• atom transfer radical polymerization (ATRP);
  • nanocomposites;
  • perfluorinated polymers;
  • polyhedral oligomeric silsesquioxane;
  • star polymers


Well-defined organic/inorganic hybrid fluorinated star polymers were synthesized via atom transfer radical polymerization (ATRP) of 2,2,3,4,4,4-hexafluorobutyl methacrylate (HFBMA) using octa(aminophenyl)silsesquioxane (OAPS) nano-cage as initiator. For this purpose, OAPS was transformed into ATRP initiator by reacting with 2-bromoisobutyrylbromide. ATR polymerization of HFBMA was carried out in trifluorotoluene at 75 °C using CuCl/2,2-bipyridine or N,N,N′,N″,N″-pentamethyldiethylenetriamine as catalyst system. GPC and 1H NMR data confirmed the synthesis of OAPS/PHFBMA hybrid star polymer. Kinetics of the ATR polymerization of HFBMA using OAPS nano-cage initiator was also investigated. The OAPS/PHFBMA hybrid stars were found to be molecularly dispersed in solution (THF); however, TEM micrographs revealed the formation of spherical particles of ∼ 120–180 nm by the OAPS/PHFBMA hybrid star polymer after solvent evaporation. Thermal characterization of the nanocomposites by differential scanning calorimetry (DSC) revealed a slightly higher glass transition temperature (Tg) (when compared with the linear PHFBMA) of higher molecular weight OAPS/PHFBMA hybrid star polymers. In contrast, lower Tg than the linear PHFBMA was observed for OAPS/PHFBMA of relatively lower molecular weight (but higher than the linear PHFBMA). Thermal gravimetric analysis (TGA) showed a significant retardation (by ∼60 °C) in thermal decomposition of nanocomposites when compared with the linear PHFBMA. Additionally, surface properties were evaluated by measuring the contact angles of water on polymer surfaces. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7287–7298, 2008