From classical to living/controlled statistical free-radical copolymerization

Progress in Polymer Science (Oxford)

Volumn 27, Issue 9, 2002, Pages 1879-1924

  Madruga, Enrique López ^a  

^a INSTITUTO DE CIENCIA Y TECNOLOGÍA DE POLÍMEROS   (Spain)

Author keywords

Chain transfer reactions; Conventional copolymerization; Free radical; High conversion copolymerization; Living controlled free radical methods; Monomer reactivity ratios; Penultimate unit effect; Radical reactivity ratios; Solvent effects

Indexed keywords

COPOLYMERS; FREE RADICAL POLYMERIZATION; FREE RADICALS; GLASS TRANSITION; MONOMERS; ORGANIC SOLVENTS; STEREOCHEMISTRY;

FREE-RADICAL COPOLYMERIZATION;

COPOLYMERIZATION;

EID: 0036833202     PISSN: 00796700     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0079-6700(02)00023-0     Document Type: Review

References (221)

1. Determination of reactivity ratios in copolymerization
2. Evaluation of alternative models for the mechanism of chain-growth copolymerization
3. Initiation, propagation and termination in free radical copolymerization
4. Copolymerization. I: Kinetics and some experimental considerations of a general theory
5. Copolymerization. XIII. Overall rates in copolymerization. Polar effects in chain initiation and termination
6. Diffusion-controlled termination in free radical copolymerization
7. A model for the termination stage of some radical copolymerizations
8. Free-radical copolymerization: 3. Determination of rate constants of propagation and termination for the styrene/methyl methacrylate system. A critical test of terminal-model kinetics
9. Free-radical copolymerization: 4. Rate constants of propagation and termination for the p-chlorostyrene/methyl acrylate system
10. Structure and compositions of copolymers
11. Copolymerization
12. Copolymerization
13. Modern aspects of quantitative theory of free-radical copolymerization
14. Reactivity in radical copolymerization
15. Copolymerization. I: A basis for comparing the behavior of monomers in copolymerization; the copolymerization of styrene and methyl methacrylate
16. The mechanism of copolymerization
17. Intramolecular reactions in vinyl polymers as a mean of investigation of the propagation step
18. The role of monomer charge-transfer complexes in free radical copolymerization. I: Derivation of terminal complex model equation
19. An analysis of the complex participation model for free-radical copolymerization
20. The effect of depropagation on copolymer composition. I: General theory for one depropagating monomer
21. Copolymerization with depropagation. III. Composition and sequence distribution from probability considerations
22. Influence of solvents on the molecular associations and on radiation initiated polymerization of acrylic acid
23. Reactivity ratios of ionizing monomers in aqueous solution
24. Solvent effect in radical copolymerization and sequence distribution of monomers in copolymers of styrene with methacrilyc acid
25. Influence of the reaction medium on the composition and microstructure of styrene-acrylic acid copolymers
26. Polymerization and copolymerization in associated monomer aggregates
27. Influence des solvants sur la copolymerzation de l'acrylamide avec l'acrylonitrile
28. Anderung der copolymerisations parameter im system styrol/acrylsaure durch losungsmitteleffekte
29. Lösungsmitteleinflüsse anf die copolymerisation der mathacrylsaüre mit methylmethacrylat
30. Influence of solvents on apparent reactivity ratios in the free radical copolymerization of polar monomers
31. Effect of the reaction medium on radical copolymerization
32. Solvent effect in radical copolymerization of methyl methacrylate with styrene
33. Solvent effect in free radical copolymerization of styrene and methacrylonitrile
34. Some kinetic aspect of radical copolymerization: Influence of the reaction medium on the reactivity ratios
35. Radical copolymerization of acrylic monomers. II. Effect of solvent on radical copolymerization of methyl methacrylate and styrene
36. A mechanistic perspective on solvent effects in free-radical copolymerization
37. Characterization of styrene-acrylamide copolymers prepared in various solvents by intrasequence cyclization
38. Solvent effects on the copolymerization of styrene with methyl methacrylate: Existence of a bootstrap effect?
39. 1H-NMR of styrene - Methyl methacrylate copolymers
40. Microstructure and tacticity in radical copolymerization. II. Stereochemical configuration of styrenemethyl methacrylate copolymers syntesized in solution
41. 1H NMR
42. 13C NMR
43. Bootstrap model for the copolymerization of the methyl methacrylate-styrene system in the presence of methyl cyanoacetate
44. Interpreting the copolymerization of styrene with maleic anhydride and with methyl methacrylate in terms of the bootstrap model
45. A kinetic study of free-radical copolymerization of butyl acrylate and methyl methacrylate in solution
46. Effect of solvent on the copolymerization of styrene and acrylonitrile. Application of the bootstrap effect to the penultimate unit model
47. Solvent effects on the copolymerization of styrene with maleic anhydride: Determination of apparent reactivity ratios from the penultimate unit model
48. Free radical copolymerization: An NMR investigation of current kinetic models
49. Solvent effects on free-radical copolymerization of styrene with butyl acrylate. I: Monomer reactivity ratios
50. Solvent effects on the free-radical copolymerization of butyl acrylate with methyl methacrylate
51. Low and high-conversion studies of the free radical copolymerization of 2-hydroxyethyl methacrylate with styrene in N,N′-dimethyformamide solution
52. Stereochemical configuration of 2-hydroxyethyl methacrylate/styrene copolymers obtained in N,N′-dimethylformamide solution over a whole range of conversion
53. Solvent effects in radical copolymerization between hydrophilic and hydrophobic monomers; 2-hydroxyethyl methacrylate and lauryl methacrylate
54. Free radical copolymerization of 2-hydroxyethyl methacrylate with butyl methacrylate: Determination of monomer reactivity ratios and glass transition temperatures
55. Copolymer hydrogels of 2-hydroxyethyl methacrylate with n-butyl methacrylate and cyclohexyl methacrylate: Synthesis, characterization and uptake of water
56. Radical copolymerization of 2-ethylacrylic acid and methacrylic acid
57. The influence of solvent on the apparent reactivity ratios in free radical copolymerization reactions between itaconic acid and 2-hydroxyethyl acrylate
58. Solvent effect on the free-radical copolymerization of 2-hydroxyethyl methacrylate with ter-butyl acrylate
59. Dependence of copolymer composition upon molecular weight in homogeneous radical copolymerization
60. Thermodynamics of mixing of some vinyl monomers. On the possibility of predicting deviations from the classical scheme of copolymerization
61. The effect of monomer preferential solvation in radical copolymerization: Reactivity ratios and compositional distribution
62. Preferential sorption of monomers and molecular weight effects in radical copolymerization
63. Quantitative theory of free-radical copolymerization for the phenomena of preferential sorption
64. Molecular orbital study of radical complexation with relevance to radical polymerization in aromatic solvents
65. Stability constant of some complexes of t-butyl mesityl nitroxide
66. Zur polymerisation von methylmethacrylat in bromobenzol
67. The effect of aromatic solvnets on the absolute rate coefficients in the polymerization of methyl methacrylate
68. The effect of benzyl alcohol on pulsed laser polymerization of styrene and methylmethacrylate
69. Re-examination of free-radical copolymerization kinetics
70. Diffusion-controlled termination during the initial stages of free radical polymerization of methyl methacrylate
71. The laser-flash-initiated polymerization as a tool of evaluating (individual) kinetic constants of free-radical polymerization. 2. The direct determination of the rate constant of chain propagation
72. Evaluation of individual rate constants from the chain-length distribution of polymer samples prepared by intermittent (rotating sector) photopolymerization. 2. The copolymerization system styrene-methyl methacrylate
73. Laser-flash-initiated polymerization as a tool of evaluating (individual) kinetic constants of free radical polymerization. 7. Copolymerization system 1H8-(methyl methacrylate)/2H8-(methyl methacrylate)
74. Determination of propagation rate constants for the copolymerization of methyl methacrylate and styrene using a pulsed laser technique
75. Copolymerization propagation kinetics of styrene with alkyl methacrylates
76. Copolymerization propagation kinetics of styrene with alkyl acrylates
77. Penultimate-unit effects in free-radical copolymerization
78. Modeling copolymerization kinetics
79. Kinetic of free radical copolymerization
80. Propagation and termination processes in free radical copolymerization
81. Copolymerization kinetics of 4-methoxystyrene with methyl methacrylate and 4-methoxystyrene with styrene: A test of the penultimate model
82. The termination reaction in free radical copolymerization. I: Methyl methacrylate and butyl- or dodecyl methacrylate
83. Copolymerization propagation kinetics of para-substituted styrenes: A critical test of the implicit penultimate model
84. Free-radical copolymerization. VII. Reinterpretation of velocity of copolymerization data
85. A kinetic Study on the radical copolymerization of dimethyl itaconate and methyl methacrylate in benzene
86. Free-Radical Homopolymerization and copolymerization of di-n-butyl itaconate
87. Kinetic study of free-radical copolymerization of metyl acrylate and methyl methacrylate in benzene
88. Kinetic study of free radical copolymerization of styene/butyl acrylate
89. Copolymerization propagation kinetics of styrene and methyl methacrylate-revisited. 2. Kinetic analysis
90. The measurement and meaning of radical reactivity ratios
91. Copolymerization propagation kinetics of styrene and methyl methacrylate-revisited. 1. Pulsed laser polymerization study
92. Propagation and termination processes in free-radical copolymerization of styrene and ethyl acrylate
93. Free radical polymerization up to high conversion. A general kinetic treatment
94. The mechanism of propagation in free-radical copolymerization
95. Propagation rate coefficients of acrylate-methacrylate free-radical bulk copolymerization
96. A pulsed-laser study of penultimate copolymerization propagation kinetics for methyl methacrylate/n-butyl acrylate
97. Free-radical copolymerization. 6. New interpretation for the propagation rate versus composition curve
98. Polymerizations. Introductory paper
99. Factors influencing the activation energies of reactions involving double bonds and radicals
100. Kinetic study of free-radical copolymerization of ethyl α-benzoyloxymethylacrylate with methyl methacrylate in benzene
101. Penultimate unit effect in free-radical copolymerization
102. Average propagation rate coefficients in the free-radical copolymerization of styrene and α-methylstyrene measured by pulsed-laser polymerization
103. Radical copolymerization propagation kinetics of methyl ethylacrylate and styrene
104. Copolymerization propagation kinetics of dimethyl itaconate and styrene: Strong entropic contributions to the penultimate unit effect
105. · radicals to substituted alkenes: A theoretical study of the reaction mechanism
106. The penultimate unit effect of radical copolymerization
107. The effect of remote substituents in free radical addition reactions: New evidence for the penultimate unit effect
108. Effect of the penultimate unit on radical stability and reactivity in free-radical polymerization
109. Conformational dependence of the penultimate unit effect in free-radical copolymerization
110. The mechanism of the propagation step in free-radical copolymerization
111. A comprehensive simulator/database package for reviewing free-radical copolymerizations
112. Multicomponent free-radical polymerization in batch, semi-batch and continuous reactors
113. High-conversion diffusion-controlled polymerization of styrene
114. Prediction and measurement of propagation rate coefficients in terpolymerization reactions. Part 2. Experimental study
115. The extension of the restricted penultimate scheme of binary copolymerization to ternary systems
116. A comprehensive simulator/database package for bulk/solution free-radical terpolymerizations
117. Pulsed laser terpolymerization of styrene, methyl methacrylate and methyl acrylate
118. Inter and intramolecular structure predictions in 2-hydroxyethyl methacrylate-tert-butyl acrylate copolymers obtained at high conversion
119. Sequence distribution and stereoregularity in methyl methacrylate-methyl acrylate copolymers at high conversions
120. Kinetic study of high-conversion copolymerization of butyl acrylate with methyl methacrylate in solution
121. High conversion copolymerization of di-n-butyl itaconate with methyl methacrylate in benzene solution
122. The rate of copolymerization of styrene and methyl methacrylate. I: Low-conversion kinetics
123. The study of the copolymerization of styrene and acrylonitrile to high conversion. Application of low-conversion reactivity ratios
124. Polymer NMR spectroscopy. VI. Methyl methacrylate-styrene and methyl methacrylate-αmethylstyrene copolymers
125. On the properties of polymers with random stereo-sequences
126. Monomer reactivity ratios and microstructural analysis of 2-hydroxyethyl methacrylate-tert-butyl acrylate copolymers
127. Sequence distribution - Glass transition effects
128. Relation of glass transition temperature to molecular structure of addition copolymers
129. Compositional variation of glass transition temperatures. 7. Copolymers
130. Modelling of the glass transition of random copolymers
131. Effect on the conversion and sequence distribution on the glass transition of methyl methacrylate-methyl acrylate copolymers obtained at high conversions
132. The characterization of sequence distribution in copolymers
133. Modeling and simulation of emulsion copolymerization of monomers of different polarities - Relationship polymerization process-microstructure-properties
134. Glass transition temperature of butyl acrylate-methyl methacrylate copolymers
135. Emulsion copolymer glass-transition behavior and particle morphology
136. Initiator efficiencies in 2,2′-azobisobutyronitrile-initiated free-radical polymerization of styrene
137. The rate of copolymerization of styrene and methyl methacrylate. II. The gel effect in copolymerization
138. Termination rate constant in free-radical polymerization
139. An investigation of the kinetics of copolymerization of p-methylstyrene/acrylonitrile to high conversion: Modelling diffusion-controlled termination and propagation by free-volume theory
140. On copolymerization kinetics of N-vinylpyrrolidone-methyl methacrylate at high conversion
141. High-conversion diffusion-controlled copolymerization kinetics
142. Copolymerization at moderate to high conversion level: 1. New evaluation of the relative reactivity ratios in terms of terminal model
143. 2=0
144. Copolymerization of styrene, maleic anhydride and acrylonitrile
145. Effect of the medium on copolymerization of methacrylic acid and methyl methacrylate up to high degrees of conversion
146. Copolymerization of acrylamide with various water-soluble monomers
147. On the gel effect in the presence of a chain transfer agent in methyl methacrylate polymerization and its copolymerization with various acrylates
148. Mechaims of catalytic chain transfer in free radical polymerization of methyl methacrylate and styrene
149. Chain transfer in the polymerization of styrene: The reaction of solvents with free radicals
150. Copolymerization of styrene and methyl methacrylate in the presence of a catalytic chain transfer agent
151. Use of chain length distributions in determining chain transfer constants and termination mechanisms
152. Molecular weight Distributions in free-radical polymerizations. 1. Model development and implications for data interpretation
153. Pulse laser polymerization of styrene in compartmentalized system
154. Transfer constants to monomer, polymer, catalyst, solvent and additive in free radical polymerization
155. Cross-chain transfer rate constants of styrene-terminated radicals to methyl acrylate and methyl methacrylate
156. Monomer chain-transfer constants from emulsion copolymerization data: Styrene and α-methylstyrene
157. Emulsion copolymerization of styrene and methyl methacrylate
158. Monomer chain transfer in the copolymerization of styrene and butyl acrylate
159. Moderated copolymerization: 3. Concentration changes in copolymerization with chain transfer: General equations, with special reference to moderated copolymerization
160. Moderated copolymerization. Part. 2. Transfer constant of styryl radical toward carbon tetrabromide: A penultimate unit effect in chain transfer
161. New studies of the mechanisms of some transfer and propagation reactions
162. Determination of chain transfer constant to dodecanethiol in styrene/methyl methacrylate and butyl acrylate/methyl methacrylate copolymerization and effect of chain length on composition and stereochemical configuration of copolymers
163. Homopolymerization of methyl methacrylate and styrene: Determination of chain transfer constant from Mayo equation and number distribution for n-dodecanethiol
164. Investigation of the penultimate unit effect in halogen atom chain transfer in free radical copolymerization
165. Preparation and characterization of oligomeric terpolymers of styrene, methyl methacrylate and 2-hydroxyethyl methacrylate: A comparison of conventional and catalytic chain transfer
166. Copolymerization of styrene and α-methylstyrene in the presence of a catalytic chain transfer agent
167. Copolymerization of methyl methacrylate and butyl acrylate in the presence of a chain transfer agent
168. End-group control in cataltytic chain transfer polymerization
169. Preparation of macromonomers via chain transfer with and without added chain transfer agent
170. Anionic synthesis of primary amine-functionalized polystyrenes using 1-[4-[N,N-bis(trimethylsilyl)amino]phenyl]-1-phenylethylene
171. Modern cationic vinyl polymerization
172. Group transfer polymerization - Polymerization of acrylic monomers
173. Mechanisms and kinetics of living radical polymerizations
174. Atom-transfer radical polymerization and the synthesis of polymeric materials
175. Narrow molecular weight resins by a free-radical polymerization process
176. Molecular weight control by living free radical polymerization process
177. Living/controlled radical polymerization. Transition-metal-catalyzed atom transfer radical polymerization in the presence of a conventional radical initiator
178. Polymerization of methyl methacrylate with the carbon tetrachloride/dichlorotris- (triphenylphosphine)ruthenium(II)/methylaluminum bis(2,6ditertbutylphenoxide) initiating system: Possibility of living radical polymerization
179. A more versatile route to block copolymers and other polymers of complex architecture by living radical polymerization: The RAFT process
180. New (co)polymers by atom transfer radical polymerization
181. Atom transfer radical copolymerization of styrene and butyl acrylate
182. Atom transfer radical copolymerization of methyl methacrylate and n-butyl acrylate
183. Integral and differential binary copolymerization equation
184. Analysis of linear methods for determining copolymerization reactivity ratios. IV. A comprehensive and critical reexamination of carbocationic copolymerization data
185. Atom-transfer radical copolymerization kinetics
186. A concept for quasiliving nitroxide-mediated radical copolymerization
187. Rate acceleration of N-oxyl-mediated free radical random copolymerization of styrene and n-butyl methacrylate
188. Kinetic study on nitroxide-mediated free-radical polymerization of t-butyl acrylate
189. The living free radical synthesis of random and block copolymers containing hydrophobic and hydrophilic moieties: Novel thin film dissolution behavior
190. Nitroxide-mediated living free radical polymerization: A rapid polymerization of (chloromethyl)styrene for the preparation of random, block, and segmental arborescent polymers
191. Well-defined random copolymers by a living free-radical polymerization process
192. Living free radical polymerization in absence of initiators: Controlled autopolymerization
193. Narrow polydispersity random copolymers by living radical polymerization
194. Synthesis of oligomers by stable free radical polymerization of acrylates, methacrylates, and styrene with alkoxyamine initiators
195. Narrow-polydispersity polystyrene/poly[styrene-co-(butyl methacrylate)] block copolymers by an N-oxyl mediated free radical polymerization process
196. Well-defined block copolymers comprising styrene-acrylonitrile random copolymer sequences synthesized by living radical polymerization
197. Controlled radical copolymerization of styrene and acrylonitrile
198. Analysis of the mechanism of copolymerization of styrene and acrylonitrile
199. Controlled/living free-radical polymerization of styrene and n-butyl acrylate in the presence of a novel asymmetric nitroxyl radical
200. Progress toward a universal initiator for nitroxide mediated living free radical procedures
201. Sequence diatribution and stereoregularity of methyl methacrylate and butyl acrylate statiscal copolymers synthesized by atom transfer radical polymerization
202. 2-mediated living radical polymerization of methacrylates and acrylates and their block or random copolymerizations
203. 2 as catalyst
204. Atom transfer radical copolymerization of methyl methacrylate and n-butyl acrylate
205. Copolymerization of n-butyl acrylate with methyl methacrylatee and PMMA macromonomer: Comparison of reactivity ratios in conventional and atom transfer radical copolymerization
206. A novel method of determination of reactivity ratios in binary and ternary copolymerization
207. A comparative study of methyl methacrylate/butyl acrylate copolymerization kinetic by atom transfer and conventional radical polymerization
208. Atom transfer radical copolymerization of styrene and n-butyl acrylate
209. Living random copolymerization of styrene and methyl methacrylate with a Ru(II) complex and synthesis of ABC-type block-random copolymers
210. Synthesis of alternating copolymers of N-substituted maleimides with styrene via atom transfer radical polymerization
211. Atom transfer radical polymerization of styrene and N-cyclohexylmaleimide
212. Identifying the nature of the active species in the polymerization of methacrylates
213. Living free-radical polymerization by reversible addition-fragmentation chain transfer: The RAFT process
214. Synthesis of defined polymers by reversible addition-fragmentation chain transfer: The RAFT process
215. Tailored polymers by free radical processes
216. Controlled radical copolymerization of styrene and maleic anhydride and the synthesis of novel polyolefin-based block copolymers by reversible addition-fragmentation chain-transfer (RAFT) polymerization