title: Aqueous copper-mediated living polymerization: exploiting rapid disproportionation of CuBr with Me6TREN.
abstract: A new approach to perform single-electron transfer living radical polymerization (SET-LRP) in water is described. The key step in this process is to allow full disproportionation of CuBr/Me6TREN (TREN = tris(dimethylamino)ethyl amine to Cu(0) powder and CuBr2 in water prior to addition of both monomer and initiator. This provides an extremely powerful tool for the synthesis of functional water-soluble polymers with controlled chain length and narrow molecular weight distributions (polydispersity index approximately 1.10), including poly(N-isopropylacrylamide), N,N-dimethylacrylamide, poly(ethylene glycol) acrylate, 2-hydroxyethyl acrylate (HEA), and an acrylamido glyco monomer. The polymerizations are performed at or below ambient temperature with quantitative conversions attained in minutes. Polymers have high chain end fidelity capable of undergoing chain extensions to full conversion or multiblock copolymerization via iterative monomer addition after full conversion. Activator generated by electron transfer atom transfer radical polymerization of N-isopropylacrylamide in water was also conducted as a comparison with the SET-LRP system. This shows that the addition sequence of l-ascorbic acid is crucial in determining the onset of disproportionation, or otherwise. Finally, this robust technique was applied to polymerizations under biologically relevant conditions (PBS buffer) and a complex ethanol/water mixture (tequila).
authors.affiliation: Department of Chemistry, University of Warwick, Coventry CV4 7AL, United Kingdom.
authors.forename: Qiang
authors.initials: Q
authors.lastname: Zhang
authors.forename: Paul
authors.initials: P
authors.lastname: Wilson
authors.forename: Zaidong
authors.initials: Z
authors.lastname: Li
authors.forename: Ronan
authors.initials: R
authors.lastname: McHale
authors.forename: Jamie
authors.initials: J
authors.lastname: Godfrey
authors.forename: Athina
authors.initials: A
authors.lastname: Anastasaki
authors.forename: Christopher
authors.initials: C
authors.lastname: Waldron
authors.forename: David M
authors.initials: DM
authors.lastname: Haddleton
mesh_terms: D000178:Acrylamides / Q000138:chemical synthesis; D000179:Acrylates / Q000138:chemical synthesis; D001965:Bromides / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D005029:Ethylenediamines / Q000737:chemistry*; D011092:Polyethylene Glycols / Q000138:chemical synthesis; D058105:Polymerization; D014867:Water / Q000737:chemistry*
chemical_list: D000178:Acrylamides; D000179:Acrylates; D001965:Bromides; D005029:Ethylenediamines; D014867:Water; D011092:Polyethylene Glycols; C099539:tris(2-aminoethyl)amine; D003300:Copper