A kinetic study of the reaction between a hydroxyl-terminated polybutadiene (HTPB) and isophorone diisocyanate (IPDI) was carried out in the bulk state by using quantitative Fourier transform infrared(FTIR) spectroscopy. The reaction is shown to obey a second-order rate law, being first order in both the HTPB and IPDI concentrations. The activation parameters obtained from the evaluation of kinetic data are Delta H-double dagger = 41.1 +/- 0.4 kJ mol, Delta S-double dagger = -198 +/- 2 J K-1 mol(-1) and E-a = 43.8 +/- 0.4 kJ mol(-1), which are quite different from the solution values. However, they are in agreement with the results obtained on propellants by torsional braid measurements. The large negative value of the activation entropy is indicative of an associative mechanism, which is in accord with the second-order rate law for the polyurethane formation. (C) 1997 John Wiley & Sons, Inc.