Heterophase mechanisms of thermal oxidation of polymers. Novel horizons

Based on the results of kinetic analysis of numerous experimental data, adv antages of heterogeneous-heterophase mechanisms of autooxidation of non-cry stalline polymers over homogeneous liquid-phase mechanisms of the process a re demonstrated. The supramolecular organisation of polymer chains accordin g to the pattern of spongy micelles incorporating non-uniform porous areas is chosen as the model structure. It is established that, depending on the physical state of the polymer, the oxidation kinetics corresponds either to the mechanism of reaction chain distribution over non-uniform nanophases o r to the mechanism of predominant localisation of these chains in one nanop hase. The resulting kinetic equations of macroscopic oxidation steps take i nto account the dependence of the chemical reactivity of reactants on the t hermomechanical mobility of the molecular sponge. It is demonstrated that t he tine structure of the spongy micelle plays a crucial role in the chemica l physics of polymers.