Methodology for Kinetic Modeling of Atom Transfer Radical Polymerization

A methodology for kinetic modeling of atom transfer radical polymerization is developed allowing to calculate the monomer conversion, the fraction of polymer molecules having end group functionality, the full molar mass distribution (MMD) of the dormant polymer and the number, mass, and z based average molar mass of the dead and dormant polymer. The developed methodology is based on an extension of the method of moments and allows an accurate description of the contribution of the polymer molecules with a high molar mass to the MMD of the polymer. Diffusional limitations on all considered reaction steps are systematically accounted for. Simulation results are in good agreement with experimental observations. Moreover, the methodology allows a detailed description of the broadness and the skewness of the MMD of the polymer.