Kinetics and Modeling of Solution ARGET ATRP of Styrene, Butyl Acrylate, and Methyl Methacrylate

This work reports a kinetic model for the activator-regenerated-by-electron-transfer atom-transfer radical polymerization (ARGET ATRP) and its verification by the experimental data of solution ARGET ATRP of styrene, methyl methacrylate, and butyl arylate from literatures. The effects of ATRP equilibrium constant K and apparent reducing rate coefficient k(r) on the ARGET ATRP kinetics are investigated. A highly active initiation/catalyst system with a large K results in a poor control of the polymerization while an increased k(r) promotes the polymerization rate but the formation of dead polymer chains. Reducing agent with a moderate k(r) gives good control over ARGET ATRP. It is not feasible to use a moderate catalyst system for the ARGET ATRP of highly active monomers.