超临界流体沉析制备微细颗粒的技术及其应用

快速膨胀超临界流体溶液（ＲＥＳＳ）过程和以超临界流体为稀释膨胀剂（ＧＡＳ）过程是制备微细颗粒的新技术。本文着重分析了用ＲＥＳＳ和ＧＡＳ过程制备微细颗粒的特点及影响因素，介绍了在高分子聚合物、无机盐、陶瓷材料、有机物、药物及含能材料方面的应用，提出超临界流体沉淀技术将成为制备特殊细颗粒材料、超薄膜及提纯热敏性、易氧化物质的有效手段。     

Harnessing the Melting Peculiarities of Ultra‐High Molecular Weight Polyethylene Fibers for the Processing of Compacted Fiber Composites

Summary: Compacted fiber composites offer unique properties due to their lack of an extraneous matrix. The conditions of processing ultra‐high molecular weight polyethylene (UHMWPE) fibers were simulated in a heated pressure cell. In situ X‐ray diffraction measurements were used to follow the relevant transitions and the changes in the degree of crystallinity during melting and crystallization. The results strongly support the suggestion that the hexagonal crystal phase, in which the chain conformation is extremely mobile on the segmental level, constitutes the physical basis of compaction technologies for processing UHMWPE fibers into a single‐polymer composite. This report suggests that using a pseudo‐phase diagram outlining the occurrence of different phases during slow heating and the degree of crystallinity can provide valuable insight into the technological parameters relevant for optimal processing conditions.

Degree of crystallinity as a function of pressure and temperature in a region relevant to compaction processes.     

Impregnation of silk sericin into polyester fibers using supercritical carbon dioxide

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     

Lipase-catalyzed synthesis and properties of estolides and their esters

Eight lipases were screened for their ability to synthesize estolides from a mixture that contained lesquerolic (14-hydroxy-11-eicosenoic) acid and octadecenoic acid. With the exception ofAspergillus niger lipase, all 1,3-specific enzymes (fromRhizopus arrhizus andRhizomucor miehei lipases) were unable to synthesize estolides.Candida rugosa andGeotrichum lipases catalyzed estolide formation at >40% yield, with >80% of the estolide formed being monoestolide from one lesquerolic and one octadecenoic acyl group:Pseudomonas sp. lipase synthesized estolides at 62% yield, but the product mixture contained significant amounts of monoestolide with two lesquerolic acyl groups as well as diestolide. ImmobilizedR. miehei lipase was chosen to catalyze the esterification of mono-and polyestolide, derived synthetically from oleic acid, with fatty alcohols or α,ω-diols. Yields were >95% for fatty alcohol reactions and >60% for diol reactions. In addition, the estolide linkage remained intact through the course of the esterification process. Esterification of estolides improved the estolide’s properties—for example, lower viscosity and higher viscosity index—but slightly raised the melting point. Estolides and, particularly, estolide esters may be suitable as lubricants or lubricant additives.     

超临界水中NaCl无限稀释扩散系数的研究

The molecular dynamics(MD) was employed to simulate the diffusion coefficient of sodium chloride at infinite dilution in supercritical water from 703.2K to 763.2K and from 30 MPa to 45 MPa ,Based on the simulated data and the Patel-Teja(PT) equation of state and the Liu-Ruckenstein equation,an equation for calculating the diffusion coefficient of NaCl at infinite dilution in supercritical water is proposed,Both the agreement between the simulated and correlated data,and that between the simulated and predicted data of diffusion coefficients for NaCl in supercritical water ranging from 703.2K to 803.2K and from 25 MPa to 50MPa show that this equation is applicable for calculation of diffusion coefficients.     

超临界CO2萃取的番茄红素稳定性研究

系统研究了温度、光、氨气保护、氧化剂和还原剂对超临界CO2萃取番茄红素稳定性的影响。研究表明，温度升高，番茄红素稳定性急剧下降；蔽光和氮气保护能有效的提高番茄红素的稳定性；氧化剂加速其分解；适宜浓度的还原剂可以有效的提高其稳定性。     

Supercritical CO2‐assisted synthesis of poly(acrylic acid)/Antheraea pernyi SF blend

Monomer acrylic acid (AA) and initiator azo‐bis(isobutyronitrile)were carried into Antheraea pernyi silk fibroin (SF) fibers using supercritical CO₂ as a solvent and carrier, followed by free radical polymerization at a suitable temperature, resulting in PAA/SF blends. The binary system of CO₂/AA and the ternary system of CO₂/AA/AIBN systems were studied. Different impregnation conditions, such as time, pressure, and concentration of AA in the fluid phase on mass uptake, were studied. Fourier transform infrared spectroscopy and X‐ray diffraction results confirmed that PAA was indeed present in the silk and that there were intermolecular hydrogen bonds between PAA and SF. According to thermogravimetry and DTG, blending with PAA could enhance the thermal stability of SF slightly. The water retention values indicated that the hydrophilic nature of the fibers was improved. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 864–868, 2005     

超临界CO_2萃取技术的工业应用

详细论述了超临界CO_2萃取技术在工业应用过程中遇到的工艺流程、装置设计与转产、能耗与安全等若干问题,提出了超临界CO_2萃取的工业化应用设计的总体要求。     

A Fully Continuous Supercritical Fluid Extraction System for Contaminated Soil

A fully continuous lab scale supercritical fluid extraction system has been designed, built and tested. The system continuously pumps carbon dioxide under supercritical conditions and soil slurry into a counter‐current contacting column. Delhi Loamy Sand, spiked with approximately 10 mg/g of naphthalene, was used as the testing soil. The soil slurry ranged from 0.0028 g dry soil per g slurry to 0.072 g/g. The operating temperature was 43°C and the operating pressure was 7.7 MPa. Near steady state, fully continuous flow was achieved with runs lasting as long as 2 h. All carbon dioxide samples contained measurable quantities of naphthalene and the measured mass transfer coefficients were as high as 4.6×10^?4 s^?1.     

超临界CO2GAS沉析HMX制细过程的影响因素

研究了超临界CO2GAS沉析丙酮溶液中HMX的过程压力、温度、溶液初始浓度和溶液的膨胀速度及影响晶体粒度的因素。结果表明，压力增加，沉析颗粒的平均粒度减小；温度控制沉析晶体的晶型，对颗粒度的影响相对较小，温度增加，沉析平均粒度略有增加；溶液初始浓度对平均粒度的影响相对较大，膨胀速度亦是影响粒度及其分布的一个因素。快速膨胀溶液．并使过饱和度足够大，使过饱和度主要消耗在成核上，可得到颗粒小、分布窄的HMX颗粒。