Palladium‐Catalyzed Polymerization of Perfluoroalkyl Iodide and Aromatic Alkynes for the Synthesis of Perfluoroalkylated Poly(enyne)s

Abstract Fluoropolymers with unique structures, high chemical stability, heat resistance, hydrophobicity, and insulation to electricity, have attracted much attention, owing to their applications in low surface energy coatings, dielectric materials, solid electrolytes, ion exchange membranes, and so on. However, the synthetic approaches for fluoropolymers are quite limited, and it is crucial to develop new synthetic approaches for the pursuing of new fluoropolymer structures. Herein, a series of soluble conjugated fluoropolymers with unique 1,3‐enyne structures embedded in the polymer chain and perfluoroalkyl group as sidechains are synthesized in high yields of up to 96% from a palladium‐catalyzed polymerization of aromatic terminal diynes and perfluorobutyl iodide in 1,4‐dioxane at 80 °C using K 2 CO 3 as the base. The chemical structures of the fluoropolymers are fully characterized by gas permeation chromatography (GPC), 1 H, 13 C, 19 F NMR, and IR spectra, together with the comparison with the spectra of the small molecular model compound, confirming their expected polymer structures with high selectivity, high molecular weights of up to 60 500 g mol −1 , good solubility, high thermal resistance, and hydrophobicity. This efficient polymerization provides a convenient tool for the preparation of fluoropolymers, promoting the development of polymer synthetic methodology and the exploration of new fluoropolymer structures and materials.