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1.
We report on an efficient and environmentally friendly means to modify surface properties of polymer films supported for nanoparticles. Ultrathin polystyrene (PS) films (<300 Å), in which inorganic nanoparticles were embedded, were exposed to supercritical carbon dioxide (scCO2). The swollen structure was then preserved by quickly evaporating CO2. X-ray reflectivity (XR) results showed that this procedure produced polymeric nanocomposite films with a low-density region of about 150Å at the polymer/air interface. The formation of the low-density layer was independent of the nature of the particles, indicating that the surface modification through exposure to scCO2 may be a universal phenomenon regardless of a choice of nanoparticles. 相似文献
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A. Molero G mez E. Mart nez de la Ossa 《Journal of the American Oil Chemists' Society》2000,77(9):969-974
The extraction of wheat germ oil by liquid and supercritical CO2 is described from the point of view of both operative method and pretreatment of raw material. The best conditions for wheat
germ oil extraction are: pressure, 150 bar; temperature, 40°C; and solvent flow rate, 1.5 L/min at standard temperature and
pressure. The yields and fatty acid compositions obtained are very similar to those resulting from the conventional extraction
process using hexane as solvent (8.0 wt%), although a higher-quality oil is obtained by using CO2 as solvent (free fatty acids, 12.4%; tocopherol content, 416.7 mg tocopherol/g wheat germ oil). These factors lead to the
conclusion that the extraction process using CO2 could be economically competitive with the conventional process, since it considerably simplifies the oil refinement stages
and completely eliminates the solvent distillation stage, which are the most costly processing steps in terms of energy consumption. 相似文献
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Silk sericin was impregnated into polyester fabric using supercritical carbon dioxide (SCCO2) to overcome polyester hydrophobicity. The effects of sericin molecular weight, pH of sericin, solution and cosolvent types on sericin impregnation were investigated. Enzyme‐hydrolyzed, acid‐, based‐hydrolyzed sericin in SCCO2, and a 30 kDa sericin in SCCO2 modified with cosolvents such as water, methanol, 1‐propanol, and acetone; and a modifier: sodium hydroxide solution were used in this work. Impregnation of sericin in polyester was indicated by Fourier transform infrared spectrophotometry (FTIR) and dyeing with acid dye. Degradation of polyester fibers during SCCO2 process was indicated by scanning electron microscopy (SEM). Methylene blue dyeing was used to realize carboxyl group in polyester. The results showed no impregnation of sericin into polyester by using SCCO2 modified with cosolvents. However, sericin was impregnated into modified surface polyester since hydrophilic groups such as carboxyl and hydroxyl groups were regenerated by alkaline hydrolysis. Samples impregnated with hydrolyzed sericin showed high color strength of Supranolechtbordeaux B acid dye. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007 相似文献
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C. Tsitsimpikou H. Stamatis V. Sereti H. Daflos F. N. Kolisis 《Journal of chemical technology and biotechnology (Oxford, Oxfordshire : 1986)》1998,71(4):309-314
The acylation of glucose with lauric acid in a reaction catalysed by two Candida lipases and a Mucor miehei lipase in supercritical carbon dioxide (SCCO2) was investigated. A linear dependence of the reaction rate on enzyme concentration was observed. Studies on the effect of temperature on enzyme activity showed that Candida antarctica lipase remains stable at temperatures as high as 70°C. Non-immobilised Candida rugosa lipase was found to have a temperature optimum at 60°C. The acylation reaction rate depended on the initial water activity of both substrates and enzyme; the optimum was 0·75 for Candida antarctica lipase, 0·53 for Candida rugosa lipase, and between 0·3 and 0·5 for Mucor miehei lipase. Candida rugosa lipase was most active at a molar ratio of sugar: acyl donor of 1: 3, while the optimum ratio was found to increase to 1: 6 when the reaction was catalysed by Candida antarctica and Mucor miehei lipases. © 1998 SCI 相似文献
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Lei Ye Keiichi Yoshimatsu Dorota Kolodziej Jos Da Cruz Francisco Estera S. Dey 《应用聚合物科学杂志》2006,102(3):2863-2867
Molecularly imprinted polymer nanoparticles were prepared in supercritical carbon dioxide using a noncovalent imprinting approach. In the present work, propranolol was used as a model template, methacrylic acid as a functional monomer, and divinylbenzene as a crosslinker. Under a high dilution condition, the heterogeneous polymerization resulted in discrete crosslinked polymer nanoparticles. Compared with the nonimprinted polymers, the imprinted nanoparticles displayed much higher propranolol uptake in a low polarity organic solvent. The use of a single enantiomer (S)‐propranolol as the template clearly demonstrated that the imprinted binding sites are chiral‐selective, with a cross‐reactivity towards (R)‐propranolol of less than 5%. The overall binding performance of the imprinted nanoparticles was comparable to imprinted polymers prepared in conventional organic solvents. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2863–2867, 2006 相似文献
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Conversion of oils to monoglycerides by glycerolysis in supercritical carbon dioxide media 总被引:1,自引:0,他引:1
Feral Temelli Jerry W. King Gary R. List 《Journal of the American Oil Chemists' Society》1996,73(6):699-706
Glycerolysis of soybean oil was conducted in a supercritical carbon dioxide (SC-CO2) atmosphere to produce monoglycerides (MG) in a stirred autoclave at 150–250°C, over a pressure range of 20.7–62.1 MPa, at
glycerol/oil molar ratios between 15–25, and water concentrations of 0–8% (wt% of glycerol). MG, di-, triglyceride, and free
fatty acid (FFA) composition of the reaction mixture as a function of time was analyzed by supercritical fluid chromatography.
Glycerolysis did not occur at 150°C but proceeded to a limited extent at 200°C within 4 h reaction time; however, it did proceed
rapidly at 250°C. At 250°C, MG formation decreased significantly (P<0.05) with pressure and increased with glycerol/oil ratio and water concentration. A maximum MG content of 49.2% was achieved
at 250°C, 20.7 MPa, a glycerol/oil ratio of 25 and 4% water after 4 h. These conditions also resulted in the formation of
14% FFA. Conversions of other oils (peanut, corn, canola, and cottonseed) were also attempted. Soybean and cottonseed oil
yielded the highest and lowest conversion to MG, respectively. Conducting this industrially important reaction in SC-CO2 atmosphere offered numerous advantages, compared to conventional alkalicatalyzed glycerolysis, including elimination of the
alkali catalyst, production of a lighter color and less odor, and ease of separation of the CO2 from the reaction products. 相似文献
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The direct methanolysis of triglycerides in flowing supercritical carbon dioxide by an immobilized lipase is described. The
reaction system consists of two syringe pumps for substrate addition and another two syringe pumps for delivering CO2 at 24.1 MPa. Corn oil is pumped into the carbon dioxide stream at a rate of 4 μL/min, and methanol is pumped at 5 μL/min
to yield fatty acid methyl esters (FAME) at >98% conversion. Direct methanolysis of soy flakes gives FAME at similar yields.
This combined extraction/reaction is performed at 17.2 MPa and 50°C. The fatty acid profiles obtained for these seed oils
matches those obtained by classical chemical synthesis. 相似文献
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Solubility of fatty acids in supercritical carbon dioxide 总被引:1,自引:0,他引:1
P. Maheshwari Z. L. Nikolov T. M. White R. Hartel 《Journal of the American Oil Chemists' Society》1992,69(11):1069-1076
The solubilities of lauric, linoleic, myristic, oleic, palmitic and stearic acid in supercritical carbon dioxide (SC-CO2) at different pressures and temperatures were measured. The solubility values obtained in this work were compared with previously
published data, and possible causes for observed discrepancies were discussed. The solubilities of the six fatty acids were
modeled by Chrastil’s equation, and estimated model parameters were used to plot the solubility isotherms of fatty acids at
313, 323 and 333°K (40, 50 and 60°C) as a function of SC-CO2 density. The comparison of solubility isotherms of fatty acids and vegetable oil suggests that separation of fatty acids
from triglycerides might be possible by using SC-CO2 at densities less than 700 kg/m3. From the effect of temperature on fatty-acid and vegetable-oil solubility, it seems that the extraction yield could be increased
without sacrificing the selectivity of SC-CO2 for fatty acids by choosing a higher operating temperature. The data also suggest that fractionation of certain fatty acids
might be possible by manipulating the processing conditions. Given the values of the constants, Chrastil’s equation could
serve as a guideline for choosing appropriate processing conditions and predicting the effect of pressure and temperature
of SC-CO2 on solute solubility. 相似文献
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A supercritical fluid extraction method has been applied to test the feasibility of tocopherol concentration from soybean
sludge with carbon dioxide at temperatures and pressures ranging from 35 to 70°C and 200 to 400 bar, respectively. The supercritical
solubility of the esterified soybean sludge was over 4–6 times greater than that of the original soybean sludge. By a simple
batch-type one-stage method the tocopherols in the esterified soybean sludge could be concentrated up to 40 wt%. The overall
results of the present study show that soybean sludge initially containing about 13–14 wt% tocopherols may require a countercurrent
multistage column to be highly and effectively concentrated. 相似文献
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The transesterification of soybean oil with glycerol, 1,2-propanediol, and methanol by an immobilized lipase in flowing supercritical
carbon dioxide for the synthesis of monoglycerides is described. A lipase from Candida antarctica was used to catalyze the reaction of soybean oil with glycerol, 1,2-propanediol, ethylene glycol, and methanol. Reactions
were performed in supercritical carbon dioxide at a density of 0.72 g/L and at a flow rate of 6 μL/min (expanded gas). The
substrates were added at flows ranging from 2.5 to 100 μL/min. Monoglycerides were obtained at up to 87 wt%, and fatty acid
methyl esters at nearly 100 wt%. The reactivity of the alcohols paralleled the solubility of the substrate in liquid carbon
dioxide. Glycerol has the slowest reaction rate, only 2% of that of methanol. 相似文献
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Absorption of a series of low molecular weight solutes into polyurethane was investigated in supercritical carbon dioxide with different conditions. The effect on the amount of solutes absorbed in polyurethane due to these factors such as pressure, temperature, absorption time, decompression time, the character of solutes, and the amount of cosolvent was examined by a gravimetric method. The absorption mechanism was discussed. The desorption of solutes in polyurethane showed a dependence on the logarithm of time. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 3162–3168, 2000 相似文献
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利用超临界二氧化碳流体脱硫再生丁基橡胶 总被引:2,自引:0,他引:2
研究了硫黄硫化的丁基橡胶在超临界二氧化碳流体辅助下的脱硫降解行为,讨论了脱硫工艺的条件,并通过凝胶渗透色谱、核磁共振、差示扫描量热等对丁基再生胶的结构和性能进行了考察。结果表明,在二氧化碳的超临界状态下丁基橡胶的脱硫降解更加充分。脱硫的最佳工艺条件为: 反应温度180 ℃,反应压力14. 1 MPa,脱硫剂二苯基二硫的用量为橡胶质量的8%; 经过120 min 脱硫反应后丁基再生胶中溶胶的质量分数为98. 5%。在有热降解和脱硫剂参与的脱硫反应的共同影响下,丁基再生胶中溶胶的数均分子量降至原胶的40%左右; 再生胶主链上接枝了部分脱硫剂的苯环; 硫化和脱硫过程中在接枝于主链上的极性基团的影响下,再生胶中溶胶主链双键氢的振动峰几乎消失,但再生胶的玻璃化转变温度并没有明显变化。 相似文献
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K. Sawada D. Terada T. Yamaoka S. Kitamura T. Fujisato 《Journal of chemical technology and biotechnology (Oxford, Oxfordshire : 1986)》2008,83(6):943-949
BACKGROUND: The objective of this work was to decellularize artificial tissue without using surfactant solutions. For this purpose, supercritical carbon dioxide was used as the extraction medium. RESULTS: Supercritical carbon dioxide containing a small amount of entrainer was a suitable medium to extract both cell nuclei and cell membranes from artificial tissue. Under gentle extraction conditions (15 MPa, 37 °C), cell nuclei were satisfactorily extracted from tissue within 1 h. In contrast, the efficiency of phospholipid removal depended strongly on the transfer rate of carbon dioxide in the interior of the tissue. Mechanical strength of tissue was not decreased even with prolonged treatment. CONCLUSION: Acellular artificial tissues could be prepared quickly by treatment with a carbon dioxide/entrainer system. The prepared acellular tissue could be obtained in absolutely dry condition. This is advantageous from the viewpoint of long‐term preservation without putrefaction and contamination. Copyright © 2008 Society of Chemical Industry 相似文献
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The copolymerization of styrene (St) and maleic anhydride (MA) was carried out in supercritical carbon dioxide (SC CO2). It was found that St and MA are easy to copolymerize in SC CO2 and the conversion can reach 97%, and that very fine and dry powders are obtained. The products were characterized using Fourier transform infrared spectroscopy (FTIR), gel permeation chromatography (GPC), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). GPC data showed that the molecular weight of the copolymer reach 3.62 × 104 g mol?1. Scanning electron microphotographs showed the minimum particle size of the product is about 200 nm. DSC measurements indicated that the glass transition temperature (Tg) of the copolymer increases with increasing the MA content in the copolymer. TGA curve showed that the copolymers were decomposed at about 350°C. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007 相似文献