Multivariate Parametric Analysis for the Determination of Kinetic Rate Constants in 2-(difluoromethoxy)ethyl Acrylate Atom-Transfer Radical Polymerization

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. (AU)