Fully oxygen-tolerant atom transfer radical polymerization triggered by sodium pyruvate

Abstract

ATRP (atom transfer radical polymerization) is one of the most robust reversible deactivation radical polymerization (RDRP) systems. However, the limited oxygen tolerance of conventional ATRP impedes its practical use in an ambient atmosphere. In this work, we developed a fully oxygen-tolerant PICAR (photoinduced initiators for continuous activator regeneration) ATRP process occurring in both water and organic solvents in an open reaction vessel. Continuous regeneration of the oxidized form of the copper catalyst with sodium pyruvate through UV excitation allowed the chemical removal of oxygen from the reaction mixture while maintaining a well-controlled polymerization of N-isopropylacrylamide (NIPAM) or methyl acrylate (MA) monomers. The polymerizations of NIPAM were conducted with 250 ppm (with respect to the monomer) or lower concentrations of CuBr₂ and a tris[2-(dimethylamino)ethyl]amine ligand. The polymers were synthesized to nearly quantitative monomer conversions (>99%), high molecular weights (M_n > 270 000), and low dispersities (1.16 < Đ < 1.44) in less than 30 min under biologically relevant conditions. The reported method provided a well-controlled ATRP (Đ = 1.16) of MA in dimethyl sulfoxide despite oxygen diffusion from the atmosphere into the reaction system.