Solid State Polymerization

SOLID STATE POLYMERIZATION......Page 4
CONTENTS......Page 10
Contributors......Page 16
Preface......Page 18
1 Fundamentals of Solid State Polymerization......Page 22
1.1.1 Polymers and Plastics......Page 23
1.1.2 Polymerization Processes......Page 24
1.1.3 Introduction to Solid State Polymerization......Page 31
1.2 Solid State Polymerization of Chain-Growth Polymers (Solid State Polyaddition)......Page 32
1.3 Solid State Polymerization of Step-Growth Polymers (Solid State Polycondensation)......Page 35
1.3.1 Monomer Solid State Polymerization (Direct SSP)......Page 37
1.3.2 Prepolymer Solid State Polymerization (Post-SSP, Solid State Finishing)......Page 42
1.4 Solid State Polymerization Apparatus and Assemblies......Page 47
1.5.2 Post–Solid State Polymerization Application in Polyamides......Page 49
1.6 Conclusions......Page 51
2 Solid State Polymerization Chemistry and Mechanisms: Unequal Reactivity of End Groups......Page 60
2.2 Special Characteristics of Solid State Polymerization......Page 61
2.3 Classical Kinetic Equations in Solid State Polymerization......Page 62
2.4.1 Definition of Chain-End Length in the Amorphous Phase......Page 63
2.4.2 How End Groups Move During Solid State Polymerization......Page 66
2.4.3 How Chain-End Length Affects the Movement of End Groups......Page 67
2.5.2 Principles of Unequal Reactivity of End Groups in Solid State Polymerization......Page 68
2.5.3 Sources of Low Reactivity of End Groups......Page 69
2.6.1 Definition of Residual Average Radius and Residual End-Group Concentration......Page 71
2.6.2 Relationship Between (r) and......Page 72
2.6.3 Relationship Between C(r), (r), and Ultimate IV......Page 73
2.6.4 Explanation of Temperature Effect on Solid State Polymerization......Page 75
2.6.5 Explanation of Initial IV Effect on Solid State Polymerization......Page 76
2.7.1 Kinetic Equation of Ideal Solid State Polymerization......Page 77
2.7.2 Empirical Kinetic Equation of Real Solid State Polymerization......Page 80
2.8 Conclusions......Page 85
3 Kinetic Aspects of Polyester Solid State Polymerization......Page 88
3.1 Introduction......Page 89
3.2.1 Possible Reactions in Solid State Polymerization of Polyesters......Page 90
3.2.2 Chain Mobility and Diffusion of Low-Molecular-Weight By-Products......Page 97
3.2.3 Kinetic and Diffusion Equations......Page 102
3.3 Modeling Solid State Polymerization of Polyesters......Page 110
3.3.1 Effects of Variables and Predictions Based on Kinetic Models......Page 119
3.4 Solid State Polymerization of Typical Polyesters......Page 126
3.4.1 Poly(ethylene terephthalate)......Page 127
3.4.2 Poly(butylene terephthalate)......Page 128
3.4.3 Poly(ethylene naphthalate)......Page 130
3.4.4 Poly(trimethylene terephthalate)......Page 131
3.4.5 Poly(L-lactic acid)......Page 133
3.5 Conclusions......Page 134
4.1 Introduction......Page 144
4.2.1 Fundamental Chemistry in Solid State Polyamidation......Page 149
4.2.2 Direct Solid State Polyamidation......Page 151
4.2.3 Prepolymer Solid State Polyamidation......Page 153
4.3 Simulation of Solid State Polyamidation......Page 157
4.4.1 Solid State Polymerization of Hexamethylenediammonium Adipate......Page 160
4.4.2 Solid State Polymerization of Poly(hexamethylene adipamide)......Page 164
4.4.3 Compositional Effects in Solid State Polymerization of Poly(hexamethylene adipamide)......Page 169
4.5 Conclusions......Page 174
5.1 Introduction......Page 180
5.2.1 Metal-Type Catalysts......Page 182
5.2.2 Phosphorus- and Sulfur-Based Catalysts......Page 185
5.3 Catalysts in Polyamide Solid State Polymerization Processes......Page 188
5.4 Reactive Additives in Solid State Polymerization Processes......Page 191
5.6 Conclusions......Page 194
6.1 Introduction......Page 200
6.2.1 Crystals and Characteristics of Monomers......Page 203
6.2.2 HP-SSP Method for Polyamide Monomer Crystals......Page 204
6.3.1 Polymerizability and Structure Formation of ω-Amino Acid Crystals to Polyamide Crystals......Page 205
6.3.2 Polymerizability of Polyamide Salt Crystals to Polyamide Crystals......Page 208
6.3.3 Structure Formation of Polyamide Salt Crystals to Polyamide Crystals......Page 212
6.4.2 Structure Formation......Page 216
7 Fundamental Process Modeling and Product Design for the Solid State Polymerization of Polyamide 6 and Poly(ethylene terephthalate)......Page 220
7.2 Solid State Polymerization Modeling Guide......Page 221
7.3.1 Material and Energy Balances......Page 224
7.3.2 Mass and Heat Transfer......Page 227
7.3.3 Reaction Kinetics......Page 230
7.3.4 Physical Properties......Page 238
7.4 Numerical Solution......Page 243
7.5 Example Simulation and Application......Page 246
7.6 Modifications to Account for Crystallization......Page 248
7.7 Conclusions......Page 250
8 Recent Developments in Solid State Polymerization of Poly(ethylene terephthalate)......Page 254
8.1 Introduction......Page 255
8.2.2 Crystallization......Page 259
8.2.3 Industrial Solid State Polymerization Processes......Page 261
8.2.4 Nitrogen Purification Units in a Solid State Polymerization Process......Page 263
8.3 New Solid State Polymerization Processes......Page 264
8.3.1 Invista NG3 Process......Page 265
8.3.2 Bepex Process......Page 267
8.3.3 Aquafil-Buhler Process......Page 268
8.3.4 M&G Process......Page 269
8.4 Poly(ethylene terephthalate) Flake Recycling Using Solid State Polymerization......Page 270
8.5 Particle Formation Technologies......Page 271
8.6.1 Additives for Direct Polymerization to High Intrinsic Viscosity......Page 273
8.6.2 Direct Melt Polymerization to High-Intrinsic-Viscosity Polymer Resin or Preform by UDHE-Inventa and Zimmer AG......Page 277
8.6.3 Du Pont Atmospheric-Pressure All-Melt Process......Page 279
8.6.4 Eastman Chemical’s IntegRex Technology......Page 280
8.6.5 Swollen/Solution Polymerization to UHMW-PET......Page 281
8.7 Poly(ethylene terephthalate) for Fluid Packaging Applications......Page 283
8.7.2 Large-Container Applications......Page 285
8.7.3 Hot-Fill Applications......Page 286
8.7.4 Flavor/CO(2) Retention Through Barrier Properties......Page 287
8.7.5 Oxygen Barrier Poly(ethylene terephthalate)......Page 288
8.7.6 Fast Heating Poly(ethylene terephthtalate)......Page 290
8.8 Conclusions......Page 291
Abbreviations and Symbols......Page 302
Index......Page 310