Volume 34, Issue 2 pp. 291-299
Article

Kinetic study of radical polymerization of dialkyl fumarates using electron spin resonance spectroscopy

Akikazu Matsumoto

Corresponding Author

Akikazu Matsumoto

Department of Applied Chemistry, Faculty of Engineering, Osaka City University, Sugimoto, Sumiyoshi-ku, Osaka 558, Japan

Department of Applied Chemistry, Faculty of Engineering, Osaka City University, Sugimoto, Sumiyoshi-ku, Osaka 558, JapanSearch for more papers by this author
Yoshinori Sano

Yoshinori Sano

Department of Applied Chemistry, Faculty of Engineering, Osaka City University, Sugimoto, Sumiyoshi-ku, Osaka 558, Japan

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Masahiro Yoshioka

Masahiro Yoshioka

Department of Applied Chemistry, Faculty of Engineering, Osaka City University, Sugimoto, Sumiyoshi-ku, Osaka 558, Japan

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Takayuki Otsu

Takayuki Otsu

Faculty of Biology-Oriented Science and Technology, Kinki University, Uchita-cho, Naga-gun, Wakayama 649-64, Japan

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Abstract

The radical polymerization of dialkyl fumarates (DRF) bearing various ester alkyl groups was kinetically studied. The propagation and termination rate constants were determined using electron spin resonance (ESR) spectroscopy. The introduction of the bulky ester alkyl groups such as a tert-butyl group decreased the termination rate constant as expected. However, it has also been revealed that the bulky groups promote propagation despite the steric repulsion. The propagation rate and mechanism are discussed in relation to the propagation manner, i.e., tacticity of the polymer. © 1996 John Wiley & Sons, Inc.

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