Rheokinetic cure characterization of epoxy–anhydride polymer system with shape memory characteristics

An epoxy resin capable of exhibiting shape memory property was derived by curing diglycidyl ether of bisphenol A (DGEBA) with a blend of carboxy telechelic poly(tetramethyleneoxide) (PTAC) and pyromellitic dianhydride (PMDA). The cure kinetics of DGEBA/PTAC/PMDA blend of varying compositions was investigated using isothermal rheological analysis. The overall reaction conformed to a second-order autocatalytic model. The kinetic parameters including reaction order, kinetic constants and activation energy were determined. The results showed that increase of PTAC decreased the overall activation energy and frequency factor of the cure reaction. This effect resulted in a diminution of the overall rate of curing. The catalysis by PTAC has its origin from the activation of epoxy groups by the protons of the COOH groups. The autocatalysis was caused by the COOH groups generated by the reaction of alcohol groups with anhydride. The activation energy for the autocatalysis was more than that for the primary reaction as the COOH groups responsible for autocatalysis were generated on a sterically hindered polymer backbone. The kinetics helped generate a master equation conforming to second-order autocatalytic model that could predict the cure profile of a specified resin system at a given temperature, leading to cure optimization.