Search results for " carbon dioxide"
showing 10 items of 200 documents
Copolymerization of VDF and HFP in Supercritical Carbon Dioxide: A Robust Approach for Modeling Precipitation and Dispersion Kinetics
2011
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…
Critical Micelle Density for the Self-Assembly of Block Copolymer Surfactants in Supercritical Carbon Dioxide
1999
The parameters which influence the self-assembly of molecules in solution include the temperature and solvent quality, and this study illustrates the use of these variables to regulate the degree of association of block copolymer amphiphiles in highly compressible supercritical carbon dioxide. Small-angle neutron scattering (SANS) has been used to examine the association behavior of a block copolymer containing a CO2-phobic moiety, poly(vinyl acetate), and a CO2-philic block, poly(1,1-dihydroperfluoro-octylacrylate). By adjustment of the density of the medium through pressure and temperature profiling, the self-assembly can be reversibly controlled from unimers to core−shell spherical micel…
A combined small-angle neutron and X-ray scattering study of block copolymers micellisation in supercritical carbon dioxide
2003
Small angle neutron and X-ray scattering (SANS and SAXS) are used to investigate the monomer–aggregate transition of fluorocarbon–hydrocarbon diblock copolymers in supercritical carbon dioxide. SANS data are analyzed using a polydisperse sphere core–shell model. Synchrotron SAXS data have been collected by profiling the pressure at different temperatures, and critical micellization densities have been obtained for a series of diblock solutions. Finally pressure jump experiments, combined with synchrotron SAXS, have revealed two steps in the dynamics of the formation of the aggregates.
Discovering Copper for Methane C–H Bond Functionalization
2015
The copper complex Tp(CF3)2,BrCu(NCMe) (1, Tp(CF3)2,Br = hydrotris((3,5-bis(trifluoromethyl)-4-bromo)-pyrazol-1-yl)borate) catalyzes the insertion of the CHCO2Et group (from ethyl diazoacetate N2CHCO2Et, EDA) into the C–H bonds of methane, in a homogeneous process that uses supercritical carbon dioxide (scCO2) as the reaction medium. Other light alkanes such as ethane, propane, and butane have been also functionalized with this copper-based catalyst, in the first example of the derivatization of the series of C1–C4 alkanes with this metal and a soluble catalyst.
Recovery of bioactive compounds from walnut (Juglans regiaL.) green husk by supercritical carbon dioxide extraction
2021
In this work, the use of supercritical carbon dioxide, a nontoxic solvent, was proposed to extract bioactive compounds from Juglans regia L. green husk and was compared to other traditional techniques based on solvents such as ethanol, methanol and water. Supercritical CO2 was combined with ethanol as an organic modifier at a rate of 20% of the total flow to achieve greater extraction of polar compounds. The extracts were characterised in terms of extraction yields, antioxidant activity, total polyphenol content, phenolic acids, juglone, volatile organic compounds and antifungal activity. The results showed that the extracts obtained with supercritical CO2 were rich in polyphenols (10750 mg…
Catalytic and anticancer activities of sawhorse-type diruthenium tetracarbonyl complexes derived from fluorinated fatty acids
2013
The reaction of fluorinated fatty acids, perfluorobutyric acid (C3F7CO2H), and perfluorododecanoic acid (C11F23CO2H), with dodecacarbonyltriruthenium (Ru3(CO)12) under reflux in tetrahydrofuran, followed by addition of two-electron donors (L) such as pyridine, 1,3,5-triaza-7-phosphatricyclo[3.3.1.1]decane, or triphenylphosphine, gives stable diruthenium complexes Ru2(CO)4(μ2-η2-O2CC3F7)2(L)2 (1a, L = C5H5N; 1b, L = PTA; 1c, L = PPh3) and Ru2(CO)4(μ2-η2-O2CC11F23)2(L)2 (2a, L = C5H5N; 2b, L = PTA; 2c, L = PPh3). The catalytic activity of the complexes for hydrogenation of styrene under supercritical carbon dioxide has been assessed and compared to the analogous triphenylphosphine complexes w…
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…
Baeyer—Villiger Oxidation in Supercritical CO2 with Potassium Peroxomonosulfate Supported on Acidic Silica Gel.
2006
Supercritical carbon dioxide (scCO2) is an efficient reaction medium to perform the Baeyer-Villiger oxidation with hydrated silica-supported potassium peroxomonosulfate (h-SiO2.KHSO5) under flow-through conditions. Hydration modulates the reactivity of the active surface by softening the acidity of the KHSO4 present in the supported reagent. The reaction in scCO2 is much more efficient than in n-hexane under similar conditions, which is attributed to better transport and solvating properties of the supercritical medium with regard to n-hexane.
Baeyer–Villiger oxidation of ketones with a silica-supported peracid in supercritical carbon dioxide under flow conditions
2009
[2-Percarboxyethyl]-functionalized silica reacts with ketones in supercritical carbon dioxide at 250 bar and 40 °C under flow conditions to yield the corresponding esters and lactones. The solid reagent can be easily recycled through treatment with 70% hydrogen peroxide in the presence of an acid at 0 °C. This procedure not only simplifies the isolation of the reaction products, but has the advantage of using only water and carbon dioxide as solvents under mild conditions.
Electrochemical reduction of carbon dioxide to formic acid at a tin cathode in divided and undivided cells: effect of carbon dioxide pressure and oth…
2016
Abstract The reduction of carbon dioxide to formic acid at a tin cathode was studied in both divided and undivided cells. In the first stage of the study, the effect of some operating parameters, including the working potential and the nature of the supporting electrolyte and of the cathode, on both the cathodic reduction of CO2 and the anodic oxidation of formic acid was investigated in a divided cell. In a second stage, the reduction of carbon dioxide was performed in an undivided cell with the aim of studying the effect on the generation of formic acid of various operating parameters such as current density, cathode to anode area ratio, mixing rate and nature of the anode and of the supp…