We have successfully synthesized two kinds of novel well-defined chain-end-functionalized polystyrenes with one, two, three, and four perfluorooctyl (C8F17) groups and structurally analogous block copolymers, poly[styrene-b-4-(3-perfluoroocyl)propoxystyrene], by means of living anionic polymerization, followed by the Williamson reaction with C8F17(CH2)3Br. The surface properties and compositions of the films prepared from both C8F17-functionalized polymers have been characterized by contact angles using water and dodecane droplets and angle-dependent XPS measurement. It was observed that C8F17 groups were segregated and preferentially enriched at their topmost surfaces and the extent of the enrichment increased with the number of C8F17 group. The dependence of extent of C8F17 group enrichment on fluorine content however appears to be different between chain-end-functionalized polymer and block copolymer.
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Sugiyama et al. (2002) studied this question.