Thermolysis of polyethylene hydroperoxides in the melt, Part 10: Product yields from bimolecular and pseudo-monomolecular hydroperoxide decomposition

Abstract

The quantitative aspects of some specific decomposition reactions of polyethylene hydroperoxides are re-examined. New data have shown that β-scission of primary alkoxy radicals is negligible in the temperature range of the thermolysis experiments. This is important for the true bimolecular hydroperoxide decomposition for which, in a first approximation, β-scission of primary and secondary alkoxy radicals had been taken into account. The calculation shows that the yields of the main oxidation products such as secondary alcohols, ketones, trans-vinylene groups and aldehydes are not considerably affected by the change. However, the theoretical yields of some minor products such as primary alcohols and of some combination reactions are strongly affected. For the pseudo-monomolecular hydroperoxide decomposition involving a segment of the polymer, the main novelty in comparison with previous work consists in taking into account β-scission of the secondary alkoxy radicals. It allows improving the accuracy of the calculated product yields. Moreover, all the theoretical calculations are on the same level of accuracy and can be used for comparison with the experimental product yields.