LAUSR

Perfluorinated gradient copolymers comprising fluorous units and hydrophobic or hydrophilic units were created as fluorous polymer materials with unique physical properties. The gradient copolymers were efficiently synthesized via the tandem catalysis of living radical polymerization and titanium alkoxide-mediated transesterification of 1H,1H,2H,2H-perfluorooctyl methacrylate (13FOMA) with alcohols. Owing to the electron-withdrawing perfluorooctyl unit, 13FOMA was efficiently transesterified into another methacrylate (RMA) with alcohols during the copolymerization of 13FOMA and RMA to afford well-controlled 13FOMA/RMA gradient copolymers. The gradient sequence gradually changed from 13FOMA to RMA-rich composition according to monomer composition varying in the polymerization solutions. The tandem catalysis is allowed to use various alcohols including 1-dodecanol, 1-octadecanol, ethanol, and poly(ethylene glycol) methyl ether; the catalysis developed herein is thus one of the most versatile systems to prod...