Copolymerization of VDF and HFP in Supercritical Carbon Dioxide: A Robust Approach for Modeling Precipitation and Dispersion Kinetics

A kinetic model is developed for the heterogeneous free-radical copolymerization of vinylidene fluoride and hexafluoropropylene in supercritical CO 2. The model accounts for polymerization in both the dispersed (polymer-rich) phase and in the continuous (polymer-free) supercritical phase, for radical interphase transport, diffusion limitations, and chain-length-dependent termination in the polymer-rich phase. A parameter evaluation strategy is developed and detailed to estimate most of the kinetic parameters a priori while minimizing their evaluation by direct fitting. The resulting model predictions compare favorably with the experimental results of conversion and MWD at varying monomer feed composition, monomer concentration, interphase area, and pressure of the system. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.