DGEBA epoxy resin was cured with different proportions of 1,5,7,11-tetraoxaspiro[5.5]undecane (TOSU) with ytterbium and lanthanum triflates as catalysts. The curing was Studied by differential scanning calorimetry (DSC) and Fourier transform infrared in the attenuated-total-reflexion mode (FTIR/ATR). FITR/ATR was used to monitor the competitive reactive processes and to quantify the evolution of the epoxide, orthocarbonate, linear carbonate and other groups formed in the curing process. The T, of the cured materials decreased when the proportion of TOSU increased. The kinetics were studied by DSC experiments and analyzed with iso-conversional procedures. The systems catalyzed by ytterbium triflate had a higher curing rate and reached a higher degree of cross-linking. The addition of TOSU reduced the degree of overall shrinkage and even led to one material expanding. The flexibility and the degradability of these materials were improved by introducing higher proportions of TOSU. (c) 2005 Elsevier Ltd. All rights reserved.