Ultra-high cross-linked active ester-cured epoxy resins: Side group cross-linking for performance enhancement

Active ester hardeners are a unique class of epoxy hardeners that undergo a curing reaction without generating secondary hydroxyl groups. This characteristic enables the production of low dielectric and low moisture absorption epoxy resins. In this study, two active ester hardeners, bisphenol A diisobutyrate (DIB) and bisphenol A dimethacrylate (DMA), were used to prepare epoxy resins by reacting with a resveratrol-based epoxy monomer (REP). By cross-linking the double bonds in the resin (using dicumyl peroxide, DCP), the properties of the resin can be dramatically changed. Among the resins prepared, REP/DMA/DCP exhibited the highest cross-linking density, approximately 48 times that of REP/DIB. Its storage modulus at 300 ˚C remained at 600 MPa, indicating an equivalent glass transition temperature (Tg) higher than 300 ˚C. Additionally, the cross-linking of the ester side groups increased the initial degradation temperature by 12-13 ˚C, reaching 395-396 ˚C. Regarding the coefficient of thermal expansion (CTE), the cross-linking of ester side groups had no significant effect on the CTE in the glassy state. However, it drastically reduced the CTE above the glass transition temperature. The average CTE (30-300 ˚C) of REP/DMA/DCP was only 106 ppm/˚C. Furthermore, the cross-linking of the ester side groups appeared to reduce the dielectric constant but increased the dielectric loss and the water absorption rate. Nevertheless, REP/DMA/DCP's dielectric constant at 10 MHz of 3.07, dielectric loss of 0.01, and saturated water absorption of 0.77 wt% remain in the low range.