Computation-Assisted Investigation of Polymer Kinetics: Mechanism of the Hybridization of Cobalt-Mediated Radical Polymerization and Atom Transfer Radical Polymerization

Abstract

In this study, we combined the kinetic measurement and the computational simulation to build a kinetic model for the hybridization of cobalt-mediated radical polymerization (CMRP) and atom transfer radical polymerization (ATRP), which is a novel method for the one-pot synthesis of block copolymers of less activated monomers and more activated monomers, such as PVAc-b-PMMA and PVAc-b-PSty. The rate constants of the two most important reactions for PVAc radical, the dissociation of PVAc-Coᴵᴵᴵ(acac)₂ and the deactivation with Cuᴵᴵ(PMDETA)Br₂, have been evaluated at 40 °C as 4.99 × 10–³ s–¹ and 4.19 × 10⁶ M–¹ s–¹, respectively. These two kinetic parameters associated with other rate constants allowed us to build a quantitative model that can simulate the polymerization behavior observed in the hybridization of CMRP and ATRP and thus rationalize the mechanism more precisely.