Reaction mechanism, cure behavior and properties of a multifunctional epoxy resin, TGDDM, with latent curing agent dicyandiamide

Abstract

A novel resin system was prepared using the glycidyl amide type multifunctional epoxy resin N,N,N′,N′-tetraglycidyl-4,4′-diaminodiphenylmethane (TGDDM) and latent curing agent dicyandiamide (DICY). The curing reaction mechanism of the TGDDM/DICY system was studied by Fourier transform infrared (FTIR) spectrometry and the non-isothermal cure behaviors of the mixture were investigated with differential scanning calorimetry (DSC) measurements. The FTIR results demonstrated that there were two main reactions occurring in the curing process of the TGDDM/DICY system. The DSC thermogram of the blend exhibited two different cure regimes in the temperature range of 140–358 °C, and the system experienced two autocatalytic curing processes with α = 0.45 as the boundary; the corresponding average activation energies calculated by the Kissinger method were 69.7 and 88.7 kJ mol⁻¹, respectively. In addition, the correlation between activation energy E_a and fractional conversion α was determined by applying model-free isoconversional analysis with Flynn–Wall–Ozawa (FWO) and Starink methods. Results showed that both methods revealed similar trends and possessed approximately the same values at each fractional conversion. Activation energy varied greatly with fractional conversion and the possible causes behind the variations were analyzed in detail. The cured TGDDM/DICY exhibited outstanding mechanical and adhesive properties with tensile and shear strengths of 27.1 MPa at 25 °C and12.6 MPa at 200 °C, good dielectric properties with a low dielectric constant of 3.26 at 1000 kHz and a low water absorption of 0.41%.