Aqueous copper-mediated living polymerization: Exploiting rapid disproportionation of CuBr with Me6TREN

Qiang Zhang, Paul Wilson, Zaidong Li, Ronan McHale, Jamie Godfrey, Athina Anastasaki, Christopher Waldron, David M. Haddleton

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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).

Original languageEnglish
Pages (from-to)7355-7363
Number of pages9
JournalJournal of the American Chemical Society
Issue number19
Publication statusPublished - 15 May 2013
Externally publishedYes

Cite this

Zhang, Q., Wilson, P., Li, Z., McHale, R., Godfrey, J., Anastasaki, A., Waldron, C., & Haddleton, D. M. (2013). Aqueous copper-mediated living polymerization: Exploiting rapid disproportionation of CuBr with Me6TREN. Journal of the American Chemical Society, 135(19), 7355-7363.