Polymer 50 (2009) 2341–2348

We present the synthesis and self-assembly behavior of a new semi-fluorinated amphiphilic triblock copolymer. A series of perfluorocyclobutyl aryl ether-based amphiphilic ABA triblock copolymer containing hydrophilic poly(ethylene glycol) segment as the middle block were synthesized by atom transfer radical polymerization (ATRP). ATRP of 4-(40-p-tolyloxyperfluorocyclobutoxy)benzyl methacrylate was initiated by PEG-based bifunctional macroinitiators with different molecular weights to obtain the desired copolymers with narrow molecular weight distributions (Mw/Mn  1.30) and the
number of perfluorocyclobutyl linkage can be tuned by the feed ratio and the conversion of the fluorinecontaining methacrylic monomer. The critical micelle concentrations of these amphiphilic ABA triblock copolymers in aqueous media were determined by fluorescence probe technique. They could aggregate to form spherical and cylindrical micelles visualized by TEM with varying the content of hydrophobic segment.