Substantial improvement of thermal conductivity and mechanical properties of polymer composites by incorporation of boron nitride nanosheets and modulation of thermal curing reaction

Abstract Thermal conductive polymer‐based composites synchronously with stable dielectric and excellent mechanical properties are urgently needed for high‐temperature‐resistant electronic devices. Here, a significant improvement in the thermal conductivity (TC), thermal stability, dielectric, and mechanical performance was simultaneously achieved in the polyarylene ether nitrile (PEN)/divinyl siloxane‐bisbenzocyclobutene (BCB) matrix through the incorporation of boron nitride nanosheets (BNNS) combined together with the post‐solid phase chemical reaction technique. The significant increase in the effective filler‐filler and filler‐crystal contacts in the composites was the main reason for the improvement in TC and dielectric constant. Besides, glass transition temperature ( T g ) and mechanicals were enhanced in the presence of cross‐linked networks. By synchronously adding 15 vol% BNNS, the TC of composites after treatment reached up to 5.582 W/m.K, enhanced by 4.4 times higher than untreated. The dielectric constant was down to 2.93 at 1 MHz and the loss remained at a relatively low level. Meanwhile, the composite showed significantly enhanced thermal stability, mechanicals, and hydrophobicity ( T g = 336°C, T 5% = 529°C, tensile strength and modulus was 94.5 MPa and 5.3 GPa, respectively, the contact angle was 101.76°). Thus, it promotes an effective strategy for fabricating a high‐performance‐polymer composite, which has the potential used in electronic materials. Highlights Crystallization‐crosslinking strategy optimizes overall performance. Crystals fill gaps between BNNS layers and connect thermal conductive pathway. Crosslinked networks limit molecular chain motion to reduce phonon scattering. The highest TC of the PEN/BCB/BNNS composite is up to 7.451 W/m.K. Thermal property shows significant improvement after crosslinking especially T g .