Chemical interpretation of the relaxed permittivity during epoxy resin cure

The isothermal cure of a diglycidyl ether of Bisphenol‐A (DGEBA) epoxy resin with diaminodiphenylsulfone has been characterized by microdielectrometry and differential scanning calorimetry. The cure temperatures ranged from 410 to 460K. The behavior of the relaxed (or static) dielectric permittivity vs. cure time and temperature was determined from the microdielectrometry data. The DSC data was fit to an autocatalyzed reaction kinetics model, which was then used to predict reactive group concentrations as a function of cure time and temperature. The temperature dependence of the relaxed permittivity at constant chemical conversion was examined in the context of the Onsager theory for the relaxed permittivity of a system of independent dipoles. This analysis indicated that the dipoles in the resin are not independent, as assumed by the Onsager theory, and that the behavior is similar to that observed in polyethers. An empirical modification to the Onsager theory was used in conjunction with the kinetic model to estimate dipole moments for the epoxide, primary amine, and reacted (secondary and tertiary) amine groups. The relative and absolute values of the dipole moments were in good agreement with estimates based on the structures, leading to the conclusion that the observed decrease of the relaxed permittivity during cure of this epoxy/amine system is due to the changing concentrations of polar reactive groups.