Atom transfer radical polymerization (ATRP) has become a powerful tool for the synthesis of polymers and advanced materials. However, like any radical polymerization, ATRP is inhibited by oxygen. This hampers its practical use under aerobic conditions and specialized equipment is often needed to achieve good results. Conventional ATRP methods thus tend to be time-consuming and challenging for non-experts.<br/>In recent years, more attention is focused on tackling the problem of oxygen intolerance in ATRP. Possible approaches can be divided into two broad groups: activator regeneration and oxygen scavenging. However, the vast majority of reported methods suffer from at least one critical flaw, such as complexity, use of high loadings of copper catalysts, limited oxygen tolerance, or incompatibility with a wide spectrum of solvents.<br/>Herein, we demonstrate the oxygen–tolerant photoinduced ATRP occurring in both water and organic solvent in an open reaction vessel. Sodium pyruvate is the essential component in this novel method, acting as a hydrogen peroxide scavenger and enabling the continuous regeneration of the copper activator under UV irradiation (Scheme 1). This protocol proved to be highly efficient in the polymerization of <i>N</i>-isopropylacrylamide with ppm level of Cu catalyst in aqueous media. The polymers were synthesized to nearly quantitative monomer conversions, high molecular weights, and low dispersities in less than 30 min. Moreover, the well-controlled polymerization of methyl acrylate was achieved in dimethyl sulfoxide in open-air conditions without compromising the control over the molecular weight distribution.

Fully oxygen-tolerant photoinduced ATRP

ACS Spring Meeting 2021

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