Introduction to polymer science and chemistry: a problem solving approach
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| Main Author: | |
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| Format: | Book |
| Language: | English |
| Published: |
Boca Raton, Fla. [u.a.]
CRC
2006
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| Subjects: | |
| Online Access: | Inhaltsverzeichnis |
| Item Description: | Includes bibliographical references and index |
| Physical Description: | XVIII, 640 S. Ill., graph. Darst. |
| ISBN: | 0849373840 9780849373848 |
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MARC
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| 245 | 1 | 0 | |a Introduction to polymer science and chemistry |b a problem solving approach |c Manas Chanda |
| 264 | 1 | |a Boca Raton, Fla. [u.a.] |b CRC |c 2006 | |
| 300 | |a XVIII, 640 S. |b Ill., graph. Darst. | ||
| 336 | |b txt |2 rdacontent | ||
| 337 | |b n |2 rdamedia | ||
| 338 | |b nc |2 rdacarrier | ||
| 500 | |a Includes bibliographical references and index | ||
| 650 | 4 | |a Polymerization | |
| 650 | 4 | |a Polymerization |v Problems, exercises, etc | |
| 650 | 4 | |a Polymers | |
| 650 | 4 | |a Polymers |v Problems, exercises, etc | |
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| _version_ | 1804137149759488000 |
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| adam_text | Contents
Preface v
1 Introductory Concepts 1
1.1 Basic Definitions 1
1.1.1 Polymer 1
1.1.2 Monomer 2
1.1.3 Molecular Weight and Molar Mass 3
1.1.4 EndGroups 4
1.1.5 Degree of Polymerization 4
1.1.6 Copolymers 4
1.2 Polymerization and Functionality 6
1.3 Polymerization Processes 7
1.3.1 Addition or Chain Polymerization 7
1.3.2 Step Polymerization 11
1.3.3 Supramolecular Polymerization 14
1.4 Molecular Architecture 19
1.5 Classification of Polymers 23
1.5.1 Thermoplastics and Thermosets 24
1.6 Plastics, Fibers, and Elastomers 28
1.7 Polymer Nomenclature 31
REFERENCES 34
EXERCISES 34
2 Chain Dimensions, Structures, and Transitional Phenomena 37
2.1 Introduction 37
2.2 Polymer Chains: Structures and Dimensions 37
2.2.1 Conformational Changes 38
2.2.1.1 Polyethylene 39
2.2.1.2 Polyisobutylene 41
ix
x Contents
2.2.1.3 Polypropylene 42
2.2.2 Polymer Conformations in Crystals 43
2.2.3 Polymer Size in the Amorphous State 45
2.2.3.1 Freely Jointed Chains 45
2.2.3.2 Real Polymer Chains 47
2.3 Constitutional and Configurational Isomerism 51
2.3.1 Constitutional Isomerism 51
2.3.2 Configurational Isomerism 54
2.3.2.1 Geometrical Isomerism 54
2.3.2.2 Stereoisomerism 55
Optical Activity in Polymers 55
Tacticity in Polymers 56
Meso- and Racemic Placements 57
NMR Measurement of Tacticity 61
2.4 Crystallinity in Polymers 63
2.4.1 Structure of Bulk Polymers 64
2.4.1.1 Spherulites 66
2.5 Thermal Transitions in Polymers 68
2.5.1 TgandTm 68
2.5.2 First-and Second-Order Transitions 69
2.6 Regions of Viscoelastic Behavior 70
2.7 Factors Affecting Tg 74
2.8 Factors Affecting Tm 75
2.9 Relation Between Tm and Tg 76
2.10 Theoretical Treatment of Glass Transition 77
2.10.1 Quantitative Effects of Factors on Tg 83
2.11 Chain Movements in Amorphous State 89
2.11.1 The Reptation Model 91
2.12 Thermodynamics of Rubber Elasticity 93
2.12.1 Stress-Strain Behavior of Crosslinked Elastomers 95
2.12.2 Nonideal Networks 101
2.12.2.1 Network Defects 101
2.12.2.2 Elastically Active Chain Sections 101
REFERENCES 103
EXERCISES 104
3 Polymers in Solution 111
3.1 Introduction 111
3.2 Thermodynamics of Liquid Mixtures 111
3.2.1 Low-Molecular-Weight Mixtures: van Laar Model .... 114
3.2.2 Polymer-Solvent Mixtures: Flory-Huggins Model .... 118
Contents xi
3.2.2.1 Flory-Huggins Expressions for Thermodynamic
Functions 122
3.2.2.2 Colligative Properties and Interaction Parame¬
ter^ 124
Relative Vapor Pressure and 125
Osmotic Pressure and^ 127
3.2.2.3 Virial Coefficients 129
Virial Coefficient and^ 130
3.2.2.4 Modification of Flory-Huggins Theory 131
Significance of t// and k 132
Methods to Determine Theta Solvents 133
3.2.2.5 Flory-Krigbaum Theory 133
3.2.2.6 Excluded Volume Theory 134
Expansion Factor 136
3.3 Phase Equilibria in Poor Solvents 139
3.3.1 Upper and Lower Critical Solution Temperatures 143
3.4 Solubility Behavior of Polymers 144
3.5 Swelling of Crossslinked Polymers 153
3.5.1 Determination of^-from Swelling 157
3.6 Frictional Properties of Polymer Molecules
in Dilute Solution 159
3.6.1 Viscosity of Dilute Polymer Solutions 160
3.6.1.1 Determination of Polymer Molecular Dimen-
sions from Viscosity 164
REFERENCES 168
EXERCISES 169
4 Polymer Molecular Weights 177
4.1 Introduction 177
4.2 Molecular Weight Averages 178
4.2.1 Arithmetic Mean 178
4.2.2 Number-Average Molecular Weight 178
4.2.3 Weight-Average Molecular Weight 180
4.3 Molecular Weights in Terms of Moments 181
4.3.1 Ratio of First and Zeroth Moments 183
4.3.2 Ratios of Higher Moments 184
4.4 Molecular Weight Determination 185
4.4.1 End-Group Analysis 186
4.4.2 Colligative Property Measurement 188
4.4.2.1 Ebulliometry (Boiling Point Elevation) 188
4.4.2.2 Cryoscopy (Freezing Point Depression) 188
xji Contents
4.4.2.3 Membrane Osmometry 189
Virial Equations 192
Practical Aspects of Osmometry 193
4.4.2.4 Vapor-Phase Osmometry 197
Practical Aspects 198
4.4.3 Light-Scattering Method 200
4.4.3.1 Rayleigh Ratio 200
4.4.3.2 Turbidity and Rayleigh Ratio 202
4.4.3.3 Turbidity and Molecular Weight of Polymer . . 204
4.4.3.4 Dissymmetry of Scattering 208
Intraparticle Interference 208
Scattering Factor 211
4.4.3.5 ZimmPlots 211
4.4.4 Dilute Solution Viscometry 214
4.4.4.1 Calibration of the Mark-Hou wink-Sakurada Equa-
tion 217
4.4.4.2 Measurement of Intrinsic Viscosity 218
4.4.5 Gel Permeation Chromatography 222
4.4.5.1 Data Interpretation and Calibration 224
REFERENCES 229
EXERCISES 230
5 Condensation (Step-Growth) Polymerization 235
5.1 Introduction 235
5.2 Rates of Polycondensation Reactions 236
5.2.1 Irreversible Polycondensation Kinetics 237
5.2.2 Reversible Polycondensation Kinetics 245
5.3 Number-Average Degree of Polymerization 247
5.4 Controlof Molecular Weight 250
5.4.1 Quantitative Effect of Stoichiometric Imbalance 252
5.5 Molecular Weight Distribution (MWD) 256
5.5.1 BreadthofMWD 258
5.6 Nonlinear Step Polymerization 266
5.6.1 Branching 266
5.6.2 Crosslinking and Gelation 267
Average Functionality Approach 269
5.6.2.1 Statistical Approach 271
Systems withone type ofbranchunit 271
Systems withdifferenttypesof branchunits . . . 276
5.6.2.2 Model for Gelation Process 280
5.6.2.3 Molecular Size Distribution 280
Contents xiii
5.6.2.4 Post-gel Relations 283
5.7 Recursive Approach for Average Properties 285
5.7-1 Linear Step-Growth Polymerization 285
5.7.2 Nonlinear Step-Growth Polymerization 289
5.7.2.1 Polymerization of A/(/ 2) 289
5.7.2.2 Polymerization ofA/(/ 2) +B2 291
5.7.2.3 Polymerization of 2 A, + £B; 293
5.7.3 Post-gel Properties 297
5.7.3.1 Polymerization of A/ 297
Gel-point Conversion 297
Weight Fraction Solubles and Crosslink Density . 299
5.7.3.2 Polymerization of A/+ B2 301
5.8 Polycondensation of A^B Monomers 304
5.8.1 Dendritic and Hyperbranched Polymers 305
REFERENCES 307
EXERCISES 309
6 Free Radical Polymerization 315
6.1 Introduction 315
6.2 Scheme of Radical Chain Polymerization 316
6.2.1 Overall Scheme 316
6.2-2 Chain Initiation 317
6.2-3 Chain Propagation 318
6.2-4 Chain Termination 318
6.2-5 Rate of Polymerization 320
6.2-6 Overall Extent of Polymerization 322
6.3 Experimental Determination of Rp: Dilatometry 324
6.4 Methodsof Initiation 327
6.4.1 Thermal Decomposition of Initiators 328
6.4.1.1 Initiator Efficiency 328
Determination of Initiator Efficiency 332
6.4.2 Redox Initiation 333
6.4-3 Photochemical Initiation 336
6.4.3.1 Direct Photoinitiation 336
6.4.3.2 Photosensitization 337
6.4.3.3 Rate of Photoinitiated Polymerization 338
6.4.4 Initiation by High-Energy Radiations 340
6.4-5 Thermal Initiation in Absence of Initiator 341
6.5 Dead-End Polymerization 342
6.6 Determination of Absolute Rate Constants 344
6.6.1 Nonsteady-State Kinetics 345
xjv Contents
6.7 Chain Length and Degree of Polymerization 351
6.7.1 Kinetic Chain Length 351
6.7.2 Mode of Chain Termination 352
6.7.3 Average Lifetime of Kinetic Chains 354
6.8 Chain Transfer 355
6.8.1 Degree of Polymerization 358
6.8.2 Chain Transfer to Polymer 364
6.8.3 Allylic Transfer 366
6.9 Deviations from Ideal Kinetics 367
6.9.1 Primary Radical Termination 367
6.9.2 Initiator-Monomer Complex Formation 368
6.9.3 Degradative Initiator Transfer 369
6.9.4 Autoacceleration 371
6.10 Inhibition/Retardation of Polymerization 373
6.10.1 Inhibition/Retardation Kinetics 375
6.11 EffectsofTemperature 378
6.11.1 Rate of Polymerization 378
6.11.2 Degree of Polymerization 381
6.11.3 Polymerization-DepolymerizationEquilibrium 382
6.12 Molecular Weight Distribution 385
6.12.1 Low-Conversion Polymerization 386
6.12.1.1 Termination by Disproportionation and/or Trans¬
fer 386
6.12.1.2 Termination by Coupling 387
6.12.1.3 Termination by Coupling, Disproportionation
and Chain Transfer 388
6.12.2 High-Conversion Polymerization 390
6.13 Polymerization Processes 390
6.13.1 Emulsion Polymerization 392
6.13.1.1 Qualitative Picture 393
6.13.1.2 Kinetics of Emulsion Polymerization 396
Rate of Polymerization 398
Degree of Polymerization 400
6.13.1.3 Other Theories 403
6.13.2 Photoemulsion Polymerization 404
6.13.3 Grafting-from Polymerization 406
6.14 Living Radical Polymerization 408
6.14.1 Reversible Termination by Coupling 410
6.14.2 Atom Transfer Radical Polymerization 414
6.14.3 Degenerative Chain Transfer 414
6.14.4 Reversible Addition-Fragmentation Chain Transfer . . . .416
Contents xv
REFERENCES 417
EXERCISES 419
7 Chain Copolymerization 425
7.1 Introduction 425
7.2 Binary Copolymer Composition - Terminal Model 426
7.2.1 Significance of Monomer Reactivity Ratios 428
7.2.2 Types of Copolymerization 430
7.2.2.1 Alternating Copolymerization 430
7.2.2.2 Ideal (random) Copolymerization 430
7.2.2.3 Random-Alternating Copolymerization 431
7.2.2.4 Block Copolymerization 432
7.2.3 Instantaneous Copolymer Composition 432
7.2.4 Integrated Binary Copolymer Equation 435
7.2.5 Evaluation of Monomer Reactivity Ratios 439
7.2.5.1 Plotof r Versus T2 440
7.2.5.2 PlotofF Versus/i 440
7.2.5.3 Direct Curve Fitting 442
7.2.6 The Q-e Scheine 443
7.2.7 Sequence Length Distribution 445
7.2.8 Rate of Binary Free-Radical Copolymerization 449
7.3 Multicomponent Copolymerization: Terpolymerization 453
7.4 Deviations from Terminal Model 457
7.4.1 Penultimate Model 457
7.4.2 Complex-Participation Model 458
7.5 Copolymerization and Crosslinking 458
7.5.1 Vinyl and Divinyl Monomers of Equal Reactivity 459
7.5.2 Vinyl and Divinyl Monomers of Different Reactivities . .462
7.5.3 One Group of Divinyl Monomer Having Lower Reactivity 464
7.6 Block and Graft Copolymerization 465
7.6.1 Block Copolymerization 465
7.6.1.1 Producing Internal Peroxide Linkages 465
7.6.1.2 Introducing Peroxide End Groups 466
7.6.1.3 Mechanical Cleaving of Polymer Chains .... 467
7.6.1.4 Controlled Radical Polymerization 467
7.6.2 Graft Copolymerization 467
7.6.2.1 Chain Transfer Methods 468
7.6.2.2 Irradiation with Ionizing Radiation 468
REFERENCES 470
EXERCISES 471
xvi Contents
8 lonic Chain Polymerization 475
8.1 Introduction 475
8.2 lonic Polymerizability of Monomers 477
8.3 Anionic Polymerization 479
8.3.1 Anionic Initiation 479
8.3.1.1 Nucleophilic Attack 479
8.3.1.2 Electron Transfer 481
Alkali Metals 481
Alkali Metal Complexes 481
8.3.2 Termination Reactions 483
8.3.2.1 Living Polymerization 483
8.3.2.2 Termination by Transfer Agents 484
8.3.2.3 Spontaneous Termination 485
8.3.3 Polymerization with Complete Dissociation of Initiator . .485
8.3.3.1 Polymerization Kinetics 486
8.3.3.2 Experimental Methods 487
8.3.3.3 Average Kinetic Chain Length 488
8.3.3.4 Average Degree of Polymerization 489
8.3.3.5 Distribution of the Degree of Polymerization . . 491
Polydispersity Index 494
8.3.3.6 EffectsofReaction Media 495
8.3.3.7 Effect of Excess Counterion 499
8.3.4 Polymerization with Incomplete Dissociation of Initiator . 502
8.3.5 Polymerization with Simultaneous Propagation and Ter¬
mination 503
8.4 Anionic Copolymerization 505
8.4.1 Reactivity Groups 506
8.4.2 Block Copolymers 508
8.4.2.1 Sequential Monomer Addition 509
Monofunctional Initiators 509
Bifunctional Initiators 510
8.4.2.2 Coupling Reactions 510
8.5 Cationic Polymerization 512
8.5.1 Cationic Initiation 513
8.5.1.1 Protonic Acids 513
8.5.1.2 Lewis Acids 513
8.5.2 Propagation of Cationic Chain 514
8.5.3 Chain Transfer and Termination 516
8.5.3.1 Chain Transfer to Monomer 516
8.5.3.2 Spontaneous Termination 516
8.5.3.3 Combination with Counterion 517
Contents xvü
8.5.3.4 Transfer to Solvents/Reagents 518
8.5.3.5 Chain Transfer to Polymer 519
8.5.4 Kinetics 520
8.5.4.1 Ions and Ion Pairs 520
8.5.4.2 Simplified Kinetic Scheme 521
8.5.4.3 Degree of Polymerization 527
8.5.5 Molecular Weight Distribution 529
8.5.6 Cationic Copolymerization 531
REFERENCES 532
EXERCISES 534
9 Coordination Addition Polymerization 539
9.1 Introduction 539
9.2 Ziegler-Natta Catalysts 540
9.2.1 Catalyst Composition 540
9.2.2 Natureofthe Catalyst 541
9.2.3 Evolution of the Titanium-Aluminum System 542
9.3 Mechanism of Ziegler-Natta Polymerization 543
9.3.1 Mechanism of Stereospecific Placement 543
9.3.2 Bimetallic and Monometallic Mechanisms 544
9.3.2.1 Bimetallic Mechanism 545
9.3.2.2 Monometallic Mechanism 545
Stereoregulation 549
9.4 Kinetics of Ziegler-Natta Polymerization 549
9.4.1 Typical Shapes of Kinetic Curves 549
9.4.2 Effectof Catalyst Particle Size 551
9.4.3 Chain Termination 552
9.4.4 Kinetic Models 553
9.4.4.1 Early Models 553
Chain Initiation 553
Chain Propagation 553
Chain Transfer 553
9.4.4.2 Adsorption Models 556
9.4.4.3 Average Degree of polymerization 569
9.5 Supported Metal Oxide Catalysts 569
9.5.1 Polymerization Mechanism 570
9.5.1.1 Bound-Ion-Radical Mechanism 570
9.5.1.2 Bound-Ion-Coordination Mechanism 574
9.6 Ziegler-Natta Copolymerization 575
9.7 Metallocene-Based Ziegler-Natta Catalysts 577
9.7.1 Catalyst Composition 578
xviü Contents
9.7.2 The Active Center 580
9.7.3 Polymerization Mechanism 581
9.7.4 Kinetic Models 581
9.7.4.1 Ewen s Model 581
9.7.4.2 Chien s Model 583
9.7.4.3 Molecular Weight and Chain Transfer 585
jß-Hydrogen Elimination 586
Chain Transfer by Monomer 586
Chain Transfer to MAO 586
y3-CH3 Elimination 586
9.8 Immobilized Metallocene Catalysts 587
9.9 Oscillating Metallocene Catalysts 590
REFERENCES 591
EXERCISES 594
10 Ring-Opening Polymerization 597
10.1 Introduction 597
10.2 Polymerization Mechanism and Kinetics 599
10.2.1 Cyclic Ethers/Epoxides 600
10.2.1.1 Anionic Polymerization 600
Kinetics 601
Exchange Reactions 604
10.2.1.2 Cationic Polymerization 605
Chain Initiation and Propagation 605
Chain Transfer and Termination 608
Kinetics 608
Degree of Polymerization 611
10.2.2 Lactams 614
10.2.2.1 Hydrolytic Polymerization 614
Kinetics 616
10.2.2.2 Anionic Polymerization 617
10.2.3 Lactones 620
REFERENCES 622
EXERCISES 623
A Conversionof Units 625
B Fundamental Constants 627
|
| adam_txt |
Contents
Preface v
1 Introductory Concepts 1
1.1 Basic Definitions 1
1.1.1 Polymer 1
1.1.2 Monomer 2
1.1.3 Molecular Weight and Molar Mass 3
1.1.4 EndGroups 4
1.1.5 Degree of Polymerization 4
1.1.6 Copolymers 4
1.2 Polymerization and Functionality 6
1.3 Polymerization Processes 7
1.3.1 Addition or Chain Polymerization 7
1.3.2 Step Polymerization 11
1.3.3 Supramolecular Polymerization 14
1.4 Molecular Architecture 19
1.5 Classification of Polymers 23
1.5.1 Thermoplastics and Thermosets 24
1.6 Plastics, Fibers, and Elastomers 28
1.7 Polymer Nomenclature 31
REFERENCES 34
EXERCISES 34
2 Chain Dimensions, Structures, and Transitional Phenomena 37
2.1 Introduction 37
2.2 Polymer Chains: Structures and Dimensions 37
2.2.1 Conformational Changes 38
2.2.1.1 Polyethylene 39
2.2.1.2 Polyisobutylene 41
ix
x Contents
2.2.1.3 Polypropylene 42
2.2.2 Polymer Conformations in Crystals 43
2.2.3 Polymer Size in the Amorphous State 45
2.2.3.1 Freely Jointed Chains 45
2.2.3.2 Real Polymer Chains 47
2.3 Constitutional and Configurational Isomerism 51
2.3.1 Constitutional Isomerism 51
2.3.2 Configurational Isomerism 54
2.3.2.1 Geometrical Isomerism 54
2.3.2.2 Stereoisomerism 55
Optical Activity in Polymers 55
Tacticity in Polymers 56
Meso- and Racemic Placements 57
NMR Measurement of Tacticity 61
2.4 Crystallinity in Polymers 63
2.4.1 Structure of Bulk Polymers 64
2.4.1.1 Spherulites 66
2.5 Thermal Transitions in Polymers 68
2.5.1 TgandTm 68
2.5.2 First-and Second-Order Transitions 69
2.6 Regions of Viscoelastic Behavior 70
2.7 Factors Affecting Tg 74
2.8 Factors Affecting Tm 75
2.9 Relation Between Tm and Tg 76
2.10 Theoretical Treatment of Glass Transition 77
2.10.1 Quantitative Effects of Factors on Tg 83
2.11 Chain Movements in Amorphous State 89
2.11.1 The Reptation Model 91
2.12 Thermodynamics of Rubber Elasticity 93
2.12.1 Stress-Strain Behavior of Crosslinked Elastomers 95
2.12.2 Nonideal Networks 101
2.12.2.1 Network Defects 101
2.12.2.2 Elastically Active Chain Sections 101
REFERENCES 103
EXERCISES 104
3 Polymers in Solution 111
3.1 Introduction 111
3.2 Thermodynamics of Liquid Mixtures 111
3.2.1 Low-Molecular-Weight Mixtures: van Laar Model . 114
3.2.2 Polymer-Solvent Mixtures: Flory-Huggins Model . 118
Contents xi
3.2.2.1 Flory-Huggins Expressions for Thermodynamic
Functions 122
3.2.2.2 Colligative Properties and Interaction Parame¬
ter^ 124
Relative Vapor Pressure and \ 125
Osmotic Pressure and^ 127
3.2.2.3 Virial Coefficients 129
Virial Coefficient and^ 130
3.2.2.4 Modification of Flory-Huggins Theory 131
Significance of t// and k 132
Methods to Determine Theta Solvents 133
3.2.2.5 Flory-Krigbaum Theory 133
3.2.2.6 Excluded Volume Theory 134
Expansion Factor 136
3.3 Phase Equilibria in Poor Solvents 139
3.3.1 Upper and Lower Critical Solution Temperatures 143
3.4 Solubility Behavior of Polymers 144
3.5 Swelling of Crossslinked Polymers 153
3.5.1 Determination of^-from Swelling 157
3.6 Frictional Properties of Polymer Molecules
in Dilute Solution 159
3.6.1 Viscosity of Dilute Polymer Solutions 160
3.6.1.1 Determination of Polymer Molecular Dimen-
sions from Viscosity 164
REFERENCES 168
EXERCISES 169
4 Polymer Molecular Weights 177
4.1 Introduction 177
4.2 Molecular Weight Averages 178
4.2.1 Arithmetic Mean 178
4.2.2 Number-Average Molecular Weight 178
4.2.3 Weight-Average Molecular Weight 180
4.3 Molecular Weights in Terms of Moments 181
4.3.1 Ratio of First and Zeroth Moments 183
4.3.2 Ratios of Higher Moments 184
4.4 Molecular Weight Determination 185
4.4.1 End-Group Analysis 186
4.4.2 Colligative Property Measurement 188
4.4.2.1 Ebulliometry (Boiling Point Elevation) 188
4.4.2.2 Cryoscopy (Freezing Point Depression) 188
xji Contents
4.4.2.3 Membrane Osmometry 189
Virial Equations 192
Practical Aspects of Osmometry 193
4.4.2.4 Vapor-Phase Osmometry 197
Practical Aspects 198
4.4.3 Light-Scattering Method 200
4.4.3.1 Rayleigh Ratio 200
4.4.3.2 Turbidity and Rayleigh Ratio 202
4.4.3.3 Turbidity and Molecular Weight of Polymer . . 204
4.4.3.4 Dissymmetry of Scattering 208
Intraparticle Interference 208
Scattering Factor 211
4.4.3.5 ZimmPlots 211
4.4.4 Dilute Solution Viscometry 214
4.4.4.1 Calibration of the Mark-Hou wink-Sakurada Equa-
tion 217
4.4.4.2 Measurement of Intrinsic Viscosity 218
4.4.5 Gel Permeation Chromatography 222
4.4.5.1 Data Interpretation and Calibration 224
REFERENCES 229
EXERCISES 230
5 Condensation (Step-Growth) Polymerization 235
5.1 Introduction 235
5.2 Rates of Polycondensation Reactions 236
5.2.1 Irreversible Polycondensation Kinetics 237
5.2.2 Reversible Polycondensation Kinetics 245
5.3 Number-Average Degree of Polymerization 247
5.4 Controlof Molecular Weight 250
5.4.1 Quantitative Effect of Stoichiometric Imbalance 252
5.5 Molecular Weight Distribution (MWD) 256
5.5.1 BreadthofMWD 258
5.6 Nonlinear Step Polymerization 266
5.6.1 Branching 266
5.6.2 Crosslinking and Gelation 267
Average Functionality Approach 269
5.6.2.1 Statistical Approach 271
Systems withone type ofbranchunit 271
Systems withdifferenttypesof branchunits . . . 276
5.6.2.2 Model for Gelation Process 280
5.6.2.3 Molecular Size Distribution 280
Contents xiii
5.6.2.4 Post-gel Relations 283
5.7 Recursive Approach for Average Properties 285
5.7-1 Linear Step-Growth Polymerization 285
5.7.2 Nonlinear Step-Growth Polymerization 289
5.7.2.1 Polymerization of A/(/ 2) 289
5.7.2.2 Polymerization ofA/(/ 2) +B2 291
5.7.2.3 Polymerization of 2 A, + £B; 293
5.7.3 Post-gel Properties 297
5.7.3.1 Polymerization of A/ 297
Gel-point Conversion 297
Weight Fraction Solubles and Crosslink Density . 299
5.7.3.2 Polymerization of A/+ B2 301
5.8 Polycondensation of A^B Monomers 304
5.8.1 Dendritic and Hyperbranched Polymers 305
REFERENCES 307
EXERCISES 309
6 Free Radical Polymerization 315
6.1 Introduction 315
6.2 Scheme of Radical Chain Polymerization 316
6.2.1 Overall Scheme 316
6.2-2 Chain Initiation 317
6.2-3 Chain Propagation 318
6.2-4 Chain Termination 318
6.2-5 Rate of Polymerization 320
6.2-6 Overall Extent of Polymerization 322
6.3 Experimental Determination of Rp: Dilatometry 324
6.4 Methodsof Initiation 327
6.4.1 Thermal Decomposition of Initiators 328
6.4.1.1 Initiator Efficiency 328
Determination of Initiator Efficiency 332
6.4.2 Redox Initiation 333
6.4-3 Photochemical Initiation 336
6.4.3.1 Direct Photoinitiation 336
6.4.3.2 Photosensitization 337
6.4.3.3 Rate of Photoinitiated Polymerization 338
6.4.4 Initiation by High-Energy Radiations 340
6.4-5 Thermal Initiation in Absence of Initiator 341
6.5 Dead-End Polymerization 342
6.6 Determination of Absolute Rate Constants 344
6.6.1 Nonsteady-State Kinetics 345
xjv Contents
6.7 Chain Length and Degree of Polymerization 351
6.7.1 Kinetic Chain Length 351
6.7.2 Mode of Chain Termination 352
6.7.3 Average Lifetime of Kinetic Chains 354
6.8 Chain Transfer 355
6.8.1 Degree of Polymerization 358
6.8.2 Chain Transfer to Polymer 364
6.8.3 Allylic Transfer 366
6.9 Deviations from Ideal Kinetics 367
6.9.1 Primary Radical Termination 367
6.9.2 Initiator-Monomer Complex Formation 368
6.9.3 Degradative Initiator Transfer 369
6.9.4 Autoacceleration 371
6.10 Inhibition/Retardation of Polymerization 373
6.10.1 Inhibition/Retardation Kinetics 375
6.11 EffectsofTemperature 378
6.11.1 Rate of Polymerization 378
6.11.2 Degree of Polymerization 381
6.11.3 Polymerization-DepolymerizationEquilibrium 382
6.12 Molecular Weight Distribution 385
6.12.1 Low-Conversion Polymerization 386
6.12.1.1 Termination by Disproportionation and/or Trans¬
fer 386
6.12.1.2 Termination by Coupling 387
6.12.1.3 Termination by Coupling, Disproportionation
and Chain Transfer 388
6.12.2 High-Conversion Polymerization 390
6.13 Polymerization Processes 390
6.13.1 Emulsion Polymerization 392
6.13.1.1 Qualitative Picture 393
6.13.1.2 Kinetics of Emulsion Polymerization 396
Rate of Polymerization 398
Degree of Polymerization 400
6.13.1.3 Other Theories 403
6.13.2 Photoemulsion Polymerization 404
6.13.3 "Grafting-from" Polymerization 406
6.14 Living Radical Polymerization 408
6.14.1 Reversible Termination by Coupling 410
6.14.2 Atom Transfer Radical Polymerization 414
6.14.3 Degenerative Chain Transfer 414
6.14.4 Reversible Addition-Fragmentation Chain Transfer . . . .416
Contents xv
REFERENCES 417
EXERCISES 419
7 Chain Copolymerization 425
7.1 Introduction 425
7.2 Binary Copolymer Composition - Terminal Model 426
7.2.1 Significance of Monomer Reactivity Ratios 428
7.2.2 Types of Copolymerization 430
7.2.2.1 Alternating Copolymerization 430
7.2.2.2 Ideal (random) Copolymerization 430
7.2.2.3 Random-Alternating Copolymerization 431
7.2.2.4 Block Copolymerization 432
7.2.3 Instantaneous Copolymer Composition 432
7.2.4 Integrated Binary Copolymer Equation 435
7.2.5 Evaluation of Monomer Reactivity Ratios 439
7.2.5.1 Plotof r\ Versus T2 440
7.2.5.2 PlotofF\ Versus/i 440
7.2.5.3 Direct Curve Fitting 442
7.2.6 The Q-e Scheine 443
7.2.7 Sequence Length Distribution 445
7.2.8 Rate of Binary Free-Radical Copolymerization 449
7.3 Multicomponent Copolymerization: Terpolymerization 453
7.4 Deviations from Terminal Model 457
7.4.1 Penultimate Model 457
7.4.2 Complex-Participation Model 458
7.5 Copolymerization and Crosslinking 458
7.5.1 Vinyl and Divinyl Monomers of Equal Reactivity 459
7.5.2 Vinyl and Divinyl Monomers of Different Reactivities . .462
7.5.3 One Group of Divinyl Monomer Having Lower Reactivity 464
7.6 Block and Graft Copolymerization 465
7.6.1 Block Copolymerization 465
7.6.1.1 Producing Internal Peroxide Linkages 465
7.6.1.2 Introducing Peroxide End Groups 466
7.6.1.3 Mechanical Cleaving of Polymer Chains . 467
7.6.1.4 Controlled Radical Polymerization 467
7.6.2 Graft Copolymerization 467
7.6.2.1 Chain Transfer Methods 468
7.6.2.2 Irradiation with Ionizing Radiation 468
REFERENCES 470
EXERCISES 471
xvi Contents
8 lonic Chain Polymerization 475
8.1 Introduction 475
8.2 lonic Polymerizability of Monomers 477
8.3 Anionic Polymerization 479
8.3.1 Anionic Initiation 479
8.3.1.1 Nucleophilic Attack 479
8.3.1.2 Electron Transfer 481
Alkali Metals 481
Alkali Metal Complexes 481
8.3.2 Termination Reactions 483
8.3.2.1 Living Polymerization 483
8.3.2.2 Termination by Transfer Agents 484
8.3.2.3 Spontaneous Termination 485
8.3.3 Polymerization with Complete Dissociation of Initiator . .485
8.3.3.1 Polymerization Kinetics 486
8.3.3.2 Experimental Methods 487
8.3.3.3 Average Kinetic Chain Length 488
8.3.3.4 Average Degree of Polymerization 489
8.3.3.5 Distribution of the Degree of Polymerization . . 491
Polydispersity Index 494
8.3.3.6 EffectsofReaction Media 495
8.3.3.7 Effect of Excess Counterion 499
8.3.4 Polymerization with Incomplete Dissociation of Initiator . 502
8.3.5 Polymerization with Simultaneous Propagation and Ter¬
mination 503
8.4 Anionic Copolymerization 505
8.4.1 Reactivity Groups 506
8.4.2 Block Copolymers 508
8.4.2.1 Sequential Monomer Addition 509
Monofunctional Initiators 509
Bifunctional Initiators 510
8.4.2.2 Coupling Reactions 510
8.5 Cationic Polymerization 512
8.5.1 Cationic Initiation 513
8.5.1.1 Protonic Acids 513
8.5.1.2 Lewis Acids 513
8.5.2 Propagation of Cationic Chain 514
8.5.3 Chain Transfer and Termination 516
8.5.3.1 Chain Transfer to Monomer 516
8.5.3.2 Spontaneous Termination 516
8.5.3.3 Combination with Counterion 517
Contents xvü
8.5.3.4 Transfer to Solvents/Reagents 518
8.5.3.5 Chain Transfer to Polymer 519
8.5.4 Kinetics 520
8.5.4.1 Ions and Ion Pairs 520
8.5.4.2 Simplified Kinetic Scheme 521
8.5.4.3 Degree of Polymerization 527
8.5.5 Molecular Weight Distribution 529
8.5.6 Cationic Copolymerization 531
REFERENCES 532
EXERCISES 534
9 Coordination Addition Polymerization 539
9.1 Introduction 539
9.2 Ziegler-Natta Catalysts 540
9.2.1 Catalyst Composition 540
9.2.2 Natureofthe Catalyst 541
9.2.3 Evolution of the Titanium-Aluminum System 542
9.3 Mechanism of Ziegler-Natta Polymerization 543
9.3.1 Mechanism of Stereospecific Placement 543
9.3.2 Bimetallic and Monometallic Mechanisms 544
9.3.2.1 Bimetallic Mechanism 545
9.3.2.2 Monometallic Mechanism 545
Stereoregulation 549
9.4 Kinetics of Ziegler-Natta Polymerization 549
9.4.1 Typical Shapes of Kinetic Curves 549
9.4.2 Effectof Catalyst Particle Size 551
9.4.3 Chain Termination 552
9.4.4 Kinetic Models 553
9.4.4.1 Early Models 553
Chain Initiation 553
Chain Propagation 553
Chain Transfer 553
9.4.4.2 Adsorption Models 556
9.4.4.3 Average Degree of polymerization 569
9.5 Supported Metal Oxide Catalysts 569
9.5.1 Polymerization Mechanism 570
9.5.1.1 Bound-Ion-Radical Mechanism 570
9.5.1.2 Bound-Ion-Coordination Mechanism 574
9.6 Ziegler-Natta Copolymerization 575
9.7 Metallocene-Based Ziegler-Natta Catalysts 577
9.7.1 Catalyst Composition 578
xviü Contents
9.7.2 The Active Center 580
9.7.3 Polymerization Mechanism 581
9.7.4 Kinetic Models 581
9.7.4.1 Ewen's Model 581
9.7.4.2 Chien's Model 583
9.7.4.3 Molecular Weight and Chain Transfer 585
jß-Hydrogen Elimination 586
Chain Transfer by Monomer 586
Chain Transfer to MAO 586
y3-CH3 Elimination 586
9.8 Immobilized Metallocene Catalysts 587
9.9 Oscillating Metallocene Catalysts 590
REFERENCES 591
EXERCISES 594
10 Ring-Opening Polymerization 597
10.1 Introduction 597
10.2 Polymerization Mechanism and Kinetics 599
10.2.1 Cyclic Ethers/Epoxides 600
10.2.1.1 Anionic Polymerization 600
Kinetics 601
Exchange Reactions 604
10.2.1.2 Cationic Polymerization 605
Chain Initiation and Propagation 605
Chain Transfer and Termination 608
Kinetics 608
Degree of Polymerization 611
10.2.2 Lactams 614
10.2.2.1 Hydrolytic Polymerization 614
Kinetics 616
10.2.2.2 Anionic Polymerization 617
10.2.3 Lactones 620
REFERENCES 622
EXERCISES 623
A Conversionof Units 625
B Fundamental Constants 627 |
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| id | DE-604.BV022884534 |
| illustrated | Illustrated |
| index_date | 2024-07-02T18:51:32Z |
| indexdate | 2024-07-09T21:07:42Z |
| institution | BVB |
| isbn | 0849373840 9780849373848 |
| language | English |
| lccn | 006040490 |
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| physical | XVIII, 640 S. Ill., graph. Darst. |
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| spelling | Chanda, Manas 1940- Verfasser (DE-588)136724868 aut Introduction to polymer science and chemistry a problem solving approach Manas Chanda Boca Raton, Fla. [u.a.] CRC 2006 XVIII, 640 S. Ill., graph. Darst. txt rdacontent n rdamedia nc rdacarrier Includes bibliographical references and index Polymerization Polymerization Problems, exercises, etc Polymers Polymers Problems, exercises, etc Polymerisation (DE-588)4046704-1 gnd rswk-swf Polymere (DE-588)4046699-1 gnd rswk-swf Polymere (DE-588)4046699-1 s 1\p DE-604 Polymerisation (DE-588)4046704-1 s 2\p DE-604 HBZ Datenaustausch application/pdf http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=016089460&sequence=000002&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA Inhaltsverzeichnis 1\p cgwrk 20201028 DE-101 https://d-nb.info/provenance/plan#cgwrk 2\p cgwrk 20201028 DE-101 https://d-nb.info/provenance/plan#cgwrk |
| spellingShingle | Chanda, Manas 1940- Introduction to polymer science and chemistry a problem solving approach Polymerization Polymerization Problems, exercises, etc Polymers Polymers Problems, exercises, etc Polymerisation (DE-588)4046704-1 gnd Polymere (DE-588)4046699-1 gnd |
| subject_GND | (DE-588)4046704-1 (DE-588)4046699-1 |
| title | Introduction to polymer science and chemistry a problem solving approach |
| title_auth | Introduction to polymer science and chemistry a problem solving approach |
| title_exact_search | Introduction to polymer science and chemistry a problem solving approach |
| title_exact_search_txtP | Introduction to polymer science and chemistry a problem solving approach |
| title_full | Introduction to polymer science and chemistry a problem solving approach Manas Chanda |
| title_fullStr | Introduction to polymer science and chemistry a problem solving approach Manas Chanda |
| title_full_unstemmed | Introduction to polymer science and chemistry a problem solving approach Manas Chanda |
| title_short | Introduction to polymer science and chemistry |
| title_sort | introduction to polymer science and chemistry a problem solving approach |
| title_sub | a problem solving approach |
| topic | Polymerization Polymerization Problems, exercises, etc Polymers Polymers Problems, exercises, etc Polymerisation (DE-588)4046704-1 gnd Polymere (DE-588)4046699-1 gnd |
| topic_facet | Polymerization Polymerization Problems, exercises, etc Polymers Polymers Problems, exercises, etc Polymerisation Polymere |
| url | http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=016089460&sequence=000002&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA |
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