Investigating Cu(0)‐Mediated Polymerizations: New Kinetic Insights Based on a Comparison of Kinetic Modeling with Experimental Data

A kinetic model is developed mimicking experimental results obtained via detailed kinetic investigation of Cu 0 ‐mediated LRP processes of butyl acrylate in variable solvents at 50 °C. In all polymerizations, a pronounced offset in the $\overline {M} _{{\rm n}} $ versus conversion profile is observed. The kinetic modeling predicts that conventional FRP is responsible for a high molecular weight fraction of terminated polymer. The initial $\overline {M} _{{\rm n}} $ offset is congruent with a relatively slow establishment of the controlling equilibrium. Kinetic modeling and experiments demonstrate that the conversion versus time data cannot be adequately described by a first‐order kinetic analysis. For selected rate coefficients ( k a , k d , and k dis_cu ) a range is assigned, which affords a well controlled polymerization.