Search results for "DISPERSION"
showing 10 items of 1101 documents
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…
Synthesis of hydrophilic polymers in supercritical carbon dioxide in the presence of a siloxane-based macromonomer surfactant: Heterogeneous polymeri…
2003
Batch free radical polymerization of 1-vinyl-2-pyrrolidone (VP) in super- critical carbon dioxide (scCO2) was studied in the presence of a reactive polysiloxane surfactant (PDMS-mMA). Phase behavior investigation showed that when the initial concentration of the surface active macromonomer was higher than 2.5% w/w with respect to the monomer, the reaction mixture, in the absence of efficient stirring, was initially opaque to the visible light, and it slowly turned to an orange tint. Polymeriza- tion experiments carried out with surfactant concentration higher than the aforemen- tioned value proceeded with a fast kinetics, and led to the formation of spherical nanoparticles with almost quant…
Dispersion polymerization of methyl methacrylate in supercritical carbon dioxide stabilized with poly(ethylene glycol)-b-perfluoroalkyl compounds
2004
Abstract In this work selected components of an easily synthesible class of poly(ethylene glycol)-perfluoroalkyl block compounds were tested as stabilizers for the dispersion polymerization of methyl methacrylate in scCO 2 . As already observed in the case of different block surfactants the anchor soluble balance (ASB) of the stabilizer is the crucial parameter affecting the efficacy of the stabilization and the kinetics of the polymerization process. When stabilizers with appropriate ASB were used, high molecular weight poly(methyl methacrylate) was synthesized under the form of microspherical polymer particles with yields ranging up to 80%. In these experiments the occurrence of a gel-eff…
Dispersion Polymerization of Vinylidene Fluoride in Supercritical Carbon Dioxide
2006
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.
Copolymerization of vinylidene fluoride and acrylic acid in supercritical carbon dioxide
2009
The free-radical copolymerization of vinylidene fluoride (VDF) and acrylic acid (AA) was carried out in supercritical carbon dioxide using both precipitation and dispersion techniques in the presence of an ammonium carboxylate perfluoropolyether compound. Formation of a copolymer was confirmed by variable contact time CP MAS NMR spectroscopy. Macromolecular matrices were significantly enriched in AA with respect to the initial feed composition and we found that the nonfluorinated monomer has a much higher reactivity ratio with respect to VDF. The cumulative concentration, crystallinity, and water affinity of the synthesized copolymers could be modified changing the initial feed composition,…
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…
Dispersion polymerization of vinyl monomers in supercritical carbon dioxide in the presence of drug molecules: A one-pot route for the preparation of…
2008
The polymerization of 1-vinyl-2-pyrrolidone in supercritical carbon di- oxide in the presence of ibuprofen as a model drug was investigated as a new one-pot process for the preparation of polymer-based drug delivery systems (DDSs). The com- posites were prepared at 65 � C and P ¼ 31-42 MPa by changing the initial con- centration of the drug and the concentration of a crosslinking agent and that of a hydrophobic comonomer. The effects of these parameters on the performances of the polymerization and on the in vitro release kinetics of ibuprofen were studied. In all the experiments, part of the drug was entrapped inside the polymer particles and dissolved more slowly with respect to the pure …
Liquid-Crystalline Colloidal Particles
2004
Here we report about the synthesis of colloidal particles of nematic and smectic liquid-crystalline polymers. For this purpose mesogen-containing acrylate monomers were synthesized and polymerized in a special modification of a precipitation polymerization called dispection polymerization. By variation of the polymerization conditions colloidal particles of different size and polydispersity could be obtained including very narrowly distributed samples in optimized batches. On azobenzene-containing colloidal particles switching experiments with polarized light were performed. It could be observed that the nematic director of the mesogens within the colloidal particles can be rotated due to t…
Control of mesogen configuration in colloids of liquid crystalline polymers
2010
We report on a method to chemically predetermine the surface anchoring of mesogens in liquid crystalline colloids formed by different types of dispersion polymerization, and hence to achieve control over the mesogen configuration in such colloids. The surface anchoring is controlled by the chemical linkage of the polymers forming the colloids to the surfactants stabilizing the colloids towards the dispergent. We find that the hydroxypropyl cellulose used in conventional dispersion poylmerization induces parallel mesogen surface anchoring that in turn leads to bipolar director-field configurations, while a methacrylate terminated polysiloxane stabilizer, which is used in nonpolar dispersion …
Polymerization of methyl methacrylate through ionizing radiation in CO2-based dense systems
2000
Herein, we report the use of ionizing radiation to induce a dispersion polymerization reaction in dense CO2. As a model system, the polymerization of methyl methacrylate in the presence of poly(dimethylsiloxane) stabilizers was investigated. It was demonstrated that the dose plays the key role in the progress of the reaction and in the morphology of the resulting polymer. Dispersion polymerization carried out in the presence of mono- and bifunctionalized surfactants gave differently structured polymers. The polymers obtained have been characterized by scanning electron microscopy, solubility tests, and gel permeation chromatography, and the molecular structure has been related to dynamic me…