Application of Model-Free and Model-Based Kinetic Methods in Evaluation of Reactions Complexity during Thermo-Oxidative Degradation Process: Case Study of [4-(Hydroxymethyl)phenoxymethyl] Polystyrene Resin

This work examined the possibilities and limitations of model-free and model-based methods related to decrypting the kinetic complexity of multi-step thermo-oxidative degradation processes (as a testing system, a [4-(hydroxymethyl)phenoxymethyl] polystyrene resin was used), monitored by thermal analysis (TGA-DTG-DTA) techniques. It was found that isoconversional methods could successfully determine the correct number of process stages and presence of multiple reactions based on derived Ea(α) profiles and identify the negative dependence of the rate constant on the temperature. These methods could not overcome the problem that arose due to mass transfer limitations. The model-based method overcame more successfully the problem associated with mass transfer because its calculation machinery had capabilities for the correct solution of the total mass balance equation. However, a perfect fit with the experimental data was not achieved due to the dependence on the thermal history of the contribution (ctb.) of a given reaction step inside a fitting procedure cycle. On the other hand, through this approach, it was possible to estimate the rate-controlling steps of the process regarding the influence of the heating rate. It was found that for consecutive reaction mechanisms, the production of benzaldehyde and gases in high yields was controlled by the heating rate, where low heating rates were strongly recommended (≤10 K/min). Also, it was shown that the transport phenomenon may be also the rate-determining step (within the set of “intrinsic” kinetic parameters). It was also established that external heat transfer controls the overall rate, where the “pure” kinetic control regime had not been reached but was approached when lowering the temperature and size of the resin particles.