Heterophase mechanisms of thermal oxidation of polymers. Novel horizons

Based on the results of kinetic analysis of numerous experimental data, advantages of heterogeneous-heterophase mechanisms of autooxidation of non-crystalline polymers over homogeneous liquid-phase mechanisms of the process are demonstrated. The supramolecular organisation of polymer chains according 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 or to the mechanism of predominant localisation of these chains in one nanophase. The resulting kinetic equations of macroscopic oxidation steps take into account the dependence of the chemical reactivity of reactants on the thermomechanical mobility of the molecular sponge. It is demonstrated that the tine structure of the spongy micelle plays a crucial role in the chemical physics of polymers.