Fundamentals of polymerization:
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| Format: | Book |
| Language: | English |
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New Jersey [u.a.]
World Scientific
2013
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| Online Access: | Inhaltsverzeichnis |
| Physical Description: | XXII, 445 S. graph. Darst. |
| ISBN: | 9789814322461 |
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| adam_text | Titel: Fundamentals of polymerization
Autor: Mandal, Broja Mohan
Jahr: 2013
Contents
Preface
List of Abbreviations
vn
xix
Chapter 1. Introduction 1
1.1 Nomenclature............................. 2
1.2 Structural and Repeating (or Repeat) Units.............. 3
1.3 Classification............................. 3
1.3.1 Condensation and addition polymers and polymerizations . 3
1.3.2 Step-growth and chain-growth polymers and
polymerizations ....................... 7
1.4 Functionality............................. 9
1.5 Designed Branched Polymers..................... 12
1.5.1 Star polymers......................... 12
1.5.2 Hyperbranched polymers................... 13
1.5.3 Dendrimers.......................... 14
1.6 Physical State............................. 14
1.7 Structure-Property Relationship.................... 17
1.7.1 Nonconjugated polymers................... 17
1.7.1.1 Stereoregularity in vinyl polymers........ 23
1.7.1.2 Regioregularity in vinyl polymers........ 24
1.7.2 Conjugated polymers..................... 25
1.8 Thermodynamics of Polymerization................. 28
1.9 Polymerizability of Internal Olefins.................. 30
1.10 Molecular Weights and Molecular Weight Distributions....... 31
References.................................. 33
Problems................................... 35
Chapter 2. Step Polymerization 37
2.1 Principle of Equal Reactivity of Functional Groups and
Kinetics of Polymerization...................... 37
2.2 Ring vs. Chain Formation....................... 41
2.3 Intermolecular Interchange Reactions ................ 46
Fundamentals of Polymerization
2.4 Degree of Polymerization....................... 47
2.4.1 Carothers equation...................... 47
2.4.1.1 Bifunctional polycondensation.......... 48
2.4.1.2 Control of degree of polymerization....... 49
2.4.1.2.1 Polymerization of nonequivalent
monomer mixtures......... 49
2.4.1.2.2 Departure from Carothers equation
in interfacial polycondensation ... 51
2.5 Molecular Weight Distribution.................... 52
2.5.1 Molecular weight distribution in bifunctional
polycondensation....................... 52
2.5.2 Average degree of polymerization for most probable
distribution.......................... 55
2.6 Prediction of Gel Point in Polyfunctional Polycondensation..... 56
2.6.1 Prediction based on Carothers equation........... 56
2.6.2 Prediction based on Statistical method of Flory....... 59
2.6.2.1 Gel-forming ränge of monomer proportions ... 61
2.6.2.1.1 Polycondensation of Af and B-B
monomers.............. 62
2.6.2.1.2 Polymerization of a ternary mixture
ofA-A, B-B, and A3 monomers . . 62
2.7 Thermosetting Resins......................... 62
2.7.1 Phenolic resins........................ 62
2.7.2 Amino resins......................... 65
2.7.3 Unsaturated polyesters and alkyd resins........... 66
2.7.4 Polyurethanes and polyureas................. 67
2.7.5 Epoxy resins......................... 69
2.7.6 Polysiloxanes......................... 70
2.7.7 Aliphatic polysulfides .................... 72
2.8 Engineering Plastics.......................... 72
2.8.1 Polyamides.......................... 74
2.8.1.1 Aliphatic polyamides............... 74
2.8.1.2 Aromatic polyamides............... 75
2.8.2 Polyesters........................... 76
2.8.2.1 Aliphatic-aromatic polyesters.......... 77
2.8.2.2 Aromatic polyesters ............... 78
2.8.3 Polycarbonates........................ 79
2.8.4 Poly(phenylene oxide)s ................... 80
2.9 High Performance Polymers ..................... 81
2.9.1 Liquid crystalline polymers (LCPs)............. 81
2.9.2 Poly(p-phenylene sulfide).................. 83
2.9.3 Poly(arylene ether)s..................... 83
Contents xj
2.9.4 Polyimides.......................... 84
2.9.4.1 Thermoplastic polyimides............ 85
2.9.4.2 Thermosetting polyimides............ 86
2.9.5 Polybenzimidazoles..................... 87
2.9.6 Polybenzoxazoles and polybenzothiazoles.......... 88
2.10 Nonconventional Step Polymerization................ 88
References.................................. 90
Problems................................... 95
Chapter 3. Radical Polymerization 97
3.1 General Features ........................... 97
3.1.1 Monomer types........................ 97
3.1.2 Reactivity of monomers and radicals ............ 98
3.2 Kinetics of Homogeneous Radical Polymerization.......... 99
3.3 Reaction Orders in Initiator and Monomer.............. 104
3.4 Initiators................................ 105
3.4.1 Thermal initiators ...................... 106
3.4.2 Photoinitiators........................ 107
3.4.3 Redox initiators ....................... 108
3.5 Determination of Polymer End Groups................ 110
3.6 Initiator Efficiency........................... 111
3.7 Thermal Polymerization and its Kinetics............... 112
3.8 Kinetic Chain Length, Degree of Polymerization, and Chain Transfer 113
3.8.1 The general DP equation................... 114
3.8.1.1 Solvent transfer.................. 115
3.8.1.2 Monomer transfer................ 116
3.8.1.3 Initiator transfer................. 118
3.8.1.4 Regulator transfer................ 120
3.8.1.5 Addition-fragmentation chain transfer (AFCT) . 120
3.8.1.6 Polymer transfer................. 121
3.8.1.7 Redox transfer.................. 122
3.8.1.8 Catalytic chain transfer (CCT).......... 123
3.8.1.9 Instantaneous chain length distribution (CLD)
and chain transfer ................ 123
3.8.2 Factors influencing chain transfer.............. 124
3.8.2.1 Quantifying the resonance and polar effects ... 126
3.8.2.1.1 The Q,e Scheme.......... 126
3.8.2.1.2 The radical reactivity pattern
scheme............... 127
3.8.3 Telomerization........................ 128
3.9 Inhibition and Retardation of Polymerization............. 129
3.9.1 Oxidative and reductive termination............. 131
Fundamentals of Polymerization
3.9.2 Oxygen as an inhibitor.................... 133
3.10 Rate Constants of Propagation and Termination........... 133
3.10.1 The PLP-SEC method.................... 136
3.10.2 The single pulse-pulsed laser polymerization (SP-PLP)
method for determining kt.................. 138
3.10.3 Propagation rate constants.................. 139
3.10.4 Termination rate constants.................. 140
3.10.5 Variation of kt with monomer conversion.......... 141
3.10.6 Chain length dependence of kp and kt............ 142
3.10.7 Temperature dependence of rate of polymerization
and molecular weight .................... 142
3.11 The Course of Polymerization and Gel Effect ............ 143
3.12 Popcorn Polymerization........................ 144
3.13 Dead End Polymerization....................... 144
3.14 Molecular Weight Distribution.................... 145
3.15 Living Radical Polymerization (LRP) ................ 148
3.15.1 Persistent radical effect in reversible deactivation...... 151
3.15.2 Kinetic equations for LRP with reversible deactivation . . . 153
3.15.2.1 Gel effect in living radical polymerization . . . . 154
3.15.3 Molecular weight....................... 155
3.15.3.1 Molecular weight distribution and polydispersity
index....................... 156
3.15.4 Nitroxide mediated polymerization............. 158
3.15.4.1 Selection of initiator............... 161
3.15.4.2 Polymerization of styrene............ 162
3.15.4.3 Polymerization of (meth)acrylates and other
monomers .................... 164
3.15.4.4 Rate constants and equilibrium constants .... 165
3.15.4.5 Synthesis of block copolymers.......... 166
3.15.5 Metalloradical mediated polymerization........... 167
3.15.6 Atom transfer radical polymerization............ 167
3.15.6.1 Initiators..................... 168
3.15.6.1.1 Halide exchange effect....... 171
3.15.6.2 Ligands...................... 172
3.15.6.3 Solvents ..................... 174
3.15.6.4 Kinetics of ATRP................. 175
3.15.6.5 Molecular weight and polydispersity ...... 178
3.15.6.6 Effect of temperature............... 178
3.15.6.7 ATRP with activator generated in situ...... 179
3.15.6.7.1 Reverse ATRP ........... 179
3.15.6.7.2 SR and NI ATRP.......... 180
3.15.6.7.3 AGETATRP............ 180
Contents xjjj
3.15.6.7.4 ARGETATRP........... 181
3.15.6.7.5 ICARATRP............. 182
3.15.6.8 Synthesis of high molecular weight polymers . . 182
3.15.6.9 Synthesis of block copolymers.......... 184
3.15.7 Reversible addition-fragmentation chain transfer (RAFT)
polymerization........................ 186
3.15.7.1 Tuning the RAFT agent............. 188
3.15.7.1.1 Selection ofZgroup........ 188
3.15.7.1.2 Selection ofRgroup........ 190
3.15.7.2 Kinetics of RAFT polymerization........ 192
3.15.7.2.1 Retardation............. 193
3.15.7.2.2 Chain transfer constant....... 195
3.15.7.2.3 Rate constant for exchange
and activation............ 197
3.15.7.3 Synthesis of block copolymers.......... 198
3.15.7.4 Star polymers................... 198
References.................................. 199
Problems................................... 211
Chapter 4. Anionic Polymerization 213
4.1 Living Anionic Polymerization.................... 214
4.1.1 General features....................... 214
4.1.1.1 Molecular weight and molecular weight
distribution.................... 216
4.1.1.2 Long term stability of living polymers...... 218
4.1.1.3 Initiators..................... 219
4.1.1.3.1 Initiation by nucleophile addition . 219
4.1.1.3.2 Initiation by electron transfer from
alkali or alkaline earth metal .... 219
4.1.1.3.3 Initiation by electron transfer from
aromatic radical anions....... 220
4.1.1.3.4 Electron transfer initiation
by electrochemical means ..... 222
4.1.2 Living anionic polymerization of nonpolar monomers
in hydrocarbon solvents................... 222
4.1.2.1 Kinetics...................... 223
4.1.2.2 Effect of additives................ 225
4.1.2.3 Living anionic polymerization at elevated
temperatures - retarded anionic polymerization 226
4.1.2.4 Stereospecificity................. 226
4.1.3 Living Anionic Polymerization of Styrene in Ethereal
Solvents ........................... 227
xiv Fundamentals of Polymerization
4.1.3.1 Kinetics...................... 227
4.1.3.2 Temperature dependence of k* ......... 233
4.1.3.3 Ion association beyond ion-pair......... 235
4.1.4 Living anionic polymerization of polar monomers ..... 236
4.1.4.1 Side reactions................... 236
4.1.4.2 Living anionic polymerization of methyl
methacrylate in polar solvents in the absence of
additives..................... 237
4.1.4.2.1 Nature of ion pairs and their
aggregates.............. 238
4.1.4.2.2 Rate constants of propagation . . . 239
4.1.4.3 Ligated living anionic polymerization...... 240
4.1.5 End functionalized polymers................. 242
4.1.6 Synthesis of block copolymers................ 243
4.1.7 Synthesis of star polymers.................. 244
4.1.8 Synthesis of comb polymers................. 246
4.1.9 Group transfer polymerization................ 247
4.1.10 Metal-free living anionic polymerization.......... 250
References.................................. 251
Problems................................... 257
Chapter 5. Coordination Polymerization 259
5.1 Ziegler-Natta Catalysts........................ 259
5.1.1 Isotactic polypropylene ................... 260
5.1.2 Syndiotactic polypropylene ................. 263
5.1.3 Polyethylene and ethylene copolymers ........... 264
5.1.4 Polymerization of conjugated dienes............. 264
5.1.5 Degree of stereoregularity.................. 265
5.1.6 Mechanism.......................... 266
5.1.6.1 Isotactic propagation............... 267
5.1.6.2 Syndiotactic propagation............. 271
5.1.7 Polymerization of acetylene................. 272
5.1.8 Chain transfer and regulation of molecular weight..... 272
5.1.9 Branching in Polyethylene.................. 273
5.2 Metallocene Catalysts......................... 274
5.2.1 Mechanism of activation................... 275
5.3 Late Transition Metal Catalysts.................... 276
5.4 Living Polymerization of Alkenes................... 279
References.................................. 279
Problems................................... 283
Chapter 6. Cationic Polymerization 285
6.1 The Nucleophilicity and Electrophilicity Scales........... 285
Contents xv
6.2 Bronsted Acids as Initiators...................... 286
6.3 Lewis Acids as Coinitiators...................... 289
6.3.1 Controlled initiation..................... 290
6.3.2 Controlled termination.................... 291
6.3.3 Chain transfer ........................ 291
6.3.4 Molecular weight dependence on temperature
of polymerization....................... 296
6.3.5 Reversible termination.................... 296
6.3.6 Living carbocationic polymerization............. 298
6.3.6.1 Selection of initiator............... 299
6.3.6.2 Effect of added nucleophiles, proton traps,
and common anion salts............. 301
6.3.6.3 Test of livingness................. 303
6.3.6.4 Kinetics...................... 305
6.3.6.5 Molecular weight and molecular weight
distribution.................... 306
6.3.6.6 Block copolymerization............. 308
6.4 End Functionalized Polymers..................... 308
6.4.1 Living polymerization method................ 308
6.4.2 Inifermethod......................... 309
6.5 Photoinitiated Cationic Polymerization................ 310
6.6 Propagation Rate Constants...................... 311
6.6.1 The diffusion clock method................. 311
6.6.1.1 Competition experiment (method 1)....... 311
6.6.1.2 Competition experiment (method 2)....... 313
6.6.2 Values of rate constants of propagation ........... 314
References.................................. 314
Problems................................... 321
Chapter 7. Ring-Opening Polymerization and Ring-Opening
Metathesis Polymerization 323
7.1 General Features ........................... 324
7.1.1 Polymerizability....................... 324
7.1.2 Ring-chain equilibrium.................... 326
7.1.3 The nature and reactivity of propagating species ...... 327
7.1.4 Backbiting and intermolecular interchange......... 328
7.1.5 Bridged cyclic monomers.................. 330
7.2 Cyclic Ethers............................. 331
7.2.1 Anionic polymerization ................... 331
7.2.1.1 Kinetics...................... 333
7.2.2 Cationic polymerization................... 334
7.2.2.1 Kinetics...................... 336
xvi Fundamentals of Polymerization
7.2.2.1.1 Macroion-macroester interconversion 339
7.2.2.2 Backbiting and intermolecular interchange . . . 339
7.2.3 Activated monomer mechanism of polymerization..... 340
7.3 Cyclic Acetals............................. 342
7.4 Cyclic Esters ............................. 343
7.4.1 Anionic polymerization ................... 344
7.4.2 Coordination polymerization................. 345
7.4.2.1 Backbiting and intermolecular interchange . . . 348
7.4.3 Cationic polymerization................... 349
7.4.4 Enzymatic polymerization.................. 349
7.5 Lactams................................ 350
7.5.1 Anionic polymerization ................... 350
7.5.2 Cationic polymerization................... 351
7.5.3 Hydrolytic polymerization.................. 352
7.6 N-Carboxy-a-aminoacid Anhydrides................. 353
7.7 Oxazolines (Cyclic Imino Ethers)................... 355
7.8 Cyclic Amines............................. 355
7.9 Cyclic Sulfides ............................ 356
7.10 Cyclosiloxanes ............................ 357
7.10.1 Anionic polymerization ................... 357
7.10.2 Cationic polymerization................... 358
7.11 Cyclotriphosphazenes......................... 359
7.12 Cyclic Olefins............................. 360
7.12.1 Initiators........................... 361
7.12.2 Livimg character....................... 362
7.12.3 Initiators with high functional group tolerance ....... 363
7.12.4 Synthesis of polyacetylene.................. 363
7.12.5 Backbiting and intermolecular interchange......... 364
7.12.6 Alicyclic diene metathesis (ADMET) polymerization . . . . 364
References.................................. 365
Problems................................... 371
Chapter 8. Chain Copolymerization 373
8.1 Terminal Model of Copolymerization................. 374
8.1.1 Copolymer composition equation.............. 374
8.1.1.1 Types of Copolymerization ........... 377
8.1.1.2 Determination of monomer reactivity ratios . . . 381
8.1.1.3 Substituent effect on monomer reactivity .... 382
8.1.1.4 Substituent effect on radical reactivity...... 383
8.1.1.5 Resonance and polar effects in radical addition . 384
8.1.1.5.1 Q, e Scheme ............ 384
8.1.1.5.2 The revised pattern scheme..... 386
Contents xvjj
8.1.2 Statistical treatmentof copolymerization.......... 386
8.1.2.1 Monomer sequence distribution......... 388
8.1.2.1.1 Triad fractions and monomer
reactivity ratios........... 389
8.1.3 Kinetics of radical copolymerization based on terminal
model............................. 392
8.1.4 Ionic copolymerization.................... 393
8.1.5 Validity of the terminal model................ 395
8.2 Penultimate Model of Copolymerization............... 395
8.2.1 Mean rate constant of propagation.............. 397
8.2.2 The copolymer composition equation............ 399
8.3 Living Radical Copolymerization................... 400
References.................................. 402
Problems................................... 405
Chapter 9. Heterophase Polymerization 407
9.1 Particle Stabilization Mechanisms .................. 407
9.2 Suspension Polymerization...................... 409
9.3 Emulsion Polymerization....................... 410
9.3.1 The three periods of polymerization............. 413
9.3.2 Harkins qualitative theory.................. 413
9.3.3 Quantitative theory of Smith and Ewart........... 414
9.3.4 Applicability of Smith-Ewart theory with oil soluble
initiators........................... 416
9.3.5 Number density of particles................. 417
9.3.6 Particle nucleation in the aqueous phase........... 417
9.4 Inverse Emulsion Polymerization................... 419
9.5 Miniemulsion Polymerization..................... 419
9.6 Microemulsion Polymerization.................... 420
9.7 Dispersion Polymerization...................... 421
9.8 Heterophase Living Radical Polymerization............. 422
References.................................. 3
Problems................................... 427
Index 429
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| spelling | Mandal, Broja M. Verfasser aut Fundamentals of polymerization Broja M. Mandal New Jersey [u.a.] World Scientific 2013 XXII, 445 S. graph. Darst. txt rdacontent n rdamedia nc rdacarrier Polymerisation (DE-588)4046704-1 gnd rswk-swf Polymerisation (DE-588)4046704-1 s DE-604 HBZ Datenaustausch application/pdf http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=025175493&sequence=000002&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA Inhaltsverzeichnis |
| spellingShingle | Mandal, Broja M. Fundamentals of polymerization Polymerisation (DE-588)4046704-1 gnd |
| subject_GND | (DE-588)4046704-1 |
| title | Fundamentals of polymerization |
| title_auth | Fundamentals of polymerization |
| title_exact_search | Fundamentals of polymerization |
| title_full | Fundamentals of polymerization Broja M. Mandal |
| title_fullStr | Fundamentals of polymerization Broja M. Mandal |
| title_full_unstemmed | Fundamentals of polymerization Broja M. Mandal |
| title_short | Fundamentals of polymerization |
| title_sort | fundamentals of polymerization |
| topic | Polymerisation (DE-588)4046704-1 gnd |
| topic_facet | Polymerisation |
| url | http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=025175493&sequence=000002&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA |
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