We have synthesized well-defined poly (butyl methacrylate (BMA)), poly (butyl acrylate (BA)) and BMA/BA copolymers using Activators ReGenerated by Electron Transfer Atom Transfer Radical Polymerization (ARGET ATRP) with parts per million (ppm) levels of copper (Cu) catalyst in less than six hours under a broad range of conditions. The observed polymerization rate and initiator efficiency decrease significantly with decreasing amounts of initial Cu added. At the lower copper levels (35 ppm), only a large increase in the reducing agent concentration results in a sufficiently high polymerization rate. As a result, a semi-batch feed of reducing agent was implemented (see Figure 1). In addition, increasing BA content led to a significant increase in the initiator efficiency of the copolymerization of BMA and BA.Kinetic modeling with Predici and Monte Carlo methods attributed the decreased polymerization rate to slow initiation, a finding subsequently confirmed experimentally. This study is expanded to the copolymerization of BA/BMA to gain further understanding through kinetic modeling. Slow initiation is also present in the model, with the increase in initiator efficiency with increasing BA content attributed to the significant difference in activation/deactivation rate coefficients for the two monomers.

ARGET ATRP of BMA/BA: Understanding distinct activation/deactivation rates with kinetic modeling

248th National Meeting (2014)

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