A Fourier transform infrared (FTIR) spectroscopy technique was developed to investigate the effects of reaction temperature and reactant composition on the isothermal curing kinetics of commercial vinyl nester resins comprised of vinyl-ester monomer (dimethacrylate of diglycidyl ether of bisphenol A DGEBA) and styrene. This technique enables a more complete evaluation of the bulk copolymerization reaction of vinyl-ester-styrene systems by monitoring the depletion of vinyl-ester and styrene double bonds independently. The results indicate that the rate of fractional conversion of styrene double bonds is initially less than that of vinyl-ester vinyl groups. However, styrene monomer continues to react after conversion of vinyl-eater double bonds has ceased. In addition, the overall extent of conversion was found to increase with increasing isothermal cure temperature, and it was observed that higher styrene concentration enhances final conversion of vinyl-eater double bonds and not styrene double bonds. Increasing styrene monomer concentration also resulted in lowering the apparent activation energy for the reaction of vinyl groups from both monomers as characterized by an empirical autocatalytic model used to fit the conversion results for styrene and vinyl-ester double bonds independently. The results of this work demonstrate that reaction temperature and resin composition significantly affect the cure behavior of vinyl-ester resins and provide insight into the development of the resulting network structure. (C) 2000 John Wiley & Sons, Inc.