Ytterbium and lanthanum triflates were used as initiators to cure a mixture of diglycidylether of bisphenol A (DGEBA) and 5,5-dimethyl-1,3-dioxane-2-one (DMTMC). The evolution of the curing was studied by differential scanning calorimetry (DSC) and Fourier transform infrared in the attenuated-total-refiection mode (FTIR/ATR). FTIR/ATR was used to monitor the competitive reactive processes and to quantify the evolution of the groups involved in the curing process. We observed the formation of a five-membered cyclic carbonate, which remains unreacted at the chain ends because of an equilibrium process between the spiroortho carbonates that had formed as intermediate species and also the loss of CO2, which was quantified by thermogravimetry. The kinetics were studied by DSC and analyzed by isoconversional procedures. Thermogravimetric analysis (TGA) and dynamic mechanical thermal analysis (DMTA) experiments were used to evaluate the properties of the thermosets obtained. The phenomenological changes that take place during curing were studied and represented in a time-temperature-transformation (TTT) diagram. (c) 2006 Wiley Periodicals, Inc.