Facile Synthesis of Functional Processable Fluoropolydienes by Alkyne-Based Multicomponent Polycouplings

A facile alkyne-based multicomponent polymerization route was developed for the construction of solution-processable fluoropolymers with multiple functionalities. The palladium-catalyzed one-pot polycouplings of diynes, arylboronic acids, and perfluoroalkyl diiodides proceed efficiently in THF/H2O mixtures at 39 °C for 12 h under nitrogen atmosphere, furnishing E-configuration-predominant fluoropolydienes (FPDs) with high molecular weights (Mw up to 69,400) in satisfactory yields (up to 90.3%). This polymerization method shows good tolerance to moisture and various functional groups. The obtained fluoropolymers possess good solution processability and film-forming ability, which enable them to be used as functional films. Their thin films exhibit photoresponsive fluorescence and high refractive indices. Well-resolved fluorescent 2D-photopatterns can be readily generated by the photolithography technique. Besides, these polymers show good thermal stability with high degradation temperatures at 5% weight loss of up to 364 °C.