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Ytterbium and lanthanum triflates were used as catalysts to cure diglycidylether of bisphenol A with different proportions of 1,3‐dioxan‐2‐one. 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 process. We observed the formation of a five‐membered cyclic carbonate that remains unreacted at the chain ends, because of an equilibrium process between the spiroorthocarbonates that had formed as intermediate species. The kinetics were studied by DSC experiments and analyzed with isoconversional procedures. The system catalyzed by ytterbium triflate had a higher curing rate. Thermogravimetric analysis and dynamic mechanical thermal analysis experiments were used to evaluate the properties of the materials obtained. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5799–5813, 2005

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 5,5dimethyl-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 CO 2 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.

Diglycidyl ether of bisphenol A or 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate were mixed with different proportions of 4-methyl-1,3-dioxolan-2-one and cured using lanthanide triflates as initiators. In order to compare the materials obtained, conventional initiators such as boron trifluoride complexes and N,N-dimethylaminopyridine were also tested. The curing process was followed by differential scanning calorimetry (DSC) and Fourier transform IR in attenuated total reflectance mode. This technique proved that the carbonate accelerates the curing process because it helps to form the active initiating species, although it was not chemically incorporated into the network and remained entrapped in the material. The DSC kinetic study was also reported.

Mixtures of diglycidylether of bisphenol A (DGEBA) with 1,3-benzodioxolane-2-one (CC) or 4-phenoxymethyl-1,3-dioxolane-2-one (PGEC) were cured in the presence of lanthanum triflate. FTIR/ATR was used to study the evolution of carbonate and epoxide groups to follow the reactive processes that take place during curing. DSC was applied to study the thermal characteristics of the curing process and to determine the glass-transition temperatures of the cured materials. The kinetics of the curing was studied isothermally by means of FTIR and the kinetic model was selected through the isokinetic relationships. DSC experiments were used to study the kinetics in nonisothermal conditions by means of isoconversional procedures and the Coats-Redfern and Criado methodologies. By TMA we could monitor the evolution of the shrinkage during isothermal curing.