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Introduction to POLYMER CHEMISTRY • Second Edition
Charles E. Carraher, Jr.
The first edition of the critically acclaimed Introduction to Polymer Chemistry provided readers with a much-needed, well-rounded presentation of the principles and applications of natural, synthetic, inorganic, and organic polymers. With an emphasis on the environment and green chemistry and materials, this second edition continues that tradition, offering detailed coverage of natural and synthetic giant molecules, inorganic and organic polymers, elastomers, adhesives, coatings, fibers, plastics, blends, caulks, composites, and ceramics.
Using simple fundamentals, the author shows how the basic principles of one polymer group can be applied to all of the other groups. He covers synthesis and polymerization reactions, reactivities, techniques for characterization and analysis, energy absorption and thermal conductivity, physical and optical properties, and practical applications. This edition also addresses environmental concerns and green polymeric materials, including biodegradable polymers and microorganisms for synthesizing materials. Brief case studies are woven within the text as historical accounts to illustrate various developments and the societal and scientific contexts in which these changes occurred.
Features
- Covers organic, organometallic, natural, and inorganic polymers
- Discusses the analytical and physical nature of materials
- Presents polymerization processes that include addition polymerization, condensation polymerization, and self-assembly
- Explores additives and polymer-based technologies, such as nanocomposites, lubricants, foams, coatings, adhesives, and polylactides
- Highlights novel applications in biomedicine, drug discovery, and electronics
- Integrates case studies throughout that put various discoveries and advances in a historical perspective
Introduction to Polymer Chemistry, Second Edition remains the premier text for understanding the behavior of polymers while offering new material on environmental science.
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Preface
There is an appropriate and necessary move toward green materials and green chemistry. This trend is captured in this book as it is both integrated within the appropriate sections and treated separately in a section on green materials. There also exists a greater awareness of health concerns within our society, and this awareness is also mirrored in this book.
Polymers are all about us and are the basis of life itself; they are used for communication (both natural and synthetic), for our nutrition and clothing, for recording history, and for constructing buildings and highways. In fact it is difficult to imagine society without synthetic polymers, and life without natural polymers. Part of being an educated and responsible citizen involves knowing the correct questions to ask and knowing (possible) the correct answers. In our ever-increasingly technological world, science plays a crucial role in providing solutions to critical problems of food; clean and abundant water, energy, and air; and health. This book provides both the information and the insights that allow a better understanding of these large molecules that are all about us.
Most books on polymers are aimed at either graduate students or are hybrids aimed at both undergraduate, but mostly graduate students. This book is aimed mainly at undergraduate students but can also serve graduate students. Thus, a strong bond is forged between science, history, and the crucible that is today's society. Information gained from the basic core science courses are brought to bear on understanding giant molecules. This information includes factual, theoretical, and practical concepts presented in science. It is of use to those who want to simply be well educated, as well as to those who want to pursue a career in medicine, engineering, physics, chemistry, biomedical sciences, law, and business.
This book provides a detailed coverage of polymers including natural and synthetic giant molecules; inorganic and organic polymers; and elastomers, adhesives, coatings, fibers, plastics, blends, c aulks, composites, and ceramics. The basic principles that apply to one polymer group apply to all of the other groups when used with some simple fundamentals. These fundamentals are integrated into the fabric of this book.
We have kept in mind the saying that we should be students of history so we do not repeat the ame mistakes; at the same time we should also be students of history so that we might repeat the successes. Brief case studies are woven within the fabric of this book as historical accounts illustrating the purposes in back of change as well as the societal and scientific contexts within which these changes occurred.
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Contents
Preface xiii
Acknowledgments xv
Author xvii
How to Study Polymers xix
Polymer Nomenclature xxi
Chapter 1 Introduction to Polymers 1
1.1 History of Polymers 1
1.2 Why Polymers? 9
1.3 Today's Marketplace 13
1.4 Environmental Assessment 15
1.4.1 Environmental Impact Assessment 15
1.4.2 Ecological Footprint 17
1.4.3 Life Cycle Assessment 17
1.5 Managing Sustainability 17
1.6 Summary 20
Glossary 20
Exercises 21
Further Readings 21
Chapter 2 Polymer Structure (Morphology) 23
2.1 Stereochemistry of Polymers 24
2.2 Molecular Interactions 29
2.3 Polymer Crystals 35
2.4 Amorphous Bulk States 39
2.5 Polymer Structure-Property Relationships 40
2.6 Crystalline and Amorphous Combinations 42
2.7 Cross-Linking 43
2.8 Summary 45
Glossary 46
Exercises 47
Further Readings 48
Chapter 3 Molecular Weight of Polymers 51
3.1 Introduction 51
3.2 Solubility 52
3.3 Average Molecular Weight Values 55
3.4 Fractionation of Polydisperse Systems 60
3.5 Chromatography 60
3.6 Colligative Molecular Weights 63
3.6.1 O smometr y 63
3.6.2 End-Group Analysis 64
3.6.3 Eublliometry and Cryometry 64
3.7 Light-Scattering Photometry 64
3.8 Other Techniques 70
3.8.1 Ultracentrifugation 70
3.8.2 Mass Spectrometry 72
3.9 Viscometry 73
3.10 Summary 79
Glossary 80
Exercises 81
Further Readings 83
Chapter 4 Naturally Occurring Polymers 85
4.1 Polysaccharides 87
4.2 Cellulose 87
4.2.1 Paper 90
4.3 Cellulose—Regenerating Processes 92
4.4 Esters and Ethers of Cellulose 94
4.4.1 Inorganic Esters 94
4.4.2 Organic Esters 95
4.4.3 Organic Ethers 97
4.5 Starch 98
4.6 Other Polysaccharides 100
4.7 Proteins 104
4.7.1 Primary Structure 106
4.7.2 Secondary Structure 106
4.7.2.1 Keratins 109
4.7.3 Tertiary Structure Ill
4.7.3.1 Globular Proteins Ill
4.7.3.2 Fibrous Proteins 113
4.7.3.3 Collagen 113
4.7.3.4 Elastin 114
4.7.3.5 Membrane Proteins 114
4.7.4 Quaternary Structure 114
4.8 Nucleic Acids 117
4.8.1 Flow of Biological Information 120
4.9 Naturally Occurring Polyisoprenes 123
4.9.1 Balloons 126
4.9.2 Resins 127
4.10 Lignin 128
4.11 Melanins 130
4.12 Polymer Structure 131
4.13 Genetic Engineering 133
4.14 DNA Profiling 135
4.15 Asphalt 137
4.16 Summary 137
Glossary 139
Exercises 141
Further Readings 142
Chapter 5 Step-Reaction Polymerization (Polycondensation Reactions) 143
5.1 Comparison between the Polymer Type and the Kinetics of Polymerization 143
5.2 Introduction 148
5.3 Stepwise Kinetics 148
5.4 Polycondensation Mechanisms 152
5.5 Polyesters and Polycarbonates 154
5.6 Synthetic Poly amides 159
5.7 Polyimides 164
5.8 Polybenzimidazoles and Related Polymers 164
5.9 Polyurethanes and Poly ureas 165
5.10 Polysulfides 167
5.11 Polyethers 167
5.12 Polysulfones 170
5.13 Poly (Ether Ether Ketone) and Polyketones 170
5.14 Phenolic and Amino Plastics 172
5.15 Synthetic Routes 173
5.16 Liquid Crystals 175
5.17 Microfibers 177
5.18 Summary 178
Glossary 178
Exercises 180
Further Readings 181
Chapter 6 Ionic Chain Reaction and Complex Coordination Polymerization (Addition Polymerization) 183
6.1 Chain Growth Polymerization—General 184
6.2 Cationic Polymerization 185
6.3 Anionic Polymerization 188
6.4 Stereoregularity and Stereogeometry 191
6.5 Polymerization with Complex Coordination Catalysts 192
6.6 Soluble Stereoregulating Catalysis 193
6.7 Polyethylenes 196
6.8 Polypropylene 201
6.9 Polymers from 1,4-Dienes 205
6.10 Polyisobutylene 207
6.11 Metathesis Reactions 208
6.12 Zwitterionic Polymerization 208
6.13 Isomerization Polymerization 209
6.14 Precipitation Polymerization 209
6.15 Summary 210
Glossary 211
Exercises 212
Further Readings 213
Chapter 7 Free Radical Chain Polymerization (Addition Polymerization) 215
7.1 Initiators for Free Radical Chain Polymerization 215
7.2 Mechanism for Free Radical Chain Polymerization 219
7.3 Chain Transfer 225
7.4 Polymerization Techniques 226
7.4.1 Bulk Polymerization 226
7.4.2 Suspension Polymerization 229
7.4.3 Solution Polymerization 229
7.4.4 Emulsion Polymerization 230
7.5 Fluorine-Containing Polymers 232
7.6 Polystyrene 235
7.7 Polyvinyl Chloride) 236
7.8 Poly(Methyl Methacrylate) 238
7.9 Polyacrylonitrile 239
7.10 Solid-State Irradiation Polymerization 239
7.11 Plasma Polymerization 240
7.12 Summary 241
Glossary 241
Exercises 242
Further Readings 244
Chapter 8 Copolymerization 245
8.1 Kinetics of Copolymerization 246
8.2 The Q-e Scheme 249
8.3 Commercial Copolymers 250
8.4 Block Copolymers 251
8.5 Graft Copolymers 252
8.6 Elastomers 253
8.6.1 Thermoplastic Elastomers 253
8.7 Blends 255
8.7.1 Immiscible Blends 256
8.7.2 Miscible Blends 257
8.8 Polymer Mixtures—IPNS and Alloys 259
8.9 Dendrites 259
8.10 Ionomers 260
8.11 Fluoroelastomers 261
8.12 Nitrile Rubber 262
8.13 Acrylonitrile Butadiene Styrene Terpolymers 262
8.14 EPDM Rubber 263
8.15 Summary 264
Glossary 264
Exercises 265
Further Readings 266
Chapter 9 Organometallic and Metalloid Polymers 269
9.1 Introduction 269
9.2 Inorganic Reaction Mechanisms 270
9.3 Condensation Organometallic Polymers 272
9.4 Coordination Polymers 277
9.5 Addition Polymers 279
9.6 Summary 283
Glossary 283
Exercises 284
Further Readings 284
Chapter 10 Inorganic Polymers 287
10.1 Introduction 287
10.2 Portland Cement 287
10.3 Other Cements 290
10.4 Silicates 290
10.4.1 Network 293
10.4.2 Layer 293
10.4.3 Chain 294
10.5 Silicon Dioxide (Amorphous) 294
10.5.1 Kinds of Glasses 296
10.5.2 Safety Glass 298
10.6 Sol-Gel 300
10.6.1 Aerogels 300
10.7 Silicon Dioxide (Crystalline Forms)—Quartz Forms 302
10.8 Silicon Dioxide in Electronic Chips 304
10.9 Asbestos 304
10.10 Polymeric Carbon—Diamond 305
10.11 Polymeric Carbon—Graphite 306
10.12 Internal Cyclization—Carbon Fibers and Related Materials 307
10.13 Carbon Nanotubes 308
10.13.1 Structures 309
10.14 Bitumens 313
10.15 Carbon Black 313
10.16 Polysulfur 315
10.17 Ceramics 315
10.18 High-Temperature Superconductors 317
10.18.1 Discovery of the 123-Compound 317
10.18.2 Structure of the 123-Compound 317
10.19 Zeolites 318
10.20 Summary 319
Glossary 320
Exercises 321
Further Readings 321
Chapter 11 Reactions of Polymers 323
11.1 Reactions with Polyolefines and Polyenes 323
11.2 Reactions of Aromatic and Aliphatic Pendant Groups 324
11.3 Degradation 325
11.4 Cross-Linking 327
11.5 Reactivities of End Groups 328
11.6 Supramolecules and Self-Assembly 329
11.7 Transfer and Retention of Oxygen 332
11.8 Nature's Macromolecular Catalysts 335
11.9 Photosynthesis 340
11.9.1 Purple Photosynthetic Bacteria 341
11.9.2 Green Sulfur Bacteria 343
11.10 Mechanisms of Energy Absorption 343
11.11 Breakage of Polymeric Materials 345
11.12 Summary 346
Glossary 347
Exercises 347
Further Readings 348
Chapter 12 Testing and Spectrometric Characterization of Polymers 349
12.1 Spectronic Characterization of Polymers 350
12.1.1 Infrared Spectroscopy 350
12.1.2 Raman Spectroscopy 351
12.1.3 Nuclear Magnetic Resonance Spectroscopy 351
12.1.4 NMR Applications 353
12.1.5 Electron Paramagnetic Resonance Spectroscopy 353
12.1.6 X-Ray Spectroscopy 353
12.2 Surface Characterization 354
12.2.1 Auger Electron Spectroscopy and X-Ray Photoelectron Spectroscopy 355
12.2.2 Near-Field Scanning Optical Microscopy 355
12.2.3 Electron Microscopy 356
12.2.4 Scanning Probe Microscopy 356
12.2.5 Secondary Ion Mass Spectroscopy 359
12.3 Amorphous Region Determinations 359
12.4 Thermal Analysis 360
12.5 Thermal Property Tests 362
12.5.1 Thermal Conductivity 362
12.5.2 Thermal Expansion 362
12.5.3 Glass Transition Temperatures 363
12.6 Flammability 363
12.7 Electrical Properties: Theory 363
12.8 Electric Measurements 365
12.9 Weatherability 366
12.10 Optical Properties—Tests 366
12.10.1 Index of Refraction 367
12.10.2 Optical Clarity 367
12.10.3 Absorption and Reflectance 367
12.11 Chemical Resistance 368
12.12 Summary 369
Glossary 369
Exercises 370
Further Readings 370
Chapter 13 Rheology and Physical Tests 373
13.1 Rheology 373
13.1.1 Rheology and Physical Tests 376
13.1.2 Response Time 379
13.2 Typical Stress-Strain Behavior 379
13.3 Stress-Strain Relationships 382
13.4 Specific Physical Tests 384
13.4.1 Tensile Strength 384
13.4.2 Tensile Strength of Inorganic and Metallic Fibers and Whiskers 385
13.4.3 Compressive Strength 386
13.4.4 Impact Strength 386
13.4.5 Hardness 386
13.4.6 Failure 387
13.5 Summary 387
Glossary 388
Exercises 389
Further Readings 389
Chapter 14 Additives 391
14.1 Fillers 391
14.2 Reinforcements 394
14.2.1 Fibers and Resins 395
14.2.2 Applications 396
14.3 Nanocomposites 399
14.4 Plasticizers 401
14.5 Antioxidants 403
14.6 Heat Stabilizers 404
14.7 Ultraviolet Stabilizers 404
14.8 Flame Retardants 405
14.9 Colorants 405
14.10 Curing Agents 406
14.11 Antistatic Agents—Antistats 407
14.12 Chemical Blowing Agents 407
14.13 Compatibilizers 408
14.14 Impact Modifiers 408
14.15 Processing Aids 408
14.16 Lubricants 408
14.17 Microorganism Inhibitors 408
14.18 Summary 408
Glossary 409
Exercises 411
Further Readings 412
Chapter 15 Synthesis of Reactants and Intermediates for Polymers 413
15.1 Monomer Synthesis from Basic Feedstocks 413
15.2 Reactants for Step-Reaction Polymerization 418
15.3 Synthesis of Vinyl Monomers 424
15.4 Summary 428
Glossary 428
Exercises 428
Further Readings 429
Chapter 16 Polymer Technology 431
16.1 Polymer Processing 431
16.2 Secondary Structures—Mesophases 432
16.3 Fibers 435
16.3.1 Polymer Processing—Spinning and Fiber Production 435
16.3.1.1 Introduction 435
16.3.1.2 Melt Spinning 435
16.3.1.3 Dry Spinning 437
16.3.1.4 Wet Spinning 437
16.4 Elastomers 438
16.4.1 Elastomer Processing 438
16.5 Films and Sheets 440
16.5.1 Calendering 441
16.6 Polymeric Foams 441
16.7 Reinforced Plastics (Composites) and Laminates 441
16.7.1 Composites 441
16.7.2 Particle-Reinforced Composites—Large-Particle Composites 443
16.7.3 Fiber-Reinforced Composites 443
16.7.4 Processing of Fiber-Reinforced Composites 444
16.7.5 Structural Composites 444
16.7.6 Laminating 445
16.8 Molding 445
16.8.1 Injection Molding 445
16.8.2 Blow Molding 447
16.8.3 Rotational Molding 449
16.8.4 Compression and Transfer Moldings 449
16.8.5 Thermoforming 450
16.9 Casting 450
16.10 Extrusion 451
16.11 Coatings 451
16.11.1 Processing 453
16.12 Adhesives 455
16.13 Conductive Polymeric Materials 457
16.13.1 Photoconductive and Photonic Polymers 457
16.13.2 Electrically Conductive Polymers 458
16.14 Drug Design and Activity 462
16.15 Synthetic Biomedical Polymers 464
16.16 Dental Materials 468
16.17 Emerging Polymers 470
16.18 Green Materials 473
16.19 Summary 477
Glossary 478
Exercises 479
Further Readings 480
Appendix A: Structures of Common Polymers 483
Appendix B: Syllabus 487
Appendix C: American Chemical Society Committee on Professional Training Requirements 489
Appendix D: Comments on Health 491
Appendix E: ISO 9000 and 14000 493
Appendix F: Symbols 495
Appendix G: Web Information 499
Index 501
