The thermal curing behavior of tetraglycidyl-4,4'-diaminodiphenylmethane (TGDDM) and a co-anhydride mixture consisting of maleic anhydride (MA) and hexahydrophthalic anhydride (HHPA) was studied from 55 to 100 degreesC by real-time FT-Raman spectroscopy. The quantitative changes in concentrations of anhydride, epoxy, and new-formed ester were measured and empirical reaction rate curves were constructed reflecting the kinetics of the curing process. After an induction period a simple kinetic scheme that is first order in both epoxy and anhydride monomer consumption described the reaction profile until the reaction was influenced by chemo-rheological changes due to vitrification transition. FT-Raman analysis revealed that curing propagation mainly occurs by polyesterification between epoxide and anhydride. Possible side reactions including the homopolymerization of MA are considered. The main side reaction is decarboxylation of MA that may produces some autocatalysis, but this is a minor contribution to the kinetics of cure. No conclusive evidence has been found for homopolymerization of MA or initiation of the curing reaction by the reaction product of TGDDM and MA, compared to the polyesterification. (C) 2004 Elsevier Ltd. All rights reserved.