Numerical Simulation of Atom-Transfer Radical Polymerization of tert-butyl Methacrylate

Abstract

Block copolymers based on tert-butyl methacrylate (tBMA) have many uses, such as thermoresponsive polymers, amphiphilic copolymers, and many applications in the medical field. Atom-transfer radical polymerization (ATRP) is the main technique to produce these controlled macromolecular architectures. This paper provides a simplified kinetic modeling and computational study of tBMA ATRP. The main objective is to understand the behavior of chemical species in the reaction and its influence on polymer properties (molecular weight and dispersity). The proposed model presented good reproducibility of the experimental data, with average errors less than 10%. The simulations indicated a strong initiator and catalyst concentration dependence on the monomer conversion. Although the highest initiator proportion induced a dispersity increase in conversions less than 20%, in general, for tBMA ATRP, the range of operational condition cannot affect dispersity directly. In addition, our finds about the effect of Keq on polymer properties indicated that to conduct the reaction using catalyst systems with Keq around 10-5 - 10-6 would provide very low dispersity polymers in a fast reaction time.