Contents |
|
v | |
Index to Tables |
|
xvi | |
Index to Figures |
|
xx | |
Preface to the First Edition |
|
xxiii | |
Preface to the Second Edition |
|
xxv | |
Acknowledgments |
|
xxvi | |
|
|
1 | (10) |
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8 | (3) |
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|
11 | (38) |
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|
11 | (1) |
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12 | (4) |
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|
12 | (2) |
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|
14 | (1) |
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|
14 | (2) |
|
Addition to Carbon-Carbon Double Bonds |
|
|
16 | (13) |
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|
19 | (2) |
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|
21 | (1) |
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|
22 | (1) |
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|
23 | (1) |
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|
24 | (1) |
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|
24 | (1) |
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|
24 | (1) |
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|
25 | (1) |
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|
26 | (2) |
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|
28 | (1) |
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|
29 | (7) |
|
Bond Dissociation Energies |
|
|
30 | (1) |
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|
30 | (1) |
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|
31 | (1) |
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|
32 | (1) |
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|
33 | (1) |
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|
34 | (2) |
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|
36 | (1) |
|
Radical-Radical Reactions |
|
|
36 | (8) |
|
|
37 | (1) |
|
Pathways for Disproportionation |
|
|
38 | (1) |
|
Combination vs Disproportionation |
|
|
39 | (1) |
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|
39 | (1) |
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|
40 | (1) |
|
|
41 | (1) |
|
Stereoelectronic and other factors |
|
|
41 | (1) |
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|
42 | (1) |
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|
43 | (1) |
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|
44 | (5) |
|
|
49 | (118) |
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|
49 | (1) |
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|
50 | (14) |
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|
51 | (3) |
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|
54 | (1) |
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Reaction with Solvents, Additives, or Impurities |
|
|
55 | (1) |
|
Effects of Temperature and Reaction Medium on Radical Reactivity |
|
|
55 | (1) |
|
|
56 | (1) |
|
Initiator Efficiency in Thermal Initiation |
|
|
57 | (1) |
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|
58 | (2) |
|
Cage Reaction and Initiator-Derived Byproducts |
|
|
60 | (1) |
|
Primary Radical Termination |
|
|
61 | (1) |
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|
62 | (1) |
|
Initiation in Heterogeneous Polymerization |
|
|
63 | (1) |
|
|
64 | (47) |
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|
68 | (1) |
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|
68 | (4) |
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|
72 | (2) |
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Photochemical decomposition |
|
|
74 | (1) |
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|
74 | (3) |
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|
77 | (1) |
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|
78 | (1) |
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|
79 | (3) |
|
Diacyl or diaroyl peroxides |
|
|
82 | (1) |
|
|
82 | (1) |
|
Photochemical decomposition |
|
|
83 | (1) |
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|
84 | (1) |
|
Transfer to initiator and induced decomposition |
|
|
85 | (1) |
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|
85 | (2) |
|
Dialkyl peroxydicarbonates |
|
|
87 | (1) |
|
|
88 | (1) |
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|
88 | (2) |
|
Photochemical decomposition |
|
|
90 | (1) |
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|
90 | (2) |
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|
92 | (1) |
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|
93 | (1) |
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|
94 | (2) |
|
|
96 | (1) |
|
Multifunctional Initiators |
|
|
96 | (1) |
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|
97 | (1) |
|
Non-concerted decomposition |
|
|
97 | (1) |
|
|
98 | (1) |
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Aromatic carbonyl compounds |
|
|
98 | (1) |
|
Benzoin and related compounds |
|
|
99 | (3) |
|
Carbonyl compound-tertiary amine systems |
|
|
102 | (1) |
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103 | (1) |
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|
104 | (1) |
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Metal complex-organic halide redox systems |
|
|
104 | (1) |
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105 | (1) |
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|
106 | (1) |
|
Styrene homopolymerization |
|
|
107 | (2) |
|
Acrylate homopolymerization |
|
|
109 | (1) |
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110 | (1) |
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111 | (22) |
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|
112 | (1) |
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|
112 | (1) |
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113 | (4) |
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|
117 | (1) |
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|
117 | (1) |
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|
118 | (1) |
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|
118 | (1) |
|
|
119 | (5) |
|
|
124 | (1) |
|
Primary and secondary alkoxy radical |
|
|
125 | (1) |
|
Acyloxy and alkoxycarbonyloxy radicals |
|
|
125 | (1) |
|
|
126 | (1) |
|
Alkoxycarbonyloxy radicals |
|
|
127 | (1) |
|
|
128 | (1) |
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|
129 | (1) |
|
|
130 | (1) |
|
Other Heteroatom-Centered Radicals |
|
|
131 | (1) |
|
Silicon-centered radicals |
|
|
131 | (1) |
|
Sulfur- and selenium-centered radicals |
|
|
132 | (1) |
|
Phosphorus-centered radicals |
|
|
132 | (1) |
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|
133 | (16) |
|
|
133 | (1) |
|
|
133 | (1) |
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|
134 | (2) |
|
|
136 | (1) |
|
|
137 | (1) |
|
|
138 | (2) |
|
|
140 | (1) |
|
Direct Detection of End Groups |
|
|
141 | (1) |
|
Infra-red and UV-visible spectroscopy |
|
|
141 | (1) |
|
Nuclear magnetic resonance spectroscopy |
|
|
142 | (1) |
|
Electron paramagnetic resonance spectroscopy |
|
|
143 | (1) |
|
|
143 | (1) |
|
|
144 | (1) |
|
|
145 | (1) |
|
|
145 | (1) |
|
Stable isotopes and nuclear magnetic resonance |
|
|
146 | (3) |
|
|
149 | (18) |
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|
167 | (66) |
|
|
167 | (1) |
|
Stereosequence Isomerism - Tacticity |
|
|
168 | (8) |
|
Terminology and Mechanisms |
|
|
168 | (5) |
|
Experimental Methods for Determining Tacticity |
|
|
173 | (1) |
|
|
173 | (3) |
|
Regiosequence Isomerism - Head vs Tail Addition |
|
|
176 | (9) |
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|
176 | (2) |
|
|
178 | (1) |
|
|
179 | (1) |
|
|
180 | (1) |
|
|
181 | (1) |
|
|
182 | (1) |
|
Conjugated Diene Polymers |
|
|
182 | (2) |
|
|
184 | (1) |
|
Polychloroprene, polyisoprene |
|
|
184 | (1) |
|
Structural Isomerism - Rearrangement |
|
|
185 | (28) |
|
|
185 | (1) |
|
|
186 | (5) |
|
|
191 | (1) |
|
|
192 | (1) |
|
1,7-and higher 1, n-dienes |
|
|
193 | (1) |
|
|
194 | (1) |
|
Ring-Opening Polymerization |
|
|
194 | (2) |
|
Vinyl substituted cyclic compounds |
|
|
196 | (3) |
|
Methylene substituted cyclic compounds |
|
|
199 | (6) |
|
Double ring-opening polymerization |
|
|
205 | (3) |
|
Intramolecular Atom Transfer |
|
|
208 | (1) |
|
Polyethylene and copolymers |
|
|
208 | (3) |
|
|
211 | (1) |
|
Acrylate esters and other monosubstituted monomers |
|
|
211 | (1) |
|
Addition-abstraction polymerization |
|
|
212 | (1) |
|
Propagation Kinetics and Thermodynamics |
|
|
213 | (8) |
|
Polymerization Thermodynamics |
|
|
213 | (3) |
|
Measurement of Propagation Rate Constants |
|
|
216 | (2) |
|
Dependence of Propagation Rate Constant on Monomer Structure |
|
|
218 | (2) |
|
Chain Length Dependence of Propagation Rate Constants |
|
|
220 | (1) |
|
|
221 | (12) |
|
|
233 | (46) |
|
|
233 | (1) |
|
Radical-Radical Termination |
|
|
234 | (30) |
|
|
235 | (1) |
|
|
235 | (3) |
|
Molecular weights and molecular weight averages |
|
|
238 | (2) |
|
Molecular weight distributions |
|
|
240 | (2) |
|
Diffusion controlled termination |
|
|
242 | (2) |
|
Termination at low conversion |
|
|
244 | (4) |
|
Termination at medium to high conversions |
|
|
248 | (1) |
|
Termination in heterogeneous polymerization |
|
|
249 | (1) |
|
Termination during living radical polymerization |
|
|
250 | (1) |
|
Disproportionation vs Combination |
|
|
251 | (1) |
|
|
252 | (1) |
|
Polystyrene and derivatives |
|
|
253 | (2) |
|
Poly(alkyl methacrylates) |
|
|
255 | (1) |
|
|
256 | (2) |
|
|
258 | (1) |
|
|
258 | (2) |
|
|
260 | (1) |
|
Poly(alkyl methacrylates) |
|
|
261 | (1) |
|
|
262 | (1) |
|
|
262 | (1) |
|
|
262 | (1) |
|
|
263 | (1) |
|
|
263 | (1) |
|
|
263 | (1) |
|
Inhibition and Retardation |
|
|
264 | (9) |
|
|
267 | (1) |
|
|
268 | (1) |
|
|
269 | (1) |
|
|
270 | (1) |
|
|
271 | (1) |
|
|
272 | (1) |
|
Nitrones, Nitro- and Nitroso-Compounds |
|
|
272 | (1) |
|
|
273 | (1) |
|
|
273 | (6) |
|
|
279 | (1) |
|
|
279 | (54) |
|
|
279 | (1) |
|
|
279 | (46) |
|
Measurement of Transfer Constants |
|
|
283 | (4) |
|
|
287 | (1) |
|
Reversible chain transfer |
|
|
288 | (1) |
|
Homolytic Substitution Chain Transfer Agents |
|
|
289 | (1) |
|
|
290 | (1) |
|
|
291 | (1) |
|
|
292 | (1) |
|
|
293 | (1) |
|
Solvents and other reagents |
|
|
294 | (2) |
|
Addition-Fragmentation Chain Transfer Agents |
|
|
296 | (2) |
|
|
298 | (1) |
|
Allyl sulfides, sulfonates, halides, phosphonates, silanes |
|
|
299 | (4) |
|
|
303 | (2) |
|
|
305 | (3) |
|
Thionoester and related transfer agents |
|
|
308 | (1) |
|
Abstraction-Fragmentation Chain Transfer |
|
|
309 | (1) |
|
|
310 | (1) |
|
|
310 | (3) |
|
|
313 | (1) |
|
Cobalt porphyrin and related complexes |
|
|
313 | (1) |
|
|
313 | (1) |
|
|
314 | (1) |
|
|
315 | (1) |
|
|
315 | (1) |
|
|
316 | (1) |
|
|
317 | (1) |
|
|
318 | (1) |
|
|
318 | (1) |
|
|
319 | (1) |
|
|
320 | (1) |
|
|
321 | (1) |
|
Poly(alkyl methacrylates) |
|
|
321 | (1) |
|
|
322 | (1) |
|
|
323 | (2) |
|
|
325 | (1) |
|
|
325 | (1) |
|
|
325 | (1) |
|
|
325 | (8) |
|
|
333 | (80) |
|
|
333 | (2) |
|
|
335 | (1) |
|
Propagation in Statistical Copolymerization |
|
|
335 | (31) |
|
Propagation Mechanisms in Copolymerization |
|
|
337 | (1) |
|
|
337 | (5) |
|
|
342 | (1) |
|
|
342 | (2) |
|
Remote substituent effects on radical addition |
|
|
344 | (3) |
|
|
347 | (1) |
|
|
348 | (1) |
|
Origin of penultimate unit effects |
|
|
349 | (1) |
|
Models involving monomer complexes |
|
|
350 | (3) |
|
Copolymerization with depropagation |
|
|
353 | (1) |
|
|
354 | (1) |
|
Binary copolymerization according to the terminal model |
|
|
354 | (1) |
|
Binary copolymerization according to the penultimate model |
|
|
355 | (1) |
|
Binary copolymerization according to other models |
|
|
356 | (1) |
|
|
357 | (2) |
|
Estimation of Reactivity Ratios |
|
|
359 | (1) |
|
|
360 | (2) |
|
Monomer sequence distribution |
|
|
362 | (1) |
|
Prediction of Reactivity Ratios |
|
|
363 | (1) |
|
|
363 | (2) |
|
Patterns of reactivity scheme |
|
|
365 | (1) |
|
Termination in Statistical Copolymerization |
|
|
366 | (8) |
|
|
366 | (2) |
|
|
368 | (2) |
|
Combination and Disproportionation during Copolymerization |
|
|
370 | (1) |
|
Poly(methyl methacrylate-co-styrene) |
|
|
371 | (2) |
|
Poly(methacrylonitrile-co- styrene) |
|
|
373 | (1) |
|
Poly(butyl methacrylate-co-methacrylonitrile) |
|
|
374 | (1) |
|
Poly(butyl methacrylate-co-methyl methacrylate) |
|
|
374 | (1) |
|
Poly(ethylene-co-methacrylonitrile) |
|
|
374 | (1) |
|
Functional and End-Functional Polymers |
|
|
374 | (10) |
|
|
375 | (2) |
|
Functional Transfer Agents |
|
|
377 | (1) |
|
|
378 | (1) |
|
|
379 | (2) |
|
|
381 | (1) |
|
Compositional Heterogeneity in Functional Copolymers |
|
|
381 | (3) |
|
Block & Graft Copolymerization |
|
|
384 | (17) |
|
Polymeric and Multifunctional Initiators |
|
|
385 | (2) |
|
|
387 | (2) |
|
Radiation-Induced Grafting Processes |
|
|
389 | (1) |
|
Radical-Induced Grafting Processes |
|
|
390 | (2) |
|
Maleic anhydride graft polyolefins |
|
|
392 | (4) |
|
Maleate ester and maleimide graft polyolefins |
|
|
396 | (1) |
|
(Meth)acrylate graft polyolefins |
|
|
397 | (2) |
|
Styrenic graft polyolefins |
|
|
399 | (1) |
|
Vinylsilane graft polyolefins |
|
|
399 | (1) |
|
Vinyl oxazoline graft polyolefins |
|
|
400 | (1) |
|
Polymerization and Copolymerization of Macromonomers |
|
|
400 | (1) |
|
|
401 | (12) |
|
Controlling Polymerization |
|
|
413 | (38) |
|
|
413 | (1) |
|
Controlling Structural Irregularities |
|
|
414 | (7) |
|
``Defect Structures'' in Polystyrene |
|
|
414 | (3) |
|
``Defect Structures'' in Poly(methyl methacrylate) |
|
|
417 | (3) |
|
``Defect Structures'' in Poly(vinyl chloride) |
|
|
420 | (1) |
|
|
421 | (22) |
|
Organic Solvents and Water |
|
|
425 | (1) |
|
|
426 | (3) |
|
|
429 | (3) |
|
Supercritical Carbon Dioxide |
|
|
432 | (1) |
|
|
432 | (1) |
|
Lewis Acids and Inorganics |
|
|
433 | (1) |
|
|
433 | (2) |
|
|
435 | (2) |
|
|
437 | (1) |
|
Non-covalently bonded templates |
|
|
437 | (1) |
|
Covalently bonded templates |
|
|
438 | (2) |
|
Enzyme Mediated Polymerization |
|
|
440 | (1) |
|
Topological Radical Polymerization |
|
|
441 | (2) |
|
|
443 | (8) |
|
Living Radical Polymerization |
|
|
451 | (136) |
|
|
451 | (3) |
|
Living? Controlled? Mediated? |
|
|
451 | (1) |
|
Tests for Living (Radical) Polymerization |
|
|
452 | (2) |
|
Agents Providing Reversible Deactivation |
|
|
454 | (3) |
|
Deactivation by Reversible Coupling and Unimolecular Activation |
|
|
457 | (29) |
|
|
457 | (1) |
|
Initiators, iniferters, initers |
|
|
457 | (1) |
|
Molecular weights and distributions |
|
|
458 | (2) |
|
|
460 | (1) |
|
Sulfur-Centered Radical Mediated Polymerization |
|
|
461 | (1) |
|
|
461 | (2) |
|
|
463 | (2) |
|
Monomers, mechanism, side reactions |
|
|
465 | (1) |
|
Selenium-Centered Radical Mediated Polymerization |
|
|
466 | (1) |
|
Carbon-Centered Radical Mediated Polymerization |
|
|
467 | (2) |
|
Monomers, mechanism, side reactions |
|
|
469 | (1) |
|
Reversible Addition-Fragmentation |
|
|
470 | (1) |
|
Nitroxide Mediated Polymerization |
|
|
471 | (1) |
|
|
472 | (3) |
|
|
475 | (3) |
|
|
478 | (1) |
|
|
479 | (1) |
|
|
480 | (1) |
|
|
480 | (1) |
|
|
480 | (1) |
|
|
481 | (1) |
|
|
481 | (1) |
|
Heterogeneous polymerization |
|
|
481 | (2) |
|
Other Oxygen-Centered Radical Mediated Polymerization |
|
|
483 | (1) |
|
Nitrogen-Centered Radical Mediated Polymerization |
|
|
483 | (1) |
|
Metal Complex-Mediated Radical Polymerization |
|
|
484 | (2) |
|
Atom Transfer Radical Polymerization |
|
|
486 | (12) |
|
|
488 | (2) |
|
Molecular weights and distributions |
|
|
490 | (1) |
|
|
491 | (1) |
|
|
492 | (1) |
|
|
492 | (1) |
|
|
493 | (2) |
|
|
495 | (1) |
|
|
496 | (1) |
|
|
496 | (1) |
|
Monomers and Reaction Conditions |
|
|
497 | (1) |
|
|
497 | (1) |
|
Heterogeneous polymerization |
|
|
497 | (1) |
|
Reversible Chain Transfer |
|
|
498 | (27) |
|
Molecular Weights and Distributions |
|
|
499 | (2) |
|
|
501 | (1) |
|
|
502 | (1) |
|
|
503 | (2) |
|
|
505 | (10) |
|
|
515 | (2) |
|
|
517 | (1) |
|
|
518 | (2) |
|
Heterogeneous polymerization |
|
|
520 | (1) |
|
Iodine-Transfer Polymerization |
|
|
521 | (1) |
|
Telluride-Mediated Polymerization |
|
|
522 | (2) |
|
Stibine-Mediated Polymerization |
|
|
524 | (1) |
|
Living Radical Copolymerization |
|
|
525 | (6) |
|
|
525 | (1) |
|
|
526 | (1) |
|
|
527 | (1) |
|
|
528 | (1) |
|
|
529 | (2) |
|
|
531 | (9) |
|
|
531 | (1) |
|
|
531 | (2) |
|
|
533 | (1) |
|
|
533 | (1) |
|
|
533 | (3) |
|
|
536 | (2) |
|
|
538 | (1) |
|
|
538 | (1) |
|
|
539 | (1) |
|
|
540 | (8) |
|
|
541 | (1) |
|
|
541 | (1) |
|
|
541 | (2) |
|
|
543 | (1) |
|
|
544 | (1) |
|
|
545 | (1) |
|
|
545 | (1) |
|
|
546 | (1) |
|
|
546 | (1) |
|
Segmented Block Copolymers |
|
|
547 | (1) |
|
|
548 | (10) |
|
Core-first Star Synthesis |
|
|
549 | (5) |
|
|
554 | (1) |
|
|
555 | (1) |
|
Self-condensing vinyl polymerization |
|
|
555 | (1) |
|
|
556 | (2) |
|
Graft Copolymers/Polymer Brushes |
|
|
558 | (5) |
|
Grafting Through - Copolymerization of Macromonomers |
|
|
558 | (2) |
|
Grafting From - Surface Initiated Polymerization |
|
|
560 | (1) |
|
Grafting from polymer surfaces |
|
|
560 | (2) |
|
Grafting from inorganic surfaces |
|
|
562 | (1) |
|
Grafting To - Use of End-Functional Polymers |
|
|
563 | (1) |
|
Outlook for Living Radical Polymerization |
|
|
563 | (1) |
|
|
564 | (23) |
Abbreviations |
|
587 | (4) |
Subject Index |
|
591 | |