Atom Transfer Radical Polymerization in Supercritical Carbon Dioxide

Atom transfer radical polymerization (ATRP) has been successfully carried out in supercritical carbon dioxide (scCO<INF>2</INF>) for the polymerization of fluorinated (meth)acrylates. In particular, well-controlled polymerizations have been obtained with the use of a fluoroalkyl-substituted 2,2‘-bipyridine ligand. Block copolymers comprised of fluorinated (meth)acrylates and poly(MMA) (MMA = methyl methacrylate) or poly(DMAEMA) (DMAEMA = 2-(dimethylamino)ethyl methacrylate) were produced in scCO<INF>2</INF> by ATRP. In addition, the dispersion polymerization of MMA using ATRP in scCO<INF>2</INF> in the presence of a fluorinated polymeric surfactant stabilizer was successfully carried out to yield poly(MMA) latex particles with controlled molecular weight and a narrow molecular weight distribution.