Search results for "Free radical polymerization"

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

2012

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…

Copolymerization of VDF and HFP in Supercritical Carbon Dioxide: Experimental Analysis of the Reaction Loci

2010

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

2012

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…

Leach-Proof Sol–Gel Microcapsules as Curing Agents for One-Pot Thermosetting Resins

2013

The sol-gel microencapsulation of free-radical initiator benzoyl peroxide in sol-gel methyl-modified silica microcapsules of core/shell geometry allows curing of acrylate-based polyurethane and polyester resin formulations sprayed from a pressurized can without the need to compartmentalize reactants from the initiator to cross-link. These results open the route to widespread application of sol-gel microcapsules to efficiently cure polymer and composite mixtures that are widely used as functional coatings, molding compounds, adhesives, and sealants.

Free radical copolymerization of vinylidene fluoride and acrylic acid in supercritical carbon dioxide

2010

Preparation of drug-polymer composites by polymerization in supercritical carbon dioxide: a new method to increase the dissolution rate of bioactive …

2008

Dispersion Copolymerization of Vinyl Monomers in Supercritical Carbon Dioxide.

2003

The thermally initiated free-radical dispersion copolymerization of methyl methacrylate (MMA) and N,N-dimethylacrylamide (DMA) in supercritical carbon dioxide has been studied in the presence of polysiloxane surfactants. The formation of a stable latex seems to be related to the presence of at least one reactive end group in the surfactant macromolecule, thus suggesting that anchoring of the stabilizer to the surface of the growing polymer particles occurs through chemical grafting. In the case of a molar ratio of DMA to MMA lower than 0.40, microspherical copolymer particles with yields ranging from 81 to 97% were collected from batch polymerizations carried out at 65 °C and 23-28 MPa usin…

γ-radiation-initiated polymerization of vinylidene fluoride in dense carbon dioxide

2002

The γ-ray-initiated batch polymerization of vinylidene fluoride (VF2) has been investigated in dense carbon dioxide under relatively mild operative conditions (T ≤ 40 °C and P < 25 MPa). When the initial VF2 molar concentration was increased from 3.4 to 6.4 mol/L, monomer conversion increased from 20 to 73%; a similar trend was observed for the number-average molecular weight and the molecular complexity of synthesized poly(vinylidene fluoride) (PVDF) as determined from rheological measurements. Under all adopted experimental conditions, a synthesized PVDF polymer was collected in the form of a white powder. Despite the inherent heterogeneous character of the polymerization process, a homog…