The kinetics of the curing reaction for a system of o-cresol formaldehyde epoxy resin (o-CFER) with 4,4'-diaminodiphenyl ether (DDE) as a curing agent were investigated with differential scanning calorimetry (DSC). An analysis of the DSC data indicated that an autocatalytic behavior appeared in the first stages of the cure for the system, and this could be well described by the model proposed by Kamal, which includes two rate constants and two reaction orders (m and n). The overall reaction order (m + n) was 2.7-3.1, and the activation energies were 66.79 and 49.29 kJ mol(-1), respectively. In the later stages, a crosslinked network was formed, and the reaction was mainly controlled by diffusion. For a more precise consideration of the diffusion effect, a diffusion factor was added to Kamal's equation. In this way, the curing kinetics were predicted well over the entire range of conversions, covering both the previtrification and postvitrification stages. The glass-transition temperatures of the o-CFER/DDE samples were determined via torsional braid analysis. The results showed that the glass-transition temperatures increased with the curing temperature and conversion up to a constant value of approximately 370 K. The thermal degradation kinetics of the system were investigated with thermogravimetric analysis, which revealed two decomposition steps. (C) 2004 Wiley Periodicals, Inc.