Autoxidation of atactic polypropylene and related alkanes. Rates and reactivities toward peroxy radicals.
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概要
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Rates of autoxidations of atactic polypropylene, polystyrene, and several alkanes in solution initiated by azobiscyclohexanecarbonitrile were measured at 90 °C in the absence and presence of added hydroperoxide and the reactivities toward <I>tert</I>-butylperoxyl and tetralylperoxyl radicals were measured. Atactic polypropylene was found to be oxidized faster than expected from the related alkanes. On the other hand, polystyrene was quite resistant to autoxidation. The relative reactivities of secondary and tertiary hydrogens toward <I>t</I>-butylperoxyl radical were obtained as 1: 9.7 and that for primary hydrogen was estimated to be quite small. The observed reactivity of 2,2,4-trimethylpentane was much smaller than the calculated reactivity from the results of simple alkanes, whereas the observed reactivity of atactic polypropylene was higher than the calculated one. The high reactivity of atactic polypropylene for oxidation and toward peroxyl radicals was interpreted as being due to a fast intramolecular propagation. Tetralylperoxyl radical was 3.6 times as reactive as <I>t</I>-butylperoxyl radical toward both atactic polypropylene and 2,6,10,14-tetramethylpentadecane.
- 公益社団法人 日本化学会の論文
著者
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Kamiya Yoshio
Department of Applied Chemistry Faculty of Engineering The University of Tokyo
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Niki Etsuo
Department of Reaction Chemistry, Faculty of Engineering, The University of Tokyo
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Niki Etsuo
Department of Reaction Chemistry, Faculty of Engineering, University of Tokyo
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