Abstract
During the initial stage of the thermooxidation of unstabilized LDPE at 95°C the rate of initiation has been found to be first order in hydroperoxide concentration whereas the initiation of radiation-induced oxidation at 25°C was independent of the hydroperoxide concentration. In both cases, the ketone accumulation is much more important than that of hydroperoxide. According to a kinetic analysis of thermooxidation, this result can be attributed to a chain reaction in which secondary peroxy radicals abstract tertiary hydrogen atoms from secondary hydroperoxides to form hydroperoxy alkyl radicals R 1Ċ(OOH)R 2 which decompose by β-scission to give ketones and hydroxyl radicals. The overall result of these reactions is the production of ketones and water in equal amounts and the regeneration of hydroperoxide. Kinetic analysis of the radiation-induced oxidation leads to the conclusion that hydroperoxy radicals HO . 2 also participate in the attack on the tertiary hydrogen of the secondary hydroperoxides.
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