Report No. 94 POLYAMIDES OTHER THAN NYLONS 6 AND 66 PART I by YEN-CHEN YEN November 1974 A private report by the PROCESS ECONOMICS PROGRAM STANFORD RESEARCH INSTITUTE I MENLO PARK, CALIFORNIA
CONTENTS, PART I 1 SUMMARY AND COMMERCIAL ASPECTS... 1 Scope... 2 Aramids... 2 Nylon Fibers... 7 Nylon Resins... 9 Polyamides Other than Nylons and Aramids.... 11 Technical Aspects... 12 2 The usual Introduction, Summary, and Industry Status 3 sections are combined in Section 1 of this report...... 15 4 REVIEW OF PROCESSES... 17 Polymerization Processes.... 17 Spinning.... 22 Additives... 23 5 ARAMIDS WHOLLY PARA-LINKED.... 139 Review of Processes... 143 Process Description... 154 Process Discussion... 170 Cost Estimates.... 171 6 ARAMIDS NOT WHOLLY PAR-LINKED.... 183 Review of Processes... 184 Process Description... 199 Process Discussion... 209 Cost Estimates... 209 7 PARTIALLY AROMATIC POLYAMIDES... 217 Review of Products and Processes... 217 A Process for Making Poly(Hexamethylene Terephthalamide).. 237 Process Description... 237 Process Discussion... 247 Cost Estimates... 247 A Process for Making Nylon 3M6,T... 251 Process Description... 251 Process Discussion... 259 Cost Estimates... 259 vii
CONTENTS, PART II 8 ALICYCLIC POLYAMIDES... 263 Review of Processes... 263 A Process for Making Nylon PACM,12... 278 Process Description... 278 Process Discussion... 287 Cost Estimates... 287 9 ALIPHATIC POLYAMIDES FROM DIAMINES AND DIACIDS... 295 Review of Products and Processes... 295 Process Description... 305 Process Discussion... 315 Cost Estimates... 315 10 ALIPHATIC POLYAMIDES OTHER THAN NYLON 12, 11, OR 4 FROM LACTAMS OR AMINO ACIDS... 321 General... 321 Nylon3... 324 Nylon7..... 333 Nylon9..... 334 Nylon13... 335 Nylon2... 335 Nylon8... 336 Nylon5... 336 Nylon10... 337 11 NYLON12....................,.... 339 Chemistry... 339 Review of Processes... 340 Process Description... 347 Process Discussion... 354 Cost Estimates... 355 12 NYLON ll... 359 Chemistry... 359 Review of Processes... 360 Process Description... 360 Process Discussion... 368 Cost Estimates... 368 viii
CONTENTS, PART II 13 NYLON4... 373 Chemistry... 373 Review of Processes... 375 Process Description... 380 Process Discussion... 387 Cost Estimates... 387 14 OTHERPOLYAMIDES... 391 Polyamides Containing Heterocyclic Groups... 391 Polyamides from Fatty Acids... 392 Unsaturated Polyamides... 392 Polyamides Containing Hetero Atoms... 392 Polyamides Containing N-Alkoxyalkyl Groups... 393 Copolyamides and Polyamide Blends... 393 Bicomponent Fibers... 393 APPENDIX A DESIGN AND COST BASES............... 443 APPENDIX B PHYSICAL AND CHEMICAL DATA............. 445 APPENDIX C SOME CONVERSIONS.................. 459 APPENDIX D NYLON NOMENCLATURE................. 461 CITED REFERENCES........................ 463 PATENT REFERENCES BY COMPANY.................. 615 ix
ILLUSTRATIONS, PART I 5.1 Elongations at Break and Initial Moduli of Para Aramids Compared with Those of Other Polyamides, Glass, andsteel... 141 5.2 Tensile Strengths and Initial Moduli of Para Arsmids Compared with Those of Other Polyamides, Glass, andsteel... 142 5.3 FlowSheet......................... 161 5.4 Hexamethylphosphoramide Manufacture Flow Sheet............... ;..... 167 5.5 Effect of Operating Level and Plant Capacity on Production Cost..................... 182 6.1 Flow Sheet......................... 203 6.2 Effect of Operating Level and Plant Capacity on Production Cost..................... 215 7.1 Poly(Hexamethylene Terephthalamide) Resin by Interfacial Flow Sheet......................... 243 7.2 Nylon 3M6,T Chip Manufacture Flow Sheet......................... 255 7.3 Nylon 3M6,T Chip Manufacture Effect of Operating Level and Plant Capacity on Production Cost..................... 262 xi
TABLES, PART I 1.1 World Producers of Aramids and Nylons Other than Nylons 6 and 66................. 3 1.2 Cost Features of Certain Polyamide Fibers and Chips for Fibers...,.,... 8 1.3 Cost Features of Certain Nylon Resins........... 10 4.1 Polyamides by Batch Polymerization Patent Summary....................... 26 4.2 Polyamides by Continuous Polymerization Patent Summary....................... 27 4.3 Polyamides by Bulk Polymerization Patent Summary....................... 35 4.4 Polyamides by Polymerization in a Nonaqueous Medium Patent Summary....................... 36 4.5 Polyamides by Solid Phase Polymerization Patentsummary... 37 4.6 Polyamides by Interfacial Processes Patent Summary....................... 38 4.7 Polylactams by Anionic Polymerization Patent Summary....................... 39 4.8 Removal of Monomers and Oligomers from Polyamides Patent Summary....................... 44 4.9 Miscellaneous Catalysts for Polyamides Preparation Patentsummary... 45 4.10 Polyamides from Diamines and Dibasic Acids via Derivatives Patent Summary....................... 46 4.11 Polyamides from Diisocyanates Patent Summary....................... 47 4.12 Miscellaneous Processes for Polyamides Preparation Patent Summary....................... 48 4.13 Drying of Polyamides Patent Summary....................... 50 4.14 Production of Polyamide Powder Patent Summary....................... 51 4.15 Recovery and Treatment of Polyamide Waste Patent Summary....................... 52 xiii
TABLES, PART I 4.16 4.17 4.18 4.19 4.20 4.21 4.22 4.23 4.24 4.25 4.26 4.27 4.28 4.29 4.30 4.31 4.32 Means of Cleaning Equipment for Producing Polyamides Patent Summary...........,......,.... Melt-Spinning of Polyamides Patent Summary....................... Spin-Drawing of Polyamide Fiber Patent Summary.....,................. Spinnerets for Producing Polyamide Fibers Having Noncircular Cross Sections Patent Summary....................... Solution Spinning of Polyamides Patent Summary....................... Pigmenting and Delustering of Polyamides Patent Summary....................... Stabilizers for Polyamides Patent Summary....................... Antistatic Additives for Polyamides Patentsummary... Additives To Increase Hydrophilicity of Polyamides Patent Summary....................... Additives To Change Dyeability of Polyamides Patent Summary....................... Nucleating Agents for Polyamides Patent Summary... Plasticizers for Polyamides Patent Summary,...................... Additives To Facilitate Processing of Polyamides Patentsummary... Additives or Techniques for Increasing Melt Viscosity of Polyamides Patentsummary... Means for Increasing Molecular Weight of Polyamides Patent Summary... Viscosity Stabilizers for Polyamides Patent Summary....................... Additives for Improving Mechanical Properties of Polyamides Patent Summary....................... xiv 55 56 59 62 63 65 69 97 115 116 122 123 124 126 127 129 130
TABLES, PART I 4.33 4.34 4.35 5.1 5.2 5.3 5.4 5.5 5.6 5.7 5.8 5.9 5.10 5.11 5.12 5.13 5.14 5.15 Additives for Improving Transparency of Polyamides Patentsummary... 132 Additives for Improving Flame Retardance in Polyamides Patent Summary....................... 133 Miscellaneous Additives for Polyamides Patent Summary.........,....,........ 136 Para Aramids Patentsummary... 145 Aromatic Polyhydrazides Patentsummary... 151 Design Bases and Assumptions..............,. 154 Major Process Equipment and Utilities Summary....... 159 Stream Flows... 165 Waste Streams....................... 166 Hexamethylphosphoramide Manufacture Major Process Equipment and Utilities Summary....... 167 Hexamethylphosphoramide Manufacture Stream Flows... 169 Hexamethylphosphoramide Manufacture Total Capital Investment.................. 173 Hexamethylphosphoramide Manufacture Production Costs...................... 174 Total Capital Investment.................. 175 Production Costs...................... 177 Poly(p-Phenylene Terephthalamide) Yam Heat Treatment Total Fixed Capital.................... 179 Poly(p-Phenylene Terephthalamide) Heat-Treated Yarn Production Costs...................... 180 Comparison of Costs for Different Deniers......... 181 xv
TABLES, PART I 6.1 6.2 6.3 6.4 6.5 6.6 6.7 6.8 6.9 6.10 7.1 7.2 7.3 7.4 7.5 7.6 Poly(m-Phenvlene Isophthalamide).s Patent Summary...-... 185 Aramid Patent Aramid Patent Ordered Copolymers Summary... 190 Limited-Order Copolymers Summary...,...,... 192 Other Aramids Patent Summary....................... 194 Design Bases and Assumptions................ 199 Major Process Equipment and Utilities Summary........ 203 Stream Flows... 207 Waste Streams....................... 208 Total Capital Investment.................. 211 Production Costs.............,......... 213 Polyamides from Diacids Containing Aromatic Groups and Aliphatic Diamines Patent Summary....................... 218 Polyamides from Aromatic Diacids and Branched Aliphatic Diamines Patent Summary....................... 228 Polyamides from Aliphatic Diacids and Diamines, Other Than Xylylenediamines, Containing Aromatic Rings Patent Summary........................ 230 Polyamides from Xylylenediamines Patent Summary....................... 233 Polyamides from Amino Acids Containing Aromatic Rings Patent Summary....................... 238 Polyamides from Diamines and Diacids, Both Containing Aryl Rings... 239 xvi
TABLES, PART I 7.7 Poly(Hexamethylene Terephthalamide) Resin by Interfacial Design Bases and Assumptions...,............ 240 7.8 Poly(Hexamethylene Terephthalamide) Resin by Interfacial Major Process Equipment and Utilities Summary....... 241 7.9 Poly(Hexamethylene Terephthalamide) Resin by Interfacial Stream Flows... 245 7.10 Poly(Hexamethylene Terephthalamide) Resin by Interfacial Waste Streams....................... 246 7.11 Poly(Hexamethylene Terephthalamide) Resin by Interfacial Total Capital Investment.................. 248 7.12 Poly(Hexamethylene Terephthalamide) Resin by Interfacial Production Costs...................... 249 7.i3 Nylon 3M6,T Chip Manufacture Design Bases and Assumptions................ 251 7.14 Nylon 3M6,T Chip Manufacture Major Process Equipment and Utilities Summary....... 253 7.15 Nylon 3M6,T Chip Manufacture Stream Flows........................ 257 7.16 Nylon 3M6,T Chip Manufacture Waste Streams....................... 258 7.17 Nylon 3M6,T Chip Manufacture Total Capital Investment.................. 260 7.18 Nylon 3M6,T Chip Manufacture Production Costs...................... 261 xvii