Introduction to Polymer Chemistry

Polymer Chemistry
 
Author:
Charles E. Carraher
Release at: 2013
Pages: 545
Edition:
Third Edition
File Size: 10 MB
File Type: pdf
Language: English


Content of Introduction to Polymer Chemistry



Chapter 1  Introduction to Polymers 1

1.1  History of Polymers 1
1.2  Why Polymers? 10
1.3  Today’s Marketplace 13
1.4  Environmental Assessment 17
1.4.1  Environmental Impact Assessment 17
1.4.2  Ecological Footprint 17
1.4.3  Life Cycle Assessment 19
1.5  Managing Sustainability 19
1.6  Summary 21
Glossary 22
Exercises 23
Further Readings 23
General Encyclopedias and Dictionaries 24

Chapter 2  Polymer Structure (Morphology) 25

2.1  Stereochemistry of Polymers 26
2.2  Molecular Interactions 32
2.3  Polymer Crystals 39
2.4  Amorphous Bulk State 42
2.5  Polymer Structure–Property Relationships 43
2.6  Crystalline and Amorphous Combinations 44
2.7  Cross-linking 47
2.8  Summary 48
Glossary 49
Exercises 51
Further Readings 52

Chapter 3  Molecular Weight of Polymers 53

3.1  Introduction 53
3.2  Solubility 54
3.3  Average Molecular Weight Values 58
3.4  Fractionation of Polydisperse Systems 63
3.5  Chromatography 63
3.6  Colligative Molecular Weights 66
3.6.1  Osmometry 66
3.6.2  End-Group Analysis 67
3.6.3  Ebulliometry and Cryometry 67
3.7  Light-Scattering Photometry 67
3.8  Other Techniques 74
3.8.1  Ultracentrifugation 74
3.8.2  Mass Spectrometry 75
3.9  Viscometry 76
3.10  Summary 82
Glossary 83
Exercises 85
Further Readings 87

Chapter 4  Naturally Occurring Polymers 89

4.1  Polysaccharides 91
4.2  Cellulose 93
4.2.1  Paper 95
4.2.1.1  Paper Recycling 96
4.3  Cellulose-Regenerating Processes 97
4.4  Esters and Ethers of Cellulose 99
4.4.1  Inorganic Esters 99
4.4.2  Organic Esters 100
4.4.3  Organic Ethers 102
4.5  Starch 103
4.6  Other Polysaccharides 106
4.7  Proteins 109
4.7.1  Primary Structure 112
4.7.2  Secondary Structure 112
4.7.2.1  Keratines  114
4.7.3  Tertiary Structure  116
4.7.3.1  Globular Proteins  116
4.7.3.2  Fibrous Proteins  118
4.7.3.3  Elastin  119
4.7.3.4  Membrane Proteins  119
4.7.4  Quaternary Structure 119
4.8  Nucleic Acids 122
4.8.1  Flow of Biological Information 125
4.9  Naturally Occurring Polyisoprenes and Other Synthetic Elastomers 128
4.9.1  Balloons 132
4.9.2  Resins 133
4.10 Lignin 134
4.11 Melanins 135
4.12 Polymer Structure 137
4.13 Genetic Engineering 139
4.14 DNA Profiling  141
4.15 Asphalt 142
4.16 Summary 143
Glossary 144
Exercises 147
Further Readings 148

Chapter 5  Step-Reaction Polymerization (Polycondensation Reactions) 149

5.1  Comparison between Polymer Type and Kinetics of Polymerization 149
5.2  Introduction 154
5.3  Stepwise Kinetics 154
5.4  Polycondensation Mechanisms 159
5.5  Polyesters and Polycarbonates  161
5.6  Synthetic Polyamides 166
5.7  Polyimides 172
5.8  Polybenzimidazoles and Related Polymers 173
5.9  Polyurethanes and Polyureas  174
5.10  Polysulfides  176
5.11  Polyethers  176
5.12  Polysulfones 178
5.13  Poly(Ether Ether Ketone) and Polyketones 179
5.14  Phenolic and Amino Plastics 180
5.15  Synthetic Routes 182
5.16  Liquid Crystals 183
5.17  Microfibers 185
5.18  Summary 186
Glossary 186
Exercises 188
Further Readings 189

Chapter 6  Ionic Chain-Reaction and Complex Coordination Polymerization (Addition Polymerization) 191

6.1  Cationic Polymerization 193
6.2  Anionic Polymerization 197
6.3  Stereoregularity and Stereogeometry 199
6.4  Polymerization with Complex Coordination Catalysts 200
6.5  Soluble Stereoregulating Catalysis 201
6.6  Polyethylenes 205
6.7  Polypropylene  211
6.8  Polymers from 1,4-Dienes 215
6.9  Polyisobutylene  217
6.10  Metathesis Reactions  218
6.11  Zwitterionic Polymerization 219
6.12 Isomerization Polymerization 219
6.13 Precipitation Polymerization 220
6.14  Summary 220
Glossary 221
Exercises 222
Further Readings 224

Chapter 7  Free Radical Chain Polymerization (Addition Polymerization) 225

7.1  Initiators for Free Radical Chain Polymerization 225
7.2  Mechanism for Free Radical Chain Polymerization 229
7.3  Chain Transfer 235
7.4  Polymerization Techniques 237
7.4.1  Bulk Polymerization 237
7.4.2  Suspension Polymerization 240
7.4.3  Solution Polymerization 240
7.4.4  Emulsion Polymerization 241
7.5  Fluorine-Containing Polymers 243
7.6  Polystyrene 246
7.7  Poly(Vinyl Chloride) 248
7.8  Poly(Methyl Methacrylate) 250
7.9  Polyacrylonitrile 251
7.10  Solid-State Irradiation Polymerization 252
7.11  Plasma Polymerizations 252
7.12  Summary 253
Glossary 254
Exercises 255
Further Readings 256

Chapter 8  Copolymerization 257

8.1  Kinetics of Copolymerization 258
8.2  The Q–e Scheme 261
8.3  Commercial Copolymers 262
8.4  Block Copolymers 263
8.5  Graft Copolymers 264
8.6  Elastomers 264
8.6.1  Thermoplastic Elastomers 266
8.7  Blends 267
8.7.1  Immiscible Blends 268
8.7.2  Miscible Blends 269
8.8  Polymer Mixtures: IPNS and Alloys 270
8.9  Dendrites 271
8.10  Ionomers 272
8.11  Fluoroelastomers 273
8.12 Nitrile Rubber 274
8.13 Acrylonitrile Butadiene Styrene Terpolymers 274
8.14  EPDM Rubber 275
8.15 Summary 275
Glossary 276
Exercises 277
Further Readings 278

Chapter 9  Organometallic and Metalloid Polymers 281

9.1  Introduction 281
9.2  Inorganic Reaction Mechanisms 283
9.3  Condensation Organometallic Polymers 284
9.4  Coordination Polymers 289
9.5  Addition Polymers 291
9.6  Summary 295
Glossary 295
Exercises 295
Further Readings 296

Chapter 10 Inorganic Polymers 297

10.1 Introduction 297
10.2 Portland Cement 297
10.3 Other Cements 300
10.4 Silicates 300
10.4.1 Network 303
10.4.2 Layer 303
10.4.3 Chain 304
10.5 Silicon Dioxide (Amorphous) 304
10.5.1 Kinds of Glass 306
10.5.2 Safety Glass 308
10.6 Sol–Gel  310
10.6.1 Aerogels  310
10.7 Silicon Dioxide (Crystalline Forms): Quartz Forms 312
10.8 Silicon Dioxide in Electronic Chips  314
10.9 Asbestos  314
10.10 Fly Ash and Aluminosilicates 315
10.11 Polymeric Carbon: Diamond  317
10.12 Polymeric Carbon: Graphite  318
10.13 Internal Cyclization: Carbon Fibers and Related Materials  319
10.14 Carbon Nanotubes 321
10.14.1 Structures 321
10.14.1.1 Electrical 323
10.14.1.2 Mechanical 324
10.14.1.3 Field Emission 324
10.14.1.4 Hydrogen and Ion Storage 324
10.14.1.5 Chemical and Genetic Probes 324
10.14.1.6 Analytical Tools 324
10.14.1.7 Superconductors 324
10.15 Bitumens 325
10.16 Carbon Black 326
10.17 Polysulfur 327
10.18 Ceramics 327
10.19 High-Temperature Superconductors 329
10.19.1 Discovery of the 123-Compound 329
10.19.2 Structure of the 123-Compound 329
10.20 Zeolites 330
10.21 Summary 331
Glossary 332
Exercises 333
Further Readings 333

Chapter 11 Reactions of Polymers 335

11.1 Reactions with Polyolefins and Polyenes 335
11.2 Reactions of Aromatic and Aliphatic Pendant Groups 336
11.3 Degradation 337
11.4 Cross-Linking 339
11.5 Reactivities of End Groups 339
11.6 Supramolecules and Self-Assembly 340
11.7 Transfer and Retention of Oxygen 344
11.8 Nature’s Macromolecular Catalysts...347
11.9 Photosynthesis 352
11.9.1 Purple Photosynthetic Bacteria 353
11.9.2 Green Sulfur Bacteria 355
11.10 Mechanisms of Energy Physical Absorption 355
11.11 Breakage of Polymeric Materials 356
11.12 Summary 358
Glossary 358
Exercises 359
Further Readings 360

Chapter 12 Testing and Spectrometric Characterization of Polymers 361

12.1 Spectronic Characterization of Polymers 362
12.1.1 Infrared Spectroscopy 362
12.1.2 Raman Spectroscopy 363
12.1.3 Nuclear Magnetic Resonance Spectroscopy 363
12.1.4 NMR Applications 365
12.1.5 Electron Paramagnetic Resonance Spectroscopy 365
12.1.6 X-Ray Spectroscopy 365
12.2 Surface Characterization 366
12.2.1 Auger Electron Spectroscopy and X-Ray Photoelectron
Spectroscopy 367
12.2.2 Near-Field Scanning Optical Microscopy 367
12.2.3 Electron Microscopy 368
12.2.4 Scanning Probe Microscopy 368
12.2.5 Secondary Ion Mass Spectroscopy 371
12.3 Amorphous Region Determinations 371
12.4 Thermal Analysis 372
12.5 Thermal Property Tests 374
12.5.1 Thermal Conductivity 374
12.5.2 Thermal Expansion 374
12.5.3 Glass Transition Temperatures 375
12.6 Flammability 375
12.7 Electrical Properties: Theory 375
12.8 Electric Measurements 377
12.9 Weatherability 378
12.10 Optical Properties Tests 378
12.10.1 Index of Refraction 379
12.10.2 Optical Clarity 379
12.10.3 Absorption and Reflectance 379
12.11 Chemical Resistance..380
12.12 Summary 381
Glossary 381
Exercises 383
Further Readings 383

Chapter 13 Rheology and Physical Tests 385

13.1 Rheology385
13.1.1 Rheology and Physical Tests 388
13.1.2 Response Time 391
13.2 Typical Stress–Strain Behavior 391
13.3 Stress–Strain Relationships 394
13.4 Specific Physical Tests 396
13.4.1 Tensile Strength 396
13.4.2 Tensile Strength of Inorganic and Metallic Fibers and Whiskers 397
13.4.3 Compressive Strength 398
13.4.4 Impact Strength 398
13.4.5 Hardness 398
13.4.6 Failure 399
13.5 Summary 399
Glossary 400
Exercises 400
Further Readings 401

Chapter 14 Additives 403

14.1 Fillers 403
14.2 Reinforcements 406
14.2.1 Fibers and Resins 407
14.2.2 Applications 408
14.3 Nanocomposites. 411
14.4 Plasticizers 413
14.5 Antioxidants 415
14.6 Heat Stabilizers  416
14.7 Ultraviolet Stabilizers  416
14.8 Flame Retardants  417
14.9 Colorants  418
14.10 Curing Agents  418
14.11 Antistatic Agents: Antistats  419
14.12 Chemical Blowing Agents 420
14.13 Compatibilizers 420
14.14 Impact Modifiers 420
14.15 Processing Aids 420
14.16 Lubricants 420
14.17 Microorganism Inhibitors 421
14.18 Summary 421
Glossary 422
Exercises 424
Further Readings 425

Chapter 15 Synthesis of Reactants and Intermediates for Polymers 427

15.1 Monomer Synthesis from Basic Feedstocks 427
15.2 Reactants for Step-Reaction Polymerization 434
15.3 Synthesis of Vinyl Monomers 440
15.4 Summary 445
Glossary 445
Exercises 445
Further Readings 446

Chapter 16 Polymer Technology 447

16.1 Polymer Processing 447
16.2 Secondary Structures: Mesophases 449
16.3 Fibers 450
16.3.1 Polymer Processing: Spinning and Fiber Production 450
16.3.1.1 Introduction 450
16.3.1.2 Melt Spinning 451
16.3.1.3 Dry Spinning 452
16.3.1.4 Wet Spinning 453
16.4 Elastomers 453
16.4.1 Elastomer Processing 454
16.5 Films and Sheets 456
16.5.1 Calendering 456
16.6 Polymeric Foams 457
16.7 Reinforced Plastics (Composites) and Laminates 457
16.7.1 Composites 457
16.7.2 Particle-Reinforced Composites, Large-Particle Composites 458
16.7.3 Fiber-Reinforced Composites 459
16.7.4 Processing of Fiber-Reinforced Composites 459
16.7.5 Structural Composites 460
16.7.6 Laminating 460
16.8 Molding 461
16.8.1 Injection Molding.461
16.8.2 Blow Molding 462
16.8.3 Rotational Molding 464
16.8.4 Compression and Transfer Molding 464
16.8.5 Thermoforming 465
16.9 Casting 466
16.10 Extrusion 466
16.11 Coatings 466
16.11.1 Processing 468
16.11.2 Rainwear 470
16.12 Adhesives 470
16.13 Conductive Polymeric Materials 474
16.13.1 Photoconductive and Photonic Polymers 474
16.13.2 Electrically Conductive Polymers 475
16.14 Drug Design and Activity 479
16.15 Synthetic Biomedical Polymers 481
16.16 Dental Materials 485
16.17 Emerging Polymers 486
16.18 Green Materials 490
16.19 Summary 496
Glossary 497
Exercises 498
Further Readings 499

Appendix A: Structures of Common Polymers 501
Appendix B: Symbols 505
Appendix C: Comments on Health and Toxicological Aspects of Polymers  511
Appendix D: ISO 9000 and 14000 515
Appendix E: Web Resources  517

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