Polymer dielectric composites featuring great thermal stability, excellent mechanicals, and good dielectric properties have sparked considerable attention. Here, the preparation of hybrid filler was first performed. The hydroxyl end-capped polyarylene ether nitrile (PEN-OH) was synthesized and then hydroxy BNNS (BNNS-OH) was combined with PEN-OH to obtain PEN-OH@BNNS-OH, which is fabricated by ultrasonic combined with applying post-solid phase chemical reaction technology. The aim is to use the -OH interactions of BNNS-OH and PEN-OH to form hydrogen bonds that greatly enhance interfacial heat transport. Next, the post-solid phase chemical reaction is utilized to make PEN-OH crystallize, and its crystals located on the two-dimensional planes of BNNS-OH or between the layers can serve as a thermal bridge. Then, the as-prepared film with 10 wt% hybrid filler displays high thermal conductivity (1.17 W/m.K), 13.67%-fold higher than pure PEN film, boasts outstanding mechanical properties (stress 105 MPa, strain 6%), high glass transition temperature (Tg: 224 ℃), a dielectric constant (4.30 at 106 Hz), together with low dielectric loss (0.007 at 106 Hz). Besides, the film was post-treated to increase the thermal conductivity to 1.77 W/m.K, reach a higher Tg of 263 ℃, reduce the dielectric constant and loss to 3.68 and 0.006 at 106 Hz. Thus, it is suitable as a high-temperature-resistant dielectric material.
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