Abstract
1. Acrylic and methacrylic esters of polyhydric alcohols (neopentyl glycol, trimethylolpropane, and pentaerythritol) oxidize through a radical chain mechanism with second-power chain rupture. Chain extension proceeds through peroxide radical addition at the double bond. Values of k2·k6−1/2 (k2 and k6 are the respective rate constants for chain extension and rupture) have been determined for five esters. 2. By studying oxidation in the presence of cumene hydroperoxide it has been possible to determine rate constants for double-bond addition of cumene peroxide radicals in acrylic and methacrylic esters of polyhydric alcohols. The reactivity of the double bond diminishes as the number of ethereal groups in the molecule is increased, possibly because of multidipole interaction in the initial and transition states.
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