Poly(2‐(difluoromethoxy)ethyl acrylate), synthesized via ATRP, enables the synthesis of amphiphilic block copolymers that can self‐assemble into spherical micelles quite easily. The new monomer used, 2‐(difluoromethoxy)ethyl acrylate (DFMOEA), presents great potential to lead the development of new advanced materials with partially fluorinated segments, since it is easily synthesized, and the polymers derived may present unique characteristics. Currently, few studies detail the polymerization kinetics of this class of monomers with thorough information on the influence of operational and kinetic parameters on the synthesis. This research develops a deterministic modeling to simulate the synthesis of poly‐DFMOEA via ATRP. A multivariate parametric analysis is performed to evaluate the combined effect of process parameters on the polymerization kinetics and on the properties. A statistical modeling is obtained with a mathematical simplicity that allows the determination of the parameters by adjusting curves to the experimental data of literature. The estimated parameters are used to compare the monomer conversion, molar mass, and dispersity with the experimental data using deterministic modeling. The good adjustment obtained confirms the feasibility of using the methodology proposed. Simulations of different reagent ratios suggest the use of high concentration of catalyst to obtain polymers with ideal characteristics for future applications in self‐assembled materials.
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 K eq on polymer properties indicated that to conduct the reaction using catalyst systems with K eq around 10-5-10-6 would provide very low dispersity polymers in a fast reaction time.
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