New efficient reaction media for SET‐LRP produced from binary mixtures of organic solvents and H2O

SET‐LRP is mediated by a combination of solvent and ligand that promotes disproportionation of Cu(I)X into Cu(0) and Cu(II)X₂. Therefore, the diversity of solvents suitable for SET‐LRP is limited. SET‐LRP of MA in a library of solvents with different equilibrium constants for disproportionation of Cu(I)X such as DMSO, DMF, DMAC, EC, PC, EtOH, MeOH, methoxyethanol, NMP, acetone and in their binary mixtures with H₂O was examined. H₂O exhibits the highest equilibrium constant for disproportionation of Cu(I)X. The apparent rate constant of the polymerization exhibits a linear increase with the addition of H₂O. This is consistent with higher equilibrium constants for disproportionation generated by addition of H₂O to organic solvents. Furthermore, with the exception of alcohols and carbonates, the rate constant of polymerization in binary mixtures could be correlated with the Dimroth‐Reichardt solvent polarity parameter. This is consistent with the single‐electron transfer mechanism proposed for SET‐LRP that involves a polar transition state. These experiments demonstrate that the use of binary mixtures of solvents with H₂O provides a new, simple and efficient method for the elaboration of a large diversity of reaction media that are suitable for SET‐LRP even when one of the two solvents does not mediate disproportionation of Cu(I)X. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5577–5590, 2009