SP–PLP–EPR Measurement of Cu^II-Mediated ATRP Deactivation and Cu^I‑Mediated Organometallic Reactions in Butyl Acrylate Polymerization

The SP–PLP–EPR technique has been used to measure Cu^II-mediated ATRP deactivation and Cu^I-mediated organometallic reactions for butyl acrylate (BA) polymerization. The deactivation rate is by more than 1 order of magnitude higher than in dodecyl methacrylate (DMA) polymerization, thus enabling well-controlled ATRP despite the enhanced BA propagation rate. The organometallic reaction of Cu^I with BA radicals was found to play a role only with highly active Cu catalysts, as demonstrated for the Cu/TPMA-mediated ATRP of BA.