Atom transfer radical polymerization (ATRP) equilibrium constants () were measured during polymerization of methyl acrylate (MA) with CuBr/CuBr in either dimethyl sulfoxide (DMSO) or acetonitrile (MeCN) in the presence of either tris(2-pyridylmethyl)amine (TPMA) or tris[2-(dimethylamino)ethyl]amine (MeTREN) as the ligand and with ethyl 2-bromopropionate as the initiator. The ln() values changed linearly with the volume fraction of solvents in the reaction medium, allowing extrapolation of the values for to bulk conditions, which were 2 × 10 and 3 × 10 for TPMA and MeTREN ligands at 25 °C, respectively. The temperature effect on values was studied in MA/MeCN = 1/1 (v/v) with TPMA as the ligand in the temperature range from 0 to 60 °C. The values increased with temperature providing Δ = 36 kJ mol in MeCN.
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