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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

2.3.2 Industrial Processes......................................................................................... 70

2.3.2.1 General Operations ........................................................................... 70

2.3.2.2 Nylon-6 Polyamide ........................................................................... 72

2.3.2.3 Nylon-6,6 Polyamide......................................................................... 73

2.3.2.4 Other Polyamides.............................................................................. 73

2.3.2.5 Nanocomposites................................................................................ 74

2.3.2.6 Process Simulation ............................................................................ 74

2.4 Preparation of Polyamide Fibers ............................................................................... 78

2.4.1 Melt Spinning ................................................................................................. 78

2.4.2 Dynamics of Melt Spinning ............................................................................ 80

2.4.3 Quenching....................................................................................................... 80

2.4.4 Spin Finish...................................................................................................... 81

2.4.5 Drawing .......................................................................................................... 81

2.4.6 Process Integration ......................................................................................... 82

2.4.6.1 Draw-Twisting .................................................................................. 83

2.4.6.2 Spinning–Drawing–Texturing ........................................................... 84

2.4.7 High-Speed Spinning ...................................................................................... 84

2.4.8 Textile Finishing Operations........................................................................... 85

2.4.8.1 Texturing........................................................................................... 85

2.4.8.2 False-Twist Texturing ....................................................................... 85

2.4.8.3 Crimp Texturing ............................................................................... 86

2.4.8.4 Commingling, Interlacing, and Air-Jet Texturing............................. 87

2.4.9 Winding and Yarn Package............................................................................ 87

2.5 Structures and Properties of Polyamide Fibers.......................................................... 87

2.5.1 Polymer Chain Structure ................................................................................ 87

2.5.2 Characteristics of Crystalline and Amorphous Structures.............................. 88

2.5.2.1 Crystalline Forms.............................................................................. 88

2.5.2.2 Crystalline Structures in Fibers......................................................... 92

2.5.2.3 Structural Models ............................................................................. 93

2.5.3 Thermal Transitions of Crystalline Phase....................................................... 94

2.5.3.1 Melt Temperature ............................................................................. 94

2.5.3.2 Glass Transition Temperature .......................................................... 96

2.5.4 Characterization of Structural Parameters ..................................................... 98

2.5.4.1 X-Ray Diffraction............................................................................. 98

2.5.4.2 Crystallite Size................................................................................... 99

2.5.4.3 Degree of Orientation ....................................................................... 99

2.5.4.4 Birefringence .....................................................................................100

2.5.4.5 Crystallinity and Crystalline Indices .................................................101

2.5.5 Typical Fiber Properties .................................................................................105

2.5.5.1 Tensile Behavior................................................................................107

2.5.5.2 Chemical Properties ..........................................................................113

2.5.5.3 Degradation Behavior.......................................................................113

2.5.5.4 Polymer Stabilization ........................................................................118

2.5.5.5 Antistatic...........................................................................................118

2.5.5.6 Flammability .....................................................................................119

2.5.5.7 Transparency.....................................................................................120

2.5.5.8 Dye Diffusion....................................................................................120

2.5.6 Process–Structure–Property Relationship.......................................................120

2.5.6.1 Effect of Molecular Weight...............................................................121

2.5.6.2 Effect of Water..................................................................................121

32 Handbook of Fiber Chemistry

2.5.6.3 Effect of Spinning and Drawing ....................................................... 121

2.5.6.4 Effect of Spinning Conditions...........................................................122

2.6 Commercialization and Future Outlook....................................................................122

2.6.1 Polyamide Fiber Products...............................................................................122

2.6.1.1 Filament Yarn and Staple................................................................. 122

2.6.1.2 Bicomponent Fibers ..........................................................................122

2.6.1.3 Microfibers........................................................................................123

2.6.2 End-Uses.........................................................................................................124

2.6.2.1 Textiles ..............................................................................................124

2.6.2.2 Carpets ..............................................................................................124

2.6.2.3 Industrial Applications...................................................................... 124

2.6.2.4 Specialty Fibers .................................................................................124

2.6.2.5 Nonwovens........................................................................................124

2.6.2.6 Nonfiber Uses ...................................................................................125

2.6.3 Worldwide Consumption of Polyamide Fibers...............................................125

2.6.4 Future Outlook...............................................................................................126

2.6.4.1 Technology........................................................................................126

2.6.4.2 Market Share ....................................................................................126

Acknowledgment................................................................................................................126

References ..........................................................................................................................127

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