Ultrasonication-Induced Aqueous Atom Transfer Radical Polymerization.

A new procedure for ultrasonication-induced atom transfer radical polymerization (sono-ATRP) in aqueous media was developed. Polymerizations of oligo(ethylene oxide) methyl ether methacrylate (OEOMA) and 2-hydroxyethyl acrylate (HEA) in water were successfully carried out in the presence of ppm amounts of CuBr2 catalyst and tris(2-pyridylmethyl)amine ligand when exposed to ultrasonication (40 kHz, 110 W) at room temperature. Aqueous sono-ATRP enabled polymerization of water-soluble monomers with excellent control over the molecular weight, dispersity, and high retention of chain-end functionality. Temporal control over the polymer chain growth was demonstrated by switching the ultrasound on/off due to the regeneration of activators by hydroxyl radicals formed by ultrasonication. The synthesis of a well-defined block copolymer and DNA-polymer biohybrid was also successful using this process.