Networks containing oxazolidone, isocyanurate, urethane, allophanate and ether groups were prepared by copolymerization of mixtures of diglycidylether of bisphenol A and toluene-2,4-diisocyanate in presence of ytterbium triflate. It has been demonstrated that ytterbium triflate promotes six elemental reactions that coexist during curing and yield the aforementioned groups. Changes during curing, fraction of different groups present in the network and final properties of the cured materials were investigated by thermal analysis and infrared spectroscopy. The influence of the molar ratio of isocyanate to epoxide groups on the properties and curing has been studied. The curing kinetics were analyzed by means of an integral isoconversional non-isothermal procedure. The results obtained were compared with those obtained by using a common catalyst such as the benzyldimethylamine. The structure and the properties of the resulting thermosets are controlled by the initial composition of the formulation and the catalyst used. (C) 2012 Elsevier B.V. All rights reserved.