Rheo-kinetic evaluation on the formation of urethane networks based on hydroxyl-terminated polybutadiene

Rheo-kinetic studies on bulk polymerization reaction between hydroxyl-terminated polybutadiene (HTPB) and di-isocyanates such as toluene-di-isocyanate (TDI), hexamethylene-di-isocyanate (HMDI), and isophorone-di-isocyanate (IPDI) were undertaken by following the buildup of viscosity of the reaction mixture during the cure reaction. Rheo-kinetic plots were obtained by plotting ln (viscosity) vs. time. The cure reaction was found to proceed in two stages with TDI and IPDI, and in a single stage with HMDI. The rate constants for the two stages k1 and k2 were determined from the rheo-kinetic plots. The rate constants in both the stages were found to increase with catalyst concentration and decrease with NCO/OH equivalent ratio (r-value). The ratio between the rate constants, k1/k2 also increased with catalyst concentration and r-value. The extent of cure reaction at the point of stage separation (xi) increased with catalyst concentration and r-value. Increase in temperature caused merger of stages. Arrhenus parameters for the uncatalyzed HTPB-isocyanate reactions were evaluated.