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Provides an overview of the family of polyester polymers which comprise an important group of plastics that span the range of commodity polymers to engineering resins. It describes the preparation, properties and applications of polyesters. Readers will also find details on polyester-based elastomers, biodegradable aliphatic polyester, liquid crystal polyesters and unsaturated polyesters for glass-reinforced composites.
Presents an overview of the most recent developments.
Explores synthesis, catalysts, processes, properties and applications.
Looks at emerging polyester materials as well as existing ones.
Written by foremost experts from both academia and industry, ensuring that both fundamentals and practical applications are covered.
Contents
Contributors. Series Preface.
Preface.
About the Editors.
I HISTORICAL OVERVIEW.
1 The Historical Development of Polyesters (J. Eric McIntyre).
1 Introduction.
2 Alkyd and Related Resins.
3 Fibres from Partially Aromatic Polyesters.
3.1 Early Work Leading to Poly(ethylene Terephthalate).
3.2 Spread of Polyester Fibre Production.
3.3 Intermediates.
3.4 Continuous Polymerisation.
3.5 Solid-phase Polymerisation.
3.6 End-use Development.
3.7 High-speed Spinning.
3.8 Ultra-fine Fibres.
4 Other Uses for Semi-aromatic Polyesters.
4.1 Films.
4.2 Moulding Products.
4.3 Bottles.
5 Liquid-crystalline Polyesters.
6 Polyesters as Components of Elastomers.
7 Surface-active Agents.
8 Absorbable Fibres.
9 Polycarbonates.
10 Natural Polyesters.
10.1 Occurrence.
10.2 Poly(β-hydroxyalkanoate)s.
11 Conclusion.
References.
II POLYMERIZATION AND POLYCONDENSATION.
2 Poly(ethylene Terephthalate) Polymerization - Mechanism, Catalysis, Kinetics, Mass Transfer and Reactor Design (Thomas Rieckmann and Susanne Volker).
Notation.
1 Introduction .35
2 Chemistry, Reaction Mechanisms, Kinetics and Catalysis.
2.1 Esterification/Hydrolysis.
2.2 Transesterification/Glycolysis.
2.3 Reactions with Co-monomers.
2.4 Formation of Short Chain Oligomers.
2.5 Formation of Diethylene Glycol and Dioxane.
2.6 Thermal Degradation of Diester Groups and Formation of Acetaldehyde.
2.7 Yellowing.
2.8 Chemical Recycling.
2.9 Conclusions.
3 Phase Equilibria, Molecular Diffusion and Mass Transfer.
3.1 Phase Equilibria.
3.2 Diffusion and Mass Transfer in Melt-phase Polycondensation.
3.3 Diffusion and Mass Transfer in Solid-state Polycondensation.
3.4 Conclusions.
4 Polycondensation Processes and Polycondensation Plants.
4.1 Batch Processes.
4.2 Continuous Processes.
5 Reactor Design for Continuous Melt-phase Polycondensation.
5.1 Esterification Reactors.
5.2 Polycondensation Reactors for Low Melt Viscosity.
5.3 Polycondensation Reactors for High Melt Viscosity.
6 Future Developments and Scientific Requirements.
Acknowledgements .
References.
3 Synthesis and Polymerization of Cyclic Polyester Oligomers (Daniel J. Brunelle).
1 Introduction.
2 History.
3 Preparation of Polyester Cyclic Oligomers from Acid Chlorides.
4 Polyester Cyclic Oligomers via Ring-Chain Equilibration (Depolymerization).
5 Mechanism for Formation of Cyclics via Depolymerization.
6 Polymerization of Oligomeric Ester Cyclics.
7 Conclusions.
References.
4 Continuous Solid-state Polycondensation of Polyesters (Brent Culbert and Andreas Christel).
1 Introduction.
2 The Chemical Reactions of PET in the Solid State.
2.1 Basic Chemistry.
2.2 Mechanism and Kinetics.
2.3 Parameters Affecting SSP.
3 Crystallization of PET.
3.1 Nucleation and Spherulite Growth.
3.2 Crystal Annealing.
4 Continuous Solid-state Polycondensation Processing.
4.1 PET-SSP for Bottle Grade.
4.2 Buhler PET-SSP Bottle-grade Process.
4.3 Process Comparison.
4.4 PET-SSP for Tyre Cord.
4.5 Other Polyesters.
5 PET Recycling.
5.1 PET Recycling Market.
5.2 Material Flow.
5.3 Solid-state Polycondensation in PET Recycling.
References .
5 Solid-state Polycondensation of Polyester Resins: Fundamentals and Industrial Production (Wolfgang Goltner).
1 Introduction.
2 Principles.
2.1 Aspects of Molten-state Polycondensation.
2.2 Aspects of Solid-state Polycondensation.
2.3 Physical Aspects.
3 Equipment.
3.1 Batch Process.
3.2 Continuous Process.
3.3 SSP of Small Particles and Powders.
3.4 SSP in the Suspended State.
4 Practical Aspects of the Reaction Steps.
4.1 Crystallization and Drying.
4.2 Solid-state Polycondensation.
5 Economic Considerations.
6 Solid-state Polycondensation of Other Polyesters.
7 Conclusions.
References.
III TYPES OF POLYESTERS
6 New Poly(Ethylene Terephthalate) Copolymers (David A. Schiraldi).
1 Introduction.
2 Crystallinity and Crystallization Rate Modification.
2.1 Amorphous Copolyesters of PET.
2.2 Increased Crystallization Rates and Crystallinity in PET .3 PET Copolymers with Increased Modulus and Thermal Properties.
3.1 Semicrystalline Materials.
3.2 Liquid Crystalline Copolyesters of PET.
4 Increased Flexibility Copolymers of PET.
5 Copolymers as a Scaffold for Additional Chemical Reactions.
6 Other PET Copolymers.
6.1 Textile-related Copolymers.
6.2 Surfaced-modified PET.
6.3 Biodegradable PET Copolymers.
6.4 Terephthalate Ring Substitutions.
6.5 Flame-retardant PET.
7 Summary and Comments.
References.
7 Amorphous and Crystalline Polyesters based on 1,4-Cyclohexanedimethanol (S. Richardurner, Robert W. Seymour and John R. Dombroski).
Notation.
1 Introduction.
2 1,4-Cyclohexanedimethanol.
3 1,3- and 1,2-Cyclohexanedimethanol: Other CHDM Isomers.
3.1 Definitions: PCT, PCTG, PCTA and PETG.
4 Synthesis of CHDM-based Polyesters.
5 Poly(1,4-Cyclohexylenedimethylene Terephthalate).
5.1 Preparation and Properties.
5.2 Other Crystalline Polymers Based on PCT or CHDM.
5.3 Processing of Crystalline PCT-based Polymers.
5.4 Applications For PCT-based Polymers.
6 GLYCOL-modified PCT Copolyester: Preparation and Properties.
7 CHDM-modified PET Copolyester: Preparation and Properties.
8 Dibasic-acid-modified PCT Copolyester: Preparation and Properties.
9 Modification of CHDM-based Polyesters with Other Glycols and Acids.
9.1 CHDM-based Copolyesters with Dimethyl 2,6-naphthalenedicarboxylate.
9.2 Polyesters Prepared with 1,4-Cyclohexanedicarboxylic Acid.
9.3 CHDM-based Copolyesters with 2,2,4,4-tetramethyl-1,3-cyclobutanediol.
9.4 CHDM-based Copolyesters with Other Selected Monomers.
Acknowledgments.
References.
8 Poly(Butylene Terephthalate) (Robert R. Gallucci and Bimal R. Patel).
1 Introduction.
2 Polymerization of PBT.
2.1 Monomers.
Acid.
2.2 Catalysts.
2.3 Process Chemistry.
2.4 Commercial Processes.
3 Properties of PBT.
3.1 Unfilled PBT.
3.2 Fiberglass-filled PBT.
3.3 Mineral-filled PBT.
4 PBT Polymer Blends.
4.1 PBT-PET Blends.
4.2 PBT-Polycarbonate Blends.
4.3 Impact-modified PBT and PBT-PC Blends.
4.4 PBT Blends with Styrenic Copolymers.
5 Flame-retardant Additives.
6 PBT and Water.
7 Conclusions.
References.
9 Properties and Applications of Poly(Ethylene 2,6-naphthalene), its Copolyesters and Blends (Doug D. Callander).
1 Introduction.
2 Manufacture of PEN.
3 Properties of PEN.
4 Thermal Transitions of PEN.
5 Comparison of the Properties of PEN and PET.
6 Optical Properties of PEN.
7 Solid-state Polymerization of PEN.
8 Copolyesters.
8.1 Benefits of Naphthalate-modified Copolyesters.
8.2 Manufacture of Copolyesters.
9 Naphthalate-based Blends.
10 Applications for PEN, its Copolyesters and Blends.
10.1 Films.
10.2 Fiber and Monofilament.
10.3 Containers.
10.4 Cosmetic and Pharmaceutical Containers.
11 Summary.
References.
10 Biaxially Oriented Poly(Ethylene 2,6-naphthalene) Films: Manufacture, Properties and Commercial Applications (Bin Hu, Raphael M. Ottenbrite and Junaid A. Siddiqui).
1 Introduction.
2 The Manufacturing Process for PEN Films.
2.1 Synthesis of Dimethyl-2,6-naphthalene Dicarboxylate.
2.2 Preparation Process of PEN Resin.
2.3 Continuous Process for the Manufacture of Biaxially Oriented PEN Film.
3 Properties of PEN.
3.1 Morphology of PEN.
3.2 Chemical Stability.
3.3 Thermal Properties.
3.4 Mechanical Properties.
3.5 Gas-barrier Properties.
3.6 Electrical Properties.
3.7 Optical Properties.
4 Applications for PEN Films.
4.1 Motors and Machine Parts.
4.2 Electrical Devices.
4.3 Photographic Films.
4.4 Cable and Wires Insulation.
4.5 Tapes and Belts.
4.6 Labels.
4.7 Printing and Embossing Films.
4.8 Packaging Materials.
4.9 Medical Uses.
4.10 Miscellaneous Industrial Applications.
References.
11 Synthesis, Properties and Applications of Poly(Trimethylene Terephthalate) (Hoe H. Chuah).
1 Introduction.
2 Polymerization.
2.1 1,3-Propanediol Monomer.
2.2 The Polymerization Stage.
2.3 Side Reactions and Products.
3 Physical Properties.
3.1 Intrinsic Viscosity and Molecular Weights.
3.2 Crystal Structure.
3.3 Crystal Density.
3.4 Thermal Properties.
3.5 Crystallization Kinetics.
3.6 Non-isothermal Crystallization Kinetics.
3.7 Heat Capacity and Heat of Fusion.
3.8 Glass Transition and Dynamic Mechanical Properties.
3.9 Mechanical and Physical Properties.
3.10 Melt Rheology.
4 Fiber Properties.
4.1 Tensile Properties.
4.2 Elastic Recovery.
4.3 Large Strain Deformation and Conformational Changes.
4.4 Drawing Behavior.
4.5 Crystal Orientation.
5 Processing and Applications.
5.1 Applications.
5.2 Fiber Processing.
5.3 Dyeing.
5.4 Injection Molding.
6 PTT Copolymers.
7 Health and Safety.
References.
IV FIBERS AND COMPOUNDS.
12 Polyester Fibers: Fiber Formation and End-use Applications (Glen Reese).
1 Introduction.
2 General Applications.
3 Chemical and Physical Structure.
3.1 Melt Behavior.
3.2 Polymer Structure.
3.3 Fiber Geometry.
4 Melt Spinning of PET Fibers.
4.1 Spinning Process Control.
5 Drawing of Spun Filaments.
5.1 Commercial Drawing Processes.
6 Specialized Applications.
6.1 Light Reflectance.
6.2 Low Pill Fibers.
6.3 Deep Dye Fibers.
6.4 Ionic Dyeability.
6.5 Antistatic/Antisoil Fibers.
6.6 High-shrink Fibers.
6.7 Low-melt Fibers.
6.8 Bicomponent (Bico) Fibers.
6.9 Hollow Fibers.
6.10 Microfibers.
6.11 Surface Friction and Adhesion.
6.12 Antiflammability and Other Applications.
7 The Future of Polyester Fibers.
References.
13 Relationship Between Polyester Quality and Processability: Hands-on Experience(Wolfgang Goltner).
1 Introduction.
2 Polyesters for Filament and Staple Fiber Applications.
2.1 Spinnability.
2.2 Yarn Break.
3 Polymer Contamination.
3.1 Oligomeric Contaminants.
3.2 Technological Aspects.
3.3 Thermal, Thermo-oxidative and Hydrolytic Degradation.
3.4 Insoluble Polyesters.
3.5 Gas Bubbles and Voids.
3.6 Dyeability.
4 Films.
4.1 Surface Properties.
4.2 Streaks.
4.3 Processability.
5 Bottles .
5.1 Processing.
5.2 The Quality of Polyester Bottle Polymer.
6 Other Polyesters.
7 Conclusions.
References .
14 Additives for the Modification of Poly(ethylene Terephthalate) to Produce Engineering-grade Polymer (John Scheirs).
1 Introduction.
2 Chain Extenders.
2.1 Pyromellitic Dianhydride.
2.2 Phenylenebisoxazoline.
2.3 Diepoxide Chain Extenders.
2.4 Tetraepoxide Chain Extenders.
2.5 Phosphites Chain Extension Promoters.
2.6 Carbonyl Bis(1-caprolactam).
3 Solid-stating Accelerators.
4 Impact Modifiers (Tougheners).
4.1 Reactive Impact Modifiers.
4.2 Non-reactive Impact Modifiers (Co-modifiers) .
4.3 Theory of Impact Modification of PET.
5 Nucleating Agents.
6 Nucleation/Crystallization Promoters.
7 Anti-hydrolysis Additives.
8 Reinforcements.
9 Flame Retardants.
10 Polymeric Modifiers for PET.
11 Specialty Additives.
11.1 Melt Strength Enhancers.
11.2 Carboxyl Acid Scavengers.
11.3 Transesterification Inhibitors.
11.4 Gloss Enhancers.
11.5 Alloying (Coupling) Agents.
11.6 Processing Stabilizers.
12 Technology of Commercial PET Engineering Polymers.
12.1 Rynite.
12.2 Petra.
12.3 Impet.
13 Compounding Principles for Preparing Engineering-grade PET Resins.
14 Commercial Glass-filled and Toughened PET Grades.
15 'Supertough' PET.
16 Automotive Applications for Modified PET.
References.
15 Thermoplastic Polyester Composites (Andrew E. Brink).
1 Introduction.
2 Poly(ethylene Terephthalate).
2.1 Crystallization of Poly(ethylene Terephthalate).
2.2 Advantages of Poly(ethylene Terephthalate).
3 Comparison of Thermoplastic Polyesters.
3.1 Poly(butylene Terephthalate).
3.2 Poly(1,4-cyclohexylenedimethylene Terephthalate).
3.3 Poly(trimethylene Terephthalate).
4 Composite Properties.
4.1 Kelly-Tyson Equation.
4.2 Interfacial Shear Strength - The Importance of Sizing.
4.3 Carbon Fiber Reinforcements.
5 New Composite Applications.
References.
V DEPOLYMERIZATION AND DEGRADATION.
16 Recycling Polyesters by Chemical Depolymerization (David D. Cornell).
1 Introduction.
2 Chemistry.
3 Background.
4 Technology for Polyester Depolymerization .
5 Commercial Application.
6 Criteria for Commercial Success.
7 Evaluation of Technologies.
7.1 Feedstock.
7.2 Capital.
8 Results.
9 Conclusions.
10 Acknowledgement and disclaimer.
References.
17 Controlled Degradation Polyesters (F. Glenn Gallagher).
1 Introduction.
2 Why Degradable Polymers?
3 Polymer Degradation.
4 Degradable Polyester Applications.
4.1 Medical.
4.2 Aquatic.
4.3 Terrestrial.
4.4 Solid Waste.
5 Selecting a Polymer for an Application.
5.1 Understand Application Requirement for a Specific Location.
5.2 Degradation Testing Protocol including Goal Degradation Product.
5.3 Lessons from Natural Products.
6 Degradable Polyesters.
6.1 Aromatic Polyesters.
6.2 Aliphatic Polyesters.
6.3 Copolyesters of Terephthalate to Control Degradation.
7 Conclusions.
References.
18 Photodegradation of Poly(ethylene Terephthalate) and Poly(ethylene/1,4-Cyclohexylenedimethylene Terephthalate) (David R. Fagerburg and Horst Clauberg ).
1 Introduction.
2 Weather-induced Degradation.
2.1 Important Climate Variables.
2.2 Artificial Weathering Devices.
3 Recent Results for Degradation in PECT.
3.1 Coloration.
3.2 Loss of Toughness.
3.3 Depth Profile of the Damage.
4 Degradation Mechanisms in PET and PECT.
5 Summary.
References and Notes.
VI LIQUID CRYSTAL POLYESTERS.
19 High-performance Liquid Crystal Polyesters with Controlled Molecular Structure (Toshihide Inoue and Toru Yamanaka).
1 Introduction - Chemical Structures and Liquid Crystallinity.
2 Experimental.
2.1 Synthesis of Polyarylates.
2.2 Preparation of Fibers.
2.3 Preparation of Specimens.
3 Measurements.
3.1 Flexural Modulus.
3.2 Dynamic Storage Modulus.
3.3 Anisotropic Melting Temperature and Clearing Point.
3.4 Melting Temperature and Glass Transition Temperature.
3.5 Orientation Function of Nematic Domains.
3.6 Relative Degree of Crystallinity.
3.7 Morphology.
3.8 Heat Distortion Temperatures.
4 Results and Discussion.
4.1 Moduli of As-spun Fibers.
4.2 Moduli of Injection Molded Specimens.
4.3 Heat Resistance.
4.3.1 Glass Transition Temperature.
4.3.2 Heat Distortion Temperature.
5 Conclusions.
6 Acknowledgement.
References.
20 Thermotropic Liquid Crystal Polymer Reinforced Polyesters (Seong H. Kim).
1 Introduction.
2 PHB/PEN/PET Mechanical Blends.
2.1 The Liquid Crystalline Phase.
2.2 Thermal behavior.
2.3 Mechanical properties.
2.4 Transesterification.
3 Effect of a catalyst on the compatibility of LCP/PEN Blends.
3.1 Mechanical property improvement.
3.2 Dispersion of LCP in PEN.
3.3 Heterogeneity of the blend.
4 Thermodynamic miscibility determination of TLCP and polyesters.
5 Crystallization kinetics of LCP with polyesters.
5.1 Non-isothermal crystallization dynamics.
5.2 Isothermal crystallization dynamics.
6 Conclusions.
7 Acknowledgements.
References.
VII UNSATURATED POLYESTERS.
21 Preparation, Properties and Applications of Unsaturated Polyesters (Keith G. Johnson and Lau S. Yang ).
1 Introduction.
2 Preparation of Unsaturated Polyester Resins.
2.1 Three Types of Unsaturated Polyester Resin Products.
3 Properties of Unsaturated Polyester Resins.
3.1 Chemical Constituents.
3.2 Additives.
3.3 Fillers.
3.4 Reinforcements.
4 Applications of Unsaturated Polyester Resins.
4.1 Marine.
4.2 Construction.
4.3 Transportation.
5 Future Developments.
References.
22 PEER Polymers: New Unsaturated Polyesters for Fiber-reinforced Composite Materials (Lau S. Yang).
1 Introduction.
2 Experimental.
2.1 Materials.
2.2 General Procedure for the Preparation of Unsaturated Polyester Resin from a Polyether Polyol .
2.3 A Typical Example of the Preparation of Cured Polyesters.
2.4 Other Examples of Cured Polyester Processes.
3 Results and Discussion .
3.1 Ether Cleavage Reaction Leading to Poly(Ether Ester) Resins.
3.2 Reaction Conditions and Mechanisms.
3.3 The Early Product and Strong-acid Catalysis Development.
3.4 Liquid properties of PEER Resins.
3.5 Physical properties of Cured PEER Resins.
4 Applications.
5 Acknowledgements.
References.
Index.
