Unprecendeted fluoroalkene-based copolymers through cobalt-mediated radical polymerization

Abstract

The precision design of fluorinated copolymers is challenging but also attractive for future developments in a wide range of applications involving fluoropolymers, such as advanced coatings or purification membranes. In particular, controlling the radical polymerization of fluoroalkenes remains extremely difficult because of the high reactivity of these monomers due to the lack of resonance stabilizing group on their double bond. Herein, Cobalt-Mediated Radical Polymerization (CMRP) was used to efficiently control the bulk copolymerization of perfluorohexylethylene (PFHE) and vinyl acetate (VAc). Well-defined statistical poly(PFHE-stat-VAc) copolymers with different compositions (0 < FPFHE < 0.5) were obtained accordingly. In some cases, fluorinated monomer content as high as 80 % by weight were achieved. Reactivity ratios were determined (rVAc = 0.18 and rPFHE = 0) and emphasized a clear tendency for alternation. Single step approach and sequential polymerization were assessed for the synthesis of novel PFHE/VAc block copolymers. Finally, the acidic hydrolysis of the pendant ester groups of these block copolymers led to the formation of novel highly amphiphilic macromolecules bearing a PVOH hydrophilic segment and a hydrophobic PFHE-based block