Polymer - Chemistry - (Contents)

Contents
Preface to the Third Edition........................................................................................................... xiii
Chapter 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...........................................................................................8
1.4 Addition, Condensation, and Naturally Occurring Polymers.......................... 10
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....................................................................... 23
1.7 Molecular Weights and Molecular Weight Averages.......................................25
1.7.1 Number-, Weight-, and z-Average Molecular Weights........................25
1.7.2 Dispersity and Standard Deviation..................................................... 27
1.7.3 Examples of Distributions................................................................... 29
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...............................................................34
1.9 Preview of Things to Come.............................................................................. 36
1.10 Chapter Summary............................................................................................ 37
Problems...................................................................................................................... 38
References...................................................................................................................40
Further Readings......................................................................................................... 41
Copyright © 2020. Taylor & Francis Group. All rights reserved.
Chapter 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 A First Look at the Distribution of Products......................................44
2.2.3 A First Look at Reactivity and Reaction Rates...................................46
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 with
Theoretical Rate Laws?....................................................................... 51
2.3.3 Uncatalyzed Step-Growth Reactions.................................................. 53
Lodge, Timothy P., and Paul C. Hiemenz. Polymer Chemistry, Taylor & Francis Group, 2020. ProQuest Ebook Central,
http://ebookcentral.proquest.com/lib/snulibrary-ebooks/detail.action?docID=6236342.
Created from snulibrary-ebooks on 2023-03-13 03:14:33.
vi Contents
2.4 Distribution of Molecular Sizes........................................................................ 56

2.4.1 Mole Fractions of Species................................................................... 57
2.4.2 Weight Fractions of Species................................................................ 58
2.5 Polyesters.......................................................................................................... 61
2.6 Polyamides........................................................................................................ 65
2.7 Other Examples of Important Step-growth Polymers...................................... 68
2.7.1 Polycarbonates..................................................................................... 68
2.7.2 Polyimides........................................................................................... 69
2.7.3 Polyurethanes...................................................................................... 69
2.7.4 Polysiloxanes....................................................................................... 70
2.7.5 Polythiophenes.................................................................................... 71
2.8 Stoichiometric Imbalance................................................................................. 71
2.9 Chapter Summary............................................................................................ 75
Problems...................................................................................................................... 76
References................................................................................................................... 82
Further Readings......................................................................................................... 82
Chapter 3 Chain-Growth Polymerization.................................................................................... 83

3.1 Introduction...................................................................................................... 83
3.2 Chain-Growth and Step-Growth Polymerizations:
Some Comparisons........................................................................................... 83
3.3 Initiation........................................................................................................... 85
3.3.1 Initiation Reactions............................................................................. 86
3.3.2 Fate of Free Radicals........................................................................... 87
3.3.3 Kinetics of Initiation........................................................................... 89
3.3.4 Temperature Dependence of Initiation Rates...................................... 91
3.4 Termination......................................................................................................92
3.4.1 Combination and Disproportionation..................................................92
3.4.2 Effect of Termination on Conversion to Polymer...............................94
3.4.3 Steady-State Radical Concentration.................................................... 95
3.5 Propagation.......................................................................................................97
3.5.1 Rate Laws for Propagation..................................................................97
3.5.2 Temperature Dependence of Propagation Rates.................................99
3.5.3 Kinetic Chain Length........................................................................ 101
3.6 Radical Lifetime............................................................................................. 103
3.7 Distribution of Molecular Weights................................................................. 106
3.7.1 Distribution of i-mers: Termination

by Disproportionation....................................................................... 106
3.7.2 Distribution of i-mers: Termination
by Combination................................................................................. 109
3.8 Chain Transfer................................................................................................ 111
3.8.1 Chain Transfer Reactions.................................................................. 111
3.8.2 Evaluation of Chain Transfer Constants........................................... 113
3.8.3 Chain Transfer to Polymer................................................................ 115
3.8.4 Suppressing Polymerization.............................................................. 116
3.9 Chapter Summary.......................................................................................... 117
Problems.................................................................................................................... 118
References................................................................................................................. 124
Further Readings....................................................................................................... 124
Contents vii
Chapter 4 Controlled Polymerization........................................................................................ 125

4.1 Introduction.................................................................................................... 125
4.2 Poisson Distribution for an Ideal Living Polymerization............................... 126
4.2.1 Kinetic Scheme................................................................................. 127
4.2.2 Breadth of the Poisson Distribution.................................................. 130
4.3 Anionic Polymerization.................................................................................. 134
4.4 Block Copolymers, End-Functional Polymers, and Branched
Polymers by Anionic Polymerization............................................................. 138
4.4.1 Block Copolymers............................................................................. 138
4.4.2 End-Functional Polymers.................................................................. 142
4.4.3 Regular Branched Architectures....................................................... 144
4.5 Cationic Polymerization................................................................................. 147
4.5.1 Aspects of Cationic Polymerization.................................................. 147
4.5.2 Living Cationic Polymerization........................................................ 150
4.6 Controlled Radical Polymerization................................................................ 152
4.6.1 General Principles of Controlled Radical
Polymerization.................................................................................. 153
4.6.2 Particular Realizations of Controlled Radical
Polymerization.................................................................................. 154
4.6.2.1 Atom Transfer Radical Polymerization (ATRP)............... 155
4.6.2.2 Stable Free-Radical Polymerization (SFRP)..................... 156
4.6.2.3 Reversible Addition-Fragmentation Chain-Transfer
(RAFT) Polymerization..................................................... 157
4.7 Polymerization Equilibrium........................................................................... 160
4.8 Ring-Opening Polymerization (ROP)............................................................ 163
4.8.1 General Aspects................................................................................ 163
4.8.2 Specific Examples of Living Ring-Opening Polymerizations.......... 165
4.8.2.1 Poly(ethylene oxide)........................................................... 165
4.8.2.2 Polylactide.......................................................................... 166
4.8.2.3 Poly(dimethylsiloxane)....................................................... 167
4.8.2.4 Ring-Opening Metathesis Polymerization (ROMP)......... 168
4.9 Dendrimers..................................................................................................... 169
4.10 Chapter Summary.......................................................................................... 173
Problems.................................................................................................................... 174
References................................................................................................................. 176
Chapter 5 Copolymers, Microstructure, and Stereoregularity.................................................. 179

5.1 Introduction.................................................................................................... 179
5.2 Copolymer Composition................................................................................. 180
5.2.1 Rate Laws.......................................................................................... 180
5.2.2 Composition versus Feedstock.......................................................... 182
5.3 Reactivity Ratios............................................................................................ 185
5.3.1 Effects of r Values............................................................................. 185
5.3.2 Relation of Reactivity Ratios to Chemical Structure........................ 187
5.4 Resonance and Reactivity.............................................................................. 189
5.5 A Closer Look at Microstructure................................................................... 194
5.5.1 Sequence Distributions...................................................................... 195
5.5.2 Terminal and Penultimate Models.................................................... 199
viii Contents
5.6 Copolymer Composition and Microstructure: Experimental Aspects........... 201

5.6.1 Evaluating Reactivity Ratios from Composition Data...................... 201
5.6.2 Spectroscopic Techniques................................................................. 203
5.6.3 Sequence Distribution: Experimental Determination.......................205
5.7 Characterizing Stereoregularity.....................................................................209
5.8 A Statistical Description of Stereoregularity................................................. 212
5.9 Assessing Stereoregularity by Nuclear Magnetic Resonance........................ 216
5.10 Ziegler–Natta Catalysts.................................................................................. 221
5.11 Single-Site Catalysts.......................................................................................224
5.12 Chapter Summary.......................................................................................... 227
Problems.................................................................................................................... 228
References................................................................................................................. 232
Chapter 6 Polymer Conformations............................................................................................ 235

6.1 Conformations, Bond Rotation, and Polymer Size......................................... 235
6.2 Average End-to-End Distance for Model Chains........................................... 237
Case 6.2.1 The Freely Jointed Chain.............................................................. 238
Case 6.2.2 The Freely Rotating Chain............................................................ 239
Case 6.2.3 Hindered Rotation Chain.............................................................. 241
6.3 Characteristic Ratio and Statistical Segment Length..................................... 241
6.4 Semiflexible Chains and the Persistence Length........................................... 245
6.4.1 Persistence Length of Flexible Chains..............................................246
6.4.2 Worm-Like Chains............................................................................ 247
6.5 Radius of Gyration......................................................................................... 249
6.6 Distributions for End-to-End Distance and Segment Density....................... 254
6.6.1 Distribution of the End-to-End Vector.............................................. 255
6.6.2 Distribution of the End-to-End Distance.......................................... 257
6.6.3 Distribution about the Center of Mass.............................................. 258
6.7 Spheres, Rods, Coils, and Chain Overlap....................................................... 261
6.8 Self-Avoiding Chains: A First Look............................................................... 263
6.9 Chapter Summary..........................................................................................264
Problems.................................................................................................................... 265
References................................................................................................................. 269
Chapter 7 Thermodynamics of Polymer Mixtures.................................................................... 271

7.1 Review of Thermodynamic and Statistical Thermodynamic Concepts........... 271

7.2 Regular Solution Theory................................................................................ 273
7.2.1 Regular Solution Theory: Entropy of Mixing................................... 274
7.2.2 Regular Solution Theory: Enthalpy of Mixing................................. 276
7.3 Flory–Huggins Theory................................................................................... 278
7.3.1 Flory–Huggins Theory: Entropy of Mixing by a Quick Route............ 279
7.3.2 Flory–Huggins Theory: Entropy of Mixing by a Longer Route..........280
7.3.3 Flory–Huggins Theory: Enthalpy of Mixing.................................... 282
7.3.4 Flory–Huggins Theory: Summary of Assumptions.......................... 283
7.4 Osmotic Pressure............................................................................................ 283
7.4.1 Osmotic Pressure: General Case.......................................................284
7.4.2 Osmotic Pressure: Flory–Huggins Theory....................................... 289
Contents ix
7.5 Phase Behavior of Polymer Solutions............................................................. 291

7.5.1 Overview of the Phase Diagram....................................................... 291
7.5.2 Finding the Binodal........................................................................... 294
7.5.3 Finding the Spinodal......................................................................... 295
7.5.4 Finding the Critical Point.................................................................. 296
7.5.5 Phase Diagram from Flory–Huggins Theory................................... 298
7.6 Flory–Huggins Theory for Binary Polymer Blends.......................................302
7.7 What’s in χ?....................................................................................................304
7.7.1 χ from Regular Solution Theory.......................................................304
7.7.2 χ from Experiment............................................................................307
7.7.3 Further Approaches to χ....................................................................308
7.8 Excluded Volume and Chains in a Good Solvent........................................... 310
7.9 Chapter Summary.......................................................................................... 314
Problems.................................................................................................................... 315
References................................................................................................................. 324
Chapter 8 Light Scattering by Polymer Solutions...................................................................... 325

8.1 Introduction: Light Waves.............................................................................. 325
Basic Concepts of Scattering.......................................................................... 327
8.2 Basic Concepts of Scattering.......................................................................... 328
8.2.1 Scattering from Randomly Placed Objects....................................... 328
8.2.2 Scattering from a Perfect Crystal...................................................... 328
8.2.3 Origins of Incoherent and Coherent Scattering................................ 329
8.2.4 Bragg’s Law and the Scattering Vector............................................. 330
8.3 Scattering by an Isolated Small Molecule...................................................... 332
8.4 Scattering from a Dilute Polymer Solution.................................................... 334
8.5 The Form Factor and the Zimm Equation......................................................340
8.5.1 Mathematical Expression for the Form Factor.................................. 341
8.5.2 Form Factor for Isotropic Solutions.................................................. 343
8.5.3 Form Factor as qRg→0......................................................................344
8.5.4 Zimm Equation.................................................................................344
8.5.5 Zimm Plot.......................................................................................... 345
8.6 Scattering Regimes and Particular Form Factors..........................................348
8.7 Experimental Aspects of Light Scattering..................................................... 350
8.7.1 Instrumentation................................................................................. 351
8.7.2 Calibration......................................................................................... 353
8.7.3 Samples and Solutions....................................................................... 354

8.7.4 Refractive Index Increment............................................................... 355
8.8 Introduction to Small-Angle Neutron Scattering........................................... 355
8.8.1 Basics of the SANS Process and SANS
Instrumentation................................................................................. 356
8.8.2 SANS from Polymer Blends..............................................................360
Case 8.8.1 An Isotope Blend.......................................................................... 361
Case 8.8.2 A Non-interacting Binary Blend................................................... 363
Case 8.8.3 A Binary Blend with Interactions.................................................364
8.9 Chapter Summary.......................................................................................... 366
Problems.................................................................................................................... 366
References................................................................................................................. 376
x Contents
Chapter 9 Dynamics of Dilute Polymer Solutions..................................................................... 377

9.1 Introduction: Friction and Viscosity............................................................... 377
9.2 Stokes’ Law and Einstein’s Law..................................................................... 381
9.2.1 Viscous Forces on Rigid Spheres...................................................... 381
9.2.2 Suspension of Spheres....................................................................... 382
9.3 Intrinsic Viscosity........................................................................................... 385
9.3.1 General Considerations..................................................................... 385
9.3.2 Mark–Houwink Equation.................................................................. 386
9.3.3 Relation between Coil Overlap Concentration, c*,
and Intrinsic Viscosity....................................................................... 392
9.4 Measurement of Viscosity.............................................................................. 393
9.4.1 Poiseuille Equation and Capillary Viscometers................................ 393
9.4.2 Concentric Cylinder Viscometers..................................................... 397
9.5 Diffusion Coefficient and Friction Factor...................................................... 398
9.5.1 Tracer Diffusion and Hydrodynamic Radius.................................... 399
9.5.2 Mutual Diffusion and Fick’s Laws....................................................400
9.6 Dynamic Light Scattering (DLS)...................................................................406
9.7 Hydrodynamic Interactions and Draining......................................................409
9.8 Size Exclusion Chromatography (SEC).......................................................... 412
9.8.1 Basic Separation Process................................................................... 413
9.8.2 Separation Mechanism...................................................................... 417
9.8.3 Two Calibration Strategies................................................................ 419
9.8.4 Size Exclusion Chromatography Detectors....................................... 422
9.9 Chapter Summary.......................................................................................... 425
Problems.................................................................................................................... 425
References................................................................................................................. 437
Chapter 10 Networks, Gels, and Rubber Elasticity..................................................................... 439

10.1 Formation of Networks by Random Cross-Linking....................................... 439
10.1.1 Definitions......................................................................................... 439
10.1.2 Gel Point............................................................................................ 441
10.2 Polymerization with Multifunctional Monomers........................................... 443
10.2.1 Calculation of the Branching Coefficient.......................................... 445
10.2.2 Gel Point............................................................................................446
10.2.3 Molecular-Weight Averages.............................................................. 447
10.3 Elastic Deformation........................................................................................ 450

10.4 Thermodynamics of Elasticity....................................................................... 452
10.4.1 Equation of State............................................................................... 452
10.4.2 Ideal Elastomers................................................................................ 454
10.4.3 Some Experiments on Real Rubbers................................................. 455
10.5 Statistical Mechanical Theory of Rubber Elasticity:
Ideal Case....................................................................................................... 456
10.5.1 Force to Extend a Gaussian Chain.................................................... 457
10.5.2 Network of Gaussian Strands............................................................ 459
10.5.3 Modulus of the Affine Gaussian Network.........................................460
10.6 Further Developments in Rubber Elasticity................................................... 462
10.6.1 Non-Gaussian Force Law.................................................................. 463
10.6.2 Front Factor.......................................................................................465
Contents xi
10.6.3 Network Defects................................................................................466

10.6.4 Mooney-Rivlin Equation...................................................................468
10.7 Swelling of Gels.............................................................................................469
10.7.1 Modulus of a Swollen Rubber........................................................... 470
10.7.2 Swelling Equilibrium........................................................................ 471
10.8 Chapter Summary.......................................................................................... 474
Problems.................................................................................................................... 475
References................................................................................................................. 479
Chapter 11 Linear Viscoelasticity................................................................................................ 481

11.1 Basic Concepts............................................................................................... 481
11.1.1 Stress and Strain................................................................................ 483
11.1.2 Viscosity, Modulus, and Compliance................................................ 483
11.1.3 Viscous and Elastic Responses.........................................................484
11.2 Response of the Maxwell and Voigt Elements............................................... 485
11.2.1 Transient Response: Stress Relaxation.............................................. 485
11.2.2 Transient Response: Creep................................................................ 487
11.2.3 Dynamic Response: Loss and Storage Moduli................................. 489
11.2.4 Dynamic Response: Complex Modulus and Complex
Viscosity............................................................................................ 492
11.3 Boltzmann Superposition Principle................................................................ 493
11.4 Bead–Spring Model........................................................................................ 494
11.4.1 Ingredients of the Bead–Spring Model............................................. 495
11.4.2 Predictions of the Bead–Spring Model............................................. 496
11.5 Zimm Model for Dilute Solutions, Rouse Model for Unentangled Melts............ 502
11.6 Phenomenology of Entanglement...................................................................506
11.6.1 Rubbery Plateau................................................................................506
11.6.2 Dependence of Me on Molecular Structure.......................................509
11.7 Reptation Model............................................................................................. 513
11.7.1 Reptation Model: Longest Relaxation Time and Diffusivity............ 513
11.7.2 Reptation Model: Viscoelastic Properties......................................... 517
11.7.3 Reptation Model: Additional Relaxation Processes.......................... 519
11.8 Aspects of Experimental Rheometry............................................................. 520
11.8.1 Shear Sandwich and Cone and Plate Rheometers............................. 521
11.8.2 Further Comments about Rheometry............................................... 522
11.9 Chapter Summary.......................................................................................... 523
Problems.................................................................................................................... 524
References................................................................................................................. 531
Chapter 12 Glass Transition......................................................................................................... 533

12.1 Introduction.................................................................................................... 533
12.1.1 Definition of a Glass.......................................................................... 533
12.1.2 Glass and Melting Transitions........................................................... 534
12.2 Thermodynamic Aspects of the Glass Transition.......................................... 536
12.2.1 First-Order and Second-Order Phase Transitions............................. 537
12.2.2 Kauzmann Temperature.................................................................... 539
12.2.3 Theory of Gibbs and DiMarzio.........................................................540
xii Contents
12.3 Locating the Glass Transition Temperature................................................... 542

12.3.1 Dilatometry....................................................................................... 542
12.3.2 Calorimetry.......................................................................................544
12.3.3 Dynamic Mechanical Analysis.........................................................546
12.4 Free Volume Description of the Glass Transition.......................................... 547
12.4.1 Temperature Dependence of the Free Volume.................................. 547
12.4.2 Free Volume Changes Inferred from the Viscosity.......................... 549
12.4.3 Williams–Landel–Ferry Equation.................................................... 551
12.5 Time-Temperature Superposition................................................................... 553
12.6 Factors that Affect the Glass Transition Temperature.................................... 559
12.6.1 Dependence on Chemical Structure.................................................. 559
12.6.2 Dependence on Molecular Weight.................................................... 559
12.6.3 Dependence on Composition............................................................. 560
12.7 Mechanical Properties of Glassy Polymers.................................................... 563
12.7.1 Basic Concepts..................................................................................564
12.7.2 Crazing, Yielding, and the Brittle-to-Ductile Transition.................. 566
12.7.3 Role of Chain Stiffness and Entanglements...................................... 568
12.8 Chapter Summary.......................................................................................... 572
Problems.................................................................................................................... 572
References................................................................................................................. 580
Chapter 13 Crystalline Polymers................................................................................................. 581

13.1 Introduction and Overview............................................................................. 581
13.2 Structure and Characterization of Unit Cells................................................. 583
13.2.1 Classes of Crystals............................................................................ 583
13.2.2 X-ray Diffraction............................................................................... 584
13.2.3 Examples of Unit Cells...................................................................... 587
13.3 Thermodynamics of Crystallization: Relation of Melting
Temperature to Molecular Structure.............................................................. 590
13.4 Structure and Melting of Lamellae................................................................ 595
13.4.1 Surface Contributions to Phase Transitions...................................... 595
13.4.2 Dependence of Tm on Lamellar Thickness........................................ 596
13.4.3 Dependence of Tm on Molecular Weight...........................................600
13.4.4 Experimental Characterization of Lamellar Structure..................... 601
13.5 Kinetics of Nucleation and Growth................................................................605
13.5.1 Primary Nucleation...........................................................................606
13.5.2 Crystal Growth.................................................................................. 610

13.6 Morphology of Semicrystalline Polymers...................................................... 614
13.6.1 Spherulites......................................................................................... 614
13.6.2 Nonspherulitic Morphologies............................................................ 618
13.7 Kinetics of Bulk Crystallization..................................................................... 620
13.7.1 Avrami Equation............................................................................... 621
13.7.2 Kinetics of Crystallization: Experimental Aspects........................... 626
13.8 Chapter Summary.......................................................................................... 630
Problems.................................................................................................................... 631
References................................................................................................................. 638
Appendix .......................................................................................................................................639
Index...............................................................................................................................................647

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Contents

Preface to the Third Edition........................................................................................................... xiii

Chapter 1 Introduction to Chain Molecules...................................................................................1

Chapter 2 Step-Growth Polymerization....................................................................................... 43

2.4 Distribution of Molecular Sizes........................................................................ 56

Chapter 3 Chain-Growth Polymerization.................................................................................... 83

3.7.1 Distribution of i-mers: Termination

Chapter 4 Controlled Polymerization........................................................................................ 125

Chapter 5 Copolymers, Microstructure, and Stereoregularity.................................................. 179

5.6 Copolymer Composition and Microstructure: Experimental Aspects........... 201

Chapter 6 Polymer Conformations............................................................................................ 235

Chapter 7 Thermodynamics of Polymer Mixtures.................................................................... 271

7.1 Review of Thermodynamic and Statistical Thermodynamic Concepts........... 271

7.5 Phase Behavior of Polymer Solutions............................................................. 291

Chapter 8 Light Scattering by Polymer Solutions...................................................................... 325

8.7.3 Samples and Solutions....................................................................... 354

Chapter 9 Dynamics of Dilute Polymer Solutions..................................................................... 377

Chapter 10 Networks, Gels, and Rubber Elasticity..................................................................... 439

10.3 Elastic Deformation........................................................................................ 450

10.6.3 Network Defects................................................................................466

Chapter 11 Linear Viscoelasticity................................................................................................ 481

Chapter 12 Glass Transition......................................................................................................... 533

12.3 Locating the Glass Transition Temperature................................................... 542

Chapter 13 Crystalline Polymers................................................................................................. 581

13.5.2 Crystal Growth.................................................................................. 610

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