A kinetic study on the rate retardation in radical polymerization of styrene with addition-fragmentation chain transfer

Yungwan Kwak; Atsushi Goto; Yoshinobu Tsujii; Yasujiro Murata; Koichi Komatsu; Takeshi Fukuda

doi:10.1021/ma0118421

A kinetic study on the rate retardation in radical polymerization of styrene with addition-fragmentation chain transfer

Yungwan Kwak, Atsushi Goto, Yoshinobu Tsujii, Yasujiro Murata, Koichi Komatsu, Takeshi Fukuda^*

^*Corresponding author for this work

Kyoto University

Research output: Contribution to journal › Article › peer-review

286 Citations (Scopus)

Abstract

The polymerization of styrene mediated by a polystyryl dithiobenzoate was studied by electron spin resonance spectroscopy to determine the concentration of the intermediate radical produced by the addition of polystyryl radical to the dithiobenzoate. The polymerization was also followed by dilatometry to estimate the concentration of the growing radical. The results showed that the fragmentation of the intermediate radical is a fast process with a relevant rate constant on the order of 10⁴ s^-1 (at 60 °C) and that the intermediate radical undergoes the cross-termination with polystyryl radical to form a 3-arm star chain, thus causing a retardation in the rate of polymerization. The rate constant of cross-termination was estimated to be similar to (somewhat smaller than) that of the termination between polystyryl radicals. The formation of the star was evidenced by an independent model experiment.

Original language	English
Pages (from-to)	3026-3029
Number of pages	4
Journal	Macromolecules
Volume	35
Issue number	8
DOIs	https://doi.org/10.1021/ma0118421
Publication status	Published - Apr 9 2002
Externally published	Yes

ASJC Scopus Subject Areas

Organic Chemistry
Polymers and Plastics
Inorganic Chemistry
Materials Chemistry

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10.1021/ma0118421

Cite this

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title = "A kinetic study on the rate retardation in radical polymerization of styrene with addition-fragmentation chain transfer",

abstract = "The polymerization of styrene mediated by a polystyryl dithiobenzoate was studied by electron spin resonance spectroscopy to determine the concentration of the intermediate radical produced by the addition of polystyryl radical to the dithiobenzoate. The polymerization was also followed by dilatometry to estimate the concentration of the growing radical. The results showed that the fragmentation of the intermediate radical is a fast process with a relevant rate constant on the order of 104 s-1 (at 60 °C) and that the intermediate radical undergoes the cross-termination with polystyryl radical to form a 3-arm star chain, thus causing a retardation in the rate of polymerization. The rate constant of cross-termination was estimated to be similar to (somewhat smaller than) that of the termination between polystyryl radicals. The formation of the star was evidenced by an independent model experiment.",

author = "Yungwan Kwak and Atsushi Goto and Yoshinobu Tsujii and Yasujiro Murata and Koichi Komatsu and Takeshi Fukuda",

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T1 - A kinetic study on the rate retardation in radical polymerization of styrene with addition-fragmentation chain transfer

AU - Kwak, Yungwan

AU - Goto, Atsushi

AU - Tsujii, Yoshinobu

AU - Murata, Yasujiro

AU - Komatsu, Koichi

AU - Fukuda, Takeshi

PY - 2002/4/9

Y1 - 2002/4/9

N2 - The polymerization of styrene mediated by a polystyryl dithiobenzoate was studied by electron spin resonance spectroscopy to determine the concentration of the intermediate radical produced by the addition of polystyryl radical to the dithiobenzoate. The polymerization was also followed by dilatometry to estimate the concentration of the growing radical. The results showed that the fragmentation of the intermediate radical is a fast process with a relevant rate constant on the order of 104 s-1 (at 60 °C) and that the intermediate radical undergoes the cross-termination with polystyryl radical to form a 3-arm star chain, thus causing a retardation in the rate of polymerization. The rate constant of cross-termination was estimated to be similar to (somewhat smaller than) that of the termination between polystyryl radicals. The formation of the star was evidenced by an independent model experiment.

AB - The polymerization of styrene mediated by a polystyryl dithiobenzoate was studied by electron spin resonance spectroscopy to determine the concentration of the intermediate radical produced by the addition of polystyryl radical to the dithiobenzoate. The polymerization was also followed by dilatometry to estimate the concentration of the growing radical. The results showed that the fragmentation of the intermediate radical is a fast process with a relevant rate constant on the order of 104 s-1 (at 60 °C) and that the intermediate radical undergoes the cross-termination with polystyryl radical to form a 3-arm star chain, thus causing a retardation in the rate of polymerization. The rate constant of cross-termination was estimated to be similar to (somewhat smaller than) that of the termination between polystyryl radicals. The formation of the star was evidenced by an independent model experiment.

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A kinetic study on the rate retardation in radical polymerization of styrene with addition-fragmentation chain transfer

Abstract

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