Syntheses and characterization of statistical and block fluorinated copolymers with linear and star-like architectures via ATRP

The synthesis of a fluorinated macroinitiator for copper-catalyzed atom transfer radical polymerization (ATRP) is reported, as well as its use for the controlled living polymerization of poly(propylene glycol) methacrylate (PPGM) in MEK at 80 °C. The ATRP system used was efficient for polymerization of the functionalized monomer and the molecular weight of the polymer estimated by NMR spectroscopy was in close agreement with the theoretical molecular weight, as expected for controlled processes. The statistical copolymerization of PPGM or methyl ether poly(ethylene glycol) methacrylate (MPEGMA) with a perfluoroalkyl ethyl methacrylate by copper-mediated ATRP was also investigated and led to copolymers with essentially random incorporation of monomers. The syntheses and characterization of star-like homopolymers of MPEGMA or the fluorinated monomer via ATRP are also reported, as well as an amphiphilic star-like block copolymer containing ethyleneglycol units as the core and fluorinated moieties in the shell. The micellar behavior of this copolymer was investigated as a function of the external environment.