Investigation of the Effect of Diisocyanate on the Thermal Degradation Behavior and Degradation Kinetics of Polyether-Based Polyurethanes

Low molecular weight polyether (PE) or polyester polyols can produce novel elastomeric urethane products when cured with diisocyanate which are then utilized for formation of castable energetic composites in addition to many more applications. In this work four different kinds of diisocyanates, isophorone diisocyanate (IPDI), methylenediphenyl diisocyanate (MDI), 2,2,4-trimethyl hexamethylene diisocyanate (TMDI), and toluene diisocyanate (TDI), were used to react with a PE to form PE-based polyurethanes (PUs); they were denoted PE/IPDI, PE/MDI, PE/TMDI, and PE/TDI, respectively. The effect of the four diisocyanate groups in the PE-based PUs on the thermal degradation behavior, thermal degradation kinetics, reaction model, and thermodynamic parameters of the PE/IPDI, PE/MDI, PE/TMDI, and PE/TDI samples were investigated by thermogravimetric analysis (TGA) and derivative thermal gravimetric analysis (DTGA) methods. On the basis of the degradation peak temperature at a high heating rate, the thermal stability of the PU followed the order PE/TDI > PE/TMDI > PE/MDI > PE/IPDI. The activation energy for the thermal degradation was derived using the Flynn–Wall–Ozawa (FWO) method from the TGA data and the average values of the PE/IPDI, PE/MDI, PE/TMDI, and PE/TDI samples were found to be 136.9, 148.0, 132.3, and 155.7 kJ mol‒1, each at various conversions from 0.05 to 0.95, respectively. In addition, the results of the activation energies obtained from the Kissinger–Akahira–Sunnse (KAS) method were in good agreement and consistent with those obtained the FWO method. The reaction models of the degradation reaction were investigated through the Coats–Redfern method and all PUs samples were probably best described by the Avarami–Erofeyev (A2) and reaction order (F1) models. The kinetic and thermodynamic parameters for formation of the activated complex of all PUs, such as the activation energy (Ea), enthalpy of activation (ΔH#), Gibbs free energy of activation (ΔG#), and entropy of activation (ΔS#), were investigated. The investigated thermal kinetic and thermodynamic parameters indicated that there was significant variation in the properties of the PUs containing the different diisocyanate groups.