Modeling of the Kinetics of Polyoxymethylene Decomposition under Oxidative and Non-Oxidative Conditions

Research on the thermal and thermo-oxidative degradation of polyacetals allows for the development of effective methods of utilization of the waste of these polymers towards the recovery of monomers. For this purpose, in addition to qualitative analysis, it is necessary to understand the mechanisms of chemical reactions accompanying the decomposition process under the influence of temperature. Therefore, in this article, with the experimental results from the thermal analysis of the POM homopolymer of three various stages of life—POM-P—unprocessed sample; POM-R—recycled sample, and POM-O—sample waste—we took steps to determine the basic kinetic parameters using two well-known and commonly used kinetic models: Friedman and Ozawa-Flynn-Wall (OFW). Knowing the values of the course of changes in apparent activation energy as a function of partial mass loss, theoretical curves were fitted to the experimental data. The applied calculation models turned out to be consistent in terms of the nature of the curve changes and similar in terms of E(a) in the entire range of mass loss. Both kinetic models showed a very similar course of the E(a) curves. The samples that decompose under oxidative conditions obtained the best fit for the reaction of nth order with autocatalysis by product B model and the samples that decompose under inert conditions for the n-dimensional nucleation according to the Avrami–Erofeev model.