Polymer Chemistry An Introduction

by Stevens, Malcolm P.

• ISBN13: 9780195124446
• ISBN10: 0195124448
• Edition: 3rd
• Format: Hardcover
• Copyright: 1998-11-19
• Publisher: Oxford University Press

Summary

Now updated to incorporate recent developments in the field, the third edition of this successful text offers an excellent introduction to polymer chemistry. Ideal for graduate students, advanced undergraduates, and industrial chemists who work with polymers, it is the only current polymertextbook that discusses polymer types according to functional groups. It provides a comprehensive and up-to-date overview of the chemistry of macromolecular substances, with particular emphasis on polymers that are important commercially and the properties that make them important. Major topicsinclude polymer synthesis and nomenclature; molecular weight and molecular weight distribution; reactions of polymers; recycling of polymers; methods used for characterizing and testing polymers; morphology; stereoregular polymers; polymer blends; step-growth, chain-growth, and ring-openingpolymerization; commercially important addition and condensation polymers; and heterocyclic, inorganic, and natural polymers. Review exercises, many including journal references, are provided to help lead students into the polymer literature. Polymer Chemistry, 3/e, offers the most up-to-date treatment available of new developments in this rapidly changing field. It covers dendritic and hyperbranched polymers, olefin polymerization using metallocene catalysts, living free radical polymerization, biodegradable bacterial polyesters,mass spectrometric methods for determining molecular weights of polymers, atomic force microscopy for characterizing polymer surfaces, and polymers exhibiting nonlinear optical properties.

Table of Contents

Preface	xvii
PART I POLYMER STRUCTURE AND PROPERTIES	3	(164)
1. Basic principles	3	(32)
1.1 Introduction and historical development	3	(3)
1.2 Definitions	6	(4)
1.3 Polymerization processes	10	(2)
1.4 Step-reaction polymerization	12	(1)
1.5 Chain-reaction polymerization	13	(2)
1.6 Step-reaction addition and chain-reaction condensation	15	(1)
1.7 Nomenclature	16	(9)
1.7.1 Vinyl polymers	17	(3)
1.7.2 Vinyl copolymers	20	(1)
1.7.3 Nonvinyl polymers	21	(3)
1.7.4 Nonvinyl copolymers	24	(1)
1.7.5 End groups	24	(1)
1.7.6 Abbreviations	25	(1)
1.8 Industrial polymers	25	(5)
1.8.1 Plastics	25	(2)
1.8.2 Fibers	27	(1)
1.8.3 Rubber (elastomers)	28	(1)
1.8.4 Coatings and adhesives	29	(1)
1.9 Polymer recycling	30	(1)
References	31	(1)
Review exercises	32	(3)
2. Molecular weight and polymer solutions	35	(26)
2.1 Number average and weight average molecular weight	35	(2)
2.2 Polymer solutions	37	(5)
2.3 Measurement of number average molecular weight	42	(6)
2.3.1 End-group analysis	42	(1)
2.3.2 Membrane osmometry	43	(3)
2.3.3 Cryoscopy and ebulliometry	46	(1)
2.3.4 Vapor pressure osmometry	46	(1)
2.3.5 Mass spectrometry	46	(2)
2.3.6 Refractive index measurements	48	(1)
2.4 Measurement of weight average molecular weight	48	(2)
2.4.1 Light scattering	48	(2)
2.4.2 Ulcentrifugation	50	(1)
2.5 Viscometry	50	(3)
2.6 Molecular weight distribution	53	(5)
2.6.1 Gel permeation chromatography (GPC)	53	(4)
2.6.2 Fractional solution	57	(1)
2.6.3 Fractional precipitation	58	(1)
2.6.4 Thin-layer chromatography (TLC)	58	(1)
References	58	(1)
Review exercises	59	(2)
3. Chemical structure and polymer morphology	61	(35)
3.1 Introduction	61	(1)
3.2 Molecular weight and intermolecular forces	62	(1)
3.3 The amorphous state--rheology	63	(7)
3.4 Glass transition temperature	70	(4)
3.5 Stereochemistry	74	(5)
3.6 Crystallinity	79	(4)
3.7 Liquid crystallinity	83	(2)
3.8 Chemical crosslinking	85	(1)
3.9 Physical crosslinking	86	(1)
3.10 Polymer blends	87	(4)
References	91	(2)
Review exercises	93	(3)
4. Chemical structure and polymer properties	96	(33)
4.1 Introduction	96	(1)
4.2 Fabrication methods	96	(4)
4.3 Mechanical properties	100	(6)
4.4 Thermal stability	106	(4)
4.5 Flammability and flame resistance	110	(2)
4.6 Chemical resistance	112	(2)
4.7 Degradability	114	(3)
4.8 Electrical conductivity	117	(3)
4.9 Nonlinear optical properties	120	(1)
4.10 Additives	121	(3)
References	124	(3)
Review exercises	127	(2)
5. Evaluation, characterization, and analysis of polymers	129	(38)
5.1 Introduction	129	(1)
5.2 Chemical methods of analysis	130	(1)
5.3 Spectroscopic methods of analysis	130	(10)
5.3.1 Infrared	131	(2)
5.3.2 Raman	133	(1)
5.3.3 Nuclear magnetic resonance	134	(4)
5.3.4 Electron spin resonance	138	(1)
5.3.5 Ultraviolet (UV)-visible	139	(1)
5.3.6 Fluorescence	139	(1)
5.4 X-ray, electron, and neutron scattering	140	(1)
5.5 Characterization and analysis of polymer surfaces	141	(8)
5.5.1 Scanning electron microscopy (SEM)	143	(1)
5.5.2 Attenuated total reflectance spectroscopy (ATR)	143	(1)
5.5.3 Photoacoustic spectroscopy (PAS)	144	(1)
5.5.4 Electron spectroscopy for chemical analysis (or applications) (ESCA) and Auger electron spectroscopy (AES)	145	(2)
5.5.5 Secondary-ion mass spectrometry (SIMS) and ion-scattering spectroscopy (ISS)	147	(1)
5.5.6 Atomic force microscopy (AFM)	148	(1)
5.6 Thermal analysis	149	(7)
5.6.1 Differential scanning calorimetry (DSC) and differential thermal analysis (DTA)	149	(3)
5.6.2 Thermomechanical analysis (TMA)	152	(1)
5.6.3 Thermogravimetric analysis (TGA)	152	(1)
5.6.4 Pyrolysis-gas chromatography (PGC)	153	(1)
5.6.5 Flammability testing	154	(2)
5.7 Measurement of mechanical properties	156	(3)
5.8 Evaluation of chemical resistance	159	(1)
5.9 Evaluation of electrical properties	159	(1)
References	160	(3)
Review exercises	163	(4)
PART II VINYL POLYMERS	167	(118)
6. Free radical polymerization	167	(38)
6.1 Introduction	167	(2)
6.2 Free radical initiators	169	(4)
6.2.1 Peroxides and hydroperoxides	169	(2)
6.2.2 Azo compounds	171	(1)
6.2.3 Redox initiators	171	(1)
6.2.4 Photoinitiators	172	(1)
6.2.5 Thermal polymerization	172	(1)
6.2.6 Electrochemical polymerization	173	(1)
6.3 Techniques of free radical polymerization	173	(3)
6.3.1 Bulk	174	(1)
6.3.2 Suspension	174	(1)
6.3.3 Solution	174	(1)
6.3.4 Emulsion	175	(1)
6.4 Kinetics and mechanism of polymerization	176	(10)
6.5 Stereochemistry of polymerization	186	(2)
6.6 Polymerization of dienes	188	(3)
6.6.1 Isolated dienes	188	(1)
6.6.2 Conjugated dienes	189	(2)
6.7 Monomer reactivity	191	(3)
6.8 Copolymerization	194	(7)
References	201	(1)
Review exercises	202	(3)
7. Ionic polymerization	205	(29)
7.1 Introduction	205	(1)
7.2 Cationic polymerization	205	(12)
7.2.1 Cationic initiators	205	(2)
7.2.2 Mechanism, kinetics, and reactivity in cationic polymerization	207	(6)
7.2.3 Stereochemistry of cationic polymerization	213	(2)
7.2.4 Cationic copolymerization	215	(2)
7.2.5 Isomerization in cationic polymerization	217	(1)
7.3 Anionic polymerization	217	(10)
7.3.1 Anionic initiators	217	(2)
7.3.2 Mechanism, kinetics, and reactivity in anionic polymerization	219	(4)
7.3.3 Stereochemistry of anionic polymerization	223	(2)
7.3.4 Anionic copolymerization	225	(2)
7.4 Group transfer polymerization	227	(3)
References	230	(1)
Review exercises	231	(3)
8. Vinyl polymerization with complex coordination catalysts	234	(25)
8.1 Introduction	234	(2)
8.2 Heterogeneous Ziegler-Natta polymerization	236	(9)
8.2.1 Heterogeneous catalysts	236	(2)
8.2.2 Mechanism and reactivity in heterogeneous polymerization	238	(4)
8.2.3 Stereochemistry of heterogeneous polymerization	242	(1)
8.2.4 Polymerization of dienes	243	(2)
8.3 Homogeneous Ziegler-Natta polymerization	245	(4)
8.3.1 Metallocene catalysts	245	(1)
8.3.2 Mechanism and reactivity with metallocene catalysts	246	(2)
8.3.3 Stereochemistry of metallocene-catalyzed polymerization	248	(1)
8.4 Ziegler-Natta copolymerization	249	(2)
8.5 Supported metal oxide catalysts	251	(1)
8.6 Alfin catalysts	252	(1)
8.7 Metathesis polymerization	252	(3)
8.7.1 Ring-opening metathesis polymerization	253	(2)
8.7.2 Acyclic diene metathesis polymerization	255	(1)
References	255	(2)
Review exercises	257	(2)
9. Reactions of vinyl polymers	259	(26)
9.1 Introduction	259	(1)
9.2 Functional group reactions	260	(3)
9.2.1 Introduction of new functional groups	260	(1)
9.2.2 Conversion of functional groups	261	(2)
9.3 Ring-forming reactions	263	(2)
9.4 Crosslinking	265	(7)
9.4.1 Vulcanization	265	(2)
9.4.2 Radiation crosslinking	267	(1)
9.4.3 Photochemical crosslinking	267	(4)
9.4.4 Crosslinking through labile functional groups	271	(1)
9.4.5 Ionic crosslinking	272	(1)
9.5 Block and graft copolymer formation	272	(4)
9.5.1 Block copolymers	272	(1)
9.5.2 Graft copolymers	273	(3)
9.6 Polymer degradation	276	(3)
9.6.1 Chemical degradation	276	(1)
9.6.2 Thermal degradation	277	(1)
9.6.3 Degradation by radiation	278	(1)
References	279	(2)
Review exercises	281	(4)
PART III NONVINYL POLYMERS	285	(230)
10. Step-reaction and ring-opening polymerization	285	(24)
10.1 Introduction	285	(1)
10.2 Step-reaction polymerization--kinetics	285	(5)
10.3 Stoichiometric imbalance	290	(2)
10.4 Molecular weight distribution	292	(3)
10.5 Network step polymerization	295	(2)
10.6 Step-reaction copolymerization	297	(1)
10.7 Step polymerization techniques	298	(3)
10.8 Dendritic polymers	301	(3)
10.9 Ring-opening polymerization	304	(2)
References	306	(1)
Review exercises	307	(2)
11. Polyethers, polysulfides, and related polymers	309	(29)
11.1 Introduction	309	(1)
11.2 Preparation of polyethers by chain-reaction and ring-opening polymerization	309	(12)
11.2.1 Polymerization of carbonyl compounds	309	(4)
11.2.2 Stereochemistry of aldehyde polymerization	313	(1)
11.2.3 Polymerization of cyclic ethers	314	(6)
11.2.4 Stereochemistry of epoxide polymerization	320	(1)
11.3 Preparation of polyethers by step-reaction polymerization	321	(8)
11.3.1 Synthesis of polyethers from glycols and bisphenols	321	(1)
11.3.2 Polyacetals and polyketals	322	(2)
11.3.3 Poly(phenylene oxide)s	324	(2)
11.3.4 Epoxy resins	326	(3)
11.4 Polysulfides, poly(alkylene polysulfide)s, and polysulfones	329	(4)
11.4.1 Polysulfides	329	(2)
11.4.2 Poly(alkylene polysulfide)s	331	(1)
11.4.3 Polysulfones	332	(1)
References	333	(1)
Review exercises	334	(4)
12. Polyesters	338	(26)
12.1 Introduction	338	(3)
12.2 Linear polyesters	341	(12)
12.2.1 Preparation of polyesters by polycondensation reactions	341	(5)
12.2.2 Polycarbonates	346	(2)
12.2.3 Preparation of polyesters by ring-opening polymerization	348	(4)
12.2.4 Microbial polyesters	352	(1)
12.3 Hyperbranched polyesters	353	(1)
12.4 Crosslinked polyesters	354	(5)
12.4.1 Saturated polyester resins	354	(2)
12.4.2 Unsaturated polyesters	356	(3)
References	359	(1)
Review exercises	360	(4)
13. Polyamides and related polymers	364	(31)
13.1 Introduction	364	(2)
13.2 Polyamides	366	(8)
13.2.1 Preparation of polyamides by polycondensation reactions	366	(3)
13.2.2 Polymerization of lactams	369	(3)
13.2.3 Miscellaneous methods of preparing polyamides	372	(2)
13.3 Properties of polyamides	374	(3)
13.4 Polyureas	377	(1)
13.5 Polyurethanes	378	(4)
13.6 Polyhydrazides	382	(1)
13.7 Polyimides	382	(6)
References	388	(2)
Review exercises	390	(5)
14. Phenol-, urea-, and melamine-formaldehyde polymers	395	(14)
14.1 Introduction	395	(1)
14.2 Phenol-formaldehyde polymers: resoles	396	(3)
14.3 Phenol-formaldehyde polymers: novolacs	399	(3)
14.4 Chemical modifications of phenolic resins	402	(2)
14.5 Urea-formaldehyde polymers	404	(2)
14.6 Melamine-formaldehyde polymers	406	(1)
References	407	(1)
Review exercises	408	(1)
15. Heterocyclic polymers	409	(16)
15.1 Introduction	409	(3)
15.2 Polypyrrole, polyfuran, and polythiophene	412	(1)
15.3 Polycyanurate and polyphthalocyanine resins	413	(1)
15.4 Heterocyclic polymers formed from precursor polymers	414	(1)
15.5 Heterocyclic polymers formed from polyfunctional monomers	415	(6)
15.5.1 Polybenzimidazoles	415	(2)
15.5.2 Polybenzoxazoles and polybenzothiazoles	417	(1)
15.5.3 Polyhydantoins	418	(1)
15.5.4 Poly(parabanic acid)s	418	(1)
15.5.5 Polyquinoxalines and polypyrazines	419	(1)
15.5.6 Polypyrazoles and polyimidazoles	419	(1)
15.5.7 Poly(as-triazine)s and polytriazolines	420	(1)
15.5.8 Polyquinolines and polyanthrazolines	421	(1)
References	421	(1)
Review exercises	422	(3)
16. Inorganic and partially inorganic polymers	425	(22)
16.1 Introduction	425	(1)
16.2 Poly(sulfur nitride)	426	(1)
16.3 Polysiloxanes	427	(3)
16.4 Polysilanes	430	(1)
16.5 Polyphosphazenes	431	(3)
16.6 Carborane polymers	434	(2)
16.7 Organometallic polymers	436	(2)
16.8 Coordination polymers	438	(4)
References	442	(2)
Review exercises	444	(3)
17. Miscellaneous organic polymers	447	(29)
17.1 Introduction	447	(1)
17.2 Miscellaneous unsaturated polymers	447	(5)
17.2.1 Polycarbodiimides	447	(2)
17.2.2 Polyimines	449	(1)
17.2.3 Polymers containing carbon-carbon double bonds	450	(1)
17.2.4 Azo polymers	450	(1)
17.2.5 Polymers containing carbon-carbon triple bonds	451	(1)
17.3 Poly(p-phenylene) and poly(p-xylylene)	452	(3)
17.3.1 Poly(p-phenylene)	452	(2)
17.3.2 Poly(p-xylylene)	454	(1)
17.4 Friedel-Crafts polymers	455	(1)
17.5 Cycloaddition polymerization	456	(4)
17.5.1 Diels-Alder polymerization	456	(3)
17.5.2 2 + 2 Cycloaddition polymerization	459	(1)
17.6 Polyanhydrides	460	(1)
17.7 Polyamines	461	(3)
17.8 Charge-transfer polymers	464	(3)
17.9 Ionic polymers	467	(2)
References	469	(2)
Review exercises	471	(5)
18. Natural polymers	476	(39)
18.1 Introduction	476	(1)
18.2 Miscellaneous natural polymers	476	(8)
18.2.1 Rubber	476	(3)
18.2.2 Lignin, humus, coal, and kerogen	479	(2)
18.2.3 Asphaltenes	481	(1)
18.2.4 Shellac	481	(1)
18.2.5 Amber	482	(1)
18.2.6 Tall oil-derived polymers	482	(2)
18.3 Polysaccharides	484	(8)
18.3.1 Cellulose	484	(1)
18.3.2 Regenerated cellulose	485	(1)
18.3.3 Derivatives of cellulose	486	(3)
18.3.4 Starch	489	(1)
18.3.5 Derivatives of starch	490	(1)
18.3.6 Other polysaccharides	491	(1)
18.4 Proteins	492	(10)
18.4.1 Amino acids, polypeptides, and proteins	492	(3)
18.4.2 Protein structure	495	(3)
18.4.3 Synthesis of polypeptides and proteins	498	(2)
18.4.4 Wool, silk, collagen, and regenerated protein	500	(2)
18.5 Nucleic acids	502	(8)
18.5.1 Nucleic acid structure	502	(5)
18.5.2 Nucleic acid synthesis	507	(3)
18.6 Conclusion	510	(1)
References	510	(3)
Review exercises	513	(2)
Appendix A Commonly used polymer abbreviations	515	(2)
Appendix B Polymer literature	517	(9)
Appendix C Sources of laboratory experiments in polymer chemistry	526	(9)
Index	535