Fluoride‐Catalyzed Siloxane Exchange as a Robust Dynamic Chemistry for High‐Performance Vitrimers

Abstract Sustainable development of new technologies requires materials having advanced physical and chemical properties while maintaining reprocessability and recyclability. Vitrimers are designed for this purpose; however, their dynamic covalent chemistries often have drawbacks or are limited to specialized polymers. Here, fluoride‐catalyzed siloxane exchange is reported as an exceptionally robust chemistry for scalable production of high‐performance vitrimers through industrial processing of commodity polymers such as poly(methyl methacrylate), polyethylene, and polypropylene. The vitrimers show improved resistance to creep, heat, oxidation, and hydrolysis, while maintaining excellent melt flow for processing and recycling. Furthermore, the siloxane exchange between different vitrimers during mechanical blending results in self‐compatibilized blends without any compatibilizers. This offers a general, scalable method for producing sustainable high‐performance vitrimers and a new strategy for recycling mixed plastic wastes.