Natanya M. L. Hansen, Michael Gerstenberg, David M. Haddleton and Søren Hvilsted
2,2,2-trifluoroethyl methacrylate (3FM), 2,2,3,3,4,4,5,5-octafluoropentyl methacrylate, and 1,1,2,2-tetrahydroperfluorodecyl methacrylate have been copolymerized with methyl methacrylate via ATRP catalyzed by Cu(I)Br/N-(n-propyl)-2-pyridylmethanimine. 3FM was furthermore copolymerized with 2-methoxyethyl acrylate and poly(ethylene glycol) methyl ether methacrylate. Homopolymerization of 3FM at temperatures of 80–110 °C yielded kpapp of 1.6·10−4 s−1 to 2.9·10−4 s−1 and Ea of 24 kJ/mol. The thermal stability of the fluorinated poly(methacrylates) in inert atmosphere is less than that of the nonfluorinated poly((meth)acrylates). In all instances, the presence of fluorinated blocks significantly increases the advancing water contact angle (up to 118°) of thin films deposited on glass in comparison to equivalent nonfluorinated films.