Rapidly self-deoxygenating controlled radical polymerization in water <i>via in situ</i> disproportionation of Cu(<scp>i</scp>)

Abstract

Rapidly <i>self-deoxygenating</i> Cu-RDRP in aqueous media is investigated. The disproportionation of Cu(i)/Me₆Tren in water towards Cu(ii) and highly reactive Cu(0) leads to O₂-free reaction environments within the first seconds of the reaction, even when the reaction takes place in the open-air. By leveraging this significantly fast O₂-reducing activity of the disproportionation reaction, a range of well-defined water-soluble polymers with narrow dispersity are attained in a few minutes or less. This methodology provides the ability to prepare block copolymers <i>via</i> sequential monomer addition with little evidence for chain termination over the lifetime of the polymerization and allows for the synthesis of star-shaped polymers with the use of multi-functional initiators. The mechanism of <i>self-deoxygenation</i> is elucidated with the use of various characterization tools, and the species that participate in the rapid oxygen consumption is identified and discussed in detail.