Curing and thermomechanical properties of off-stoichiometric anhydride-epoxy thermosets

n the present work, we report the preparation and characterization of a new family of thermosets based on off-stoichiometric anhydride–epoxy formulations in the presence of an anionic initiator. Diglycidyl ether of bisphenol A (DGEBA) and hexahydro-4-methylphthalic anhydride (HHMPA) have been used as epoxy and anhydride comonomers, respectively, and 1-methylimidazole (1MI) has been used as anionic initiator. The isothermal curing kinetics and the thermal properties of the stoichiometric and the off-stoichiometric systems have been compared. The kinetics of the isothermal curing has been analyzed by differential scanning calorimetry (DSC) using an isoconversional method and the S ¿esta ´k–Berggren equation to determine the activation energy, the frequency factor and the reaction orders. The materials obtained were characterized by DSC and dynamic mechanical analysis. Gelation during epoxy–anhydride condensation was determined by thermomechanical analysis. At the same curing temperature, the reaction is faster in the system with excess of epoxy groups. However, the glass transition temperatures of the partially cured stoichiometric system are greater. The gelation time of the off-stoichiometric system is shorter than that of the stoichiometric one. The results indicate that the dual-curing character of off-stoichiometric DGEBA/HHMPA thermosets with 1MI as anionic initiator makes them suitable for multistage curing processes with easy control of degree of cure and material properties in the intermediate stage and enhanced ¿nal material properties