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To effectively reduce the fire hazard of flexible polyvinyl chloride (PVC), this study explored the synthesis of perovskite‐type copper hydroxystannate (CuSn(OH)6) microspheres by co‐precipitation method. Then an organic–inorganic hybrid microsphere (CuSn(OH)6@PZS) with core‐shell structure was fabricated by in situ coating with poly(cyclotriphosphazene‐co‐4,4′‐sulfonyldiphenol) (PZS). The results showed that CuSn(OH)6@PZS performs most significantly in reducing the total heat release, while the CuSn(OH)6 alone achieves the best smoke suppression effect. The limiting oxygen index (LOI) value of the PVC composites is improved from 29.0% to a maximum of 35.3%. During combustion, the peak heat release rate (PHRR) and total smoke production (TSP) decrease by a maximum of 50.8% and 44.9%, respectively. Significantly, the presence of the PZS coating also improves the interfacial compatibility with PVC. The mechanical properties were significantly improved and the elongation at break improving by 40.9%.

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