Conventional Radical Polymerization and Iodine-Transfer Polymerization of 40-Nonafluorobutyl styrene: Surface and Thermal Characterizations of the Resulting Poly(fluorostyrene)s

40-Nonafluorobutylstyrene (3) was synthesized and polymerized by conventional and controlled radical polymerization (iodine transfer polymerization (ITP)). Such an aromatic fluoromonomer was prepared from Ullmann coupling between 1-iodoperfluorobutane and 4-bromoacetophenone followed by a reduction and a dehydration in 50% overall yield. Two radical polymerizations of (3) were initiated by AIBN either under conventional or controlled conditions, with 1-iodoperfluorohexane in 84% monomer conversion and in 50% yield. ITP of (3) featured a fast monomer conversion and a linear evolution of the ln([M]0/[M]) versus time. The kinetics of radical homopolymerization of (3) enabled one to assess its square of the propagation rate to the termination rate (kp 2/ kt) in ITP conditions (36.21022 lmol22sec22 at 80 C) from the Tobolsky’s kinetic law. Polydispersity index (-D) of the fluoropolymer achieved by conventional polymerization was 1.30 while it worthed 1.15 when synthesized by ITP. Thermal stabilities of these oligomers were satisfactory (10% weight loss under air occurred from 305 C) whereas the melting point was 47 C. Contact angles and surface energies assessed from spin-coated poly(3) films obtained by conventional (hysteresis 5 18, surface energy 18 mN.m21) and ITP (hysteresis 5 47, surface energy 15 mN.m21) evidenced -D values’ influence onto surface properties of the synthesized polymers.