Search results for "Supercritical carbon dioxide"

Fixed Bed Adsorption of Drugs on Silica Aerogel from Supercritical Carbon Dioxide Solutions

2013

Supercritical adsorption coupled with the high adsorption capacity of silica aerogel allows the preparation of a new kind of delivery systems of poor water soluble drugs. In order to overcome drawbacks of conventional techniques where the use of liquid solvents can cause the fracture of aerogel porous structure, in this work a new adsorption process of drugs from a supercritical mixture is proposed. Adsorption takes place from a fluid solution of the drug in supercritical CO2and ethanol as cosolvent. A fixed bed adsorption plant has been developed to allow fast mixing of fluid phase and effective contact in the adsorption column. The use of ethanol as cosolvent allows to overcome the limita…

Grafting of Maleic Anhydride onto Isotactic Polypropylene in the Presence of Supercritical Carbon Dioxide as a Solvent and Swelling Fluid

2004

Grafting of maleic anhydride (MA) onto isotactic polypropylene (iPP) was carried out by thermal decomposition of dicumylperoxide (DCP) using supercritical carbon dioxide (scCO2) as a solvent and swelling fluid. Provided that the initial concentration of anhydride dissolved in scCO2 is higher than 1% w/w, the grafting occurs without significant molecular weight modification of the polymer, and with a proper selection of the operative conditions, a grafting level higher than 0.5% w/w with respect to the polymer mass was obtained. The amount of grafted MA was determined by FT-IR spectroscopy and polymer degradation was monitored by dynamic mechanical tests in the melt state. The effect of MA a…

Nimesulide adsorbed on silica aerogel using supercritical carbon dioxide

2012

Silica aerogel (SA) was loaded with nimesulide, a drug model compound, to demonstrate the potentiality of adsorption processes based on the usage of supercritical carbon dioxide to treat poorly water-soluble drugs, forming new kinds of drug delivery systems. Adsorption isotherms and kinetics were measured and described by models. The effect of pressure, temperature and solution concentration on loaded SA were also studied. Modelling of kinetic data showed that the sorption process was best described by a pseudo-second-order model. The adsorption isotherm data were best fitted by the Freundlich isotherm. The drug/SA composites were characterized using scanning electron microscopy, X-ray micr…

Silver-Catalyzed C-C Bond Formation between Methane and Ethyl Diazoacetate in Supercritical CO2

2011

Even in the context of hydrocarbons’ general resistance to selective functionalization, methane’s volatility and strong bonds pose a particular challenge. We report here that silver complexes bearing perfluorinated indazolylborate ligands catalyze the reaction of methane (CH4) with ethyl diazoacetate (N2CHCO2Et) to yield ethyl propionate (CH3CH2CO2Et). The use of supercritical carbon dioxide (scCO2) as the solvent is key to the reaction’s success. Although the catalyst is only sparingly soluble in CH4/CO2 mixtures, optimized conditions presently result in a 19% yield of ethyl propionate (based on starting quantity of the diazoester) at 40°C over 14 hours.

Homogeneous Metal-Based Catalysis in Supercritical Carbon Dioxide as Reaction Medium

2016

Above 31.1 degrees C and 73.8 bar, carbon dioxide reaches the supercritical state, being transformed into a fluid (scCO(2)) that has attracted interest in the last few decades as reaction medium for several transition-metal-catalyzed organic transformations. The main feature of this fluid rests on its capability to dissolve large amounts of other gases such as hydrogen, carbon monoxide, ethylene, or even methane and light alkanes. In this manner, very high concentrations of these reactants are available for catalysis. In this contribution a review of the main achievements of the use of transition-metal complexes as catalysts in scCO(2) is presented.

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…

Order-Order Phase Transitions Induced by Supercritical Carbon Dioxide in Triblock Copolymer Thin Films

2019

We study the influence of supercritical carbon dioxide (scCO2) on the phase behavior of a cylinder-forming polystyrene-block-polybutadiene-b-polystyrenetriblock copolymer thin film. Solvent annealing with scCO2 can produce patterns with long-range order but these structures become unstable for thin films with small thicknesses. These results are in good agreement with self-consistent mean field calculations, which indicate that a drying transition occurs for thicknesses below the radius of gyration of the molecule.After decompression and solvent extraction, the initially swollen polymer nanostructure suffers a strong reduction in the average domain spacing, which has a deleterious effect on…

Direct synthesis of dimethyl carbonate with supercritical carbon dioxide: characterization of a key organotin oxide intermediate

2006

The direct synthesis of dimethyl carbonate (DMC) using carbon dioxide as solvent and reagent for its fixation to methanol was explored with din-butyldimethoxystannane in order to get insight into the reaction mechanism for activity improvement. Catalytic runs including recycling experiments allowed isolation and characterization by NMR, IR, and single-crystal X-ray diffraction of a new tin complex containing 10 tin atoms. This compound could be prepared independently and is considered as a resting species. The yield of DMC is highest under 20 MPa pressure that fits with a monophasic supercritical medium in agreement with fluid phase equilibria calculations. In line, preliminary kinetics and…

NOVEL PROCESSES FOR THE MODIFICATION AND THE STERILIZATION OF MACROMOLECULAR MATRICES

Catalytic Functionalization of Methane and Light Alkanes in Supercritical Carbon Dioxide

2014

International audience; The development of catalytic methods for the effective functionalization of methane yet remains a challenge. The best system known to date is the so-called Catalytica Process based on the use of platinum catalysts to convert methane into methyl bisulfate with a TOF rate of 10−3 s. In this contribution, we report a series of silver complexes containing perfluorinated tris(indazolyl)borate ligands that catalyze the functionalization of methane into ethyl propionate upon reaction with ethyl diazoacetate (EDA) by using supercritical carbon dioxide (scCO2) as the reaction medium. The employment of this reaction medium has also allowed the functionalization of ethane, prop…