Diglycidyl ether of bisphenol A was cured with different proportions of caprolactone with ytterbium triflate as an initiator. The curing was studied by means of differential scanning calorimetry and Fourier transform infrared in the attenuated total reflection mode. The latter was used to monitor the competitive reactive processes and to quantify the conversions of the epoxide, lactone, and intermediate spiro-orthoester groups. A partial depolymerization process from the cured material to free gamma-caprolactone was also identified. The formation of a stable carbocation and the coordinative capability of ytterbium triflate were the reasons for this unexpected process. The thermal and dynamic mechanical properties of the cured materials were determined with differential scanning calorimetry, thermogravimetric analysis, and dynamic mechanical thermal analysis. An increase in the proportion of gamma-caprolactone resulted in an increased curing rate, a decrease in the shrinkage after gelation, and a significant decrease in the glass transition temperature. The introduction of ester linkages into the three-dimensional structure led to more thermally degradable thermosets. (c) 2006 Wiley Periodicals, Inc.