Three series of methacrylate homopolymers with oligo(hexafluoropropene oxide), (HFPO)n, side groups and copolymers based on methyl methacrylate were prepared by free radical polymerization. Each series consisted of a polymethacrylate backbone with substituted HFPO side chains of different length ranging from the corresponding tri-and tetramers to a pentamer. In case of the (HFPO)3MA copolymers, glass transition temperatures decreased linearly with increasing (HFPO)3MA content over the entire composition range. In contrast, two different regimes were distinguished for (HFPO)5MAcontaining copolymers, and also for the (HFPO)4MA homopolymer two Tg's were discerned. At low HFPO content the glass transition temperatures decreased with increasing (HFPO)5MA substitution. Above 50 mol % two glass transitions were observed, indicating microphase separation. Copolymers with only 10 mol % of (HFPO)nMA exhibited a low surface energy as is typical for highly fluorinated polymers. Dispersion force surface energies were determined by the Good-Girifalco-Fowkes-Young method and resulted in a minimum value of 11 ( 1 mN/m.
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