N,N-Dimethylaminopyridine (DMAP) was used as initiator to cure mixtures of diglycidylether of bisphenol A (DGEBA) and 1,3-dioxan-2-one (TMC) or 5,5-dimethyl-1,3-dioxan-2-one (DMTMC). The curing was studied by differential scanning calorimetry (DSC) and Fourier transform infrared in the attenuated-total-reflection 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. We observed the formation of five-membered cyclic carbonates and anionic carbonate groups that remain unreacted at the chain ends. The formation of these groups was explained by the attack of the anionic propagation species on the methylene carbon of the carbonate group, which leads to an alkyl-oxygen rupture. By performing the cure in the thermobalance we could evaluate the loss Of CO2 produced in the samples containing carbonates. The kinetics were studied by DSC and analyzed with isoconversional procedures. The addition of carbonates slows down the curing rate. Thermogravimetric analysis (TGA) and dynamic mechanical thermal analysis (DMTA) experiments were used to evaluate the properties of the materials obtained. (c) 2006 Wiley Periodicals, Inc.