Kinetic modeling of thermal degradation of TDI/MDI-based flexible polyurethane foam under nitrogen and air atmospheres with Shuffled Complex Evolution algorithm: Insights from TG-FTIR analysis

Abstract

This study investigates the thermal degradation mechanisms and kinetics of TDI/MDI-based flexible polyurethane foam (FPUF) under nitrogen and air atmospheres, employing thermogravimetric (TG) analysis in conjunction with TG-FTIR technique. The information gleaned from these analysis is used to construct kinetic model based on model-free approaches coupled with the Shuffled Complex Evolution optimization algorithm. The results uncovered the five-step complex thermal degradation process of TDI/MDI-based FPUF compared to TDI-based or MDI-based polyurethane in both atmospheres. In nitrogen atmosphere, this involve the dissociation of TDI- and MDI-based urethane bonds, breakage of recombined urea bonds, random chain scission of polyol, and further degradation of incompletely pyrolyzed solid products. In air atmosphere, the process emcompasses dissociation of TDI- and MDI-based urethane linkages, accelerated oxidation of polyol chains, consumption of urea groups, and combustion of partially oxidized intermediates. This work also emphasizes the limitations of solely relying on TG tests for kinetic modeling, necessitating the integration of TG tests and TG-FTIR technique to obtain a comprehensive understanding of degradation mechanisms. The significance of the acquired insights lies in their potential to reshape the design of thermo-chemical reactors, resulting in heightened resource recovery, diminished environmental impact, and a stride towards a circular economy within the polyurethane industry.