Table of Contents
Chapter 1 Polyester Fibers ………………………………………………………………………………….. 1
Michael Jaffe and Anthony J. East
Chapter 2 Polyamide Fibers………………………………………………………………………………… 31
H.H. Yang
Chapter 3 Polypropylene Fibers……………………………………………………………………………139
Mei-Fang Zhu and H.H. Yang
Chapter 4 Vinyl Fibers………………………………………………………………………………………..261
Ichiro Sakurada and Takuji Okaya
Chapter 5 Wool and Related Mammalian Fibers…………………………………………………… 331
Leslie N. Jones, Donald E. Rivett, and Daryl J. Tucker
Chapter 6 Silk ……………………………………………………………………………………………………383
Akira Matsumoto, Hyeon Joo Kim, Irene Y. Tsai, Xianyan Wang,
Peggy Cebe, and David L. Kaplan
Chapter 7 Jute and Kenaf ……………………………………………………………………………………405
Roger M. Rowell and Harry P. Stout
Chapter 8 Other Long Vegetable Fibers: Abaca, Banana, Sisal, Henequen,
Flax, Ramie, Hemp, Sunn, and Coir ……………………………………………………..453
Subhash K. Batra
Chapter 9 Cotton Fibers ……………………………………………………………………………………..521
Philip J. Wakelyn, Noelie R. Bertoniere, Alfred D. French, Devron P. Thibodeaux,
Barbara A. Triplett, Marie-Alice Rousselle, Wilton R. Goynes, Jr., J.Vincent Edwards,
Lawrance Hunter, David D. McAlister, and Gary R. Gamble
Chapter 10 Regenerated Cellulose Fibers ………………………………………………………………667
Richard Kotek
Chapter 11 Cellulose Acetate and Triacetate Fibers ………………………………………………..773
Herman L. LaNieve
Chapter 12 Acrylic Fibers …………………………………………………………………………………. 811
Bruce G. Frushour and Raymond S. Knorr
Chapter 13 Aramid Fibers ………………………………………………………………………………… 975
Vlodek Gabara, Jon D. Hartzler, Kiu-Seung Lee, David J. Rodini, and H.H. Yang
Index……………………………………………………………………………………….. 1031
1 Polyester Fibers
Michael Jaffe and Anthony J. East
CONTENTS
1.1 Introduction …………………………………………………………………………………………………. 2
1.2 PET History…………………………………………………………………………………………………. 3
1.3 PET Polymerization ………………………………………………………………………………………. 3
1.3.1 Monomer Production ………………………………………………………………………….. 3
1.3.2 Polymerization……………………………………………………………………………………. 4
1.3.3 Characterization of Poly(ethylene Terephthalate) Chip…………………………….. 5
1.3.4 PET Processing—Melt Spinning……………………………………………………………. 5
1.3.5 PET Processing—Drawing……………………………………………………………………. 10
1.3.6 PET Yarn after Processing—Heat-Setting and Bulking ……………………………. 12
1.3.7 Polyester Yarns for Specific Applications……………………………………………….. 12
1.3.8 Physical Properties of PET …………………………………………………………………… 13
1.4 Other Polyesters ……………………………………………………………………………………………. 14
1.4.1 Polyester Fibers Based on Terephthalic Acid ………………………………………….. 14
1.4.2 High-Performance Polyester Fibers—PEN and LCPs………………………………. 15
1.4.3 Fibers from Main-Chain Thermotropic Polyesters—LCPs ……………………….. 15
1.4.3.1 Chemical Structure of LCPs …………………………………………………….. 15
1.4.3.2 Processing of Thermotropic Polyesters ………………………………………. 16
1.4.3.3 Structure–Property Relationships ……………………………………………… 17
1.5 Biodegradable Fibers …………………………………………………………………………………….. 18
1.6 Modification of Polyester Fibers—Specific Solutions for
Specific Applications……………………………………………………………………………………… 19
1.6.1 Spin Finishes………………………………………………………………………………………. 19
1.6.2 Tire Cord …………………………………………………………………………………………… 19
1.6.3 Low-Pill Staple Polyester ……………………………………………………………………… 19
1.6.4 Noncircular Cross-Section Fibers ………………………………………………………….. 20
1.6.5 Antistatic and Antisoiling Fibers…………………………………………………………… 20
1.7 Dyeing Polyesters………………………………………………………………………………………….. 21
1.7.1 Introduction……………………………………………………………………………………….. 21
1.7.2 Disperse Dyes …………………………………………………………………………………….. 21
1.7.3 Anionic and Cationic Dyes for Polyester ……………………………………………….. 22
1.7.4 Mass Dyeing ………………………………………………………………………………………. 22
1.8 Bicomponent Fibers and Microfibers ………………………………………………………………. 23
1.8.1 Side–Side Bicomponent Fibers ……………………………………………………………… 23
1.8.2 Core–Sheath Bicomponent Fibers …………………………………………………………. 24
1.8.3 Multiple Core Bicomponent Fibers ……………………………………………………….. 24
1.8.4 Hollow Fibers …………………………………………………………………………………….. 24
2 Polyamide Fibers
H.H. Yang
CONTENTS
2.1 Introduction …………………………………………………………………………………………………. 33
2.1.1 Historic Perspective …………………………………………………………………………….. 33
2.1.2 Aliphatic Polyamides …………………………………………………………………………… 34
2.1.2.1 Definition of Polyamides ……………………………………………………….. 34
2.1.2.2 Examples of Polyamide Compositions……………………………………… 34
2.2 Basic Chemistry of Aliphatic Polyamides …………………………………………………………. 35
2.2.1 Synthetic Routes …………………………………………………………………………………. 35
2.2.2 Amidation Reactions …………………………………………………………………………… 36
2.2.3 Ring-Opening Reactions………………………………………………………………………. 38
2.2.4 Molecular Weight and Molecular Weight Distribution…………………………….. 40
2.2.5 Nylon-6,6 Polyamide …………………………………………………………………………… 45
2.2.5.1 Synthetic Procedure ………………………………………………………………. 45
2.2.5.2 Kinetics and Thermodynamics ……………………………………………….. 45
2.2.5.3 Solid-State Polymerization……………………………………………………… 46
2.2.6 Nylon-6 Polyamide ……………………………………………………………………………… 47
2.2.6.1 Synthetic Procedure ………………………………………………………………. 47
2.2.6.2 Kinetics and Thermodynamics ……………………………………………….. 47
2.2.7 Other Polyamides………………………………………………………………………………… 56
2.2.7.1 Nylon-3 ……………………………………………………………………………….. 56
2.2.7.2 Nylon-4 ……………………………………………………………………………….. 56
2.2.7.3 Nylon-7 ……………………………………………………………………………….. 56
2.2.7.4 Nylon-8 ……………………………………………………………………………….. 56
2.2.7.5 Nylon-11 ……………………………………………………………………………… 58
2.2.7.6 Nylon-12 ……………………………………………………………………………… 58
2.2.7.7 Nylon-4,2 …………………………………………………………………………….. 58
2.2.7.8 Nylon-4,6 …………………………………………………………………………….. 58
2.2.7.9 Nylon-6,12 …………………………………………………………………………… 58
2.2.7.10 Nylon-4,1……………………………………………………………………………… 58
2.2.7.11 Nylon-6,1……………………………………………………………………………… 58
2.2.7.12 Nylon-6,T …………………………………………………………………………….. 59
2.2.7.13 PACM,12 …………………………………………………………………………….. 59
2.3 Polymerization Processes ……………………………………………………………………………….. 59
2.3.1 Monomer Syntheses…………………………………………………………………………….. 59
2.3.1.1 Caprolactam ………………………………………………………………………… 59
2.3.1.2 Adipic Acid………………………………………………………………………….. 65
2.3.1.3 Hexamethylene Diamine ………………………………………………………… 67
3 Polypropylene Fibers
Mei-Fang Zhu and H.H. Yang
CONTENTS
3.1 Introduction …………………………………………………………………………………………………141
3.1.1 Evolution of Polypropylene Fiber …………………………………………………………141
3.1.2 Market Growth…………………………………………………………………………………..142
3.1.2.1 Worldwide Growth …………………………………………………………………143
3.1.2.2 Regional Productivity ……………………………………………………………..143
3.1.2.3 Other Synthetic Fibers ……………………………………………………………. 144
3.2 Major End-Uses……………………………………………………………………………………………144
3.2.1 Carpet and Furnishing…………………………………………………………………………146
3.2.1.1 Carpet …………………………………………………………………………………..146
3.2.1.2 Home Furnishing ……………………………………………………………………147
3.2.1.3 Automotive Furnishing ……………………………………………………………147
3.2.2 Nonwoven Fabrics………………………………………………………………………………147
3.2.3 Industrial Applications ………………………………………………………………………..148
3.2.3.1 Ropes ……………………………………………………………………………………148
3.2.3.2 Civil Construction…………………………………………………………………..148
3.2.3.3 Cement Reinforcement……………………………………………………………. 148
3.2.3.4 All Synthetic Paper …………………………………………………………………149
3.2.4 Apparel ……………………………………………………………………………………………..149
3.3 Preparation of Propylene Polymer…………………………………………………………………..149
3.3.1 Basic Polymerization Reaction ……………………………………………………………..149
3.3.2 Reaction Mechanism …………………………………………………………………………..150
3.3.2.1 Catalyst Type and Concentration ……………………………………………..152
3.3.2.2 Monomer Concentration and Hydrogen ……………………………………152
3.3.2.3 Polymerization Temperature and Time……………………………………… 152
3.3.2.4 Polymerization Medium…………………………………………………………..152
3.3.3 Catalyst Systems …………………………………………………………………………………152
3.3.3.1 Ziegler–Natta Catalysts……………………………………………………………153
3.3.3.2 Metallocene Catalysts ……………………………………………………………..153
3.3.4 Polymerization Processes ……………………………………………………………………..154
3.3.4.1 Basic Processes ……………………………………………………………………….154
3.3.4.2 Industrial Operations ………………………………………………………………156
3.4 Basic Polymer Properties ……………………………………………………………………………….157
3.4.1 Molecular Weight and Molecular Weight Distribution…………………………….158
3.4.2 Crystalline Structure ……………………………………………………………………………160
3.4.3 Melt Behavior …………………………………………………………………………………….160
3.4.3.1 Phase Transitions ……………………………………………………………………160
3.4.3.2 Melt Rheology ……………………………………………………………………….160
3.4.3.3 Comparison of ZNPP and MiPP………………………………………………172
3.5 Additives for Fiber Preparation………………………………………………………………………174
3.5.1 Stabilizers…………………………………………………………………………………………..175
3.5.1.1 Degradation of Unstabilized Fiber ……………………………………………175
3.5.1.2 Melt Extrusion Stability…………………………………………………………..176
3.5.1.3 Long-Term Thermal Stability …………………………………………………..178
3.5.1.4 UV Stability …………………………………………………………………………..180
3.5.2 Pigments…………………………………………………………………………………………….184
3.5.2.1 Fiber-Processing Requirement ………………………………………………….184
3.5.2.2 Stability Requirements …………………………………………………………….185
3.5.2.3 Interaction with Other Additives ………………………………………………187
3.5.2.4 Effects on Fiber Stability …………………………………………………………188
3.5.3 Dyeability Modifiers ……………………………………………………………………………190
3.5.3.1 Copolymerization……………………………………………………………………190
3.5.3.2 Grafting…………………………………………………………………………………191
3.5.3.3 Polymeric Modifiers ………………………………………………………………..191
3.5.3.4 Fiber Blends …………………………………………………………………………..192
3.5.3.5 Organic Metal Salts…………………………………………………………………192
3.5.3.6 Surface Modification……………………………………………………………….193
3.5.3.7 Halogen Compounds ………………………………………………………………193
3.5.4 Flame Retardants ……………………………………………………………………………….193
3.5.5 Fiber Finishes …………………………………………………………………………………….195
3.6 Preparation of Polypropylene Fibers ……………………………………………………………….195
3.6.1 Long Air-Quench Melt Spinning …………………………………………………………..196
3.6.1.1 Metering Pump ………………………………………………………………………196
3.6.1.2 Spin Pack ………………………………………………………………………………197
3.6.1.3 Spinneret ……………………………………………………………………………….197
3.6.1.4 Quenching ……………………………………………………………………………..198
3.6.1.5 Finish Application ………………………………………………………………….198
3.6.1.6 Drawing and Annealing …………………………………………………………..199
3.6.2 Short Air-Quench Melt Spinning…………………………………………………………..200
3.6.3 Water-Quench Melt Spinning ……………………………………………………………….200
3.6.3.1 Spinning and Quenching ………………………………………………………….200
3.6.3.2 Draw Resonance …………………………………………………………………….201
3.6.3.3 Drawing ………………………………………………………………………………..201
3.6.4 Spun-Bonding Process …………………………………………………………………………201
3.6.4.1 Spun-Bonding ………………………………………………………………………..202
3.6.4.2 Melt-Blowing …………………………………………………………………………202
3.6.5 Fibers from Film…………………………………………………………………………………203
3.6.5.1 Sheet Film Extrusion ………………………………………………………………203
3.6.5.2 Drawing and Annealing …………………………………………………………..203
3.6.5.3 Fibrillation …………………………………………………………………………….203
3.7 Fiber Properties ……………………………………………………………………………………………204
3.7.1 As-Spun Fibers …………………………………………………………………………………..204
3.7.1.1 Crystalline Structure ……………………………………………………………….204
3.7.1.2 Spinning Stress ……………………………………………………………………….205
3.7.1.3 Mechanical Properties……………………………………………………………..211
3.7.2 Drawn Fibers ……………………………………………………………………………………..213
3.7.2.1 Deformation Model ………………………………………………………………..213
3.7.2.2 Effect of Temperature ……………………………………………………………..215
3.7.2.3 Effect of Draw Rate………………………………………………………………..217
3.7.2.4 Crystalline Structure ……………………………………………………………….220
3.7.2.5 Structure–Property Relationship………………………………………………. 225
3.7.3 Annealed Fiber …………………………………………………………………………………..227
3.7.4 Melting Behavior ………………………………………………………………………………..229
3.8 New Generation of Polypropylene Fibers…………………………………………………………236
3.8.1 Three-Dimensional Helical Staple …………………………………………………………236
3.8.2 High-Strength, High-Modulus Fiber ……………………………………………………..238
3.8.2.1 Rapid Quenching ……………………………………………………………………238
3.8.2.2 Two-Stage Drawing ………………………………………………………………..239
3.8.2.3 Fibrillar Crystallization……………………………………………………………243
3.8.2.4 Gel Spinning ………………………………………………………………………….243
3.8.2.5 Current Efforts……………………………………………………………………….244
3.8.2.6 Commercial Products………………………………………………………………246
3.8.3 High-Shrinkage Fiber ………………………………………………………………………….246
3.8.3.1 Fiber Preparation……………………………………………………………………246
3.8.3.2 Fiber Properties………………………………………………………………………247
3.8.3.3 Applications …………………………………………………………………………..248
3.8.4 Conductive Fibers……………………………………………………………………………….248
3.8.5 Fibers from Polymer Blends …………………………………………………………………248
3.8.5.1 PP–PP Blend ………………………………………………………………………….249
3.8.5.2 PP–PS Blend ………………………………………………………………………….249
3.8.6 Fibers from Nanocomposites………………………………………………………………..251
3.8.6.1 Macroscopic Morphology……………………………………………………….. 252
3.8.6.2 Crystallization Behavior…………………………………………………………..252
3.8.6.3 Rheological Behavior ………………………………………………………………253
3.8.6.4 Fiber Spinning………………………………………………………………………..253
3.8.6.5 Dyeability………………………………………………………………………………253
Acknowledgment…………………………………………………………………….254
References ……………………………………………………………………………………254
4 Vinyl Fibers
Ichiro Sakuraday and Takuji Okaya*
CONTENTS
4.1 Introduction …………………………………………………………………………………………………262
4.1.1 History ………………………………………………………………………………………………262
4.1.2 Outline of the Chemistry ……………………………………………………………………..263
4.2 Polyvinyl Acetate ………………………………………………………………………………………….265
4.2.1 Manufacture of Monomer ……………………………………………………………………266
4.2.2 Polymerization……………………………………………………………………………………266
4.2.2.1 Mechanism of Polymerization…………………………………………………..266
4.2.2.2 Rate of Polymerization ……………………………………………………………267
4.2.2.3 Chain Transfer and Degree of Polymerization ……………………………268
4.2.2.4 Chain Transfer to Dead Polymer………………………………………………269
4.2.2.5 Industrial Process of Polymerization …………………………………………273
4.2.3 Conversion to Polyvinyl Alcohol…………………………………………………………..274
4.2.3.1 Methanolysis and Hydrolysis…………………………………………………… 274
4.2.3.2 Drop in the Degree of Polymerization……………………………………….276
4.2.3.3 Process of Deacetylation ………………………………………………………….276
4.3 Structure and Properties of Polyvinyl Alcohol ………………………………………………….277
4.3.1 Molecular Structure …………………………………………………………………………….277
4.3.1.1 Chain Configuration ……………………………………………………………….277
4.3.1.2 End Groups……………………………………………………………………………278
4.3.1.3 Stereostructure ……………………………………………………………………….279
4.3.1.4 Branching ………………………………………………………………………………281
4.3.1.5 Molecular Weight……………………………………………………………………281
4.3.2 Crystal Structure…………………………………………………………………………………283
4.3.2.1 Unit Cell………………………………………………………………………………..284
4.3.2.2 Effect of Water……………………………………………………………………….284
4.3.2.3 Crystal Structure Model…………………………………………………………..285
4.3.2.4 Degree of Crystallinity ……………………………………………………………. 285
4.3.3 Physicochemical Properties …………………………………………………………………..288
4.3.3.1 Melting Point …………………………………………………………………………288
4.3.3.2 Glass Transition Temperature ………………………………………………….288
4.3.3.3 Density ………………………………………………………………………………….289
4.3.3.4 Orientation and Strength …………………………………………………………290
4.3.3.5 Swelling …………………………………………………………………………………291
4.3.3.6 Aqueous Solution……………………………………………………………………292
4.3.4 Chemical Reactions …………………………………………………………………………….293
4.3.4.1 Acetalization ………………………………………………………………………….293
4.3.4.2 Esterification ………………………………………………………………………….295
4.3.4.3 Etherification …………………………………………………………………………295
4.3.4.4 Complex Formation………………………………………………………………..296
4.3.4.5 Grafting…………………………………………………………………………………296
4.3.4.6 Decomposition ……………………………………………………………………….296
4.4 Manufacture of Polyvinyl Alcohol Fiber………………………………………………………….297
4.4.1 Traditional Process of Wet-Spinning ……………………………………………………..297
4.4.1.1 Fiber Formation …………………………………………………………………….297
4.4.1.2 Drawing ………………………………………………………………………………..299
4.4.1.3 Heat Treatment ………………………………………………………………………300
4.4.1.4 Acetalization ………………………………………………………………………….301
4.4.2 Different Processes of Spinning …………………………………………………………….303
4.4.2.1 Wet-Spinning with Alkali Bath…………………………………………………303
4.4.2.2 Wet-Spinning of PVA Solution Containing Boric Acid………………..306
4.4.2.3 Dry-Spinning………………………………………………………………………….306
4.4.2.4 Spinning Using Organic Solvent ……………………………………………….307
4.4.2.5 Biodegradability of Polyvinyl Alcohol ……………………………………….309
4.4.2.6 Miscellaneous…………………………………………………………………………309
4.4.3 Bicomponent Fiber (PVC=PVA) …………………………………………………………..310
4.4.3.1 Emulsion-Spinning………………………………………………………………….311
4.4.3.2 Polychlal………………………………………………………………………………..312
4.5 Polyvinyl Chloride Fibers ………………………………………………………………………………313
4.5.1 Manufacture of Polyvinyl Chloride ……………………………………………………….313
4.5.1.1 Vinyl Chloride Monomer…………………………………………………………313
4.5.1.2 Polymerization ……………………………………………………………………….315
4.5.2 Manufacture of Fiber ………………………………………………………………………….316
4.5.2.1 Dry-Spinning………………………………………………………………………….316
4.5.2.2 Other Methods of Spinning ……………………………………………………..320
4.5.3 Properties of Fiber………………………………………………………………………………321
4.5.3.1 Flame Retardance …………………………………………………………………..321
4.5.3.2 Chemical Resistance………………………………………………………………..321
4.5.3.3 Triboelectricity ……………………………………………………………………….322
4.5.3.4 Dimensional Stability ………………………………………………………………323
4.6 Applications and Future Trends …………………………………………………………….323
Acknowledgments …………………………………………………………………………………….326
References ………………………………………………………………………………………….326