• atom transfer radical polymerization;
  • block copolymers;
  • perfluorocyclobutyl;
  • self-assembly;
  • synthesis


A series of perfluorocyclobutyl (PFCB) aryl ether-based amphiphilic diblock copolymers containing hydrophilic poly(acrylic acid) (PAA) and fluorophilic poly(p-(2-(p-tolyloxy)perfluorocyclobutoxy)phenyl methacrylate) segments were synthesized via successive atom transfer radical polymerization (ATRP). 2-MBP-initiated and CuBr/N,N,N,N,N″-pentamethyldiethylenetriamine-catalyzed ATRP homopolymerization of the PFCB-containing methacrylate monomer, p-(2-(p-tolyloxy)perfluorocyclobutoxy)phenyl methacrylate, can be performed in a controlled mode as confirmed by the fact that the number-average molecular weights (Mn) increased linearly with the conversions of the monomer while the polydispersity indices kept below 1.38. The block copolymers with narrow molecular weight distributions (Mw/Mn ≤ 1.36) were synthesized by ATRP using Br-end-functionalized poly(tert-butyl acrylate) (PtBA) as macroinitiator followed by the acidolysis of hydrophobic PtBA block into hydrophilic PAA segment. The critical micelle concentrations of the amphiphilic diblock copolymers in different surroundings were determined by fluorescence spectroscopy using N-phenyl-1-naphthylamine as probe. The morphology and size of the micelles were investigated by transmission electron microscopy and dynamic laser light scattering, respectively. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010