Associative properties of perfluorooctyl end-functionalized polystyrene-poly(ethylene oxide) diblock copolymers

The synthesis of 2,2,3,3-tetrahydro-perfluoroundecanoyl end-functionalized polystyrene-poly(ethylene oxide) block (PS-block-PEO-R-F) copolymers and their matching PS-block-PEO diblock copolymers was carried out by sequential anionic polymerization. Viscometry and F-19 NMR studies show that the PS-block-PEO copolymers, in contrast to their matching PS-block-PEO-R-F copolymers, exhibit a micellar rather than the associative behavior seen for the latter. However, the presence of an excess of fluorinated acid, used for end-functionalization, produces a reduction of the associative behavior above the overlap concentration, with the fluorinated acid acting like a surfactant. A competition may also occur between PS-and R-F-mediated micellization. (C) 2004 Society of Chemical Industry.