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E-raamat: Chemistry of Radical Polymerization

(Melbourne University, Parkville, Australia), (Commonwealth Scientific and Industrial Research Organisation (CSIRO), Clayton, Victoria, Australia)
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  • Ilmumisaeg: 06-Dec-2005
  • Kirjastus: Elsevier / The Lancet
  • Keel: eng
  • ISBN-13: 9780080454795
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  • Formaat: PDF+DRM
  • Ilmumisaeg: 06-Dec-2005
  • Kirjastus: Elsevier / The Lancet
  • Keel: eng
  • ISBN-13: 9780080454795
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In the ten years since the first edition appeared the renaissance in Free Radical Polymerization has continued and gained momentum.
In this second revised edition, the authors critically evaluate the findings of the last decade, where necessary reinterpreting earlier work in the light of these ideas, and point to the areas where current and future research is being directed. The overall aim is to provide a framework for further extending our understanding of free radical polymerization and create a definable link between synthesis conditions and polymer structure and properties.

The authors have updated all chapters, and added many new references and two new chapters to reflect the significant advances made in radical polymerization. One new chapter has been devoted to
the area of living radical polymerization which is now responsible for a very substantial fraction of the papers in the field.


In addition to offering polymers with unique compositions and properties not achievable with other methodologies, living radical polymerization has also been combined with other
processes and mechanisms to give structures and architectures that were not previously thought possible.


The developments are seen to have great application particularly in the emerging areas of electronics, biotechnology and nanotechnology.

* A new chapter devoted to the growing field of living radical polymerization
* Seven chapters revised and updated with eight years of new research
* An excellent text suitable for graduates in polymer chemistry and a reference source for researchers and practitioners in radical polymerization
Contents v
Index to Tables xvi
Index to Figures xx
Preface to the First Edition xxiii
Preface to the Second Edition xxv
Acknowledgments xxvi
Introduction
1(10)
References
8(3)
Radical Reactions
11(38)
Introduction
11(1)
Properties of Radicals
12(4)
Structures of Radicals
12(2)
Stabilities of Radicals
14(1)
Detection of Radicals
14(2)
Addition to Carbon-Carbon Double Bonds
16(13)
Steric Factors
19(2)
Polar Factors
21(1)
Bond Strengths
22(1)
Stereoelectronic Factors
23(1)
Entropic Considerations
24(1)
Reaction Conditions
24(1)
Temperature
24(1)
Solvent
25(1)
Theoretical Treatments
26(2)
Summary
28(1)
Hydrogen Atom Transfer
29(7)
Bond Dissociation Energies
30(1)
Steric Factors
30(1)
Polar Factors
31(1)
Stereoelectronic Factors
32(1)
Reaction Conditions
33(1)
Abstraction vs Addition
34(2)
Summary
36(1)
Radical-Radical Reactions
36(8)
Pathways for Combination
37(1)
Pathways for Disproportionation
38(1)
Combination vs Disproportionation
39(1)
Statistical factors
39(1)
Steric factors
40(1)
Polar factors
41(1)
Stereoelectronic and other factors
41(1)
Reaction conditions
42(1)
Summary
43(1)
References
44(5)
Initiation
49(118)
Introduction
49(1)
The Initiation Process
50(14)
Reaction with Monomer
51(3)
Fragmentation
54(1)
Reaction with Solvents, Additives, or Impurities
55(1)
Effects of Temperature and Reaction Medium on Radical Reactivity
55(1)
Reaction with Oxygen
56(1)
Initiator Efficiency in Thermal Initiation
57(1)
Photoinitiation
58(2)
Cage Reaction and Initiator-Derived Byproducts
60(1)
Primary Radical Termination
61(1)
Transfer to Initiator
62(1)
Initiation in Heterogeneous Polymerization
63(1)
The Initiators
64(47)
Azo-Compounds
68(1)
Dialkyldiazenes
68(4)
Thermal decomposition
72(2)
Photochemical decomposition
74(1)
Initiator efficiency
74(3)
Transfer to initiator
77(1)
Hyponitrites
78(1)
Peroxides
79(3)
Diacyl or diaroyl peroxides
82(1)
Thermal decomposition
82(1)
Photochemical decomposition
83(1)
Initiator efficiency
84(1)
Transfer to initiator and induced decomposition
85(1)
Redox reactions
85(2)
Dialkyl peroxydicarbonates
87(1)
Peroxyesters
88(1)
Thermal decomposition
88(2)
Photochemical decomposition
90(1)
Dialkyl peroxides
90(2)
Alkyl hydroperoxides
92(1)
Inorganic peroxides
93(1)
Persulfate
94(2)
Hydrogen peroxide
96(1)
Multifunctional Initiators
96(1)
Concerted decomposition
97(1)
Non-concerted decomposition
97(1)
Photochemical Initiators
98(1)
Aromatic carbonyl compounds
98(1)
Benzoin and related compounds
99(3)
Carbonyl compound-tertiary amine systems
102(1)
Sulfur compounds
103(1)
Redox Initiators
104(1)
Metal complex-organic halide redox systems
104(1)
Ceric ion systems
105(1)
Thermal Initiation
106(1)
Styrene homopolymerization
107(2)
Acrylate homopolymerization
109(1)
Copolymerization
110(1)
The Radicals
111(22)
Carbon-Centered Radicals
112(1)
Alkyl radicals
112(1)
α-Cyanoalkyl radicals
113(4)
Aryl radicals
117(1)
Acyl radicals
117(1)
Oxygen-Centered Radicals
118(1)
Alkoxy radical
118(1)
t-Butoxy radicals
119(5)
Other t-alkoxy radicals
124(1)
Primary and secondary alkoxy radical
125(1)
Acyloxy and alkoxycarbonyloxy radicals
125(1)
Benzoyloxy radicals
126(1)
Alkoxycarbonyloxy radicals
127(1)
Hydroxy radicals
128(1)
Sulfate radical anion
129(1)
Alkylperoxy radicals
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)
Techniques
133(16)
Kinetic Studies
133(1)
Radical Trapping
133(1)
Spin traps
134(2)
Transition metal salts
136(1)
Metal hydrides
137(1)
Nitroxides
138(2)
α-Methystyrene dimer
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)
Mass spectrometry
143(1)
Chemical methods
144(1)
Labeling Techniques
145(1)
Radiolabeling
145(1)
Stable isotopes and nuclear magnetic resonance
146(3)
References
149(18)
Propagation
167(66)
Introduction
167(1)
Stereosequence Isomerism - Tacticity
168(8)
Terminology and Mechanisms
168(5)
Experimental Methods for Determining Tacticity
173(1)
Tacticities of Polymers
173(3)
Regiosequence Isomerism - Head vs Tail Addition
176(9)
Monoene Polymers
176(2)
Poly(vinyl acetate)
178(1)
Poly(vinyl chloride)
179(1)
Fluoro-olefin polymers
180(1)
Allyl polymers
181(1)
Acrylic polymers
182(1)
Conjugated Diene Polymers
182(2)
Polybutadiene
184(1)
Polychloroprene, polyisoprene
184(1)
Structural Isomerism - Rearrangement
185(28)
Cyclopolymerization
185(1)
1,6-Dienes
186(5)
Triene monomers
191(1)
1,4- and 1,5-dienes
192(1)
1,7-and higher 1, n-dienes
193(1)
Cyclo-copolymerization
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)
Vinyl polymers
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)
References
221(12)
Termination
233(46)
Introduction
233(1)
Radical-Radical Termination
234(30)
Termination Kinetics
235(1)
Classical kinetics
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)
Model studies
252(1)
Polystyrene and derivatives
253(2)
Poly(alkyl methacrylates)
255(1)
Poly(methacrylonitrile)
256(2)
Polyethylene
258(1)
Polymerization
258(2)
Polystyrene
260(1)
Poly(alkyl methacrylates)
261(1)
Poly(methacrylonitrile)
262(1)
Poly(alkyl acrylates)
262(1)
Poly(acrylonitrile)
262(1)
Poly(vinyl acetate)
263(1)
Poly(vinyl chloride)
263(1)
Summary
263(1)
Inhibition and Retardation
264(9)
'Stable' Radicals
267(1)
Oxygen
268(1)
Monomers
269(1)
Phenols
270(1)
Quinones
271(1)
Phenothiazine
272(1)
Nitrones, Nitro- and Nitroso-Compounds
272(1)
Transition Metal Salts
273(1)
References
273(6)
References
279(1)
Chain Transfer
279(54)
Introduction
279(1)
Chain Transfer
279(46)
Measurement of Transfer Constants
283(4)
Addition-fragmentation
287(1)
Reversible chain transfer
288(1)
Homolytic Substitution Chain Transfer Agents
289(1)
Thiols
290(1)
Disulfides
291(1)
Monosulfides
292(1)
Halocarbons
293(1)
Solvents and other reagents
294(2)
Addition-Fragmentation Chain Transfer Agents
296(2)
Vinyl ethers
298(1)
Allyl sulfides, sulfonates, halides, phosphonates, silanes
299(4)
Allyl peroxides
303(2)
Macromonomers
305(3)
Thionoester and related transfer agents
308(1)
Abstraction-Fragmentation Chain Transfer
309(1)
Catalytic Chain Transfer
310(1)
Mechanism
310(3)
Catalysts
313(1)
Cobalt porphyrin and related complexes
313(1)
Cobalt (II) cobaloximes
313(1)
Cobalt (III) cobaloximes
314(1)
Other catalysts
315(1)
Reaction conditions
315(1)
Transfer to Monomer
316(1)
Styrene
317(1)
Vinyl acetate
318(1)
Vinyl chloride
318(1)
Allyl monomers
319(1)
Transfer to Polymer
320(1)
Polyethylene
321(1)
Poly(alkyl methacrylates)
321(1)
Poly(alkyl acrylates)
322(1)
Poly(vinyl acetate)
323(2)
Poly(vinyl chloride)
325(1)
Poly(vinyl fluoride)
325(1)
Transfer to Initiator
325(1)
References
325(8)
Copolymerization
333(80)
Introduction
333(2)
Copolymer Depiction
335(1)
Propagation in Statistical Copolymerization
335(31)
Propagation Mechanisms in Copolymerization
337(1)
Terminal model
337(5)
Penultimate model
342(1)
Model description
342(2)
Remote substituent effects on radical addition
344(3)
MMA-S copolymerization
347(1)
Other copolymerizations
348(1)
Origin of penultimate unit effects
349(1)
Models involving monomer complexes
350(3)
Copolymerization with depropagation
353(1)
Chain Statistics
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)
Terpolymerization
357(2)
Estimation of Reactivity Ratios
359(1)
Composition data
360(2)
Monomer sequence distribution
362(1)
Prediction of Reactivity Ratios
363(1)
Q-e scheme
363(2)
Patterns of reactivity scheme
365(1)
Termination in Statistical Copolymerization
366(8)
Chemical Control Model
366(2)
Diffusion Control Models
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)
Functional Initiators
375(2)
Functional Transfer Agents
377(1)
Thiol-ene Polymerization
378(1)
Functional Monomers
379(2)
Functional Inhibitors
381(1)
Compositional Heterogeneity in Functional Copolymers
381(3)
Block & Graft Copolymerization
384(17)
Polymeric and Multifunctional Initiators
385(2)
Transformation Reactions
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)
References
401(12)
Controlling Polymerization
413(38)
Introduction
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)
Controlling Propagation
421(22)
Organic Solvents and Water
425(1)
Homopolymerization
426(3)
Copolymerization
429(3)
Supercritical Carbon Dioxide
432(1)
Ionic liquids
432(1)
Lewis Acids and Inorganics
433(1)
Homopolymerization
433(2)
Copolymerization
435(2)
Template Polymerization
437(1)
Non-covalently bonded templates
437(1)
Covalently bonded templates
438(2)
Enzyme Mediated Polymerization
440(1)
Topological Radical Polymerization
441(2)
References
443(8)
Living Radical Polymerization
451(136)
Introduction
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)
Kinetics and Mechanism
457(1)
Initiators, iniferters, initers
457(1)
Molecular weights and distributions
458(2)
Polymerization kinetics
460(1)
Sulfur-Centered Radical Mediated Polymerization
461(1)
Disulfide initiators
461(2)
Monosulfide initiators
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)
Nitroxides
472(3)
Initiation
475(3)
Side reactions
478(1)
Rate enhancement
479(1)
Monomers
480(1)
Styrene, vinyl aromatics
480(1)
Acrylates
480(1)
Methacrylates
481(1)
Diene monomers
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)
Initiators
488(2)
Molecular weights and distributions
490(1)
Reverse ATRP
491(1)
Initiator activity
492(1)
Catalysts
492(1)
Copper complexes
493(2)
Ruthenium complexes
495(1)
Iron complexes
496(1)
Nickel complexes
496(1)
Monomers and Reaction Conditions
497(1)
Solution polymerization
497(1)
Heterogeneous polymerization
497(1)
Reversible Chain Transfer
498(27)
Molecular Weights and Distributions
499(2)
Macromonomer RAFT
501(1)
Thiocarbonylthio RAFT
502(1)
Mechanism
503(2)
RAFT agents
505(10)
RAFT agent synthesis
515(2)
Side Reactions
517(1)
Reaction conditions
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)
Reactivity Ratios
525(1)
Gradient Copolymers
526(1)
NMP
527(1)
ATRP
528(1)
RAFT
529(2)
End-Functional Polymers
531(9)
NMP
531(1)
ω-Functionalization
531(2)
α-Functionalization
533(1)
ATRP
533(1)
ω-Functionalization
533(3)
α-Functionalization
536(2)
RAFT
538(1)
ω-Functionalization
538(1)
α-Functionalization
539(1)
Block Copolymers
540(8)
Direct Diblock Synthesis
541(1)
NMP
541(1)
ATRP
541(2)
RAFT
543(1)
Transformation Reactions
544(1)
Second step NMP
545(1)
Second step ATRP
545(1)
Second step RAFT
546(1)
Triblock Copolymers
546(1)
Segmented Block Copolymers
547(1)
Star Polymers
548(10)
Core-first Star Synthesis
549(5)
Arm-first Star Synthesis
554(1)
Hyperbranched Polymers
555(1)
Self-condensing vinyl polymerization
555(1)
Dendritic polymers
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)
References
564(23)
Abbreviations 587(4)
Subject Index 591


Graeme Moad, PhD, FAA, FRACIChief Research Scientist, Materials Science and EngineeringCommonwealth Scientific and Industrial Research Organisation (CSIRO)Clayton, Victoria, Australia