Elements of Polymer Science & Engineering (eBook)

Front Cover 1
The Elements of Polymer Science and Engineering 4
Copyright Page 5
Contents 8
Preface 16
Chapter 1. Introductory Concepts and Definitions 20
1.1 Some Definitions 20
1.2 Degree of Polymerization 25
1.3 Polymerization and Functionality 26
1.4 Why Are Synthetic Polymers Useful? 31
1.5 Copolymers 35
1.6 Molecular Architecture 39
1.7 Thermoplastics and Thermosets 42
1.8 Elastorncrs, Fibers, and Plastics 43
1.9 Miscellaneous Terms 46
1.10 Polymer Nomenclature 47
Problems 53
References 58
Chapter 2. Basic Principles of Polymer Molecular Weights 60
2.1 Importance of Molecular Weight Control 60
2.2 Plan of This Chapter 61
2.3 Arithmetic Mean 62
2.4 Molecular Weight Averages as Ratios of Moments 66
2.5 Breadth of the Distribution 72
2.6 Summarizing the Molecular Weight Distribution 75
2.7 Mz > = Mw >
2.8 Integral and Summative Expressions 76
2.9 Direct Measurements of Average Molecular Weights 77
2.10 Colligative Properties and Mn 79
2.11 Virial Equations 84
2.12 Virial Coefficients 85
Problems 88
Reference 90
Chapter 3. Practical Aspects of Molecular Weight Measurements 92
3.1 Mn Methods 92
3.2 Light Scattering 99
3.3 Dilute Solution Viscometry 109
3.4 Size Exclusion Chromatography 122
Problems 134
Reference 138
Chapter 4. Effects of Polymer Isomerism and Conformational Changes 140
4.1 Constitutional Isomerism 140
4.2 Conligurational Isomerism 145
4.3 Polymer Conformation 151
4.4 Molecular Dimensions in the Amorphous State 154
4.5 Rubber Elasticity 160
4.6 Rodlike Macrontoleculcs 169
Problems 170
Reference 172
Chapter 5. Step-Growth Polymerizations 174
5.1 Condensation and Addition Polymers 174
5.2 Step-Growth and Chain-Growth Polynicrizations 177
5.3 Requirents for Step-Growth Polyinerization 180
5.4 Polymer Size and Extent of Conversion of Functional Groups in Equilibrium Step-Growth Polymerizations 185
5.5 Interfacial and Solution Polymerizations of Acid Chlorides and Other Reactive Monomers 201
5.6 Step-Growth Copolymerizations 203
Problems 204
Reference 207
Chapter 6. Free-Radical Polymerization 208
6.1 scope 208
6.2 Polymerizability of Monomers 209
6.3 Overall Kinetics of Radical Polymerization 211
6.4 A Note on Termination Rate Constants 217
6.5 Methods of Producing Radicals 218
6.6 Length of the Kinetic Chain and Number Average Degree of Polymerization of the Polymer 225
6.7 Modes of Termination 226
6.8 Chain Transfer 227
6.9 Inhibition and Retardation 238
6.10 Readily Observable Features of Free-Radical Polymerizations 240
6.11 Radical Lifetimes and Concentrations 241
6.12 Determination of kp and kt 243
6.13 Deviations from Ideal Kinetics 243
6.14 Molecular Weight Distribution 246
6.15 Free-Radical Techniques for Polymers with Narrower Molecular Weight Distributions 250
6.16 Effects of Temperature 251
6.17 Free-Radical Polymerization Processes 255
Problems 255
Reference 258
Chapter 7. Copolymerization 260
7.1 Chain-Growth Copolymerization 260
7.2 Simple Copolymer Equation 261
7.3 Copolymer Structure Inferences from Feactivity Ratios 264
7.4 Azeotropic Compositions 268
7.5 Integrated Binary Copolymer Equation 269
7.6 Determination or Reactivity Ratios 272
7.7 Multicomponent Copolyinerizations 276
7.8 Sequence Distribution in Copolymers 277
7.9 Gel Forination During Copolytnerization and Cross-Linking 279
7.10 Kcactivities of lladicals and Monomers 282
7.11 Analysis of Reactivity Data 285
7.12 Effect of Rcaction Conditions 287
7.13 Rates of Free-Radical Copolymerizations 290
7.14 Alternative Copolymerization Models 291
Problems 292
Reference 295
Chapter 8. Dispersion and Emulsion Polymerizations 296
8.1 Dispersion Polymerization 297
8.2 Emulsion Polymerization 300
8.3 Other Ingredients in Emulsion Recipes 315
8.4 Emulsion Polymerization Processes 316
Problems 317
Referece 317
Chapter 9. Ionic and Coordinated Polymerizations 320
9.1 Comparison of Ionic and Free-Radical Polymerizations 320
9.2 Anionic Polymerization 322
9.3 Group Transfer Polymerization 337
9.4 Cationic Polymerization 339
9.5 Coordination Polymerization 352
9.6 Olefin Metathesis Catalysts 363
Problems 365
Reference 366
Chapter 10. Polymer Reaction Engineering 368
10.1 scope 368
10.2 Step-Growth Polymerizations 368
10.3 Chain-Growth Polymerizations 372
10.4 Homogeneous and Heterogeneous Polymerization Processes 373
10.5 Batch, Semibatch, and Continuous Processes 384
10.6 Polymerization Reactors 385
Problems 393
Reference 395
Chapter 11. Mechanical Properties of Polymer Solids and Liquids 396
11.1 Introduction 396
11.2 Thermal Transitions 397
11.3 Crystallization of Polymers 401
11.4 The Glass Transition 413
11.5 Polymer Viscoelasticity 422
11.6 Dynamic Mechanical Behavior at Thermal Transitions 435
11.7 Stress–Strain Tests 438
11.8 Crazing in Glassy Polymers 442
11.9 Fracture Mechanics 445
11.10 Toughness and Brittleness 448
11.11 Rheology 451
11.12 Effects of Fabrication Processes 459
Problems 460
Reference 462
Chapter 12. Polymer Mixtures 464
12.1 Compatibility 464
12.2 Thermodynamic Theories 465
12.3 Solvents and Plasticizers 479
12.4 Fractionation 481
12.5 Practical Aspects of Polymer Blending 483
12.6 Reinforced Elastomers 496
12.7 Reinforced Plastics 497
Problems 500
Reference 501
Appendix A. Conversion of Units 504
Appendix B. List of Symbols 506
Index 516