Handbook of Fiber Chemistry Edited by Menachem Lewin

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Handbook of Fiber Chemistry, Third Edition
Edited by Menachem Lewin
Handbook of Fiber Chemistry

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

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