Atom Transfer Radical Copolymerization of Styrene and Butyl Acrylate

Chambard, Grégory; Klumperman, Bert

doi:10.1021/bk-2000-0768.ch014

Cited by 23 publications

(23 citation statements)

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“…Accordingly, as soon as the equilibrium has been established, the ratio of the concentration of the two different propagating radicals, [lM9]/[lB9], is constant for a specific molar feed composition, independently of the radical polymerization method. [22] This fact has also been pointed out by Chambard and Klumperman [17] for styrene (S) and B copolymerization. Using simulations these authors have evaluated the influence of activation and deactivation processes on the copolymerization kinetics and hence on the reactivity ratios.…”

Section: Resultssupporting

confidence: 68%

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A Comparative Study of Methyl Methacrylate/Butyl Acrylate Copolymerization Kinetics by Atom-Transfer and Conventional Radical Polymerization

Fuente

Fernández-Sanz

Madruga³

2001

Macromol. Rapid Commun.

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Section: Resultssupporting

confidence: 68%

“…[7][8][9][10][11][12][13][14][15][16][17] Several research groups have carried out living/controlled free-radical copolymerization of methyl methacrylate with butyl acrylate. In some cases only a feed composition of equimolar amounts of monomers has been copolymerized.…”

Section: Introductionmentioning

confidence: 99%

A Comparative Study of Methyl Methacrylate/Butyl Acrylate Copolymerization Kinetics by Atom-Transfer and Conventional Radical Polymerization

Fuente

Fernández-Sanz

Madruga³

2001

Macromol. Rapid Commun.

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“…9,[12][13][14][15][16][17][18][19] Similarly, reactivity ratios in "living" carbocationic systems are close to those in conventional cationic polymerizations. 5 Small differences have been noted but were primarily ascribed to differences in reaction conditions, conversion, precision of measurements, involvement of additives, etc.…”

Section: Introductionmentioning

confidence: 66%

Factors Affecting Rates of Comonomer Consumption in Copolymerization Processes with Intermittent Activation

Matyjaszewski

2002

Macromolecules

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Many controlled polymerization processes proceed via intermittent activation (i.e., by a series of activation/deactivation cycles), and this interrupted growth process may affect not only polydispersities but also (co)polymer microstructure. The computer modeling indicates that, in systems with intermittent and selective activation, rates of consumption of comonomers may be different from conventional systems, and this can result in different copolymer composition, microstructure, and different apparent reactivity ratios. The effect of several parameters such as concentration of the involved reagents, rate constants of homopropagation, cross-propagation, activation, and deactivation on the copolymer composition was studied. Deviations from the conventional systems are predicted for systems such as controlled/living radical polymerization, atom transfer radical polymerization, group transfer radical polymerization, "living" carbocationic polymerization, and other systems with intermittent activation. Use of chiral activators/deactivators may convert stereoselective polymerization to stereoelective polymerization even in the presence of nonselective initiators. The topology of polymers formed by self-condensing vinyl polymerization (branch distribution) may also depend on the dynamics of exchange reactions.

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“…The monomer reactivity ratios were obtained from the compositions of copolymers with conversions between 15% and 50% with the modified Kelen–Tüdos equation,27 in which variation of the monomer feed composition with conversion is considered. A conversion interval of 15% was utilized as the low value to avoid the effect on the copolymer chain composition of the initiator structure, which may preferentially react with one comonomer,28, 29 and 50% was used as the high value, following the recommendation of Kelen et al27 From the Kelen–Tüdos diagram shown in Figure 1(a), the estimated values were calculated as r S = 0.74 ± 0.01 and r BA = 0.29 ± 0.02. These data are within the 95% joint confidence interval of those obtained in conventional free‐radical copolymerization by Chambart et al,30 who found values of r S = 0.81 and r BA = 0.23 at 120 °C.…”

Section: Resultsmentioning

confidence: 99%

Nitroxide‐mediated free‐radical copolymerization of styrene with butyl acrylate

Cuervo-Rodríguez

Bordegé

Fernández‐Monreal

et al. 2004

J. Polym. Sci. A Polym. Chem.

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Controlled free‐radical copolymerization of styrene (S) and butyl acrylate (BA) was achieved by using a second‐generation nitroxide, N‐tert‐butyl‐N‐[1‐diethylphosphono‐(2,2‐dimethylpropyl)] nitroxide (DEPN), and 2,2‐azobisisobutyronitrile (AIBN) at 120 °C. The time‐conversion first‐order plot was linear, and the number‐average molecular weight increased in direct proportion to the ratio of monomer conversion to the initial concentration, providing copolymers with low polydispersity. The monomer reactivity ratios obtained were rS = 0.74 and rBA = 0.29, respectively. To analyze the convenience of applying the Mayo–Lewis terminal model, the cumulative copolymer composition against conversion and the individual conversion of each monomer as a function of copolymerization time were studied. The theoretical values of the propagating radical concentration ratio were also examined to investigate the copolymerization rate behavior. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4168–4176, 2004

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Atom Transfer Radical Copolymerization of Styrene and Butyl Acrylate

Cited by 23 publications

References 0 publications

A Comparative Study of Methyl Methacrylate/Butyl Acrylate Copolymerization Kinetics by Atom-Transfer and Conventional Radical Polymerization

A Comparative Study of Methyl Methacrylate/Butyl Acrylate Copolymerization Kinetics by Atom-Transfer and Conventional Radical Polymerization

Factors Affecting Rates of Comonomer Consumption in Copolymerization Processes with Intermittent Activation

Nitroxide‐mediated free‐radical copolymerization of styrene with butyl acrylate

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