Novel Perfluorocyclobutyl Aryl Ether-Based Well-Defined Amphiphilic Block Copolymer

A series of fluorine-containing amphiphilic diblock copolymers comprising hydrophobic poly(p-(2-(p-tolyloxy)perfluorocyclobutoxy)phenyl methacrylate) (PTPFCBPMA) and hydrophilic poly(2-(diethylamino) ethyl methacrylate) (PDEAEMA) segments were synthesized via successive reversible addition fragmentation chain transfer (RAFT) polymerizations. RAFT homopolymerization of p-(2-(p-tolyloxy)perfluorocyclobutoxy)phenyl methacrylate was first initiated by 2,2'-azobisisobutyronitrile using cumyl dithiobenzoate as chain transfer agent, and the results show that the procedure was conducted in a controlled way as confirmed by the fact that the number-average molecular weights increased linearly with the conversions of the monomer while the polydispersity indices kept below 1.30. Dithiobenzoate-capped PTPFCHPMA homopolymer was then used as macro-RAFT agent to mediate RAFT polymerization of 2-(diethylamino) ethyl methacrylate, which afforded PTPFCBPMA-b-PDEAEMA amphiphilic diblock copolymers with different block lengths and narrow molecular weight distributions (M-w/M-n <= 1.28). The critical micelle concentrations of the obtained amphiphilic diblock copolymers were determined by fluorescence spectroscopy technique using N-phenyl-1-naphthylamine as probe. The morphology and size of the formed micelles were investigated by transmission electron microscopy and dynamic light scattering, respectively. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 4433-4440, 2011