Copolymerization of VDF and HFP in Supercritical Carbon Dioxide: Experimental Analysis of the Reaction Loci
Free radical copolymerization reactions of vinylidene fluoride (VDF) and hexafluoropropylene (HFP) were carried out in supercritical carbon dioxide at T=50 °C. When ammonium carboxylate perfluoropolyether surfactants were used, the formation of polymer particles was observed provided that HFP mole fraction in the feed was not larger than 0.30. Under these conditions, the effect of the total interphase area of the polymer phase, Ap, on the product propertieswas investigated by comparing experiments with largely different amounts of stabilizer, i.e., ranging from precipitation (smaller Ap) to dispersion (larger Ap) polymerization systems. We found that the copolymer molecular weight distribut…
Dispersion Polymerization of Vinylidene Fluoride in Supercritical Carbon Dioxide
The dispersion polymerization of vinylidene fluoride in supercritical carbon dioxide is investigated using two ammonium carboxylate perfluoropolyether stabilizers of different molecular weights. Under suitable operating conditions a polymer made of well-dispersed spherical particles has been obtained up to relatively high conversion. The experimental data of polymerization rate and molecular weight distribution are in good agreement with the predictions of a model previously developed. Such an agreement supports the conclusion that the polymerization kinetics is dominated by the interphase transport of the active radicals between the continuous phase and the polymer particles.
The rate of polymerization in two loci reaction systems: VDF-HFP precipitation copolymerization in supercritical carbon dioxide
When the copolymerization of vinylidene fluoride (VDF) and hexafluoropropylene (HFP) is carried out in supercritical carbon dioxide (scCO 2) under heterogeneous conditions, the reaction occurs both in the continuous CO 2-rich phase and in the dispersed polymer-rich phase. The two phases being characterized by different values of reactant concentrations and kinetic parameters, one would expect that the reaction kinetics is affected by the polymer phase holdup in the reactor. However, the reaction rate is almost insensitive to the amount of produced polymer, at least at specific reaction conditions. This apparent contradiction is discussed and clarified in this paper by a series of comparativ…
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 CO2. 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 fee…