Polymer chemistry
"Written by well-established professors in the field, Polymer Chemistry, Second Edition provides a well-rounded examination of polymer properties at the molecular level, focusing on chemical structures and the fundamental principles of polymer synthesis, characterization, and properties. This b...
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| Sprache: | English |
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Boca Raton [u.a.]
CRC Press
2007
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| Ausgabe: | 2. ed. |
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| 100 | 1 | |a Hiemenz, Paul C. |e Verfasser |4 aut | |
| 245 | 1 | 0 | |a Polymer chemistry |c Paul C. Hiemenz ; Timothy P. Lodge |
| 250 | |a 2. ed. | ||
| 264 | 1 | |a Boca Raton [u.a.] |b CRC Press |c 2007 | |
| 300 | |a XVII, 587 S. |b Ill., graph. Darst. | ||
| 336 | |b txt |2 rdacontent | ||
| 337 | |b n |2 rdamedia | ||
| 338 | |b nc |2 rdacarrier | ||
| 520 | 1 | |a "Written by well-established professors in the field, Polymer Chemistry, Second Edition provides a well-rounded examination of polymer properties at the molecular level, focusing on chemical structures and the fundamental principles of polymer synthesis, characterization, and properties. This book offers a logical presentation of topics that can be scaled to meet the needs of introductory as well as more advanced courses in chemistry, materials science, and chemical engineering."--BOOK JACKET. | |
| 650 | 4 | |a Polymères | |
| 650 | 4 | |a Polymérisation | |
| 650 | 4 | |a Polymerization | |
| 650 | 4 | |a Polymers | |
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Datensatz im Suchindex
| DE-BY-TUM_call_number | 1002/CHE 700f 2013 B 1175(2) 0302/CHE 700f 2007 A 3586(2) |
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| DE-BY-TUM_katkey | 1583967 |
| DE-BY-TUM_media_number | 040080292019 040030486494 |
| _version_ | 1816712678918324224 |
| adam_text | Contents
1 Introduction to Chain Molecules 1
1.1 Introduction 1
1.2 How Big Is Big? 3
1.2.1 Molecular Weight 3
1.2.2 Spatial Extent 5
1.3 Linear and Branched Polymers, Homopolymers, and Copolymers 7
1.3.1 Branched Structures 7
1.3.2 Copolymers 9
1.4 Addition, Condensation, and Natural Polymers 11
1.4.1 Addition and Condensation Polymers 11
1.4.2 Natural Polymers 13
1.5 Polymer Nomenclature 18
1.6 Structural Isomerism 20
1.6.1 Positional Isomerism 20
1.6.2 Stereo Isomerism 21
1.6.3 Geometrical Isomerism 22
1.7 Molecular Weights and Molecular Weight Averages 24
1.7.1 Number-, Weight-, and z-Average Molecular Weights 25
1.7.2 Polydispersity Index and Standard Deviation 26
1.7.3 Examples of Distributions 28
1.8 Measurement of Molecular Weight 31
1.8.1 General Considerations 31
1.8.2 End Group Analysis 32
1.8.3 MALDI Mass Spectrometry 35
1.9 Preview of Things to Come 37
1.10 Chapter Summary 38
Problems 38
References 41
Further Readings 41
2 Step-Growth Polymerization 43
2.1 Introduction 43
2.2 Condensation Polymers: One Step at a Time 43
2.2.1 Classes of Step-Growth Polymers 43
2.2.2 First Look at the Distribution of Products 44
2.2.3 A First Look at Reactivity and Reaction Rates 46
ix
2.3 Kinetics of Step-Growth Polymerization ........ 49
2.3.1 Catalyzed Step-Growth Reactions •-....-• 50
2.3.2 HoW Should Experimental Data Be Compared witn
Theoretical Rate Laws? .... 52
2.3.3 Uncatalyzed Step-Growth Reactions ........ 53
2.4 Distribution of Molecular Sizes 55
2.4.1 Mole Practions of Species 56
2.4.2 Weight Fractions of Species ..... 5g
2.5 Polyesters 60
2.6 Polyamides 64
2.7 Stoichiometric imbalance 67
2.8 Chapter Summary 71
Problems , 71
References , 76
Further Readings 75
3 Chain-Growth Polymerization 77
3.1 Introduction 77
3.2 Chain-Growth and Step-Growth Polymerizations: Some C°rnparisons 77
3.3 Initiation 79
3.3.1 Initiation Reactions 80
3.3.2 Fate of Free Radicals 81
3.3.3 Kinetics of Initiation •—....—• 82
3.3.4 Photochemical Initiation 84
3.3.5 Temperature Dependence of Initiation Rates...... 85
3.4 Termination 86
3.4.1 Combination and Disproportionation 86
3.4.2 Effect of Termination on Conversion to Polymer 88
3.4.3 Stationary-State Radical Concentration 89
3.5 Propagation 90
3.5.1 Rate Laws for Propagation .-... 91
3.5.2 Temperature Dependence of Propagation Rates 92
3.5.3 Kinetic Chain Length 94
3.6 Radical Lifetime 96
3.7 Distribution of Molecular Weights 99
3.7.1 Distribution of /-mers: Termination by DispröPortionation 99
3.7.2 Distribution of j-mers: Termination by Combine^n 102
3.8 Chain Transfer ... ................. 104
3.8.1 Chain Transfer Reactions 105
3.8.2 Evaluation of Chain Transfer Constants 106
3.8.3 Chain Transfer to Polymer 108
3.8.4 Suppressing Polymerization 109
3.9 Chapter Summary 110
Problems ... l10
References 114
Further Readings ... 115
4 Controlled Polymerization 117
4.1 Introduction 117
4.2 Poisson Distribution for an Ideal Living Polymerization 118
4.2.1 Kinetic Scheme 119
4.2.2 Breadth of the Poisson Distribution 122
4.3 Anionic Polymerization 126
4.4 Block Copolymers, End-Functional Polymers, and Branched
Polymers by Anionic Polymerization 129
4.4.1 Block Copolymers 129
4.4.2 End-Functional Polymers 133
4.4.3 Regulär Branched Architectures 135
4.5 Cationic Polymerization 137
4.5.1 Aspects of Cationic Polymerization 138
4.5.2 Living Cationic Polymerization 140
4.6 Controlled Radical Polymerization 142
4.6.1 General Principles of Controlled Radical Polymerization 142
4.6.2 Particular Realizations of Controlled Radical Polymerization 144
4.6.2.1 Atom Transfer Radical Polymerization (ATRP) 144
4.6.2.2 Stable Free-Radical Polymerization (SFRP) 145
4.6.2.3 Reversible Addition-Fragmentation Transfer (RAFT)
Polymerization 146
4.7 Polymerization Equilibrium 147
4.8 Ring-Opening Polymerization (ROP) 150
4.8.1 General Aspects 150
4.8.2 Specific Examples of Living Ring-Opening Polymerizations 152
4.8.2.1 Polyäthylene oxide) 152
4.8.2.2 Polylactide 153
4.8.2.3 Poly(dimethylsiloxane) 154
4.8.2.4 Ring-Opening Metathesis Polymerization (ROMP) 155
4.9 Dendrimers 156
4.10 Chapter Summary 160
Problems 161
References 163
Further Readings 163
5 Copolymers, Microstructure, and Stereoregularity 165
5.1 Introduction 165
5.2 Copolymer Composition 166
5.2.1 Rate Laws 166
5.2.2 Composition versus Feedstock 168
5.3 Reactivity Ratios 170
5.3.1 Effects of r Values 171
5.3.2 Relation of Reactivity Ratios to Chemical Structure 173
5.4 Resonance and Reactivity 175
5.5 A Closer Look at Microstructure 179
5.5.1 Sequence Distributions 180
5.5.2 Terminal and Penultimate Models 183
5.6 Copolymer Composition and Microstructure: Experimental Aspects 185
5.6.1 Evaluating Reactivity Ratios from Composition Data 185
5.6.2 Spectroscopic Techniques 188
5.6.3 Sequence Distribution: Experimental Determination 190
5.7 Characterizing Stereoregularity 193
5.8 A Statistical Description of Stereoregularity 196
5.9 Assessing Stereoregularity by Nuclear Magnetic Resonance 200
5.10 Ziegler-Natta Catalysts 205
5.11 Single-Site Catalysts 208
5.12 Chapter Summary 211
Problems 212
References 216
Further Readings 216
6 Polymer Conformations 217
6.1 Conformations, Bond Rotation, and Polymer Size 217
6.2 Average End-to-End Distance for Model Chains 219
Case 6.2.1 The Freely Jointed Chain 220
Case 6.2.2 The Freely Rotating Chain 221
Case 6.2.3 Hindered Rotation Chain 222
6.3 Characteristic Ratio and Statistical Segment Length 223
6.4 Semiflexible Chains and the Persistence Length 225
6.4.1 Persistence Length of Flexible Chains 227
6.4.2 Worm-Like Chains 228
6.5 Radius of Gyration 230
6.6 Spheres, Rods, and Coils 234
6.7 Distributions for End-to-End Distance and Segment Density 235
6.7.1 Distribution of the End-to-End Vector 236
6.7.2 Distribution of the End-to-End Distance 239
6.7.3 Distribution about the Center of Mass 240
6.8 Self-Avoiding Chains: A First Look 241
6.9 Chapter Summary 242
Problems 242
References 244
Further Readings 245
7 Thermodynamics of Polymer Solutions 247
7.1 Review of Thermodynamic and Statistical Thermodynamic Concepts 247
7.2 Regulär Solution Theory 249
7.2.1 Regulär Solution Theory: Entropy of Mixing 249
7.2.2 Regulär Solution Theory: Enthalpy of Mixing 251
7.3 Flory-Huggins Theory 254
7.3.1 Flory-Huggins Theory: Entropy of Mixing by a Quick Route 255
7.3.2 Flory-Huggins Theory: Entropy of Mixing by a Longer Route 255
7.3.3 Flory-Huggins Theory: Enthalpy of Mixing 257
7.3.4 Flory-Huggins Theory: Summary of Assumptions 258
7.4 Osmotic Pressure 258
7.4.1 Osmotic Pressure: General Case 259
7.4.1.1 Number-Average Molecular Weight 261
7.4.2 Osmotic Pressure: Flory-Huggins Theory 263
7.5 Phase Behavior of Polymer Solutions 264
7.5.1 Overview of the Phase Diagram 265
7.5.2 Finding the Binodal 268
7.5.3 Finding the Spinodal 269
7.5.4 Finding the Critical Point 270
7.5.5 Phase Diagram from Flory-Huggins Theory 271
7.6 What sin*? 275
7.6.1 x fr°m Regulär Solution Theory 275
7.6.2 x from Experiment 276
7.6.3 Further Approaches to x 278
7.7 Excluded Volume and Chains in a Good Solvent 280
7.8 Chapter Summary 283
Problems 284
References 287
Further Readings 288
8 Light Scattering by Polymer Solutions 289
8.1 Introduction: Light Waves 289
8.2 Basic Concepts of Scattering 291
8.2.1 Scattering from Randomly Placed Objects 292
8.2.2 Scattering from a Perfect Crystal 292
8.2.3 Origins of Incoherent and Coherent Scattering 293
8.2.4 Bragg s Law and the Scattering Vector 294
8.3 Scattering by an Isolated Small Molecule 296
8.4 Scattering from a Dilute Polymer Solution 298
8.5 The Form Factor and the Zimm Equation 304
8.5.1 Mathematical Expression for the Form Factor 305
8.5.2 Form Factor for Isotropie Solutions 306
8.5.3 Form Factor as qRg^0 307
8.5.4 Zimm Equation 307
8.5.5 ZimmPlot 308
8.6 Scattering Regimes and Particular Form Factors 312
8.7 Experimental Aspects of Light Scattering 314
8.7.1 Instrumentation 316
8.7.2 Calibration 317
8.7.3 Samples and Solutions 319
8.7.4 Refractive Index Increment 319
8.8 Chapter Summary 320
Problems 321
References 325
Further Readings 325
9 Dynamics of Dilute Polymer Solutions 327
9.1 Introduction: Friction and Viscosity 327
9.2 Stokes Law and Einstein s Law 330
9.2.1 Viscous Forces on Rigid Spheres 331
9.2.2 Suspension of Spheres 332
9.3 Intrinsic Viscosity 334
9.3.1 General Considerations 334
9.3.2 Mark-Houwink Equation 336
9.4 Measurement of Viscosity 341
9.4.1 Poiseuille Equation and Capillary Viscometers 341
9.4.2 Concentric Cylinder Viscometers 345
9.5 Diffusion Coefficient and Friction Factor 346
9.5.1 Tracer Diffusion and Hydrodynamic Radius 347
9.5.2 Mutual Diffusion and Fick s Laws 348
9.6 Dynamic Light Scattering 354
9.7 Hydrodynamic Interactions and Draining 357
9.8 Size Exclusion Chromatography (SEC) 360
9.8.1 Basic Separation Process 361
9.8.2 Separation Mechanism 365
9.8.3 Two Calibration Strategies 367
9.8.3.1 Limitations of Calibration by Standards 367
9.8.3.2 Universal Calibration 368
9.8.4 Size Exclusion Chromatography Detectors 369
9.8.4.1 RIDetector 369
9.8.4.2 UV-Vis Detector 370
9.8.4.3 Light Scattering Detector 371
9.8.4.4 Viscometer 372
9.9 Chapter Summary 372
Problems 373
References 378
Further Readings 379
10 Networks, Gels, and Rubber Elasticity 381
10.1 Formation of Networks by Random Cross-Linking 381
10.1.1 Definitions 381
10.1.2 Gel Point 383
10.2 Polymerization with Multifunctional Monomers 386
10.2.1 Calculation of the Branching Coefficient 387
10.2.2 Gel Point 388
10.2.3 Molecular-Weight Averages 389
10.3 Elastic Deformation 392
10.4 Thermodynamics of Elasticity 394
10.4.1 Equation of State 394
10.4.2 Ideal Elastomers 396
10.4.3 Some Experiments on Real Rubbers 397
10.5 Statistical Mechanical Theory of Rubber Elasticity: Ideal Case 398
10.5.1 Force to Extend a Gaussian Chain 400
10.5.2 Network of Gaussian Strands 402
10.5.3 Modulus of the Gaussian Network 403
10.6 Further Developments in Rubber Elasticity 406
10.6.1 Non-Gaussian Force Law 406
10.6.2 Front Factor 407
10.6.3 Network Defects 408
10.6.4 Mooney-Rivlin Equation 409
10.7 Swelling of Gels 410
10.7.1 Modulus of a Swollen Rubber 411
10.7.2 Swelling Equilibrium 412
10.8 Chapter Summary 414
Problems 416
References 418
Further Readings 418
11 Linear Viscoelasticity 419
11.1 Basic Concepts 419
11.1.1 Stress and Strain 421
11.1.2 Viscosity, Modulus, and Compliance 421
11.1.3 Viscous and Elastic Responses 422
11.2 Response of the Maxwell and Voigt Elements 423
11.2.1 Transient Response: Stress Relaxation 423
11.2.2 Transient Response: Creep 425
11.2.3 Dynamic Response: Loss and Storage Moduli 426
11.2.4 Dynamic Response: Complex Modulus and Complex Viscosity 429
11.3 Boltzmann Superposition Principle 430
11.4 Bead-Spring Model 432
11.4.1 Ingredients of the Bead-Spring Model 432
11.4.2 Predictions of the Bead-Spring Model 434
11.5 Zimm Model for Dilute Solutions, Rouse Model
for Unentangled Melts 439
11.6 Phenomenology of Entanglement 444
11.6.1 Rubbery Plateau 444
11.6.2 Dependence of Me on Molecular Structure 447
11.7 Reptation Model 450
11.7.1 Reptation Model: Longest Relaxation Time and Diffusivity 451
11.7.2 Reptation Model: Viscoelastic Properties 453
11.7.3 Reptation Model: Additional Relaxation Processes 456
11.8 Aspects of Experimental Rheometry 458
11.8.1 Shear Sandwich and Cone and Plate Rheometers 458
11.8.2 Further Comments about Rheometry 459
11.9 Chapter Summary 460
Problems 461
References 464
Further Readings 464
12 Glass Transition 465
12.1 Introduction 465
12.1.1 Definition of a Glass 465
12.1.2 Glass and Melting Transitions 466
12.2 Thermodynamic Aspects of the Glass Transition 468
12.2.1 First-Order and Second-Order Phase Transitions 469
12.2.2 Kauzmann Temperature 471
12.2.3 Theory of Gibbs and DiMarzio 472
12.3 Locating the Glass Transition Temperature 474
12.3.1 Dilatometry 474
12.3.2 Calorimetry 476
12.3.3 Dynamic Mechanical Analysis 478
12.4 Free Volume Description of the Glass Transition 479
12.4.1 Temperature Dependence of the Free Volume 480
12.4.2 Free Volume Changes Inferred from the Viscosity 481
12.4.3 Williams-Landel-Ferry Equation 483
12.5 Time-Temperature Superposition 486
12.6 Factors that Affect the Glass Transition Temperature 491
12.6.1 Dependence on Chemical Structure 491
12.6.2 Dependence on Molecular Weight 492
12.6.3 Dependence on Composition 492
12.7 Mechanical Properties of Glassy Polymers 496
12.7.1 Basic Concepts 496
12.7.2 Crazing, Yielding, and the Brittle-to-Ductile Transition 498
12.7.3 Role of Chain Stiffness and Entanglements 501
12.8 Chapter Summary 504
Problems 505
References 508
Further Readings 508
13 Crystalline Polymers 511
13.1 Introduction and Overview 511
13.2 Structure and Characterization of Unit Cells 513
13.2.1 Classes of Crystals 513
13.2.2 X-Ray Diffraction 515
13.2.3 Examples of Unit Cells 518
13.3 Thermodynamics of Crystallization: Relation of Melting Temperature
to Molecular Structure 521
13.4 Structure and Melting of Lamellae 526
13.4.1 Surface Contributions to Phase Transitions 526
13.4.2 Dependence of Tm on Lamellar Thickness 527
13.4.3 Dependence of Tm on Molecular Weight 530
13.4.4 Experimental Characterization of Lamellar Structure 532
13.5 Kinetics of Nucleation and Growth 536
13.5.1 Primary Nucleation 537
13.5.2 Crystal Growth 539
13.6 Morphology of Semicrystalline Polymers 545
13.6.1 Spherulites 545
13.6.2 Nonspherulitic Morphologies 548
13.7 Kinetics of Bulk Crystallization 551
13.7.1 Avrami Equation 552
13.7.2 Kinetics of Crystallization: Experimental Aspects 556
13.8 Chapter Summary 561
Problems 562
References 565
Further Readings 565
Appendix 567
A.l Series Expansions 567
A.2 Summation Formulae 568
A.3 Transformation to Spherical Coordinates 569
A.4 Some Integrals of Gaussian Functions 570
A.5 Complex Numbers 572
Index 575
|
| adam_txt |
Contents
1 Introduction to Chain Molecules 1
1.1 Introduction 1
1.2 How Big Is Big? 3
1.2.1 Molecular Weight 3
1.2.2 Spatial Extent 5
1.3 Linear and Branched Polymers, Homopolymers, and Copolymers 7
1.3.1 Branched Structures 7
1.3.2 Copolymers 9
1.4 Addition, Condensation, and Natural Polymers 11
1.4.1 Addition and Condensation Polymers 11
1.4.2 Natural Polymers 13
1.5 Polymer Nomenclature 18
1.6 Structural Isomerism 20
1.6.1 Positional Isomerism 20
1.6.2 Stereo Isomerism 21
1.6.3 Geometrical Isomerism 22
1.7 Molecular Weights and Molecular Weight Averages 24
1.7.1 Number-, Weight-, and z-Average Molecular Weights 25
1.7.2 Polydispersity Index and Standard Deviation 26
1.7.3 Examples of Distributions 28
1.8 Measurement of Molecular Weight 31
1.8.1 General Considerations 31
1.8.2 End Group Analysis 32
1.8.3 MALDI Mass Spectrometry 35
1.9 Preview of Things to Come 37
1.10 Chapter Summary 38
Problems 38
References 41
Further Readings 41
2 Step-Growth Polymerization 43
2.1 Introduction 43
2.2 Condensation Polymers: One Step at a Time 43
2.2.1 Classes of Step-Growth Polymers 43
2.2.2 First Look at the Distribution of Products 44
2.2.3 A First Look at Reactivity and Reaction Rates 46
ix
2.3 Kinetics of Step-Growth Polymerization . 49
2.3.1 Catalyzed Step-Growth Reactions •-.-• 50
2.3.2 HoW Should Experimental Data Be Compared witn
Theoretical Rate Laws? . 52
2.3.3 Uncatalyzed Step-Growth Reactions . 53
2.4 Distribution of Molecular Sizes 55
2.4.1 Mole Practions of Species 56
2.4.2 Weight Fractions of Species . 5g
2.5 Polyesters 60
2.6 Polyamides 64
2.7 Stoichiometric imbalance 67
2.8 Chapter Summary 71
Problems , 71
References , 76
Further Readings 75
3 Chain-Growth Polymerization 77
3.1 Introduction 77
3.2 Chain-Growth and Step-Growth Polymerizations: Some C°rnparisons 77
3.3 Initiation 79
3.3.1 Initiation Reactions 80
3.3.2 Fate of Free Radicals 81
3.3.3 Kinetics of Initiation •—.—• 82
3.3.4 Photochemical Initiation 84
3.3.5 Temperature Dependence of Initiation Rates. 85
3.4 Termination 86
3.4.1 Combination and Disproportionation 86
3.4.2 Effect of Termination on Conversion to Polymer 88
3.4.3 Stationary-State Radical Concentration 89
3.5 Propagation 90
3.5.1 Rate Laws for Propagation .-. 91
3.5.2 Temperature Dependence of Propagation Rates 92
3.5.3 Kinetic Chain Length 94
3.6 Radical Lifetime 96
3.7 Distribution of Molecular Weights 99
3.7.1 Distribution of /-mers: Termination by DispröPortionation 99
3.7.2 Distribution of j-mers: Termination by Combine^n 102
3.8 Chain Transfer . . 104
3.8.1 Chain Transfer Reactions 105
3.8.2 Evaluation of Chain Transfer Constants 106
3.8.3 Chain Transfer to Polymer 108
3.8.4 Suppressing Polymerization 109
3.9 Chapter Summary 110
Problems .'" l10
References 114
Further Readings . 115
4 Controlled Polymerization 117
4.1 Introduction 117
4.2 Poisson Distribution for an Ideal Living Polymerization 118
4.2.1 Kinetic Scheme 119
4.2.2 Breadth of the Poisson Distribution 122
4.3 Anionic Polymerization 126
4.4 Block Copolymers, End-Functional Polymers, and Branched
Polymers by Anionic Polymerization 129
4.4.1 Block Copolymers 129
4.4.2 End-Functional Polymers 133
4.4.3 Regulär Branched Architectures 135
4.5 Cationic Polymerization 137
4.5.1 Aspects of Cationic Polymerization 138
4.5.2 Living Cationic Polymerization 140
4.6 Controlled Radical Polymerization 142
4.6.1 General Principles of Controlled Radical Polymerization 142
4.6.2 Particular Realizations of Controlled Radical Polymerization 144
4.6.2.1 Atom Transfer Radical Polymerization (ATRP) 144
4.6.2.2 Stable Free-Radical Polymerization (SFRP) 145
4.6.2.3 Reversible Addition-Fragmentation Transfer (RAFT)
Polymerization 146
4.7 Polymerization Equilibrium 147
4.8 Ring-Opening Polymerization (ROP) 150
4.8.1 General Aspects 150
4.8.2 Specific Examples of Living Ring-Opening Polymerizations 152
4.8.2.1 Polyäthylene oxide) 152
4.8.2.2 Polylactide 153
4.8.2.3 Poly(dimethylsiloxane) 154
4.8.2.4 Ring-Opening Metathesis Polymerization (ROMP) 155
4.9 Dendrimers 156
4.10 Chapter Summary 160
Problems 161
References 163
Further Readings 163
5 Copolymers, Microstructure, and Stereoregularity 165
5.1 Introduction 165
5.2 Copolymer Composition 166
5.2.1 Rate Laws 166
5.2.2 Composition versus Feedstock 168
5.3 Reactivity Ratios 170
5.3.1 Effects of r Values 171
5.3.2 Relation of Reactivity Ratios to Chemical Structure 173
5.4 Resonance and Reactivity 175
5.5 A Closer Look at Microstructure 179
5.5.1 Sequence Distributions 180
5.5.2 Terminal and Penultimate Models 183
5.6 Copolymer Composition and Microstructure: Experimental Aspects 185
5.6.1 Evaluating Reactivity Ratios from Composition Data 185
5.6.2 Spectroscopic Techniques 188
5.6.3 Sequence Distribution: Experimental Determination 190
5.7 Characterizing Stereoregularity 193
5.8 A Statistical Description of Stereoregularity 196
5.9 Assessing Stereoregularity by Nuclear Magnetic Resonance 200
5.10 Ziegler-Natta Catalysts 205
5.11 Single-Site Catalysts 208
5.12 Chapter Summary 211
Problems 212
References 216
Further Readings 216
6 Polymer Conformations 217
6.1 Conformations, Bond Rotation, and Polymer Size 217
6.2 Average End-to-End Distance for Model Chains 219
Case 6.2.1 The Freely Jointed Chain 220
Case 6.2.2 The Freely Rotating Chain 221
Case 6.2.3 Hindered Rotation Chain 222
6.3 Characteristic Ratio and Statistical Segment Length 223
6.4 Semiflexible Chains and the Persistence Length 225
6.4.1 Persistence Length of Flexible Chains 227
6.4.2 Worm-Like Chains 228
6.5 Radius of Gyration 230
6.6 Spheres, Rods, and Coils 234
6.7 Distributions for End-to-End Distance and Segment Density 235
6.7.1 Distribution of the End-to-End Vector 236
6.7.2 Distribution of the End-to-End Distance 239
6.7.3 Distribution about the Center of Mass 240
6.8 Self-Avoiding Chains: A First Look 241
6.9 Chapter Summary 242
Problems 242
References 244
Further Readings 245
7 Thermodynamics of Polymer Solutions 247
7.1 Review of Thermodynamic and Statistical Thermodynamic Concepts 247
7.2 Regulär Solution Theory 249
7.2.1 Regulär Solution Theory: Entropy of Mixing 249
7.2.2 Regulär Solution Theory: Enthalpy of Mixing 251
7.3 Flory-Huggins Theory 254
7.3.1 Flory-Huggins Theory: Entropy of Mixing by a Quick Route 255
7.3.2 Flory-Huggins Theory: Entropy of Mixing by a Longer Route 255
7.3.3 Flory-Huggins Theory: Enthalpy of Mixing 257
7.3.4 Flory-Huggins Theory: Summary of Assumptions 258
7.4 Osmotic Pressure 258
7.4.1 Osmotic Pressure: General Case 259
7.4.1.1 Number-Average Molecular Weight 261
7.4.2 Osmotic Pressure: Flory-Huggins Theory 263
7.5 Phase Behavior of Polymer Solutions 264
7.5.1 Overview of the Phase Diagram 265
7.5.2 Finding the Binodal 268
7.5.3 Finding the Spinodal 269
7.5.4 Finding the Critical Point 270
7.5.5 Phase Diagram from Flory-Huggins Theory 271
7.6 What'sin*? 275
7.6.1 x fr°m Regulär Solution Theory 275
7.6.2 x from Experiment 276
7.6.3 Further Approaches to x 278
7.7 Excluded Volume and Chains in a Good Solvent 280
7.8 Chapter Summary 283
Problems 284
References 287
Further Readings 288
8 Light Scattering by Polymer Solutions 289
8.1 Introduction: Light Waves 289
8.2 Basic Concepts of Scattering 291
8.2.1 Scattering from Randomly Placed Objects 292
8.2.2 Scattering from a Perfect Crystal 292
8.2.3 Origins of Incoherent and Coherent Scattering 293
8.2.4 Bragg's Law and the Scattering Vector 294
8.3 Scattering by an Isolated Small Molecule 296
8.4 Scattering from a Dilute Polymer Solution 298
8.5 The Form Factor and the Zimm Equation 304
8.5.1 Mathematical Expression for the Form Factor 305
8.5.2 Form Factor for Isotropie Solutions 306
8.5.3 Form Factor as qRg^0 307
8.5.4 Zimm Equation 307
8.5.5 ZimmPlot 308
8.6 Scattering Regimes and Particular Form Factors 312
8.7 Experimental Aspects of Light Scattering 314
8.7.1 Instrumentation 316
8.7.2 Calibration 317
8.7.3 Samples and Solutions 319
8.7.4 Refractive Index Increment 319
8.8 Chapter Summary 320
Problems 321
References 325
Further Readings 325
9 Dynamics of Dilute Polymer Solutions 327
9.1 Introduction: Friction and Viscosity 327
9.2 Stokes' Law and Einstein's Law 330
9.2.1 Viscous Forces on Rigid Spheres 331
9.2.2 Suspension of Spheres 332
9.3 Intrinsic Viscosity 334
9.3.1 General Considerations 334
9.3.2 Mark-Houwink Equation 336
9.4 Measurement of Viscosity 341
9.4.1 Poiseuille Equation and Capillary Viscometers 341
9.4.2 Concentric Cylinder Viscometers 345
9.5 Diffusion Coefficient and Friction Factor 346
9.5.1 Tracer Diffusion and Hydrodynamic Radius 347
9.5.2 Mutual Diffusion and Fick's Laws 348
9.6 Dynamic Light Scattering 354
9.7 Hydrodynamic Interactions and Draining 357
9.8 Size Exclusion Chromatography (SEC) 360
9.8.1 Basic Separation Process 361
9.8.2 Separation Mechanism 365
9.8.3 Two Calibration Strategies 367
9.8.3.1 Limitations of Calibration by Standards 367
9.8.3.2 Universal Calibration 368
9.8.4 Size Exclusion Chromatography Detectors 369
9.8.4.1 RIDetector 369
9.8.4.2 UV-Vis Detector 370
9.8.4.3 Light Scattering Detector 371
9.8.4.4 Viscometer 372
9.9 Chapter Summary 372
Problems 373
References 378
Further Readings 379
10 Networks, Gels, and Rubber Elasticity 381
10.1 Formation of Networks by Random Cross-Linking 381
10.1.1 Definitions 381
10.1.2 Gel Point 383
10.2 Polymerization with Multifunctional Monomers 386
10.2.1 Calculation of the Branching Coefficient 387
10.2.2 Gel Point 388
10.2.3 Molecular-Weight Averages 389
10.3 Elastic Deformation 392
10.4 Thermodynamics of Elasticity 394
10.4.1 Equation of State 394
10.4.2 Ideal Elastomers 396
10.4.3 Some Experiments on Real Rubbers 397
10.5 Statistical Mechanical Theory of Rubber Elasticity: Ideal Case 398
10.5.1 Force to Extend a Gaussian Chain 400
10.5.2 Network of Gaussian Strands 402
10.5.3 Modulus of the Gaussian Network 403
10.6 Further Developments in Rubber Elasticity 406
10.6.1 Non-Gaussian Force Law 406
10.6.2 Front Factor 407
10.6.3 Network Defects 408
10.6.4 Mooney-Rivlin Equation 409
10.7 Swelling of Gels 410
10.7.1 Modulus of a Swollen Rubber 411
10.7.2 Swelling Equilibrium 412
10.8 Chapter Summary 414
Problems 416
References 418
Further Readings 418
11 Linear Viscoelasticity 419
11.1 Basic Concepts 419
11.1.1 Stress and Strain 421
11.1.2 Viscosity, Modulus, and Compliance 421
11.1.3 Viscous and Elastic Responses 422
11.2 Response of the Maxwell and Voigt Elements 423
11.2.1 Transient Response: Stress Relaxation 423
11.2.2 Transient Response: Creep 425
11.2.3 Dynamic Response: Loss and Storage Moduli 426
11.2.4 Dynamic Response: Complex Modulus and Complex Viscosity 429
11.3 Boltzmann Superposition Principle 430
11.4 Bead-Spring Model 432
11.4.1 Ingredients of the Bead-Spring Model 432
11.4.2 Predictions of the Bead-Spring Model 434
11.5 Zimm Model for Dilute Solutions, Rouse Model
for Unentangled Melts 439
11.6 Phenomenology of Entanglement 444
11.6.1 Rubbery Plateau 444
11.6.2 Dependence of Me on Molecular Structure 447
11.7 Reptation Model 450
11.7.1 Reptation Model: Longest Relaxation Time and Diffusivity 451
11.7.2 Reptation Model: Viscoelastic Properties 453
11.7.3 Reptation Model: Additional Relaxation Processes 456
11.8 Aspects of Experimental Rheometry 458
11.8.1 Shear Sandwich and Cone and Plate Rheometers 458
11.8.2 Further Comments about Rheometry 459
11.9 Chapter Summary 460
Problems 461
References 464
Further Readings 464
12 Glass Transition 465
12.1 Introduction 465
12.1.1 Definition of a Glass 465
12.1.2 Glass and Melting Transitions 466
12.2 Thermodynamic Aspects of the Glass Transition 468
12.2.1 First-Order and Second-Order Phase Transitions 469
12.2.2 Kauzmann Temperature 471
12.2.3 Theory of Gibbs and DiMarzio 472
12.3 Locating the Glass Transition Temperature 474
12.3.1 Dilatometry 474
12.3.2 Calorimetry 476
12.3.3 Dynamic Mechanical Analysis 478
12.4 Free Volume Description of the Glass Transition 479
12.4.1 Temperature Dependence of the Free Volume 480
12.4.2 Free Volume Changes Inferred from the Viscosity 481
12.4.3 Williams-Landel-Ferry Equation 483
12.5 Time-Temperature Superposition 486
12.6 Factors that Affect the Glass Transition Temperature 491
12.6.1 Dependence on Chemical Structure 491
12.6.2 Dependence on Molecular Weight 492
12.6.3 Dependence on Composition 492
12.7 Mechanical Properties of Glassy Polymers 496
12.7.1 Basic Concepts 496
12.7.2 Crazing, Yielding, and the Brittle-to-Ductile Transition 498
12.7.3 Role of Chain Stiffness and Entanglements 501
12.8 Chapter Summary 504
Problems 505
References 508
Further Readings 508
13 Crystalline Polymers 511
13.1 Introduction and Overview 511
13.2 Structure and Characterization of Unit Cells 513
13.2.1 Classes of Crystals 513
13.2.2 X-Ray Diffraction 515
13.2.3 Examples of Unit Cells 518
13.3 Thermodynamics of Crystallization: Relation of Melting Temperature
to Molecular Structure 521
13.4 Structure and Melting of Lamellae 526
13.4.1 Surface Contributions to Phase Transitions 526
13.4.2 Dependence of Tm on Lamellar Thickness 527
13.4.3 Dependence of Tm on Molecular Weight 530
13.4.4 Experimental Characterization of Lamellar Structure 532
13.5 Kinetics of Nucleation and Growth 536
13.5.1 Primary Nucleation 537
13.5.2 Crystal Growth 539
13.6 Morphology of Semicrystalline Polymers 545
13.6.1 Spherulites 545
13.6.2 Nonspherulitic Morphologies 548
13.7 Kinetics of Bulk Crystallization 551
13.7.1 Avrami Equation 552
13.7.2 Kinetics of Crystallization: Experimental Aspects 556
13.8 Chapter Summary 561
Problems 562
References 565
Further Readings 565
Appendix 567
A.l Series Expansions 567
A.2 Summation Formulae 568
A.3 Transformation to Spherical Coordinates 569
A.4 Some Integrals of Gaussian Functions 570
A.5 Complex Numbers 572
Index 575 |
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| author | Hiemenz, Paul C. Lodge, Timothy P. |
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| ctrlnum | (OCoLC)77520762 (DE-599)BVBBV022205236 |
| dewey-full | 547.7 |
| dewey-hundreds | 500 - Natural sciences and mathematics |
| dewey-ones | 547 - Organic chemistry |
| dewey-raw | 547.7 |
| dewey-search | 547.7 |
| dewey-sort | 3547.7 |
| dewey-tens | 540 - Chemistry and allied sciences |
| discipline | Chemie / Pharmazie Chemie |
| discipline_str_mv | Chemie / Pharmazie Chemie |
| edition | 2. ed. |
| format | Book |
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| id | DE-604.BV022205236 |
| illustrated | Illustrated |
| index_date | 2024-07-02T16:25:12Z |
| indexdate | 2024-11-25T17:26:05Z |
| institution | BVB |
| isbn | 1574447793 9781574447798 |
| language | English |
| oai_aleph_id | oai:aleph.bib-bvb.de:BVB01-015416636 |
| oclc_num | 77520762 |
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| owner_facet | DE-20 DE-703 DE-91G DE-BY-TUM DE-19 DE-BY-UBM DE-29T DE-92 DE-M49 DE-BY-TUM |
| physical | XVII, 587 S. Ill., graph. Darst. |
| publishDate | 2007 |
| publishDateSearch | 2007 |
| publishDateSort | 2007 |
| publisher | CRC Press |
| record_format | marc |
| spellingShingle | Hiemenz, Paul C. Lodge, Timothy P. Polymer chemistry Polymères Polymérisation Polymerization Polymers Makromolekulare Chemie (DE-588)4168684-6 gnd Polymere (DE-588)4046699-1 gnd Chemie (DE-588)4009816-3 gnd Polymerisation (DE-588)4046704-1 gnd |
| subject_GND | (DE-588)4168684-6 (DE-588)4046699-1 (DE-588)4009816-3 (DE-588)4046704-1 |
| title | Polymer chemistry |
| title_auth | Polymer chemistry |
| title_exact_search | Polymer chemistry |
| title_exact_search_txtP | Polymer chemistry |
| title_full | Polymer chemistry Paul C. Hiemenz ; Timothy P. Lodge |
| title_fullStr | Polymer chemistry Paul C. Hiemenz ; Timothy P. Lodge |
| title_full_unstemmed | Polymer chemistry Paul C. Hiemenz ; Timothy P. Lodge |
| title_short | Polymer chemistry |
| title_sort | polymer chemistry |
| topic | Polymères Polymérisation Polymerization Polymers Makromolekulare Chemie (DE-588)4168684-6 gnd Polymere (DE-588)4046699-1 gnd Chemie (DE-588)4009816-3 gnd Polymerisation (DE-588)4046704-1 gnd |
| topic_facet | Polymères Polymérisation Polymerization Polymers Makromolekulare Chemie Polymere Chemie Polymerisation |
| url | http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=015416636&sequence=000002&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA |
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