Opening and Addition Modes in Propagation During Radical Polymerization of Fumaric and Maleic Derivatives |
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| Authors: | Akikazu Matsumoto Keiichi Shimizu Takayuki Otsu |
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| Affiliation: | 1. Department of Applied Chemistry , Faculty of Engineering Osaka City University Sugimoto , Sumiyoshi-ku, Osaka, 558, Japan;2. Faculty of Biology-Oriented Science and Technology Kinki University Uchita-cho , Naga-gun, Wakayama, 649-64, Japan |
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| Abstract: | Abstract Polymers of bis(trimethylsilyl) fumarate, di-tert-amyl fumarate, and methyl tert-amyl fumarate were prepared by radical polymerization at 60 or 120°C. The polymers were converted into poly(dimethyl fumarate) via thermolysis or hydrolysis and subsequent methylation to determine the tacticity using 13C-NMR spectroscopy. The probabilities of meso addition (P m) were revealed to be 0.66 (60°C) for the bis(trimethylsilyl) ester, 0.60 (60°C) and 0.52 (120°C) for the di-tert-amyl ester, and 0.54 (60 and 120°C) for the methyl tert-amyl ester. From the temperature dependence of the P m values, the differences in activation enthalpies and entropies for the meso and racemo additions were evaluated. The microstructure of poly(dimethyl fumarate) derived from poly(maleic anhydride) was also examined. The opening and addition modes in propagation of the fumaric and maleic derivatives were discussed based on the results obtained in the present and previous work. |
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