Optimizing thermal and dielectric properties of ethylene-tetrafluoroethylene (ETFE)/h-BN composites via interface engineering: activation of C–F bonds on ETFE for surface grafting†

With the increasing demand for dielectric materials in high-frequency microwave applications, fluoropolymer-based dielectric materials have been widely utilized due to their excellent dielectric and insulation properties. However, the low thermal conductivity limits their ability to meet the thermal dissipation requirements during high-frequency and high-speed signal transmission. The present study introduces a pioneering interface engineering strategy wherein C–F bonds on the surface of ethylene-tetrafluoroethylene copolymer (ETFE) are photo-catalytically activated, enabling successful grafting of poly(glycidyl methacrylate) (PGMA) chain segments. Subsequently, the resulting graft copolymers are blended with thermally conductive h-BN filler to prepare composite dielectric materials. The results demonstrate that the incorporation of PGMA segments significantly enhances the interfacial compatibility between the ETFE matrix and h-BN filler, resulting in composites with a dense microstructure and outstanding dielectric and thermal properties. At a filler content of 30 vol%, the ETFE-g-PGMA@BN composite achieves an in-plane thermal conductivity of 4.2 W (m K)⁻¹ and a through-plane thermal conductivity of 0.77 W (m K)⁻¹. Moreover, at 1 GHz, the composite exhibits a dielectric constant of 2.2 and a dielectric loss of 0.004. This work presents a novel interface design strategy for surface modification of PTFE-based fluoropolymers, expanding their potential applications in printed circuit boards (PCBs) and providing a new direction for the design of polymer-based dielectric materials.