Solid State Polymerization

by Papaspyrides, Constantine D.; Vouyiouka, Stamatina N.

• ISBN13: 9780470084182
• ISBN10: 0470084189
• Edition: 1st
• Format: Hardcover
• Copyright: 2009-05-26
• Publisher: Wiley

Summary

SSP presents significant advantages over other techniques due to its use of low operating temperatures, inexpensive equipment, and simple and environmentally sound procedures. The only book currently available on the principles and applications of this technique, Solid-State Polymerization is an indispensable tool in the design and manufacture of commercially important polymers, plastics, and fibers. It provides a one-stop resource for academic and industry professionals as well as graduate and post graduate-level students in polymer chemistry, polymer engineering, polymer processing, chemical engineering, plastics engineering, and materials science and engineering.

Author Biography

Constantine D. Papaspyrides is Professor and Director of the Laboratory of Polymer Technology in the School of Chemical Engineering at the National Technical University of Athens, Greece. He has been ex-President of the School and Visiting Professor/Consultant in Massachusetts Institute of Technology (MIT), Eidgenssische Technische Hochschule Zrich (ETH), E.I. du Pont de Nemours & Company, Inc. / Invista, Inc., and Ciba Lampertheim GmbH. He serves on the editorial board for the journals Advances in Polymer Technology Journal (Wiley) and Progress in Rubber, Plastics and Recycling Technology Journal (Rapra Technology).

Stamatina N. Vouyiouka is elected Lecturer in the School of Chemical Engineering at the National Technical University of Athens in Greece.

Table of Contents

Contributors	p. xiii
Preface	p. xv
Fundamentals of Solid State Polymerization	p. 1
Introduction	p. 2
Polymers and Plastics	p. 2
Polymerization Processes	p. 3
Introduction to Solid State Polymerization	p. 10
Solid State Polymerization of Chain-Growth Polymers (Solid State Polyaddition)	p. 11
Solid State Polymerization of Step-Growth Polymers (Solid State Polycondensation)	p. 14
Monomer Solid State Polymerization (Direct SSP)	p. 16
Prepolymer Solid State Polymerization (Post-SSP, Solid State Finishing)	p. 21
Solid State Polymerization Apparatus and Assemblies	p. 26
Solid State Applications in the Polymer Industry	p. 28
Solid State Polymerization Advantages	p. 28
Post-Solid State Polymerization Application in Polyamides	p. 28
Conclusions	p. 30
Solid State Polymerization Chemistry and Mechanisms: Unequal Reactivity of End Groups	p. 39
Introduction	p. 40
Special Characteristics of Solid State Polymerization	p. 40
Classical Kinetic Equations in Solid State Polymerization	p. 41
Model of Molecular Morphology and Chain-End Movement	p. 42
Definition of Chain-End Length in the Amorphous Phase	p. 42
How End Groups Move During Solid State Polymerization	p. 45
How Chain-End Length Affects the Movement of End Groups	p. 46
Reactivity of End Groups	p. 47
Principles of Equal Reactivity of End Groups in Melt Polymerization	p. 47
Principles of Unequal Reactivity of End Groups in Solid State Polymerization	p. 47
Sources of Low Reactivity of End Groups	p. 48
Why Intrinsic Viscosity Levels Off During Solid State Polymerization	p. 50
Definition of Residual Average Radius and Residual End-Group Concentration	p. 50
Relationship Between &Rbar;r, and &Rbar;r	p. 51
Relationship Between Cr, &Rbar;r, and Ultimate IV	p. 52
Explanation of Temperature Effect on Solid State Polymerization	p. 54
Explanation of Initial IV Effect on Solid State Polymerization	p. 55
Solid State Polymerization Kinetics	p. 56
Kinetic Equation of Ideal Solid State Polymerization	p. 56
Empirical Kinetic Equation of Real Solid State Polymerization	p. 59
Conclusions	p. 64
Kinetic Aspects of Polyester Solid State Polymerization	p. 67
Introduction	p. 68
Phenomena Involved in Solid State Polymerization of Polyesters	p. 69
Possible Reactions in Solid State Polymerization of Polyesters	p. 69
Chain Mobility and Diffusion of Low-Molecular-Weight By-Products	p. 76
Kinetic and Diffusion Equations	p. 81
Modeling Solid State Polymerization of Polyesters	p. 89
Effects of Variables and Predictions Based on Kinetic Models	p. 98
Solid State Polymerization of Typical Polyesters	p. 105
Poly(ethylene terephthalate)	p. 106
Poly(butylene terephthalate)	p. 107
Poly(ethylene naphthalate)	p. 109
Poly(trimethylene terephthalate)	p. 110
Poly(L-lactic acid)	p. 112
Conclusions	p. 113
Kinetic Aspects of Polyamide Solid State Polymerization	p. 123
Introduction	p. 123
Simple Kinetic Models of Solid State Polymidation	p. 128
Fundamental Chemistry in Solid State Polyamidation	p. 128
Direct Solid State Polyamidation	p. 130
Prepolymer Solid State Polyamidation	p. 132
Simulation of Solid State Polyamidation	p. 136
Simple SSP Kinetics: The Case of Poly(hexamethylene adipamide)	p. 139
Solid State Polymerization of Hexamethylenediammonium Adipate	p. 139
Solid State Polymerization of Poly(hexamethylene adipamide)	p. 143
Compositional Effects in Solid State Polymerization of Poly(hexamethylene adipamide)	p. 148
Conclusions	p. 153
Catalysis in Solid State Polymerization Processes	p. 159
Introduction	p. 159
Catalysts in Polyester Solid State Polymerization Processes	p. 161
Metal-Type Catalysts	p. 161
Phosphorus- and Sulfur-Based Catalysts	p. 164
Catalysts in Polyamide Solid State Polymerization Processes	p. 167
Reactive Additives in Solid State Polymerization Processes	p. 170
Inert Additives in Solid State Polymerization Processes	p. 173
Conclusions	p. 173
High-Pressure Solid State Polymerization of Polyamide Monomer Crystals	p. 179
Introduction	p. 179
High-Pressure Solid State Polymerization	p. 182
Crystals and Characteristics of Monomers	p. 182
HP-SSP Method for Polyamide Monomer Crystals	p. 183
Polymerizability and Structure Formation	p. 184
Polymerizability and Structure Formation of ¿-Amino Acid Crystals to Polyamide Crystals	p. 184
Polymerizability of Polyamide Salt Crystals to Polyamide Crystals	p. 187
Structure Formation of Polyamide Salt Crystals to Polyamide Crystals	p. 191
Conclusions	p. 195
Polymerizability	p. 195
Structure Formation	p. 195
Fundamental Process Modeling and Product Design for the Solid State Polymerization of Polyamide 6 and Poly(ethylene terephthalate)	p. 199
Introduction	p. 200
Solid State Polymerization Modeling Guide	p. 200
Fundamentals of Solid State Polymerization Reactors	p. 203
Material and Energy Balances	p. 203
Mass and Heat Transfer	p. 206
Reaction Kinetics	p. 209
Physical Properties	p. 217
Numerical Solution	p. 222
Example Simulation and Application	p. 225
Modifications to Account for Crystallization	p. 227
Conclusions	p. 229
Recent Developments in Solid State Polymerization of Poly(ethylene terephthalate)	p. 233
Introduction	p. 234
Conventional Solid State Polymerization Processes	p. 238
Moisture Removal	p. 238
Crystallization	p. 238
Industrial Solid State Polymerization Processes	p. 240
Nitrogen Purification Units in a Solid State Polymerization Process	p. 242
New Solid State Polymerization Processes	p. 243
Invista NG3 Process	p. 244
Bepex Process	p. 246
Aquafil-Buhler Process	p. 247
M&G Process	p. 248
Poly(ethylene terephthalate) Flake Recycling Using Solid State Polymerization	p. 249
Particle Formation Technologies	p. 250
Alternatives to Solid State Polymerization	p. 252
Additives for Direct Polymerization to High Intrinsic Viscosity	p. 252
Direct Melt Polymerization to High-Intrinsic-Viscosity Polymer Resin or Preform by UDHE-Inventa and Zimmer AG	p. 256
Du Pont Atmospheric-Pressure All-Melt Process	p. 258
Eastman Chemical's IntegRex Technology	p. 259
Swollen/Solution Polymerization to UHMW-PET	p. 262
Poly(ethylene terephthalate) for Fluid Packaging Applications	p. 262
Mineral Water	p. 264
Large-Container Applications	p. 264
Hot-Fill Applications	p. 265
Flavor/CO2 Retention Through Barrier Properties	p. 266
Oxygen Barrier Poly(ethylene terephthalate)	p. 267
Fast Heating Poly(ethylene terephthtalate)	p. 269
Conclusions	p. 270
Abbreviations and Symbols	p. 281
Index	p. 289
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