Kinetics and conversion monitoring in a RIM themoplastic polyurethane system^†

Kinetic data are reported for the fast polymerization of a thermoplastic polyurethane under conditions similar to that of commercial reaction injection molding (RIM). The components were a 2000 molecular weight polyester polyol, butanediol and 4,4′-diphenylmethane diisocyanate. Three catalysts–dibutyltin dilaurate, phenyl mercuric propionate, and triethylenediamine–as well as uncatalyzed formulations were studied. Kinetic parameters were obtained by numerically fitting adiabatic temperature rise data with both second-order and hyperbolic models. The hyperbolic model gave consistently better fits and is supported by mechanistic studies in the literature. Activation energies compare well to literature values. The uncatalyzed rate was found to be significant. The kinetic parameters obtained by this method are useful measures of catalyst performance in the RIM systems. Moreover, the models provide a conveient way to predict the extent of reaction during the production of parts by the RIM process. The shape of the reaction pathway (extent of reaction time) may be important in the development of physical properties of polymers produced by the RIM process. Physical properties for these samples compare favorably to those for a conventionally produced (batch) polyurethane of the same formulation.