POLYMER CHEMISTRY: An Introduction, 3rd Edition

Each chapter ends with pertinent references and a set of review exercises, many taken from the polymer literature, with the literature references included so that students can check their answers. This is designed to encourage students to read the literature.

CONTENTS

PART I. POLYMER STRUCTURE AND PROPERTIES



Chapter 1. Basic Principles

1.1 Introduction and historical development

1.2 Definitions

1.3 Polymerization processes

1.4 Step-reaction polymerization

1.5 Chain-reaction polymerization

1.6 Step-reaction addition and chain-reaction condensation

1.7 Nomenclature

1.7.1 Vinyl polymers

1.7.2 Vinyl copolymers

1.7.3 Nonvinyl polymers

1.7.4 Nonvinyl copolymers

1.7.5 End groups

1.7.6 Abbreviations

1.8 Industrial polymers

1.9 Polymer recycling



Chapter 2. Molecular Weight and Polymer Solutions

2.1 Number average and weight average molecular weight

2.2 Polymer solutions

2.3 Measurement of number average molecular weight

2.3.1 End-group analysis

2.3.2 Membrane osmometry

2.3.3 Cryoscopy and ebulliometry

2.3.4 Vapor pressure osmometry

2.3.5 Mass spectrometry

2.3.6 Refractive index measurements

2.4 Measurement of weight average molecular weight

2.4.1 Light scattering

2.4.2 Ultracentrifugation

2.5 Viscometry

2.6 Molecular weight distribution

2.6.1 Gel permeation chromatography

2.6.2 Fractional solution

2.6.3 Fractional precipitation

2.6.4 Thin-layer chromatography



Chapter 3. Chemical Structure and Polymer Morphology

3.1 Introduction

3.2 Molecular weight and intermolecular forces

3.3 The amorphous state: rheology

3.4 Glass transition temperature

3.5 Stereochemistry

3.6 Crystallinity

3.7 Liquid crystallinity

3.8 Chemical crosslinking

3.9 Physical crosslinking

3.10 Polymer blends



Chapter 4. Chemical Structure and Polymer Properties

4.1 Introduction

4.2 Fabrication methods

4.3 Mechanical properties

4.4 Thermal stability

4.5 Flammability and flame resistance

4.6 Chemical resistance

4.7 Degradability

4.8 Electrical conductivity

4.9 Nonlinear optical properties

4.10 Additives



Chapter 5. Evaluation, Characterization, and Analysis of Polymers

5.1 Introduction

5.2 Chemical methods of analysis

5.3 Spectroscopic methods of analysis

5.3.1 Infrared

5.3.2 Raman

5.3.3 Nuclear magnetic resonance

5.3.4 Electron spin resonance

5.3.5 Ultraviolet-visible

5.3.6 Fluorescence

5.4 X-ray, electron, and neutron scattering

5.5 Characterization and analysis of polymer surfaces

5.5.1 Scanning electron microscopy

5.5.2 Attenuated total reflectance spectroscopy

5.5.3 Photoacoustic spectroscopy

5.5.4 Electron spectroscopy for chemical analysis and Augér electron spectroscopy

5.5.5 Secondary-ion mass spectrometry and ion-scattering spectroscopy

5.5.6 Atomic force microscopy

5.6 Thermal analysis

5.6.1 Differential scanning calorimetry and differential thermal analysis

5.6.2 Thermomechanical analysis

5.6.3 Thrmogravimetric analysis

5.6.4 Pyrolysis-gas chromatography

5.6.5 Flammability testing

5.7 Measurement of mechanical properties

5.8 Evaluation of chemical resistance

5.9 Evaluation of electrical properties



PART II. VINYL POLYMERS



Chapter 6. Free Radical Polymerization

6.1 Introduction

6.2 Free radical initiators

6.2.1 Peroxides and hydroperoxides

6.2.2 Azo compounds

6.2.3 Redox initiators

6.2.4 Photoinitiators

6.2.5 Thermal polymerization

6.2.6 Electrochemical polymerization

6.3 Techniques of free radical polymerization

6.3.1 Bulk

6.3.2 Suspension

6.3.3 Solution

6.3.4 Emulsion

6.4 Kinetics and mechanism of polymerization

6.5 Stereochemistry of polymerization

6.6 Polymerization of dienes

6.6.1 Isolated dienes

6.6.2 Conjugated dienes

6.7 Monomer reactivity

6.8 Copolymerization



Chapter 7. Ionic polymerization

7.1 Introduction

7.2 Cationic polymerization

7.2.1 Cationic initiators

7.2.2 Mechanism, kinetics, and reactivity in cationic polymerization

7.2.3 Stereochemistry of cationic polymerization

7.2.4 Cationic copolymerization

7.2.5 Isomerization in cationic polymerization

7.3 Anionic polymerization

7.3.1 Anionic initiators

7.3.2 Mechanism, kinetics, and reactivity in anionic polymerization

7.3.3 Stereochemistry of anionic polymerization

7.3.4 Anionic copolymerization

7.4 Group transfer polymerization



Chapter 8. Vinyl Polymerization with Complex Coordination Catalysts

8.1 Introduction

8.2 Heterogeneous Ziegler-Natta polymerization

8.2.1 Heterogeneous catalysts

8.2.2 Mechanism and reactivity in heterogeneous polymerization

8.2.3 Stereochemistry of heterogeneous polymerization

8.2.4 Polymerization of dienes

8.3 Homogeneous Ziegler-Natta polymerization

8.3.1 Metallocene catalysts

8.3.2 Mechanism and reactivity with metallocene catalysts

8.3.3 Stereochemistry of metallocene-catalyzed polymerization

8.4 Ziegler-Natta copolymerization

8.5 Supported metal oxide catalysts

8.6 Alfin catalysts

8.7 Metathesis polymerization

8.7.1 Ring-opening metathesis polymerization

8.7.2 Acyclic diene metathesis polymerization



Chapter 9. Reactions of Vinyl Polymers

9.1 Introduction

9.2 Functional group reactions

9.2.1 Introduction of new functional groups

9.2.2 Conversion of functional groups

9.3 Ring-forming reactions

9.4 Crosslinking

9.4.1 Vulcanization

9.4.2 Radiation crosslinking

9.4.3 Photochemical crosslinking

9.4.4 Crosslinking through labile functional groups

9.4.5 Ionic crosslinking

9.5 Block and graft copolymer formation

9.5.1 Block copolymers

9.5.2 Graft copolymers

9.6 Polymer degradation

9.6.1 Chemical degradation

9.6.2 Thermal degradation

9.6.3 Degradation by radiation



PART III. NONVINYL POLYMERS



Chapter 10. Step-Reaction and Ring-Opening polymerization

10.1 Introduction

10.2 Step-reaction polymerization: kinetics

10.3 Stoichiometric imbalance

10.4 Molecular weight distribution

10.5 Network step polymerization

10.6 Step-reaction copolymerization

10.7 Step polymerization techniques

10.8 Dendritic polymers

10.9 Ring-opening polymerization



Chapter 11. Polyethers and related Polymers

11.1 Introduction

11.2 Preparation of polyethers by chain-reaction and ring-opening

polymerization

11.2.1 Polymerization of carbonyl compounds

11.2.2 Stereochemistry of aldehyde polymerization

11.2.3 Polymerization of cyclic ethers

11.2.4 Stereochemistry of epoxide polymerization

11.3 Preparation of polyethers by step-reaction polymerization

11.3.1 Synthesis of polyethers from glycols and bisphenols

11.3.2 Polyacetals and polyketals

11.3.3 Poly(phenylene oxide)s

11.3.4 Epoxy resins

11.4 Polysulfides, poly(alkylene polysulfide)s, and polysulfones

11.4.1 Polysulfides

11.4.2 Poly(alkylene polysulfide)s

11.4.3 Polysulfones



Chapter 12 Polyesters

12.1 Introduction

12.2 Linear polyesters

12.2.1 Preparation of polyesters by polycondensation reactions

12.2.2 Polycarbonates

12.2.3 Preparation of polyesters by ring-opening polymerization

12.2.4 Microbial polyesters

12.3 Hyperbranched polyesters

12.4 Crosslinked polyesters

12.4.1 Saturated polyester resins

12.4.2 Unsaturated polyesters



Chapter 13. Polyamides and Related Polymers

13.1 Introduction

13.2 Polyamides

13.2.1 Preparation of polyamides by polycondensation reactions

13.2.2 Polymerization of lactams

13.2.3 Miscellaneous methods of preparing polyamides

13.3 Properties of polyamides

13.4 Polyureas

13.5 Polyurethanes

13.6 Polyhydrazides

13.7 Polyimides



Chapter 14. Phenol- Urea-, and Melamine-formaldehyde Polymers

14.1 Introduction

14.2 Phenol-formaldehyde polymers: resoles

14.3 Phenol-formaldehyde polymers: novolacs

14.4 Chemical modifications of phenolic resins

14.5 Urea-formaldehyde polymers

14.6 Melamine-formaldehyde polymers



15. Heterocyclic Polymers

15.1 Introduction

15.2 Polypyrrole, polyfuran, and polythiophene

15.2 Polycyanurate and polyphthalocyanine resins

15.4 Heterocyclic polymers formed from precursor polymers

15.5 Heterocyclic polymers formed from polyfunctional monomers

15.5.1 Polybenzimidazoles

15.5.2 Polybenzoxazoles and polybenzothiazoles

15.5.3 Polyhydantoins

15.5.4 Poly(parabanic acid)s

15.5.5 Polyquinoxalines and polypyrazines

15.5.6 Polypyrazoles and polyimidazoles

15.5.7 Poly(as-triazine)s and polytriazolines

15.5.8 Polyquinolines and polyanthrazolines



Chapter 16. Inorganic and Partially Inorganic Polymers

16.1 Introduction

16.2 Poly(sulfur nitride)

16.3 Polysiloxanes

16.4 Polysilanes

16.5 Polyphosphazenes

16.6 Carborane polymers

16.7 Organometallic polymers

16.8 Coordination polymers



Chapter 17. Miscellaneous Organic Polymers

17.1 Introduction

17.2 Miscellaneous unsaturated polymers

17.2.1 Polycarbodiimides

17.2.2 Polyimines

17.2.3 Polymers containing carbon-carbon double bonds

17.2.4 Azo polymers

17.2.5 Polymers containing carbon-carbon triple bonds

17.3 Poly(p-phenylene) and poly(p-xylylene)

17.3.1 Poly(p-phenylene)

17.3.2 Poly(p-xylylene)

17.4 Friedel-Crafts polymers

17.5 Cycloaddition polymerization

17.5.1 Diels-Alder polymerization

17.5.2 2 + 2 Cycloaddition polymerization

17.6 Polyanhydrides

17.7 Polyamines

17.8 Charge-transfer polymers

17.9 Ionic polymers



Chapter 18. Natural Polymers

18.1 Introduction

18.2 Miscellaneous natural polymers

18.2.1 Rubber

18.2.2 Lignin, humus, coal, and kerogen

18.2.3 Asphaltenes

18.2.4 Shellac

18.2.5 Amber

18.2.6 Tall oil-derived polymers

18.3 Polysaccharides

18.3.1 Cellulose

18.3.2 Regenerated cellulose

18.3.3 Derivatives of cellulose

18.3.4 Starch

18.3.5 Derivatives of starch

18.3.6 Other polysaccharides

18.4 Proteins

18.4.1 Amino acids, polypeptides and proteins

18.4.2 Protein structure

18.4.3 Synthesis of polypeptides and proteins

18.4.4 Wool, silk, collagen, and regenerated protein

18.5 Nucleic acids

18.5.1 Nucleic acid structure

18.5.2 Nucleic acid synthesis

18.6 Conclusion



Appendix A. Commonly used Polymer Abbreviations

Appendix B. Polymer Literature

Appendix C. Sources of Laboratory Experiments in Polymer Chemistry

Index

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