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…

Preparation of fluorinated polymer matrixes modified for biomedical applications

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…

Modification of Poly(vinilydenefluoride) Porous Membranes by Grafting of Acrylic Acid Assisted by Supercritical Carbon Dioxide

Aim of this work is to study the preparation of pH sensitive membranes for biomedical applications via thermally induced graft polymerization of acrylic acid (AA) on poly(vinilydenefluoride) (PVDF) assisted by supercritical carbon dioxide (scCO2). Using scCO2 as a solvent and swelling agent, the monomer and the initiator (benzoyl peroxide) could diffuse faster into the polymer matrix, distribute more uniformly and allows a better control of the final molecular architecture promoting grafting reactions rather than chain degradation processes. As polymer matrixes we are using commercial hydrophobic porous PVDF membranes. Grafted polymers are characterized by Fourier transform infrared spectro…

Preparation of pH sensitive poly(vinilydenefluoride) porous membranes by grafting of acrylic acid assisted by supercritical carbon dioxide

Aim of this work is to study the preparation of pH sensitive membranes for biomedical applications via thermal induced graft polymerization of acrylic acid (AA) on poly(vinilydenefluoride) (PVDF) assisted by supercritical carbon dioxide (scCO2). Using scCO2 as a solvent and swelling agent, the monomer and initiator (benzoyl peroxide) could diffuse faster and distribute more uniformly into the polymer matrix. A better control of the final molecular architecture should be achieved because bimolecular grafting reactions are accelerated with respect to chain degradation processes. Commercial hydrophobic PVDF porous matrixes were selected as model membranes. Grafted polymers were characterized b…

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 fe…

Preparation of pH sensitive poly(vinilydenefluoride) porous membranes by grafting of acrylic acid assisted by supercritical carbon dioxide

Free radical grafting of acrylic acid (AA) on poly(vinilydenefluoride) (PVDF) porous membranes was studied at 65°C using supercritical carbon dioxide (scCO 2) as a solvent and delivery agent. The process was initiated by the thermal decomposition of benzoylperoxide (BPO). Spectroscopic analyses confirmed the presence of poly(AA) chains linked to treated membranes. The mass fraction of grafted AA increased with grafting time and BPO concentration while it decreased when the density of the fluid phase was enhanced. A not-monotonic trend was obtained when the effect of the initial AA concentration was studied. The grafting process was accompanied by a reduction of the crystallinity of the PVDF…