The kinetic and structural analyses of the polymer resulting from the Cu(0)/Me 6 -TREN-mediated polymerization of methyl acrylate (MA) initiated with methyl 2-bromopropionate (MBP) in solvents mediating different degrees of disproportionation are reported. Accurate analyses of the polymerization and of the resulting polymer demand a minimum combination of techniques that includes kinetics, GPC, 1 H NMR, and MALDI-TOF both performed before and after chainend functionalization via thio−bromo "click" chemistry and reinitiation experiments. At [MA] 0 /[MBP] 0 = 222 the use of the disproportionating solvent DMSO generated first-order kinetics and 97% active chain ends of the polymer at 89% conversion. The less disproportionating solvent MeCN produced two linear firstorder kinetics and a decrease of bromine chain-end functionality of the polymer with conversion, yielding 77% active chain ends at 89% conversion. The nondisproportionating solvent toluene, in the presence of TEMPO, produced two linear first-order kinetics with only 50% active chain ends of the polymer at 92% conversion.

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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]/[Me 6 -TREN]/[CuBr 2 ] ¼ 60/1/0.21/0.01 and [MA]/[BPE]/[TREN]/[CuBr 2 ] ¼ 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 cm 2 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 CuBr 2 the activated Cu(0) wire/Me 6 -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. V C 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 50: 860-873, 2012

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The Cu(0)/Me6-TREN-catalyzed polymerization of methyl acrylate (MA) initiated by methyl 2-bromopropionate (MBP) in DMSO at 25 °C was performed in a UV cuvette, and the absorbance of CuBr2 was monitored online in a UV–vis spectrophotometer as a function of the monomer conversion. A continuous increase of CuBr2 absorbance throughout the reaction demonstrated no reduction of CuBr2 concentration during the entire polymerization process. In addition, the 100% chain-end functionality of the polymer observed from 10% to 95% monomer conversion indicated that in this polymerization the bimolecular termination required to provide the persistent radical effect in ATRP was not responsible for the production of CuBr2.

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