymerized, and synthetic resins made - in chief value of vinyl acetate. - - [3] Preliminary. - - Source: Compiled by the U. S. Tariff Commission from official - statistics of the U. S. Department of Commerce. - -Prior to January 1, 1936, the rate of duty on imports of vinyl resins -was 6 cents per pound and 30 percent ad valorem under paragraph 2, and -4 cents per pound and 30 percent ad valorem under paragraph 11 of the -Tariff Act of 1930. Under the terms of the trade agreement with Canada, -the duty under both paragraphs was reduced to 3 cents per pound and 15 -percent ad valorem. This rate was generalized to the other countries from -which we have received imports, with the exception of Germany. - - -Exports from the United States. - -Exports of vinyl resins are not separately shown in official statistics. - - - - -11. OTHER SYNTHETIC RESINS - - -The synthetic resins already discussed are those in substantial -commercial production but, by no means, the only ones known or produced. -Several thousand new ones have been reported and the search continues -in laboratories throughout the world. A successful new product must be -one made from inexpensive raw materials or must possess some property or -advantage that will permit its sale at a price level above that of other -resins. - -No attempt is here made to list the host of less important resins. -Certain ones of unusual interest or possessing unique properties are -described below. These include resins obtained from adipic acid, aniline, -citric acid, diphenyl, furfural, lignin, sugar, and sulphonamide. - - -Adipic acid resins. - -The resins from adipic acid are classed as alkyd resins. Those obtained -by the condensation of adipic acid and glycerin are soft and rubbery and -are used to some extent in surface coatings and in photographic films. -In these the resin is formed in three stages as in other alkyd types: A -soluble liquid, a viscous rubbery product, and a form insoluble in the -usual solvents. - -Commercial domestic production of these resins was reported for the first -time in 1935 and the output has increased each year since then. - - -Aniline resins. - -Resins obtained by condensing aniline and formaldehyde have been -developed in recent years. Much of the research on this type of resin -was done in Switzerland by the Ciba Co., which holds a number of patents -on it. The Swiss product, called Cibanite, has excellent electrical and -mechanical properties. At least one domestic manufacturer is licensed -under the Swiss-owned patents. - - -Citric acid resins. - -Considerable interest has recently been manifest in synthetic resins -derived from citric acid. The sharp decline in the price of citric acid, -as a result of large scale synthesis from sugar has placed it within the -realm of possibility as a raw material for synthetic resins. - -The citric acid resins, classed as alkyd resins, are obtained by -condensing citric acid and glycerin. Commercial production is said to -have started in Europe, but there is no known domestic production as yet. - - -Diphenyl resins. - -A series of products known as Aroclors and made by chlorinating diphenyl -are available in commercial quantities. - -Diphenyl was commercially produced for the first time by Swann Research, -Inc., at Anniston, Ala., about 1928. The demand for it as a heat-transfer -medium resulted in large scale output. Later it was found that certain of -the chlorinated compounds of diphenyl possess valuable resin properties. - -The Aroclors range from a clear mobile oily liquid to an amber colored -transparent solid. They are thermoplastic, do not polymerize or oxidize, -and are therefore nondrying. They may be dissolved in varnish oils, such -as tung oil and linseed oil, to give varnishes which are resistant to -alkali and water. The diphenyl resins are good adhesives on metal and -glass and give strong joints between such surfaces. They have a high -dielectric constant, resistivity, and a low power factor. Their chief use -is in wire insulation. - -The domestic production of chlorinated diphenyls is, at present, solely -by the Monsanto Chemical Company, St. Louis, Mo. - - -Furfural resins. - -Large scale commercial production of furfural, an aldehyde obtained from -oat hulls and other farm waste, has made it available for synthetic resin -manufacture. - -Tar-acid furfural resins possess certain outstanding properties, such -as great dimensional accuracy, great reaction speed to the infusible -solid stage, and unusual strength and toughness. They are available in -dark shades only. Printing plates as large as those of metropolitan -daily papers are molded from them as are radio tube bases, all sorts -of electrical parts, and machined parts requiring great dimensional -accuracy. Other uses are in abrasive wheels, varnishes, and adhesives. - -Probably the largest domestic maker of furfural resins is the Durite -Plastics Division of Stokes and Smith Company, Philadelphia, Pa. - - -Resins from sugar. - -Many attempts have been made to utilize sugar as a raw material for -synthetic resins. United States Patent No. 1,949,831, dated March 6, -1934, claims a process for the manufacture of molding compounds by -condensing saccharide with aldehydes and urea. Pure sucrose yields a -clear, colorless, nonresilient resin, while molasses and cane sugar -give dark-colored resins. The trade name Sakaloid is used to designate -certain of these resins; there is, however, no known domestic production. -Sucrolite is the trade name of a brand of resins from sugar produced in -Europe. - - -Sulphonamide resins. - -The sulphonamide resins were developed from para toluenesulphonamide, a -byproduct obtained in the manufacture of saccharin (synthetic sweetening -agent). - -Para toluenesulphonamide, condensed with formaldehyde or other aldehyde, -forms a viscous mass which, on heating, is converted to a hard -colorless resin. Such resins are compatible with cellulose acetate or -nitrocellulose in lacquers, the combination yielding clear, colorless -lacquers of good gloss and adhesion. Other possible uses are as an -adhesive in safety glass, in certain molding compositions, in insulating -materials, and to deluster artificial silk. - -Domestic production of sulphonamide resin is entirely by the Monsanto -Chemical Co., St. Louis, Mo. It is marketed under the trade name -Santolite. - - - - -12. ORGANIZATION OF THE SYNTHETIC RESIN INDUSTRY - - -The discussion of the various synthetic resins on pages 11 to 52 carries -in each case, under the heading of production, a notation of the number -of companies producing that particular resin; and the discussion on pages -86 to 141 of important raw materials for these resins describes briefly -the conditions under which these materials are produced. We shall now -consider the interrelationships between industries producing the several -resins, and the relation of the resin industries to their raw materials -and to some of the important resin-consuming industries. - -No description of the organization of a rapidly expanding industry can be -expected to remain accurate for long. But regardless of future changes -that may be expected, the general pattern seems definite enough to -make possible a few broad generalizations. At present the producers of -synthetic resins may be classified in two groups: those making alkyd and -tar-acid resins, and those making all other synthetic resins. - -The alkyd resins and the tar-acid resins are produced in large volume, -and for these resins the patent situation is such that there is nothing -to exclude new producers. The result has been that new firms have entered -the field and there has been a marked tendency for concerns using these -resins on a large scale to produce them. This general situation may be -expected to continue as long as the volume of consumption of these resins -is rising. But when consumption levels off, it would not be surprising if -increased competition for new business resulted in consolidations of some -of the producing units. - -Each of the other synthetic resins is produced by a small number of -firms and this may be expected to continue as long as the production of -a particular resin is small, or basic patents dominate the situation. -When and if the situation in these respects changes for some of the other -resins, they will probably develop the same tendencies as now exist in -the production of the tar-acid and alkyd resins. - - -Horizontal relationships between resin producers. - -Horizontal relationships between companies are those between different -units in the same industry (say two tar-acid resin producers), or in -different industries each operating at the same stage of industrial -production (say a tar-acid resin producer and a producer of urea -resin). As a rule, extensive horizontal relationships are not common -in relatively young industries, and this is true of the production -of synthetic resins. In general, it has not been necessary to absorb -competitors to achieve a greater volume of sales, and efforts have been -directed to exploiting the possibilities of expansion in a growing -market. This necessitated solving technical problems concerning -improvement of the product and its production on an ever larger scale; -legal problems regarding patents (protection of those owned, and the -policy to be adopted toward unadjudicated patents owned by others); and -the marketing problem of convincing prospective customers of the worth -of a new product. These and other problems incidental to successful -competitive production and sale of a given type of synthetic resin have -been sufficient to restrain the desire to produce more than one type. - -The patent situation of most synthetic resins is extremely complicated. -In the case of tar-acid molding resins the basic Baekeland patents have -expired, but for other synthetic resins either the basic patent is -still in force, or it is difficult to say which is the basic patent, -because of lack of adjudication by the courts. In all cases dozens of -supplementary patents are in force and sometimes hundreds. As a result -the patent situation, though one of the bars against entering into a new -field, frequently forces some relationship between producing units in -the same synthetic resin field. Cast phenolic resins afford an example -of patent-licensing of several corporations by another with the payment -of royalties as compensation. In a number of other branches of the resin -industry, such as the laminated tar-acid resins and the alkyd resins, the -mutual desire of producers to avoid litigation has apparently resulted in -“gentlemen’s agreements” not to sue. - - -Vertical relationships of resin producers. - -A vertical relationship is one between producers operating at different -stages of industrial production, such as a firm producing resin and a -firm producing a resin raw material or between the former and a firm that -is a resin consumer. The incentive for a consuming industry operating on -a large scale to make its own resins is naturally greater than for one -using only small quantities. Therefore we may expect to find instances -where a process consuming the resin in quantity and resin manufacture are -both performed by the same company provided other conditions (such as the -patent situation and knowledge of the art of manufacture) are favorable. - -_Tar-acid resins for molding._—The present practice of molding resins -is favorable to large-scale production. The shaping of the mold is -expensive, involving skilled labor upon hardened steel; but once the mold -is made it may be used to produce tens or hundreds of thousands of units. -Subsequent labor upon the molded product is usually limited to the simple -task of smoothing the line where the flash is broken off, since the -product comes from the mold in the color and with the surface and shape -desired. - -The usual arrangement at the present time is to have a battery of -presses, grouped around central units which supply hydraulic pressure -and steam for heat. A measured amount of molding powder or a pellet -of compressed molding powder is applied to each cavity by the press -operator, who controls by hand the time of application of heat and -pressure and removes the article from the press. The cycle is a matter of -minutes, and since each cycle produces a finished article if the molding -is large, or a number of them if it is small, daily production per worker -is high. The estimated average costs of the different elements in the -process have been apportioned as follows: the cost of raw material is -about one-third the cost of the finished product; and the combined cost -of the mold allocated per unit, the labor cost per unit, and overhead -the remaining two thirds.[5] On small runs labor cost and particularly -allocated mold cost would be much higher, so that molding is usually -uneconomic where only small quantities of the finished product are -desired. - -In 1937 there were eight molders that produced their own tar-acid resins -in whole or in part. One of these molders was the third largest producer -of such resins. In the same year six producers of tar-acid resins for -molding, including the first, second, fourth, and fifth largest, confined -their activities to resin making. One producer of raw materials for -tar-acid resins also made the resin on a moderate scale. - -This picture of interstage relationship as it existed in 1937 may be -somewhat modified by new developments in molding presses. There are -now available self-contained presses which are not dependent upon -other units for their supplies of heat and pressure and which are -either semiautomatic or automatic. The semiautomatic press requires an -operator for charging the cavity and removing the molded product, but -once adjusted automatically applies the heat and pressure and controls -the time of the pressing cycle. The automatic press, adapted as yet -only to the simpler moldings, requires no attention whatever. These -presses are more expensive, but may be set up anywhere and require less -skilled labor. There is the possibility that they may be installed by -some industrial users of molded articles, and thus take some business -from the custom molder. If this occurs, such molders will presumably buy -their resin from companies that are primarily resin makers, since their -requirements of the material would not ordinarily be large enough to -justify making their own. - -_Tar-acid resins for laminating._—The manufacture of laminated resin -products is most economic when done on a large scale, in which case the -impregnation of the paper or fabric becomes a continuous process, the -material feeding from a roll through resin sirup and then through drying -towers, where time and heat may be controlled. The impregnated material -contains resin in the B-stage. The material is then cut up and the sheets -piled together (the number depending on the thickness desired) and sent -to huge presses which, with heat and pressure, compact and unite the -layers and convert the resin to the C-stage. If it is desired to produce -decorative panels with a smooth surface, the top sheet used is one -colored or printed with a design (perhaps a photographic reproduction -of the surface of a cabinet wood) and placed between polished -chromium-plated metal sheets before going to the press. Rods and coil -forms as well as flat sheets are commonly made from laminated material. -Any of these forms may undergo subsequent fabrication; rods and coil -forms cut to required length, thin sheets stamped to shape, gear blanks -cut to final form on automatic gear machines, and decorative panels sawed -to shape. - -Many laminators purchase all their resin requirements, but a number of -them make part or all of the tar-acid resin they use. In 1937 there -were seven laminators who made tar-acid resins (including the second, -third, and fourth largest producers of such resins) and four producers -of tar-acid resins for this use (including the largest) which did no -laminating. - -_Cast phenolic resins._—The firms producing cast phenolic resins market -them in sheets, rods, and tubes. The castings are made in molds of lead -or glass, and the range of possible shapes is limited. The consumers of -these products fabricate them into finished form by cutting, turning, -and polishing, much as they might fabricate wood or soft metal. Since -considerable labor is required per unit, fabrication is not particularly -adapted to large-scale production. In 1937 there were nine producers of -cast phenolic resins. One of the smaller producers was also a fabricator -of cast resins, and another a producer of raw materials used in making -the resin. - -_Tar-acid resins for coatings._—The use of tar-acid resins in surface -coatings has been overshadowed by the more rapid development of alkyd -resins. Nevertheless the volume of tar-acid resins used as raw materials -by varnish and lacquer manufacturers is growing rapidly. They are used in -marine varnishes unmodified by other synthetic resins, but to a greater -extent in combination with other plastics, especially the alkyds and -nitrocellulose. The coating industry includes many units producing on -a large as well as a greater number producing on a smaller scale. In -general, they are not producing their own tar-acid resins. In 1937 there -were 11 producers of tar acid resins for coatings (including the three -largest) who confined their activities to resin production. In addition -there were eight manufacturers of varnishes and lacquers and one producer -of resin raw materials, who also produced tar-acid resins for use in -coatings. - -_Tar-acid resins for miscellaneous uses._—The chief uses for tar-acid -resins other than for molding, casting, laminating, and in coatings are -as a bonding material, and as an adhesive. These resins form a valuable -bonding agent for asbestos in brake linings and chemical tanks, for -abrasives and for ground cork in special uses. As an adhesive they are -used in making moisture-resistant plywood. - -In 1937 there were five producers of tar-acid resins for miscellaneous -uses, including the largest, who confined their activities to the making -of resins and two, including the second largest, who also made products -in which these resins were consumed. - -_Alkyd resins made from phthalic anhydride._—The rapid increase in -the production of alkyd resins for use in coatings is one of the most -remarkable in the whole resin industry. They go into varnishes, lacquers, -and enamels for spraying, brushing, and dipping. The coatings may be -air-dried, with a wide range of drying time, or dried by oven baking. The -volume of alkyd resins used by the coating industry has grown so large -that a number of coating firms have gone into the production of alkyds -and now make part or all of their own requirements. In 1937 there were -24 paint, varnish, and lacquer firms producing alkyd resins. Included in -this number were the first and second largest producers of such resins. -Eleven producers of these resins, including the third and fourth largest, -made alkyd resins for sale only. Each of these groups included one firm -which also made phthalic anhydride. - -_Alkyd resins made from maleic anhydride._—In 1937 there were seven -producers of alkyd resins from maleic anhydride who produced for sale -only. This group included the two largest producers and also one firm -which produced maleic anhydride. In addition there were five paint, -varnish, and lacquer firms producing part or all of their needs of -resins of this type. The general conditions under which these resins are -consumed are the same as for alkyd resins made from phthalic anhydride. - -_Urea resins for molding._—The conditions under which urea resins are -molded are not greatly different from those already discussed for -tar-acid resins. The molding cycle is somewhat longer and, because of -the light colors used, special precautions must be taken to prevent -discoloration of the molded product by dirt or flecks of molding powder -from other operations, carried through the air or upon the person of the -laborer. In 1937 there were four producers of urea resins for molding. -Three of them, including the two largest, produced for sale only; the -other consumed his own production. - -_Urea resins for other uses._—Until recently urea resins were thought -of exclusively for molding, but they are now being used for laminating, -for surface coatings, and also as an adhesive. Ordinarily the ureas are -used only in impregnating the outside laminae of a laminated sheet where -they are valuable for the light colors they make possible. The volume of -urea resins used in surface coatings is small compared with the alkyd or -tar-acid resins used for this purpose, but is increasing. The use of urea -resins in adhesives is still new but promises to become important. - -In 1937 there were four producers of the ureas for uses other than -molding, who produced for sale only; and two producers who consumed their -own product. - -_Coumarone and indene resins._—Coumarone and indene resins are produced -in connection with the production of solvent naphtha. There were three -producers in 1937, all of whom sold their product. These resins go into -varnishes, where they replace natural resins or ester gum. - -_Other resins._—In 1937 there were four producers of vinyl resins in -the United States, and two of these also produced their raw materials. -The vinyl resins were used chiefly in surface coatings, molding, and -in safety glass. The polystyrene resins, used chiefly for molding and -laminating, were offered by two producers for the first time in 1937. -Two other producers offered acrylate resins, which are cast, molded, or -used in surface coatings. In the same year petroleum resins were sold in -good volume, their only producer obtaining them as a byproduct of the oil -industry. - - -Relationship of the resin industry to other industries. - -The term “synthetic resin industry” is a very broad one, referring -in reality to a group of industries producing the varied synthetic -resins—much as the term “steel industry” includes the manufacture of pig -iron, structural steel, tin plate, and wire. But it is interesting to -examine briefly the connection of the synthetic resin industry with some -of the other large industrial groupings. - -_Relationship to the chemical industry._—Since the processes involved -in the production of the synthetic resins are essentially of a chemical -nature, the whole industry might be legitimately classed as a branch -of the chemical industry. Historically, the synthetic resin industry -in the United States developed outside of the chemical industry as -it was constituted at the time, but with the passage of years and -the development of a greater variety of resins the connections have -multiplied. Chemical companies supply some of the important raw materials -for synthetic resins; their skilled experts possess the technical -training to develop new resin processes; their research programs from -time to time lead to the discovery of valuable facts regarding resin; -and they possess, or can, more easily than a new company, obtain the -capital necessary to exploit a process. - -At present the interest of the large chemical corporations in synthetic -resins ranges from active participation to apparent indifference; but -the growing number of corporations thought of as chemical which are -now engaged in experimental production would seem to indicate that in -time they will be increasingly important in the production of synthetic -resins. Some of the larger chemical companies that are important -producers of synthetic resins in 1938 are: - - American Cyanamid Co Urea resins. - Carbide & Carbon Chemicals Corporation Vinyl resins. - Dow Chemical Co Polystyrene resins. - E. I. du Pont de Nemours & Co Alkyd, acrylate, vinyl resins. - Monsanto Chemical Co Petroleum resins. - -_Relationship to the surface coating industry._—The use of tar-acid, -alkyd, urea, and vinyl resins as raw material for the surface coating -industry has already been mentioned, and also the fact that the coating -industry is manufacturing a substantial part of its consumption of alkyd -resins. - -At present the synthetic resins go chiefly into varnishes, lacquers, and -enamels for inside use and into finishes for outside use on metal. Now -that coatings incorporating synthetic resins are successfully adapted to -outside finishes on wood, the incentive for the production of resins by -the coating industry will presumably increase because of the large volume -of house paints sold. - -_Relationship to the electric industry._—The electric industry offered -one of the first large markets for synthetic resin products. Molded and -laminated parts for appliances and fixtures gave good insulation at -ordinary voltages, and frequently allowed a simplification of the design. -This development, coming at a time of rapid expansion in the manufacture -of electric equipment, was a distinct benefit to both the electrical and -synthetic resin industries. The larger electrical manufacturing firms -soon began to do their own molding and laminating and became important -as custom molders. Later the General Electric Co. and the Westinghouse -Electric & Manufacturing Co. manufactured their own tar-acid resins. - -Another important outlet for synthetic resins appeared with the -development of the radio industry. Radio now offers a market for -special synthetic resins possessing high dielectric constants at radio -frequencies, and much larger volumes of tar-acid and urea resins are used -in molding the smaller cabinets. As a rule the radio industry purchases -its resin products already molded to order. - -_The relationship to the auto industry._—The automobile manufacturing -industry and makers of automobile parts together furnish a substantial -market for synthetic resins. In general, the automobile manufacturers -purchase parts made of resin, already fabricated; parts makers usually -purchase the resins they require. The Ford Motor Co. makes tar-acid -resins for its own use. Working parts, such as timer heads and horn -buttons, are usually of molding tar acid resin; the timing gear usually -of laminated tar-acid resin. For decorative parts, such as dash -instrument knobs and radiator ornaments, urea and cast phenolic resins -have been used. Most of these parts are small, but altogether they -have taken a substantial volume of synthetic resin. Safety glass for -automobile windshields is now being made from vinyl resin. - -The future possibilities are difficult to appraise. The automobile -industry is constantly experimenting with new materials and methods, and -its policy of bringing out models annually makes possible rapid adoption -of new developments. Molded window frames have been tried, and such a -use, or use for the complete instrument panel, would obviously consume -synthetic resins in much larger volume. Even whole motor car bodies of -laminated resin have been suggested. - - - - -13. THE UNITED STATES TARIFF AND INTERNATIONAL TRADE IN SYNTHETIC RESINS - - -Synthetic resins enter into the foreign trade of the United States only -to a small extent. This becomes apparent if a comparison is made between -the United States production of these resins and our imports and exports -of them. Table 13 gives the imports and production of synthetic resins in -the United States for 1934 through 1937. Exports are so small that they -are not separately reported. - -TABLE 13.—_Synthetic resins: United States production and imports, -1934-37_ - - [Pounds] - -------------------+------------+------------+-------------+------------ - | 1934 | 1935 | 1936 | 1937 - -------------------+------------+------------+-------------+------------ - Production in the | | | | - United States[1] | 56,059,489 | 95,133,384 | 132,912,821 | 162,104,713 - Imports into the | | | | - United States | [2] 19,795 | [2] 21,120 | [3] 626,608 | [3] 673,880 - -------------------+------------+------------+-------------+------------ - - [1] Does not include coumarone and indene resins, sulfonamide - resins. - - [2] Does not include imports of vinyl acetate resins which were - not shown separately until 1936. - - [3] Includes vinyl acetate resins and all other types imported. - -The small size of the international trade in synthetic resins is also -emphasized if we compare the imports of all synthetic resins with the -imports or exports of some of the important raw materials used in their -manufacture. Table 14 makes such a comparison. - -TABLE 14.—_Comparison of international trade of the United States in -synthetic resins and in certain raw materials for resins, 1934-37_ - - [1,000 pounds] - -----------------------------+--------+--------+--------+-------- - Imports into or exports from | | | | - the United States | 1934 | 1935 | 1936 | 1937[1] - -----------------------------+--------+--------+--------+-------- - Imports: | | | | - Resins | 20 | 21 | 627 | 674 - Crude cresylic acid[2] | 7,332 | 7,010 | 13,794 | 16,745 - Crude naphthalene | 47,995 | 48,455 | 39,806 | 52,664 - Crude glycerin | 15,081 | 8,220 | 11,149 | 13,441 - Refined glycerin | 2,214 | 69 | 3,447 | 7,535 - Exports: | | | | - Phenol | 329 | 323 | 149 | ([3]) - Formaldehyde | 2,597 | 2,598 | 1,844 | 2,865 - -----------------------------+--------+--------+--------+-------- - - [1] Preliminary. - - [2] Conversion factor 8.7 pounds per gallon. - - [3] Not available. - -There are three factors that together largely account for the small size -of our foreign trade in synthetic resins. As a result of the comparative -youth of the resin industry, the complicated patent situation, and the -substantial tariff rates upon imports of resins into the United States, -domestic producers have experienced little competition from abroad. The -first two of these forces plus the tariff barriers of other countries -have caused them to pay little attention to export markets. But it -should be observed that both of the first two forces will become less -important with the passage of time. When home markets have been more -fully exploited, problems of production have become less pressing, and -most of the basic patents on resins have expired, international trade in -synthetic resins may be expected to increase from its present low levels. -If this occurs, the United States, with its large scale production for -the home market and with its generally favorable position with regard to -the raw materials and the technical skills necessary, is more likely to -become a net exporter than a net importer of synthetic resins. - - -Rapid expansion of business in home markets. - -Being young industries and having potentially large home markets awaiting -development, the synthetic resin industries in the United States -naturally began by concentrating first on their numerous production -problems to meet a rapidly expanding domestic demand, improving their -products and devising useful applications. - -The tar-acid-formaldehyde resins for molding were the first to develop. -The industry producing them may be said to have started around 1910, -but did not become important until after the World War, when the drop -in price of phenol made the resins available at lower prices. The alkyd -resins and the urea-formaldehyde resins in the United States began to be -important in 1929 and 1930, respectively. The others may be said to be -still in their earliest stages of development as industries, however much -research work may have been done as to their properties and production. - - -The effect of patents on international trade. - -A second factor involved in limiting international trade in resins is -that relating to patents. The basic patents on tar-acid resins have -expired; but while they were in force, they prevented imports into the -United States. In the United States a valid patent can be enforced at -law not only against domestic products which infringe but also against -imports. In addition to court action, the provisions of our tariff law -prohibiting unfair competition in the import trade were invoked to -prevent entry of synthetic phenolic (tar-acid) resin, form C, but when -the basic patent for this material expired, the exclusion order no longer -applied to single color material, except in the matter of certain marking -requirements.[6] - -The patent situation may militate against exports as well as imports. -Where a company owns foreign patents it may set up a company to exploit -them abroad, or it may license their use by others. Again, mutual -interest may dictate an exchange (by cross-licensing) of certain patents. -International licensing of patents is usually accompanied by divisions -of international markets through formal or informal understanding. Such -agreements may outlive the life of the patents, especially if bolstered -with financial connections. But unless the original producers continue -to dominate their respective markets, any agreements between them are -likely to diminish in importance, because after the patents expire new -competitors would have a free hand in foreign as well as domestic markets. - -The original United States producer of tar-acid resins set up or -licensed companies to manufacture in a number of foreign countries. The -urea-formaldehyde process was developed in Europe and the first American -producer was a licensee of a British corporation. Similar arrangements -exist with regard to most of the other resins. - - -The United States tariff on resins and resin products. - -_Synthetic resins._—Imports of tar-acid, alkyd, coumarone and indene, -styrol, adipic, and aniline resins are dutiable under the provisions of -paragraph 28 of the Tariff Act of 1930, which reads in part: “synthetic -phenolic resin and all resinlike products prepared from phenol, cresol, -phthalic anhydride, coumarone, indene, or from any other article or -material provided for in paragraph 27 [coal-tar intermediates] or -[paragraph] 1651 [coal-tar crudes], all these products whether in a -solid, semisolid, or liquid condition; ... 45 per centum ad valorem -[based on American selling price[7] or United States value[8]] and 7 -cents per pound.” Where these resins are produced in the United States, -imports are “competitive” and the dutiable value is based upon American -selling price. If the American selling price is higher than the foreign -value, the effect of this method of valuation is to increase the duty -to which imports are subject. The duty of 45 per cent ad valorem and 7 -cents per pound was equivalent to 54 per cent ad valorem on the American -selling price of the small imports of coal-tar resins in 1937. If it -could calculated upon foreign value it would be much higher. - -Synthetic resins of non-coal-tar origin, except vinyl resins, are -dutiable under paragraph 11, which reads “synthetic gums and resins not -specially provided for, 4 cents per pound and 30 per centum ad valorem” -on foreign value. This rate was the equivalent of 48 per cent ad valorem -upon the small amount of imports in 1937. The most important resins -included are the urea and acrylate resins. - -Between 1930 and 1936 there was some doubt whether vinyl resins were -dutiable under paragraph 11 at the rate quoted or under paragraph 2 -which provided for “vinyl alcohol ... homologues and polymers of all the -foregoing; ethers, esters, salts and nitrogenous compounds of any of -the foregoing, whether polymerized or unpolymerized, ... not specially -provided for, 6 cents per pound and 30 per centum ad valorem” on foreign -value. But the Canadian trade agreement, effective January 1, 1936, -reduced the rate on vinyl resins under either paragraph 2 or paragraph 11 -to 3 cents per pound and 15 percent ad valorem.[9] The reduced rate was -equivalent to 25 percent ad valorem upon the imports in 1937. - -Under these rates, imports of synthetic resins, other than vinyl resins, -have been insignificant.[10] After the reduction of duty, imports of -vinyl resins in 1936 amounted to approximately 600,000 pounds, valued at -$145,000 and in 1937 to 650,000 pounds, valued at $200,000. (See table -11.) - -_Articles made of synthetic resins._—Laminated products of which -synthetic resin is the chief binding agent and manufactures of such -products are dutiable under paragraph 1539 (b) at the following rates: -15 cents per pound and 25 percent on laminated sheets or plates[11]; -50 cents per pound and 40 percent on laminated rods, tubes, blocks, -strips, blanks, or other forms; and 50 cents per pound and 40 percent on -manufactures of such laminated products. Paragraph 1539 (b) also provides -a duty of 50 cents per pound and 40 percent on manufactures of any other -product of which any synthetic resin is the chief binding agent. These -are, for the most part, molded synthetic resin articles. Paragraph 1539 -(b) does not cover articles made entirely of synthetic resin (cast -synthetic resin articles). Such articles unless specifically provided for -in the law are dutiable under paragraph 1558 as manufactured articles, -not specially provided for, at 20 percent ad valorem. - -A great many articles, which are made in whole or in part of synthetic -resin, are not dutiable under either paragraph 1539 (b) or paragraph -1558. These are articles which are specifically mentioned in other -paragraphs and subject to the duties provided therein. Table 15 lists a -number of them. - -TABLE 15.—_Tariff classification and rates of duty in Tariff Act of 1930 -on certain articles made of synthetic resin_ - - ------------------------------+-----------+------------------------ - Article | Tariff | Rate of duty - | paragraph | - ------------------------------+-----------+------------------------ - Beads | 1503 | 75 percent ad valorem. - Buttons | 1510 | 45 percent ad valorem. - Dice, dominoes, chessmen, and | | - poker chips | 1512 | 50 percent ad valorem. - Phonograph records | 1542 | 30 percent ad valorem. - Cigar and cigarette holders | 1552 | 5 cents each plus 60 - | | percent ad valorem. - Ash trays, humidors, etc. | 1552 | 60 percent ad valorem. - Umbrella handles | 1554 | 75 percent ad valorem. - ------------------------------+-----------+------------------------ - -In general, the available statistics of imports do not segregate imports -of the specified articles made of synthetic resin from those of the same -articles made of other materials; and the same situation is true of -imports of unspecified articles wholly of synthetic resin which enter -under paragraph 1558. Imports of manufactured articles, n. s. p. f. in -which synthetic resin is the chief binding agent under paragraph 1539 -have been small. Figures for recent years are given in table 16. - -TABLE 16.—_Manufactured articles n. s. p. f. in which synthetic resin is -the chief binding agent: United States imports for consumption, 1931-37_ - - ----------------------------+--------+--------+--------+-------- - Type | 1931 | 1932 | 1933 | 1934 - ----------------------------+--------+--------+--------+-------- - _Quantity (pounds)_ | | | | - Laminated products: | | | | - Sheets and plates | | 10 | | 13 - Rods, tubes, blocks, etc. | 215 | 13 | | - Manufactures, n. e. s. | 203 | 453 | 787 | 783 - Nonlaminated | 17,623 | 8,511 | 5,352 | 5,729 - +--------+--------+--------+-------- - Total | 18,041 | 8,987 | 6,139 | 6,525 - | | | | - _Value (dollars)_ | | | | - Laminated products: | | | | - Sheets and plates | | 9 | | 16 - Rods, tubes, blocks, etc. | 612 | 71 | | - Manufactures, n. e. s. | 1,001 | 883 | 2,133 | 2,299 - Nonlaminated products | 31,992 | 10,113 | 7,914 | 10,673 - +--------+--------+--------+-------- - Total | 33,605 | 11,076 | 10,047 | 12,988 - ----------------------------+--------+--------+--------+-------- - - ----------------------------+--------+--------+---------- - Type | 1935 | 1936 | 1937[1] - ----------------------------+--------+--------+---------- - _Quantity (pounds)_ | | | - Laminated products: | | | - Sheets and plates | | | - Rods, tubes, blocks, etc. | 609 | 514 | 668 - Manufactures, n. e. s. | 1,703 | 3,260 | 10,397 - Nonlaminated | 8,423 | 8,069 | 8,759 - ----------------------------+--------+--------+---------- - Total | 10,735 | 11,843 | 19,824 - | | | - _Value (dollars)_ | | | - Laminated products: | | | - Sheets and plates | | | - Rods, tubes, blocks, etc. | 579 | 1,329 | 1,920 - Manufactures, n. e. s. | 3,778 | 9,468 | 39,232 - Nonlaminated products | 11,064 | 10,846 | 18,001 - ----------------------------+--------+--------+---------- - Total | 15,421 | 21,643 | 59,153 - ----------------------------+--------+--------+---------- - - [1] Preliminary. - - Source: Compiled from Department of Commerce statistics. - - - - -14. SYNTHETIC RESIN PRICES, PROPERTIES, AND USES - - -Synthetic resins as substitutes. - -Any new material will in the course of time be applied to the uses -for which it has special advantages, displacing older materials which -formerly served those purposes. The resulting product may sometimes be -used in the same manner as before, or the properties of the substitute -material may widen the usefulness of the finished product, or even make -possible a product almost wholly new. - -Before the development of molded synthetic resins, electrical plugs and -sockets were usually made of porcelain or molded of marble dust and -shellac. In this use substitution has been almost complete. Wall plates -for electric switches and outlets were usually of brass. Today molded -tar-acid or molded urea resins are substituted in part. In neither of -these examples has the substituted material any important effect upon the -use of the product. - -An example of a substitute material widening the usefulness of the -product is afforded by a new computing scale, where a molded urea resin -casing (substituted for metal in the older model) has aided in decreasing -the weight and has improved the appearance. Another example is the use -of laminated synthetic resin coil forms in radio frequency transformers -which, because of their better electrical properties at high frequencies, -have aided in the design of more compact units. - -Examples of synthetic resins making possible a wholly new product are -more difficult to find, but the following will serve as illustrations: -Cast acrylate sheets to form curved cockpit enclosures for airplanes; -molded acrylate buttons for reflecting road markers; and new special -coatings, which make possible the use of metal cans for preserving foods -and beverages hitherto impossible to can without loss of flavor. - - -Motives for substitution. - -One of the most important reasons why a manufacturer may decide to -substitute a synthetic resin for another material is the resulting -economy in the sense of economy in total costs. As a rule, the synthetic -resin will be more expensive pound for pound than the material for which -it is substituted; but frequently the manufacturing cost is enough lower -to more than make good the difference in material cost, because the resin -part will come from the mold almost in finished form, whereas the part -made of wood or metal will require considerable fabrication. In some -cases there may be a saving in marketing costs. For example, the shades -for large office fixture lights are now made of synthetic resin as well -as of opal glass. The resin shades are less expensive to ship because -they are lighter and require less expensive packing. - -Another incentive toward substitution is to give novelty, and hence sales -appeal, to an old product. In many cases the use of synthetic resins fits -in with the present tendency to redesign an old-style product so that it -will be more compact, have more pleasing lines, and more color. - -Still another incentive toward substitution is to give the product -greater usefulness, or lower costs in use. The great expansion in the -use of synthetic resins in surface coatings has come about because, with -these materials, coatings can be developed to fit special purposes, and -dry rapidly, which means an important saving to those who use them. - - -Materials displaced by synthetic resins. - -The wide range of uses to which synthetic resins are now applied implies -that the materials displaced are numerous. For example, cast or wrought -iron or steel is displaced in timing gears and in many small machine -parts, such as cradle-type telephones; nonferrous metals in small machine -parts and novelties, such as inexpensive bracelets; glass in lamp shades -and in cosmetic containers; natural resins in lacquers; plastics, such -as cellulose acetate in safety glass or cellulose nitrate in colored -lacquers; other adhesives in bonding plywood; and cork or metal in bottle -closures. - -In general, the quantity of material displaced is a very small part of -that material’s total market. Frequently, however, industries producing -the finished product have had to make substantial changes in their -equipment in order to use synthetic resins. This has been true in the -button industry, in the bottle closure industry, in the varnish and -lacquer industry, and in the various electrical supply industries; and -readjustment is now proceeding in the fancy container industry and in the -safety glass industry. - - -Competition between synthetic resins. - -Any particular synthetic resin must compete for its market with other -synthetic resins, as well as with other materials. The basis of choice -or substitution will be the same as that which has already been briefly -discussed in connection with the displacement of other materials by -resins. As between a number of resins with properties fitting them for a -particular use, the total costs of using each will be compared and the -choice will go to the least expensive; but where a resin has special -advantages in a particular use it may win out over a less expensive -resin. - -It should be emphasized that this battle of materials for markets -is a never-ending one. The fact that a specific synthetic resin has -achieved a certain position is no guarantee that it may not lose it -wholly or in part to some newer resin or other material. Thus cast -phenolic resin was for a time the only resin available in light colors -but urea resins became available in pastel shades and more recently -water-clear polystyrene and acrylate resins have come on the market. -Until recently tar-acid resins were without competition in laminating, -but urea resins now are used to some extent for the surface laminae and -the tar-acid resins now face a potential threat in a new product offered -to laminators. If the use of this cellulose sheet, which looks much like -blotting paper and which has lignin incorporated in it to act as a binder -in the press, should materially decrease the cost of laminated sheets, it -will mean serious new competition for the tar-acid laminating resins. - -The general effect of the increase in number of types of synthetic resin -has been to modify the market outlook of the producers of each type. They -are now more inclined to view the market as being limited by the price -at which they can supply their product and by the physical properties of -each resin rather than attempt to exploit it as a universal resin for all -purposes. - - -Resins classified by cost. - -At present the resins produced in largest volume are the alkyd resins for -use in surface coatings; the tar-acid resins for molding, laminating, and -surface coatings; the urea resins, chiefly for moldings; and the cast -phenolic resins. Roughly, the price per pound of pure resin material[12] -for these various resins may be compared as follows: - - _Average sales price - of net resin, 1937 - (per pound)_ - Type of resin: - Cast phenolic $0.41 - Tar-acid: - For molding .18 - For laminating .13 - For coatings .17 - Alkyd .20 - Urea .45 - -Because the cost of the filler is less per pound than the cost of the -resin, the cost of the tar-acid and urea molding powders will be less -than the figures given for the pure resin. On the other hand, wholesale -prices paid by consumers will include transportation and distribution -costs not included in the figures of manufacturers’ sales. - -Vinyl resins, acrylate resins, and polystyrene resins are at present -produced in much smaller volume than those just listed. If and when the -volume of production is increased the price may be decreased. In 1937, -the price per pound of pure resin[12] was as follows: - - _Average sales price - of net resin, 1937 - (per pound)_ - Type of resin: - Vinyl $0.69 - Acrylate 1.66 - -Early in 1938, acrylate resins were being offered for sale at 85 cents -per pound for molding powder and $1.25 per pound for the cast material; -polystyrene resins at 72 cents per pound. - -Petroleum resins, in 1937, sold for an average of 2 cents per pound net -resin content.[12] This low price puts them beyond competition of the -other synthetic resins in the uses in laminating and coating to which -they are adapted. - - -The physical properties of a resin and its uses. - -A more expensive resin will be used in preference to a cheaper one, only -if the higher cost is more than offset by some physical property, such as -color, which makes it more desirable in a particular use. The most common -molding resin at present is the tar-acid type, but it is available only -in the darker colors and therefore has been at a disadvantage, where a -light color is desired, in competition with cellulose nitrate (celluloid) -and cellulose acetate plastics or with urea and cast phenolic resins. In -recent years the production of cellulose acetate molding compounds and -of urea resins has increased rapidly, largely under this stimulus. The -desire for color also promises well for the future of the acrylate and -polystyrene resins which are produced in water-clear grades or colored -with dyes or pigments. - -TABLE 17.—_Synthetic resins and other plastics: Properties that affect -appearance_ - - -----------------------+---------+-------------+-----------+------------- - Type |Machining| Clarity | Color |Burning rate - |qualities| possibilities - -----------------------+---------+-------------+-----------+------------- - Synthetic resins: | | | | - | | | | - Tar-acid—Formaldehyde:| | | | - | | | | - Molded, wood flour | Fair to | Opaque | Limited | Very low - filler. | good | | | - | | | | - Molded, mineral | do | do | do | Nil - filler. | | | | - | | | | - Molded, fabric | do | do | do |Approximately - filler. | | | | nil - | | | | - Laminated, paper | Fair to | do | do | Very low - base. |excellent| | | - | | | | - Laminated, fabric | do | do | do | do - base. | | | | - | | | | - Laminated, asbestos | do | do | do |Approximately - cloth base. | | | | nil - | | | | - Cast |Excellent|Transparent, | Unlimited | Very low - | |translucent, | | - | | opaque | | - | | | | - Tar-acid—Furfural: | | | | - | | | | - Wood flour filler. | Fair to | Opaque | Limited | do - | good | | | - | | | | - Mineral filler. | do | do | do | Nil - | | | | - Fabric filler. | do | do | do | do - | | | | - Urea—Formaldehyde. | Fair |Translucent, | Unlimited | Very low - | | opaque | pastel | - | | | shades | - | | | | - Vinyl, unfilled. | Good |Transparent, | Unlimited | Nil - | |translucent, | pastels | - | | opaque | to black | - | | | | - Vinyl, filled. |Excellent| do | do |Approximately - |(organic | | | nil - | filler) | | | - | | | | - Acrylate |Very good|Transparent | Unlimited | Slow - | |(95% light | | - | |transmission)| | - | | | | - Polystyrene | Poor to |Transparent, | do | do - | good | opaque | | - | | | | - Other plastics: | | | | - | | | | - Shellac compound. | do | Opaque | Limited, | High (wood - | | | pastels | filler) - | | | excluded | - | | | | - Cold molded: | | | | - | | | | - Nonrefractory. | Poor | do |Dark colors| Nil - | | | only | - | | | | - Refractory. | do | do | Gray | do - | | | | - Rubber compounds: | | | | - | | | | - Chlorinated rubber. | |Translucent, | Unlimited | do - | | opaque | | - | | | | - Modified isomerized | Good |Transparent | do | Slow - rubber. | | | | - | | | | - Hard rubber. | Fair | Opaque | Limited | Medium - | | | | - Casein | Good |Translucent, | Unlimited | Very low - | | opaque | | - | | | | - Cellulose compounds: | | | | - | | | | - Ethyl cellulose | do |Transparent, | do | Slow - | |translucent, | | - | | opaque | | - | | | | - Cellulose acetate | do | do | do | do - sheet | | | | - | | | | - Cellulose acetate | do | do | do | do - molding | | | | - | | | | - Cellulose nitrate | do | do | do | Very high - -----------------------+---------+-------------+-----------+------------- - - -----------------------+---------------+--------------+----------- - Type | Effect of age | Effect of |Refractive - | | sunlight |index No[1] - -----------------------+---------------+--------------+----------- - Synthetic resins: | | | - | | | - Tar-acid—Formaldehyde:| | | - | | | - Molded, wood flour | None | Light shades | - filler. | | discolor | - | | | - Molded, mineral | do | do | - filler. | | | - | | | - Molded, fabric | do | do | - filler. | | | - | | | - Laminated, paper | Improves | Lowers | - base. | mechanical | surface | - | and | resistance | - | electrical | | - | properties | | - | | | - Laminated, fabric | do | do | - base. | | | - | | | - Laminated, asbestos | do | | - cloth base. | | | - | | | - Cast | Hardens | Colors | 1.5-1.7 - | slightly | may fade | - | | | - Tar-acid—Furfural: | | | - | | | - Wood flour filler. | do |Light shades | - | | discolor | - | | | - Mineral filler. | do | do | - | | | - Fabric filler. | do | do | - | | | - Urea—Formaldehyde. | do | None | 1.54-1.6 - | | | - Vinyl, unfilled. | Strength | Darkens | 1.53 - | unaffected | | - | | | - Vinyl, filled. | None | Discolors | - | | | - Acrylate | do | None | 1.49 - | | | - Polystyrene | do | Yellows | 1.67 - | | | - Other plastics: | | | - | | | - Shellac compound. | | None | - | | | - Cold molded: | | | - | | | - Nonrefractory. | | | - | | | - Refractory. | | | - | | | - Rubber compounds: | | | - | | | - Chlorinated rubber. | Slight | Darkens | 1.56 - | embrittlement | | - | | | - Modified isomerized | None | Slight | - rubber. | | surface | - | | crazing | - | | | - Hard rubber. | do | Discolors | - | | surface, | - | | resistivity | - | | decrease | - | | | - Casein | Hardens | Colors | - | slightly | may fade | - | | | - Cellulose compounds: | | | - | | | - Ethyl cellulose | Slight | Slight | 1.47 - | | | - Cellulose acetate | do | do | 1.49-1.50 - sheet | | | - | | | - Cellulose acetate | do | do | 1.47-1.50 - molding | | | - | | | - Cellulose nitrate | Slight |Discolors and | 1.50 - | hardening | becomes | - | | brittle | - -----------------------+---------------+--------------+----------- - - [1] Specified refractive degree. - - NOTE.—The values for the properties in this table are based upon - maximum and minimum figures submitted to Modern Plastics by a - number of manufacturers of each type of material. Differences in - test procedures and sizes of test specimens may lead to erroneous - conclusions in some cases if direct comparisons are attempted. - Special grades of materials are often available which excel in - one particular property. - - Source: Modern Plastics, vol. 15, no. 2, opp. p. 120. October - 1937. - -TABLE 18.—_Synthetic resins and other plastics: Molding properties_ - - ------------------------------+--------------+-------------+------------- - | General | Compression | Compression - Type. | molding | molding | molding - | qualities | temperature | pressure - ------------------------------+--------------+-------------+------------- - | | _°F._ |_Pounds per - | | | square inch_ - Synthetic resins: | | | - Tar-acid—Formaldehyde: | | | - Molded, wood flour filler | Excellent | 280-360 | 1,600-4,500 - Molded, mineral filler | Excellent | 270-350 | 1,600-6,000 - | to fair | | - Molded, fabric filler | Good to fair | 270-330 | 3,000-8,000 - Laminated, paper base | | 250-365 | 1,000-3,000 - Laminated, fabric base | | 250-365 | 1,000-3,000 - Laminated, asbestos cloth | | 250-325 | 1,000-3,000 - base | | | - Cast | | | - Tar-acid—Furfural: | | | - Wood flour filler | Excellent | 330-400 | 1,000-3,000 - Mineral filler | do | 330-360 | 1,000-3,000 - Fabric filler | Good to fair | 300-360 | 1,000-3,000 - Urea—Formaldehyde (alpha | Excellent | 290-325 | 1,500-6,000 - cellulose filler) | | | - Vinyl, unfilled | Good | 240-275 | 1,500-2,000 - Vinyl, filled | Excellent | 250-300 | 2,000-2,500 - Acrylate | do | 285-315 | 1,500-5,000 - Polystyrene | Good | 280-325 | 300-2,000 - Other plastics: | | | - Shellac compound | do | 240 | 1,000-1,200 - Cold molded: | | | - Nonrefractory | Fair | |4,000-12,000 - Refractory | do | |4,000-12,000 - Rubber compounds: | | | - Chlorinated rubber | do | 200-225 | 2,000-5,000 - Modified isomerized rubber| Good | 260-300 | 1,200-4,000 - Hard rubber | Fair | 285-350 | 1,200-1,800 - Casein | Poor | 200-225 | 2,000-2,500 - Cellulose compounds: | | | - Ethyl cellulose | Excellent | 212-300 | 1,000-5,000 - Cellulose acetate sheet | do | 210-320 | 500-5,000 - Cellulose acetate molding | do | 250-350 | 500-5,000 - Cellulose nitrate | Good | 185-250 | 2,000-5,000 - ------------------------------+--------------+-------------+------------- - - ------------------------------+-------------+--------------+------------- - | Injection | Injection | Compression - Type. | molding | molding | ratio - | temperature | pressure | - ------------------------------+-------------+--------------+------------- - | _°F._ | _Pounds per | - | | square inch_| - Synthetic resins: | | | - Tar-acid—Formaldehyde: | | _| - Molded, wood flour filler | 275-375 | 2,000-10,000 | 2.5-3.0 - Molded, mineral filler | 275-350 | 2,000-15,000 | 2.2-7.1 - Molded, fabric filler | | | 2.5-11.0 - Laminated, paper base | | | 1.5-3.0 - Laminated, fabric base | | | 1.5-3.0 - Laminated, asbestos cloth | | | - base | | | - Cast | | | - Tar-acid—Furfural: | | | - Wood flour filler | 250-290 | 300-5,000 | 2.5-3.0 - Mineral filler | 250-290 | 300-5,000 | 2.5-6.0 - Fabric filler | 250-290 | 300-50,000 | 4.0-15.0 - Urea—Formaldehyde (alpha | | | 3.0 - cellulose filler) | | | - Vinyl, unfilled | | | 2.0 - Vinyl, filled | | | 1.5-3.5 - Acrylate | 325-475 | 3,000-30,000 | 2.0 - Polystyrene | 300-375 | 3,000-30,000 | 2.5 - Other plastics: | | | - Shellac compound | | | - Cold molded: | | | - Nonrefractory | | | 2.5 - Refractory | | | 3.5 - Rubber compounds: | | | - Chlorinated rubber | | | 2.0-3.0 - Modified isomerized rubber| | | 3.0 - Hard rubber | 180-220 | 2,000-5,000 | 4.0-6.0 - Casein | | | - Cellulose compounds: | | | - Ethyl cellulose | | | 2.2-2.9 - Cellulose acetate sheet | | | - Cellulose acetate molding | 300-440 | 3,000-30,000 | 2.0-2.8 - Cellulose nitrate | | | - ------------------------------+-------------+--------------+------------- - - ------------------------------+-------------------+----------- - | Mold | Effect - Type. | shrinkage | on metal - | | inserts - ------------------------------+-------------------+----------- - | _Inches per inch_ | - Synthetic resins: | | - Tar-acid—Formaldehyde: | | - Molded, wood flour filler | 0.006-0.010 | Inert. - Molded, mineral filler | .002- .006 | Do. - | | - Molded, fabric filler | .003- .007 | Do. - Laminated, paper base | | Do. - Laminated, fabric base | | Do. - Laminated, asbestos cloth | | Do. - base | | - Cast | | Do. - Tar-acid—Furfural: | | - Wood flour filler | .005- .009 | Do. - Mineral filler | .002- .006 | Do. - Fabric filler | .0025-.006 | Do. - Urea—Formaldehyde (alpha | .007- .011 | Do. - cellulose filler) | | - Vinyl, unfilled | .001 | Not used. - Vinyl, filled | .000 | Inert. - Acrylate | .002- .003 | - Polystyrene | .002-.0025 | - Other plastics: | | - Shellac compound | .002 | Do. - Cold molded: | | - Nonrefractory | .000- .022 | Do. - Refractory | .000 | Do. - Rubber compounds: | | - Chlorinated rubber | | - Modified isomerized rubber| .000 | Do. - Hard rubber | | - Casein | | - Cellulose compounds: | | - Ethyl cellulose | .0003-.0007 | Do. - Cellulose acetate sheet | ([1]) | Do. - Cellulose acetate molding | ([1]) | Do. - Cellulose nitrate | | - ------------------------------+-------------------+----------- - - [1] Positive and injection 0.002-0.003; semipositive 0.005-0.007; - flash 0.008-0.009. - - NOTE.—The values for the properties in this table are based upon - maximum and minimum figures submitted to Modern Plastics by a - number of manufacturers of each type of material. Differences in - test procedures and sizes of test specimens may lead to erroneous - conclusions in some cases if direct comparisons are attempted. - Special grades of materials are often available which excel in - one particular property. - - Source: Modern Plastics, vol. 15, No. 2, opp. p. 120. October - 1937. - -Table 17 lists the properties which affect appearance and gives in -addition to the color range, the clarity, material, the burning rate, -the effect of age and sunlight, the refractive index, and the machining -quality of each synthetic resin. - -Table 18 lists molding properties of synthetic resins. Of special -interest are the possibilities of using a resin in injection molding. The -thermoplastic resins and plastics (see softening point in table 20) are -generally preferred to the thermosetting materials for injection molding -because they permit the reuse of material otherwise wasted. - -Table 19 lists the strength properties of the synthetic resins; table 20 -the heat properties; table 21 the electrical properties; and table 22 the -resistance to acids, alkalies, and solvents. All of these qualities are -important in some uses and each quality may be paramount in a few. Each -material has its limitations and its special advantages and the consuming -industry must choose the one best suited to its purposes. The tie-up -between specific properties and particular uses is exemplified by vinyl -resins, which because of their great elasticity at low temperatures, are -used in safety glass, and by the polystyrene resins, which because of -their electrical properties at high frequencies, are used in laminated -electrical parts. As production of the various resins increases new uses -will probably be found for most of them. - -TABLE 19.—_Synthetic resins and other plastics: Strength properties_ - - -------------------------------+--------------+------------+------------- - Type | Tensile | Elongation | Modulus of - | strength | | elasticity - -------------------------------+--------------+------------+------------- - |_Pounds per | _Percent_ |_Pounds per - | square inch_ | | square inch_ - Synthetic resins: | | | _× 10³_ - Tar-acid—Formaldehyde: | | | - Molded, wood flour filler | 6,000-11,000 | | 10-15 - Molded, mineral filler | 5,000-10,000 | | 10-45 - Molded, fabric filler | 6,500- 8,000 | | 7-12 - Laminated, paper base | 6,000-13,000 | | 5-20 - Laminated, fabric base | 8,000-12,000 | | 5-15 - Laminated, asbestos cloth | 9,000 | | - base | | | - Cast | 5,000-12,000 | | 5-15 - Tar-acid—Furfural: | | | - Wood flour filler | 5,000-12,000 | | 10-25 - Mineral filler | 4,000-12,000 | | 10-45 - Fabric filler | 5,000-10,000 | | 7-12 - Urea—Formaldehyde | 8,000-13,000 | | 16 - Vinyl, unfilled | 8,000-10,000 | | 3.5-4.1 - Vinyl, filled | 6,000-12,000 | | 3.5-8.5 - Acrylate | 7,000- 9,000 | 1.0 | 6 - Polystyrene | 5,500- 7,500 | 1.0 | 4.6-5.1 - Other plastics: | | | - Shellac compound | 900- 2,000 | | - Cold molded | | | - Nonrefractory | | | - Refractory | | | - Rubber compounds: | | | - Chlorinated rubber | | | - Modified isomerized rubber | 4,300 | 0.013 | 4.7 - Hard rubber | 4,000-10,000 | 8-15 | 5.3 - Casein | 7,600 | | 5.1-5.7 - Cellulose compounds: | | | - Ethyl cellulose | 2,000- 7,000 | | 2.8 - Cellulose acetate sheet | 6,000-11,000 | 20-55 | 1-3 - Cellulose acetate molding | 3,500-10,000 | 10-48 | 2-4 - Cellulose nitrate | 5,000-10,000 | 10-40 | 2-4 - -------------------------------+--------------+------------+------------- - - -------------------------------+---------------+--------------- - Type | Compressive | Flexural - | strength | strength - -------------------------------+---------------+--------------- - | _Pounds per | _Pounds per - | square inch_ | square inch_ - Synthetic resins: | | - Tar-acid—Formaldehyde: | | - Molded, wood flour filler | 16,000-36,000 | 8,000-15,000 - Molded, mineral filler | 18,000-36,000 | 8,000-20,000 - Molded, fabric filler | 20,000-32,000 | 10,000-13,000 - Laminated, paper base | 20,060-40,000 | 13,000-20,000 - Laminated, fabric base | 20,000-44,000 | 13,000-20,000 - Laminated, asbestos cloth | 18,000-40,000 | 17,000 - base | | - Cast | 15,000-30,000 | - Tar-acid—Furfural: | | - Wood flour filler | 28,000-36,000 | 10,000-16,000 - Mineral filler | 24,000-36,000 | 8,000-14,000 - Fabric filler | 26,000-30,000 | 10,000-16,000 - Urea—Formaldehyde | 24,000-35,000 | 13,000-15,000 - Vinyl, unfilled | | 10,000-13,000 - Vinyl, filled | | - Acrylate | 8,000 | 15,000-17,000 - Polystyrene | 13,000-13,500 | 6,500- 8,000 - Other plastics: | | - Shellac compound | | - Cold molded | 6,000-15,000 | 5,300- 7,500 - Nonrefractory |} 16,000 | 6,000 - Refractory |} | - Rubber compounds: | | - Chlorinated rubber | | - Modified isomerized rubber | 8,500-11,000 | 7,000- 9,000 - Hard rubber | 8,000-12,000 | - Casein | | - Cellulose compounds: | | - Ethyl cellulose | | - Cellulose acetate sheet | 4,000-16,000 | - Cellulose acetate molding | 11,000-16,000 | 5,200- 8,800 - Cellulose nitrate | | - -------------------------------+---------------+--------------- - - -------------------------------+----------------------------+------------ - Type | Impact strength[1] | Hardness[2] - | (foot pounds) | - -------------------------------+----------------------------+------------ - | | - | |_Brinell No_ - Synthetic resins: | | - Tar-acid—Formaldehyde: | | - Molded, wood flour filler | 0.10-0.28; I, N | 30-45 - Molded, mineral filler | 0.11-0.36; I, N | - Molded, fabric filler | 0.4-2.4; I, N | - Laminated, paper base | 0.4-1.2; I, N | 24-40 - Laminated, fabric base | 0.8-5.2; I, N | 30-45 - Laminated, asbestos cloth | | - base | | - Cast | 0.1-1.5; I, N | 30-45 - Tar-acid—Furfural: | | - Wood flour filler | 0.08-0.52; C, N | [3]35-40 - Mineral filler | 0.08-0.48; C, N | [3]44-46 - Fabric filler | 1.6-3.1; C, N | [3]30-35 - Urea—Formaldehyde | 0.7-1.5; C, U | [4]48-54 - Vinyl, unfilled | 0.3-0.6; I, N | 15-25 - Vinyl, filled | 0.1-0.7; I, N | 15-25 - Acrylate | 0.25-0.5; C, N | [4]18-20 - Polystyrene | 0.16-0.25; I, N | 20-30 - Other plastics: | | - Shellac compound | | - Cold molded | 0.4; C | - Nonrefractory | 0.4; C | - Refractory | | - Rubber compounds: | | - Chlorinated rubber | 3.0+; C, U | - Modified isomerized rubber | 2.6-6.2; I, N | [5]85-90 - Hard rubber | 0.5; I | 31 - Casein | 1.0; I | 23 - Cellulose compounds: | | - Ethyl cellulose | 1-4; I, N (per in. sq.) | - Cellulose acetate sheet | 2-7; C, N (per in. sq.) | [6]6-11 - Cellulose acetate molding | 3-12; C, N (per in. sq.) | [6]6-7.5 - Cellulose nitrate | 3-12; C, N (per in. sq.) | [6]8-11 - -------------------------------+----------------------------+------------ - - [1] ASTM D256-34T. C = Charpy; I = izod; N = notched; U = - unnotched. - - [2] 2.5 mm ball; 25 kg. load unless otherwise noted. - - [3] 50 kg. load. - - [4] 10 mm. ball; 500 kg. load. - - [5] Shore. - - [6] 10 kg. load. - - NOTE.—The values for the properties in this table are based upon - maximum and minimum figures submitted to Modern Plastics by a - number of manufacturers of each type of material. Differences in - test procedures and sizes of test specimens may lead to erroneous - conclusions in some cases if direct comparisons are attempted. - Special grades of materials are often available which excel in - one particular property. - - Source: Modern Plastics, vol. 15, No. 2, opp. p. 120; October - 1937. - -TABLE 20.—_Synthetic resins and other plastics: Heat properties_ - - -----------------------------------+--------------------+--------------- - | Thermal | Specific - | conductivity | heat - +--------------------+--------------- - Type | 10⁻⁴ calories | - | per second per | - | square centimeter | Calories per - | per 1°C. | °C. per gram - | per centimeter | - -----------------------------------+--------------------+--------------- - Synthetic resins: | | - Tar-acid—Formaldehyde: | | - Molded, wood flour filler | 4-12.2 | 0.35-0.36 - Molded, mineral filler | 8-20 | 0.25-0.35 - Molded, fabric filler | 3-5 | 0.30-0.35 - Laminated, paper base | 5-8 | 0.3 -0.4 - Laminated, fabric base | 5-8 | 0.3 -0.4 - Laminated, asbestos cloth base | | - Cast | 3-5 | 0.3- 0.4 - Tar-acid—Furfural: | | - Wood flour filler | 3.5-5 | 0.3- 0.4 - Mineral filler | 10-20 | 0.3- 0.4 - Fabric filler | 5-8 | 0.3- 0.4 - Urea—Formaldehyde | 7.13 | - Vinyl, unfilled | 4 | 0.244 - Vinyl, filled | Varies | Varies - Acrylate | 4.3-6.8 | 0.45 - Styrol | 1.9 | 0.324 - Other plastics: | | - Shellac compound | | - Cold molded: | | - Nonrefractory | | - Refractory | | - Rubber compounds: | | - Chlorinated rubber | | - Modified isomerized rubber | 2.6-2.9 | - Hard rubber | 3.2 | 0.33 - Casein | | - Cellulose compounds: | | - Ethyl cellulose | | - Cellulose acetate sheet | 5.4-8.7 | 0.3- 0.4 - Cellulose acetate molding | 5.4-8.7 | 0.3- 0.45 - Cellulose nitrate | 3.1-5.1 | 0.34-0.38 - -----------------------------------+--------------------+--------------- - - -----------------------------------+-------------------+---------------- - | Thermal | Resistance to - | expansion |continuous heat - +-------------------+---------------- - Type | | - | | - | 10⁻⁶ per °C. | °F. - | | - | | - -----------------------------------+-------------------+---------------- - Synthetic resins: | | - Tar-acid—Formaldehyde: | | - Molded, wood flour filler | 3.7-7.5 | 350 - Molded, mineral filler | 2.5-4 | 450 - Molded, fabric filler | 2-6 | 250-350 - Laminated, paper base | 2 | 212-300 - Laminated, fabric base | 3 | 212-350 - Laminated, asbestos cloth base | 2 | 400-500 - Cast | 2.8 | 160 - Tar-acid—Furfural: | | - Wood flour filler | 3 | 280-400 - Mineral filler | 2 | 350-500 - Fabric filler | 4.5 | 280-350 - Urea—Formaldehyde | 1.5 | 160 - Vinyl, unfilled | 6.9 | - Vinyl, filled | Varies | - Acrylate | 8.5 | - Styrol | 10.2 | - Other plastics: | | - Shellac compound | | 150-190 - Cold molded: | | - Nonrefractory | | 500 - Refractory | | 1,300 - Rubber compounds: | | - Chlorinated rubber | | - Modified isomerized rubber | 7-8 | - Hard rubber | 8.0 | - Casein | 8 | - Cellulose compounds: | | - Ethyl cellulose | | - Cellulose acetate sheet | 14-16 | 140-180 - Cellulose acetate molding | 14-16 | 140-180 - Cellulose nitrate | 12-16 | ca. 140 - -----------------------------------+-------------------+---------------- - - -----------------------------------+-----------+------------+----------- - | Softening | Distortion | - | point | under heat | - +-----------+------------+ - Type | | | - | | | Tendency - | °F. | °F. | to cold - | | | flow - | | | - -----------------------------------+-----------+------------+----------- - Synthetic resins: | | | - Tar-acid—Formaldehyde: | | | - Molded, wood flour filler | None | 240-285 | None. - Molded, mineral filler | do. | | Do. - Molded, fabric filler | do. | | Do. - Laminated, paper base | do. | 320 | Do. - Laminated, fabric base | do. | | Do. - Laminated, asbestos cloth base | do. | | Do. - Cast | | | - Tar-acid—Furfural: | | | - Wood flour filler | Chars 450 | 268-288 | Do. - Mineral filler | Chars 550 | 277-297 | Do. - Fabric filler | Chars 400 | | Do. - Urea—Formaldehyde | None | 260 | Do. - Vinyl, unfilled | 130-160 | 140-150 | Slight. - Vinyl, filled | 130-160 | 140-158 | Do. - Acrylate | 170-235 | 158 | Do. - Styrol | 110-200 | 185 | Do. - Other plastics: | | | - Shellac compound | 150 | | Do. - Cold molded: | | | - Nonrefractory | | | - Refractory | | | - Rubber compounds: | | | - Chlorinated rubber | 175-230 | 140 | Do. - Modified isomerized rubber | 165-220 | 167-221 | Do. - Hard rubber | 150-190 | | Do. - Casein | | 200 | - Cellulose compounds: | | | - Ethyl cellulose | | 210-266 | - Cellulose acetate sheet | 140-230 | 122-212 | Do. - Cellulose acetate molding | 145-260 | 122-212 | Do. - Cellulose nitrate | 160-195 | | - -----------------------------------+-----------+------------+----------- - - NOTE.—The values for the properties in this table are based upon - maximum and minimum figures submitted to Modern Plastics by a - number of manufacturers of each type of material. Differences in - test procedures and sizes of test specimens may lead to erroneous - conclusions in some cases if direct comparisons are attempted. - Special grades of materials are often available which excel in - one particular property. - - Source: Modern Plastics, vol. 15, No. 2, opp. p. 120. October 1937. - -TABLE 21.—_Synthetic resins and other plastics: Electrical properties_ - - ----------------------------------+-------------------+---------------- - |Volume resistivity | Breakdown - | (50 percent | voltage, 60 - Type |relative humidity) | cycles (volts - | (ohm = cms) | per mil - | |(instantaneous)) - ----------------------------------+-------------------+---------------- - Synthetic resins: | | - Tar-acid—Formaldehyde: | | - Molded, wood flour filler |10¹⁰-10¹² |300-500 - Molded, mineral filler |10⁹-10¹¹ |250-400 - Molded, fabric filler |10⁹-10¹¹ |300-450 - Laminated, paper base |10¹⁰-10¹³ |400-1,300 - Laminated, fabric base |10¹⁰-10¹² |150-600 - Laminated, asbestos cloth base| |90 - Cast |10⁹-10¹⁴ |300-450 - Tar-acid—Furfural: | | - Wood flour filler |10¹⁰-10¹² |400-600 - Mineral filler |10⁹-10¹¹ |200-500 - Fabric filler |0.4 × 10¹¹ |200-500 - Urea—Formaldehyde |(2-2.8) × 10¹³ |650-720 - Vinyl, unfilled |10¹⁴ |400-500 - Vinyl, filled |10¹¹ |350-400 - Acrylate |10¹⁵ |480 - Polystyrene |10¹⁷-10¹⁸ |500-700 - Other plastics: | | - Shellac compound | |100-400 - Cold molded: | | - Nonrefractory |1.3 × 10¹² |85 - Refractory | | - Rubber compounds: | | - Chlorinated rubber | |2,300 - Modified isomerized rubber |(5-7) × 10¹⁶ | - Hard rubber |10¹²-10¹⁵ |250-900 - Casein | |400-700 - Cellulose compounds: | | - Ethyl cellulose | |1,500 - Cellulose acetate sheet |(5-30) × 10¹² |800-2,500 - Cellulose acetate molding |(4.2-6.2) × 10¹² |800-850 - Cellulose nitrate |(2-30) × 10¹⁰ |600-1,200 - ----------------------------------+-------------------+---------------- - - ----------------------------------+------------------------------- - | Dielectric constant - +---------+----------+---------- - Type | | | - |60 cycles|10³ cycles|10⁶ cycles - | | | - ----------------------------------+---------+----------+---------- - Synthetic resins: | | | - Tar-acid—Formaldehyde: | | | - Molded, wood flour filler |5-12 |4-8 |4.5-8 - Molded, mineral filler |5-20 |4.5-20 |4.5-20 - Molded, fabric filler |5-10 |4.5-6 |4.5-6 - Laminated, paper base | | |4-6 - Laminated, fabric base | | |4.5-7 - Laminated, asbestos cloth base| | | - Cast |5-10 | |5-7 - Tar-acid—Furfural: | | | - Wood flour filler | |4-8 |6-7.5 - Mineral filler | |4.5-20 |5-18 - Fabric filler | |4.5-6 |5-7.5 - Urea—Formaldehyde |6.6 | |6 - Vinyl, unfilled | | |4 - Vinyl, filled | |4.7 |4 - Acrylate |4-6 | |2.8 - Polystyrene |2.6 |2.65 |2.7 - Other plastics: | | | - Shellac compound | | | - Cold molded: | | | - Nonrefractory |15 | |6 - Refractory | | | - Rubber compounds: | | | - Chlorinated rubber |ca. 3 | | - Modified isomerized rubber |2.7 |2.68 | - Hard rubber |2.8 | |3 - Casein | | |6.15-6.8 - Cellulose compounds: | | | - Ethyl cellulose | |3.72 | - Cellulose acetate sheet |5.1-7.5 | |4.2-5.3 - Cellulose acetate molding |5.8-6.0 | |4.4-4.6 - Cellulose nitrate |6.7-7.3 | |6.15 - ----------------------------------+---------+----------+---------- - - ----------------------------------+---------------------------------- - | Power factor - +-----------+----------+----------- - Type | | | - | 60 cycles |10³ cycles|10⁶ cycles - | | | - ----------------------------------+-----------+----------+----------- - Synthetic resins: | | | - Tar-acid—Formaldehyde: | | | - Molded, wood flour filler |0.04-0.30 |0.04-0.15 |0.035-0.1 - Molded, mineral filler |0.10-0.30 |0.10-0.15 |0.005-0.1 - Molded, fabric filler |0.08-0.30 |0.08-0.20 |0.04-0.1 - Laminated, paper base | | |0.02-0.05 - Laminated, fabric base | | |0.02-0.08 - Laminated, asbestos cloth base| | | - Cast |0.025-0.20 |0.005-0.08|0.01-0.045 - Tar-acid—Furfural: | | | - Wood flour filler | |0.04-0.15 |0.035-0.1 - Mineral filler | |0.1-0.15 |0.04-0.1 - Fabric filler | |0.08-0.20 |0.035-0.1 - Urea—Formaldehyde |0.034 | |0.01-0.03 - Vinyl, unfilled | |0.0143 |0.0175 - Vinyl, filled | |0.02-0.15 |0.02-0.065 - Acrylate |0.06-0.08 | |0.02 - Polystyrene |0.0003 |0.0001 |0.0001 - Other plastics: | | | - Shellac compound | | | - Cold molded: | | | - Nonrefractory |0.20 | |0.07 - Refractory | | | - Rubber compounds: | | | - Chlorinated rubber |0.003 | | - Modified isomerized rubber |0.006 | |0.0016 - Hard rubber | | |0.003-0.008 - Casein | | |0.052 - Cellulose compounds: | | | - Ethyl cellulose | |0.011 | - Cellulose acetate sheet |0.025-0.07 | |0.038-0.091 - Cellulose acetate molding |0.042-0.058| |0.038-0.042 - Cellulose nitrate |0.062-0.144| |0.074-0.097 - ----------------------------------+-----------+----------+----------- - - NOTE.—The values for the properties in this table are based upon - maximum and minimum figures submitted to Modern Plastics by a - number of manufacturers of each type of material. Differences in - test procedures and sizes of test specimens may lead to erroneous - conclusions in some cases if direct comparisons are attempted. - Special grades of materials are often available which excel in - one particular property. - - Source: Modern Plastics, vol. 15, No. 2, opp. p. 120. October 1937. - -TABLE 22.—_Synthetic resins and other plastics: Specific gravity, -specific volume, and resistance to other substances_ - - ------------------------------+---------+--------------+----------- - | | |Water - Type |Specific | Specific |absorption, - | gravity | volume |immersion - | | |24 hours[1] - ------------------------------+---------+--------------+----------- - Synthetic resins: | |_Cubic inches | - Tar-acid—Formaldehyde: | | per pound_ | - Molded, wood flour filler |1.34-1.52| 20.7-18.2 |0.2-0.6 - Molded, mineral filler |1.70-2.09| 16.4-13.3 |0.01-0.3 - Molded, fabric filler |1.37-1.40| 20.2-19.8 |1.0-1.3 - Laminated, paper base |1.34-1.55| 20.7-17.8 |0.5-9.0 - Laminated, fabric base |1.34-1.55| 20.7-17.8 |0.5-9.0 - Laminated, asbestos cloth |1.6-1.65 | 17.3-16.8 |0.5 - base | | | - Cast |1.27-1.32| 21.8-20.0 |0.01-0.5 - Tar-acid—Furfural: | | | - Wood flour filler |1.3-1.4 | 21.3-19.8 |0.2-0.6 - Mineral filler |1.6-2.0 | 17.3-13.9 |0.01-0.15 - Fabric filler |1.3-1.4 | 21.3-19.8 |0.8-1.4 - Urea—Formaldehyde |1.48-1.50| 18.7-16.5 |1-2 - Vinyl, unfilled |1.34-1.36| 20.7-20.4 |0.05-0.15 - Vinyl, filled |1.35-2.5 | 20.5-11.1 |0.2-4.0 - Acrylate |1.18 | 23.3 |0.3 - Polystyrene |1.05-1.07| 26.3-25.8 |0 - Other plastics: | | | - Shellac compound |1.1-2.7 | 25.2-10.3 | - Cold molded: | | | - Nonrefractory |1.98-2.0 | 14.0-13.9 |1.5 - Refractory |2.2 | 12.6 |0.5-15 - Rubber compounds: | | | - Chlorinated rubber |1.5 | 18.5 |0.1-0.3 - Modified isomerized rubber|1.06 | 26.1 |0.02 - Hard rubber |1.12-1.8 | 24.7-15.4 |0.02 - Casein |1.35 | 20.5 |3-7 - Cellulose compounds: | | | - Ethyl cellulose |1.14 | 24.3 |[6]1.25 - Cellulose acetate sheet |1.27-1.37| 21.8-20.2 |1.5-3.0 - Cellulose acetate molding |1.27-1.63| 21.8-17.0 |1.4-2.8 - Cellulose nitrate |1.35-1.60| 20.5-17.3 |1.0-3.0 - ------------------------------+---------+--------------+----------- - - ------------------------------+---------------+------------------ - | | - Type |Effect of weak | Effect of strong - | acids | acids - | | - ------------------------------+---------------+------------------ - Synthetic resins: | | - Tar-acid—Formaldehyde: | | - Molded, wood flour filler |None to slight.|Varies[2] - Molded, mineral filler | do | do[2] - Molded, fabric filler | do | do[2] - Laminated, paper base | do | do[2] - Laminated, fabric base | do | do[2] - Laminated, asbestos cloth | do | do[2] - base | | - Cast | do | - Tar-acid—Furfural: | | - Wood flour filler | do | do[2] - Mineral filler | do | do[2] - Fabric filler | do | do[2] - Urea—Formaldehyde | do |Decomposed or - | |surface attacked - Vinyl, unfilled |Resistant |Resistant - Vinyl, filled |Dependent on |Dependent on - | filler. |filler. - Acrylate |None |Oxidizing acids - | |attack surface. - Polystyrene | do |None - Other plastics: | | - Shellac compound |Deteriorates |Deteriorates - Cold molded: | | - Nonrefractory |Slight |Decomposes - Refractory |Decomposes | do - Rubber compounds: | | - Chlorinated rubber |Resistant |Resistant - Modified isomerized rubber| do | do - Hard rubber | do |Attacked by - | |oxidizing acids - Casein | do |Decomposes - Cellulose compounds: | | - Ethyl cellulose |Slight |Decomposes - Cellulose acetate sheet | do | do - Cellulose acetate molding | do | do - Cellulose nitrate | do | do - ------------------------------+---------------+------------------ - - ------------------------------+------------+------------+--------------- - | | | - Type | Effect of | Effect of | Effect of - | weak | strong | organic - | alkalies | alkalies | solvents - ------------------------------+------------+------------+--------------- - Synthetic resins: | | | - Tar-acid—Formaldehyde: | | | - Molded, wood flour filler | Slight to |Decomposes |None.[3] - | marked | | - Molded, mineral filler | do | do | do[3] - Molded, fabric filler | do | do | do[3] - Laminated, paper base | do | do | do[3] - Laminated, fabric base | do | do | do[3] - Laminated, asbestos cloth | do | do | do[3] - base | | | - Cast | do | do | do - Tar-acid—Furfural: | | | - Wood flour filler | do | do | do - Mineral filler | do | do | do - Fabric filler | do | do | do - Urea—Formaldehyde | do | do | do - | | | - Vinyl, unfilled |Resistant |Resistant |([4]). - Vinyl, filled |Dependent on|Dependent on|([4]). - | filler. | filler. | - Acrylate |None |Slight |([5]). - | | | - Polystyrene | do |None |Widely soluble. - Other plastics: | | | - Shellac compound |Deteriorates|Deteriorates|Attacked by - | | | some. - Cold molded: | | | - Nonrefractory |Decomposes |Decomposes | do - Refractory |None |None |None. - Rubber compounds: | | | - Chlorinated rubber |Resistant |Resistant |Soluble in - | | | aromatic - | | | hydrocarbons. - Modified isomerized rubber| do | do |Attacked by - | | | some. - Hard rubber | do | do | do - | | | - Casein |Softens |Decomposes |Resistant. - Cellulose compounds: | | | - Ethyl cellulose |None |None. |Widely soluble. - Cellulose acetate sheet |Slight |Decomposes |([7]). - Cellulose acetate molding | do | do |([7]). - Cellulose nitrate | do | do |([7]). - ------------------------------+------------+------------+--------------- - - [1] ASTM D48-33. - - [2] Decomposed by oxidizing acids; reducing and organic acids no - effect. - - [3] On bleed-proof materials. - - [4] Resists alcohols, aliphatic hydrocarbons, and oils. Soluble - in ketones and esters; swells in aromatic hydrocarbons. - - [5] Soluble in ketones, esters, and aromatic hydrocarbons. - - [6] 48 hours. - - [7] Soluble in ketones and esters; softened by alcohols; little - affected by hydrocarbons. - - NOTE.—The values for the properties in this table are based upon - maximum and minimum figures submitted to Modern Plastics by a - number of manufacturers of each type of material. Differences in - test procedure and sizes of test specimens may lead to erroneous - conclusions in some cases if direct comparisons are attempted. - Special grades of materials are often available which excel in - one particular property. - - Source: Modern Plastics, vol. 15, No. 2, opp. p. 120. October - 1937. - - - - -15. SYNTHETIC RESINS IN OTHER COUNTRIES - - -Large-scale production of synthetic resins is confined principally to -the United States, Germany, and Great Britain. There is small production -in many other countries, of which the most important are France, Italy, -Czechoslovakia, Canada, and Japan. - -In 1934 the world output was estimated at 135 million pounds, of which -the United States produced about 44 percent, Germany 26 percent, and -Great Britain 24 percent. In 1937 world output was estimated at 360 -million pounds, the United States’ share of the total being almost -50 percent, followed by 27 percent for Germany, 20 percent for Great -Britain, and the remaining 3 percent scattered. - -European estimates indicate that about 40 percent of the output goes into -surface coatings and that 60 percent of the surface-coating resins are -tar-acid and 40 percent alkyds. The Tariff Commission found that in 1937 -50 percent of the United States production of all synthetic resins went -into surface coatings, 27 percent into molded articles, and the remaining -23 percent into laminating and miscellaneous uses. Approximately -three-fourths of the surface-coating resins were alkyds and one-fourth -tar-acid resins. - - -GERMANY - - -Production. - -In recent years Germany’s production of synthetic resins has increased -rapidly, each succeeding year registering the attainment of a new record. -In 1933 production totaled 17,500,000 pounds and by 1935 had increased to -55,000,000 pounds. A further expansion of about 30 percent to 70,000,000 -pounds in 1936 and present production trends indicate a gain of about 40 -percent more in 1937, to an estimated total of 100,000,000 pounds. - -Although tar-acid resins comprise the bulk of the German output, -considerable gains are shown for other types, notably injection molding -resins of the polystyrene and vinyl types. The development of completely -automatic injection molding machinery has given an impetus to these -types. While technical progress, including improvement of molding -equipment, has contributed to the expanded production, the use of -synthetic resins in Germany has had a strong stimulus because they are -made almost wholly of domestic materials. Under the “Four-Year Plan” for -the greatest possible national economic independence, synthetic resins -are replacing imported materials, such as the heavier nonferrous metals, -iron, hardwoods, cork, and natural gums and resins in many uses. This -displacement of materials has also affected such domestic products as -glass and porcelain, which caused the Government to intervene and impose -restrictions upon the use of resins for purposes adequately served by -other materials of German origin. - -Germany’s expanding production of synthetic resin has also been aided by -a sharp increase in exports, which have increased well over 100 percent -since 1932. - -_Tar-acid resins._—German output of tar-acid resins has been estimated -at 35 million pounds in 1934, at 49 million pounds in 1935, and at 63 -million pounds in 1936. Such resins comprise the bulk of the German -production of molding resins. - -There are at least seven producers of tar-acid resins in Germany and nine -producers of molding powders and pellets. Tar-acid resins for surface -coatings are produced by a number of these concerns. Among the important -makers in Germany are The Bakelite Gesellschaft (organized in 1910 to -operate under the Baekeland patents); the explosives and munitions firm -of Dynamit A.G.; Dr. Kurt Albert G.m.b.H.; the I.G. Farbenindustrie; -Beckacite Kunstharzfabrik G.m.b.H.; and Rohm & Haas A.G. The Beckacite -firm has associates in the United States and in the United Kingdom, and -Rohm & Haas, an associate in the United States. - -_Alkyd resins._—The manufacture of alkyd resins has developed in -Germany in the past few years. Demand for these resins has been given a -marked impetus by the development of a new standardized substitute for -linseed-oil varnish known as El Varnish, the use of which is required by -the Control Board for Industrial Fats for certain interior and exterior -painting. - -There are five makers of resins for paints, varnishes, and lacquers. -The output of alkyd resins has increased sharply since 1934, probably -reaching 10 million pounds in 1936. - -_Urea resins._—The output of urea resins in Germany is relatively small; -two of the more important types are known as Locron and Pollopas. - -_Polystyrene and vinyl resins._—In 1936 Germany’s production of -thermoplastic resins exceeded 1 million pounds, principally of the -polystyrene and vinyl types. Among the vinyl resins are Acronal and -Mowilith, both of which are manufactured by the I.G. Farbenindustrie. -This combine also produces several types of polystyrene resins known as -Mollit and Metastyrol. Dynamit A.G. produces a polystyrene resin known as -Trolitul. - - -Uses of synthetic resins. - -The original and most important use of synthetic resins in Germany was -for electrical insulation. This use was so extensive that the industry -was organized in 1924 into an association known as non-rubber insulation -materials industry. Materials were standardized and classified into 14 -types, of which 5 were tar-acid resins and 1 was a urea resin. Every -type must meet certain specifications in order to be recognized by the -Reich Testing Institute. More than 100 firms produce insulating materials -meeting the institute’s specifications. - -Radio panels of the popular sets sponsored by the Government are made of -synthetic resins. Consumption in the automobile industry is increasing -for such parts as instrument panels, electrical equipment, steering -wheels, gear-shift knobs, and numerous others. The latest airplanes show -increased use of synthetic resins, where they contribute light weight, -great strength, and resistance to corrosion. - -In cameras and moving-picture equipment, wood and metal have been in part -replaced by synthetic resins. Other applications of resins in Germany -include bearings for rolling mills, goggles and spectacles (including the -lens), and perfume and medicine bottles. - -Resins for surface coatings are undergoing rapid development in Germany, -owing to the shortage of linseed oil. Alkyd resins in coatings are being -promoted by the Government, which prohibits or limits the use of the -older oil-type coatings for certain uses so as to decrease the use of -linseed oil and other paint oils that must be imported and hence require -outlays of foreign exchange. Penalties have been imposed for violating -the regulations.[13] - - -Organization. - -The synthetic-resin industry in Germany is a unit within the national -industrial organization. It is a subdivision of the industrial chemical -group, called Fachgruppe Kunststoffe, or Group 13 of the 19 trade groups -in the chemical division. This subdivision controls casein and cellulose -plastics as well as synthetic resins, and is further divided as follows: -(1) Casein plastics, (2) cast phenolic resins, (3) molding compositions, -(4) resins for lacquers, (5) celluloid and zellon, (6) transparent -sheeting, (7) linoleum, and (8) miscellaneous (such as vulcanized fiber, -bottle caps, and die-casting resins). - -There are two cartels distinct from the national organization, which -expressly excludes all functions and activities of cartels. One cartel -represents the firms interested in molding compositions and the other -those interested in synthetic resins for other purposes. Some of the -producers are members of both cartels. - - -Foreign trade. - -Imports of synthetic resins are negligible, although the duty of 4.6 -cents per pound (25 marks per 100 kilograms) on imports into Germany is -not prohibitive. Exports have increased practically every year since -1930, when they were first recorded separately. - -Table 23 shows the quantity and value of exports in recent years. - -TABLE 23.—_Synthetic resins: German exports, 1930-37_ - - -------+----------------------+---------------------- - | Hardening resins | Nonhardening resins - +------+---------------+------+--------------- - Year | | Value | | Value - |1,000 +-------+-------+1,000 +-----+--------- - |pounds|1,000 | 1,000 |pounds|1,000|1,000 - | |marks |dollars| |marks|dollars - -------+------+-------+-------+------+-----+--------- - | | | | | | - 1930 | 2,549| 1,973| 472| | | - 1931 | 3,775| 2,757| 651| | | - 1932 | 3,162| 2,112| 501| | | - 1933 | 4,009| 2,625| 801| 6,628|3,566| 1,088 - 1934 | 4,924| 3,162| 1,246| 7,076|3,415| 1,346 - 1935 | 4,948| 2,993| 1,206| 6,921|3,445| 1,388 - 1936 | 6,392| 3,501| 1,411| 7,764|3,820| 1,539 - 1937[1]| 8,706| 4,402| 1,770|10,866|5,389| 2,117 - -------+------+-------+-------+------+-----+---------- - - [1] Preliminary. - - Source: Consular reports. - -German exports of synthetic resins are, for the most part, destined -to European countries, most of which have increased their purchases -considerably in recent years. Exports to Latin American countries have -increased recently, especially to Brazil. Table 24 shows the distribution -of exports in recent years. - -TABLE 24.—_Synthetic resins: German exports, by countries, 1934-37_ - - [Thousands of marks] - ------------------------------+-----+-----+-----+------- - Destination |1934 |1935 |1936 |1937[1] - ------------------------------+-----+-----+-----+------- - Austria | 259| 352| 446| 593 - Belgium | 215| 259| 297| 420 - Czechoslovakia | 347| 345| 604| 825 - Denmark | 316| 391| 473| 540 - France | 626| 651| 680| 734 - Great Britain |1,247| 563| 596| 844 - Hungary | 240| 135| 182|([2]) - Italy | 252| 359| 523| 615 - Netherlands | 530| 572| 645|1,031 - Spain | 225| 302| 178| 57 - Sweden | 415| 457| 463| 691 - Switzerland | 721| 705| 714| 749 - Other European countries | 370| 618| 706|([2]) - Argentina | 250| 207| 194|([2]) - Brazil | 46| 77| 109|([2]) - Other Latin American countries| 17| 18| 75|([2]) - All other countries | 501| 427| 436|2,692 - +-----+-----+-----+----- - Total |6,577|6,438|7,321|9,791 - ------------------------------+-----+-----+-----+----- - - [1] Preliminary. - - [2] Included in all other countries. - - Source: Official German statistics. - - -GREAT BRITAIN[14] - -As in most other countries, the history of the synthetic-resin industry -in Great Britain begins with the acquisition of rights by a British -concern to manufacture under the original Bakelite patents. The Damard -Lacquer Co., Ltd. was probably the pioneer maker of phenolic resins in -England. The principal product was a baking lacquer sold under the trade -name Damarda, marketed for and used principally as a coating to prevent -corrosion on brass. The outbreak of the World War created such an urgent -demand for laminated materials that this firm started production of -them for the British Government. In 1926 this concern was merged with -Mouldesite, Ltd. and Redmanol, Ltd., under the name of Bakelite, Ltd. - - -Production. - -Statistics of production of synthetic resins in Great Britain are -available only for 1934 and 1935. They are given in table 25. - -TABLE 25.—_Synthetic resins: Production in Great Britain, 1934 and 1935_ - - -------------------------------------------+--------------------- - Type | 1934 | 1935 - -------------------------------------------+----------+---------- - | _Pounds_ | _Pounds_ - Solid, liquid, cured, uncured, and hardened|25,558,400|13,283,200 - Molding powder, 50 percent or more resin | |25,872,000 - Laminated sheets, rods, blocks, tubes | 1,164,800| 1,646,400 - +----------+---------- - Total |26,723,200|40,801,600 - -------------------------------------------+----------+---------- - - Source: Great Britain. Board of Trade, Census of Production. - -Capital invested in the British industry is reported as 15,000,000 pounds -sterling and direct employment as 20,000 people. - -_Tar-acid resins._—Many large moldings are made in England, such as large -radio cases, desk files, trays, and drain boards. Cast phenolic resin -production has just been started in England. - -Among the novelties recently produced in England is a toy railway molded -of tar-acid resin. The trains and track spacers are of nonconducting -resin; the molded rails are made conductive by a thin covering of metal -which is pressed in and secured at the ends. Two trains may be run on the -same set of rails at different speeds, or one can go forward and another -backward, since the two outer rails are separate conductors, the third -rail acting as a common return. - -Molded piano parts are being tried in an attempt to solve the troubles -hitherto encountered with wood, owing to variations in humidity. Resins -have long been used in facing the keys, but the production of piano -action parts has presented many technical difficulties. The secret of -success with molded resin parts lies in molding the joints in position -when the main body is molded. There are 88 sections in each piano. - -_Urea resins._—British Cyanides, Ltd., well-known makers of synthetic -resins in England, acquired the Pollopas patents for the manufacture -of urea resins in the United Kingdom, in certain continental European -countries, and in the British Empire except Canada. The agreement called -for a full exchange of patents and other information with the other -licensees of the Pollopas patents. These arrangements were made for -the purpose of consolidating the patent position and for the pooling -of technical data already existing on manufacture, with the object of -improving quality. - -_Acrylate resins._—An outstanding development in Great Britain has been -the production of the thermoplastic resins known as Diakon and Perspex. -These are made from methyl methacrylate and are developments of the -Imperial Chemical Industries, Ltd. Diakon is for molding powders and -Perspex is in the form of cast sheets, rods, tubes, and optical forms. - -These new commercial resins are considered the best combination thus far -obtained of strength, transparency, and light weight. Applications in -England include fittings for aircraft, transparent inspection covers for -machinery, medical equipment, instrument windows, lenses and prisms in -optical systems, and aircraft windscreens. They are used in subways for -lenses for deflecting and diffusing light and in battery cases and coil -forms. - -The general properties of the acrylate resins include transparency -to both visible and ultraviolet light, almost unlimited color range, -resistance to acids and alkalies, and superior electrical properties. - -_Aniline resin._—Panilax is an aniline-formaldehyde condensation -product made in England. It has high electrical and thermal insulating -properties, great mechanical strength, is odorless and odor repelling, -and practically unaffected by water, oil, and alkalies. - - -Organization. - -Most of the British producers of synthetic resins are members of the -British Plastics Federation, Ltd. - -Several years ago a 10-year contract was made between the Imperial -Chemical Industries, Ltd. and the Toledo Synthetic Products Co. (now -Plaskon Co.) of Toledo, Ohio. This agreement provides for an exchange -of all technical and commercial information on urea-resin products and -processes and the granting of free licenses under present or future -patents. - -Agreements probably also exist between the British Bakelite Co. and the -American firm on tar-acid resins; between Nobel Chemical Finishes, Ltd. -and E. I. du Pont de Nemours & Co. on alkyd resins; between British -Thompson Houston Co., Ltd., and the General Electric Co. on alkyd resins; -between Imperial Chemical Industries, Ltd. and du Pont on acrylate -resins; and between Beetle Products Co. and American Cyanamid Co. on urea -resins. - - -Foreign trade in resins. - -British imports of synthetic resins, by principal sources, are shown in -table 26. - -TABLE 26.—_Synthetic resins: Imports into the United Kingdom, in selected -years, 1930-36_ - - [1,000 pounds] - --------------------+------+-------+-------+-------+-------+------ - Source | 1930 | 1931 | 1933 | 1934 | 1935 | 1936 - --------------------+------+-------+-------+-------+-------+------ - British countries. | 1 | ([1]) | 5 | 2 | 19 | 24 - Germany | 508 | 1,621 | 2,267 | 2,259 | 1,476 | 914 - Netherlands | 679 | 667 | 151 | 114 | ([2]) | ([2]) - UNITED STATES | 119 | 229 | 656 | 902 | 986 | 1,056 - All other countries | 65 | 281 | 246 | 257 | 323 | 435 - +------+-------+-------+-------+-------+------ - Total |1,372 | 2,798 | 3,470 | 3,534 | 2,804 | 2,429 - --------------------+------+-------+-------+-------+-------+------ - - [1] Less than 500. - - [2] Included in “All other countries.” - - Source: Official statistics of the United Kingdom. - -British exports of synthetic resins to principal countries are shown in -table 27. - -TABLE 27.—_Synthetic resins: Exports from the United Kingdom, in selected -years, 1930-36_ - - [1,000 pounds] - --------------------+------+-------+-------+-------+-------+------ - Source | 1930 | 1931 | 1933 | 1934 | 1935 | 1936 - --------------------+------+-------+-------+-------+-------+------ - British countries | 138 | 170 | 992 | 1,350 | 1,788 | 2,732 - Sweden | 40 | 69 | 242 | 452 | 558 | 650 - Denmark |([1]) | ([1]) | 99 | 140 | 159 | 150 - Belgium |([1]) | ([1]) | 104 | 205 | 237 | 203 - Italy |([1]) | ([1]) | 49 | 95 | ([1]) | ([1]) - Argentina |([1]) | ([1]) | 28 | 198 | 156 | 238 - All other countries | 104 | 171 | 366 | 505 | 735 | 1,084 - +------+-------+-------+-------+-------+------ - Total | 282 | 410 | 1,880 | 2,945 | 3,633 | 5,057 - --------------------+------+-------+-------+-------+-------+------ - - [1] Not available; included in “All other countries.” - - Source: Official statistics of the United Kingdom. - - -FRANCE[15] - - -Producers. - -Statistics of French production and sales of synthetic resin are not -available. Larousse Commercial Illustré describes the French synthetic -resin industry as not important and estimates the output in 1930 at -2,000,000 pounds. The Revue Général des Matières Plastiques, most -important technical review in France, estimates the production in 1931 as -about 3,500,000 pounds. - -The comparatively few French companies producing synthetic resins -are, for the most part, under British or German control. The types of -synthetic resin made in France, the trade names, and the names of the -manufacturers, follow: - -_Bakelite._—Tar-acid molding compounds and laminating materials; cast -phenolic resins; Cie La Bakelite, Bezous, Seine. - -_Plastose and Ferodo._—Tar-acid molding compounds; Société -Ferodo-Plastose, Saint Ouen, Seine. - -_Pollopas._—Urea molding compounds and laminating materials; -Établissements Kuhlmann, Paris. - - -Foreign trade. - -French imports of synthetic resins are classified under tariff item No. -0376 bis: Synthetic resins (solid or resinous products of the Bakelite, -Albertol, Plastose types, etc.) derived from the condensation of -aldehydes with phenols, amines, and amides. Several subclassifications -are shown: (_a_) Soluble in oil and not polymerizable, (_b_) which may be -rendered insoluble and infusible, and (_c_) infusible. Imports in recent -years, from principal sources, are shown in table 28. - -TABLE 28.—_Synthetic resins: French imports, by types and by countries, -1931 and 1933-37_ - - [Pounds] - --------------+-------+---------+---------+---------+---------+---------- - Source | 1931 | 1933 | 1934 | 1935 | 1936 | 1937[1] - --------------+-------+---------+---------+---------+---------+---------- - | - | Soluble in oil - +-------+---------+---------+---------+---------+---------- - Germany |563,860|1,003,860|1,359,600|1,164,470|1,085,766| ([2]) - UNITED STATES |174,900| 126,280| 185,680| 284,458| 162,699| ([2]) - United Kingdom|184,800| 131,120| 80,520| 109,789| 18,960| ([2]) - Austria | | 35,640| 162,580| 193,564| 575,180| ([2]) - Netherlands | | 49,720| | 16,755| ([2]) | ([2]) - All other | | | | | | - countries | 4,620| 5,720| 3,080| 11,023| 33,069| ([2]) - +-------+---------+---------+---------+---------+---------- - Total |928,180|1,352,340|1,791,460|1,744,059|1,875,894|1,794,985 - +-------+---------+---------+---------+---------+---------- - | Molding compounds - +-------+---------+---------+---------+---------+---------- - United Kingdom| 21,780| 71,060| 10,340| 11,243| 23,589| ([2]) - Germany |248,600| 49,060| 20,460| 68,563| 39,242| ([2]) - Switzerland | | 13,200| 31,900| 11,464| ([2]) | ([2]) - UNITED STATES | 11,220| 18,920| 22,660| 20,062| 66,799| ([2]) - Belgium | | 31,240| 49,500| 7,716| ([2]) | ([2]) - All other | | | | | | - countries | 3,080| | 4,840| 6,173| 5,732| ([2]) - +-------+---------+---------+---------+---------+---------- - Total |284,680| 183,480| 139,700| 125,221| 135,362| 105,380 - +-------+---------+---------+---------+---------+---------- - | Molded, cast, and laminated articles - +-------+---------+---------+---------+---------+---------- - Germany | 12,980| 7,700| 4,840| 9,039| 17,857| ([2]) - Netherlands | | | | 220| | ([2]) - Austria | 4,840| 440| 220| | | ([2]) - United Kingdom| | | 220| | | ([2]) - UNITED STATES | | 220| | 220| | ([2]) - All other | | | | | | - countries | 1,320| | | | 1,984| ([2]) - +-------+---------+---------+---------+---------+---------- - Total | 19,140| 8,360| 5,280| 9,479| 19,841| 8,377 - --------------+-------+---------+---------+---------+---------+---------- - [1] Preliminary. - - [2] Not separately reported. - - Source: Consular reports. - -Exports of synthetic resins from France, by principal markets, are shown -in table 29. - -TABLE 29.—_Synthetic resins: French exports 1931 and 1933-37_ - - [Pounds] - --------------+-------+---------+---------+---------+---------+--------- - Destination | 1931 | 1933 | 1934 | 1935 | 1936 | 1937 - --------------+-------+---------+---------+---------+---------+--------- - Belgium |203,060| 224,180 | 186,780 | 113,757 | 165,565 | ([1]) - Argentina | | 69,080 | 91,300 | ([1]) | ([1]) | ([1]) - Switzerland | | | 16,940 | 12,787 | 37,258 | ([1]) - Italy | 12,980| | | ([1]) | ([1]) | ([1]) - All other | | | | | | - countries | 4,840| 29,260 | 15,180 | 54,895 | 36,376 | ([1]) - +-------+---------+---------+---------+---------+--------- - Total |220,880| 322,520 | 310,200 | 181,439 | 239,199 | 417,772 - --------------+-------+---------+---------+---------+---------+--------- - - [1] Not separately reported. - - Source: Consular reports. - -CZECHOSLOVAKIA - -Production of phenolic resins in Czechoslovakia has increased rapidly in -recent years and is ample to supply domestic requirements. Most of the -raw materials are imported from Germany, Great Britain, and France, but -formaldehyde is produced locally in sufficient quantities. - -The principal makers of synthetic resins in Czechoslovakia are: - - (1) Bratislavska tovarna na kable Bratislava. - (2) Schreiber & Co. Lipnik - (3) Ing. Alex Reiber Sered - (4) J. Elias Prague - (5) Mathias Oechsler & Sohn Riegersdorf - (6) J. Batistello, Jr. Gablonz - -Resin products are widely used by the electrical industries for wall -plates, plugs, switches, fuse boxes, etc. Other articles made of -synthetic resins are: handles and knobs for furniture and kitchen -equipment, bottle caps, fountain pens and pencils, clock and radio -housings, tableware, cutlery handles, trays, buttons, toilet ware and -toys. - -Imports of synthetic resins in 1934 totaled 1,270,500 pounds; Germany -supplied 46 percent and Great Britain 22 percent of this total. Exports -of synthetic resins during the same year amounted to 166,540 pounds and -went principally to Poland, Yugoslavia, Germany, and Argentina. - - -ITALY - -The Societa Italiana Resine, an affiliate of the important chemical firm, -Chimiche Forestali, is a leading maker of tar-acid resins in Italy. A new -and modern plant is located at Milan in close proximity to the electrical -and textile industries, both important markets for resins. - -In 1936 the Ministry of Corporations granted Montecatini Societe Generale -per l’Industria Mineraria, Milan, a permit to develop a factory for alkyd -resins; and also Societe Italiana Ebonite and Sostituti, Milan, one to -produce tar-acid resins. In 1937 a permit was granted to Montecatini S.A. -for a plant to manufacture acrylic acid resins at the Villadossola works -of the Soc. Elletrochimica del Toce. - - -JAPAN[16] - -The history of the synthetic resin industry in Japan goes back to 1913 -when Dr. Jokichi Takamine, discoverer of adrenalin and takadiastase, -acquired the right to manufacture and sell tar-acid resin Products in -Japan. The business was financed by the Sankyo Co., Ltd., and a factory -was built at Shinagawa, near Tokyo. In 1923 a subsidiary company known -as the Japan Bakelite Co., Ltd., was formed with a paid-in capital of -1,200,000 yen. This firm considers itself an affiliate of the Bakelite -Corporation of the United States and, according to an existing agreement, -cannot export to the United States. Its territory includes the Japanese -Empire and Manchukuo. China is considered an open market. - -The original plant at Shinagawa was partially destroyed by fire in 1919, -and the following year was moved to Mukojima, Tokyo. The firm makes -tar-acid resins, and a full line of products covered by the patents of -the American concern. Included are laminated sheets, molding compounds, -molded articles, surface coating resins, laminated resin gears and -spindles for rayon mills. An interesting development is the adaption of -tar-acid resin lacquers to the production of Japanese lacquer ware such -as bowls, vases, etc. - -Since the establishment of the Japan Bakelite Co., several other firms -have started the production of synthetic resins. The Tokyo Electric Co., -an affiliate of the General Electric Co., makes tar-acid resins under -the trade name Tecolite. Products are used principally for insulation, -although molding compositions and molded articles such as are used by the -electrical trade are commercially produced. - -The Matsushita Electrical Works at Osaka are producers of tar-acid -resins and articles made therefrom. The output is used largely for -radio and electrical equipment. The Nissholite Manufacturing Co., Ltd., -with a factory at Yasui-cho, Uzumasa, Kyoto specializes in decorative -laminated material sold under the trade name Nissholite. The Japan -Nitrogenous Fertilizer Co. (Nippon Chisso Hirijo Kabushiki Kaisha) is an -important maker of tar-acid resins, marketing them under the trade names -Chissolite, Safeloid, and Minaloid. The Yokahama Resin Co., a relatively -small company, produces tar-acid resins and markets them in the form of -molding powders. The firms listed account for practically all of the -Japanese production of synthetic resins and for about 50 percent of the -molded articles made from them. The remaining 50 percent of the output of -molded articles is made by a large number of small firms, the majority -being household industries. It is reported that there are about 2,000 of -these so-called plants already engaged in this relatively new industry. - - -Production. - -The Japanese production of manufactures of tar-acid resin reported by -the Department of Commerce and Industry is shown in table 30. These data -include the output of plants employing more than five operators and -apparently account for only half of the total. - -TABLE 30.—_Manufactures of tar-acid resins: Production in Japan, 1929-35_ - - ------------+-----------+---------------------------------------- - | | Value - | +-------------+---------------+---------- - Year | Quantity | | | - | | Of quantity | Additional[1] | Total - | | reported | | - ------------+-----------+-------------+---------------+---------- - | _Pounds_ | | | - 1929 | 28,681 | $46,594 | $125,404 | $171,998 - 1930 | 607,800 | 52,409 | 442,583 | 494,992 - 1931 | 744,119 | 99,907 | 268,594 | 368,501 - 1932 | 286,422 | 36,584 | 367,220 | 403,804 - 1933 | 229,854 | 26,747 | 516,903 | 543,650 - 1934 | 1,435,977 | 193,857 | 926,951 | 1,120,808 - 1935 | 3,176,441 | 477,526 | 923,546 | 1,401,072 - ------------+-----------+-------------+---------------+---------- - - [1] Quantity not reported. - - Source: Factory statistics of Department of Commerce and - Industry, Japan. - -Estimates from other sources of Japanese productions of tar-acid resins -indicate an output of 2,600,000 pounds of resin and 3,600,000 pounds -of molded resin articles in 1933, and of 4,900,000 pounds of resin and -7,500,000 pounds of resin articles in 1935. - -It was recently announced that the Gosei Chemical Co. will manufacture -vinyl resins in Japan. This firm’s principal interest is in acetate fiber -and rayon manufacture. Later in 1936 the Showa Fertilizer Co. announced -the successful development of a process for making urea. Urea resins -are in commercial production by the Toyo Gosei Kagaku Kogyo K.K., an -affiliate of Chugoku Toyo K.K. - -The resin industry in Japan is expected to undergo considerable -development in the near future. Raw materials are available in sufficient -quantities and the art of molding is fairly well developed. - - -CANADA - -The producers of synthetic resins in Canada are: - - Bakelite Corporation of Canada, Ltd. Toronto. - Shawinigan Chemicals, Ltd. Shawinigan Falls. - Canadian General Electric Co. Toronto. - Canadian Industries, Ltd. Toronto. - -The Bakelite Corporation of Canada, Ltd., an affiliate of the firm of -the same name in the United States, was formed in 1925. This plant -makes molding materials, laminating materials, and an extensive line of -technical varnishes. Molded parts were made at this factory until 1932. - -Shawinigan Chemicals, Ltd. is the pioneer organic chemical maker in -Canada. A modern plant at Shawinigan Falls, Quebec, produces synthetic -acetic acid, acetaldehyde, vinyl acetate, vinyl resins, and other -chemicals. The vinyl resins manufactured by this firm have already been -described (see p. 44). Appreciable quantities of these resins have been -exported to the United States in the past but the construction of a -factory (jointly owned by Shawinigan Chemicals, Ltd., and the Fiberloid -Corporation) at Indian Orchard, Mass., for the manufacture of vinyl -resins will probably result in a decrease of exports from Canada to the -United States. - -The Canadian General Electric Co. makes alkyd resins for use in surface -coatings. Phthalic anhydride and other raw materials are imported from -the United States. Canadian Industries, Ltd., produces alkyd resins at a -plant in Toronto, Ontario. - -There are about 14 molders of synthetic resins in Canada, of which all -but 3 are in Ontario. These firms make a general line of molded articles -including electrical articles, closures, costume jewelry, and smokers’ -accessories. Appreciable quantities of molded articles are imported from -the United States and smaller quantities from Germany. - - -UNION OF SOVIET SOCIALIST REPUBLICS - -The synthetic resin industry in the Union of Soviet Socialist -Republics is concentrated in two public departments, known as Public -Commissariates: (a) Public Department for Heavy Industry and (b) Public -Department for Light Industry. - -The Department for Heavy Industry, known as Soyuzchemplastmass, controls -the following plants: - -1. Karbolit-pawod in Ljubatschani, producing tar-acid resin laminated -fabric known as Textolite. - -2. Karbolit-stroj in Ljubatschani, making cast phenolic resins. - -3. Karbolitni-pawer in Dubrowka, making tar-acid resin molding compounds. -This plant has at least 350 molding presses producing electrical parts -and automotive parts. The number of presses was to have been increased to -1,000 in 1937. - -4. Komsomolskaja prawda in Leningrad manufactures articles, including -phone sets, from cast phenolic resins. - -5. Ochtenski Chimkombinat in Ochta. This plant makes nitrocellulose -plastics. No information could be obtained by our Chargé d’Affaires at -Moscow concerning its production of synthetic resins, although it is -believed to be considerable. - -The Department for Light Industry has a resin section known as -Mosplastmass producing casein plastics only. - - -THE NETHERLANDS - -There has been no production of synthetic resins in the Netherlands; -but a plant is under construction (October 1937) at Groningen for the -manufacture of alkyd resins. The manufacture of surface coating and -electrical parts from imported resins is carried on, chiefly by N. V. -Philips’ Gloeilampenfabrieken, Afdeeling Inkoop, Eindhaven, manufacturers -of radios, filament lamps, and electrical appliances. Efforts are being -made to employ resins for other purposes, such as the bonding of plywood -and the manufacture of closures and novelties, but little has been -accomplished thus far. The relatively high cost of the resins is the -principal difficulty. Molding compounds and laminated sheets, rods, and -tubes are imported from Germany, Great Britain, Austria, and the United -States. - -The paint, varnish, and lacquer industry in the Netherlands has been -experimenting with synthetic resins for several years. Alkyd resins -of the glycerol phthalate type are being used by Dutch paint makers, -imported principally from Germany and Austria. In spite of high cost, -they have been found to have many advantages, especially better and more -uniform quality. The prices of gums and resins in the Netherlands during -the latter part of 1936 are shown in table 31. - -TABLE 31.—_Prices of gums and resins in the Netherlands, 1936_ - - --------------------------------------+------------ - |Florins per - Type | 100 kilos - --------------------------------------+------------ - Damar |37. - Congo copal (various qualities) |12 to 45. - Indian copal (various qualities) |20 to 35. - Kauri (various qualities) |25 to 200. - Shellac (various qualities) |37 to 52. - Pine resin (rosin) (various qualities)|13 to 14. - Synthetic resins |80 to 120. - --------------------------------------+------------ - -The Dutch aviation industry is using tar-acid resins to bond plywood for -wing surfacing on Fokker-type wooden planes. The advantages obtained -are excellent adhesiveness and resistance to moisture and temperature -changes. In this application they have replaced casein. - -Germany supplies more than 85 percent of the Netherland imports of -synthetic resins, as shown in table 32. - -TABLE 32.—_Synthetic resins: Netherland imports by countries, 1931 and -1933-37_ - - [Pounds] - ---------------+---------+---------+--------- - Source | 1931 | 1933 | 1934 - ---------------+---------+---------+--------- - Germany |1,203,393|1,257,568|1,207,857 - United Kingdom | 8,520| 47,843| 64,458 - Austria | 63,758| 7,297| 30,886 - UNITED STATES | 3,168| 24,193| 27,434 - Belgium | 2,640| 3,923| - France | | 3,120| 4,129 - Czechoslovakia | 3,326| 4,948| - Switzerland | 1,789| 4,193| - Other countries| 1,450| 1,027| 2,629 - +---------+---------+--------- - Total |1,288,044|1,354,112|1,337,393 - ---------------+---------+---------+--------- - - [Pounds] - ---------------+---------+---------+--------- - Source | 1935 | 1936 | 1937[1] - ---------------+---------+---------+--------- - Germany |1,351,581|1,490,310|2,449,311 - United Kingdom | 94,565| 335,099|1,223,553 - Austria | 63,642| ([2]) | 132,276 - UNITED STATES | 50,888| ([2]) | ([2]) - Belgium | 1,514| ([2]) | ([2]) - France | 616| ([2]) | ([2]) - Czechoslovakia | | ([2]) | ([2]) - Switzerland | | ([2]) | ([2]) - Other countries| 1,573| 216,051| 207,232 - +---------+---------+--------- - Total |1,564,379|2,041,460|4,012,372 - ---------------+---------+---------+--------- - - [1] Preliminary. - - [2] Not separately reported. - - Source: Consular reports. - - -DENMARK - -The annual output of synthetic resins in Denmark is about 500,000 pounds, -almost entirely of the tar-acid type. - -Bakelite is produced by the Nordiske Kabel and Traadfabrikker A. S. -Fabrikvej at Copenhagen. Other brands made in Denmark are Nokait, -Helomit, and Etronit. There are 14 manufacturers of finished products, -making electrical equipment principally. - - -POLAND - -Production of synthetic resins in Poland in 1936 totaled 660,000 pounds, -entirely of the tar-acid type. - - - - -16. RAW MATERIALS FOR ALKYD RESINS - - -The alkyd resins are made chiefly from phthalic anhydride and glycerin. -Phthalic anhydride in turn is made from naphthalene. Polybasic acids -such as maleic, succinic, etc., may also be used with glycerin to form -alkyd resins. Naphthalene, phthalic anhydride, maleic and other polybasic -acids, and glycerin are discussed in the order named. - - -NAPHTHALENE - -The discovery of naphthalene in coal tar was made simultaneously by -Garden and Brande in 1819, and its composition was determined by Faraday -in 1826 and later by Laurent in 1832. Naphthalene is almost invariably -a constituent of the products obtained when organic matter is heated -to comparatively high temperatures. For example, it is formed in small -quantities when acetylene, alcohol, acetic acid, benzene, or toluene are -heated to high temperatures. Together with certain aromatic hydrocarbons -it is formed in the cracking of petroleum and in the hydrogenation of -petroleum fractions. Naphthalene is a constituent of the principal -varieties of tar produced from coal in the manufacture of gas and coke -under ordinary conditions, but not of low-temperature tar. It is present -in coal gas although its presence must be kept as low as possible to -avoid blocking service pipes in cold weather. The proportion in gas -tar varies with the kinds of coal used and is greater the higher the -temperature used during carbonization; it usually amounts to 4 to 6 -percent but is sometimes as much as 10 percent. In tars obtained from -byproduct coke ovens the proportion of naphthalene and other aromatic -hydrocarbons depends on the type of oven used. Byproduct coke-oven tar -averages 10 to 11 percent naphthalene; blast-furnace tar contains only -very small amounts. - -Processes to synthesize naphthalene were described as early as 1873 by -Aronheim, in 1876 by Wroden and Znatowicz, and in 1884 by Baeyer and -Perkin. English Patent No. 26,061 of 1898 claims that it may be obtained -by heating barium carbide with barium hydroxide to a high temperature. -None of these processes has become of commercial importance. - - -Recovery of naphthalene. - -Naphthalene is recovered in the distillation of coal tar, in the fraction -boiling at 180° to 250° C., in the creosote oil fraction boiling at 240° -to 270° C. and most abundantly in the carbolate or middle oil fraction -boiling at 200° to 250° C. When these fractions are allowed to cool most -of the naphthalene crystallizes out and is separated by draining and -hot-pressing. This crude material is partially purified by washing with -hot caustic soda solution to remove tar acids and then with mineral acid -to remove basic substances. Refined naphthalene is obtained by subliming, -or preferably by distilling the crude product. - - -Description and uses. - -The Tariff Act of 1930 defines crude naphthalene as naphthalene -solidifying under 79° C. after the removal of all water present; and -refined naphthalene as that having a solidifying point at or above 79° C. -after the removal of all water present. - -Crude grades, melting between 70° and 78.5° C., are found in commerce as -yellow, red, or brown crystalline solids. These grades are used in the -manufacture of phthalic anhydride and other coal-tar intermediates; in -the manufacture of lampblack; to enrich illuminating gas and sometimes -motor fuel; in synthetic tanning materials; and in certain insecticides. -Probably its most important outlets are as a raw material for phthalic -anhydride (see p. 98) and refined naphthalene. - -Refined grades, melting above 79° C., are marketed as white, crystalline -lumps or flakes. Their principal uses are in the manufacture of -intermediates, dyes, medicinals, solvents, and textile assistants; as -moth repellants; as a lubricant when mixed with rapeseed oil; to remove -the “bloom” from lubricating oils; as a preservative for rubber goods -and animal skins; and in explosives (trinitro naphthalene). In 1936 more -than 75 coal-tar intermediates made from naphthalene were commercially -produced in the United States. Of the 75 million pounds of these -intermediates produced in that year, 31 million pounds were phthalic -anhydride, an important component of synthetic resins of the alkyd type. - - -United States production. - -Crude naphthalene is produced in the United States by byproduct coke-oven -operators, gas works that produce their own coal tar, and also by firms -that purchase coal tar and distill it. Statistics of production by groups -are shown in table 33. - -TABLE 33.—_Crude naphthalene: United States production, 1918-37_ - - ----+-----------------------------+------------------------------ - | By producers of tar | By purchasers of tar - ----+----------+---------+--------+----------+----------+-------- - | Quantity | | Unit | Quantity | | Unit - | | Value | value | | Value | value - ----+----------+---------+--------+----------+----------+-------- - | _1,000 | | _Per | _1,000 | | _Per - | pounds_ | | pound_ | pounds_ | | pound_ - 1918| | | | 40,138|$1,281,440| $0.032 - 1919| | | | 12,612| 327,201| .030 - 1923| 11,872| $201,824| $0,017| 41,453| 652,148| .016 - 1925| 9,239| 92,389| .010| 34,135| 519,773| .015 - 1926| 7,747| 100,709| .013| 45,166| 494,986| .011 - 1927| 8,303| 91,331| .011| 45,298| 470,806| .010 - 1928| [1]12,182| 146,186| .012| 35,180| 395,059| .011 - 1929| [1]19,761| 316,182| .016| 19,502| 366,491| .020 - 1930| [1]12,640| 151,681| .012| 18,617| 304,574| .020 - 1931| [1]7,623| 76,229| .010| 13,311| 199,665| .015 - 1932| [1]4,632| 41,690| .09| 8,961| 125,453| .014 - 1933| [1]6,618| 66,181| .010| 24,003| 360,040| .015 - 1934| [1]10,743| 139,665| .013| 27,179| 489,222| .018 - 1935| [1]12,937| 168,185| .013| 34,716| 624,890| .018 - 1936| [1]37,552| 600,836| .016| 51,984| 1,195,632| .023 - 1937| [1]60,797|1,215,942| .020| 55,182| 1,545,100| .028 - ----+----------+---------+--------+----------+----------+-------- - - ----+------------------------------ - | Total production - ----+----------+----------+-------- - | Quantity | | Unit - | | Value | value - ----+----------+----------+-------- - | _1,000 | | _Per - | pounds_ | | pound_ - 1918| 40,138|$1,281,440|$0.032 - 1919| 12,612| 327,201| .026 - 1923| 53,325| 853,972| .016 - 1925| 43,374| 612,162| .014 - 1926| 52,913| 595,695| .011 - 1927| 53,601| 562,137| .010 - 1928| 47,362| 541,245| .011 - 1929| 39,263| 682,673| .017 - 1930| 31,257| 456,255| .015 - 1931| 20,934| 275,894| .013 - 1932| 13,593| 167,143| .012 - 1933| 30,621| 426,221| .014 - 1934| 37,922| 628,887| .016 - 1935| 47,653| 793,075| .017 - 1936| 89,536| 1,796,468| .020 - 1937| 115,979| 2,667,522| .023 - ----+----------+----------+-------- - - [1] Crude and refined. Refined naphthalene included here is - probably small so that the figures here and those for total - production are substantially accurate. - - Source: Bureau of Mines and U.S. Tariff Commission. - -Refined naphthalene is obtained from domestic crude, imported crude, -and recently from petroleum cracking and hydrogenation. Table 34 shows -the annual production and sales of refined naphthalene since 1916. The -difference between the figures for the quantity produced and that sold -represents the amount used by refiners in the manufacture of other -products. - -TABLE 34.—_Refined naphthalene: United States production and sales, -1917-37_ - - ------+-------------------------------+-------------------------------- - | Production | Sales - Year +----------+-----------+--------+----------+-----------+--------- - | Quantity | Value | Value | Quantity | Value | Value - ------+----------+-----------+--------+----------+-----------+--------- - | _1,000 | _1,000 | _Per | _1,000 | _1,000 | _Per - | pounds_ | dollars_ | pound_ | pounds_ | dollars_ | pound_ - 1917 | 35,343 | 2,334 | $0.07 | | | - 1918 | 28,112 | 2,163 | .08 | | | - 1919 | 17,625 | 1,161 | .07 | | | - 1920 | 30,231 | 2,309 | .08 | | | - 1921 | 13,554 | | | 13,183 | 741 | $0.056 - 1922 | 17,420 | | | 14,060 | 794 | .057 - 1923 | 28,184 | | | 21,871 | 1,271 | .058 - 1924 | 15,324 | | | 11,961 | 603 | .050 - 1925 | 17,581 | | | 12,508 | 610 | .049 - 1926 | 18,072 | | | 12,456 | 576 | .046 - 1927 | 21,233 | | | ([1]) | | - 1928 | 24,992 | | | ([1]) | | - 1929 | 31,144 | | | 21,120 | 1,027 | .049 - 1930 | 31,956 | | | 20,171 | 949 | .047 - 1931 | 34,959 | | | 21,260 | 829 | .039 - 1932 | 25,825 | | | 18,877 | 783 | .041 - 1933 | 42,708 | | | 28,658 | 1,065 | .037 - 1934 | 38,730 | | | 21,257 | 1,100 | .052 - 1935 | 46,564 | | | 28,761 | 1,212 | .042 - 1936 | 52,694 | | | 30,499 | 1,841 | .060 - 1937 | 52,194 | | | 29,657 | 1,893 | .060 - ------+----------+-----------+--------+----------+-----------+--------- - - [1] Not publishable. - - Source: Compiled from annual reports of the Tariff Commission on - dyes and other synthetic organic chemicals in the United States. - -_Organization of the industry._—There are 10 domestic producers of crude -naphthalene, operating 52 tar-distilling plants in the following States: -Ohio (7), Pennsylvania (6), Illinois and New York (5 each), Alabama, -Minnesota, and New Jersey (3 each), Missouri, Rhode Island, Wisconsin, -Utah, West Virginia (2 each), and Michigan, Massachusetts, Maryland, -Kentucky, Oregon, Connecticut, Tennessee, Indiana, Virginia, and -Washington (1 each). Although these plants do not all recover naphthalene -as such, they are equipped to recover a crude mixture of naphthalene and -tar acids for shipment to a central extracting and refining plant. The -principal producing plants are located in Pennsylvania (2), New Jersey -(2), Illinois (1), Indiana (1), and West Virginia (1). - -The purchasers of tar produced 77 percent of the total output of crude -naphthalene in 1935 and 58 percent in 1936. - -There are 8 producers of refined naphthalene located in the following -States: New Jersey (3), Pennsylvania (2), California, Indiana, and Ohio -(1 each). - -_Trend of production._—Although the United States is the largest producer -of coal tar, the limited demand for the main products of tar distillation -(creosote oil and pitch) has tended to restrict the amount distilled, -thereby reducing the output of naphthalene and the tar acids to a point -where the domestic output was not sufficient to meet our requirements. As -a result, large quantities of these products have been imported. In 1936 -we produced 560 million gallons of coal tar, containing from 400 million -to 500 million pounds of naphthalene.[17] In the same year we distilled -about 300 million gallons of tar, containing 230 million to 270 million -pounds of naphthalene,[17] and our actual recovery of crude naphthalene -was 89,536,000 pounds. - -Early in 1935 the price of crude naphthalene was about 1.5 cents per -pound or 15 cents per gallon, at which level there was little incentive -to isolate it from the various fractions of tar distillation. Late in -1935 and in 1936 a serious shortage in naphthalene prevailed, largely -because of increased demand by synthetic resin makers but also because -of restrictions on exports from certain European countries. The price -of the crude then advanced in domestic markets to from 2.5 to 3 cents -per pound, with the demand greatly exceeding the supply. Between 1930 -and 1936 the apparent consumption of crude naphthalene (production plus -imports) increased from 59 million to 129 million pounds, or more than -100 percent. During the same period production increased from 31 million -to 89 million pounds; and imports increased from 27 million pounds in -1930 to 48 million pounds in 1935 but declined to 40 million pounds in -1936. - -Domestic producers of naphthalene are increasing their output, and they -state that continued prices of 2.5 to 3 cents per pound for naphthalene -solidifying at about 75° C. or slightly higher will stimulate production -sufficiently to meet all present and near-future requirements. Estimates -obtained in the summer of 1936 from the large tar distillers and a -petroleum refiner indicate that production was appreciably greater in -1937 than in 1935. These estimates included the potential output of two -new tar distillation plants under construction, the topping of large -quantities of tar (hitherto used as fuel without removing any of the -products), the recovery of appreciable quantities of naphthalene by -several petroleum refiners, and increased output by other producers. - -Imports of crude naphthalene in 1937 amounted to 52,664,277 pounds valued -at $1,133,157, or 2.2 cents per pound. - - -World production. - -The output of naphthalene in the principal producing countries, in 1933 -and 1935, is shown in table 35. Most of these statistics were estimated -from the output of tar or of other distillation products given in -official reports of the countries or in consular reports. - -The figures in table 35 indicate that the output in 1935 was an increase -of about 100 million pounds over 1933 or 41 percent. Notwithstanding -this sharp increase in world production, consumers had difficulty in -obtaining their requirements. It is believed that the world output in -1937 substantially exceeded that in 1935. - -TABLE 35.—_Naphthalene (all grades): World production, by countries, 1933 -and 1935_ - - [In thousands of pounds] - --------------+---------+--------- - Country | 1933 | 1935 - --------------+---------+--------- - Germany | 109,148| 145,530 - Great Britain | 45,750|[1]55,000 - UNITED STATES | 30,620| 47,653 - France | 30,000|[1]33,000 - Netherlands |[1]15,000|[1]15,000 - Belgium | 11,025|[1]25,000 - Czechoslovakia| 6,835| 10,805 - U. S. S. R. |[1]10,000|[1]15,000 - Poland | [1]5,000| [1]8,000 - Spain | [1]1,250| [1]2,000 - Italy | [1]2,500| [1]3,000 - Canada | [1]2,000| [1]3,000 - Total | 269,128| 362,988 - --------------+---------+--------- - - [1] Estimated. - - Source: Official statistics of the several countries and consular - reports. - -_Germany._—Germany is the largest producer of naphthalene and the third -largest producer of coal tar. With increased production of coal tar and -intensive efforts to recover the maximum of naphthalene there has been a -larger output of naphthalene in recent years, but increased consumption -has created a scarcity in Germany as in all other important producing -countries. As a result, greatly reduced quantities are available for -export, a situation that is in marked contrast to earlier periods when -superabundant production created a marketing problem. The manufacture of -phthalic anhydride for alkyd resins is requiring increased quantities of -naphthalene. - -The demand for alkyd resins has been given a marked impetus by the -development of a new standardized linseed oil varnish substitute known -as El Varnish, the use of which is required by the Control Board for -Industrial Fats in Germany for certain interior and exterior painting -(see p. 77). Increased requirements for other important purposes such as -intermediates, dyes, black pigments, and explosives have also contributed -to the scarcity of naphthalene. In order to conserve domestic supplies, -the Reich Government, from December 1935 until late in 1937 prohibited -its export without special permit. The prospect of continued strong -domestic demand apparently will curtail for an indefinite period the -quantities available for export. - -The international scarcity of naphthalene resulted in a sharp increase -in its price in Germany as elsewhere. The export embargo augmented the -domestic German supply, although a shortage still existed and large -consumers found it difficult to secure adequate amounts. The shortage of -foreign exchange greatly curtailed imports of naphthalene from nearby -countries. - -The German Government issued a decree requiring that beginning July 1, -1936, the entire national output of coal tar should be delivered to -plants equipped for the recovery of tar products distilling up to 240° C. -(naphthalene boils at 218° C.). This measure assured maximum recovery of -benzol, toluol, xylol, solvent naphtha, phenol, cresol, xylenol, other -tar acids, and naphthalene. The decree contemplated an official list of -distillation units, and all tar producers were required to report to -the official trade control board for mineral oil their monthly output, -quantities distilled, and quantities delivered to other distillation -plants. - -German production, imports, exports, and apparent consumption of -naphthalene are shown in table 36. Production increased from 108 million -pounds in 1928 to 146 million pounds in 1935; imports decreased from 9 -to 4 million pounds; exports decreased from 48 to 22 million pounds; and -apparent consumption increased from 69 to 128 million pounds in the same -years. - -TABLE 36.—_Naphthalene: German production, imports, exports, and apparent -consumption, 1928-37_ - - [In thousands of pounds] - ----+----------+-------+-------+--------------- - Year|Production|Imports|Exports| Apparent - | | | | consumption[1] - ----+----------+-------+-------+--------------- - 1928| 108,173| 9,471| 48,332| 69,312 - 1929| 124,362| 8,032| 39,739| 92,655 - 1930| 103,194| 3,892| 34,614| 72,472 - 1931| 92,169| 2,403| 39,077| 55,495 - 1932| 90,626| 952| 29,720| 61,852 - 1933| 109,148| 7,483| 31,842| 84,783 - 1934| 132,300| 8,641| 35,044| 105,891 - 1935| 145,530| 4,246| 22,169| 127,603 - 1936| ([2]) | 493| 8,153| ([2]) - 1937| ([2]) | 33| 24,966| ([2]) - ----+----------+-------+-------+--------------- - - [1] Production plus imports, minus exports. - - [2] Not available. - - Sources: Consular reports (production); Der auswartige Handel - (imports and exports). - -Imports of naphthalene into Germany in past years have been supplied by -nearby countries, notably the Saar (which became an integral part of -Germany in February 1935), Belgium, Czechoslovakia, Poland, the Soviet -Union, and others. The United States has been the most important foreign -market for German naphthalene, taking from 50 to 75 percent of the total -quantity exported. Other important buyers were Belgium, Italy, Japan, and -France. Table 92 (see p. 144) shows the quantity and value of imports and -exports by countries in recent years. - -_Great Britain._—The recovery and distillation of coal tar in Great -Britain is highly developed. The annual output of tar, principally -gas-works tar, is somewhat smaller than in the United States, although -the quantities distilled for the recovery of separate components exceed -the quantities distilled in the United States. In 1935 the tar distilled -in England and Wales totaled 330 million gallons and in Scotland, 31 -million gallons, or a combined total of 361 million gallons as compared -with about 280 million distilled in this country. - -Production of naphthalene in Great Britain is shown in table 37. - -TABLE 37.—_Naphthalene: Production in Great Britain, in specified years_ - - -------+-------------- - Year | Production - -------+-------------- - |_1,000 pounds_ - 1924 | 13,730 - 1930 | 41,400 - 1933 | 45,750 - 1935[1]| 55,000 - 1936[1]| 70,000 - -------+------------ - - [1] Estimated. - - Source: Consular reports. - -Table 38 shows exports of naphthalene from Great Britain in recent years. -The United States has been the best customer, in most recent years taking -50 percent or more of the total exported. Our imports from Great Britain -have been entirely crude naphthalene, duty-free. - -Imports of naphthalene into Great Britain are not shown separately in -official statistics. It is known that the Netherlands exported small -quantities to Great Britain in 1929 and 1933. - -TABLE 38.—_Naphthalene: Exports from the United Kingdom_ - - ----+-------------------+--------------------------------------- - | Quantity | Value - +---------+---------+-------------------+------------------- - Year| | | To all countries | To United States - | To all |To United+--------+----------+--------+---------- - |countries| States | Pounds |Dollars[1]| Pounds |Dollars[1] - | | |sterling| |sterling| - ----+---------+---------+--------+----------+--------+---------- - | _1,000 | _1,000 | | | | - | pounds_| pounds_| | | | - 1928| 5,132| ([2]) | 20,607| 100,278| ([2]) | ([2]) - 1929| 9,185| 4,312| 32,348| 157,110| 12,558| 60,993 - 1932| 11,132| 7,514| 26,869| 94,205| 14,274| 50,046 - 1933| 14,718| 10,480| 38,172| 161,728| 19,604| 83,059 - 1934| 11,955| 6,492| 35,226| 177,514| 13,025| 65,637 - 1935| 14,490| 7,999| 49,939| 244,789| 18,413| 90,256 - 1936| 26,332| 13,412| 120,372| 598,357| 46,158| 229,447 - ----+---------+---------+--------+----------+--------+---------- - - [1] Conversion to dollars at annual average quotations of the - Federal Reserve Board. - - [2] Not available. - - Source: The Trade of the United Kingdom, 1929 and 1936. - -_Belgium._—The distillation of coal tar is one of the oldest and most -important branches of the Belgian chemical industry. Approximately 90 -batteries of byproduct-coke ovens, with a total of 3,000 ovens are in -operation. Practically all of the coal tar produced in these operations -is distilled for the recovery of the several products. The output of -naphthalene is shown in table 39. - -TABLE 39.—_Naphthalene: Belgian production, 1928-35_ - - -------+-------------- - Year | Quantity - -------+-------------- - |_1,000 pounds_ - 1928 | 26,000 - 1929 | 26,500 - 1930 | 24,200 - 1931 | 22,000 - 1933 | 12,000 - 1935[1]| 25,000 - -------+------------ - - [1] Estimated. - - Source: Consular reports. - -Belgian imports and exports of naphthalene, by countries, are shown in -tables 93 and 94 (see pp. 146, 147). Belgium is a net importer of crude -naphthalene and a net exporter of refined naphthalene. In 1937, it -imported 9 million pounds and exported 6.7 million of crude; it imported -only 19 thousand pounds and exported 14 million pounds of refined. - -_Czechoslovakia._—The annual output of naphthalene in Czechoslovakia is -shown in table 40. - -TABLE 40.—_Naphthalene: Czechoslovak production, in specified years, -1928-35_ - - ----+-------------- - Year| Quantity - ----+-------------- - |_1,000 pounds_ - 1928| 5,733 - 1930| 6,174 - 1931| 2,205 - 1932| 1,543 - 1933| 6,835 - 1934| 9,040 - 1935| 10,805 - ----+------------- - - Source: Consular reports. - -_France._—Naphthalene is produced in France by a number of manufacturers, -most of whom consume their production in their own factories. The -French output is said to be insufficient to meet domestic requirements. -Estimated production is given as approximately 30 million pounds -annually. Appreciable quantities are imported from nearby countries. -Imports from Belgium in recent years average between 1 million and 3 -million pounds. - -_Poland._—Production of crude naphthalene in Poland is shown in table 41. - -TABLE 41.—_Crude naphthalene: Polish production, 1928-36_ - - ----+-------------- - Year| Quantity - ----+-------------- - |_1,000 pounds_ - 1928| 4,708 - 1929| 5,257 - 1930| 3,925 - 1931| 3,486 - 1932| 3,704 - 1933| 4,795 - 1934| 7,705 - 1935| 5,021 - 1936| 2,836 - ----+-------------- - - Source: Consular reports. - -_The Netherlands._—Statistics of production are not available. Exports in -recent years, however, have averaged about 10 million pounds annually. It -is believed that the production of crude naphthalene exceeds 15 million -pounds a year. - -Table 95 (see p. 148) shows Netherland imports and exports of naphthalene -by countries in recent years. Imports in 1937 amounted to 2 million -pounds and exports to 15 million pounds. - -_Canada._—Statistics of production are not available. The annual output -of crude naphthalene is estimated at 2 to 3 million pounds. - -Imports of refined naphthalene are usually about 1 million pounds (see -table 96, p. 150). Exports are probably small, although in 1929 and 1934 -those to the United States alone were over 1 million pounds. - -_The Soviet Union._—Statistics of production of naphthalene in the -Soviet Union are not available. The annual output has been estimated at -10 million pounds in 1933 and 15 million pounds in 1935. Exports have -increased substantially in recent years, those to the United States from -1 million pounds in 1934 to 6 million pounds in 1935. Exports to Germany -were 361 thousand pounds in 1933; 1 million pounds in 1934; and 531 -thousand pounds in 1935. - -_Japan._—Japanese production of naphthalene has been small compared with -the output of other tar products. The output of crude naphthalene in 1934 -was reported to have been 381 thousand pounds. Expansion of the byproduct -coking industry in Japan and Manchuria has increased the production -of coal tar, byproduct ammonia, and benzol. Japan has imported large -quantities of naphthalene in recent years, principally from Germany and -Belgium. The increased consumption in Europe may so reduce supplies from -these sources as to cause Japan to increase the recovery at home. - -Japanese imports of naphthalene from principal sources, are shown in -table 97 (see p. 150). In 1936, 12.6 million pounds were imported. - - -United States imports. - -_Rates of duty._—Prior to September 8, 1916, all grades of naphthalene -were imported free of duty. Since that time crude naphthalene has -remained free but refined naphthalene has been subject to the tariff -treatment shown in table 42. - -TABLE 42.—_Naphthalene: Rates of duty upon imports into the United -States, 1916-38_ - - -------------------+------------------------+---------------------------- - | Rate of duty | - +------+-----------------+ - Period | | | Authority - |Crude | Refined | - -------------------+------+-----------------+---------------------------- - To Sept. 8, 1916 | Free | Free | Free under par. 452 of the - | | | act of 1913 and - | | | under previous acts. - | | | - Sept. 9, 1916, to | do. | 15 percent ad | Revenue Act of 1916. - Sept. 8, 1921. | | valorem and | - | | 2½ cents | - | | per pound. | - | | | - Sept. 9, 1921, to | do. | 15 percent ad | Emergency Tariff Act of - Sept. 21, 1922. | | valorem and | 1921. (Title V, - | | 2 cents | prohibited imports for - | | per pound. | 3 months except when - | | | not obtainable in - | | | sufficient quantities - | | | or on reasonable terms - | | | as to quality, price, - | | | and terms of delivery). - | | | - Sept. 22, 1922, to | do. | 55 percent ad | Crude, free under par. 1549 - Sept. 21, 1924. | | valorem and | and refined dutiable - | | 7 cents | under par. 27 of the - | | per pound.[1] | Tariff Act of 1922. - | | | - | | | - Sept. 22, 1924, to | do. | 40 percent ad | Ad valorem rate on refined - June 17, 1930. | | valorem and | reduced as provided for - | | 7 cents | in Tariff Act of 1922. - | | per pound.[1] | - | | | - June 18, 1930, to | do. | do. | Crude, free under par. 1651 - Apr. 30, 1935. | | | and refined dutiable - | | | under par. 27 Tariff Act - | | | of 1930. - | | | - May 1, 1935, to— | do. | 20 percent ad | Refined reduced under - | | valorem and | trade agreement - | | 3½ cents | with Belgium.[2] - | | per pound.[1] | - -------------------+------+-----------------+---------------------------- - - [1] Ad valorem based on American selling price or United States - value. - - [2] Generalized to all countries which do not discriminate - against United States products. - -Under the Tariff Act of 1930, crude naphthalene is on the free list[18] -and refined naphthalene is dutiable at 7 cents per pound and 40 -percent ad valorem on the basis of American selling price, since it is -competitive with refined naphthalene produced in this country.[19] Under -the trade agreement with Belgium, effective May 1, 1935, the duty on -refined naphthalene was reduced to 20 percent[20] ad valorem and 3½ cents -per pound on imports from that country. Under the Trade Agreements Act -this reduction applies also to imports from all other countries which -do not discriminate against commerce of the United States. In July 1938 -Germany was the only one not receiving the reduced rate, exports from -that country being subject to the rates specified under the Tariff Act of -1930. - -_Import statistics._—Table 43 shows imports of crude naphthalene -(solidifying at less than 79° C.) and table 44 of refined naphthalene -(solidifying at or above 79° C.) The unit invoice values of imports of -refined naphthalene in 1924, 1926, 1927, 1928, and 1935 indicate that the -imported product was probably not naphthalene as recorded but one of its -derivatives provided for elsewhere in paragraph 27. - -TABLE 43.—_Crude naphthalene (solidifying at less than 79° C.): United -States imports for consumption, in specified years, 1919-37_ - - --------------+--------------+--------------+----------+----------- - Calendar year | Rate of duty | Quantity | Value | Value per - | | | | pound - --------------+--------------+--------------+----------+----------- - | |_1,000 pounds_| | - 1919 | Free | 3,239 | $92,265 | $0.028 - 1920 | do. | 15,012 | 530,219 | .035 - 1923 | do. | 20,992 | 575,702 | .027 - 1924 | do. | 5,267 | 96,491 | .018 - 1925 | do. | 1,980 | 26,593 | .013 - 1926 | do. | 6,963 | 126,088 | .018 - 1927 | do. | 6,576 | 131,436 | .020 - 1928 | do. | 19,926 | 357,679 | .018 - 1929 | do. | 35,007 | 598,718 | .017 - 1930 | do. | 27,667 | 397,292 | .014 - 1931 | do. | 30,971 | 318,578 | .013 - 1932 | do. | 27,002 | 234,557 | .009 - 1933 | do. | 42,786 | 451,019 | .010 - 1934 | do. | 47,995 | 669,383 | .014 - 1935 | do. | 48,455 | 643,249 | .013 - 1936 | do. | 39,806 | 785,396 | .020 - 1937[1] | do. | 52,664 |1,133,157 | .022 - --------------+--------------+--------------+----------+----------- - - [1] Preliminary. - - Source: Foreign Commerce and Navigation of the United States. - -TABLE 44.—_Refined naphthalene (solidifying at or above 79° C): United -States imports for consumption, in specified years, 1919-37_ - - ---------------+---------------------+---------+-------+------+--------- - | | | | |Computed - Calendar year | Rate of duty |Quantity | Value |Unit | ad - | | | |value |valorem - | | | | | rate - ---------------+---------------------+---------+-------+------+--------- - | | _Pounds_| | |_Percent_ - 1919 |15 percent + 2½ cents| 7,650| $384|$0.050| 64.8 - | per pound | | | | - 1920 | do. |3,697,562|416,172| .112| 37.2 - 1923 |55 percent + 7 cents | 9,605| 194| .020| 401.6 - | per pound | | | | - 1924 | do. | 4,549| 1,147| .252| 82.8 - 1925 | do. | | | | - 1926 |40 percent + 7 cents | 424| 125| .295| 63.7 - | per pound | | | | - 1927 | do. | 18,668| 3,077| .165| 82.5 - 1928 | do. | 27| 6| .222| 71.5 - 1929 | do. | ⎫ | | | - 1930 | do. | ⎪ | | | - Jan. 1-June 17 | do. | ⎪ | | | - June 18-Dec. 31| | ⎬ None | | | - 1931 | do. | ⎪ | | | - 1932 | do. | ⎪ | | | - 1933 | do. | ⎭ | | | - 1934 | do. | 66| 6| .091| 116.7 - 1935 | do.[1] | 99| 31| .313| 62.4 - 1936 |20 percent + 3½ cents| 30| 20| .667| 50.5 - | per pound[2] | | | | - 1937[3] | do.[2] | 5,055| 1,085| .215| 36.3 - ---------------+---------------------+---------+-------+------+--------- - - [1] From Germany. No imports under trade agreement rate. - - [2] Belgo-Luxemburg trade agreement rate. - - [3] Preliminary. - - Source: Foreign Commerce and Navigation of the United States. - -Table 45 shows the principal sources of our imports of crude naphthalene -in recent years. Germany was the principal source until 1936; the United -Kingdom, previously the next most important source, was first in 1936 and -1937. In the last three years appreciable quantities have been received -from Poland, Czechoslovakia, and the Soviet Union, hitherto unimportant -sources. - -TABLE 45.—_Crude naphthalene (solidifying under 79° C.): United States -imports for consumption from principal sources, in specified years_ - - -------------------+---------+---------+---------+--------- - Source | 1929 | 1931 | 1933 | 1934 - -------------------+---------+---------+---------+--------- - | Quantity in thousands of pounds - -------------------+---------+---------+---------+--------- - Germany | 21,931 | 17,444 | 20,797 | 22,219 - Belgium | 2,531 | 253 | 4,970 | 7,314 - United Kingdom | 8,096 | 11,339 | 15,704 | 6,968 - Poland and Danzig | | | | 5,766 - Canada | 1,488 | 331 | 223 | 1,073 - Netherlands | 44 | 937 | 1,092 | 621 - Czechoslovakia | | | | 2,984 - U. S. S. R. | | | | 1,050 - All other countries| 918 | 667 | | - +---------+---------+---------+--------- - Total | 35,007 | 30,971 | 42,786 | 47,995 - +---------+---------+---------+--------- - | Value - +---------+---------+---------+--------- - Germany |$382,078 |$170,463 |$242,501 |$326,607 - Belgium | 48,508 | 2,506 | 57,243 | 90,424 - United Kingdom | 124,427 | 123,890 | 135,853 | 78,968 - Poland and Danzig | | | | 89,002 - Canada | 23,344 | 3,808 | 2,729 | 18,703 - Netherlands | 614 | 11,837 | 12,693 | 8,739 - Czechoslovakia | | | | 44,371 - U. S. S. R. | | | | 12,569 - All other countries| 19,747 | 6,074 | | - +---------+---------+---------+--------- - Total | 598,718 | 318,578 | 451,019 | 669,383 - +---------+---------+---------+--------- - | Value per pound - +---------+---------+---------+--------- - Germany | $0.017 | $0.010 | $0.012 | $0.015 - Belgium | .019 | .010 | .012 | .012 - United Kingdom | .015 | .011 | .009 | .011 - Poland and Danzig | | | | .015 - Canada | .016 | .011 | .012 | .017 - Netherlands | .014 | .013 | .012 | .014 - Czechoslovakia | | | | .015 - U. S. S. R. | | | | .012 - All other countries| .022 | .009 | | - +---------+---------+---------+--------- - Average | .017 | .010 | .011 | .014 - +---------+---------+---------+--------- - | Percent of total quantity - +---------+---------+---------+--------- - Germany | 62.7 | 56.3 | 48.6 | 46.3 - Belgium | 7.2 | .8 | 11.6 | 15.3 - United Kingdom | 23.1 | 36.6 | 36.7 | 14.5 - Poland and Danzig | | | | 12.0 - Canada | 4.3 | 1.1 | .5 | 2.2 - Netherlands | .1 | 3.0 | 2.6 | 1.3 - Czechoslovakia | | | | 6.2 - U. S. S. R. | | | | 2.2 - All other countries| 2.6 | 2.2 | | - +---------+---------+---------+--------- - Total | 100.0 | 100.0 | 100.0 | 100.0 - -------------------+---------+---------+---------+--------- - - -------------------+---------+---------+---------- - Source | 1935 | 1936 | 1937[1] - -------------------+---------+---------+---------- - | Quantity in thousands of pounds - -------------------+---------+---------+---------- - Germany | 15,742 | 2,712 | 12,129 - Belgium | 2,388 | 2,025 | 1,995 - United Kingdom | 10,689 | 16,301 | 17,594 - Poland and Danzig | 5,075 | 1,969 | 2,312 - Canada | 76 | 255 | 734 - Netherlands | 1,344 | 3,794 | 3,359 - Czechoslovakia | 6,960 | 6,595 | 6,414 - U. S. S. R. | 6,158 | 5,145 | 7,091 - All other countries| 22 | 1,010 | 1,038 - +---------+---------+---------- - Total | 48,455 | 39,806 | 52,664 - +---------+---------+---------- - | Value - +---------+---------+---------- - Germany |$230,820 | $75,314 | $287,901 - Belgium | 31,375 | 55,503 | 51,227 - United Kingdom | 123,545 | 273,964 | 340,760 - Poland and Danzig | 63,992 | 35,439 | 55,184 - Canada | 1,169 | 4,093 | 7,941 - Netherlands | 19,724 | 105,404 | 93,045 - Czechoslovakia | 98,099 | 120,529 | 128,197 - U. S. S. R. | 74,354 | 97,815 | 146,331 - All other countries| 171 | 17,335 | 22,571 - +---------+---------+---------- - Total | 643,249 | 785,396 |1,133,157 - +---------+---------+---------- - | Value per pound - +---------+---------+---------- - Germany | $0.015 | $0.028 | $0.024 - Belgium | .013 | .027 | .026 - United Kingdom | .012 | .017 | .019 - Poland and Danzig | .013 | .018 | .024 - Canada | .015 | .016 | .011 - Netherlands | .015 | .028 | .028 - Czechoslovakia | .014 | .018 | .020 - U. S. S. R. | .012 | .019 | .021 - All other countries| .008 | .017 | .022 - +---------+---------+---------- - Average | .013 | .020 | .022 - +---------+---------+---------- - | Percent of total quantity - +---------+---------+---------- - Germany | 32.5 | 6.8 | 23.0 - Belgium | 14.9 | 5.1 | 3.8 - United Kingdom | 22.0 | 41.0 | 33.4 - Poland and Danzig | 10.5 | 5.0 | 4.4 - Canada | .2 | .6 | 1.4 - Netherlands | 2.8 | 9.5 | 6.4 - Czechoslovakia | 14.4 | 16.6 | 12.2 - U. S. S. R. | 12.7 | 12.9 | 13.4 - All other countries| | 2.5 | 2.0 - +---------+---------+---------- - Total | 100.0 | 100.0 | 100.0 - -------------------+---------+---------+---------- - - [1] Preliminary. - - Source: Compiled from official statistics of the United States - Department of Commerce. - - -United States exports. - -Exports are not shown separately; it is doubtful if any naphthalene is -exported. Demand in the United States has exceeded domestic production. - - -Competitive conditions. - -The commercial development and widespread application of surface coatings -and finishes made from alkyd resins, in which phthalic anhydride and -glycerin are the principal components, has resulted in a world-wide -shortage of naphthalene, which is a raw material used in making phthalic -anhydride. In recent years about one-half of domestic requirements -of crude naphthalene have been imported (see table 46) from Europe, -principally Germany and the United Kingdom. Increased demand for the same -purposes, in these countries, has so reduced the quantities available -for export as to create a serious shortage in the United States. Germany -placed an embargo on exports late in 1935 and continued it until late in -1937. - -TABLE 46.—_Crude naphthalene: United States production, imports, and -apparent consumption in specified years_ - - --------+--------------+--------------+--------------+---------------- - | | | Apparent |Percent supplied - Year | Production[1]| Imports[2] |consumption[3]| by - | | | | imports - --------+--------------+--------------+--------------+---------------- - |_1,000 pounds_|_1,000 pounds_|_1,000 pounds_| - 1923 | 53,325 | 20,992 | 74,317 | 28 - 1927 | 53,601 | 6,577 | 60,178 | 11 - 1929 | 39,263 | 35,007 | 74,270 | 47 - 1931 | 20,934 | 30,971 | 51,905 | 60 - 1932 | 13,593 | 27,002 | 40,595 | 66 - 1933 | 30,621 | 42,786 | 73,407 | 58 - 1934 | 37,922 | 47,995 | 85,917 | 56 - 1935 | 47,653 | 48,455 | 96,108 | 50 - 1936 | 89,536 | 39,806 | 129,342 | 31 - 1937[4] | 115,979 | 52,664 | 168,643 | 31 - --------+--------------+--------------+--------------+---------------- - - [1] From table 33. - - [2] From table 43. - - [3] Production plus imports. - - [4] Preliminary. - -Vast quantities of naphthalene potentially available in this country were -not recovered because of the low prices prevailing until 1936. Since -then an increase in the price of crude naphthalene from 1.55 cents to -2.5 cents and 3 cents per pound has stimulated production and has led to -additional recovery. - - -PHTHALIC ANHYDRIDE - - -Description and uses. - -Phthalic anhydride is an aromatic polybasic organic acid anhydride made -from naphthalene by vapor phase catalytic oxidation. It is marketed as -white needle-shaped crystals or flakes having a melting point of 130° -to 131° C. and boiling at 284° to 285° C. It is the cheapest and most -widely used aromatic organic acid. Its most important use is in the -manufacture of synthetic resins of the alkyd type. Other important uses -are in dye intermediates; in phenolphthalein; in benzoic acid; in dyes -such as indigo, phloxines, rhodamines, erythrosines; and in esters such -as dibutyl phthalate (widely used as a plasticizer in nitrocellulose -lacquers and films and of interest as a greaseless lubricant), diethyl -phthalate (used as a perfume fixative and denaturant of alcohol), -dimethyl phthalate (used as a plasticizer in cellulose acetate films), -and diamyl phthalate (used as a plasticizer). Important new processes -using phthalic anhydride as a raw material include the syntheses of -anthraquinone, substituted anthraquinones, and benzoyl benzoic acid. - -Before the World War phthalic anhydride was made by heating naphthalene -with sulphuric acid in the presence of mercury; the sulphuric acid acted -as an oxidizer, and sulphur dioxide and carbon dioxide were liberated. -This process was used in Europe and in the United States to produce the -small quantities of phthalic anhydride needed for the manufacture of -certain dyes and intermediates. It proved highly unsatisfactory as to -operation; the yield varying widely from batch to batch. The sales price -of the phthalic anhydride produced at that time was as high as $4.25 per -pound, whereas it is 12 to 14 cents per pound today. - -In September 1916, Gibbs and Conover, working in the Color Laboratory -of the Bureau of Chemistry and Soils, United States Department of -Agriculture, developed a process for the synthesis of phthalic anhydride -by the direct vapor phase catalytic oxidation of naphthalene. This work -was done under the United States Government’s wartime investigation of -the manufacture of intermediates and dyes. Gibbs and Conover were granted -United States Patent No. 1,285,117 covering the basic process, and the -invention was assigned to the people of the United States. This process -revolutionized the manufacture of phthalic anhydride, causing the market -price to drop to $2.85 per pound in 1918, to 46 cents per pound in 1920, -and to 13 cents in 1930. With each decline in price new outlets were -found, and domestic production increased practically every year, rising -from 227,000 pounds in 1918 to 23,500,000 pounds in 1935. - -By a remarkable coincidence the same basic process was developed -in Germany, by Alfred Wohl, in the laboratories of the Interessen -Gemeinschaft Industrie A. G. (German I. G.), at almost the same time that -Gibbs and Conover made their discovery. In 1920 Wohl applied for a United -States patent covering this process, claiming invention in the summer of -1916. There was some doubt whether his discovery had been made 2 months -earlier or 3 days later than that of Gibbs and Conover, but in July 1934 -the United States Court of Customs and Patent Appeals rendered a decision -in favor of the German inventor, allowing Wohl’s claim filed with the -German patent office on June 28, 1916. Therefore, Wohl’s claim covering -the air oxidization process was upheld and he was granted United States -Patent No. 1,971,888, issued August 28, 1934 and assigned to the German -I. G. - -Several domestic firms began commercial production of phthalic anhydride -about 1918 under the patent of Gibbs and Conover and have since operated -the process continuously. Such manufacturers are presumably protected -from possible patent litigation and the payment of royalties under the -Wohl patent by section 3 of the so-called Nolan Act of 1921, which -states: “No patent granted or validated ... shall affect the right of any -citizen of the United States or his successor in business to continue -the manufacture, use, or sale commenced before the passage of this Act, -nor shall the continued manufacture, use, or sale by such citizen ... -constitute an infringement.” - - -United States production. - -Table 47 shows the production and sales of phthalic anhydride from 1917 -through 1937. - -TABLE 47.—_Phthalic anhydride: United States production and sales, -1917-37_ - - ------+------------+------------------------+----------- - | | Sales | - Year | Production +------------+-----------+ Unit value - | | Quantity | Value | - ------+------------+------------+-----------+----------- - | _Pounds_ | _Pounds_ | | - 1917 | 138,857 | 138,857 | $587,240 | $4.23 - 1918 | 227,414 | 227,414 | 648,650 | 2.85 - 1919 | 290,677 | 290,677 | 290,037 | .99 - 1920 | 796,210 | 796,210 | 362,431 | .46 - 1921 | 202,471 | 202,471 | 79,162 | .39 - 1922 | 1,629,182 | 1,317,625 | 461,944 | .35 - 1923 | 2,343,802 | 2,091,100 | 596,508 | .29 - 1924 | 2,787,308 | 2,277,073 | 556,265 | .24 - 1925 | 3,900,332 | 3,560,429 | 701,840 | .20 - 1926 | 4,379,108 | 3,446,175 | 604,949 | .18 - 1927 | 4,549,820 | 4,064,476 | 686,946 | .17 - 1928 | 6,030,854 | 5,445,432 | 888,156 | .16 - 1929 | 9,168,946 | 7,450,037 | 1,147,953 | .15 - 1930 | 6,693,001 | 5,614,012 | 724,909 | .13 - 1931 | ([1]) | | | - 1932 | 6,259,000 | 5,695,000 | 663,000 | .12 - 1933 | 14,075,844 | 11,593,716 | 1,271,887 | .11 - 1934 | 20,680,379 | 13,511,253 | 1,575,787 | .12 - 1935 | 23,421,558 | 17,931,662 | 2,105,134 | .12 - 1936 | 31,244,378 | 22,905,873 | 2,824,471 | .12 - 1937 | 45,210,784 | 17,565,905 | 2,492,473 | .14 - ------+------------+------------+-----------+----------- - - [1] Not available. - - Source: Compiled from annual reports of the Tariff Commission on - dyes and other synthetic organic chemicals in the United States. - -There are six domestic makers of phthalic anhydride, with producing units -at Bridgeville, Pa., Buffalo, N. Y., Philadelphia, Pa., Deepwater Point, -N. J., Saint Louis, Mo., and Detroit, Mich. Five of these firms have been -producing in commercial quantities continuously for a number of years and -it is therefore believed that these companies may continue to produce -without the payment of royalties. New producers using this process, -however, might be at a disadvantage unless licensed to operate without -the payment of royalties by the owner of the patent. - -The production of phthalic anhydride has increased remarkably since the -discovery of the vapor phase catalytic process of manufacture. Until 1922 -the only large outlet was the coal-tar dye industry. The development of -new uses for phthalic esters, principally dibutyl phthalate, increased -the demand during the period 1922-28. With the drop in price of phthalic -anhydride, resins made from it and glycerin became of commercial interest -and about 1929 their production began to increase sharply. Most of the -increased output since that year is accounted for by its use in alkyd -resins. As previously stated, surface coatings made from these resins -are now applied to practically all “indoor” surfaces, both wood and -metal, and to “outdoor” use on metal. Largely as a result of the growing -popularity of surface coatings of the alkyd type the domestic production -of phthalic anhydride exceeded 45 million pounds in 1937 and may reach -50 million pounds in 1938. This estimate is based on the present trend -of consumption of alkyd resins and current use therein of phthalic -anhydride. Should other polybasic acids be used in greater proportion the -estimate would have to be revised. Considerable research work is being -done on certain polybasic acids, with very promising results in some -instances. Maleic anhydride is being used commercially, as are adipic -acid, malic acid, and succinic acid. Other possibilities include such -acids as citric, tartaric, sebacic, fumaric, and oxalic. - - -Production in other countries. - -Phthalic anhydride is manufactured in Germany, England, France, Italy, -and Japan, but no statistics of foreign production or of international -trade are available. The output in Germany is known to be increasing -rapidly and is believed to be the principal reason for the German embargo -on exports of naphthalene. - -In England there are two makers: Imperial Chemical Industries, Ltd., and -Monsanto Chemicals, Ltd. The latter is a branch of the American firm of -the same name. - -In Italy, production was started in 1928 by the A. C. N. A. at Cengio. -Capacity is given as 600,000 pounds annually, and the process is -essentially the same as in this country. - -Japanese production is estimated at 6 million pounds a year. Nihon -Seuryo’s plant is the principal one, and the Nishijima mill, at Osaka, -the next in importance. - - -United States foreign trade. - -Imports of phthalic anhydride are dutiable under paragraph 27 at 7 cents -per pound and 40 percent ad valorem based on American selling price. -There were practically no imports since the World War until 1937, when -223,431 pounds were imported from England to relieve a temporary shortage. - -Exports, if any, are not shown separately in official statistics. - - -Competitive conditions. - -Phthalic anhydride is the cheapest polybasic organic acid and therefore -the most widely used in the production of alkyd resins. The rapid -rise in consumption of surface coatings and finishes made from these -resins presages greater demand for phthalic anhydride (and glycerin) -in the future, particularly if this type of outdoor finish for wood is -successful. - -The world-wide shortage of naphthalene, with attendant sharp increases -in price, raises the question of whether there may not be partial or -complete replacement of phthalic anhydride by other polybasic acids -in certain types of alkyd resins. The probability of such replacement -seems remote unless the use of other polybasic acids, at present much -higher priced, so improves the properties of the resins as to give a -superior product. Approximately 100 pounds of naphthalene are required -to produce 109 pounds of phthalic anhydride. Naphthalene at 3 cents per -pound gives phthalic anhydride a raw material cost of 2.75 cents per -pound as compared with 1.45 cents per pound when naphthalene was 1.55 -cents per pound. In other words, the increase of 1.5 cents per pound in -naphthalene, meant an increase of only about 1⅓ cents per pound in the -raw material cost of phthalic anhydride, and only approximately ¼ cent -per pound in the raw material cost of an alkyd resin surface coating -containing about 20-percent phthalic anhydride. - - -POLYBASIC ACIDS OTHER THAN PHTHALIC ANHYDRIDE - - -Maleic acid and anhydride. - -Maleic anhydride is obtained as a byproduct in the manufacture of -phthalic anhydride and as a major product by the vapor phase catalytic -oxidation of benzene. Domestic production, still small compared with -phthalic anhydride, has increased many fold during the past two or three -years. In 1937 there were three producers of maleic anhydride, with an -output totaling 2,114,176 pounds. The uses of maleic acid derivatives -other than in making resins are minor. - - -Malic acid and malomalic acid. - -Malic acid is widely distributed in the vegetable kingdom, occurring -especially in unripe apples. Commercially it is obtained by synthesis. -Domestic production was reported for the first time in 1935. Malomalic -acid is formed by heating malic acid. United States Patent No. 1,091,627 -covers a resin made from malic acid and glycerin which will increase -the toughness of phthalate resins. United States Patent No. 1,667,198 -suggests the use of malomalic acid to form resins of glass-like -appearance. - - -Adipic acid. - -Adipic acid is made by oxidation of cyclohexanol. When condensed with -glycerin it yields an alkyd resin which is soft and rubbery and which -does not harden when heated. Numerous patents have been granted on the -preparation of adipic acid and its resins. Commercial production of -adipic acid was first reported in 1935, and the output increased in 1936 -and in 1937. - - -Succinic acid and anhydride. - -Succinic acid is a white crystalline powder melting at 185° C. and -boiling at 234° C., with decomposition to succinic anhydride. It may be -obtained by the reduction of maleic acid. Condensation with glycerin -gives a resin tougher and more flexible than is obtained with phthalic -anhydride. - -In 1937 there were two commercial producers of succinic acid. It is -believed that small quantities are used in combination with phthalic -anhydride in alkyd resins. - - -Fumaric acid. - -Fumaric acid is a white crystalline powder obtained by the prolonged -heating of or by the action of mineral acids on maleic acid. Fumaric acid -and maleic acid are structurally identical and the former decomposes at -about 280° C., forming the latter. In 1937 there was one domestic maker -of fumaric acid. - - -GLYCERIN - - -Description and uses. - -Glycerin (glycerol) is a clear, colorless or almost colorless, odorless, -syrupy, hygroscopic liquid. It is obtained as a byproduct of the soap and -fatty acid (oleic acid or red oil and stearic acid) industries. Other -sources are insignificant; glycerin can be produced by the fermentation -of carbohydrates such as molasses, but when glycerin prices are low this -process is not profitable. The chief commercial grades of crude glycerin -are “soap lye” glycerin, a byproduct of the soap industry, containing -about 80 percent glycerin, and “saponification” grade, a byproduct of the -fatty acid industry, containing about 88 percent glycerin. Chemically -pure grades contain about 95 percent and dynamite grades about 98.5 -percent glycerin. Other grades include “30° yellow distilled” containing -about 96 percent glycerin. - -The uses of glycerin are extremely varied, the most important being in -the manufacture of alkyd resins and ester gums; in the manufacture of -nitroglycerin and dynamite; as a moistening, antiseptic, and sweetening -agent in tobacco; in pharmaceutical and medicinal preparations; and in -certain soft drinks, soaps, and inks. - - -United States production. - -The output of both the crude and the refined has increased in recent -years, reaching new highs in 1937. Chemically pure glycerin constitutes -about 60 percent of the total refined output and dynamite and other -grades about 40 percent. In the production statistics shown in table 48, -grades such as yellow distilled are included with the dynamite grade. -Since large soap makers refine their own crude glycerin, the sale of -crude is only a small part of the total output. - -Table 48 shows domestic production of glycerin by grades and table 49 -production for sale. - -TABLE 48.—_Glycerin: United States production by grades, in specified -years, 1919-37_ - - [In thousands of pounds] - -------------+---------------+-------------------------------- - | | Refined - Census year | Crude 80 +------------+----------+-------- - | percent basis | Chemically | Dynamite | - | | pure grade | grade | Total - -------------+---------------+------------+----------+-------- - 1919 | 61,793 | 36,693 | 25,655 | 62,348 - 1920 | 54,688 | 32,860 | 31,571 | 64,431 - 1923 | 99,579 | 47,992 | 52,369 | 100,361 - 1924 | 95,154 | 53,243 | 37,368 | 90,611 - 1925 | 103,407 | 55,448 | 52,658 | 108,106 - 1926 | 116,369 | 64,460 | 49,579 | 114,039 - 1927 | 128,209 | 59,126 | 49,266 | 108,392 - 1928 | 130,499 | 66,419 | 46,622 | 113,041 - 1929 | 140,080 | 66,791 | 58,981 | 125,772 - 1930 | 138,675 | 69,654 | 50,974 | 120,628 - 1931 | 140,002 | 70,528 | 43,366 | 113,894 - 1932 | 133,919 | 63,624 | 41,539 | 105,163 - 1933 | 119,812 | 58,585 | 45,534 | 104,119 - 1934 | 153,115 | 80,359 | 48,553 | 128,912 - 1935 | 141,185 | 74,705 | 48,685 | 123,390 - 1936 | 154,096 | 85,386 | 47,535 | 132,921 - 1937 | 167,882 | 92,889 | 51,794 | 144,683 - -------------+---------------+------------+----------+-------- - - Source: Bureau of the Census, U. S. Department of Commerce. - -TABLE 49.—_Glycerin: United States production for sale, in specified -years, 1919-35_ - - --------+-------------------------------+-------------------------------- - | Crude[1] | Refined - +----------+------------+-------+----------+-------------+------- - Year | | | Value | | | Value - | Quantity | Value | per | Quantity | Value | per - | | | pound | | | pound - --------+----------+------------+-------+----------+-------------+------- - | _1,000 | | | _1,000 | | - | pounds_ | |_Cents_| pounds_ | |_Cents_ - 1919 | 18,228 | $2,482,779 | 13.6 | 47,377 | $11,461,213 | 24.2 - 1923 | 27,444 | 3,124,470 | 11.4 | 74,105 | 12,214,012 | 16.5 - 1925 | 30,735 | 4,258,351 | 13.9 | 94,303 | 16,991,213 | 18.0 - 1927 | 27,000 | 3,942,991 | 14.6 | 89,585 | 19,184,806 | 21.4 - 1929 | 28,790 | 2,358,031 | 8.2 | 113,140 | 12,715,641 | 11.2 - 1931 | 27,530 | 1,673,733 | 6.1 | 102,510 | 10,316,347 | 10.1 - 1931[2]| 25,964 | 1,551,573 | 6.0 | 101,615 | 10,222,850 | 10.1 - 1933 | 22,161 | 1,191,000 | 5.4 | 107,853 | 7,915,000 | 7.3 - 1935 | 24,042 | 2,366,481 | 9.8 | 121,262 | 12,984,684 | 10.7 - - [1] By chemical and soap manufacturing plants only. - - [2] Adjusted for comparison with 1933. - - Source: Bureau of the Census, U. S. Department of Commerce. - -Crude glycerin is produced by about 200 soap makers and by about 12 -producers of fatty acids. Soap factories are located in more than half -the States, the principal ones being in Ohio, New York, Massachusetts, -New Jersey, Illinois, California, and Pennsylvania; the fatty acid plants -are located in five or six States, Ohio being of chief importance. Most -of the smaller producers sell their output of crude glycerin. Refiners of -glycerin are few in number compared to the producers of crude. The larger -soap plants refine their own crude glycerin and in addition purchase -crude from other plants for refining. - -The process of recovering glycerin consists of chemically treating weak -glycerin solutions separated from the soap or fatty acids, and then -concentrating and distilling under reduced pressures. The average yield -is less than 10 percent but varies from about 9 to 12 percent, depending -upon the kinds of oils and fats used. When prices are high every effort -is made to recover the maximum yield of glycerin; when prices are low, -cost of chemical treatment and distillation makes it advisable to allow -more glycerin to remain in the soap or to discard the weak solutions. - - -Production in other countries. - -As in the United States, glycerin is produced in foreign countries, as -a byproduct of the soap and fatty acid industries. The United Kingdom, -Germany, and France, and recently the Soviet Union, are the leading -producers. The output in each of these countries is estimated to be less -than a third of the output in the United States. The British Census of -1930 reports the production of crude glycerin in the United Kingdom at -44 million pounds. Authentic statistics on production in other leading -countries are not available, but most estimates show lower figures than -for the United Kingdom. In some European countries the normal production -of soap results in more glycerin than can be utilized. - - -International trade. - -France is the principal net exporter of crude glycerin and the United -Kingdom of refined glycerin. The Netherlands, Germany, and France are -also net exporters of refined glycerin. The international trade of -certain of the more important producing countries in crude and refined -glycerin is shown in table 50. - -TABLE 50.—_Glycerin: Imports and exports of principal countries, 1931 and -1933-37_ - - [In thousands of pounds] - --------------------+---------------+---------------+--------------- - | 1931 | 1933 | 1934 - +-------+-------+-------+-------+-------+------- - |Imports|Exports|Imports|Exports|Imports|Exports - --------------------+-------+-------+-------+-------+-------+------- - Crude: | | | | | | - UNITED STATES[1]| 8,782| ([2]) | 4,988| ([3]) | 13,722| ([3]) - United Kingdom | 1,702| 2,662| 4,778| 2,951| 472| 2,825 - Germany | 4,120| 2,313| 5,232| 2,939| 4,746| 1,599 - France | 1,269| 7,962| 426| 3,488| | ([2]) - Netherlands | 5,133| 859| 3,027| 2,300| 2,605| 3,796 - Refined: | | | | | | - UNITED STATES | 1,966| 328| 2,776| ([3]) | 2,214| ([3]) - United Kingdom | 2,519| 9,926| 822| 19,834| 230| 19,134 - Germany | 102| 10,092| 57| 3,562| 224| 3,818 - France | 178| 3,989| 109| 1,246| 51| 12,249 - Netherlands | 618| 8,337| 1,144| 6,620| 1,008| 5,955 - Belgium | 534| 758| 1,193| 429| 1,206| 2,360 - +-------+-------+-------+-------+-------+------- - | 1935 | 1936 | 1937[4] - +-------+-------+-------+-------+-------+------- - |Imports|Exports|Imports|Exports|Imports|Exports - +-------+-------+-------+-------+-------+------- - Crude: | | | | | | - UNITED STATES[1]| 4,092| ([2]) | 8,686| ([2]) | 10,171| ([2]) - United Kingdom | 1,119| 2,365| 2,322| 3,070| ([2]) | ([3]) - Germany | 4,091| 326| 8,247| 122| 13,567| 578 - France | 862| ([2]) | 1,176| ([2]) | 164| ([2]) - Netherlands | 5,441| 4,912| 7,185| 5,644| 9,127| 6,865 - Refined: | | | | | | - UNITED STATES | 69| 3,354| 3,448| 1,146| 7,535| 1,375 - United Kingdom | 2| 15,032| | 12,991| ([3]) | 16,029 - Germany | 108| 1,571| 30| 1,155| 71| 100 - France | 4| 12,118| 10| 9,269| 9| 17,750 - Netherlands | 694| 5,516| 739| 8,885| 500| 10,961 - Belgium | 998| 1,945| 188| 1,981| 651| 1,858 - --------------------+-------+-------+-------+-------+-------+------- - - [1] Imports from Cuba and the Philippines not included in the - United States statistics. These imports, consisting of crude - glycerin, averaged about 2,200,000 pounds annually for the period - 1931-37. - - [2] Included, if any, with refined. - - [3] Not separately reported. - - [4] Preliminary. - - Source: Official statistics of each country. - - -United States imports. - -Under the Tariff Act of 1922, paragraph 43, imports of crude glycerin -were dutiable at 1 cent per pound and refined glycerin at 2 cents per -pound. The Tariff Act of 1930, paragraph 42, carries the same rates. -Imports of crude glycerin from Cuba enjoy a preferential rate; they were -dutiable at 0.8 cent per pound up to September 3, 1934, and at 0.4 cent -per pound thereafter. Under the trade agreement with the Netherlands, -effective February 1, 1936, the rate on refined glycerin was reduced from -2 cents to 1⅔ cents per pound (⅔ cent plus regular rate on crude, but not -more than 1⅔ cents). Under the trade agreement with France, effective -June 15, 1936, the rate on crude glycerin was reduced from 1 cent to 0.8 -cent, which automatically further reduced the rate on refined glycerin -to 1¹⁴⁄₃₀ (approximately 1.47) cents per pound. The rates under these -last two trade agreements are generalized to all countries which do not -discriminate against our commerce. - -The amount of glycerin supplied by imports has greatly declined. Prior -to the World War, imports of crude glycerin ranged from 30 million to -40 million pounds annually. After the war imports were less and after -1929 declined to comparatively small quantities, except in 1934. Imports -of refined glycerin were relatively unimportant until 1924, except in -1920. They amounted to almost 11 million pounds in 1926, but declined -thereafter. Some of the imports are reexported with benefit of drawback. -In 1930, 1,006,164 pounds of imported crude glycerin and 396,792 pounds -of imported refined were thus reexported, chiefly in the refined grades. -Corresponding figures in 1932 and 1933 were 197,331 and 111,753 pounds of -crude, and 40,011 and 10,056 pounds of refined. - -Statistics of imports other than from Cuba and the Philippines are given -in table 51. Table 52 shows imports of crude from Cuba and table 53 -imports of crude from the Philippines. - -TABLE 51.—_Glycerin: United States imports[1] for consumption 1919-20 and -1923-37_ - - -------------+-------------+---------+---------+----------+------------- - | |Quantity,| | | Computed - Calendar year| Rate of | 1,000 | Value |Unit value| ad valorem - | duty | pounds | | |rate, percent - -------------+-------------+---------+---------+----------+------------- - | Crude - +-------------+---------+---------+----------+------------- - 1919 | 1 cent per | 3,564| $417,774| $0.117| 8.5 - | pound | | | | - 1920 | do | 22,272|2,912,430| .131| 7.7 - 1923 | do | 14,120|1,382,249| .098| 10.2 - 1924 | do | 13,659|1,413,593| .103| 9.7 - 1925 | do | 18,624|2,161,413| .116| 8.6 - 1926 | do | 26,729|3,849,222| .144| 6.9 - 1927 | do | 13,666|2,026,175| .148| 6.7 - 1928 | do | 3,889| 282,615| .073| 13.8 - 1929 | do | 13,681| 786,598| .058| 17.4 - 1930 | do | 10,022| 577,406| .058| 17.4 - 1931 | do | 8,782| 446,897| .051| 19.7 - 1932 | do | 3,952| 145,329| .037| 27.2 - 1933 | do | 4,988| 176,080| .035| 28.3 - 1934 | do | 13,722| 932,389| .068| 14.7 - 1935 | do | 4,092| 353,925| .086| 11.4 - 1936 | Various[2] | 8,686| 936,312| .108| 7.7 - 1937[3] | do | 10,171|1,716,351| .169| 4.8 - +-------------+---------+---------+----------+------------- - | Refined - +-------------+---------+---------+----------+------------- - 1919 | 2 cents per | 39| 4,471| .114| 17.5 - | pound | | | | - 1920 | do | 5,382|1,170,030| .217| 9.2 - 1923 | do | 586| 76,994| .131| 15.2 - 1924 | do | 1,501| 229,897| .153| 13.1 - 1925 | do | 2,044| 305,796| .150| 13.4 - 1926 | do | 10,839|2,328,936| .215| 9.3 - 1927 | do | 8,289|1,697,330| .205| 9.8 - 1928 | do | 4,218| 450,247| .107| 18.7 - 1929 | do | 5,358| 489,575| .091| 21.9 - 1930 | do | 3,137| 265,093| .085| 23.7 - 1931 | do | 1,966| 140,975| .072| 27.9 - 1932 | do | 2,348| 142,359| .061| 33.0 - 1933 | do | 2,776| 166,991| .060| 33.2 - 1934 | do | 2,214| 208,989| .094| 21.2 - 1935 | do | 69| 8,277| .121| 16.6 - 1936 |Various[2] | 3,447| 594,036| .172| 8.5 - 1937[3] | do | 7,535|1,827,189| .242| 6.2 - -------------+-------------+---------+---------+----------+------------- - - [1] Does not include products of Cuba (duty less 20 percent) and - the Philippine Islands (free). - - [2] For changes in rates, see p. 105. - - [3] Preliminary. - - Source: Foreign Commerce and Navigation of the United States. - -TABLE 52.—_Crude glycerin: United States imports (for consumption) from -Cuba, in specified years, 1919-37_ - - -------------+-------------------+--------+-------+----------+---------- - | | | | | Computed - Calendar year| Rate of duty |Quantity| Value |Unit value|ad valorem - | | | | | rate - -------------+-------------------+--------+-------+----------+---------- - | | _1,000 | | | - | | pounds_| | |_Percent_ - 1919 |⁸⁄₁₀ cent per pound| 249|$27,023| $0.108| 7.4 - 1920 | do | 139| 21,941| .158| 5.1 - 1923 | do | 429| 47,438| .111| 7.2 - 1924 | do | 768| 85,971| .112| 7.2 - 1925 | do | 624| 73,538| .118| 6.8 - 1926 | do | 835|134,893| .162| 5.0 - 1927 | do | 1,119|170,723| .153| 5.2 - 1928 | do | 690| 48,963| .071| 11.3 - 1929 | do | 921| 60,158| .065| 12.2 - 1930 | do | 843| 53,905| .064| - 1931 | do | 1,171| 67,709| .058| 13.8 - 1932 | do | 1,232| 50,147| .041| 19.7 - 1933 | do | 1,216| 56,737| .047| 17.2 - 1934 |Various[1] | 1,178| 92,692| .079| - 1935 |⁴⁄₁₀ cent per pound| 2,551|228,011| .089| 4.5 - 1936 | do | 2,160|230,340| .107| 3.8 - 1937[2] | do | 2,477|381,683| .154| - -------------+-------------------+--------+-------+----------+---------- - - [1] Trade agreement of ⁴⁄₁₀ cent per pound, effective Sept. 3, - 1934. - - [2] Preliminary. - - Source: Foreign Commerce and Navigation of the United States. - -TABLE 53.—_Crude glycerin: United States imports (for consumption) from -Philippine Islands 1925-37_ - - -------------+-------------+--------------+-------+---------- - Calendar year| Rate of duty| Quantity | Value |Unit value - -------------+-------------+--------------+-------+---------- - | |_1,000 pounds_| | - 1925 |Free | 16| $1,418| $0.089 - 1926 | do | 95| 12,115| .128 - 1927 | do | 159| 18,261| .115 - 1928 | do | 337| 24,327| .072 - 1929 | do | 250| 16,796| .067 - 1930 | do | 279| 18,805| .067 - 1931 | do | 180| 10,993| .061 - 1932 | do | 198| 9,150| .046 - 1933 | do | 268| 14,078| .052 - 1934 | do | 181| 14,984| .083 - 1935 | do | 1,579| 74,798| .047 - 1936 | do | 304| 32,708| .108 - 1937[1] | do | 793|145,348| .183 - -------------+-------------+--------------+-------+---------- - - [1] Preliminary. - - Source: Foreign Commerce and Navigation of the United States. - -France has usually been the principal source of imports of crude -glycerin, but since 1935 Cuba has ranked first. Cuban imports enter at a -preferential rate of duty (0.8 cent per pound on crude until September 3, -1934, when it was reduced to 0.4 cent). Receipts from the Philippines are -duty-free. Imports by countries for recent years are given in table 98, -page 151. - -The Netherlands has generally been the chief source of imports of refined -glycerin, although the United Kingdom was first in 1934 and 1935 and -France first in 1937. Imports by countries for recent years are given in -table 99, page 152. - - -United States exports. - -Exports of glycerin are insignificant compared with production and are -small compared with imports. They go chiefly to Mexico and Canada, -and, at times, also to Cuba, the Philippines, and Chile. Geographic -propinquity is probably the principal factor accounting for these -exports, although it is possible that some exports are destined to -foreign branch factories of an American company for making dynamite. - -Crude and refined grades were not separately distinguished in export -statistics, but it is known that exports consist principally, if not -entirely, of the refined. In 1933 and 1934 glycerin exports were not -reported. Statistics of exports are given in table 54. - -TABLE 54.—_Glycerin: United States exports, in specified years, 1919-37_ - - -------+---------+-----------+---------- - Year | Quantity| Value |Unit value - -------+---------+-----------+---------- - | | |_Cents per_ - |_Pounds_ | | _pound_ - 1919 |3,963,392| $1,190,984| 30.0 - 1920 |1,742,708| 429,116| 24.6 - 1923 |1,767,407| 318,765| 18.0 - 1924 |1,415,882| 237,639| 16.8 - 1925 |1,367,191| 282,078| 20.6 - 1926 | 767,698| 192,220| 25.0 - 1927 | 693,144| 143,700| 20.7 - 1928 |2,051,937| 259,100| 12.6 - 1929 |1,373,605| 197,986| 14.4 - 1930 | 607,690| 102,892| 16.9 - 1931 | 328,143| 48,095| 14.7 - 1932 | 260,339| 28,609| 11.0 - 1933 | ([1]) | ([1]) | - 1934 | ([1]) | ([1]) | - 1935 |3,353,625| 450,248| 13.4 - 1936 |1,146,026| 182,592| 15.9 - 1937[2]|1,375,036| 338,148| 24.6 - -------+---------+-----------+---------- - - [1] Not reported separately. - - [2] Preliminary. - - Source: Foreign Commerce and Navigation of the United States. - - -Competitive conditions. - -Glycerin occurs in chemical combination in animal and vegetable oils -and fats. Since it is obtained as a byproduct, the output is dependent -primarily upon the output of the major products, soaps and fatty acids, -and its production is largely independent of demand. At low prices, -however, less glycerin is recovered. - -The United States usually consumes more glycerin than it produces (see -table 55), whereas leading European producing nations produce more than -they consume. In recent years the domestic production has apparently been -approaching domestic requirements. A factor tending to decrease demand -is the increasing resort to substitutes in various uses, particularly -ethylene glycol, ethyl alcohol, and methyl alcohol. On the other hand, -the demand in the resin industry is expanding rapidly. - -TABLE 55.—_Refined glycerin: United States production, imports, exports, -and apparent consumption, in specified years_ - - -------+-------------+----------+----------+-------------- - Year |Production[1]|Imports[2]|Exports[3]| Apparent - | | | |consumption[4] - -------+-------------+----------+----------+-------------- - | _Pounds_ | _Pounds_ | _Pounds_ | _Pounds_ - 1927 | 108,392| 8,289| 693| 115,987 - 1929 | 125,772| 5,358| 1,374| 129,757 - 1931 | 113,894| 1,966| 328| 115,531 - 1932 | 105,163| 2,348| 260| 107,250 - 1933 | 104,120| 2,776| ([5]) | 106,895 - 1934 | 128,912| 2,214| ([5]) | 131,126 - 1935 | 123,390| 69| 3,354| 120,105 - 1936 | 132,922| 3,447| 1,146| 135,223 - 1937[6]| ([5]) | 7,535| 1,375| ([5]) - -------+-------------+----------+----------+-------------- - - [1] From table 48 (refined basis). - - [2] From table 51 (refined). - - [3] From table 54 (grade not specified, but chiefly refined). - - [4] Production plus imports minus exports. - - [5] Not available. - - [6] Preliminary. - -Up to 1924 (except 1920) imports consisted principally of crude glycerin, -much of which was refined in the United States and included in United -States production; thereafter imports of refined glycerin became -important relative to the crude. Exports are insignificant compared to -either production or imports. - - - - -17. RAW MATERIALS FOR TAR-ACID RESINS - - -The first tar-acid resins were made from phenol and formaldehyde. As a -result this group of resins is frequently spoken of as phenolic resins. -This is true despite the fact that coal-tar acids other than phenol, -particularly the cresols and xylenols, are used in large volume today. - - -THE TAR ACIDS - -The term coal-tar acids is applied to certain organic compounds either -obtained from or known to be present in coal tar. Probably the best known -is phenol or carbolic acid, produced in large quantities in the United -States and abroad. Others of commercial importance are ortho, meta, -and para cresol and the xylenols. All of these are definite chemical -compounds available as such or in mixture with other tar acids. Cresylic -acid is a term widely used in commerce for almost any mixture of tar -acids. Formerly it was used to designate a mixture of ortho, meta, and -para cresols in the proportions in which they are found in coal tar. The -higher boiling tar acids (listed in table 56 below the xylenols) have -little or no commercial importance at this time. - -Table 56 lists the tar acids by commercial name, chemical name, boiling -point of the pure compound, and average percentage present in coal -tar. Boiling point is shown because the several tariff classifications -covering tar acids under the acts of 1922 and 1930 (pars. 27 and 1651) -depend upon distillation range (boiling points) for classification and -assessment of duty (see pp. 119 and 124). - -TABLE 56.—_Tar acids: Commercial and chemical names, boiling points and -average percentage present in coal tar_ - - --------------------+-----------------------+---------+---------- - | | | Average - Commercial name | Chemical name | Boiling |percent in - | |point ° C| coal tar - --------------------+-----------------------+---------+---------- - Phenol |Phenol | 181.5| 0.7 - Orthocresol |2-methyl phenol | 190.8| .4 - Metacresol |3-methyl phenol | 202.8| .4 - Paracresol |4-methyl phenol | 201.8| .3 - 2-3 Xylenol |2-3-dimethyl phenol | 218.0| ⎫ - 2-4 Xylenol |2-4-dimethyl phenol | 211.5| ⎪ - 2-5 Xylenol |2-5-dimethyl phenol | 211.5| ⎬ .2 - 2-6 Xylenol |2-6-dimethyl phenol | 212.0| ⎪ - 3-4 Xylenol |3-4-dimethyl phenol | 225.0| ⎪ - 3-5 Xylenol |3-5-dimethyl phenol | 220.0| ⎭ - Ortho ethylphenol |2-ethyl phenol | 206.5| ⎫ - Meta ethylphenol |3-ethyl phenol | 217.0| ⎪ - Para ethylphenol |4-ethyl phenol | 218.5| ⎪ - s-methyl ethylphenol|3-methyl-5-ethyl phenol| 232.5| ⎬ .5 - Iso pseudocumenol |2-3-5-trimethyl phenol | 233.0| ⎪ - Mesitol |2-4-6-trimethyl phenol | 219.5| ⎪ - Pseudocumenol |2-4-5-trimethyl phenol | 234.0| ⎭ - --------------------+-----------------------+---------+---------- - - Source: Ellis, Chemistry of Synthetic Resins. - -Since the quantities of tar acids present in coal tar are small (see -table 56), it is usually uneconomical to distill coal tar completely -unless the creosote oil and pitch can be marketed profitably. Beginning -in 1936, production of tar acids in the United States was increased by -the practice of topping. Topping is the recovery in tar distillation of -the light fractions only, leaving a residual thin enough to flow through -the pipe lines to supply fuel to open hearth and other type furnaces. -These light fractions contain the naphthalene and tar acids. The practice -permits recovery of these products from tar to be used as fuel, thus -providing a new alternative intermediate between the two older practices -of either complete distillation or using the undistilled tar as fuel. - -In the United States, consumption of most of the tar acids greatly -exceeds the quantities extracted from tar, necessitating large production -of synthetic phenol and importation of large quantities of the cresols -and xylenols. The calculated amount of these tar acids present in the tar -produced in this country vastly exceeds present day requirements. Table -57 shows the approximate amounts of the several tar acids contained in -the coal tar produced and distilled in 1936. These estimates are based on -a 1936 production of coal tar of 560,385,578 gallons and a distillation -of 292,140,249 gallons. The calculation is made by using the percentage -of tar acids in tar shown in table 56 and converting the gallons to -pounds in accordance with the specific weights of the pure tar acids. -Actual production of all tar acids in the United States in 1936 was about -29 million pounds. - -TABLE 57.—_Tar acids available in coal tar produced and distilled in 1936_ - - -----------+--------------+-------------- - | Available in | Available in - Tar acid | tar produced | tar distilled - | in 1936[1] | in 1936[2] - -----------+--------------+-------------- - |_1,000 pounds_|_1,000 pounds_ - Phenol | 34,912 | 18,200 - Orthocresol| 19,277 | 10,050 - Metacresol | 19,277 | 10,050 - Paracresol | 14,290 | 7,450 - Xylenols | 10,200 | 5,316 - Others | 25,200 | 13,290 - -----------+--------------+-------------- - - [1] 560,385,578 gallons. - - [2] 292,140,249 gallons. - -The several tar acids are discussed in detail under the following heads: - -(_a_) Phenol. - -(_b_) The cresols, xylenols, and cresylic acid. - -(_c_) Synthetic tar acids other than phenol. - - -PHENOL - - -Description and uses. - -Phenol (commonly called carbolic acid) is a tar acid obtained from two -sources: (_a_) From one of the fractions recovered in the distillation -of coal tar, a byproduct resulting from the manufacture of coke in -byproduct ovens, and from the manufacture of coal gas; (_b_) from -benzol, by synthesis. The second source has been the more important -since 1923. Phenol, when pure, is a colorless substance of interlaced -or separate needle-shaped crystals with a characteristic aromatic odor. -It is corrosive to the skin and to mucous membrane. When pure it is -water white, melts at about 42° C., and boils at about 181.5° C. It was -discovered in 1834 by Runge. - -Phenol is used today chiefly as a component of tar-acid resins. It is -also widely used as an antiseptic and disinfectant, in the manufacture of -explosives (picric acid and ammonium picrate), and as an intermediate for -certain dyes and medicinals. Salicylic acid and its derivatives—aspirin, -salol, and methyl salicylate (artificial oil of wintergreen)—are -important medicinals made from phenol. Another use is in the extraction -of lubricating oils. The relative importance of these various uses in -recent years is indicated by table 58, which gives the estimated domestic -consumption of phenol by uses in 1936-37. - -TABLE 58.—_Phenol: Estimated consumption by industries, 1936-37_ - - ------------------------------+----------------- - Use |Percent of - |total consumption - ------------------------------+----------------- - Synthetic resins | 60-65 - Extraction of lubricating oil | 5 - Insecticides and disinfectants| 10 - Dyes and intermediates | 5 - Other | 15-20 - ------------------------------+----------------- - - -United States production. - -Prior to 1914 United States production of phenol averaged about a -million pounds a year and was entirely the natural product obtained from -distillates of coal tar. Increased demand during the World War was met -by several synthetic phenol processes, which utilized in part the vast -quantities of benzol available. Our output of phenol reached 64 million -pounds in 1917 and 107 million pounds in 1918. When the armistice was -signed stocks on hand in the United States totaled between 35 million and -40 million pounds, estimated at three times the annual consumption at -that time for nonmilitary purposes. As a result the price dropped from -about 45 cents to 6 cents a pound, and the synthetic plants were closed. - -The limited quantities of phenol available to synthetic resin makers -prior to and during the World War caused much concern to that industry -and led to research work for substitutes, work resulting in the -development of many new and modified types of resins in which tar acids -other than phenol were used. But notwithstanding the use of these -other tar acids the increased demand for synthetic resins used up the -accumulated stocks of phenol sooner than was expected. - -Of the phenol produced in the United States from 1919 through 1923 a -large part was natural phenol but the rapid increase in demand and the -improvement of processes for synthetic phenol had by 1923 resulted -in four companies beginning production of the synthetic article. The -rapid increase in output, from about 3 million pounds in 1923 to about -15 million pounds in 1925, was almost entirely in synthetic phenol. -Since then a large part of the domestic production has continued to be -synthetic, although the production of natural phenol since 1935 has been -about four times that of 1929. - -Adequate quantities of coal tar are usually available to produce -sufficient natural phenol to meet a substantial part of our requirements, -if it were all recovered, but the quantity actually produced is -determined in part by the demand for other coal-tar products, and in part -by the value of the tar as fuel. More than 50 percent of the tar produced -has been burned as fuel, principally at the coke ovens or nearby steel -mills. - -The domestic production and sales of phenol, natural and synthetic -combined, are shown in table 59. - -TABLE 59.—_Phenol: United States production and sales, in specified -years, 1918-37_ - - -----------+----------+--------------------------------+--------------- - |Production| Sales | - | | | Ratio of sales - Census year+----------+----------+----------+----------+ to total - | Quantity | Quantity | Value |Unit value| production - -----------+----------+----------+----------+----------+--------------- - | _1,000 | _1,000 | _1,000 | | _Percent_ - | pounds_ | pounds_ | dollars_ | | - 1918 | 106,794 | 106,794 | 37,270 | $0.35 | - 1919 | 1,544 | 1,544 | 156 | .10 | - 1923 | 3,311 | 2,180 | 590 | .27 | 66 - 1925 | 14,734 | 8,524 | 1,771 | .21 | 58 - 1926 | 8,691 | 5,480 | 988 | .18 | 63 - 1927 | 8,041 | 4,595 | 684 | .15 | 57 - 1928 | 10,227 | 7,746 | 912 | .12 | 76 - 1929 | 24,178 | 19,939 | 2,248 | .11 | 83 - 1930 | 21,147 | 17,715 | 1,976 | .11 | 84 - 1931 | 17,981 | 14,002 | 1,446 | .10 | 78 - 1932 | 13,965 | 12,181 | 1,269 | .10 | 87 - 1933 | 33,220 | 27,923 | 2,881 | .10 | 84 - 1934 | 44,935 | 36,241 | 3,887 | .11 | 81 - 1935 | 43,419 | 34,575 | 3,431 | .10 | 80 - 1936 | 48,724 | 40,942 | 4,235 | .10 | 84 - 1937 | 65,690 | 57,176 | 6,153 | .11 | 87 - -----------+----------+----------+----------+----------+--------------- - - Source: Compiled from annual reports of the Tariff Commission on - dyes and other synthetic organic chemicals in the United States. - -_Grades produced for resins._—Increased production of phenol in recent -years is largely due to the demand from makers of synthetic resins. A -number of grades are regularly produced for this purpose, though it is -believed that the technical grade is the principal one used in resins. -The several grades are as follows: - -(1) USP.—Either natural or synthetic. This grade contains not less than -98 percent phenol. - -(2) Technical.—Various grades containing from 80 to 95 percent phenol, of -which the two most important are 82-84 percent and 90-92 percent. - -(3) Mixtures.—Containing from 30 percent to 80 percent phenol and the -remainder of the isomeric cresols. - -_Producers._—Natural phenol is obtained in the distillation of coal tar -and to a smaller extent in the purification of ammonia liquors in coke -and gas plants. In 1937 there were four producers of natural phenol with -plants located at Philadelphia, Pa., Follansbee, W. Va., Indianapolis, -Ind., and Pittsburgh, Pa. All these are tar distillers recovering -creosote oil, pitch, cresylic acid, naphthalene, and other crudes from -coal tar. - -Synthetic phenol is made from benzene, either by sulfonation followed -by alkaline fusion, or by chlorination and subsequent heating under -pressure with caustic soda. It is produced in large quantities by two -firms, one at Midland, Mich., and the other at St. Louis, Mo. A third -producer is building a plant at North Tonawanda, N. Y., using a process -recently developed in Germany. Operation of this unit will probably start -late in 1938. - - -World production. - -Natural phenol is recovered in practically all European countries and -in Japan. Germany and the United Kingdom are the principal producers -and have also been the leading exporters. Synthetic phenol was made in -Germany as early as 1900, and during the World War. Plants for synthetic -phenol recently installed are now in operation in Germany, Great Britain, -Belgium, and Italy. - -Table 60 shows the average annual world production of phenol in recent -years by countries. Half of the total was produced in the United States. - -TABLE 60.—_Phenol: Estimated average annual production, by countries, -1933-35_ - - --------------+----------------- - | Estimated - Produced in— |annual production - --------------+----------------- - | _1,000 pounds_ - UNITED STATES | 41,000 - United Kingdom| 18,000 - Germany | 10,000 - Poland | 3,000 - Japan | 3,000 - Czechoslovakia| 1,000 - Belgium | 2,000 - France | 2,000 - Italy | 1,500 - Spain | 700 - +----------------- - Total | 82,200 - --------------+----------------- - - Source: Consular reports. - -In the United Kingdom, where tar distillation is a well developed and -highly organized industry, large quantities of gas-works tar, rich in -phenol and other tar acids, are available. Prior to the World War the -United Kingdom was the principal source of phenol, and of the other -products of tar distillation. During the war several synthetic processes -of commercial importance were developed, but they were discontinued after -its close. A new synthetic unit has recently been installed in England -and is now in operation. Increasing consumption of phenol in synthetic -resins during the last decade, particularly in the last several years, -has changed the United Kingdom from an exporter to an importer of phenol. -Estimated consumption of phenol in the United Kingdom is given as 20 -million pounds annually—principally in synthetic resins, and in lesser -quantities in dyes, intermediates, antiseptics, and disinfectants. - -In Germany the phenol recovered in 1936 amounted to about 20 million -pounds, and recently three commercial units have been installed for the -production of synthetic phenol, one with a reported daily output of -11,000 pounds. - -Natural phenol is also recovered in Belgium, France, the Netherlands, -Czechoslovakia, Poland, Italy, and Spain. Synthetic phenol has recently -been produced for the first time in Belgium and Italy. The quantities -normally produced in these countries are small and are supplemented by -imports from Great Britain and Germany. - -The production of phenol in Japan has increased rapidly and has been -sufficient since 1930 to meet domestic requirements. The estimated output -increased from 300,000 pounds in 1927 to more than 3 million pounds -annually in recent years. The Miike Dyestuffs Works is reported to be -producing synthetic phenol. - - -United States imports. - -_Rates of duty._—Prior to September 6, 1916, phenol was imported free of -duty. Since that date it has been dutiable at the various rates shown in -table 61. Under the act of 1930 the rate of duty is 3½ cents per pound -and 20 percent ad valorem on the American selling price (the wholesale -price of a similar competitive article manufactured in the United -States).[21] - -TABLE 61.—_Phenol: Rates of duty upon imports into the United States, -1916-37_ - - ------------------+------------------------+---------------------------- - Period | Rate of duty | Authority - ------------------+------------------------+---------------------------- - To Sept. 8, 1916 |Free |Free under Tariff Act of - | | 1913 and previous acts. - | | - Sept. 9, 1916, to |2½ cents per pound plus |Under Revenue Act of 1916. - Sept. 21, 1922. | 15 percent ad valorem | - | on foreign value. | - | | - Sept. 22, 1922, to|7 cents per pound plus |Under par. 27 of Tariff Act - Sept. 21, 1924. | 55 percent ad valorem | of 1922; special provision - | on American selling | for first 2 years. - | price[1] or United | - | States value.[2] | - | | - Sept. 22, 1924, to|7 cents per pound plus |Under par. 27 of Tariff Act - Nov. 29, 1927. | 40 percent ad valorem | of 1922, rate provided - | on American selling | for period after the - | price[1] or United | first 2 years. - | States value.[2] | - | | - Nov. 30, 1927, to |3½ cents per pound plus |By Presidential proclamation - June 17, 1930. | 20 percent ad valorem | following a cost of - | on American selling | production investigation - | price[1] or United | under sec. 315 of Tariff - | States value.[2] | Act of 1922. - | | - June 18, 1930 |3½ cents per pound plus |Under par. 27 (b) of Tariff - | 20 percent ad valorem | Act of 1930. - | on American selling | - | price[3] or United | - | States value.[4] | - ------------------+------------------------+---------------------------- - - [1] As defined in subdivision (f) of section 402, title IV, act - of 1922. - - [2] As defined in subdivision (d) of section 402, title IV, act - of 1922. - - [3] As defined in subsection (g) of section 402, title IV, act of - 1930. - - [4] As defined in subsection (e) of section 402, title IV, act of - 1930. - -_Import statistics._—Imports for consumption are shown in tables 62 -and 63. Table 62 shows imports of phenol or carbolic acid and table 63 -imports of “all distillates of tars yielding below 190° C. an amount of -tar acids equal to or more than 5 percent.” Imports under the latter -classification prior to 1928 were probably chiefly phenol. Phenol imports -consist entirely of the natural product. - -TABLE 62.—_Phenol: United States imports for consumption, 1910-37_ - - -------+----------------------+---------+--------+----------+---------- - | | | | | Computed - Year | Rate of duty | Quantity| Value |Unit value|ad valorem - | | | | | rate - -------+----------------------+---------+--------+----------+---------- - | | _Pounds_| | | _Percent_ - 1910[1]|Free |4,507,693|$275,600| $0.061| - 1911[1]| do |4,371,014| 265,780| .061| - 1912[1]| do |5,686,704| 521,457| .092| - 1913[1]| do |8,345,631| 688,771| .083| - 1914[1]| do |8,393,216| 531,535| .063| - 1915[1]| do |3,106,445| 179,685| .058| - 1916[1]|([2]) |2,246,256| 154,841| .069| - 1917[1]|15 percent + 2½ cents | 265,519| 17,168| .065| 53.7 - | per pound | | | | - 1918 | do | 283,337| 62,497| .221| 26.3 - 1919 | do | 2,061| 264| .128| 34.5 - 1920 | do | 1,040| 244| .235| 25.8 - 1921 | do | 250| 142| .568| 19.4 - 1922 |([3]) |} 280,224| 30,414| .109| 38.0 - | |} 69,310| 16,102| .230| 85.1 - 1923 |55 percent + 7 cents | 126,618| 21,389| .169| 96.4 - | per pound [4] | | | | - 1924 |([5]) | 176,081| 46,786| .266| 81.4 - 1925 |40 percent + 7 cents | 256,126| 58,958| .230| 70.4 - | per pound [4] | | | | - 1926 | do | 218,437| 47,351| .217| 72.3 - 1927 |([6]) | 500| 100| .200| 75.0 - 1928 |20 percent + 3½ cents | 1,653| 298| .180| 39.4 - | per pound [4] | | | | - 1929 | do | 433,385| 44,226| .102| 54.3 - 1930 | do | 500| 115| .230| 39.4 - 1931 | do | 2,365| 639| .270| 33.0 - 1932 | do | None| | | - 1933 | do | 3,440| 641| .186| 38.8 - 1934 | do | None| | | - 1935 | do | 2,605| 211| .081| 63.0 - 1936 | do | 71,429| 8,302| .116| 50.1 - 1937[7]| do | 32,238| 3,767| .117| 50.0 - -------+----------------------+---------+--------+----------+--------- - - [1] Fiscal year. - - [2] 15 percent ad valorem and 2½ cents per pound effective Sept. - 9, 1916. - - [3] 55 percent ad valorem and 7 cents per pound, effective Sept. - 22, 1922. - - [4] Ad valorem based on American selling price or United States - value under acts of 1922 and 1930. - - [5] Ad valorem reduced to 40 percent effective Sept. 22, 1924. - - [6] Duty reduced to 20 percent ad valorem and 3½ cents per pound - effective Nov. 30, 1927. - - [7] Preliminary. - - Source: Foreign Commerce and Navigation of the United States. - -TABLE 63.—_All distillates of tar yielding below 190° C. an amount of -tar acids equal to or more than 5 percent: United States imports for -consumption, 1918-37_ - - ---------+----------------------+--------+------+----------+---------- - | | | | | Computed - Calendar | Rate of duty |Quantity| Value|Unit value|ad valorem - year | | | | | rate - ---------+----------------------+--------+------+----------+---------- - | |_Pounds_| | | _Percent_ - 1918 |15 percent + 2½ cents | 1,550|$2,008| $1.30| 16.93 - | per pound | | | | - 1919 | do | 3,170| 4,587| 1.45| 16.73 - 1920 | do | 85,474|36,041| .422| 20.93 - 1921 | do | 16,240|11,811| .727| 18.43 - 1922 |([1]) | 350,764|42,912| .122| 46.27 - 1923 |55 percent + 7 cents | 245,119|30,328| .124| 111.58 - | per pound[2] | | | | - 1924 |([3]) | 662,938|49,380| .074| 134.43 - 1925 |40 percent + 7 cents | 252,382|15,441| .061| 154.41 - | per pound[2] | | | | - 1926 | do | 1,102| 5,236| 4.75| 41.47 - 1927 |([4]) | 2| 16| 8.00| 40.88 - 1928-37 | | None| | | - ---------+----------------------+--------+------+----------+---------- - - [1] 55 percent ad valorem and 7 cents per pound, effective Sept. - 22, 1922. - - [2] Ad valorem based on American selling price or United States - value under acts of 1922 and 1930. - - [3] Ad valorem reduced to 40 percent, effective Sept. 22, 1924. - - [4] Duty reduced to 20 percent ad valorem and 3½ cents per pound, - effective Nov. 30, 1927. - - Source: Foreign Commerce and Navigation of the United States. - - -United States exports. - -Exports of phenol have not been separately shown in official statistics -since 1924. In that year they went chiefly to Panama, Japan, Cuba, and -Mexico. Table 64 shows exports from 1918 to 1924, inclusive, as furnished -by the Department of Commerce. - -TABLE 64.—_Phenol: United States exports, 1918-24_ - - ----+---------+----------+---------- - Year| Quantity| Value |Unit value - ----+---------+----------+---------- - | _Pounds_| | - 1918|6,477,841|$2,666,634| $0.412 - 1919|1,243,841| 363,744| .292 - 1920|2,151,475| 388,047| .180 - 1921| 249,658| 35,994| .144 - 1922| 223,146| 23,223| .104 - 1923| 232,830| 34,389| .148 - 1924| 51,364| 8,016| .156 - ----+---------+----------+---------- - - Source: Commerce and Navigation of the United States. - -Appreciable quantities of phenol have been exported in recent years to -Japan and China, and to Great Britain and other European countries. -Export statistics, collected by the U. S. Tariff Commission from the -several domestic producers, show the following quantities exported in -recent years. - -TABLE 65.—_Phenol: United States exports, 1934-36_ - - ----+---------+--------+---------- - Year| Quantity| Value |Unit value - ----+---------+--------+---------- - | _Pounds_| | - 1934|2,622,900|$329,269| $0.126 - 1935|2,921,835| 322,933| .111 - 1936|1,258,244| 148,501| .118 - ----+---------+--------+---------- - - Source: Data obtained by the U. S. Tariff Commission through - questionnaires. - -In 1934, the principal destinations in order of importance were China, -Italy, and Canada; in 1935 Germany, China, Japan, and Belgium; and in -1936 China, Belgium, and the Netherlands. - - -Competitive conditions. - -Before the World War our average annual consumption of phenol was 5 -million pounds, of which about 80 percent was imported from Great -Britain and Germany. These countries produced phenol in excess of their -consumption, and phenol was on the free list in the United States. - -In September 1916 phenol became dutiable. The demand was increasing -rapidly because of the use of phenol in the manufacture of picric acid, -an explosive. To meet the wartime demand at home and abroad large scale -production of synthetic phenol sprang up in the United States. But the -end of the war not only shut off the largest part of the demand but left -the producers with large stocks on hand. The price dropped sharply and -the production of synthetic phenol ceased. - -Since 1922 there has been a gradually increasing demand for phenol in the -United States, chiefly for use in the manufacture of synthetic resins, -and production has increased to meet this demand as shown in table 66. - -TABLE 66.—_Phenol: United States production, imports, exports, and -apparent consumption in specified years, 1918-37_ - - [In thousands of pounds] - ----+-------------+----------+----------+--------------- - Year|Production[1]|Imports[2]|Exports[3]| Apparent - | | | |consumption[4] - ----+-------------+----------+----------+--------------- - 1918| 106,794| 285| 6,478| ([5]) - 1919| 1,544| 5| 1,244| ([5]) - 1923| 3,311| 372| 233| 3,450 - 1925| 14,734| 919| ([6]) | ([7]) - 1926| 8,691| 220| ([6]) | ([7]) - 1927| 8,041| 1| ([6]) | ([7]) - 1928| 10,227| 2| ([6]) | ([7]) - 1929| 24,178| 433| ([6]) | ([7]) - 1930| 21,147| 1| ([6]) | ([7]) - 1931| 17,981| 2| ([6]) | ([7]) - 1932| 13,965| | ([6]) | ([7]) - 1933| 33,220| 3| ([6]) | ([7]) - 1934| 44,935| | 2,623| 42,312 - 1935| 43,419| 3| 2,922| 40,500 - 1936| 48,724| 71| 1,258| 47,537 - 1937| 65,690| 32| ([6]) | ([7]) - ----+-------------+----------+----------+--------------- - - [1] From table 59. - - [2] From tables 62 and 63. - - [3] From tables 64 and 65. - - [4] Production plus imports minus exports. - - [5] Not calculated because of importance of stocks on hand. - - [6] Not available. - - [7] Not available because of absence of export figures. Exports - probably negligible up to 1929; substantial in 1933. - -The manufacture of synthetic phenol was revived about 1923. Imports were -quite small as compared with production, especially after 1927. At first -this was probably due primarily to the protection given by the duty -which had been increased in 1922.[22] But with the increase in volume of -production in the United States the price decreased and since 1933 the -United States producers have enjoyed a substantial export business. It -may therefore be doubted that in recent years there would have been any -substantial imports even if phenol had been free of duty. - - -THE CRESOLS, XYLENOLS, AND CRESYLIC ACID - -Reference to table 56, page 109, will show that, as distillation of coal -tar proceeds and the temperature of distillation is increased, the phenol -fraction is followed in order by the three cresols and then by the six -xylenols. Each of these tar acids is a definite chemical compound with -definite physical properties. Consideration of them as raw materials -for synthetic resins is complicated by the fact that they are generally -used in mixtures and that the commercial term, cresylic acid, applied -to many of these mixtures has no definite relationship to the precise -chemical terminology. Yet since the term cresylic acid is so widely used -in commerce, since the tariff provides for imports under that name, and -since the statistics available are in part in terms of cresylic acid and -in part in terms of cresols and xylenols it is impossible to present the -complete picture on the basis of the correct chemical terminology. - - -Description and uses. - -_The cresols._—The cresols are isomeric tar acids obtained from coal -tar by fractional distillation. Their combined content averages about -1 percent of domestic coal tar. The total cresol content is divided in -about the following proportions: 40 percent metacresol, 35 percent -orthocresol, and 25 percent paracresol. The cresols are marketed in a -number of types and grades including mixtures of ortho, meta, and para; -mixtures of meta and para; separated ortho, meta, and para; and also in -mixtures with phenol and the xylenols. - -_Metacresol_ (chemically, 3-methyl phenol) is a colorless to yellow -liquid with a phenol-like odor. When pure, it melts at 11° C., boils -at 202.8° C., and has a specific gravity of 1.03. It is used in the -manufacture of synthetic resins, photographic developers, explosives, -disinfectant soaps, paint and varnish removers, to remove ink from -newsprint, to soften and reclaim rubber, and in intermediates for dyes -and perfume materials. - -_Orthocresol_ (chemically, 2-methyl phenol) is a colorless, crystalline -product with a phenol-like odor, melting at 30° C., boiling at 190.8° C., -and having a specific gravity of 1.04. It is used in the manufacture of -coumarin (flavor), antiseptics, disinfectants, and fumigants. It is not -used to any extent in synthetic resins. - -_Paracresol_ (chemically, 4-methyl phenol) is a colorless, crystalline -substance with a phenol-like odor, melting at 35° C., boiling at 201.8° -C., and having a specific gravity of 1.03. It is used in the manufacture -of intermediates, dyes, disinfectants, and fumigants, in medicine, and -in mixture with metacresol in synthetic resins. Domestic production -of synthetic paracresol was announced early in 1938 by Swann & Co., -Birmingham, Ala. - -_Metaparacresol_ is a combination of approximately 60 percent meta -and 40 percent para cresol obtained in the fractional distillation of -mixed cresols. The ortho isomer is distilled off, leaving a residue of -metaparacresol. It is widely used in the manufacture of synthetic resins. - -_Cresol._—The term cresol used without further qualification indicates -a mixture of the three isomers in substantially the same proportions -in which they are found in coal tar. The United States Pharmacopoeia -describes cresol, a mixture of isomeric cresols obtained from coal tar, -as a colorless or yellowish to brownish-yellow or a pinkish, highly -refractive liquid, becoming darker with age and on exposure to light. It -is widely used in synthetic resins, antiseptics and disinfectants, and in -medicine. - -_The xylenols._—Shortly after the original patents on Bakelite resins -expired extensive research was begun for raw materials that would give -different properties to the resultant resins. This work led to a study of -the high-boiling tar acids, and methods of recovery for some of them were -commercially developed. Among those obtained from coal tar are the six -isomeric xylenols, methylethyl phenol, and one of the trimethyl phenols -(see table 56). Coal tar contains about 0.2 percent xylenols and 0.5 -percent other high-boiling tar acids. - -The principal uses for these products have been in the preparation of -high-phenol coefficient disinfectants, and recently in the replacement -of phenol and cresols in synthetic resins. It was found, for example, -that 3: 5 xylenol reacts with formaldehyde faster than either metacresol -or phenol. Numerous patents have been granted on the use of these -high-boiling acids in the production of synthetic resins. - -The xylenols, when pure, are colorless, crystalline substances boiling -between 211° and 225° C. They are usually marketed in mixtures containing -from 50 to 80 percent xylenols and 20 to 50 percent cresols. There is -commercial production of at least one of the separated xylenols (3: 5). -An appreciable part of our imports of crude cresylic acid and of our -production of cresylic acid contains high percentages of the xylenols. - -_Other high-boiling tar acids._—The other high-boiling tar acids -are ortho ethylphenol, meta ethylphenol, para ethylphenol, methyl -ethylphenol, and the three isomeric trimethyl phenols. Several of these -have been isolated from coal tar. All of them, when pure, are crystalline -compounds with boiling points ranging between 206° and 235° C. There -has been little, if any, commercial production of this group up to this -time. They are known, however, to have very high phenol coefficients, a -property which would make them suitable for use in disinfectants. Little -is known as yet concerning their application in synthetic resins. - -_Cresylic acid._—Cresylic acid is a generic term now applied to mixtures -of tar acids in widely varying proportions. As defined in the literature -and as formerly used in commerce the term identified a mixture of -ortho, meta, and para cresols in the proportions in which they occur in -coal tar. This proportion is approximately 40 percent metacresol, 35 -percent orthocresol, and 25 percent paracresol. But in recent years the -designation cresylic acid has been applied to all sorts of mixtures of -tar acids boiling above 190° C. Practically every maker of synthetic -resins, antiseptics, and disinfectants has his own specifications for -cresylic acid; it may be any mixture in almost any proportions of the -three cresols, the six isomeric xylenols, and the higher boiling tar -acids. Imports of crude cresylic acid are understood to be largely -xylenol mixtures containing low percentages of the cresols. This loose -application of cresylic acid in recent years is due to the increased -commercial application of the high-boiling tar acids, especially the -xylenols. - -Under the Tariff Act of 1930 refined cresylic acid, that having a purity -of 75 percent or more, is dutiable under paragraph 27 at 3½ cents per -pound and 20 percent ad valorem based on American selling price or United -States value; while crude cresylic acid, that having a purity of less -than 75 percent, is free under paragraph 1651. The provision in paragraph -27 reads, “cresylic acid which on being subjected to distillation -yields in the portion distilling below two hundred and fifteen degrees -centigrade, a quantity of tar acids equal to or more than 75 per centum -of the original distillate.” Under this provision cresylic acid may -include an endless number of combinations of tar acids and may or may not -contain any of the isomeric cresols. Of the 17 or more tar acids known -to exist in coal tar (see table 56), only 8 have boiling points above -215° C. It would seem to be more accurate and more in line with present -day usage to have the tariff drop the designation cresylic acid in favor -of more definite terms based on composition, such as cresols and cresol -mixes, xylenol and xylenol mixes, etc. - -About 60 percent of our consumption of cresylic acid is in synthetic -resins and the remainder in the manufacture of insecticides, antiseptics, -disinfectants, and other coal-tar products, such as intermediates for -dyes, plasticizers for nitrocellulose, etc. - - -United States production. - -_The cresols._—There is large production of cresol, metaparacresol, and -orthocresol in the United States. Commercial production of paracresol was -reported for the first time in 1934, and of metacresol in 1935. - -Statistics of domestic production and sales are publishable only for the -year 1934 because of the small number of producers. The output in that -year is shown in table 67. Production has increased appreciably since -then. - -TABLE 67.—_Meta, ortho, and para cresols: United States production and -sales, 1934_ - - ----------------+------------+----------------------------------- - | | Sales - Type | Production +-----------+----------+------------ - | | Quantity | Value | Unit value - ----------------+------------+-----------+----------+------------ - | _Pounds_ | _Pounds_ | | - Cresol | 8,929,836 | 8,559,048 | $572,738 | $0.07 - Metaparacresol | 2,033,424 | 1,692,149 | 101,324 | .06 - Orthocresol | 835,016 | ([1]) | ([1]) | - Paracresol | ([1]) | ([1]) | ([1]) | - ----------------+------------+-----------+----------+------------ - - [1] Not publishable; figures would reveal operations of - individual firms. - - Source: Dyes and Other Synthetic Organic Chemicals in the United - States. U. S. Tariff Commission. - -The trend of domestic production of the several cresols is upward. In -1937 the output of all grades and types of cresols was 13,745,271 pounds -with sales of 13,251,345 pounds, valued at $1,071,965. The practice of -topping coal tar will greatly increase the output of the cresols as well -as of other tar acids and naphthalene. - -There are five domestic producers of cresol, three each of orthocresol -and metaparacresol, and two of metacresol and paracresol. All except one -of these makers recover natural phenol, cresylic acids, and other tar -acids. Refining plants are located at Pittsburgh, Pa., Philadelphia, -Pa., Indianapolis, Ind., and Follansbee, W. Va. Domestic production of -synthetic paracresol was first announced in 1938. - -_The xylenols._—There has been a large domestic production of mixed -xylenols in recent years. These mixtures, containing from 50 to 80 -percent xylenols, are marketed as cresylic acid. Statistics of domestic -production, and sales are therefore included in table 68. It is estimated -that the output of xylenols and xylenol mixtures in 1935 exceeded 750,000 -pounds and exceeded 1,250,000 pounds in 1937. At least one of the -separated xylenols (1: 3: 5) has been produced commercially in the United -States since 1935, but statistics of its production are not publishable. - -_Other high-boiling tar acids._—There was no reported domestic production -of the other high-boiling acids prior to 1935 and the data obtained for -that year are probably incomplete. Estimated output was 200,000 pounds in -1935, 250,000 pounds in 1936, and 300,000 pounds in 1937. These estimates -are based on production of mixtures of high-boiling acids. - -_Cresylic acid._—Domestic production and sales statistics for so-called -crude cresylic acid are not publishable. It is known, however, that -production of the crude is small compared with our output of refined -cresylic acid. It is usually more economical for the producer to prepare -the mixture of tar acids to the specifications of the purchaser, rather -than to leave part of the refining operations to be performed by the -latter. The fact that imports of cresylic acid are chiefly of crude is -largely due to the different tariff treatment of crude and refined. - -Domestic production of refined cresylic acid was confined to one or two -firms until 1928, when there were four makers. Statistics of production -and sales are not publishable for the years prior to 1929, though it may -be stated that the annual domestic output increased each year to supply -the increased demand. Table 68 shows production and sales from 1929 to -1934, inclusive. Data for later years are not publishable. - -TABLE 68.—_Refined cresylic acid: United States production and sales, -1929-37_ - - -----+------------+------------------------------------- - | | Sales - Year | Production +------------+------------+----------- - | | Quantity | Value | Unit value - -----+------------+------------+------------+----------- - | _Pounds_ | _Pounds_ | | _Per pound_ - 1929 | 14,601,534 | | | $0.10 - 1930 | 17,305,308 | 16,026,407 | $1,267,155 | .08 - 1931 | 10,994,000 | 10,305,000 | 652,000 | .06 - 1932 | 8,060,000 | 4,805,000 | 251,000 | .05 - 1933 | 13,813,941 | 11,975,441 | 626,496 | .05 - 1934 | 10,949,860 | 9,230,255 | 489,231 | .05 - 1935 | ([1]) | ([1]) | ([1]) | - 1936 | ([1]) | ([1]) | ([1]) | - 1937 | ([1]) | ([1]) | ([1]) | - -----+------------+------------+------------+----------- - - [1] Not publishable; figures would reveal operations of - individual firms. - - Source: Compiled from annual reports of the Tariff Commission on - dyes and other synthetic organic chemicals in the United States. - -As previously stated, the composition of cresylic acid has gradually been -changed from a mixture of the isomeric cresols to mixtures of cresols, -xylenols, and high-boiling tar acids. The cresols, formerly included -under cresylic acid statistics, are now shown separately. For this reason -the data in table 68 do not fully reflect the increased output of these -tar acids in recent years. Statistics for years prior to 1931 probably -include all of the tar acids except phenol, while those for subsequent -years do not include the separated cresols. In 1934 the production of -refined cresylic acid was 10,949,860 pounds, and in addition recovery -of the several cresols amounted to 11,798,276 pounds making a total of -22,748,136 pounds as compared with a total of 14,601,534 pounds in 1929 -and 17,305,308 pounds in 1930. - -During 1936 and the first part of 1937 a serious shortage of cresylic -acid existed in the domestic market owing to increased demand by -synthetic resin makers. The output in 1936 exceeded that in 1935 and -the production in 1937 was appreciably higher than in 1936. These -increases are due to the recovery of appreciable quantities at several -new distillation plants, the topping of large amounts of tar hitherto not -processed, and increased production by present recovery units. - -There are many grades of cresylic acid, most of which are prepared by -mixing or blending to individual specifications. Every large consumer -apparently has his own specifications. In addition to these special -mixtures there are the following standard blends: - -(1) Ninety-nine percent high-boiling, straw color. - -(2) Low-boiling, straw color. - -(3) Special resin grade, high-boiling. - -There are four domestic producers of cresylic acid with recovery and -refining units at Pittsburgh, Pa., Philadelphia, Pa., Indianapolis, -Ind., and Follansbee, W. Va. The last three mentioned are refining -plants operated in conjunction with a number of tar distillation units -widely scattered throughout the country. These units usually recover -crude tar-acid fractions in the distillation of tar and ship them to -these refining plants for separation and refining. All in this group are -purchasers of coal tar. The fourth producer operates a byproduct recovery -unit in connection with the company’s coke-oven operations. Part of the -coal tar produced is distilled to recover the several products, including -creosote oil, tar acids, and naphthalene, and the residual pitch is mixed -with the remaining undistilled tar and used for fuel. The shortage of tar -acids and naphthalene in 1936 caused this producer to begin the topping -of tar. - - -Foreign production. - -The cresols are produced in the United Kingdom, Germany, France, the -Netherlands, Belgium, and other European countries. Coal tar recovered -in the United Kingdom is principally gas tar, which is much richer in -tar acids than coke-oven tar, the principal source in the United States. -This is true because low temperature carbonization of coal yields greater -quantities of tar acids than are obtained in the tar from byproduct coke -ovens. Exports to the United States are chiefly mixtures which can enter -as crude cresylic acid. - -Production of cresol in Germany in recent years is shown in table 69. - -TABLE 69.—_Cresol: German production, in specified years_ - - -------+------------ - Year |1,000 pounds - -------+------------ - 1929 | 23,814 - 1931[1]| 15,435 - 1933 | 11,780 - 1934 | 10,476 - -------+------------ - - [1] Includes 2,866,000 pounds of separated ortho, meta, and para - cresols. - - Source: Consular reports. - -German imports and exports of cresol, in recent years, are shown in table -70. - -TABLE 70.—_Cresol: German imports and exports, in specified years_ - - ----+--------+-------- - Year|Imports |Exports - ----+--------+-------- - |_1,000 |_1,000 - | pounds_| pounds_ - 1929| 2,037 | 8,494 - 1930| 1,277 | 6,712 - 1931| 1,874 | 7,980 - 1932| 1,541 | 3,669 - 1933| 1,832 | 4,970 - 1934| 1,960 | 6,345 - 1935| 2,117 | 8,528 - 1936| 3,737 | 4,531 - 1937| 1,787 | 4,423 - ----+--------+-------- - - Source: Consular reports (1929-33) and official German statistics - (1934-37). - -The output of cresols in Czechoslovakia in recent years is shown in table -71. - -TABLE 71.—_Cresol: Production in Czechoslovakia, in specified years_ - - -----+---------- - Year | Quantity - -----+---------- - | _1,000 - | pounds_ - 1928 | 1,984 - 1931 | 1,477 - 1932 | 1,102 - 1933 | 1,599 - 1934 | 1,918 - -----+---------- - - Source: Consular reports. - -Cresylic acid is recovered in all the countries of Europe, Great Britain -and Germany being the leading producers and the principal exporters. -Increasing demand in these countries for synthetic resins made from -cresylic acid has greatly reduced the quantities available for export in -recent years. - -Great Britain is probably the world’s largest producer of cresylic acid, -and for many years has been the principal exporter to the United States. -This position is due to the large available supply of gas-house tar, and -to an ample market for all the products of tar distillation. In 1935 -the tar distilled in England, Wales, and Scotland totaled 360 million -gallons, of which 55 percent was gas-house tar. - -British production of all grades of cresylic acid averages between 35 -million and 42 million pounds annually, of which from 12 million to 20 -million pounds are exported. Many British producers market their tar -products through pools and associations. There is a cresylic acid pool, a -phenol pool, and at least two creosote oil export associations, a pitch -marketing association, and a benzol association. One of the principal -grades of cresylic acid produced in Great Britain is “American duty-free -specification.” - -Table 72 shows British exports of cresylic acid, by countries, in recent -years. - -TABLE 72.—_Cresylic acid: British exports, by countries, 1933-37_ - - -------------------+------+------+------+------+------ - Destination | 1933 | 1934 | 1935 | 1936 | 1937 - -------------------+------+------+------+------+------ - | Quantity (in thousands of pounds) - +------+------+------+------+------ - UNITED STATES | 3,616| 5,783| 6,116|11,296|([1]) - Chile | 1,381| 2,958| 2,814| 662|([1]) - France | 358| 87| 214| 189|([1]) - Japan | 632| 203| 685| 2,002|([1]) - All other countries| 5,464| 6,965| 7,333| 9,250|([1]) - +------+------+------+------+------ - Total |11,451|15,997|17,162|23,399|26,697 - +------+------+------+------------- - | Value (in thousands of dollars) - +------+------+------+------+------ - UNITED STATES | 147| 277| 255| 620|([1]) - Chile | 28| 89| 87| 31|([1]) - France | 21| 5| 20| 14|([1]) - Japan | 38| 20| 43| 118|([1]) - All other countries| 189| 307| 330| 537|([1]) - +------+------+------+------+------ - Total | 422| 698| 734| 1,321| 2,262 - -------------------+------+------+------+------+------ - - [1] Not available. - - Source: Official British statistics. - - -Imports into the United States. - -_Rates of duty._—Prior to September 8, 1916, the cresols were imported -free of duty. Since that date they have been subject to the tariff -treatment shown in table 73. - -TABLE 73.—_The cresols: Rates of duty upon United States imports, 1916-37_ - - ------------------+------------------------------------+----------------- - | Rate of duty | - Period +----------+-------------+-----------+ Authority - |Less than | 75 to 90 | 90 percent| - |75 percent| percent | or more | - | pure | pure | pure | - ------------------+----------+-------------+-----------+----------------- - To Sept. 8, 1916. |Free |Free |Free |Free under par. - | | | | 452, Tariff Act - | | | | of 1913, and - | | | | under previous - | | | | acts. - | | | | - Sept. 9, 1916, to | do | do |15 percent |Revenue Act of - Sept. 8, 1921. | | | ad | 1916. - | | | valorem | - | | | and 2½ | - | | | cents per| - | | | pound. | - | | | | - Sept. 9, 1921, to | do | do |15 percent |Emergency Tariff - Sept. 21, 1922. | | | ad | Act of 1921. - | | | valorem | From May 28, - | | | and 2 | 1921, to Sept. - | | | cents per| 21, 1922, - | | | pound. | imports - | | | | prohibited - | | | | except when - | | | | not obtainable - | | | | in sufficient - | | | | quantities or - | | | | on reasonable - | | | | terms as to - | | | | quality, price, - | | | | and terms of - | | | | delivery. - | | | | - Sept. 22, 1922, to| do |55 percent ad|55 percent |Free under par. - Sept. 21, 1924. | | valorem and| ad | 1549 and - | | 7 cents per| valorem | dutiable under - | | pound.[1] | and 7 | par. 27 of - | | | cents per| Tariff Act of - | | | pound.[1]| 1922. - | | | | - Sept. 22, 1924, to| do |40 percent ad|40 percent |Same; ad valorem - June 17, 1930. | | valorem and| ad | reduced to 40 - | | 7 cents per| valorem | percent under - | | pound.[1] | and 7 | provisions of - | | | cents per| the Tariff Act - | | | pound.[1]| of 1922. - | | | | - June 18, 1930, to | do | do |20 percent |Free under par. - date. | | | and 3½ | 1651 and - | | | cents per| dutiable under - | | | pound.[1]| par. 27 of the - | | | | Tariff Act of - | | | | 1930. - ------------------+----------+-------------+-----------+----------------- - - [1] Ad valorem based on American selling price or United States - value. - -Under the Tariff Act of 1930 metacresol, orthocresol, and paracresol as -such or in mixture, if less than 75 percent pure, would be imported free -under paragraph 1651.[23] If from 75 to 90 percent, they are dutiable -under paragraph 27 at 7 cents a pound and 40 percent based upon American -selling price.[24] And if 90 percent pure or more, they are dutiable -under paragraph 27 at 3½ cents per pound and 20 percent, based upon -American selling price.[25] - -The duties on cresylic acid in recent years are shown in table 74. Under -the Tariff Act of 1930, cresylic acid less than 75 percent pure is free -under paragraph 1651.[23] If more than 75 percent pure it is dutiable -under paragraph 27 (b) at 3½ cents per pound and 20 percent, based on -American selling price.[26] - -TABLE 74.—_Cresylic acid: Rates of duty upon United States imports, -1916-37_ - - ------------------+----------------------------+------------------------ - | Rate of duty | - +----------+-----------------+ - Period | Less than| | Authority - |75 percent| 75 percent pure | - | pure | or more | - ------------------+----------+-----------------+------------------------ - To Sept. 8, 1916. |Free |Free |Free under par. 452 of - | | | Tariff Act of 1913 - | | | and previous acts. - | | | - Sept. 9, 1916, to | do |15 percent ad |Revenue Act of 1916. - Sept. 8, 1921. | | valorem and | - | | 2½ cents per | - | | pound. | - | | | - Sept. 9, 1921, to | do |15 percent ad |Emergency Tariff Act of - Sept. 21, 1922. | | valorem and | 1921. From May 28, - | | 2 cents per | 1921, to Sept. 21, - | | pound. | 1922, imports - | | | prohibited except - | | | when not obtainable - | | | in sufficient - | | | quantities or on - | | | reasonable terms as - | | | to quality, price, - | | | and terms of delivery. - | | | - Sept. 22, 1922, to| do |55 percent ad |Free under par. 1549 - Sept. 21, 1924. | | valorem and | and dutiable under - | | 7 cents per | par. 27 of the Tariff - | | pound.[1] | Act of 1922. - | | | - Sept. 22, 1924, to| do |40 percent ad |Same; ad valorem - Aug. 18, 1927. | | valorem and | reduced to 40 percent - | | 7 cents per | under provisions of - | | pound.[1] | the Tariff Act of - | | | 1922. - | | | - Aug. 19, 1927, to| do |20 percent ad |Duty reduced by - June 17, 1930. | | valorem and | Presidential - | | 3½ cents per | proclamation. - | | pound.[1] | - | | | - June 18, 1930, to | do |20 percent ad |Free under par. 1651 and - date. | | valorem and | dutiable under par. 27 - | | 3½ cents per | of the Tariff Act of - | | pound.[1] | 1930. - ------------------+----------+-----------------+------------------------ - - [1] Ad valorem based on American selling price or United States - value. - -_Import statistics._—Imports of the separated and mixed cresols are -combined in official statistics. Table 75 shows imports of the cresols -“90 percent pure or more.” There have been no recorded imports of less -pure grades. - -Tables 76, 77, and 78 show, by principal sources, imports of metacresol, -orthocresol, and paracresol, as obtained from invoice analyses by the -United States Tariff Commission. The sum of the three tabulations does -not equal the total shown for all cresols in table 75. The difference -in 1934 of 38,744 pounds valued at $12,906 is accounted for by mixed -cresols. Undoubtedly the differences in other years may be similarly -accounted for. - -TABLE 75.—_Metacresol, orthocresol, and paracresol, 90 percent pure or -more: United States imports for consumption, 1920, and 1923-37_ - - -----------------+-------------------+--------+------+------+---------- - | | | | Unit | Computed - Calendar year | Rate of duty[1] |Quantity| Value| value|ad valorem - | | | | | rate - -----------------+-------------------+--------+------+------+---------- - | |_Pounds_| | | _Percent_ - | | | | | - 1920 |2½ cents per pound | 2,444|$2,230|$0.912| 17.7 - | + 15 percent | | | | - 1923 |7 cents per pound | 8,754| 5,410| .618| 66.3 - | + 55 percent | | | | - 1924 |} do | 15,326| 1,995| .130| 108.8 - |}7 cents per pound | 1,000| 663| .663| 50.6 - | + 40 percent | | | | - 1925 | do | 34,874| 5,741| .165| 82.5 - 1926 | do | 105,238|15,040| .143| 89.0 - 1927 | do | 174,094|35,054| .201| 74.8 - 1928 | do | 207,897|33,638| .162| 83.3 - 1929 | do | 227,974|32,098| .141| 89.8 - 1930: | | | | | - Jan. 1-June 17 | do | 131,134|14,973| .114| 101.3 - June 18-Dec. 31|3½ cents per pound | 71,183|11,762| .165| 41.2 - | + 20 percent | | | | - | +--------+------+------+---------- - Total, 1930 | | 202,317|26,735| .132| 74.9 - 1931 | do | 151,571|26,901| .177| 39.7 - 1932 | do | 83,848|18,530| .221| 35.8 - 1933 | do | 48,511|16,205| .334| 30.5 - 1934 | do | 124,598|34,361| .276| 32.7 - 1935 | do | 65,468|18,290| .279| 32.5 - 1936 | do | 83,273|27,686| .332| 30.5 - 1937[2] | do | 167,278|36,227| .217| 36.2 - -----------------+-------------------+--------+------+------+---------- - - [1] Ad valorem rate based on American selling price or United - States value under the Tariff Acts of 1922 and 1930. - - [2] Preliminary. - - Source: Foreign Commerce and Navigation of the United States. - -TABLE 76.—_Metacresol: United States imports for consumption by principal -sources, in specified years_ - - ----------------------------+-----+------+------+------+------+--------- - Imported from | 1929 | 1931| 1933 | 1934 | 1935 | 1936 | 1937[1] - -------------------+--------+-----+------+------+------+------+--------- - | Quantity (pounds) - +--------+-----+------+------+------+------+--------- - United Kingdom | 113,057| 916|15,769|21,054| 6,500| 6,800| 40,878 - Germany | 3,235| | 4,432| | | | - All other countries|[2]1,106| | | | | |[3]11,025 - +--------+-----+------+------+------+------+--------- - Total | 117,398| 916|20,201|21,054| 6,500| 6,800| 51,903 - +--------+-----+------+------+------+------+--------- - | Invoice value - +--------+-----+------+------+------+------+--------- - United Kingdom | ([4]) |([4])|$5,264|$8,400|$2,645|$2,589| $6,951 - Germany | ([4]) |([4])| 1,548| | | | - All other countries| ([4]) |([4])| | | | | [3]4,200 - +--------+-----+------+------+------+------+--------- - Total | | | 6,812| 8,400| 2,645| 2,589| 11,151 - +--------+-----+------+------+------+------+--------- - | Invoice unit value - +--------+-----+------+------+------+------+--------- - United Kingdom | ([4]) |([4])|$0.334|$0.399|$0.407|$0.380| $0.170 - Germany | ([4]) |([4])| .349| | | | - All other countries| ([4]) |([4])| | | | | .381 - +--------+-----+------+------+------+------+--------- - Average | | | .337| .399| .407| .380| .215 - +--------+-----+------+------+------+------+--------- - | Percent of total quantity - +--------+-----+------+------+------+------+--------- - United Kingdom | 96.30|100.0| 78.06| 100.0| 100.0| 100.0| 78.76 - Germany | 2.76| | 21.94| | | | - All other countries| 2.94| | | | | | [3]21.24 - +--------+-----+------+------+------+------+--------- - Total | 100.00|100.0|100.00| 100.0| 100.0| 100.0| 100.00 - -------------------+--------+-----+------+------+------+------+--------- - - [1] Preliminary. - - [2] Netherlands. - - [3] Switzerland. - - [4] Not available. - - Source: Invoice analyses, compiled by U. S. Tariff Commission. - -TABLE 77.—_Orthocresol: United States imports for consumption, by -principal sources, in specified years_ - - -------------------+-------+------+------+------+------+------+------- - Imported from— | 1929 | 1931 | 1933 | 1934 | 1935 | 1936 |1937[1] - -------------------+-------+------+------+------+------+------+------- - | Quantity (pounds) - +-------+------+------+------+------+------+------- - United Kingdom |105,790|79,198|19,548|25,855|29,120|33,816|112,108 - Germany | 82,859| 5,914| | 10| 10| | - France | | | | | | 4,480| - All other countries| 30,600| | | | | | - +-------+------+------+------+------+------+------- - Total |219,249|85,112|19,548|25,865|29,130|38,296|112,108 - +-------+------+------+------+------+------+------- - | Invoice value - +-------+------+------+------+------+------+------- - United Kingdom |([2]) |([2]) |$1,591|$2,707|$2,529|$3,178|$14,940 - Germany |([2]) |([2]) | | 4| 4| | - France | | | | | | 336| - +-------+------+------+------+------+------+------- - Total | | | 1,591| 2,711| 2,533| 3,514| 14,940 - +-------+------+------+------+------+------+------- - | Invoice unit value - +-------+------+------+------+------+------+------- - United Kingdom |([2]) |([2]) |$0.081|$0.105|$0.087|$0.094| $0.133 - Germany |([2]) |([2]) | | .400| .400| | - France | | | | | | .075| - +-------+------+------+------+------+------+------- - Average | | | .081| .105| .087| .092| .133 - +-------+------+------+------+------+------+------- - | Percent of total quantity - +-------+------+------+------+------+------+------- - United Kingdom | 48.25| 93.05| 100.0| 99.96| 99.97| 88.30| 100.00 - Germany | 37.79| 6.95| | .04| .03| | - France | | | | | | 11.70| - All other countries| 13.96| | | | | | - +-------+------+------+------+------+------+------- - Total | 100.00|100.00| 100.0|100.00|100.00|100.00| 100.00 - -------------------+-------+------+------+------+------+------+------- - - [1] Preliminary. - - [2] Not available. - - Source: Invoice analyses, compiled by U. S. Tariff Commission. - -TABLE 78.—_Paracresol: United States imports for consumption, by -principal sources, in specified years_ - - ---------------+-----+------+------+------+------+-------+------- - Imported from— | 1929| 1931 | 1933 | 1934 | 1935 | 1936 |1937[1] - ---------------+-----+------+------+------+------+-------+------- - | Quantity (pounds) - +-----+------+------+------+------+-------+------- - United Kingdom |2,587| 458| 6,972|16,889|16,625| 32,666| 14,338 - Netherlands | |11,243| | | | | - Germany | | | | 8,818|11,023| 6,076| - France | | | |13,228| 5| 6| 4 - +-----+------+------+------+------+-------+------- - Total |2,587|11,701| 6,972|38,935|27,653| 38,748| 14,342 - +-----+------+------+------+------+-------+------- - | Invoice value - +-----+------+------+------+------+-------+------- - United Kingdom |([2])|([2]) |$2,652|$4,797|$4,485|$10,739| $5,415 - Netherlands |([2])|([2]) | | | | | - Germany |([2])|([2]) | | 1,921| 3,090| 3,079| - France |([2])|([2]) | | 3,626| 7| 7| 3 - +-----+------+------+------+------+-------+------- - Total | | | 2,652|10,344| 7,582| 13,825| 5,418 - +-----+------+------+------+------+-------+------- - | Invoice unit value - +-----+------+------+------+------+-------+------- - United Kingdom |([2])|([2]) |$0.380|$0.284|$0.270| $0.329| $0.378 - Netherlands |([2])|([2]) | | | | | - Germany |([2])|([2]) | | .218| .280| .506| - France |([2])|([2]) | | .274| 1.400| 1.167| .750 - +-----+------+------+------+------+-------+------- - Average | | | .380| .266| .274| .357| .378 - +-----+------+------+------+------+-------+------- - | Percent of total quantity - +-----+------+------+------+------+-------+------- - United Kingdom |100.0| 3.92| 100.0| 43.38| 60.12| 84.30| 99.97 - Netherlands | | 96.08| | | | | - Germany | | | | 22.65| 39.86| 15.68| - France | | | | 33.97| .02| .02| .03 - +-----+------+------+------+------+-------+------- - Total |100.0|100.00| 100.0|100.00|100.00| 100.00| 100.00 - ---------------+-----+------+------+------+------+-------+------- - - [1] Preliminary. - - [2] Not available. - - Source: Invoice analyses, compiled by U. S. Tariff Commission. - -The processes for recovery of the cresols (fractional distillation) -usually yield products more than 75 percent pure and most of the -consumers of mixed or prepared cresols require products of high purity. -This explains why there are no imports less than 75 percent pure, -notwithstanding that they are duty-free under paragraph 1651. - -Under the act of 1930 cresols of 90 percent or greater purity are -assessed for duty at 20 percent ad valorem and 3½ cents per pound while -cresols 75.1 to 89.9 percent pure are assessed for duty at 40 percent ad -valorem and 7 cents per pound. Naturally, since the duty on imports below -90 percent pure is double that on imports over 90 percent pure there are -no imports of the former. - -Imports of crude cresylic acid are shown in table 79 and those of refined -cresylic acid in table 80. Imports by principal sources are shown in -tables 81 and 82, for crude and refined, respectively. - -TABLE 79.—_Crude cresylic acid: United States imports for consumption, -1924-37_ - - -------+-----------+---------+------- - Year |Quantity[1]| Value | Unit - | | | value - -------+-----------+---------+------- - | _Pounds_ | | - 1924 | 2,327,528| $157,643|$0.068 - 1925 | 2,163,557| 122,742| .057 - 1926 | 5,702,740| 331,550| .058 - 1927 | 9,136,516| 567,802| .062 - 1928 | 10,687,109| 678,177| .063 - 1929 | 17,856,765| 952,110| .053 - 1930 | 9,009,674| 501,418| .056 - 1931 | 4,937,078| 244,631| .050 - 1932 | 4,077,700| 164,379| .040 - 1933 | 5,523,733| 178,824| .032 - 1934 | 7,163,511| 284,051| .040 - 1935 | 6,849,113| 265,485| .039 - 1936 | 13,476,427| 722,575| .054 - 1937[2]| 16,360,213|1,219,268| .075 - -------+-----------+---------+------- - - [1] Conversion factor—8.5 pounds to gallon. - - [2] Preliminary. - - Source: Foreign Commerce and Navigation of the United States. - -TABLE 80.—_Refined cresylic acid: United States imports for consumption, -in specified years, 1919-37_ - - ------------------+---------------+------------+-------+------+---------- - | | | | Unit | Computed - Calendar year | Rate of duty | Quantity | Value | value|ad valorem - | | | | | rate - ------------------+---------------+------------+-------+------+---------- - | | _Pounds_ | | | _Percent_ - 1919 |2½ cents per | 2,061| $264|$0.128| 34.5 - | pound plus | | | | - | 15 percent. | | | | - 1920 | do. | 1,040| 244| .235| 25.7 - 1923 |7 cents per | 2,815| 257| .091| 131.7 - | pound plus | | | | - | 55 percent.[1]| | | | - 1924: | +============+=======+======+========== - Jan. 1-Sept. 21 | do.[1] | 62,869| 15,169| .241| 84.0 - Sept. 22-Dec. 31|7 cents per | 378,777| 29,066| .077| 131.2 - | pound plus | | | | - | 40 percent.[1]| | | | - | +------------+-------+------+---------- - Total | | 441,646| 44,235| | - 1925 | do.[1] | 98,672| 23,618| .239| 69.2 - 1926 | do.[1] | 25,932| 4,748| .183| 78.2 - 1927: | +============+=======+======+========== - Jan. 1-Aug. 18 | do.[1] | 1,322| 978| .740| 49.5 - Aug. 19-Dec. 31 |3½ cents per | 610,488| 37,896| .062| 76.4 - | pound plus | | | | - | 20 percent.[1]| | | | - | +------------+-------+------+---------- - Total | | 611,810| 38,874| | - 1928 | do.[1] | 976,180| 70,513| .072| 68.5 - 1929 | do.[1] |[2]2,343,529|183,324| .078| 64.7 - 1930 |3½ cents per | 1,275,872| 96,047| .075| 66.5 - | pound plus | | | | - | 20 percent.[1]| | | | - 1931 | do.[1] | [3]707,105| 42,156| .060| 78.7 - 1932 | do.[1] | [4]641,899| 37,326| .058| 80.2 - 1933 | do.[1] | 121,634| 9,164| .075| 66.5 - 1934 | do.[1] | 23,964| 1,497| .062| 76.0 - 1935 | do.[1] | 16,602| 1,128| .068| 71.5 - 1936 | do.[1] | 512| 40| .078| 64.8 - 1937[5] | do.[1] | 46,479| 5,122| .110| 51.8 - ------------------+---------------+------------+-------+------+---------- - - [1] Based on American selling price or United States value. - - [2] Drawback paid on 44 percent. - - [3] Drawback paid on 80 percent. - - [4] Drawback paid on 105,285 pounds. - - [5] Preliminary. - - Source: Foreign Commerce and Navigation of the United States. - -TABLE 81.—_Crude cresylic acid: United States imports for consumption, -from principal sources, in specified years, 1929-37_ - - -------------------+----------+---------+---------+--------- - Imported from— | 1929 | 1931 | 1933 | 1934 - -------------------+----------+---------+---------+--------- - | Quantity (pounds) - +----------+---------+---------+--------- - United Kingdom |13,981,259|3,809,293|5,060,925|6,927,865 - Germany | 3,874,400|1,073,491| 357,034| 217,965 - Netherlands | 1,106| 54,294| 22,066| - All other countries| | |[2]83,708| 17,681 - +----------+---------+---------+--------- - Total |17,856,765|4,937,078|5,523,733|7,163,511 - +----------+---------+---------+--------- - | Value - +----------+---------+---------+--------- - United Kingdom | $739,385| $190,333| $165,986| $276,989 - Germany | 212,652| 51,643| 8,666| 6,263 - Netherlands | 73| 2,655| 551| - All other countries| | | [2]3,621| 799 - +----------+---------+---------+--------- - Total | 952,110| 244,631| 178,824| 284,051 - +----------+---------+---------+--------- - | Unit value - +----------+---------+---------+--------- - United Kingdom | $0.0529| $0.0500| $0.0328| $0.0400 - Germany | .0549| .0481| .0243| .0287 - Netherlands | .0660| .0489| .0250| - All other countries| | | .0432| .0452 - +----------+---------+---------+--------- - Average | .0533| .0495| .0324| .0396 - +----------+---------+---------+--------- - | Percent of total quantity - +----------+---------+---------+--------- - United Kingdom | 78.3| 77.2| 91.6| 96.7 - Germany | 21.7| 21.7| 6.5| 3.0 - Netherlands | | 1.1| .4| - All other countries| | | 1.5| .3 - +----------+---------+---------+--------- - Total | 100.0| 100.0| 100.0| 100.0 - -------------------+----------+---------+---------+--------- - - -------------------+---------+----------+---------- - Imported from— | 1935 | 1936 | 1937[1] - -------------------+---------+----------+---------- - | Quantity (pounds) - +---------+----------+---------- - United Kingdom |6,753,003|12,344,924|12,704,108 - Germany | 95,727| 626,833| 2,499,391 - Netherlands | | 17,468| - All other countries| 383|[3]487,202| 1,156,714 - +---------+----------+---------- - Total |6,849,113|13,476,427|16,360,213 - +---------+----------+---------- - | Value - +---------+----------+---------- - United Kingdom | $262,137| $661,781| $954,953 - Germany | 3,325| 33,068| 184,887 - Netherlands | | 1,190| - All other countries| 23| [3]26,536| 79,428 - +---------+----------+---------- - Total | 265,485| 722,575| 1,219,268 - +---------+----------+---------- - | Unit value - +---------+----------+---------- - United Kingdom | $0.0388| $0.0536| $0.0752 - Germany | .0347| .0528| .0740 - Netherlands | | .0681| - All other countries| .0602| .0545| .0687 - +---------+----------+---------- - Average | .0388| .0536| .0745 - +---------+----------+---------- - | Percent of total quantity - +---------+----------+---------- - United Kingdom | 98.6| 91.60| 77.65 - Germany | 1.4| 4.65| 15.28 - Netherlands | | .13| - All other countries| ([4]) | 3.62| 7.07 - +---------+----------+---------- - Total | 100.0| 100.00| 100.00 - -------------------+---------+----------+---------- - - [1] Preliminary. - - [2] Canada. - - [3] Canada and France. - - [4] Less than one-tenth of 1 percent. - - Source: Compiled from official statistics of the United States - Department of Commerce. - -TABLE 82.—_Refined cresylic acid: United States imports for consumption, -from principal sources, in specified years, 1929-37_ - - -------------------+---------+-------+-------+------- - Imported from— | 1929 | 1931 | 1932 | 1933 - -------------------+---------+-------+-------+------- - | Quantity (pounds) - +---------+-------+-------+------- - Great Britain |1,855,844|604,404|456,783|121,634 - Germany | 212,918|102,701|185,028| - All other countries| 274,767| | 88| 500 - +---------+-------+-------+------- - Total |2,343,529|707,105|641,899|121,634 - +---------+-------+-------+------- - | Value - +---------+-------+-------+------- - Great Britain | $144,630|$35,041|$24,607| $9,164 - Germany | 14,699| 7,115| 12,714| - All other countries| 23,995| | 5| - +---------+-------+-------+------- - Total | 183,324| 42,156| 37,326| 9,164 - +---------+-------+-------+------- - | Unit value - +---------+-------+-------+------- - Great Britain | $0.078| $0.058| $0.054| $0.075 - Germany | .069| .069| .069| - All other countries| .087| | .057| - +---------+-------+-------+------- - Average | 0.78| .060| .058| .075 - -------------------+---------+-------+-------+------- - - -------------------+------+------+------+------- - Imported from— | 1934 | 1935 | 1936 |1937[1] - -------------------+------+------+------+------- - | Quantity (pounds) - +------+------+------+------- - Great Britain |23,464|16,602| | 46,379 - Germany | | | 512| - All other countries| | | | 100 - +------+------+------+------- - Total |23,964|16,602| 512| 46,479 - +------+------+------+------- - | Value - +------+------+------+------- - Great Britain |$1,412|$1,128| | $5,101 - Germany | | | $40| - All other countries| 85| | | 21 - +------+------+------+------- - Total | 1,497| 1,128| 40| 5,122 - +------+------+------+------- - | Unit value - +------+------+------+------- - Great Britain |$0.060|$0.068| | $0.110 - Germany | | |$0.078| - All other countries| .170| | | .210 - +------+------+------+------- - Average | .062| .068| .078| .110 - -------------------+------+------+------+------- - - [1] Preliminary. - - Source: Foreign Commerce and Navigation of the United States. - -In 1931 practically all imports of refined cresylic acid were from the -United Kingdom and consigned to one importer in New York. In 1932 about -73 percent of the total dutiable imports were consigned to the same -firm. From these data and from a conference with representatives of the -importer it would appear that the imports were not cresylic acid in its -original meaning (a mixture of cresols in their natural proportions), nor -in the broadened commercial meaning (including with the cresols, xylenols -and higher boiling tar acids), but were chiefly a product consisting -largely of a single cresol separated from its two isomers. Treasury -Decision 46146, effective March 11, 1933, closed the classification of -refined cresylic acid to products of this type and imports thereafter -under this head have been much smaller. After 1927 substantial amounts of -the imports were reexported with benefit of drawback. - -The imports of crude cresylic acid are also not of the type which the -domestic producer would sell by that name. Far from being a straight run -mixture of the cresol and higher boiling tar acids, they are usually -a mixture of fractions which have been separated, and then chosen and -combined so that they will meet both the tariff requirement (i. e., -less than 75 percent of the total product will distill over at 215° C.) -and the specifications of the purchasers. Customer’s specifications are -so drawn that the product will fill his special needs or can easily be -broken down by fractional distillation in this country into elements, one -or more of which will be so usable. Thus although imported crude cresylic -acid must keep within the limitations set by the tariff it approaches -as nearly as possible the type of cresylic acid which, if produced in -this country, would be termed refined, since it was produced to meet the -specifications of the consumer. - - -United States exports. - -Exports of the cresols and of cresylic acid are not shown in official -statistics and exports of these products as such are probably negligible, -but there are appreciable exports of antiseptics, insecticides, and -disinfectants in which they are incorporated, as well as of products or -parts of products molded of resins made from cresylic acid. - - -Competitive conditions. - -British coal tar is principally of gas-house origin and contains a higher -percentage of tar acids (cresylic acid and phenol) than coke-oven tar, -the principal kind recovered in the United States. The recovery of these -tar acids from either kind of tar is usually not practicable, unless the -distiller can dispose of the major products, creosote oil and pitch. -British distillers have in the past ordinarily had a market for all -their products; exporting large quantities of creosote oil to the United -States, pitch to continental Europe, and tar acids and naphthalene to -the United States, Germany, and other countries. Domestic distillers -have sold cresylic acid, creosote oil, naphthalene, etc., in local -markets in competition with duty-free imports from the United Kingdom, -the Netherlands, Belgium, and Germany, but have found it difficult to -dispose of pitch. The domestic production of coal tar ordinarily exceeded -600 million gallons, approximately one-half of which has been burned as -fuel. Since the profit in distilling depends upon the markets for all -of the joint products of the distillation, the large amount remaining -undistilled can be understood. - -The domestic production of cresylic acid may be expected to increase -substantially, for several reasons: (1) The principal foreign producing -countries have decreased exports because of increased demand for some of -the coal-tar distillation products at home; (2) increased world prices; -and (3) the development of topping, which allows the production of tar -acids and naphthalene from coal tar without complete distillation. - -Imports of refined cresylic acid are unimportant because the duty on the -refined is high relative to the duty-free condition of the crude. Most of -the imports of refined are either reexported or used in the manufacture -of one proprietary antiseptic. The principal domestic market for cresylic -acid is as a raw material for synthetic resins, and most of the domestic -refined and most of the duty-free imported crude is now consumed by -this industry. It may therefore be said that practically all imports of -cresylic acid are duty-free and that, while they are sometimes refined by -the consumer, they compete directly with domestic production of refined -grades. - -Phenol, already discussed, is closely related to cresylic acid—in -chemical composition, in production by distillation from coal tar, and -in use as a raw material for synthetic resins. To a considerable extent -the proportions of phenol and cresylic acid used in the manufacture of -tar-acid resins can be altered to take advantage of the changing price -differential between the two. - -All of the separated or mixed cresols are produced in commercial -quantities in this country. Consumption in the United States, especially -of types and grades used in synthetic resins, has increased appreciably -in recent years, and is supplied chiefly by domestic production. A -comparison of the quantity and value of domestic production and of -imports in 1934 is shown in table 83. - -TABLE 83.—_The cresols: Comparison of production and imports, 1934_ - - ---------------+------------------------------+-------------------------- - | Production | Imports - Product +----------+--------+----------+--------+------+---------- - | Quantity | Value |Unit value|Quantity| Value|Unit value - ---------------+----------+--------+----------+--------+------+---------- - | _Pounds_ | | |_Pounds_| | - Metacresol | ([1]) | ([1]) | | 21,054|$8,400| $0.399 - Paracresol | ([2]) | ([2]) | $0.350| 38,935|10,344| .266 - Metaparacresol | 2,033,424|$122,005| .060| ([1]) | ([1])| - Orthocresol | 835,016| 66,801| .080| 25,865| 2,711| .105 - Orthometapara | | | | | | - cresol | 8,929,836| 625,088| .070| 38,744|12,906| .333 - +----------+--------+----------+--------+------+---------- - Total |11,798,276| 813,894| | 124,598|34,361| - ---------------+----------+--------+----------+--------+------+---------- - - [1] None, production reported for first time in 1935. - - [2] Not publishable. - - Sources: Production, Dyes and Other Synthetic Organic Chemicals - in the United States; imports, invoice analyses, U. S. Tariff - Commission. - - -SYNTHETIC TAR ACIDS OTHER THAN PHENOL - -Certain synthetic tar acids other than synthetic phenol are used -commercially in the manufacture of synthetic resins in the United States. -Among these are para tertiary amyl phenol, para tertiary butyl phenol, -ortho phenyl phenol, para phenyl phenol, and resorcinal. - - -Para tertiary amyl phenol. - -Para tertiary amyl phenol is made by reacting amylene with phenol in -the presence of sulphuric acid as a catalyst. At ordinary temperatures -it is a solid, melting at about 88° C. and boiling between 250°-265° C. -Its use is of increasing importance as a component in tar-acid resins, -especially in oil-soluble varnish resins. Owing to its phenol coefficient -of approximately 60, it is also used as a germicide, fumigant, and -insecticide. Commercial production was reported for the first time -in 1933. Since then the output has increased appreciably each year, -accompanied by material reductions in sales prices. - -According to United States Patent No. 1,800,295, dated April 14, 1931, a -resin fast to light and soluble in oils is obtained by heating 82 parts -of p-tertiary amyl phenol with 90 parts of formaldehyde, in the presence -of sodium hydroxide. This substituted phenol resin passes slowly into the -infusible state, thus permitting better control of the reaction. - - -Para tertiary butyl phenol. - -Para tertiary butyl phenol is a white solid with an aromatic odor, -melting at approximately 100° C. It is a new commercial product and is -used in resins for paints and varnishes. It is the most important resin -material in this group. - - -Phenyl phenols. - -Both ortho and para phenyl phenol are commercially produced and are used -to some extent in resins to replace phenol. The ortho isomer is a white -solid boiling at 284° C. and melting at about 56° C. It is used chiefly -as a germicide, though small quantities are used in resins. - -Para phenyl phenol is a white solid melting at about 165° C. and boiling -at 322° C. Commercial production was reported for the first time in -1933. The output has increased each year since and the selling price has -gradually declined. - - -Resorcinol. - -Resorcinol, usually obtained by fusing meta benzene disulphonic acid with -caustic soda, is a colorless, crystalline substance with a peculiar odor. -It melts at 119° C. and boils at 276° C. It is used in medicine, in the -manufacture of intermediates and dyes, and to some extent in synthetic -resins. Resorcinol condenses with formaldehyde at such a rapid rate -that some means must be applied to slow up the reaction. It is used to -increase the rate of condensation of tar-acid resins and to reduce the -danger of sticking or undercure. - -Domestic production of resorcinol has decreased in recent years. Its -relatively high cost is probably an important factor in limiting its use -in synthetic resins. - - -FORMALDEHYDE - - -Description and uses. - -At ordinary temperature and pressure formaldehyde is a gas. It enters -commerce as formalin, an aqueous solution containing 40 percent -formaldehyde by volume (37 percent by weight) and from 6 to 14 percent -methyl alcohol. It is generally made by the oxidation of methyl alcohol. -Commercial formalin contains polymers which tend to precipitate in water -solution; these are kept in solution by allowing from 6 to 14 percent -methyl alcohol to remain in the solution. - -The principal use of formaldehyde is in the manufacture of synthetic -resins. Other uses are (in the order of their importance): In the -manufacture of synthetic indigo; in the manufacture of hydrosulphite; as -a disinfectant, deodorant, and preservative; as a fungicide; in embalming -fluids; in tanning leather; and in the manufacture of coated paper and -wallpaper. - - -United States production. - -The domestic output of formaldehyde has increased with the increased -demand by resin makers. Production and sales in 1937 were more than -double those in 1930. There are three domestic makers, two of which -produce methyl alcohol, the raw material. Their plants are located in New -Jersey and Oklahoma. - -Statistics of production and sales are shown in table 84. - -TABLE 84.—_Formaldehyde: United States production and sales, in specified -years_ - - -------+----------+---------------------------- - |Production| Sales - Year +----------+--------+----------+-------- - | Quantity |Quantity| Value | Value - | | | |per lb. - -------+----------+--------+----------+-------- - | _1,000 |_1,000 | | - | pounds_ |pounds_ | | - 1914 | ([1]) | 8,426| $655,174| $0.078 - 1919 | 25,007| 19,664| 3,928,322| .200 - 1921 | 9,657| 6,056| 651,681| .108 - 1922 | 23,958| 16,140| 1,676,401| .104 - 1923 | 24,081| 18,855| 2,474,506| .131 - 1924 | 26,155| 20,542| 1,971,053| .096 - 1925 | 31,456| 23,392| 1,895,913| .081 - 1926 | 31,953| 22,552| 2,050,967| .091 - 1927 | 29,920| 24,597| 2,256,534| .092 - 1928 | 38,718| 27,934| 2,491,615| .089 - 1929 | 51,786| ([2]) | ([2]) | - 1930 | 40,763| ([2]) | ([2]) | - 1931 | ([1]) | ([1]) | ([1]) | - 1932 | ([1]) | ([1]) | ([1]) | - 1933 | 52,236| 46,424| 2,122,925| .046 - 1934-37| ([2]) | ([2]) | ([2]) | - -------+----------+--------+----------+-------- - - [1] Not available. - - [2] Not publishable; figures would disclose operations of - individual firms. - - Source: Compiled from annual reports of the Tariff Commission on - dyes and other synthetic organic chemicals in the United States. - - -Production in other countries. - -Formaldehyde is produced in England, Germany, France, Czechoslovakia, -Italy, Sweden, the Soviet Union, Japan, and Canada. Production data are -not available but Germany and England are probably the leading foreign -producers. Estimated productive capacity in the Soviet Union is given -as 10 million pounds annually; in Japan 6.5 million pounds; in France 4 -million pounds; and in Italy 3 million pounds. - - -United States imports and exports. - -Imports of formaldehyde have been negligible since 1920 when 428,444 -pounds, valued at $210,191, were imported. There were no imports from -1928 until 1935, when 375 pounds valued at $72 were imported from Canada. -In 1936 imports amounted to 20 pounds, valued at $14, from Switzerland. - -The United States exports about 5 percent of its production of -formaldehyde. Canada is the principal destination of exports, and -prior to 1934 Japan was an important market. Table 85 shows exports of -formaldehyde to principal markets, in recent years. - -TABLE 85.—_Formaldehyde: United States exports to principal markets, in -specified years, 1929-37_ - - -------------------+---------+---------+---------+--------- - Exported to— | 1929 | 1931 | 1933 | 1934 - -------------------+---------+---------+---------+--------- - | Quantity (pounds) - +---------+---------+---------+--------- - Canada | 19,321| 716,132|1,095,847|1,236,103 - Japan |1,464,763| 622,407| 729,875| 11,250 - Netherlands Indies | 626,689| 650,875| | 344,725 - United Kingdom | 303| 345,896| 305| - China | 29,030| 229,760| 215,050| 572,700 - All other countries| 448,063| 339,777| 332,101| 433,068 - +---------+---------+---------+--------- - Total |2,588,169|2,904,847|2,373,178|2,597,846 - +---------+---------+---------+--------- - | Value - +---------+---------+---------+--------- - Canada | $4,405| $36,471| $46,611| $58,348 - Japan | 124,411| 33,395| 43,254| 562 - Netherlands Indies | 42,807| 38,462| | 15,536 - United Kingdom | 510| 18,629| 192| - China | 3,354| 13,019| 11,998| 27,407 - All other countries| 49,742| 22,709| 18,966| 23,444 - +---------+---------+---------+--------- - Total | 225,229| 162,685| 121,021| 125,297 - +---------+---------+---------+--------- - | Unit value - +---------+---------+---------+--------- - Canada | $0.228| $0.051| $0.043| $0.047 - Japan | .085| .054| .059| .050 - Netherlands Indies | .068| .059| | .045 - United Kingdom | 1.683| .054| .630| - China | .116| .057| .056| .048 - All other countries| .111| .067| .057| .054 - +---------+---------+---------+--------- - Average | .087| .056| .051| .048 - +---------+---------+---------+--------- - | Percent of total quantity - +---------+---------+---------+--------- - Canada | 0.8| 24.7| 46.2| 47.6 - Japan | 56.6| 21.4| 30.7| .4 - Netherlands Indies | 24.2| 22.4| | 13.3 - United Kingdom | | 11.9| | - China | 1.1| 7.9| 9.1| 22.0 - All other countries| 17.3| 11.7| 14.0| 16.7 - +---------+---------+---------+--------- - Total | 100.0| 100.0| 100.0| 100.0 - -------------------+---------+---------+---------+--------- - - -------------------+---------+---------+--------- - Exported to— | 1935 | 1936 | 1937[1] - -------------------+---------+---------+--------- - | Quantity (pounds) - +---------+---------+--------- - Canada |1,493,993|1,105,277|1,187,661 - Japan | | | - Netherlands Indies | 71,375| 200| 335,275 - United Kingdom | | 2| - China | 598,342| 459,490| 938,700 - All other countries| 334,100| 279,289| 403,236 - +---------+---------+--------- - Total |2,497,810|1,844,258|2,864,872 - +---------+---------+--------- - | Value - +---------+---------+--------- - Canada | $83,805| $53,062| $50,780 - Japan | | | - Netherlands Indies | 2,866| 13| 13,411 - United Kingdom | | 1| - China | 28,239| 19,258| 34,274 - All other countries| 18,676| 16,520| 20,498 - +---------+---------+--------- - Total | 133,586| 88,854| 118,963 - +---------+---------+--------- - | Unit value - +---------+---------+--------- - Canada | $0.056| $0.048| $0.043 - Japan | | | - Netherlands Indies | .040| .065| .040 - United Kingdom | | .500| - China | .047| .042| .037 - All other countries| .056| .059| .051 - +---------+---------+--------- - Average | .053| .048| .042 - +---------+---------+--------- - | Percent of total quantity - +---------+---------+--------- - Canada | 59.8| 59.9| 41.4 - Japan | | | - Netherlands Indies | 2.8| | 11.7 - United Kingdom | | | - China | 24.0| 24.9| 32.8 - All other countries| 13.4| 15.2| 14.1 - +---------+---------+--------- - Total | 100.0| 100.0| 100.0 - -------------------+---------+---------+--------- - - [1] Preliminary. - - Source: Foreign Commerce and Navigation of the United States. - - -Competitive conditions. - -The competitive situation with respect to formaldehyde is determined -largely by the output and price of the raw material, methanol. The United -States produces large quantities of synthetic and natural methanol and -is a net exporter of that product. Both methanol and formaldehyde are -produced in many foreign countries, and foreign production is expanding. -Although methanol is now the main, if not the sole, raw material utilized -in making formaldehyde, plants for making the latter direct from natural -gas, or from petroleum gas hydrocarbons are contemplated or actually -under construction. Should such processes develop to an appreciable -extent, the competitive situation of the United States may change, but -in such case it is unlikely that this country would be so affected as to -change its position as a moderate exporter. - - -HEXAMETHYLENETETRAMINE - - -Description and uses. - -Hexamethylenetetramine is a white crystalline powder made by the -interaction of formaldehyde and ammonia. It is used in tar-acid resins -to replace formaldehyde, though its higher cost has limited its use to -small proportions as a finishing or hardening agent. Other uses are as -an internal antiseptic in medicine (marketed under trade names such as -Urotropin, Cystogen, Aminoform, Urisol, and Cystamin), as an accelerator -in the vulcanization of rubber (a declining use), and in artificial -cork. During the World War it was used in gas masks as an absorbent for -phosgene. - - -United States production. - -The domestic production of hexamethylenetetramine declined during the -depression, but has been increasing in the last few years. Production in -1937, however, was still below that of 1929. Statistics of production are -shown in table 86. - -TABLE 86.—_Hexamethylenetetramine: United States production and sales, -1923, and 1925-37_ - - -------+----------+----------------------------- - |Production| Sales - Year |(quantity)+---------+--------+---------- - | | Quantity| Value |Unit value - -------+----------+---------+--------+---------- - | _Pounds_ | _Pounds_| | - 1923 | 1,381,073|1,155,083|$974,877| $0.84 - 1925 | 1,657,993|1,506,286| 994,458| .66 - 1926 | 1,495,220| ([1]) | ([1]) | - 1927 | 1,315,213| ([1]) | ([1]) | - 1928 | 1,661,645| ([1]) | ([1]) | - 1929 | 2,368,020| ([1]) | ([1]) | - 1930 | 1,871,690| ([1]) | ([1]) | - 1931 | ([2]) | | ([2]) | - 1932 | ([2]) | | ([2]) | - 1933-37| ([1]) | | ([1]) | - -------+----------+---------+--------+---------- - - [1] Not publishable; figures would disclose operations of - individual firms. - - [2] Not available. - - Source: Compiled from annual reports of the Tariff Commission on - dyes and other synthetic organic chemicals in the United States. - -Hexamethylenetetramine is made by two firms in New Jersey and by one in -West Virginia. The raw materials utilized are formaldehyde and liquid -or anhydrous ammonia. One company makes its own requirements of both, -and another makes its own formaldehyde. Most of the production of -hexamethylenetetramine is sold, marketed in barrels, drums, kegs, and -cans. - - -Production in other countries. - -Hexamethylenetetramine is made in a number of foreign countries, with -Germany probably the leading foreign producer. Exports from Germany -declined from 445,000 pounds in 1931 to 182,000 pounds in 1934, the -decline being due chiefly to the expansion of production in countries -previously large importers, particularly the United Kingdom, Japan, -Czechoslovakia, and France. - - -United States imports and exports. - -Imports of hexamethylenetetramine to the United States are shown in table -87. - -TABLE 87.—_Hexamethylenetetramine: United States imports for consumption, -1923-37_ - - -----------------+--------------+--------+-------+----------+---------- - | | | | | Computed - Calendar year | Rate of duty |Quantity| Value |Unit value|ad valorem - | | | | | rate - -----------------+--------------+--------+-------+----------+---------- - | |_Pounds_| | | _Percent_ - 1923 |25 percent | 47,373|$24,722| $0.522| - 1924 | do | 3,826| 3,998| 1.045| - 1925 | do | 20,771| 10,453| .503| - 1926 | do | 23,481| 10,237| .436| - 1927 | do | 3,417| 1,715| .502| - 1928 | do | 5,898| 1,643| .279| - 1929 | do | 5,562| 1,857| .334| - 1930: | | | | | - Jan. 1-June 17 | do | | | | - June 18-Dec. 31| 11 cents | | | | - | per pound | | | | - 1931 | do | | | | - 1932 | do | 1,103| 336| .305| 36.1 - 1933 | do | 1,103| 293| .266| 41.4 - 1934 | do | 612| 273| .446| 24.7 - 1935 | do | | | | - 1936 | do | 7,496| 1,510| .201| 54.6 - 1937[1] | do | 10,895| 8,197| .200| 54.9 - -----------------+--------------+--------+-------+----------+---------- - - [1] Preliminary. - - Source: Foreign Commerce and Navigation of the United States. - -Imports of hexamethylenetetramine in 1928 came principally from the -United Kingdom, the remainder from Germany. In 1929 they came wholly from -Germany; in 1932 and 1933 from Belgium; and in 1934 principally from -Canada, with the rest from the United Kingdom. In 1936 Belgium supplied -7,166 pounds valued at $1,368 and Germany 330 pounds valued at $142. - -Exports of hexamethylenetetramine are not shown in official statistics. -It is known, however, that some has been exported, and that in 1933, at -least, exports exceeded imports. - - -Competitive conditions. - -Hexamethylenetetramine is made from formaldehyde and ammonia, of -which there are ample supplies in the United States. The market for -hexamethylenetetramine is limited, and imports are small. It is made -in numerous foreign countries, Germany being probably the principal -potential competitor. - - -FURFURAL - -Furfural is an aldehyde found in oat hulls, rice hulls, corn cobs, bran, -and other farm waste products. Commercially it is obtained in the United -States from oat hulls and in the Soviet Union from the husks of sunflower -seeds. It is a colorless liquid, boiling at 158° to 162° C. and freezing -at minus 38° C. Its principal use is in synthetic resins, of which tar -acid-furfural is probably the most important. These resins are used in -molding, for impregnating, and in coatings. Furfural is also used as a -solvent for cellulose ethers and esters, natural gums and resins, and in -the manufacture of derivatives useful as rubber chemicals. - -Domestic production is entirely by one firm, located in Iowa. Production -and sales statistics are not publishable, but the maker has stated that -consumption is in “terms of millions of pounds per year.” - - - - -18. RAW MATERIALS FOR UREA RESINS - - -The principal raw materials entering into the manufacture of urea resins -are urea and formaldehyde. Formaldehyde has already been discussed (see -pp. 133-135) and urea and thiourea are discussed below. - - -UREA - -Urea is a white crystalline material, made by condensing carbon dioxide -and ammonia under heat and pressure. It is an excellent fertilizer -because of its high nitrogen content (46.6 percent) but this use is -limited by its relatively high cost. Urea is an important synthetic -resin material, being a constituent of urea-formaldehyde resins, known -commercially under the trade names Beetleware and Plaskon. - -Production of urea in the United States was started in 1916, when the -German supply was cut off. In 1920 the domestic output was estimated at -more than 200,000 pounds of fertilizer grade. Production ceased in 1922. -Urea in ammonia solution for use in the manufacture of mixed fertilizer -was first produced in 1933. - -Crystal urea production in the United States was begun in 1935 and was -largely made possible by the larger volume of urea in ammonia solution -manufactured for fertilizer use. Prior to that time our requirements of -crystal urea were imported, principally from Germany. Consumers of resin -grade urea report that the domestic product is as good or better than the -imported from Europe. The domestic output of crystal urea in 1936 showed -an appreciable increase over that in 1935. - -Statistics of imports of urea are given in table 88, showing imports of -all grades combined. Up to 1931, and again in 1936, the imports were -probably all for fertilizer use. From 1931 through 1935 some portion of -the imports went into the manufacture of resins, but even in this period -most of the imports were probably used in fertilizer. - -TABLE 88.—_Urea: United States imports for consumption, 1919-20 and -1923-37_ - - -------------------+------------+----------+-------+---------- - Year |Rate of duty| Quantity | Value |Unit value - -------------------+------------+----------+-------+---------- - | | _Pounds_ | | - 1919 |25 percent | 14,290| $9,741| $0.682 - 1920 | do | 23,693| 14,085| .594 - 1923 |35 percent | 45,711| 5,892| .129 - 1924 | do | 94,307| 12,891| .137 - 1925 | do | 146,438| 15,886| .108 - 1926 | do | 377,729| 30,346| .080 - 1927 | do | 813,120| 51,799| .064 - 1928 | do | 1,788,927|101,900| .057 - 1929 | do | 4,588,313|228,401| .050 - 1930: | | | | - Jan. 1-June 17 | do | 2,459,140|120,263| .049 - June 18-Dec. 31|Free |17,843,840|719,982| .040 - 1931 | do |11,695,040|445,674| .038 - 1932 | do | 7,291,200|267,787| .037 - 1933 | do |12,918,080|483,238| .037 - 1934 | do |10,850,560|423,675| .039 - 1935 | do | 8,189,440|379,427| .046 - 1936 | do | 6,095,040|272,679| .045 - 1937[1] | do | 5,297,600|266,166| .050 - -------------------+------------+----------+-------+---------- - - [1] Preliminary. - - Source: Foreign Commerce and Navigation of the United States. - -Table 89 shows the sources of imports of urea in recent years. Germany -has supplied from 90 to 100 percent of the total quantity, and Canada -and the Netherlands the greater part of the remainder. There have been -occasional shipments from Belgium, France, and Japan. - -TABLE 89.—_Urea: United States imports for consumption by countries, 1931 -and 1933-37_ - - -------------------+----------+----------+---------- - Imported from— | 1931 | 1933 | 1934 - -------------------+----------+----------+---------- - | Quantity (pounds) - +----------+----------+---------- - Germany |10,496,640|12,649,280|10,660,160 - Netherlands | 922,880| 147,840| 20,160 - Canada | 185,920| 120,960| 168,000 - All other countries| 89,600| | 2,240 - +----------+----------+---------- - Total |11,695,040|12,918,080|10,850,560 - +----------+----------+---------- - | Value - +----------+----------+---------- - Germany | $401,976| $473,703| $415,777 - Netherlands | 31,523| 5,034| 666 - Canada | 9,107| 4,501| 7,032 - All other countries| 3,068| | 200 - +----------+----------+---------- - Total | 445,674| 483,238| 423,675 - +----------+----------+---------- - | Unit value - +----------+----------+---------- - Germany | $0.038| $0.037| $0.039 - Netherlands | .034| .034| .033 - Canada | .049| .037| .042 - All other countries| .034| | .089 - +----------+----------+---------- - Average | .038| .037| .039 - -------------------+----------+----------+---------- - - -------------------+---------+---------+--------- - Imported from— | 1935 | 1936 | 1937[1] - -------------------+---------+---------+--------- - | Quantity (pounds) - +---------+---------+--------- - Germany |7,869,120|6,095,040|5,297,600 - Netherlands | | | - Canada | 320,320| | - All other countries| | | - +---------+---------+--------- - Total |8,189,440|6,095,040|5,297,600 - +---------+---------+--------- - | Value - +---------+---------+--------- - Germany | $366,371| $272,679| $266,166 - Netherlands | | | - Canada | 13,056| | - All other countries| | | - +---------+---------+--------- - Total | 379,427| 272,679| 266,166 - +---------+---------+--------- - | Unit value - +---------+---------+--------- - Germany | $0.047| $0.045| $0.050 - Netherlands | | | - Canada | .041| | - All other countries| | | - +---------+---------+--------- - Average | .046| .045| .050 - +---------+---------+--------- - - [1] Preliminary. - - Source: Foreign Commerce and Navigation of the United States. - -Imports of urea enter the United States free of duty under paragraph 1793 -of the Tariff Act of 1930. In spite of that fact a substantial production -in the United States has been achieved. This is due, at least to a -considerable extent, to the production of crude urea in ammonia solution, -which is used in ammoniating superphosphates for fertilizer use. It is -shipped by tank car but would be difficult to transport by ship. The -volume market for this form of the product has aided in the production of -crystal urea for both resin and fertilizer use. - - -THIOUREA - -Thiourea (thiocarbamide) is a white crystalline solid, melting at 180° -C. It is made commercially by treating a solution of calcium cyanamide -with sulphur and ammonium sulphide or with hydrogen sulphide and -ammonia. The principal uses of thiourea are in making intermediates and -pharmaceuticals, as a photographic developer, as an insecticide, and in -medicine. Because of the water resistance it imparts it was for some -time widely used in urea resins. During the past few years, however, its -use in resins has declined sharply owing to its deleterious action on -ordinary molds and its slow rate of cure. In molding compounds, thiourea -requires about 10 minutes curing time as compared with 3 minutes or -less for urea resins and tar-acid resins. Since ways have been found -to fabricate water-resistant urea resins without using thiourea, the -consumption of thiourea in this use has declined. - -There is no known commercial domestic production of thiourea. - -Imports through the New York Customs District, according to invoice -analyses made by the Tariff Commission, are shown in table 90. Thiourea -is dutiable at 25 percent under paragraph 5 of the act of 1930. - -TABLE 90.—_Thiourea: United States imports through the New York Customs -District, 1931-37_ - - ----+--------+-------+----------+------------------------ - Year|Quantity| Value |Unit value| Source - |(pounds)| | | - ----+--------+-------+----------+------------------------ - 1931| 81,560|$24,254| $0.297|Germany and Switzerland. - 1932| 19,347| 4,760| .246|Germany. - 1933| | | | - 1934| 15,738| 5,982| .380| Do. - 1935| 29,480| 10,500| .356| Do. - 1936| 81,031| 19,782| .244| Do. - 1937| ([1]) | | | - ----+--------+-------+----------+------------------------ - - [1] Not available. - - Source: Invoice analyses of paragraph 5, of Tariff Act of 1930. - Compiled by U. S. Tariff Commission. - - - - -19. RAW MATERIALS FOR VINYL RESINS - - -Vinyl resins are made chiefly from vinyl acetate and vinyl chloride. - - -Description and uses. - -Vinyl acetate is an unsaturated ester of the hypothetical vinyl alcohol. -It is made from acetylene and acetic acid, and is a colorless liquid with -a pleasant sweetish odor, boiling at 73° C. On account of its tendency -to polymerize to polyvinyl acetate, a trace of copper salt is added for -shipment. To render the vinyl acetate chemically active again, the copper -salt is removed by distillation. At present the sole use of vinyl acetate -is for the manufacture of synthetic resins. (See pp. 43-50.) - -Vinyl chloride, a salt of vinyl alcohol, is obtained commercially from -acetylene. It is a gas (boiling at about minus 14° C.) used in the -manufacture of synthetic resins. Vinyl chloride mixed with vinyl acetate -is polymerized to a synthetic resin. - - -United States production. - -Until 1938 the one domestic maker of vinyl acetate produced only -experimental lots, the bulk of our requirements being imported from -Canada. In that year large units to manufacture vinyl acetate were built -at Niagara Falls, N. Y., and at Belle, W. Va. The remarkable properties -of safety glass made from vinyl resin sheets, together with several other -new and important applications of these resins, indicate a demand for -vinyl acetate sufficient to warrant these large manufacturing units. The -United States patents covering the processes of manufacture of vinyl -acetate are owned by the Canadian producer, who has licensed the domestic -makers. - -Domestic production of vinyl chloride has increased from experimental -quantities in 1927 to large-scale commercial output, increasing -substantially each year since 1933. - - -United States imports. - -There has been no import of vinyl chloride. Imports of vinyl acetate -(unpolymerized), entirely from Canada, are shown in table 91. - -TABLE 91.—_Vinyl acetate, unpolymerized: United States imports for -consumption, 1931-37_ - - -------+--------+--------+------ - Year |Quantity| Value | Unit - |(pounds)| | value - -------+--------+--------+------ - 1931 | 77,269| $11,489|$0.149 - 1932 | 104,129| 14,053| .135 - 1933 | 159,757| 21,134| .132 - 1934 | 217,182| 39,462| .182 - 1935 | 776,426| 149,876| 0.193 - 1936[1]| 449,905| 58,499| .130 - 1937[2]| 297,496| 39,074| .131 - -------+--------+--------+------ - - [1] Duty reduced from 30 percent ad valorem and 6 cents per pound - to 15 percent ad valorem and 3 cents per pound under Canadian - trade agreement, effective Jan. 1, 1936. - - [2] Preliminary. - - Source: Foreign Commerce and Navigation of the United States. - - -Competitive conditions. - -Domestic consumption of vinyl acetate and vinyl chloride has increased -in recent years from experimental to commercial quantities. Many years -of intensive research looking toward large outlets for the resins made -from these compounds has apparently been successful. The largest single -application indicated at this time is for safety glass sheets. - -The large increase in domestic consumption expected in the immediate -future will probably be supplied chiefly from expanding domestic -production and imports from Canada will probably decline even under -the reduced trade-agreement duty except to fill possible temporary -shortages. - - - - -APPENDIXES - - -A. Statistical tables on foreign trade in raw materials for synthetic -resins. - -B. Trade names for synthetic resins made in the United States. - -C. Trade names for synthetic resins made in Great Britain. - -D. Trade names for synthetic resins made in Germany. - -E. List of United States manufacturers of raw materials for synthetic -resins. - -F. Glossary. - - - - -APPENDIX A - - -STATISTICAL TABLES ON FOREIGN TRADE IN RAW MATERIALS FOR SYNTHETIC RESINS - -TABLE 92.—_Naphthalene: German imports and exports, by countries, 1929 -and 1932-37_ - - ------------------------+----------+----------+---------------------- - | 1929 | 1932 | 1933 - ------------------------+----------+----------+---------------------- - IMPORTS | Quantity (pounds) - +----------+----------+---------------------- - Total from all countries| 8,032,019| 952,167| 7,482,633 - +----------+----------+---------------------- - Czechoslovakia | 1,688,283| ([1]) | 2,839,304 - Saar Basin | 1,531,977| ([1]) | 1,833,125 - Netherlands | 1,457,020| ([1]) | 1,164,029 - Poland | 2,524,487| ([1]) | 832,457 - U. S. S. R | 284,834| 246,033| 361,334 - +----------+----------+---------------------- - | Value - +----------+----------+------------+--------- - | | | _1,000 | - | _Dollars_| _Dollars_|reichsmarks_|_Dollars_ - Total from all countries| 110,948| 12,112| 271| 82,704 - +----------+----------+------------+--------- - Czechoslovakia | 26,666| ([1]) | 114| 34,790 - Saar Basin | 17,380| ([1]) | 56| 17,090 - Netherlands | 14,999| ([1]) | 27| 8,240 - Poland | 38,332| ([1]) | 31| 9,461 - U. S. S. R | 4,762| 4,750| 22| 6,714 - ------------------------+----------+----------+------------+--------- - | - ------------------------+----------+----------+---------------------- - EXPORTS | Quantity (pounds) - +----------+----------+---------------------- - Total to all countries |39,738,576|29,720,213| 31,842,140 - +----------+----------+---------------------- - UNITED STATES |17,070,218|13,820,858| 21,824,879 - Belgium-Luxemburg | 8,835,596| 7,399,960| 3,958,800 - Japan | ([1]) | ([1]) | 801,152 - Italy | 4,500,691| 2,068,797| 1,163,589 - Netherlands | 734,573| 295,857| 275,134 - +----------+----------+---------------------- - | Value - +----------+----------+------------+--------- - | | | _1,000 | - | _Dollars_| _Dollars_|reichsmarks_|_Dollars_ - Total to all countries | 774,256| 288,790| 1,392| 424,809 - +----------+----------+------------+--------- - UNITED STATES | 329,273| 132,758| 921| 281,070 - Belgium-Luxemburg | 98,330| 42,749| 95| 28,992 - Japan | ([1]) | ([1]) | 50| 15,259 - Italy | 78,330| 23,324| 50| 15,259 - Netherlands | 19,761| 4,987| 21| 6,409 - ------------------------+----------+----------+------------+--------- - - ------------------------+----------------------+---------------------- - | 1934 | 1935 - ------------------------+----------------------+---------------------- - IMPORTS | Quantity (pounds) - +----------------------+---------------------- - Total from all countries| 8,640,930 | 4,245,839 - +----------------------+---------------------- - Czechoslovakia | 1,602,744 | - Saar Basin | 3,641,338 | 1,129,858 - Netherlands | 26,014 | 18,078 - Poland | 1,060,633 | 33,730 - U. S. S. R | 1,024,037 | 531,088 - +----------------------+---------------------- - | Value - +------------+---------+------------+--------- - | _1,000 | | _1,000 | - |reichsmarks_|_Dollars_|reichsmarks_|_Dollars_ - Total from all countries| 273| 107,494| 165| 66,426 - +------------+---------+------------+--------- - Czechoslovakia | 51| 20,081| | - Saar Basin | 78| 30,712| 25| 10,064 - Netherlands | 2| 788| 1| 403 - Poland | 29| 11,419| 2| 805 - U. S. S. R | 48| 18,900| 27| 10,870 - ------------------------+------------+---------+------------+--------- - | - ------------------------+----------------------+---------------------- - EXPORTS | Quantity (pounds) - +----------------------+---------------------- - Total to all countries | 35,043,660 | 22,169,458 - +----------------------+---------------------- - UNITED STATES | 21,631,535 | 12,052,769 - Belgium-Luxemburg | 5,685,663 | 2,010,816 - Japan | 3,434,767 | 1,880,965 - Italy | 695,992 | 492,728 - Netherlands | 427,913 | 413,142 - +----------------------+---------------------- - | Value - +------------+---------+------------+--------- - | _1,000 | | _1,000 | - |reichsmarks_|_Dollars_|reichsmarks_|_Dollars_ - Total to all countries | 1,504| 592,200 | 1,067| 429,553 - +------------+---------+------------+--------- - UNITED STATES | 879| 346,106| 468| 188,407 - Belgium-Luxemburg | 130| 51,188| 50| 20,129 - Japan | 203| 79,931| 131| 52,738 - Italy | 30| 11,812| 23| 9,259 - Netherlands | 29| 11,419| 19| 7,649 - ------------------------+------------+---------+------------+---------- - - ------------------------+----------------------+----------------------- - | 1936 | 1937 - ------------------------+----------------------+----------------------- - IMPORTS | Quantity (pounds) - +----------------------+----------------------- - Total from all countries| 493,169 | 33,069 - +----------------------+----------------------- - Czechoslovakia | ([1]) | ([1]) - Saar Basin | | - Netherlands | 28,660 | ([1]) - Poland | ([1]) | ([1]) - U. S. S. R | ([1]) | ([1]) - +----------------------+----------------------- - | Value - +------------+---------+------------+---------- - | _1,000 | | _1,000 | - |reichsmarks_|_Dollars_|reichsmarks_|_Dollars_ - Total from all countries| 22| 8,865| 1| 402 - +------------+---------+------------+---------- - Czechoslovakia | ([1]) | ([1]) | ([1]) | ([1]) - Saar Basin | | | | - Netherlands | 3| 1,209| ([1]) | ([1]) - Poland | ([1]) | ([1]) | ([1]) | ([1]) - U. S. S. R | ([1]) | ([1]) | ([1]) | ([1]) - ------------------------+------------+---------+------------+---------- - | - ------------------------+----------------------+----------------------- - EXPORTS | Quantity (pounds) - +----------------------+----------------------- - Total to all countries | 8,152,390 | 24,966,434 - +----------------------+----------------------- - UNITED STATES | 3,420,437 | 14,167,201 - Belgium-Luxemburg | 457,675 | 1,184,311 - Japan | 253,529 | 2,031,980 - Italy | 134,481 | 615,083 - Netherlands | 198,414 | 66,138 - +----------------------+----------------------- - | Value - +------------+---------+------------+---------- - | _1,000 | | _1,000 | - |reichsmarks_|_Dollars_|reichsmarks_|_Dollars_ - Total to all countries | 703| 283,288| 1,949| 783,576 - +------------+---------+------------+---------- - UNITED STATES | 168| 67,699| 789| 317,210 - Belgium-Luxemburg | 21| 8,462| 60| 24,122 - Japan | 29| 11,686| 177| 71,161 - Italy | 18| 7,253| 47| 18,896 - Netherlands | 14| 5,642| 7| 2,814 - ------------------------+------------+---------+------------+---------- - - [1] Not separately shown. - - Source: Der Auswärtige Handel Deutschlands, 1929. Monatliche - Nachweise über den auswärtigen Handel, Deutschlands, 1932-37. - -TABLE 93.—_Crude naphthalene: Belgian imports and exports, 1932-37_ - - ---------------+----------+-----------------+----------------- - | 1932 | 1933 | 1934 - +----------+-----------------+----------------- - IMPORTS | Quantity (pounds) - +----------+-----------------+----------------- - Total from all | | | - countries |14,114,070| 10,935,698 | 15,328,363 - +----------+-----------------+----------------- - Netherlands | 8,187,443| 7,583,163 | 9,363,598 - Germany | 5,800,744| 3,122,816 | 5,290,599 - +----------+-----------------+----------------- - | Value - +----------+-------+---------+-------+--------- - | |_1,000 | |_1,000 | - | _Dollars_|francs_|_Dollars_|francs_|_Dollars_ - Total from all | | | | | - countries | 74,299| 2,059| 73,711| 3,015| 140,419 - +----------+-------+---------+-------+--------- - Netherlands | 41,352| 1,327| 47,506| 1,881| 87,605 - Germany | 31,611| 661| 23,663| 970| 45,176 - +----------+-------+---------+-------+--------- - EXPORTS | Quantity (pounds) - +----------+-----------------+----------------- - Total to all | | | - countries | 1,102,300| 5,955,727 | 3,395,745 - +----------+-----------------+----------------- - UNITED STATES | | 3,991,428 | 2,499,355 - France | 871,699| 1,262,354 | 352,075 - +----------+-----------------+----------------- - | Value - +----------+-------+---------+-------+--------- - | |_1,000 | |_1,000 | - | _Dollars_|francs_|_Dollars_|francs_|_Dollars_ - Total to all | | | | | - countries | 10,964| 2,503| 89,605| 1,181| 55,003 - +----------+-------+---------+-------+--------- - UNITED STATES | | 1,562| 55,918| 707| 32,927 - France | 8,404| 446| 15,966| 243| 11,317 - ---------------+----------+-------+---------+-------+--------- - - ---------------+-----------------+-----------------+----------------- - | 1935 | 1936 | 1937 - +-----------------+-----------------+----------------- - IMPORTS | Quantity (pounds) - +-----------------+-----------------+----------------- - Total from all | | | - countries | 12,114,718 | 17,102,405 | 9,178,411 - +-----------------+-----------------+----------------- - Netherlands | 8,786,874 | 10,315,764 | 5,983,064 - Germany | 1,297,628 | 178,573 | ([1]) - +-----------------+-----------------+----------------- - | Value - +-------+---------+-------+---------+-------+--------- - |_1,000 | |_1,000 | |_1,000 | - |francs_|_Dollars_|francs_|_Dollars_|francs_|_Dollars_ - Total from all | | | | | | - countries | 3,299| 121,562| 7,017| 237,385| 4,277|144,357 - +-------+---------+-------+---------+-------+--------- - Netherlands | 2,139| 78,818| 3,916| 132,478| 2,808| 94,776 - Germany | 341| 12,565| 77| 2,605| ([1]) | ([1]) - +-------+---------+-------+---------+-------+--------- - EXPORTS | Quantity (pounds) - +-----------------+-----------------+----------------- - Total to all | | | - countries | 6,796,782 | 11,538,215 | 6,700,220 - +-----------------+-----------------+----------------- - UNITED STATES | 1,709,888 | 2,119,062 | 1,009,927 - France | 2,930,134 | 5,163,835 | 4,382,745 - +-----------------+-----------------+----------------- - | Value - +-------+---------+-------+---------+-------+--------- - |_1,000 | |_1,000 | |_1,000 | - |francs_|_Dollars_|francs_|_Dollars_|francs_|_Dollars_ - Total to all | | | | | | - countries | 3,059| 112,719| 7,020| 237,487| 3,918|132,240 - +-------+---------+-------+---------+-------+--------- - UNITED STATES | 543| 20,009| 1,461| 49,426| 492| 16,606 - France | 1,460| 53,798| 3,227| 109,169| 2,769| 93,459 - ---------------+-------+---------+-------+---------+-------+--------- - - [1] Not separately reported. - - Source: Bulletin Mensuel du Commerce. - -TABLE 94.—_Refined naphthalene: Belgian imports and exports, 1932-37_ - - ---------------+----------+-----------------+----------------- - | 1932 | 1933 | 1934 - +----------+-----------------+----------------- - IMPORTS | Quantity (pounds) - +----------+-----------------+----------------- - Total from all | | | - countries | 7,055| 1,323 | 7,275 - +----------+-------+---------+-------+--------- - | Value - +----------+-------+---------+-------+--------- - | |_1,000 | |_1,000 | - | _Dollars_|francs_|_Dollars_|francs_|_Dollars_ - Total from all | | | | | - countries | 150| 8| 286| 15| 699 - +----------+-------+---------+-------+--------- - EXPORTS | Quantity (pounds) - +----------+-----------------+----------------- - Total to all | | | - countries |15,362,314| 15,298,822 | 14,792,425 - +----------+-----------------+----------------- - Japan | 6,566,401| 4,582,922 | 2,867,523 - United Kingdom | 695,772| 1,297,407 | 2,168,004 - Argentina | 1,078,490| 1,130,519 | 988,102 - British India | 792,995| 996,920 | 1,153,226 - Canada | 841,496| 942,026 | 421,740 - Netherlands | 449,518| 472,225 | 510,365 - +----------+-----------------+----------------- - | Value - +----------+-------+---------+-------+--------- - | |_1,000 | |_1,000 | - | _Dollars_|francs_|_Dollars_|francs_|_Dollars_ - Total to all | | | | | - countries | 326,026| 11,310| 404,889| 10,032| 467,224 - +----------+-------+---------+-------+--------- - Japan | 130,650| 3,498| 125,226| 1,966| 91,563 - United Kingdom | 14,053| 893| 31,969| 1,524| 70,978 - Argentina | 24,154| 811| 29,033| 719| 33,486 - British India | 18,867| 752| 26,921| 764| 35,582 - Canada | 17,670| 696| 24,916| 301| 14,019 - Netherlands | 9,934| 375| 13,425| 306| 14,251 - +----------+-------+---------+-------+--------- - - ---------------+-----------------+-----------------+----------------- - | 1935 | 1936 | 1937 - +-----------------+-----------------+----------------- - IMPORTS | Quantity (pounds) - +-----------------+-----------------+----------------- - Total from all | | | - countries | 112,214 | 2,866 | 19,180 - +-------+---------+-------+---------+-------+--------- - | Value - +-------+---------+-------+---------+-------+--------- - |_1,000 | |_1,000 | |_1,000 | - |francs_|_Dollars_|francs_|_Dollars_|francs_|_Dollars_ - Total from all | | | | | | - countries | 78| 2,874| 8| 271| 42| 1,418 - +-------+---------+-------+---------+-------+--------- - EXPORTS | Quantity (pounds) - +-----------------+-----------------+----------------- - Total to all | | | - countries | 16,148,695 | 11,419,167 | 14,071,300 - +-----------------+-----------------+----------------- - Japan | 4,202,849 | 3,447,113 | 2,514,126 - United Kingdom | 315,919 | 455,029 | 1,316,808 - Argentina | 1,376,773 | 970,685 | 1,173,729 - British India | 705,252 | 243,477 | 715,172 - Canada | 90,168 | ([1]) | ([1]) - Netherlands | 971,788 | 477,516 | 571,432 - +-----------------+-----------------+----------------- - | Value - +-------+---------+-------+---------+-------+--------- - |_1,000 | |_1,000 | |_1,000 | - |francs_|_Dollars_|francs_|_Dollars_|francs_|_Dollars_ - Total to all | | | | | | - countries | 11,219| 413,400| 9,391| 317,698| 11,602| 391,591 - +-------+---------+-------+---------+-------+--------- - Japan | 2,949| 108,665| 2,454| 83,019| 1,643| 55,455 - United Kingdom | 212| 7,812| 445| 15,054| 896| 30,242 - Argentina | 976| 35,964| 615| 20,805| 991| 33,448 - British India | 498| 18,350| 321| 10,859| 640| 21,601 - Canada | 66| 2,432| ([1])| ([1])| ([1])| ([1]) - Netherlands | 695| 25,609| 568| 19,215| 697| 23,525 - +-------+---------+-------+---------+-------+--------- - - [1] Not separately reported. - - Source: Bulletin Mensuel du Commerce. - -TABLE 95.—_Crude and refined naphthalene: Netherland imports and exports -by countries, 1929 and 1932-37_ - - ---------------------+---------+---------+------------------- - | 1929 | 1932 | 1933 - ---------------------+---------+---------+------------------- - IMPORTS | Quantity (pounds) - +---------+---------+------------------- - Total from all | | | - countries | 896,908| 775,759| 908,597 - +---------+---------+------------------- - Belgium-Luxemburg| 191,044| 477,508| 569,514 - Germany | 705,820| 270,262| 330,921 - Italy | ([1])| ([1])| 2,315 - United Kingdom | | ([1])| 97 - +---------+---------+------------------- - | Value - +---------+---------+---------+--------- - | | | _1,000 | - Total from all |_Dollars_|_Dollars_|guilders_|_Dollars_ - countries | 25,874| 13,733| 38| 19,885 - +---------+---------+---------+--------- - Belgium-Luxemburg | 5,708| 8,309| 24| 12,265 - Germany | 20,153| 4,960| 13| 6,775 - Italy | ([1])| ([1])| ([1])| 681 - United Kingdom | | ([1])| ([1])| 23 - +---------+---------+---------+--------- - EXPORTS | Quantity (pounds) - +---------+---------+------------------- - Total to all | | | - countries |4,816,436|6,807,060| 10,770,410 - +---------+---------+------------------- - Belgium-Luxemburg|2,820,043|6,768,631| 8,757,006 - Germany |1,511,897| | 1,174,745 - UNITED STATES | 44,092| | 661,380 - United Kingdom | 333,902| ([1])| 100,001 - +---------+---------+------------------- - | Value - +---------+---------+---------+--------- - | | | _1,000 | - Total to all |_Dollars_|_Dollars_|guilders_|_Dollars_ - countries | 49,058| 40,784| 158| 81,490 - +---------+---------+---------+--------- - Belgium-Luxemburg| 25,503| 39,886| 124| 63,928 - Germany | 13,877| | 17| 8,756 - UNITED STATES | 482| | 12| 6,103 - United Kingdom | 5,556| ([1])| 2| 938 - ---------------------+---------+---------+---------+--------- - - ---------------------+-------------------+------------------- - | 1934 | 1935 - ---------------------+-------------------+------------------- - IMPORTS | Quantity (pounds) - +-------------------+------------------- - Total from all | | - countries | 1,186,361 | 1,177,256 - +-------------------+------------------- - Belgium-Luxemburg| 568,328 | 524,962 - Germany | 522,993 | 418,409 - Italy | ([1]) | ([1]) - United Kingdom | ([1]) | ([1]) - +-------------------+------------------- - | Value - +---------+---------+---------+--------- - | _1,000 | | _1,000 | - Total from all |guilders_|_Dollars_|guilders_|_Dollars_ - countries | 45| 30,220| 39| 26,747 - +---------+---------+---------+--------- - Belgium-Luxemburg | 22| 14,903| 21| 13,947 - Germany | 19| 13,132| 12| 7,817 - Italy | ([1])| ([1])| ([1])| ([1]) - United Kingdom | ([1])| ([1])| ([1])| ([1]) - +---------+---------+---------+--------- - EXPORTS | Quantity (pounds) - +-------------------+------------------- - Total to all | | - countries | 9,764,389 | 10,851,416 - +-------------------+------------------- - Belgium-Luxemburg| 9,307,821 | 9,178,854 - Germany | ([1]) | 17,846 - UNITED STATES | 410,225 | 681,332 - United Kingdom | ([1]) | ([1]) - +-------------------+------------------- - | Value - +---------+---------+---------+--------- - | _1,000 | | _1,000 | - Total to all |guilders_|_Dollars_|guilders_|_Dollars_ - countries | 132| 89,135| 170| 115,204 - +---------+---------+---------+--------- - Belgium-Luxemburg| 122| 82,146| 129| 87,380 - Germany | ([1])| ([1])| ([2])| 257 - UNITED STATES | 8| 5,183| 17| 11,782 - United Kingdom | ([1])| ([1])| ([1])| ([1]) - ---------------------+---------+---------+---------+--------- - - ---------------------+-------------------+------------------- - | 1936 | 1937 - ---------------------+-------------------+------------------- - IMPORTS | Quantity (pounds) - +-------------------+------------------- - Total from all | | - countries | 1,666,678 | 2,361,127 - +-------------------+------------------- - Belgium-Luxemburg| 703,267 | 835,543 - Germany | ([1]) | ([1]) - Italy | ([1]) | ([1]) - United Kingdom | 604,060 | 1,053,799 - +-------------------+------------------- - | Value - +---------+---------+---------+--------- - | _1,000 | | _1,000 | - Total from all |guilders_|_Dollars_|guilders_|_Dollars_ - countries | 83| 53,519| 115| 63,302 - +---------+---------+---------+--------- - Belgium-Luxemburg | 42| 27,082| 60| 33,027 - Germany | ([1])| ([1])| ([1])| ([1]) - Italy | ([1])| ([1])| ([1])| ([1]) - United Kingdom | 21| 13,541| 36| 19,816 - +---------+---------+---------+--------- - EXPORTS | Quantity (pounds) - +-------------------+------------------- - Total to all | | - countries | 14,422,493 | 15,330,788 - +-------------------+------------------- - Belgium-Luxemburg| 10,568,852 | 9,261,525 - Germany | ([1]) | ([1]) - UNITED STATES | 3,207,693 | 2,546,313 - United Kingdom | ([1]) | ([1]) - +-------------------+------------------- - | Value - +---------+---------+---------+--------- - | _1,000 | | _1,000 | - Total to all |guilders_|_Dollars_|guilders_|_Dollars_ - countries | 435| 280,492| 553| 304,399 - +---------+---------+---------+--------- - Belgium-Luxemburg| 255| 164,426| 294| 161,832 - Germany | ([1])| ([1])| ([1])| ([1]) - UNITED STATES | 143| 92,208| 100| 55,045 - United Kingdom | ([1])| ([1])| ([1])| ([1]) - ---------------------+---------+---------+---------+--------- - - [1] Not separately reported. - - [2] Less than 500. - - Source: Nederland-Jaarstatistiek (1929 and 1932-35) and - Maandstatistiek (1936-37). - -TABLE 96.—_Refined naphthalene: Canadian imports by countries, 1928-29 -and 1932-37_ - - ------------------------+-------+---------+---------+--------- - | 1928 | 1929 | 1932 | 1933 - ------------------------+-------+---------+---------+--------- - | Quantity (pounds) - +-------+---------+---------+--------- - Total from all countries|565,866|1,075,415|1,223,372|1,053,114 - +-------+---------+---------+--------- - UNITED STATES | 32,274| 4,049| 17,560| 9,553 - United Kingdom | 26,000| 8,600| 32,400| 148,144 - Belgium | ([2]) | 841,876|1,102,203| 895,042 - +-------+---------+---------+--------- - | Value (United States dollars) - +-------+---------+---------+--------- - Total from all countries| 18,162| 32,411| 21,787| 22,014 - +-------+---------+---------+--------- - UNITED STATES | 1,428| 245 577| 545| 188 696 - United Kingdom | 1,014| 363 670| 3,779| 13,603 - Belgium | ([2]) | 25,906| 19,401| 17,657 - ------------------------+-------+---------+---------+--------- - - ------------------------+-------+---------+-------+--------- - | 1934 | 1935 | 1936 | 1937[1] - ------------------------+-------+---------+-------+--------- - | Quantity (pounds) - ------------------------+-------+---------+-------+--------- - Total from all countries|844,929|1,342,530|884,059|1,256,289 - ------------------------+-------+---------+-------+--------- - UNITED STATES | 3,145| 3,620| 2,091| 2,018 - United Kingdom |484,868|1,321,310|879,548|1,254,271 - Belgium 895,042|347,956| 17,600| ([2]) | - ------------------------+-------+---------+-------+--------- - | Value (United States dollars) - ------------------------+-------+---------+-------+--------- - Total from all countries| 25,482| 40,060| 46,670| 57,455 - ------------------------+-------+---------+-------+--------- - UNITED STATES |243 185| 696| 243| 185 - United Kingdom | 38,865| 38,865| 46,229| 57,270 - Belgium | 11,431| 499| ([2]) | - ------------------------+-------+---------+-------+--------- - - [1] Preliminary. - - [2] Not shown separately. - - Source: Trade of Canada. - -TABLE 97.—_Naphthalene: Japanese imports by countries, 1928-29 and -1932-36_ - - ------------------------+---------+---------+---------+---------------- - | 1928 | 1929 | 1932 | 1933 - ------------------------+---------+---------+---------+---------------- - | Quantity (pounds) - +---------+---------+---------+---------------- - Total from all countries|2,773,320|2,902,686|6,765,572| 7,876,566 - +---------+---------+---------+---------------- - Belgium | 379,900| 403,180|2,857,448| 3,950,056 - Germany | 491,541| 403,180|1,935,213| 2,525,036 - Kwangtung Province |1,790,766| 864,298|1,272,372| 169,976 - +---------+---------+---------+---------------- - | Value - +---------+---------+---------+------+--------- - | | | |_1,000|_Dollars_ - |_Dollars_|_Dollars_|_Dollars_| yen_ | - Total from all countries| 62,653| 94,504| 97,265| 625| 160,286 - +---------+---------+---------+------+--------- - Belgium | 12,531| 14,291| 42,448| 309| 79,245 - Germany | 16,707| 14,291| 28,111| 200| 51,291 - Kwangtung Province | 29,238| 21,667| 13,774| 13| 3,334 - +---------+---------+---------+------+--------- - - ----------------------+----------------+----------------+--------------- - | 1934 | 1935 | 1936 - ----------------------+----------------+----------------+--------------- - | Quantity (pounds) - +----------------+----------------+---------------- - Total from all | 7,364,557| 8,979,696| 12,641,977 - countries | | | - +----------------+----------------+---------------- - Belgium | 1,590,138| 2,926,430| 3,163,801 - Germany | 4,679,670| 3,486,239| 2,727,816 - Kwangtung Province| 241,146| 1,103,322| - +----------------+----------------+---------------- - | Value - +------+---------+------+---------+------+--------- - |_1,000|_Dollars_|_1,000|_Dollars_|_1,000|_Dollars_ - | yen_ | | yen_ | | yen_ | - Total from all | 560| 166,404| 697| 200,088| 1,613| 467,680 - countries | | | | | | - +------+---------+------+---------+------+--------- - Belgium | 122| 36,252| 234| 67,174| 410| 118,997 - Germany | 357| 106,083| 283| 81,240| 394| 114,335 - Kwangtung Province| | | 12| 3,445| 93| 27,020 - +------+---------+------+---------+------+--------- - - Source: Annual Return of the Foreign Trade of Japan. - -TABLE 98.—_Crude glycerin: United States imports for consumption,[1] by -countries, 1929 and 1931-37_ - - -------------------------+----------+----------+---------+--------- - Imported from— | 1929[2] | 1931 | 1932 | 1933 - -------------------------+----------+----------+---------+--------- - | Quantity (pounds) - +----------+----------+---------+--------- - France | 4,931,691| 2,550,457|1,653,825|2,455,264 - Cuba | 1,074,271| 1,170,667|1,232,219|1,216,395 - United Kingdom | 3,847,345| 1,631,103| 582,194| 252,238 - Belgium | 759,448| 739,892| 310,855| 440,862 - Germany | 1,072,173| 674,109| 260,005| 242,901 - Philippine Islands (free)| 250,165| 180,490| 197,841| 268,449 - Argentina | 494,638| 458,068| 154,525| 288,832 - Netherlands | 262,299| 425,796| 125,733| 226,994 - Canada | 1,304,220| 1,161,085| 80,440| - Denmark | 54,988| 175,273| | 124,278 - Union of Soviet Socialist| | | | - Republics | 132,334| | 64,969| 889,618 - All other countries | 668,329| 966,023| 317,866| 67,254 - +----------+----------+---------+--------- - Total |14,851,901|10,132,963|4,980,472|6,473,085 - +----------+----------+---------+--------- - | Value - +----------+----------+---------+--------- - France | $280,062| $114,575| $53,391| $80,068 - Cuba | 69,668| 67,709| 50,147| 56,737 - United Kingdom | 216,307| 8 2,262| 19,802| 7,722 - Belgium | 49,568| 46,275| 12,362| 17,627 - Germany | 65,446| 40,596| 12,240| 10,745 - Philippine Islands (free)| 16,796| 10,993| 9,150| 14,078 - Argentina | 29,758| 23,532| 6,516| 7,947 - Netherlands | 18,963| 23,301| 5,349| 10,664 - Canada | 67,821| 59,495| 4,246| - Denmark | 2,966| 9,358| | 5,171 - Union of Soviet Socialist| | | | - Republics | 9,113| | 2,738| 34,060 - All other countries | 37,084| 47,343| 12,614| 2,076 - +----------+----------+---------+--------- - Total | 863,552| 525,599| 188,555| 246,895 - +----------+----------+---------+--------- - | Percent of total imports by quantity - +----------+----------+---------+--------- - France | 33.2| 25.2| 33.2| 37.9 - Cuba | 7.2| 11.6| 24.7| 18.8 - United Kingdom | 25.9| 16.1| 11.7| 3.9 - Belgium | 5.1| 7.3| 6.3| 6.8 - Germany | 7.2| 6.7| 5.2| 3.8 - Philippine Islands (free)| 1.7| 1.8| 4.0| 4.1 - Argentina | 3.3| 4.5| 3.1| 4.5 - Netherlands | 1.8| 4.2| 2.5| 3.5 - Canada | 8.8| 11.4| 1.6| - Denmark | .4| 1.7| | 1.9 - Union of Soviet Socialist| | | | - Republics | .9| | 1.3| 13.7 - All other countries | 4.5| 9.5| 6.4| 1.1 - +----------+----------+---------+--------- - Total | 100.0| 100.0| 100.0| 100.0 - -------------------------+----------+----------+---------+--------- - - -------------------------+----------+---------+----------+---------- - Imported from— | 1934 | 1935 | 1936 | 1937[3] - -------------------------+----------+---------+----------+---------- - | Quantity (pounds) - +----------+---------+----------+---------- - France | 4,880,013| 578,617| 1,058,692| 2,102,785 - Cuba | 1,178,238|2,550,617| 2,159,741| 2,476,790 - United Kingdom | 1,494,445| 578,231| 1,403,880| 1,640,691 - Belgium | 2,358,479| 257,290| 404,371| 818,514 - Germany | 1,539,919| 198,767| 77,723| 518,231 - Philippine Islands (free)| 180,549|1,578,523| 303,551| 793,225 - Argentina | 680,443| 100,902| 1,154,888| 2,131,068 - Netherlands | 1,393,072| 267,366| 1,037,118| 325,275 - Canada | 629,880|1,946,450| 671,465| 333,855 - Denmark | 58,449| | 442,768| 133,671 - Union of Soviet Socialist| | | | - Republics | 146,695| 14,883| 2,017,992| 1,634,874 - All other countries | 541,045| 149,288| 416,796| 532,451 - +----------+---------+----------+---------- - Total |15,081,227|8,220,934|11,148,985|13,441,430 - +----------+---------+----------+---------- - | Value - +----------+---------+----------+---------- - France | $324,840| $45,245| $121,612| $370,622 - Cuba | 92,692| 228,011| 230,340| 381,683 - United Kingdom | 97,972| 50,549| 134,475| 284,779 - Belgium | 160,301| 19,217| 46,417| 146,014 - Germany | 103,401| 22,699| 8,874| 92,446 - Philippine Islands (free)| 14,984| 74,798| 32,708| 145,348 - Argentina | 45,251| 7,972| 115,198| 349,675 - Netherlands | 92,754| 23,208| 127,050| 47,898 - Canada | 51,716| 172,426| 70,672| 53,014 - Denmark | 4,062| | 47,256| 26,220 - Union of Soviet Socialist| | | | - Republics | 10,137| 1,463| 222,347| 254,745 - All other countries | 41,955| 11,146| 42,411| 90,938 - +----------+---------+----------+---------- - Total | 1,040,065| 656,734| 1,199,360| 2,243,382 - +----------+---------+----------+---------- - | Percent of total imports by quantity - +----------+---------+----------+---------- - France | 32.4| 7.1| 9.5| 15.6 - Cuba | 7.8| 31.0| 19.4| 18.4 - United Kingdom | 9.9| 7.0| 12.6| 12.2 - Belgium | 15.6| 3.1| 3.6| 6.1 - Germany | 10.2| 2.4| .7| 3.9 - Philippine Islands (free)| 1.2| 19.2| 2.7| 5.9 - Argentina | 4.5| 1.2| 10.4| 15.8 - Netherlands | 9.2| 3.3| 9.3| 2.4 - Canada | 4.2| 23.7| 6.0| 2.5 - Denmark | .4| | 4.0| 1.0 - Union of Soviet Socialist| | | | - Republics | 1.0| .2| 18.1| 12.2 - All other countries | 3.6| 1.8| 3.7| 4.0 - +----------+---------+----------+---------- - Total | 100.0| 100.0| 100.0| 100.0 - -------------------------+----------+---------+----------+---------- - - [1] Includes imports from Cuba and shipments from Philippine Islands. - - [2] General imports. - - [3] Preliminary. - - Source: Foreign Commerce and Navigation of the United States. - -TABLE 99.—_Refined glycerin: United States imports for consumption, by -countries, 1929 and 1931-37_ - - -------------------+---------+---------+---------+--------- - Imported from— | 1929[1] | 1931 | 1932 | 1933 - -------------------+---------+---------+---------+--------- - | Quantity (pounds) - +---------+---------+---------+--------- - Netherlands |3,114,642|1,054,810|1,705,855|2,153,490 - Germany |1,824,672| 197,890| 384,131| 406,716 - United Kingdom | 165,770| 38,561| 153,289| 50,421 - France | | 592,979| 44,905| 125,889 - Canada | 105| 81,295| 14,520| - Czechoslovakia | | | | - All other countries| 388,282| | 44,808| 39,171 - +---------+---------+---------+--------- - Total |5,493,471|1,965,535|2,347,508|2,775,687 - +---------+---------+---------+--------- - | Value - +---------+---------+---------+--------- - Netherlands | $294,595| $75,462| $100,451| $132,172 - Germany | 154,432| 17,152| 26,582| 22,826 - United Kingdom | 18,301| 2,850| 9,666| 3,111 - France | | 40,005| 2,278| 7,210 - Canada | 19| 5,506| 1,358| - Czechoslovakia | | | | - All other countries| 33,383| | 2,024| 1,672 - +---------+---------+---------+--------- - Total | 500,730| 140,975| 142,359| 166,991 - +---------+---------+---------+--------- - | Percent of total imports by quantity - +---------+---------+---------+--------- - Netherlands | 56.7| 53.7| 72.7| 77.6 - Germany | 33.2| 10.1| 16.4| 14.7 - United Kingdom | 3.0| 1.9| 6.5| 1.8 - France | | 30.2| 1.9| 4.5 - Canada | | 4.1| .6| - Czechoslovakia | | | | - All other countries| 7.1| | 1.9| 1.4 - +---------+---------+---------+--------- - Total | 100.0| 100.0| 100.0| 100.0 - -------------------+---------+---------+---------+--------- - - -------------------+---------+------+---------+--------- - Imported from— | 1934 | 1935 | 1936 | 1937[2] - -------------------+---------+------+---------+--------- - | Quantity (pounds) - +---------+------+---------+--------- - Netherlands | 775,074|16,913|1,542,924|2,776,046 - Germany | 276,908| 600| 319| 352,680 - United Kingdom | 951,196|28,176| 572,919| 373,416 - France | | 584| 413,977|2,967,528 - Canada | | | 765,676| 19,782 - Czechoslovakia | | | 112,562| 506,598 - All other countries| 210,764|22,293| 39,110| 539,070 - +---------+------+---------+--------- - Total |2,213,942|68,566|3,447,487|7,535,120 - +---------+------+---------+--------- - | Value - +---------+------+---------+--------- - Netherlands | $66,445|$2,718| $273,432| $636,644 - Germany | 27,159| 252| 129| 96,542 - United Kingdom | 93,938| 2,760| 99,204| 76,001 - France | | 97| 79,242| 751,816 - Canada | | | 114,523| 4,922 - Czechoslovakia | | | 21,650| 148,612 - All other countries| 21,447| 2,450| 5,856| 112,652 - +---------+------+---------+--------- - Total | 208,989| 8,277| 594,036|1,827,189 - +---------+------+---------+--------- - | Percent of total imports by quantity - +---------+------+---------+--------- - Netherlands | 35.0| 24.7| 44.7| 36.8 - Germany | 12.5| .9| | 4.7 - United Kingdom | 43.0| 41.1| 16.6| 5.0 - France | | .8| 12.0| 39.4 - Canada | | | 22.2| .3 - Czechoslovakia | | | 3.3| 6.7 - All other countries| 9.5| 32.5| 1.2| 7.1 - +---------+------+---------+--------- - Total | 100.0| 100.0| 100.0| 100.0 - -------------------+---------+------+---------+--------- - - [1] General imports. - - [2] Preliminary. - - Source: Foreign Commerce and Navigation of the United States. - - - - -APPENDIX B - -TRADE NAMES FOR SYNTHETIC RESINS MADE IN THE UNITED STATES - - - _Trade name_ _Maker_ - - Tar-acid resins: - - Amberol Resinous Products & Chemical Co., Inc., Phila., - Pa. - Artifex Artifex Products Co., Camden, N. J. - Bakelite Bakelite Corp., New York, N. Y. - Beckacite Beck, Koller & Co., Inc., Detroit, Mich. - Beckasol Beck, Koller & Co., Inc., Detroit, Mich. - Beckopol Beck, Koller & Co., Inc., Detroit, Mich. - Catalin Catalin Corp., New York, N. Y. - Celeron Continental-Diamond Fibre Co., Newark, Del. - Coltrock Colt’s Patent Fire Arms Mfg. Co., Hartford, Conn. - Colasta Colasta Co., Inc., Hoosick Falls, N. Y. - Dilecto Continental-Diamond Fibre Co., Newark, Del. - Dura Paramet Chemical Corp., Long Island City, N. Y. - Durez General Plastics, Inc., N. Tonawanda, N. Y. - Durite Durite Plastics, Phila., Pa. - Fabroil General Electric Co., Schenectady, N. Y. - Fiberlon Fiberloid Corp., Indian Orchard, Mass. - Fibroc Fibroc Insulation Co., Valparaiso, Ind. - Gemstone A. Knoedler Co., Lancaster, Pa. - Haveg Haveg Corp., Newark, Del. - Herculite Colasta Co., Inc., Hoosick Falls, N. Y. - Indur Reilly Tar & Chemical Corp., Indianapolis, Ind. - Insurok Richardson Co., Melrose Park, Ill. - Joanite Joanite Corp., Long Island City, N. Y. - Kellite Kellogg Switchboard & Supply Co., Chicago, Ill. - Lewisol John D. Lewis, Mansfield, Mass. - Makalot Makalot Corp., Boston, Mass. - Marblette Marblette Corp., Long Island City, N. Y. - Micarta Westinghouse Electric & Mfg. Co., Trafford, Pa. - Moldarta Westinghouse Electric & Mfg. Co., Trafford, Pa. - Pandura Paramet Chemical Corp., Long Island City, N. Y. - Panelyte Panelyte Corp., Trenton, N. J. - Paranol Paramet Chemical Corp., Long Island City, N. Y. - Phenac American Cyanamid Co., New York, N. Y. - Phenalin E. I. du Pont de Nemours & Co., Wilmington, Del. - Prystal Catalin Corp., New York, N. Y. - Resinox Resinox Corp., New York, N. Y. - Spauldite Spaulding Fibre Co., Tonawanda, N. Y. - Syntex Jones-Dabney Co., Inc., Louisville, Ky. - Synthane Synthane Corp., Oaks, Pa. - Taylor Taylor Fibre Co., Norristown, Pa. - Textolite General Electric Co., Schenectady, N. Y. - Waterlite Watertown Mfg. Co., Watertown, Conn. - - Other makers of tar acid resins in the United States include:[27] - Aluminum Industries, Cincinnati, Ohio; California Flaxseed - Products Co., Los Angeles, Calif.; Cook Paint & Varnish Co., - Chicago, Ill.; Ford Motor Co., Detroit, Mich.; Heresite & - Chemical Co., Manitowoc, Wis.; Millergum Co., Chicago, Ill.; - Nubian Paint & Varnish Co., Chicago, Ill.; Varcum Chemical Co., - Niagara Falls, N. Y.; Vita Var Corp., Newark, N. J. - - Alkyd resins: - - Amberlac Resinous Products & Chemical Co., Inc., Phila., - Pa. - Aquaplex Resinous Products & Chemical Co., Inc., Phila., - Pa. - Beckol Beck, Koller & Co., Inc., Detroit, Mich. - Beckosol Beck, Koller & Co., Inc., Detroit, Mich. - Dulux E. I. du Pont de Nemours & Co., Wilmington, Del. - Duraplex Resinous Products & Chemical Co., Inc., Phila., - Pa. - Esterol Paramet Chemical Corp., Long Island City, N. Y. - Glyptal General Electric Co., Schenectady, N. Y. - Lewisol John D. Lewis, Mansfield, Mass. - Makalot Makalot Corp., Boston, Mass. - Paraplex Resinous Products & Chemical Co., Inc., Phila., - Pa. - Rauzene Robert Rauh, Inc., Newark, N. J. - Rezyl American Cyanamid Co., New York, N. Y. - Syntex Jones-Dabney Co., Inc., Louisville, Ky. - Teglac American Cyanamid Co., New York, N. Y. - - Other makers of alkyd resins in the United States include:[27] - Atlas Powder Co., Wilmington, Del.; Bakelite Corp., New York, - N. Y.; Andrew Brown Co., Los Angeles, Calif.; California - Flaxseed Products, Los Angeles, Calif.; Carboygen Chemical Co., - Garwood, N. J.; General Paint Co., Tulsa, Okla.; Hercules Powder - Co., Wilmington, Del.; Nubian Paint & Varnish, Chicago, Ill.; - Pittsburgh Plate Glass Co., Milwaukee, Wis.; Valentine & Co., - Inc., New York, N. Y. - - Urea resins: - - Beetle American Cyanamid Co., New York, N. Y. - Beckamine Beck, Koller & Co., Detroit, Mich. - Plaskon Plaskon Co., Inc., Toledo, Ohio. - RHoplex Rohm & Haas, Philadelphia, Pa. - Syntex Jones-Dabney Co., Inc., Louisville, Ky. - Uformite Resinous Products & Chemical Co., Phila., Pa. - - Other makers of urea resins in the United States include: E. I. - du Pont de Nemours & Co., Wilmington, Del.; Bakelite Corp., New - York, N. Y. - - Acrylate resins: - - Acryloid Resinous Products & Chemical Co., Phila., Pa. - Acrysol Resinous Products & Chemical Co., Phila., Pa. - Crystalite Resinous Products & Chemical Co., Phila., Pa. - Lucite E. I. du Pont de Nemours & Co., Wilmington, Del. - Plexiglas Resinous Products & Chemical Co., Phila., Pa. - Plexigum Resinous Products & Chemical Co., Phila., Pa. - Primal Resinous Products & Chemical Co., Phila., Pa. - - Coumarone-indene resins: - - Cumar Barrett Co., New York. - Neville Neville Co., Pittsburgh, Pa. - Nevindene Neville Co., Pittsburgh, Pa. - - Petroleum resins: - - Santo-Resin Monsanto Chemical Co., St. Louis, Mo. - Petropol Pure Oil Co., Chicago, Ill. - - Polystyrene resins: - - Bakelite polystyrene Bakelite Corp., New York, N. Y. - Carbide & Carbon Chemicals Corp., New York, N. Y. - Styron Dow Chemical Co., Midland, Mich. - - Vinyl resins: - - Butvar Shawinigan Products, Inc., Indian Orchard, Mass. - Vinyloid Carbide & Carbon Chemicals Corp., New York. - Vinylite Carbide & Carbon Chemicals Corp., New York. - Vinal Carbide & Carbon Chemicals Corp., New York. - Vinylseal Carbide & Carbon Chemicals Corp., New York. - Flamenol General Electric Co., Schenectady, N. Y. - Koroseal B. F. Goodrich Co., Akron, Ohio. - E. I. du Pont de Nemours & Co., Wilmington, Del. - - - - -APPENDIX C - -TRADE NAMES FOR SYNTHETIC RESINS MADE IN GREAT BRITAIN - - - _Trade name_ _Maker_ - - Tar-acid resins for moulding and laminating: - - Bakelite Bakelite, Ltd., London. - Britsulite British Insulite Ltd., Manchester. - Elo Birkby’s Ltd., Liversedge, Yorkshire. - Fabrolite British Thompson Houston Co., Ltd., Rugby. - Holite E. S. Hole, London. - Indurite Indurite Moulding Powders Ltd., Radcliffe, - Lancashire. - Lorival Lorival Mfg. Co., Ltd., Southall, Middlesex. - Mouldrite Imperial Chemical Industries, Ltd., London. - Nestorite James Ferguson & Sons, Ltd., London. - Permaplastic Permastic Ltd., Weybridge, Surrey. - Rockite F. A. Hughes & Co., Ltd., London. - - Oil soluble tar-acid resins: - - Bakelaque Attwater & Sons, Ltd., Preston, Lancashire. - Damard Bakelite, Ltd., London. - Damarda Bakelite, Ltd., London. - Epok British Resin Products, Ltd., Kingston-on-Thames. - Erinite Erinoid Ltd., Stroud, Gloucester. - Formapex Ioco Rubber & Waterproofing Co., Ltd., - Anniesland, Glasgow. - Keebush Bushings, Ltd., Hebburn-on-Tyne. - - Cast phenolic resin: - - Catalin Catalin Ltd., Waltham Abbey, Essex. - - Urea resins: - - Beetle Beetle Products Co., Ltd., Oldbury, - Worcestershire. - Mouldrite Imperial Chemical Industries, Ltd., London. - Pollopas Beetle Products Co., Ltd., Oldbury, - Worcestershire. - Scarat Beetle Products Co., Ltd., Oldbury, - Worcestershire. - - Alkyd resins: - - Albertalates Albert Products, Ltd., Erith, Kent. - Dulux Nobel Chemical Finishes Ltd., London. - Glyptal British Thompson Houston Co., Ltd., Rugby. - Micanite Micanite and Insulators Co., Ltd., Walthamstow, - London. - Paralac Imperial Chemical Industries, Ltd., London. - - Acrylate resins: - - Diakon and Perspex Mouldrite Ltd., Division of Imperial Chemical - Industries, Ltd., London. - - Aniline resins: - - Panilax Micanite and Insulators Co., Ltd., London. - - - - -APPENDIX D - -TRADE NAMES FOR SYNTHETIC RESINS MADE IN GERMANY - - - _Trade name_ _Maker_ - - Tar-acid resins: - - Alberid Dr. Kurt Albert G. m. b. H., Chemische Fabrik, - Wiesbaden-Biebrich. - Albertol Dr. Kurt Albert G. m. b. H., Chemische Fabrik, - Wiesbaden-Biebrich. - Ambresit Chemische Fabrik Ambra, Zittau i. Sachsen (in - liquidation). - Ammoplaste I. G. Farbenindustrie A. G., Frankfort-on-Main. - Backdura Bakelite G. m. b. H., Berlin. - Bakelit Bakelite G. m. b. H., Berlin. - Bakelit A (Resol) Bakelite G. m. b. H., Berlin. - Bakelit C Bakelite G. m. b. H., Berlin. - Bezet Harz Louis Blumen, Zwickau i. Sachsen. - Boschbakelite Robert Bosch A. G., Stuttgart. - Celloresen Louis Blumer, Zwickau i. Sachsen. - Dekorit Dr. F. Raschig G. m. b. H., Ludwigshafen a. - Rhein. - Durax - Durophen Dr. Kurt Albert G. m. b. H., Wiesbaden-Biebrich. - Elastolith Herold A. G., Hamburg 33. - Ethyl cellulose I. G. Farbenindustrie A. G., Frankfort-on-Main. - Faturan Dr. Heinr. Traun & Sohne, Hamburg. - Ferrozell Deutsche Ferrozell G. m. b. H., Augsburg. - Greif Faturan Dr. H. Traun & Sohne, Hamburg. - Havegit Saureschutz G. m. b. H., Berlin. - Herolith Herold A. G., Hamburg. - Hornolith Hornolith G. m b. H., Berlin S 59. - Ivorax Herold A. G., Hamburg. - Koraton Wedig & Reu. - Kunstharz 26 Z I. G. Farbenindustrie A. G., Frankfort-on-Main. - Laccain Louis Blumer, Zwickau i. Sachsen. - Leukorit Dr. F. Raschig G. m. b. H., Ludwigshafen a. - Rhein. - Lithocorn A. Elhardt Sohne, Kempten, Bayern. - Marbolith Herold A. G., Hamburg 33. - Metakalin I. G. Farbenindustrie A. G., Frankfort-on-Main. - Neoresit August Nowak A. G., Bautzen. - Novolack Bakelite G. m. b. H., Berlin. - Novotext Allgemeine Elektrizitats-Gesellschaft, Berlin. - Ornalith Herold A. G., Hamburg - Phenolplaste I. G. Farbenindustrie A. G., Frankfort-on-Main. - Redmanol (Bakelit A) Bakelite G. m. b. H., Berlin. - Resenoplast Louis Blumer, Zwickau i. Sachsen. - Resinit Bakelite G. m. b. H., Berlin. - Resinole Dr. F. Raschig G. m. b. H., Ludwigshafen a. - Rhein. - Resit Bakelite G. m. b. H., Berlin. - Resol Bakelite G. m. b. H., Berlin. - Schellackersatz I. G. Farbenindustrie A. G., Frankfort-on-Main. - Dr. A. Wacker Gesellschaft für Elektrochemische - Industrie G. m. b. H., München. - Dr. Kurt Albert, Wiesbaden-Biebrich. - Sipilite Bakelite G. m. b. H., Berlin. - Supraresen Louis Blumer, Zwickau i. Sachsen. - Syntellac Dr. A. Wacker G. m. b. H., München. - Tenazit Allgemeine Elektrizitats-Gesellschaft, Berlin. - Toplast Louis Blumer, Zwickau i. Sachsen. - Trolon Rheinisch-Westfalische Sprengstoff Fabriken, - Troisdorf. - Turbax Jaroslaw’s Erste Glimmerwarenfabrik, Berlin - SO 36. - Vigorith Dr. F. Raschig, Ludwigshafen a. Rhein. - Vinnapas Dr. A. Wacker G. m. b. H., München. - Wackerschellack Dr. A. Wacker G. m. b. H., München. - Wenjazit Kunst-Rohstoff A. G., Hamburg-Einbeck. - - Alkyd resins: - - Alftalate Dr. Kurt Albert G. m. b. H., Chemische Fabrik, - Wiesbaden-Biebrich. - Alkydal I. G. Farbenindustrie A. G., Frankfort-on-Main. - Beckacite Beckacite Kunstharzfabrik, G. m. b. H., - Hamburg-Wandsbeck. - Beckosol Beckacite Kunstharzfabrik, G. m. b. H., - Hamburg-Wandsbeck. - Duxol Louis Blumer, Zwickau i. Sachsen. - Duxalid Louis Blumer, Zwickau i. Sachsen. - Geaphthal Allgemeine Elektrizitats-Gesellschaft, Berlin. - Glyptal Dr. Kurt Albert G. m. b. H., Wiesbaden-Biebrich. - - Urea resins: - - Hares L H. Rommler A. G., Berlin W 62. - Locron I. G. Farbenindustrie, A. G., Frankfort-on-Main. - Pluviusin Kunstharzfabrik Dr. F. Pollack, Vienna, German - branch Berlin. - Pollopas Rheinisch-Westfalische Sprengstoff Fabriken, - Troisdorf, Bez. Koln. - - Vinyl resins: - - Acronal I. G. Farbenindustrie, A. G., Frankfort-on-Main. - Mowilith I. G. Farbenindustrie, A. G., Frankfort-on-Main. - - Polystyrene resins: - - Metastyrol I. G. Farbenindustrie, A. G., Frankfort-on-Main. - Mollit I. G. Farbenindustrie, A. G., Frankfort-on-Main. - Trolitul Rheinisch-Westfalische Sprengstoff Fabriken, - Troisdorf. - - Acrylate resins: - - Plexigum Rohm & Haas, Darmstadt. - - Other resins: - - Coumarone resins Kokawerke & Chemische Fabriken A. G., Berlin - N. W. 40. - Harz No. 30 Ciba A. G., Berlin-Wilmersdorf. - Harz No. 238 Ciba A. G., Berlin-Wilmersdorf. - Ultrasit Chemische Fabrik Ambra, Zittau, Sachsen, (in - liquidation). - Utilith Deutsche Rohstoffindustrie, Augsburg. - - - - -APPENDIX E - -LIST OF UNITED STATES MANUFACTURERS OF RAW MATERIALS FOR SYNTHETIC -RESINS[28] - - - Phenol: - Barrett Co., New York, N. Y. - Calco Chemical Co., Inc., Bound Brook, N. J. - Dow Chemical Co., Midland, Mich. - Koppers Co., Pittsburgh, Pa. - Monsanto Chemical Co., St. Louis, Mo. - Reilly Tar & Chemical Corp., Indianapolis, Ind. - - Cresols: - Barrett Co., New York, N. Y. - Calco Chemical Co., Inc., Bound Brook, N. J. - Givaudan-Delawanna, Inc., Delawanna, N. J. - Koppers Co., Pittsburgh, Pa. - Reilly Tar & Chemical Corp., Indianapolis, Ind. - Swann & Co., Birmingham, Ala. - - Xylenols: - Barrett Co., New York, N. Y. - Calco Chemical Co., Inc., Bound Brook, N. J. - Reilly Tar & Chemical Corp., Indianapolis, Ind. - - Butyl phenol (p-tertiary), Dow Chemical Co., Midland, Mich. - - Phenyl phenols, Dow Chemical Co., Midland, Mich. - - Resorcinol, tech.: - E. I. du Pont de Nemours & Co., Wilmington, Del. - Pennsylvania Coal Products Co., Petrolia, Pa. - - Naphthalene: - Barrett Co., New York, N. Y. - Calco Chemical Co., Inc., Bound Brook, N. J. - Coopers Creek Chemical Co., West Conshohocken, Pa. - E. I. du Pont de Nemours & Co., Wilmington, Del. - Reilly Tar & Chemical Corp., Indianapolis, Ind. - Shell Chemical Co., San Francisco, Calif. - Standard Naphthalene Products Corp., South Kearney, N. J. - White Tar Co. of N. J., Inc., Pittsburgh, Pa. - - Phthalic acid and anhydride: - American Cyanamid Co., New York, N. Y. - Barrett Co., New York, N. Y. - E. I. du Pont de Nemours & Co., Wilmington, Del. - Monsanto Chemical Co., St. Louis, Mo. - National Aniline & Chemical Co., Inc., New York, N. Y. - - Maleic acid and anhydride: - National Aniline & Chemical Co., Inc., New York, N. Y. - American Cyanamid Co., New York, N. Y. - Monsanto Chemical Co., St. Louis, Mo. - - Malic acid, National Aniline & Chemical Co., Inc., New York, N. Y. - - Adipic acid, E. I. du Pont de Nemours & Co., Wilmington, Del. - - Succinic acid and anhydride: - American Cyanamid Co., New York, N. Y. - National Aniline & Chemical Co., Inc., New York, N. Y. - - Urea, E. I. du Pont de Nemours & Co., Wilmington, Del. - - Formaldehyde: - E. I. du Pont de Nemours & Co., Wilmington, Del. - Empire Oil & Refining Co., Bartlesville, Okla. - Heyden Chemical Corp., New York, N. Y. - - Hexamethylenetetramine, tech.: - E. I. du Pont de Nemours & Co., Wilmington, Del. - Heyden Chemical Corp., New York, N. Y. - Monsanto Chemical Co., St. Louis, Mo. - - Furfural, Quaker Oats Co., Chicago, Ill. - - Vinyl acetate: - Carbide & Carbon Chemicals Corp., New York, N. Y. - E. I. du Pont de Nemours & Co., Wilmington, Del. - Niacet Chemicals Corp., Niagara Falls, N. Y. - - Vinyl chloride, Carbide & Carbon Chemicals Corp., New York, N. Y. - - - - -APPENDIX F - -GLOSSARY[29] - - -_Alkyd resin._—Any condensation product involving a polybasic acid and -a polyhydric alcohol. Typical examples are phthalic glyceride and its -modifications containing combined fatty acids or rosin. Representative -examples are Rezyls and Glyptal. - -_Aminoplast._—General terms for synthetic resins from amino or amido -compounds. A typical example is urea-formaldehyde. - -_Amorphous._—Devoid of crystalline structure. This condition is rare. -Many substances which are apparently amorphous show microcrystallinity, -particularly under X-ray examination. - -_A-stage resins._—Thermosetting resins reacted only to the initial stage -where they are soluble and fusible. The normal stage of a resin used for -impregnation. - -_Bonding strength._—The amount of adhesion between a binder and filler. -More specifically, the measure of the extent to which the composite -layers of a laminated product are bonded together. - -_Brittleness._—Liability to break, generally to a conchoidal fracture. - -_B-stage resins._—Thermosetting resins reacted to a stage where they -soften when heated and swell in contact with liquids but do not entirely -fuse or dissolve. This is the preferred stage for the resin in molding -compositions. - -_Casting._—Forming a material into a shape by pouring it when liquid into -a mold. The product from the mold is used as such or mechanically worked -in various ways to the final articles, as by sewing, cutting, blanking, -turning, drilling, forming, swaging, grinding, polishing, sanding, or -routing. - -_Compressive strength._—Resistance to deformation under applied pressure. - -_Condensation._—A chemical reaction in which two or more molecules -combine with a separation of water or some other simple substance. -Applied to synthetic resins it means the formation of a resin by -combination of a number of molecules with elimination of water, -ammonia, hydrogen chloride, or other simple substance. Examples of -condensation resins are alkyd, phenol-aldehyde, and urea-formaldehyde -resins. The final products are also called condensation-polymers. (See -Polymerization.) - -_Copolymerization._—The term applied when two or more substances -polymerize at the same time to yield a product which is not a mixture of -separate polymers but a complex having properties different from either -polymer alone. For example, vinylite is produced by polymerization of a -mixture of vinyl acetate and vinyl chloride. - -_C-stage resins._—Thermosetting resins in the final stage in which they -are infusible and insoluble. The state of the resin in the final molded -article. - -_Curing._—The change of a binder from the soluble-fusible condition -to the substantially insoluble-infusible form by chemical action. The -heat-setting of a resinoid. Action is analogous to vulcanization of -rubber. - -_Dielectric strength._—Voltage gradient at which a continuous electrical -discharge will take place between two electrodes when the material in -question is placed between the electrodes and a potential difference is -applied to them. - -_Elastic._—A substance which exhibits rubberlike properties or “high -elasticity” over a wide range of applied forces. - -_Elastic deformation._—When a substance reverts to its original -dimensions on release of an applied stress. - -_Elastic limit._—The point at which a body begins to yield under a -stress; that is, when the stress is equal to or greater than the internal -friction. - -_Elasticity._—The property by virtue of which a body reverts to its -normal bulk or shape after deformation by an applied force. - -_Extrusion molding._—A molding procedure for extended shapes of uniform -cross section, whereby a heat-softened substance is forced through an -orifice of form coinciding with the cross section of the article. - -_Flexibility._—Capability of bending without breaking. - -_Gums._—Viscous vegetable secretions which harden but, unlike resins, are -water soluble. The name is often applied, particularly in the varnish -industry, to natural resins such as copals. - -_Hardness._—Property of substances determined by their ability to -abrade or indent one another. Often measured by the extent or depth of -indentation produced by a standard substance under a predetermined load. - -_Impact strength._—The measure of toughness of a material. Generally -determined by the energy required to break a specimen in one blow. - -_Injection molding._—A molding procedure whereby a heat-softened plastic -material is forced from a receptacle into a cavity which gives the -article of desired shape. Used particularly for thermoplastics since -the scrap can be reused. As soon as the composition in the mold cools -sufficiently to be rigid, the mold is opened and the molded article -removed. An analogy of injection molding in another field is shown by the -linotype machine. - -_Inserts._—Parts of a finished molded article which are of different -material from the molding composition but are set in place or positioned -by the molding operation. - -_Laminated products._—Sheets of material united by a binder. For example, -sheets of paper or wood coated and/or impregnated with a resinous -composition and subjected to pressure, generally with heat. - -_Monomer._—The simplest repeating structural unit of a polymer. For -addition polymers this represents the originally unpolymerized compound. - -_Phenoplast._—A general term for phenol-aldehyde resins. Synonymous with -popular term “phenolics.” - -_Plastics._—All substances that can be molded. In general a plastic is a -substance which behaves as a solid at stresses less than a certain amount -known as the yield value and as a viscous liquid at stresses greater -than this. The name is also applied to substances which originally but -not ultimately fulfill this condition. For example, it is applied to -thermoset compositions or resinoids in the final stages. - -_Plasticity._—Susceptibility to and the retention of deformation. -Capacity of taking and retaining the form of a mold. The property of -solids by virtue of which they hold their shape permanently under the -action of small shearing stresses but are readily deformed, worked, or -molded under larger stresses. - -_Polymerization._—A chemical change resulting in the formation of -a new compound whose molecular weight is a multiple of that of the -original substances. The products of the reaction are called polymers. -To distinguish from those resulting from condensation (q. v.), they -are often designated addition polymers, since the reaction is that of -successive addition of a large number of relatively small molecules -(monomers) to form the final polymer. - -_Power factor._—In an insulating material, the ratio of total power -loss (watts) in the material to the product of voltage and current in a -capacitor in which that material is a dielectric. - -_Preforms._—Molding powders converted by pressure and without heat -into a denser coherent form which approximates the shape of the final -hot-pressed article. Molding material converted to preforms has about -half the bulk factor of the original powder. Other forms of densified -composition which do not necessarily approximate the shape of the final -molding are tablets, briquettes, pellets, pills, and balls. - -_Resin._—A term generally referring to a physical condition at room -temperature approximating the physical properties of natural resins. -However, the temperature of reference should not be limited to room -temperature and the term is here intended to embrace all substances which -within a certain temperature range show these, properties. For example, -many oil-modified alkyd resins are viscous liquids at room temperature -but not at lower temperatures; polystyrene is a resin at room temperature -but rubberlike when warmed. - -_Resinoids._—The class name applied to thermosetting resins. Temporary -thermoplastics. The name is also often applied to the final cured resins. - -_Softening point._—Resins have no sharp melting point. Application of -heat causes gradual change from a brittle or exceedingly thick and slow -flowing material to a softer and less viscous liquid. The softening point -is the temperature at which the material flows at a definite rate or to a -definite distance. - -_Synthetic resin._—A complex, substantially amorphous, organic semisolid -or solid material (usually a mixture of substances) built up by chemical -reaction of comparatively simple compounds and, depending upon the -temperature at which the examination is made, approximating the natural -resins in various physical properties: namely, luster, fracture, -comparative brittleness, insolubility in water, fusibility or plasticity -when heated or exposed to heat and pressure, and, at a certain more -or less narrow temperature range before fusion, showing a degree of -rubberlike extensibility; but commonly deviating widely from natural -resins in chemical constitution and behavior with reagents. - -_Synthetic rubber._—Caoutchouc synthesized in the laboratory. The term is -a misnomer and most probably represents an impossibility. - -_Tensile strength._—The greatest internal force per unit of cross section -which a material develops before failure under tension.[30] - -_Thermoplastic._—The property of softening under heat. All molding -materials are thermoplastic at the initial application of heat. One class -(the so-called thermoplastics) remains soft permanently under heat; the -other (thermosetting), after first softening, sets or cures more or less -quickly to a more solid form. A practical distinction is that with the -first class the mold must be cooled before the molded article is removed, -but not with the second. A thermoplastic substance is adequately rigid -at normal temperatures and under ordinary conditions of stress but is -capable of deformation under heat and pressure. - -_Thermosetting._—The property of undergoing a chemical change when -heated whereby a hardened product is obtained. Property most pronounced -in phenol and urea formaldehyde resins and less so with alkyds. A -thermosetting substance possesses initially the properties of a -thermoplastic but under the influence of heat undergoes chemical change -so that it is no longer thermoplastic but becomes permanently infusible. - -_Viscosity._—Internal friction or resistance to change of form of a -liquid. The constant ratio of shearing stress to rate of shear. - -_Water-absorption._—Amount of water taken up when exposed to humid -conditions or when immersed. Both rate of absorption and total absorption -are important, also change in dimensions. A certain amount of absorbed -water may improve mechanical properties but usually weakens electrical -characteristics. - - - - -FOOTNOTES - - -[1] A glossary of technical terms is included in appendix F. p. 160 of -this report. There are, however, certain fundamental terms which it would -be advisable to have clearly in mind at this point. - -[2] Shellac is a substance secreted by lac insects feeding on certain -types of hardwood trees. - -[3] Journal of the Society of Chemical industry, 1901. Vol. 20, p. 1075. - -[4] Current sales prices in the United States average between 7 and 10 -cents per pound and any imports would be dutiable under the provisions -of par. 28 of the Tariff Act of 1930 at 45 percent ad valorem based on -American selling price plus 7 cents per pound. Based on an American -selling price of 7 cents per pound, the import duty would be slightly -more than 10 cents per pound, while on an American selling price of 10 -cents per pound the duty would be 11.5 cents per pound. - -[5] Zelov, Victor I. Automatic Molding, Pt. 2, Advantages and -limitations. Modern Plastics, v. 15, No. 2, p. 206; October 1937. - -[6] For texts and interpretation of exclusion orders see Treasury -Decisions 41512; 41895; 44411; 44491; 44776; and 44977. - -[7] American selling price is defined in section 402, (g) as: “The -American selling price of any article manufactured or produced in the -United States shall be the price, including the cost of all containers -and coverings of whatever nature and all other costs, charges, and -expenses incident to placing the merchandise in condition packed ready -for delivery, at which such article is freely offered for sale to all -purchasers in the principal market of the United States, in the ordinary -course of trade and in the usual wholesale quantities in such market, or -the price that the manufacturer, producer, or owner would have received -or was willing to receive for such merchandise when sold in the ordinary -course of trade and in the usual wholesale quantities, at the time of -exportation of the imported article.” - -[8] United States value is defined in section 402, (e) as: “The United -States value of imported merchandise shall be the price at which such -or similar imported merchandise is freely offered for sale, packed -ready for delivery, in the principal market of the United States to all -purchasers, at the time of exportation of the imported merchandise, in -the usual wholesale quantities and in the ordinary course of trade, with -allowance made for duty, cost of transportation and insurance, and other -necessary expenses from the place of shipment to the place of delivery, a -commission not exceeding 6 per centum, if any has been paid or contracted -to be paid on goods secured otherwise than by purchase, or profits not to -exceed 8 per centum and a reasonable allowance for general expenses, not -to exceed 8 per centum on purchased goods.” - -[9] The reclassifications read: - -PAR. 2. “Vinyl acetate, polymerized or unpolymerized, and synthetic -resins made in chief value therefrom, not specially provided for.” - -PAR. 11. “Synthetic resins made in chief value from vinyl acetate, not -specially provided for.” - -[10] See sections on import under each resin. - -[11] Reduced May 23, 1934, from 25 cents per pound and 30 percent by -Presidential proclamation under Section 336 of the Tariff Act of 1930. - -[12] Based on the total sales in 1937 reported to the Tariff Commission; -sales in dollars dived by quantity (net resin content). - -[13] The new consumption-restriction regulations are— - - _Exterior use on plaster, brick, stone, and cement_: - - 1. Surfaces already painted with oil paint may be repainted with - oil paints, without restrictions; - - 2. Surfaces calcimined may be painted with paints containing not - more than 15 percent oil; - - 3. Unpainted surfaces may be painted only with paints free of oil. - - _Exterior use on wood_: - - Linseed oil paint may be used for the first coat, and succeeding - coats may contain up to 70 percent oil. - - _Exterior and interior use on metal_: - - Oil paints may be used without restriction. - - _Interior use on plaster, brick, stone, and cement_: - - 1. Surfaces already painted with oil paint may only be repainted - with paint containing not more than 15 percent oil. - - 2. Unpainted surfaces must be painted with paint free of oil. - - _Interior use on wood, to be cleaned with soap and soda_: - - El Varnish and oil varnish may be used for the first coat - followed by paint containing up to 70 percent oil. - - _Interior use on wood, not cleaned with soap and soda_: - - As above, except that succeeding coats may contain not more than - 40 percent oil. - -[14] Acknowledgment: Most of the information about the industry in Great -Britain was submitted by Norman Inwood of the staff of the American -consulate general at London, England. - -[15] Acknowledgment: Information obtained on the synthetic resin industry -in France was furnished by Addison E. Southard, American consul general -at Paris. - -[16] Acknowledgment: Much of the information on the Japanese synthetic -resin industry included herein was furnished by Carl H. Boehringer, -Assistant Trade Commissioner at Tokyo at the request of the U.S. Tariff -Commission. - -[17] These figures are based on an average naphthalene content of coal -tar of slightly less than 10 percent. The total amount contained would, -of course, not be recovered even under ideal market conditions as to -price and demand. - -[18] Par. 1651. Coal-tar products: ... naphthalene which after the -removal of all the water present has a solidifying point less than 79° C. -... (Free). - -[19] Par. 27. Coal-tar products: - -(_a_) (1), (5) ... naphthalene which after the removal of all water -present has a solidifying point of 79° C. or above; all the foregoing -products in this paragraph whether obtained, derived, or manufactured -from coal tar or other sources; ... 40 percent ad valorem and 7 cents per -pound. - -(_c_) The ad valorem rates provided in this paragraph shall be based upon -the American selling price (as defined in subdivision (g) of section -402, title IV), of any similar competitive article manufactured or -produced in the United States. If there is no similar competitive article -manufactured or produced in the United States then the ad valorem rate -shall be based upon the United States value, as defined in subdivision -(e) of section 402, title IV. - -(_d_) For the purposes of this paragraph any coal-tar product provided -for in this act shall be considered similar to or competitive with any -imported coal-tar product which accomplishes results substantially equal -to those accomplished by the domestic product when used in substantially -the same manner. - -[20] Upon American selling price or United States value. - -[21] The relevant provisions of this act are as follows: - -Par. 27 (b) ... phenol, carbolic acid which on being subjected to -distillation yields in the portion distilling below one hundred and -ninety degrees centigrade a quantity of tar acids equal to or more than -5 per centum of the original distillate, ..., and any mixture of any of -the foregoing products with any of the products provided for in paragraph -1651, 20 per centum ad valorem and 3½ cents per pound. - -(c) The ad valorem rates provided in this paragraph shall be based upon -the American selling price (as defined in subdivision (g) of section -402, title IV), of any similar competitive article manufactured or -produced in the United States. If there is no similar competitive article -manufactured or produced in the United States then the ad valorem rate -shall be based upon the United States value, as defined in subdivision -(e) of section 402, title IV. - -(d) For the purposes of this paragraph any coal-tar product provided -for in this Act shall be considered similar to or competitive with any -imported coal-tar product which accomplishes results substantially equal -to those accomplished by the domestic product when used in substantially -the same manner. - -[22] In 1923 the unit value of domestic sales was 27 cents per pound and -the duty on imports (computed specific rate per pound) was 16 cents; in -1925 the corresponding figures were 21 and 16 cents, respectively. - -[23] Par. 1651. Coal-tar products: ..., all mixtures of any of these -distillates and any of the foregoing pitches, and all other materials or -products found naturally in coal tar, whether produced or obtained from -coal tar or other source, and not specially provided for in pars. 27 or -28.... - -[24] Par. 27 (a) (2). Coal-tar products: All distillates (except -those provided for in sub-paragraph (b)) of coal tar, blast-furnace -tar, oil-gas tar, and water-gas tar, ..., which on being subjected to -distillation yield in the portion distilling below two hundred and -fifteen degrees centigrade a quantity of tar acids equal to or more than -75 per centum of the original distillate. - -[25] Par. 27 (b). Metacresol having a purity of 90 per centum or more, -orthocresol having a purity of 90 per centum or more, paracresol having -a purity of 90 per centum or more, ... and any mixture of any of the -foregoing products with any of the products provided for in paragraph -1651, ... - -Par. 27 (c). The ad valorem rates provided in this paragraph shall be -based upon the American selling price (as defined in subdivision (g) of -section 402, title IV), of any similar competitive article manufactured -or produced in the United States. If there is no similar competitive -article manufactured or produced in the United States then the ad -valorem rate shall be based upon the United States value, as defined in -subdivision (e) of section 402, title IV. - -Par. 27 (d). For the purposes of this paragraph any coal-tar product -provided for in this Act shall be considered similar to or competitive -with any imported coal-tar product which accomplishes results -substantially equal to those accomplished by the domestic product when -used in substantially the same manner. - -[26] Par. 27 (b). ... cresylic acid which upon being subjected to -distillation yields in the portion distilling below two hundred and -fifteen degrees centigrade a quantity of tar acids equal to or more than -75 per centum of the original distillate.... - -[27] Some of the makers of these products do not care to be identified -with their manufacture. - -[28] Some of the makers of these products are not listed because they do -not care to be so identified. - -[29] Based on pp. 321-4, Modern Plastics, October 1937. - -[30] Source: Peele’s Mining Engineers’ Handbook, Ed. 1, p. 2209. - -*** END OF THE PROJECT GUTENBERG EBOOK SYNTHETIC RESINS AND THEIR RAW -MATERIALS, REPORT NO. 131, SECOND SERIES *** - -Updated editions will replace the previous one--the old editions will -be renamed. - -Creating the works from print editions not protected by U.S. copyright -law means that no one owns a United States copyright in these works, -so the Foundation (and you!) can copy and distribute it in the -United States without permission and without paying copyright -royalties. 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