Reversible-deactivation radical polymerization (RDRP) in the presence of Cu0 is a versatile technique allowing for synthesis of well-defined polymers with complex architectures. Since 2006 a vigorous debate has continued in literature on the subject of the mechanism of this process. One proposed model, namely supplemental activator and reducing agent atom transfer radical polymerization (SARA ATRP) has CuI as the predominant activator of alkyl halides, and Cu0 as supplemental activator of alkyl halides and reducing agent of CuII through slow comproportionation process, with negligible contribution of disproportionation. Second model, named single electron transfer living radical polymerization (SET-LRP), has Cu0 as the major activator of alkyl halides. CuI does not activate alkyl halides but undergoes instantaneous disproportionation. Even though both models are based on the exactly same components (monomer, ligand, solvent), the kinetic contribution of participating reactions is vastly different. The experimental results show that experimental data and theoretical simulations both consistently agree with SARA ATRP and not SET-LRP mechanism in DMSO and also in aqueous media.

RDRP in the presence of Cu<sup>0</sup>: SARA ATRP vs. SET-LRP

248th National Meeting (2014)

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RDRP in the presence of Cu0: SARA ATRP vs. SET-LRP

RDRP in the presence of Cu⁰: SARA ATRP vs. SET-LRP