Abstract
AbstractUnlike classical radical polymerization, the kinetics of atom transfer radical polymerization show significant solvent dependence, possibly arising from solvent effects on the activation step. A kinetic study on the activation of the initiator ethyl α‐bromoisobutyrate by [CuITPMA]+ (TPMA=tris(2‐pyridylmethyl)amine), an initiator/catalyst combination frequently used in ATRP, was carried out in DMSO, DMF, MeCN, anisole, ethyl acetate, and their 50 vol % mixtures with styrene (STY) and methyl methacrylate (MMA). kact values varying about 3 orders of magnitude from 3.14×105 mol−1 dm3 s−1 in DMSO to 9.41×102 mol−1 dm3 s−1 in ethyl acetate were found. These values showed excellent correlation with the solvent polarity/polarizability parameter π*. The effect of MMA or STY depended on polarity compatibility between the monomer and the solvent: After monomer addition, kact decreased considerably in polar solvents, whereas it was almost unaffected in nonpolar solvents.
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