Abstract

AbstractSummary: Batch and semibatch butyl acrylate (BA) polymerizations are carried out using a heterogeneous atom transfer radical polymerization (ATRP) catalyst system, with excellent molecular weight (MW) control maintained at temperatures below 80 °C. A kinetic model, using rate coefficients from literature and catalyst solubility data from this study, provides a good representation of the experimental results, after modifying the model to account for the decrease in rate caused by intramolecular chain transfer. It is also demonstrated experimentally that well‐defined random, gradient, and block styrene/BA copolymers can be synthesized by manipulating monomer feed profiles in the ATRP semibatch process.

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