Abstract
The hydroperoxide concentration in an open mixer increases linearly with processing time in the initial stages. After leveling off, the concentration decreases. The maximum concentrations as well as the rate of the following decrease have been found to depend on processing temperature. In this work formal homogeneous kinetics are used to identify the chemical processes susceptible to explain the experimental results. It leads to the conclusion that hydroperoxide decomposition does not significantly contribute to initiation on processing in a mixer. This result contradicts published work involving polyethylene processing in open or closed mixers. The experimental data for hydroperoxide formation are best explained by primary initiation of free radical formation. The hydroperoxide decomposition reactions obviously yield various oxidation products. However, chain initiation by free radicals originating from hydroperoxide decomposition can be neglected in comparison with primary initiation.
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