Ultrahigh Heat/Fire‐Resistant, Mechanically Robust, and Closed‐Loop Chemical Recyclable Polycarbonate Enabled by Facile Bond Dissociation Energy Modulation

Abstract Plastics serve as an essential foundation in contemporary society. Nevertheless, meeting the rigorous performance demands in advanced applications and addressing their end‐of‐life disposal are two critical challenges that persist. Here, an innovative and facile method is introduced for the design and scalable production of polycarbonate, a key engineering plastic, simultaneously achieving high performance and closed‐loop chemical recyclability. The bisphenol framework of polycarbonate is strategically adjusted from the low‐bond‐dissociation‐energy bisphenol A to high‐bond‐dissociation‐energy 4,4′‐dihydroxydiphenyl, in combination with the incorporation of polysiloxane segments. As expected, the enhanced bond dissociation energy endows the polycarbonate with an extremely high glow‐wire flammability index surpassing 1025 °C, a 0.8 mm UL‐94 V‐0 rating, a high LOI value of 39.2%, and more than 50% reduction of heat and smoke release. Furthermore, the π‐π stacking interactions within biphenyl structures resulted in a significant enhancement of mechanical strength by as more as 37.7%, and also played a positive role in achieving a lower dielectric constant. Significantly, the copolymer exhibited outstanding closed‐loop chemical recyclability, allowing for facile depolymerization into bisphenol monomers and the repolymerized copolymer retains its high heat and fire resistance. This work provides a novel insight in the design of high‐performance and closed‐loop chemical recyclable polymeric materials.