Atom transfer radical polymerization in supercritical carbon dioxide

Atom transfer radical polymerization (ATRP) has been successfully carried out in supercritical carbon dioxide (scCO(2)) 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(2) by ATRP. In addition, the dispersion polymerization of MMA using ATRP in scCO(2) 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.