Mechanochemical pathway for converting fluoropolymers to fluorochemicals.

The growing demand for fluorochemicals has increased the production of toxic hydrogen fluoride (HF)-a widely used fluorination agent-from mineral fluorspar (CaF2). Although potassium fluoride (KF) is a safer alternative fluorination agent, its production still involves HF as an intermediate. Simultaneously, the disposal of fluoropolymer waste, especially polyvinylidene fluoride (PVDF), poses environmental challenges. We present a mechanochemical protocol that decomposes PVDF to generate KF as a nucleophilic fluorinating agent. As an advantage over traditional batch reactions, mechanochemical protocols can be performed quickly, and with or without modest volumes of solvents. We show that KF produced using this method can be used to efficiently construct S-F, C(sp2)-F and C(sp3)-F bonds, providing a sustainable solution to fluorine resource depletion and hazardous HF usage. Our approach also addresses fluoropolymer waste disposal and reduces reliance on natural fluorspar resources, marking a notable advancement in fluorine chemistry and paving the way for safer and eco-friendly fluorination techniques.