Kinetics and Thermodynamics of Synthesis of Hybrid Oligomer‐Acrylated Cycloaliphatic Epoxy in the Presence of Triphenylphosphine and Triethylamine Catalysts

The kinetics for the esterification of cycloaliphatic epoxy resin with acrylic acid was investigated in the presence of two different catalysts, namely triethylamine (TEA) and triphenylphosphine (TPP). The reactions were carried out at four different temperatures in the range of 80–110°C and 60–90°C for TPP and TEA catalysts, respectively. The power law kinetics model was adopted for analyzing experimental data to determine reaction equations. Both differential and integral methods were applied to determine the reaction orders and reaction constants. The overall reaction order for the reaction systems was found to be 2 using both differential and integral methods. According to the differential method, the reaction orders with respect to epoxide and carboxylic acid groups were calculated to be 1.2 and 0.8, respectively. The reactions could be considered as first‐order reactions with respect to each group based on integral method analysis. The activation energies and frequency factors of these esterification reactions were found to be 77.2 kJ·mol^?1 and 1.72E+10 L·mol^?1_·min^?1 in the presence of TPP and 65.3 kJ·mol^?1 and 1.44E+7 L·mol^?1·min^?1 in the presence of TEA. The thermodynamic parameters of reaction in the presence of TPP and TEA were calculated. The results confirmed that both reactions were spontaneous and irreversible. It was found that the reaction in the presence of TEA produced a highly ordered activated complex.