Polymer Chemistry, Second Edition

by Hiemenz; Paul C.

• ISBN13: 9781574447798
• ISBN10: 1574447793
• Edition: 2nd
• Format: Hardcover
• Copyright: 2007-02-15
• Publisher: CRC Press

Summary

Written by well-established professors in the field, Polymer Chemistry, Second Edition examines polymer properties at the molecular level. It focuses on chemical structures, polymer synthesis, characterization, and properties. This edition integrates theories and experiments made possible by recent advances in instrumentation. It includes new chapters on controlled polymerization and chain conformations and updated material on properties such as synthesis, viscoelasticity, solution properties, and thermodynamics. Mathematical tools, fully derived problems, and carefully organized content can be scaled to meet the needs of introductory as well as more advanced courses in chemistry, materials science, and chemical engineering.

Table of Contents

Introduction to Chain Molecules	p. 1
Introduction	p. 1
How Big Is Big?	p. 3
Molecular Weight	p. 3
Spatial Extent	p. 5
Linear and Branched Polymers, Homopolymers, and Copolymers	p. 7
Branched Structures	p. 7
Copolymers	p. 9
Addition, Condensation, and Natural Polymers	p. 11
Addition and Condensation Polymers	p. 11
Natural Polymers	p. 13
Polymer Nomenclature	p. 18
Structural Isomerism	p. 20
Positional Isomerism	p. 20
Stereo Isomerism	p. 21
Geometrical Isomerism	p. 22
Molecular Weights and Molecular Weight Averages	p. 24
Number-, Weight-, and z-Average Molecular Weights	p. 25
Polydispersity Index and Standard Deviation	p. 26
Examples of Distributions	p. 28
Measurement of Molecular Weight	p. 31
General Considerations	p. 31
End Group Analysis	p. 32
MALDI Mass Spectrometry	p. 35
Preview of Things to Come	p. 37
Chapter Summary	p. 38
Problems	p. 38
References	p. 41
Further Readings	p. 41
Step-Growth Polymerization	p. 43
Introduction	p. 43
Condensation Polymers: One Step at a Time	p. 43
Classes of Step-Growth Polymers	p. 43
First Look at the Distribution of Products	p. 44
A First Look at Reactivity and Reaction Rates	p. 46
Kinetics of Step-Growth Polymerization	p. 49
Catalyzed Step-Growth Reactions	p. 50
How Should Experimental Data Be Compared with Theoretical Rate Laws?	p. 52
Uncatalyzed Step-Growth Reactions	p. 53
Distribution of Molecular Sizes	p. 55
Mole Fractions of Species	p. 56
Weight Fractions of Species	p. 58
Polyesters	p. 60
Polyamides	p. 64
Stoichiometric Imbalance	p. 67
Chapter Summary	p. 71
Problems	p. 71
References	p. 76
Further Readings	p. 76
Chain-Growth Polymerization	p. 77
Introduction	p. 77
Chain-Growth and Step-Growth Polymerizations: Some Comparisons	p. 77
Initiation	p. 79
Initiation Reactions	p. 80
Fate of Free Radicals	p. 81
Kinetics of Initiation	p. 82
Photochemical Initiation	p. 84
Temperature Dependence of Initiation Rates	p. 85
Termination	p. 86
Combination and Disproportionation	p. 86
Effect of Termination on Conversion to Polymer	p. 88
Stationary-State Radical Concentration	p. 89
Propagation	p. 90
Rate Laws for Propagation	p. 91
Temperature Dependence of Propagation Rates	p. 92
Kinetic Chain Length	p. 94
Radical Lifetime	p. 96
Distribution of Molecular Weights	p. 99
Distribution of i-mers: Termination by Disproportionation	p. 99
Distribution of i-mers: Termination by Combination	p. 102
Chain Transfer	p. 104
Chain Transfer Reactions	p. 105
Evaluation of Chain Transfer Constants	p. 106
Chain Transfer to Polymer	p. 108
Suppressing Polymerization	p. 109
Chapter Summary	p. 110
Problems	p. 110
References	p. 114
Further Readings	p. 115
Controlled Polymerization	p. 117
Introduction	p. 117
Poisson Distribution for an Ideal Living Polymerization	p. 118
Kinetic Scheme	p. 119
Breadth of the Poisson Distribution	p. 122
Anionic Polymerization	p. 126
Block Copolymers, End-Functional Polymers, and Branched Polymers by Anionic Polymerization	p. 129
Block Copolymers	p. 129
End-Functional Polymers	p. 133
Regular Branched Architectures	p. 135
Cationic Polymerization	p. 137
Aspects of Cationic Polymerization	p. 138
Living Cationic Polymerization	p. 140
Controlled Radical Polymerization	p. 142
General Principles of Controlled Radical Polymerization	p. 142
Particular Realizations of Controlled Radical Polymerization	p. 144
Atom Transfer Radical Polymerization (ATRP)	p. 144
Stable Free-Radical Polymerization (SFRP)	p. 145
Reversible Addition-Fragmentation Transfer (RAFT) Polymerization	p. 146
Polymerization Equilibrium	p. 147
Ring-Opening Polymerization (ROP)	p. 150
General Aspects	p. 150
Specific Examples of Living Ring-Opening Polymerizations	p. 152
Poly(ethylene oxide)	p. 152
Polylactide	p. 153
Poly(dimethylsiloxane)	p. 154
Ring-Opening Metathesis Polymerization (ROMP)	p. 155
Dendrimers	p. 156
Chapter Summary	p. 160
Problems	p. 161
References	p. 163
Further Readings	p. 163
Copolymers, Microstructure, and Stereoregularity	p. 165
Introduction	p. 165
Copolymer Composition	p. 166
Rate Laws	p. 166
Composition versus Feedstock	p. 168
Reactivity Ratios	p. 170
Effects of r Values	p. 171
Relation of Reactivity Ratios to Chemical Structure	p. 173
Resonance and Reactivity	p. 175
A Closer Look at Microstructure	p. 179
Sequence Distributions	p. 180
Terminal and Penultimate Models	p. 183
Copolymer Composition and Microstructure: Experimental Aspects	p. 185
Evaluating Reactivity Ratios from Composition Data	p. 185
Spectroscopic Techniques	p. 188
Sequence Distribution: Experimental Determination	p. 190
Characterizing Stereoregularity	p. 193
A Statistical Description of Stereoregularity	p. 196
Assessing Stereoregularity by Nuclear Magnetic Resonance	p. 200
Ziegler-Natta Catalysts	p. 205
Single-Site Catalysts	p. 208
Chapter Summary	p. 211
Problems	p. 212
References	p. 216
Further Readings	p. 216
Polymer Conformations	p. 217
Conformations, Bond Rotation, and Polymer Size	p. 217
Average End-to-End Distance for Model Chains	p. 219
The Freely Jointed Chain	p. 220
The Freely Rotating Chain	p. 221
Hindered Rotation Chain	p. 222
Characteristic Ratio and Statistical Segment Length	p. 223
Semiflexible Chains and the Persistence Length	p. 225
Persistence Length of Flexible Chains	p. 227
Worm-Like Chains	p. 228
Radius of Gyration	p. 230
Spheres, Rods, and Coils	p. 234
Distributions for End-to-End Distance and Segment Density	p. 235
Distribution of the End-to-End Vector	p. 236
Distribution of the End-to-End Distance	p. 239
Distribution about the Center of Mass	p. 240
Self-Avoiding Chains: A First Look	p. 241
Chapter Summary	p. 242
Problems	p. 242
References	p. 244
Further Readings	p. 245
Thermodynamics of Polymer Solutions	p. 247
Review of Thermodynamic and Statistical Thermodynamic Concepts	p. 247
Regular Solution Theory	p. 249
Regular Solution Theory: Entropy of Mixing	p. 249
Regular Solution Theory: Enthalpy of Mixing	p. 251
Flory-Huggins Theory	p. 254
Flory-Huggins Theory: Entropy of Mixing by a Quick Route	p. 255
Flory-Huggins Theory: Entropy of Mixing by a Longer Route	p. 255
Flory-Huggins Theory: Enthalpy of Mixing	p. 257
Flory-Huggins Theory: Summary of Assumptions	p. 258
Osmotic Pressure	p. 258
Osmotic Pressure: General Case	p. 259
Number-Average Molecular Weight	p. 261
Osmotic Pressure: Flory-Huggins Theory	p. 263
Phase Behavior of Polymer Solutions	p. 264
Overview of the Phase Diagram	p. 265
Finding the Binodal	p. 268
Finding the Spinodal	p. 269
Finding the Critical Point	p. 270
Phase Diagram from Flory-Huggins Theory	p. 271
What's in [chi]?	p. 275
[chi] from Regular Solution Theory	p. 275
[chi] from Experiment	p. 276
Further Approaches to [chi]	p. 278
Excluded Volume and Chains in a Good Solvent	p. 280
Chapter Summary	p. 283
Problems	p. 284
References	p. 287
Further Readings	p. 288
Light Scattering by Polymer Solutions	p. 289
Introduction: Light Waves	p. 289
Basic Concepts of Scattering	p. 291
Scattering from Randomly Placed Objects	p. 292
Scattering from a Perfect Crystal	p. 292
Origins of Incoherent and Coherent Scattering	p. 293
Bragg's Law and the Scattering Vector	p. 294
Scattering by an Isolated Small Molecule	p. 296
Scattering from a Dilute Polymer Solution	p. 298
The Form Factor and the Zimm Equation	p. 304
Mathematical Expression for the Form Factor	p. 305
Form Factor for Isotropic Solutions	p. 306
Form Factor as qR[subscript g][Right Arrow]0	p. 307
Zimm Equation	p. 307
Zimm Plot	p. 308
Scattering Regimes and Particular Form Factors	p. 312
Experimental Aspects of Light Scattering	p. 314
Instrumentation	p. 316
Calibration	p. 317
Samples and Solutions	p. 319
Refractive Index Increment	p. 319
Chapter Summary	p. 320
Problems	p. 321
References	p. 325
Further Readings	p. 325
Dynamics of Dilute Polymer Solutions	p. 327
Introduction: Friction and Viscosity	p. 327
Stokes' Law and Einstein's Law	p. 330
Viscous Forces on Rigid Spheres	p. 331
Suspension of Spheres	p. 332
Intrinsic Viscosity	p. 334
General Considerations	p. 334
Mark-Houwink Equation	p. 336
Measurement of Viscosity	p. 341
Poiseuille Equation and Capillary Viscometers	p. 341
Concentric Cylinder Viscometers	p. 345
Diffusion Coefficient and Friction Factor	p. 346
Tracer Diffusion and Hydrodynamic Radius	p. 347
Mutual Diffusion and Fick's Laws	p. 348
Dynamic Light Scattering	p. 354
Hydrodynamic Interactions and Draining	p. 357
Size Exclusion Chromatography (SEC)	p. 360
Basic Separation Process	p. 361
Separation Mechanism	p. 365
Two Calibration Strategies	p. 367
Limitations of Calibration by Standards	p. 367
Universal Calibration	p. 368
Size Exclusion Chromatography Detectors	p. 369
RI Detector	p. 369
UV-Vis Detector	p. 370
Light Scattering Detector	p. 371
Viscometer	p. 372
Chapter Summary	p. 372
Problems	p. 373
References	p. 378
Further Readings	p. 379
Networks, Gels, and Rubber Elasticity	p. 381
Formation of Networks by Random Cross-Linking	p. 381
Definitions	p. 381
Gel Point	p. 383
Polymerization with Multifunctional Monomers	p. 386
Calculation of the Branching Coefficient	p. 387
Gel Point	p. 388
Molecular-Weight Averages	p. 389
Elastic Deformation	p. 392
Thermodynamics of Elasticity	p. 394
Equation of State	p. 394
Ideal Elastomers	p. 396
Some Experiments on Real Rubbers	p. 397
Statistical Mechanical Theory of Rubber Elasticity: Ideal Case	p. 398
Force to Extend a Gaussian Chain	p. 400
Network of Gaussian Strands	p. 402
Modulus of the Gaussian Network	p. 403
Further Developments in Rubber Elasticity	p. 406
Non-Gaussian Force Law	p. 406
Front Factor	p. 407
Network Defects	p. 408
Mooney-Rivlin Equation	p. 409
Swelling of Gels	p. 410
Modulus of a Swollen Rubber	p. 411
Swelling Equilibrium	p. 412
Chapter Summary	p. 414
Problems	p. 416
References	p. 418
Further Readings	p. 418
Linear Viscoelasticity	p. 419
Basic Concepts	p. 419
Stress and Strain	p. 421
Viscosity, Modulus, and Compliance	p. 421
Viscous and Elastic Responses	p. 422
Response of the Maxwell and Voigt Elements	p. 423
Transient Response: Stress Relaxation	p. 423
Transient Response: Creep	p. 425
Dynamic Response: Loss and Storage Moduli	p. 426
Dynamic Response: Complex Modulus and Complex Viscosity	p. 429
Boltzmann Superposition Principle	p. 430
Bead-Spring Model	p. 432
Ingredients of the Bead-Spring Model	p. 432
Predictions of the Bead-Spring Model	p. 434
Zimm Model for Dilute Solutions, Rouse Model for Unentangled Melts	p. 439
Phenomenology of Entanglement	p. 444
Rubbery Plateau	p. 444
Dependence of M[subscript e] on Molecular Structure	p. 447
Reptation Model	p. 450
Reptation Model: Longest Relaxation Time and Diffusivity	p. 451
Reptation Model: Viscoelastic Properties	p. 453
Reptation Model: Additional Relaxation Processes	p. 456
Aspects of Experimental Rheometry	p. 458
Shear Sandwich and Cone and Plate Rheometers	p. 458
Further Comments about Rheometry	p. 459
Chapter Summary	p. 460
Problems	p. 461
References	p. 464
Further Readings	p. 464
Glass Transition	p. 455
Introduction	p. 455
Definition of a Glass	p. 455
Glass and Melting Transitions	p. 466
Thermodynamic Aspects of the Glass Transition	p. 468
First-Order and Second-Order Phase Transitions	p. 469
Kauzmann Temperature	p. 471
Theory of Gibbs and DiMarzio	p. 472
Locating the Glass Transition Temperature	p. 474
Dilatometry	p. 474
Calorimetry	p. 476
Dynamic Mechanical Analysis	p. 478
Free Volume Description of the Glass Transition	p. 479
Temperature Dependence of the Free Volume	p. 480
Free Volume Changes Inferred from the Viscosity	p. 481
Williams-Landel-Ferry Equation	p. 483
Time-Temperature Superposition	p. 486
Factors that Affect the Glass Transition Temperature	p. 491
Dependence on Chemical Structure	p. 491
Dependence on Molecular Weight	p. 492
Dependence on Composition	p. 492
Mechanical Properties of Glassy Polymers	p. 496
Basic Concepts	p. 496
Crazing, Yielding, and the Brittle-to-Ductile Transition	p. 498
Role of Chain Stiffness and Entanglements	p. 501
Chapter Summary	p. 504
Problems	p. 505
References	p. 508
Further Readings	p. 508
Crystalline Polymers	p. 511
Introduction and Overview	p. 511
Structure and Characterization of Unit Cells	p. 513
Classes of Crystals	p. 513
X-Ray Diffraction	p. 515
Examples of Unit Cells	p. 518
Thermodynamics of Crystallization: Relation of Melting Temperature to Molecular Structure	p. 521
Structure and Melting of Lamellae	p. 526
Surface Contributions to Phase Transitions	p. 526
Dependence of T[subscript m] on Lamellar Thickness	p. 527
Dependence of T[subscript m] on Molecular Weight	p. 530
Experimental Characterization of Lamellar Structure	p. 532
Kinetics of Nucleation and Growth	p. 536
Primary Nucleation	p. 537
Crystal Growth	p. 539
Morphology of Semicrystalline Polymers	p. 545
Spherulites	p. 545
Nonspherulitic Morphologies	p. 548
Kinetics of Bulk Crystallization	p. 551
Avrami Equation	p. 552
Kinetics of Crystallization: Experimental Aspects	p. 556
Chapter Summary	p. 561
Problems	p. 562
References	p. 565
Further Readings	p. 565
Appendix	p. 567
Series Expansions	p. 567
Summation Formulae	p. 568
Transformation to Spherical Coordinates	p. 569
Some Integrals of Gaussian Functions	p. 570
Complex Numbers	p. 572
Index	p. 575
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