Simple tertiary amines as promotors in oxygen tolerant photochemically induced ATRP of acrylates

Well-defined poly(methyl acrylate) (PMA) and poly(n-butyl acrylate) (PBA) are prepared via photochemically induced atom transfer radical polymerization (photoATRP) using ppm amounts of CuBr2/tris[2-(dimethylamino) ethyflamine (Me6TREN) catalyst complex without degassing of the polymerization mixture. The effect of light intensity and partial replacement of the excess of expensive Me-6 TREN ligand with cheaper tertiary amines on kinetics of the polymerization was investigated in various solvents. The addition of triethylamine to photoATRP system resulted in both significant shortening the induction period and increasing the polymerization rate. High livingness of the oxygen tolerant photoATRP system containing triethylamine was proved by chain-extension polymerizations resulting in formation of PMA-b-PBA copolymer. The presented photoATRP system can have tremendous importance from an industrial point of view since the well-defined polyacrylates can be prepared almost without any induction period and in short polymerization time without necessity of both air removal and using the excess of expensive ligand.