Control in electrochemically mediated atom transfer radical polymerization (eATRP) with copper catalysts (Cu/L, L = ligand) was achieved with chronoamperometry. The CuI/CuII ratio near the working electrode surface was determined by the applied potential (Eapp) and distributed to the bulk reaction mixture through vigorous stirring. The rate of polymerization (Rp) correlated to the established CuI/CuII ratio generated by Eapp, until the diffusion limit of the catalysts was reached. In particular, �on-demand� polymerization was achieved by switching the Eapp value either to the CuI or CuII dominant range. Removal of the transition metal (Mt) was carried out by further reduction of CuI to Cu0.  The Cu0 was deposited on to the working electrode surface and reused for the next polymerization once stripped from the surface. Utilizing the control over the CuI/CuII ratio afforded by Eapp, various monomers were polymerized by eATRP including acrylates and methacrylates under organic or aqueous media. Additionally, polymers with precisely controlled architectures, such as block, star, and brush (co)polymers, were prepared by eATRP. 

Electrochemically mediated atom transfer radical polymerization

248th National Meeting (2014)

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