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Updated: May 24, 2026

Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst
Published on: April 22, 2016
Copper-mediated controlled/"living" radical polymerization in polar solvents: insights into some relevant mechanistic
Tamaz Guliashvili1, Patrícia V Mendonça, Arménio C Serra
1GE Power and Water; Water & Process Technologies, 4636 Somerton Road, Trevose, PA 19053, USA. tamaz.guliashvili@ge.com
Abstract:
The field of transition-metal-mediated controlled/"living" radical polymerization (CLRP) has become the subject of intense discussion regarding the mechanism of this widely-used and versatile process. Most mechanistic analyses (atom transfer radical polymerization (ATRP) vs. single-electron transfer living radical polymerization (SET-LRP)) have been based on model experiments, which cannot correctly mimic the true reaction conditions. We present, for the first time, a determination of the [Cu(I)Br]/[L] (L=nitrogen-based chelating ligand) ratio and the extent of Cu(I)Br/L disproportionation during CLRP of methyl acrylate (MA) in dimethylsulfoxide (DMSO) with Cu(0) wire as a transition-metal catalyst source. The results suggest that Cu(0) acts as a supplemental activator and reducing agent of Cu(II)Br(2)/L to Cu(I)Br/L. More importantly, the Cu(I)Br/L species seem to be responsible for the activation of SET-LRP.
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