SET‐LRP of methyl acrylate to complete conversion with zero termination

The single electron transfer‐living radical polymerization of methyl acrylate (MA) initiated by bis(2‐bromopropionyl)ethane (BPE) in dimethyl sulfoxide was carried out to 100% monomer conversion and complete absence of bimolecular termination under the following reaction conditions: [MA]/[BPE]/[Me₆‐TREN]/[CuBr₂] = 60/1/0.21/0.01 and [MA]/[BPE]/[TREN]/[CuBr₂] = 60/1/0.25/0.05. These polymerizations were mediated by 0.5 cm of hydrazine‐activated Cu(0) wire of 20 gauge (0.812 cm in diameter), corresponding to a surface area of 0.14 cm² of Cu(0) per 3 mL reaction volume (2/1 v/v monomer/solvent). A higher extent of bimolecular termination (5–13%) was observed at complete conversion when longer lengths of Cu(0) wire were used. In the absence of CuBr₂ the activated Cu(0) wire/Me₆‐TREN catalyst in dimethyl sulfoxide also allowed the synthesis of perfectly bifunctional and monofunctional PMAs at complete conversion. This was also demonstrated by the quantitative reinitiation experiments from the chain(s) end(s) of these macroinitiators. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012