Reversible-Deactivation Radical Polymerization in the Presence of Metallic Copper. Kinetic Simulation

Abstract

Reversible-deactivation radical polymerization (RDRP) of methyl acrylate in DMSO in the presence of Cu0 was studied by kinetic simulations. Kinetic simulations give access to the rates and contributions of all reactions, including those of activation of alkyl halides by CuI and Cu0 species, disproportionation of CuI species, and comproportionation between CuII and Cu0. Every relevant reaction was quantified by experimentally measured rate coefficients. The rates and contributions allow the exact roles of Cu0 and CuI species to be evaluated. These simulations show that the control over the polymerization is due to the atom transfer radical polymerization (ATRP) dynamic equilibrium with CuI as the major activator and CuII as the major deactivator. The ATRP equilibrium is maintained throughout the entire process. The simulations confirmed earlier experimental findings that in dimethyl sulfoxide (DMSO) with tris[2-(dimethylamino)ethyl]amine (Me6TREN) ligand comproportionation between Cu0 and CuII species domi...