Curing and Cross-Linking Processes in the Poly(3,3-bis-azidomethyl oxetane)-tetrahydrofuran/Toluene...

The physical and chemical properties of solid propellant are influenced by the composition and structure of the binder, with its network structure being formed through curing and cross-linking reactions. Therefore, understanding the mechanisms of these reactions is crucial. In this study, we investigated the curing and cross-linking mechanisms of poly(3,3-bis-azidomethyl oxetane)-tetrahydrofuran (PBT), toluene diisocyanate (TDI), and trimethylolpropane (TMP) using a combination of density functional theory (DFT) calculations and accelerated ReaxFF molecular dynamics (MD) simulations. DFT calculations revealed that the steric effect of the -CH₃ group in TDI exerts a significant influence on the curing reaction between TDI and PBT. Additionally, in the cross-linking process, the energy barrier for TDI reacting with TMP was found to be much lower than that for TDI reacting with the PBT-TDI intermediate. Subsequently, we conducted competing reaction processes of TMP/TDI-PBT-TDI cross-linking and TDI-PBT-TDI self-cross-linking using accelerated MD simulations within the fitted ReaxFF framework. The results showed that the successful frequency of TMP/TDI-PBT-TDI cross-linking was substantially higher than that of TDI-PBT-TDI self-cross-linking, consistent with the energy barrier results from DFT calculations. These findings deepen our understanding of the curing and cross-linking mechanisms of the PBT system, providing valuable insights for the optimization and design of solid propellants.