Polymer networks based on the diepoxide–diisocyanate reaction catalyzed by tertiary amines

Reactions taking place in a system consisting of a diepoxide (DGEBA, diglycidylether of bisphenol A) and a diisocyanate (TDI 80 : 20, toluene diisocyanate), catalyzed by a tertiary amine (BDMA, benzyldimethylamine), were followed by differential scanning calorimetry (DSC), infrared spectroscopy (FTIR), and chemical titration of isocyanate groups in the pre‐gel stage. It was found that the main reactions took place in series, in steps of increasing temperature: (i) isocyanurate formation, (ii) epoxy‐isocyanate reaction leading to oxazolidone rings, and (iii) isocyanurate decomposition by epoxy groups producing oxazolidone rings. Isocyanurate rings were stable in the presence of epoxides and an isocyanate excess [reaction (ii) was faster than (iii)]. Epoxy homopolymerization (secondary reaction) occurred in parallel with steps (ii) and (iii). Step (i) took place by two different mechanisms and led to a maximum conversion, possibly limited by topological restrictions. A kinetic study of TDI trimerization in the presence of an equimolar amount of DGEBA and variable amounts of BDMA led to a third‐order regression with an activation energy E = 43 kJ/mol.