Polymer Chemistry, Second Edition

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  • Edition: 2nd
  • Format: Hardcover
  • Copyright: 2007-02-15
  • Publisher: CRC Press

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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 Moleculesp. 1
Introductionp. 1
How Big Is Big?p. 3
Molecular Weightp. 3
Spatial Extentp. 5
Linear and Branched Polymers, Homopolymers, and Copolymersp. 7
Branched Structuresp. 7
Copolymersp. 9
Addition, Condensation, and Natural Polymersp. 11
Addition and Condensation Polymersp. 11
Natural Polymersp. 13
Polymer Nomenclaturep. 18
Structural Isomerismp. 20
Positional Isomerismp. 20
Stereo Isomerismp. 21
Geometrical Isomerismp. 22
Molecular Weights and Molecular Weight Averagesp. 24
Number-, Weight-, and z-Average Molecular Weightsp. 25
Polydispersity Index and Standard Deviationp. 26
Examples of Distributionsp. 28
Measurement of Molecular Weightp. 31
General Considerationsp. 31
End Group Analysisp. 32
MALDI Mass Spectrometryp. 35
Preview of Things to Comep. 37
Chapter Summaryp. 38
Problemsp. 38
Referencesp. 41
Further Readingsp. 41
Step-Growth Polymerizationp. 43
Introductionp. 43
Condensation Polymers: One Step at a Timep. 43
Classes of Step-Growth Polymersp. 43
First Look at the Distribution of Productsp. 44
A First Look at Reactivity and Reaction Ratesp. 46
Kinetics of Step-Growth Polymerizationp. 49
Catalyzed Step-Growth Reactionsp. 50
How Should Experimental Data Be Compared with Theoretical Rate Laws?p. 52
Uncatalyzed Step-Growth Reactionsp. 53
Distribution of Molecular Sizesp. 55
Mole Fractions of Speciesp. 56
Weight Fractions of Speciesp. 58
Polyestersp. 60
Polyamidesp. 64
Stoichiometric Imbalancep. 67
Chapter Summaryp. 71
Problemsp. 71
Referencesp. 76
Further Readingsp. 76
Chain-Growth Polymerizationp. 77
Introductionp. 77
Chain-Growth and Step-Growth Polymerizations: Some Comparisonsp. 77
Initiationp. 79
Initiation Reactionsp. 80
Fate of Free Radicalsp. 81
Kinetics of Initiationp. 82
Photochemical Initiationp. 84
Temperature Dependence of Initiation Ratesp. 85
Terminationp. 86
Combination and Disproportionationp. 86
Effect of Termination on Conversion to Polymerp. 88
Stationary-State Radical Concentrationp. 89
Propagationp. 90
Rate Laws for Propagationp. 91
Temperature Dependence of Propagation Ratesp. 92
Kinetic Chain Lengthp. 94
Radical Lifetimep. 96
Distribution of Molecular Weightsp. 99
Distribution of i-mers: Termination by Disproportionationp. 99
Distribution of i-mers: Termination by Combinationp. 102
Chain Transferp. 104
Chain Transfer Reactionsp. 105
Evaluation of Chain Transfer Constantsp. 106
Chain Transfer to Polymerp. 108
Suppressing Polymerizationp. 109
Chapter Summaryp. 110
Problemsp. 110
Referencesp. 114
Further Readingsp. 115
Controlled Polymerizationp. 117
Introductionp. 117
Poisson Distribution for an Ideal Living Polymerizationp. 118
Kinetic Schemep. 119
Breadth of the Poisson Distributionp. 122
Anionic Polymerizationp. 126
Block Copolymers, End-Functional Polymers, and Branched Polymers by Anionic Polymerizationp. 129
Block Copolymersp. 129
End-Functional Polymersp. 133
Regular Branched Architecturesp. 135
Cationic Polymerizationp. 137
Aspects of Cationic Polymerizationp. 138
Living Cationic Polymerizationp. 140
Controlled Radical Polymerizationp. 142
General Principles of Controlled Radical Polymerizationp. 142
Particular Realizations of Controlled Radical Polymerizationp. 144
Atom Transfer Radical Polymerization (ATRP)p. 144
Stable Free-Radical Polymerization (SFRP)p. 145
Reversible Addition-Fragmentation Transfer (RAFT) Polymerizationp. 146
Polymerization Equilibriump. 147
Ring-Opening Polymerization (ROP)p. 150
General Aspectsp. 150
Specific Examples of Living Ring-Opening Polymerizationsp. 152
Poly(ethylene oxide)p. 152
Polylactidep. 153
Poly(dimethylsiloxane)p. 154
Ring-Opening Metathesis Polymerization (ROMP)p. 155
Dendrimersp. 156
Chapter Summaryp. 160
Problemsp. 161
Referencesp. 163
Further Readingsp. 163
Copolymers, Microstructure, and Stereoregularityp. 165
Introductionp. 165
Copolymer Compositionp. 166
Rate Lawsp. 166
Composition versus Feedstockp. 168
Reactivity Ratiosp. 170
Effects of r Valuesp. 171
Relation of Reactivity Ratios to Chemical Structurep. 173
Resonance and Reactivityp. 175
A Closer Look at Microstructurep. 179
Sequence Distributionsp. 180
Terminal and Penultimate Modelsp. 183
Copolymer Composition and Microstructure: Experimental Aspectsp. 185
Evaluating Reactivity Ratios from Composition Datap. 185
Spectroscopic Techniquesp. 188
Sequence Distribution: Experimental Determinationp. 190
Characterizing Stereoregularityp. 193
A Statistical Description of Stereoregularityp. 196
Assessing Stereoregularity by Nuclear Magnetic Resonancep. 200
Ziegler-Natta Catalystsp. 205
Single-Site Catalystsp. 208
Chapter Summaryp. 211
Problemsp. 212
Referencesp. 216
Further Readingsp. 216
Polymer Conformationsp. 217
Conformations, Bond Rotation, and Polymer Sizep. 217
Average End-to-End Distance for Model Chainsp. 219
The Freely Jointed Chainp. 220
The Freely Rotating Chainp. 221
Hindered Rotation Chainp. 222
Characteristic Ratio and Statistical Segment Lengthp. 223
Semiflexible Chains and the Persistence Lengthp. 225
Persistence Length of Flexible Chainsp. 227
Worm-Like Chainsp. 228
Radius of Gyrationp. 230
Spheres, Rods, and Coilsp. 234
Distributions for End-to-End Distance and Segment Densityp. 235
Distribution of the End-to-End Vectorp. 236
Distribution of the End-to-End Distancep. 239
Distribution about the Center of Massp. 240
Self-Avoiding Chains: A First Lookp. 241
Chapter Summaryp. 242
Problemsp. 242
Referencesp. 244
Further Readingsp. 245
Thermodynamics of Polymer Solutionsp. 247
Review of Thermodynamic and Statistical Thermodynamic Conceptsp. 247
Regular Solution Theoryp. 249
Regular Solution Theory: Entropy of Mixingp. 249
Regular Solution Theory: Enthalpy of Mixingp. 251
Flory-Huggins Theoryp. 254
Flory-Huggins Theory: Entropy of Mixing by a Quick Routep. 255
Flory-Huggins Theory: Entropy of Mixing by a Longer Routep. 255
Flory-Huggins Theory: Enthalpy of Mixingp. 257
Flory-Huggins Theory: Summary of Assumptionsp. 258
Osmotic Pressurep. 258
Osmotic Pressure: General Casep. 259
Number-Average Molecular Weightp. 261
Osmotic Pressure: Flory-Huggins Theoryp. 263
Phase Behavior of Polymer Solutionsp. 264
Overview of the Phase Diagramp. 265
Finding the Binodalp. 268
Finding the Spinodalp. 269
Finding the Critical Pointp. 270
Phase Diagram from Flory-Huggins Theoryp. 271
What's in [chi]?p. 275
[chi] from Regular Solution Theoryp. 275
[chi] from Experimentp. 276
Further Approaches to [chi]p. 278
Excluded Volume and Chains in a Good Solventp. 280
Chapter Summaryp. 283
Problemsp. 284
Referencesp. 287
Further Readingsp. 288
Light Scattering by Polymer Solutionsp. 289
Introduction: Light Wavesp. 289
Basic Concepts of Scatteringp. 291
Scattering from Randomly Placed Objectsp. 292
Scattering from a Perfect Crystalp. 292
Origins of Incoherent and Coherent Scatteringp. 293
Bragg's Law and the Scattering Vectorp. 294
Scattering by an Isolated Small Moleculep. 296
Scattering from a Dilute Polymer Solutionp. 298
The Form Factor and the Zimm Equationp. 304
Mathematical Expression for the Form Factorp. 305
Form Factor for Isotropic Solutionsp. 306
Form Factor as qR[subscript g][Right Arrow]0p. 307
Zimm Equationp. 307
Zimm Plotp. 308
Scattering Regimes and Particular Form Factorsp. 312
Experimental Aspects of Light Scatteringp. 314
Instrumentationp. 316
Calibrationp. 317
Samples and Solutionsp. 319
Refractive Index Incrementp. 319
Chapter Summaryp. 320
Problemsp. 321
Referencesp. 325
Further Readingsp. 325
Dynamics of Dilute Polymer Solutionsp. 327
Introduction: Friction and Viscosityp. 327
Stokes' Law and Einstein's Lawp. 330
Viscous Forces on Rigid Spheresp. 331
Suspension of Spheresp. 332
Intrinsic Viscosityp. 334
General Considerationsp. 334
Mark-Houwink Equationp. 336
Measurement of Viscosityp. 341
Poiseuille Equation and Capillary Viscometersp. 341
Concentric Cylinder Viscometersp. 345
Diffusion Coefficient and Friction Factorp. 346
Tracer Diffusion and Hydrodynamic Radiusp. 347
Mutual Diffusion and Fick's Lawsp. 348
Dynamic Light Scatteringp. 354
Hydrodynamic Interactions and Drainingp. 357
Size Exclusion Chromatography (SEC)p. 360
Basic Separation Processp. 361
Separation Mechanismp. 365
Two Calibration Strategiesp. 367
Limitations of Calibration by Standardsp. 367
Universal Calibrationp. 368
Size Exclusion Chromatography Detectorsp. 369
RI Detectorp. 369
UV-Vis Detectorp. 370
Light Scattering Detectorp. 371
Viscometerp. 372
Chapter Summaryp. 372
Problemsp. 373
Referencesp. 378
Further Readingsp. 379
Networks, Gels, and Rubber Elasticityp. 381
Formation of Networks by Random Cross-Linkingp. 381
Definitionsp. 381
Gel Pointp. 383
Polymerization with Multifunctional Monomersp. 386
Calculation of the Branching Coefficientp. 387
Gel Pointp. 388
Molecular-Weight Averagesp. 389
Elastic Deformationp. 392
Thermodynamics of Elasticityp. 394
Equation of Statep. 394
Ideal Elastomersp. 396
Some Experiments on Real Rubbersp. 397
Statistical Mechanical Theory of Rubber Elasticity: Ideal Casep. 398
Force to Extend a Gaussian Chainp. 400
Network of Gaussian Strandsp. 402
Modulus of the Gaussian Networkp. 403
Further Developments in Rubber Elasticityp. 406
Non-Gaussian Force Lawp. 406
Front Factorp. 407
Network Defectsp. 408
Mooney-Rivlin Equationp. 409
Swelling of Gelsp. 410
Modulus of a Swollen Rubberp. 411
Swelling Equilibriump. 412
Chapter Summaryp. 414
Problemsp. 416
Referencesp. 418
Further Readingsp. 418
Linear Viscoelasticityp. 419
Basic Conceptsp. 419
Stress and Strainp. 421
Viscosity, Modulus, and Compliancep. 421
Viscous and Elastic Responsesp. 422
Response of the Maxwell and Voigt Elementsp. 423
Transient Response: Stress Relaxationp. 423
Transient Response: Creepp. 425
Dynamic Response: Loss and Storage Modulip. 426
Dynamic Response: Complex Modulus and Complex Viscosityp. 429
Boltzmann Superposition Principlep. 430
Bead-Spring Modelp. 432
Ingredients of the Bead-Spring Modelp. 432
Predictions of the Bead-Spring Modelp. 434
Zimm Model for Dilute Solutions, Rouse Model for Unentangled Meltsp. 439
Phenomenology of Entanglementp. 444
Rubbery Plateaup. 444
Dependence of M[subscript e] on Molecular Structurep. 447
Reptation Modelp. 450
Reptation Model: Longest Relaxation Time and Diffusivityp. 451
Reptation Model: Viscoelastic Propertiesp. 453
Reptation Model: Additional Relaxation Processesp. 456
Aspects of Experimental Rheometryp. 458
Shear Sandwich and Cone and Plate Rheometersp. 458
Further Comments about Rheometryp. 459
Chapter Summaryp. 460
Problemsp. 461
Referencesp. 464
Further Readingsp. 464
Glass Transitionp. 455
Introductionp. 455
Definition of a Glassp. 455
Glass and Melting Transitionsp. 466
Thermodynamic Aspects of the Glass Transitionp. 468
First-Order and Second-Order Phase Transitionsp. 469
Kauzmann Temperaturep. 471
Theory of Gibbs and DiMarziop. 472
Locating the Glass Transition Temperaturep. 474
Dilatometryp. 474
Calorimetryp. 476
Dynamic Mechanical Analysisp. 478
Free Volume Description of the Glass Transitionp. 479
Temperature Dependence of the Free Volumep. 480
Free Volume Changes Inferred from the Viscosityp. 481
Williams-Landel-Ferry Equationp. 483
Time-Temperature Superpositionp. 486
Factors that Affect the Glass Transition Temperaturep. 491
Dependence on Chemical Structurep. 491
Dependence on Molecular Weightp. 492
Dependence on Compositionp. 492
Mechanical Properties of Glassy Polymersp. 496
Basic Conceptsp. 496
Crazing, Yielding, and the Brittle-to-Ductile Transitionp. 498
Role of Chain Stiffness and Entanglementsp. 501
Chapter Summaryp. 504
Problemsp. 505
Referencesp. 508
Further Readingsp. 508
Crystalline Polymersp. 511
Introduction and Overviewp. 511
Structure and Characterization of Unit Cellsp. 513
Classes of Crystalsp. 513
X-Ray Diffractionp. 515
Examples of Unit Cellsp. 518
Thermodynamics of Crystallization: Relation of Melting Temperature to Molecular Structurep. 521
Structure and Melting of Lamellaep. 526
Surface Contributions to Phase Transitionsp. 526
Dependence of T[subscript m] on Lamellar Thicknessp. 527
Dependence of T[subscript m] on Molecular Weightp. 530
Experimental Characterization of Lamellar Structurep. 532
Kinetics of Nucleation and Growthp. 536
Primary Nucleationp. 537
Crystal Growthp. 539
Morphology of Semicrystalline Polymersp. 545
Spherulitesp. 545
Nonspherulitic Morphologiesp. 548
Kinetics of Bulk Crystallizationp. 551
Avrami Equationp. 552
Kinetics of Crystallization: Experimental Aspectsp. 556
Chapter Summaryp. 561
Problemsp. 562
Referencesp. 565
Further Readingsp. 565
Appendixp. 567
Series Expansionsp. 567
Summation Formulaep. 568
Transformation to Spherical Coordinatesp. 569
Some Integrals of Gaussian Functionsp. 570
Complex Numbersp. 572
Indexp. 575
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