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Effect of polymer structure on ease of hydrogen abstraction by cumyloxy radicals
Authors:Joginder Lal  James E. McGrath  Robert D. Board
Abstract:Vulcanizates of five elastomers having different chemical structures were prepared with recipes comprising dicumyl peroxide. Cumyl alcohol/acetophenone molar ratios were determined by gas–liquid chromatography (GLC) on acetone extracts of vulcanizates. Diphenyl ether was used as the internal standard. The ease of hydrogen abstraction by cumyloxy radicals, reflected by the cumyl alcohol/acetophenone ratio, decreases in the following order: cis-1,4-polyisoprene > poly(propylene oxide) > poly(vinyl n-butyl ether) > poly-1-heptene ? EPR. This order is in qualitative agreement with the order based on calculated relative rates of hydrogen abstraction by methyl and tert-butoxy radicals and literature data on oxygen absorption of some of these polymers as a result of hydrogen abstraction by peroxy radicals.
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