Coal‐based environment‐friendly PVC/ASA flame‐retardant and antistatic composites were made by melt blending poly(vinyl chloride)/acrylonitrile–styrene‐acrylate (PVC/ASA) with self‐made alkaline calcium‐based coal gangue thermal stabilizer (Y‐CG) and dimethyl sulfoxide (DMSO) intercalation modified Coal (A‐Coal). The flame‐retardant mechanism of PVC/ASA/A‐Coal/Y‐CG composites was due to incombustible gas, maze effect, carbon residue layer and blowing‐out effect through limiting oxygen index (LOI), vertical combustion (UL‐94) and scanning electron microscope (SEM) test. The results indicated that PVC/ASA/12A‐Coal/10Y‐CG composites had the best flame‐retardant properties with LOI value of 31.8% and can pass the V‐0 rating in the UL‐94 test. After combustion, PVC/ASA/12A‐Coal/10Y‐CG composites formed a dense carbon layer that inhibits gas released and heat transferred. The surface resistivity (ρs) and volume resistivity (ρv) of PVC/ASA/A‐Coal/Y‐CG composites first decreased and then increased with the increase of A‐Coal content. The ρs and ρv values of PVC/ASA/12A‐Coal/10Y‐CG composites decreased to the minimum values of 5.14 × 106 Ω and 9.05 × 105 Ω·cm. The tensile strength and impact strength of PVC/ASA/A‐Coal/Y‐CG composites first increased and then decreased with A‐Coal content. The tensile strength and impact strength of PVC/ASA/12A‐Coal/10Y‐CG composites reached the maximum of 65.03 MPa and 17.52 kJ/m2, respectively. To sum up, the incorporation of A‐Coal and Y‐CG can reinforce and toughen PVC/ASA composites, but it can also enhance their flame‐retardant, antistatic properties.

With the rapid development of electronic devices and rubber tires, the industry has put forward new requirements for the heat dissipation of rubber components. With excellent thermal conductivity, oxidation resistance, and thermal stability, hexagonal boron nitride (h-BN) is often added to plastics or rubber as a thermally conductive filler, but is less effective when used directly. In this study, h-BN-K was prepared by direct modification of the mixed solution of KH-550, and KH-570, while h-BN-PK was prepared by co-modification of dopamine, KH-550, and KH-570. Two modified h-BN were added to natural rubber (NR) to improve the vulcanization properties, mechanical properties, and thermal conductivity. It was found that the tensile strength and thermal conductivity of 20 wt% h-BN-PK/NR composites were 30.6 MPa and 0.335 W/mK, which were 39.1% and 110.7% higher compared to pure NR (22.0 MPa and 0.159 W/mK), respectively. In addition, the addition of h-BN improved the thermal stability performance of NR to some extent. In conclusion, the h-BN-PK/NR composites provide a certain reference for the use of thermally conductive NR and suggest new ideas for heat dissipation of electronic devices.