Abstract
Polyethylene oxidation on processing in air has been discussed several times. In spite of substantial amounts of work, there remains considerable uncertainty with respect to the mechanisms and kinetics involved. The aim of this work is presenting additional data and highlighting similarities and differences between the rates of formation of various oxidation products. The data available point to significant correlation between the rates of formation of alcohol, ketone and trans-vinylene groups. Hence, these groups should be formed in the same or, at least, in similar processes. There is no general correlation between the formation of carboxylic acids and γ-lactones. There is also no direct relation between the two last oxidation products and the other products detected in the system. The Arrhenius-plots of the experimental rates deduced from fitting the data to two elementary rate equations yield many values for the activation energy. However, usually, these values cannot be related to well-defined chemical reactions. Even if the values look reasonable, there remains considerable doubt concerning the correct attribution to some reaction. In fact, further work shows that the apparent agreement is mainly fortuitous. It seems mandatory to take a new approach at data interpretation.
Published Version
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