皮革的CO2超临界流体脱灰

浸灰和脱灰是皮革制造过程的重要工序。在浸灰工序中,通过高浓度石灰乳液对动物皮的长时间处理,使其纤维介质被溶解,胶原纤维得到分散。脱灰是其后续工序,目的是除去动物皮中吸附和沉积的Ｃａ2+;调节ｐＨ值至中性并使其肿胀状态得以消除;促进鞣铬剂的发渗而与胶原纤维有效结合。常规制革工艺中,铵盐被广泛用作脱灰剂,其缺点是中和作用不充分不能有效除去Ｃａ2+,Ｃａ2+与动物油脂反应会产生“钙斑”,并产生令人不愉快的氨污染环境。而硼酸、甲酸、乙酸、柠檬酸等以单独或组合方式与铵盐一道用于脱灰[1]价格昂贵,还易引起裸皮的酸肿影响皮…     

超临界CO2技术制备微孔聚合物中的基本问题

微发泡聚合物材料以环境友好的超临界CO₂为发泡剂, 具有优异的材料性能. 本文对本课题组的研究工作做了归纳总结, 对聚合物微发泡中CO₂的传质、微发泡过程中泡孔结构参数的变化以及多相/多组分聚合物体系的微发泡行为等内容做了针对性的综述. 结合对聚合物微发泡过程理论模拟研究工作的评述, 展望了超临界CO₂微发泡技术未来的发展方向.     

Sorption and swelling of semicrystalline polymers in supercritical CO2

The equilibrium sorption and swelling behavior of four different polymers—poly(methyl methacrylate), poly(tetrafluoroethylene), poly(vinylidene fluoride), and the random copolymer tetrafluoroethylene–perfluoromethylvinylether–in supercritical CO₂—are studied at different temperatures (from 40 to 80 °C) and pressures (up to 200 bar). Swelling is measured by visualization, and sorption through a gravimetric technique. From these data, the behavior of amorphous and semicrystalline polymers can be compared, particularly in terms of partial molar volume of CO₂ in the polymer matrix. Both poly(methyl methacrylate) and the copolymer of tetrafluoroethylene exhibit a behavior typical of rubbery systems. On the contrary, polymers with a considerable degree of crystallinity, such as poly(tetrafluoroethylene) and poly (vinylidene fluoride), show larger values of partial molar volume. These can be related to the limited mobility of the polymer chains in a semicrystalline matrix, which causes the structure to “freeze” during the sorption process into a nonequilibrium state that can differ significantly from the actual thermodynamic equilibrium. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1531–1546, 2006     

用超临界CO2萃取香草兰香料

香草兰是一种多年生藤本热带香料植物 ,有“食品香料之王”的美称 ,经济价值很高 ,要靠进口满足国内需求[1 ] 。在水果制品中添入香草兰 ,可使果香味增浓 ,但不增加热量[2 ] ;香草兰还用于化妆品业、烟草业和药品业等[3] 。它是由提取香草兰豆荚制备的。传统方法是用有机溶剂萃取 ,成本高、费时、溶剂会残留。近 2 0年才发展起来的超临界流体萃取 (Ｓｕｐｅｒｃｒｉｔｉｃａｌｆｌｕｉｄｅｘｔｒａｃｔｉｏｎ ,简称ＳＣＦＥ)技术 ,在天然产物提取以及食品工业的应用方面取得较好效果[4] 。本文用超临界ＣＯ2萃取香草兰香料 ,研究了压力、温…     

超临界二氧化碳介质中过渡金融催化反应研究进展

超临界介质中的化学反应研究是目前热点研究领域之一，对超临界CO2介质中 过渡金属催化反应研究进行了总结和述评，同时讨论了有关提高过渡金属催化剂在 超临界CO2中溶液度的方法。     

超临界CO2萃取香草兰化学成分分析

香草兰 ,学名 :ＶａｎｉｌｌａｐｌａｎｉｆｏｌｉａＡｎｄｒ.,又名香荚兰 ,香子兰 ,属兰科香子兰属 ,是一种名贵的多年生热带藤本植物 ,有独特的香味 ,被称誉为“食品香料之王”。香草兰经加工后 ,是食品工业的重要天然香料 ,也用于烟草业、化妆品业和药物[1,2 ] 。香草兰原产于墨西哥 ,主产国还有马达加斯加、印尼、牙买加等[3 ] 。近年来 ,我国海南、云南等地也大力种植和推广。超临界流体萃取 (ＳｕｐｅｒｃｒｉｔｉｃａｌＦｌｕｉｄＥｘｔｒａｃｔｉｏｎ ,简称ＳＣＦＥ)是近 2 0年发展起来的现代提取分离技术 ,具有工艺简单、成本低、…     

Enhanced corrosion protection performance with MWCNT dispersed epoxy coating prepared under supercritical CO2 assistance

The corrosion protection performance of epoxy coatings could be enhanced by incorporation of nanofillers such as MWCNT. However, a homogeneous dispersion of MWCNT in epoxy polymer is still a teasing challenge. Herein, we report an environmentally benign single‐step supercritical CO₂ processing method to improve the dispersion of MWCNT in epoxy matrix in order to achieve an effective anticorrosive coating. The executed approach provides a cluster‐free uniform distribution of MWCNT in epoxy matrix as characterized with UV‐visible spectroscopy, Fourier transforms infrared spectroscopy, X‐ray diffraction, and surface analysis. The anticorrosive characteristics of MWCNT/epoxy coating were studied in NaCl as well as in photodegraded dye medium through electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization measurements. We observed the remarkable corrosion of model metal substrate in photodegraded dye medium besides NaCl medium. In both mediums, the protection efficacy of MWCNT/epoxy coating was deduced from the stable impedance arcs in Nyquist plot and increased impedance modulus. The electrochemical impedance spectra were best fitted with equivalent circuits showing the higher values of pore resistance. Also, the MWCNT/epoxy coating exhibited a positive shift of corrosion potential and possessed a lower corrosion rate as compared with neat epoxy coating. More direct evidence of the excellent barrier properties for MWCNT/epoxy coating was visualized in SEM images. The obtained results implied that the superior dispersion of MWCNT into epoxy matrix significantly reduces the porosity of coating and inhibits the permeability of corrosive ions. We expect supercritical CO₂ assisted dispersion method can offer an efficient, cost‐effective, and industrially viable route to develop high performance protective coatings for varied commercialized applications.     

Solubility of stearic acid in supercritical CO_2-acetonitrile mixtures

The solubility of stearic acid in supercritical CO2 with acetonitrile (CH3CN) cosolvent was measured at 318.15 K in the pressure range from 9.5 to 16.5 MPa, and the cosolvent concentration ranges from 0. 0 to 5.5 mol% . The solubility increases with acetonitrile concentration and pressure, and it also increases with the apparent density of CO2 d1(moles of CO2 in per liter of fluid) at higher cosolvent concentrations. At lower d1, however, the solubility of the acid at lower acetonitrile concentrations is lower than that in pure CO2 provided that d1 is fixed, which is discussed qualitatively based on the clustering of the components in the system.     

超临界CO2萃取异甘草素的提取工艺

采用正交试验与单因素试验相结合方法对异甘草素的超临界CO2提取工艺进行了研究,并与常规索氏提取法的实验结果进行了对比。得到的最佳工艺参数为:萃取压力30 MPa、萃取温度45℃、夹带剂85％乙醇、液固比为5:1、CO2流量10 kg／h、分离压力5．5 MPa、分离温度35℃。实验结果表明,在优化的条件下,超临界CO2萃取异甘草素的提取率为0．035％,异甘草素在提取物中的质量分数为0．84％,分别是索氏提取法提取率的3．5倍,质量分数的3．0倍。超临界CO2萃取异甘草素所用时间短、溶剂用量少、提取效率高、环境友好,是一种高效、快速提取异甘草素的方法。     

Graft copolymerization of maleic anhydride/styrene onto isotactic polypropylene using supercritical CO2

The free‐radical grafting of maleic anhydride (MAH) and styrene (St) onto isotactic polypropylene (iPP) was studied by thermal decomposition of dicumyl peroxide (DCP) using supercritical CO₂ as a solvent and swelling agent. Several effects of molar ratio of monomer, soaking temperature and time, reaction time, and reaction pressure on the graft degree were discussed. It was found that the addition of St to the grafting system as a comonomer could significantly enhance the graft degree of the grafted PP. Under the optimal reaction condition, the maximum of iPP grafting MAH and St in supercritical CO₂ medium was 10.58%. The chemical structures and properties of grafting copolymers were characterized by Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC). The results showed that the supercritical CO₂ method had noticeable advantages over the existed method when compared, such as a lower temperature, a higher graft degree, easy separation, and environmentally benign. Copyright © 2007 John Wiley & Sons, Ltd.     

Thermal and morphological characterization of micronized acetylsalicylic acid powders prepared by rapid expansion of a supercritical solution

Aim of this work was to investigate the solid-state characteristics of micronized acetylsalicylic acid (ASA), produced by rapid expansion of a supercritical carbon dioxide solution (RESS) and to assess whether a correlation could be found between process parameters and solid-state characteristics. Drug solubility in supercritical CO₂ was first assessed under various pressure and temperature conditions. DSC, FT-IR, PXRD, SEM, laser light scattering and HPLC were used to characterise the solid phases produced by the RESS. The obtained particles were crystalline, with spectroscopical and diffractometrical pattern overlapping those of the starting available product. However, a strong reduction of particle size was obtained, linearly correlated to pressure imposed during the RESS process, while temperature did not seem to have a major effect. Similar influence of pressure was observed on the final melting temperature of the micronized ASA. The application of a mathematical model allowed to conclude that the melting temperature depression of RESS-prepared ASA powders can be attributed to the decrease of particle dimension rather than to the formation of different solid phases or impurities. This revised version was published online in July 2006 with corrections to the Cover Date.     

One-Step Synthesis of Spin Crossover Nanoparticles Using Flow Chemistry and Supercritical CO2

Switchable materials are increasingly considered for implementation in devices or multifunctional composites leading to a strong need in terms of reliable synthetic productions of well-defined objects. Here, an innovative and robust template-free continuous process was developed to synthesize nanoparticles of a switchable coordination polymer, including the use of supercritical CO₂, aiming at both quenching the particle growth and drying the powder. This all-in-one process offers a 12-fold size reduction in a few minutes while maintaining the switching properties of the selected spin crossover coordination polymer.     

Viscosity studies of poly(DL‐lactic acid) in supercritical CO2

The effect of supercritical CO₂ on the viscosity and activation energy to viscous flow of P_DLLA is investigated, using a high pressure parallel plate rheometer, over a range of temperatures (50–140 °C) and pressures (5–12 MPa). The Cross model is fitted to the data to enable calculation of the zero shear viscosity and critical shear rate. A significant decrease in the viscosity is observed on increasing both variables; however, at high temperatures, the pressure effect becomes negligible. An increase in the critical shear rate is also observed on raising the pressure, indicative of a reduction in the relaxation time of the polymer. Manipulation of the Arrhenius equation shows a reduction in the activation energy to viscous flow as the pressure is increased. Together, these results show that the melt processing temperature of P_DLLA can be reduced in the presence of supercritical and high pressure CO₂. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Use of supercritical CO2‐aided and conventional melt extrusion for enhancing the dissolution rate of an active pharmaceutical ingredient

Dispersing at the molecular level a drug in a polymer matrix is a major challenge to be addressed by the pharmaceutical industry to enhance its bioavailability or to control its release. Melt extrusion and supercritical CO₂‐aided melt extrusion of solid pharmaceutical formulations were performed to enhance the dissolution rate of carvedilol, taken as a model of poorly soluble drug. The presence of the drug improved the processability of the polyacrylate matrix (Eudragit E) through its plasticizing effect. The supercritical method was found gentle compared with melt extrusion owing to the shorter residence time and lower processing temperature and melt viscosity. No traces of decomposition of the drug could be detected after the supercritical extrusion process based on capillary electrophoresis results. This extrusion process resulted in effective homogenization of the components and amorphization of the drug according to Raman mapping, Fourier transform infrared spectrometry, X‐ray diffraction, and polarized light microscopy. The kinetics of dissolution can be dramatically improved. Copyright © 2011 John Wiley & Sons, Ltd.     

Enhanced morphological heterogeneity of PCL in the presence of PVC with isothermal supercritical CO2 treatment

This report presents a continuing study of the morphological changes of polycaprolactone (PCL) with isothermal supercritical CO₂ treatments at 304 atm and 35 °C in the presence of poly(vinyl chloride) (PVC). DSC and small‐angle X‐ray scattering (SAXS) data find that the CO₂‐assisted melting of PCL at 304 atm and 35 °C recrystallized in the presence of PVC during depressurization of CO₂ can result in a decreased thickness of crystal lamellar layers. Heterogeneity, with a size (21.7 nm for pure PCL) larger than the crystal layer thickness (8.2 nm for pure PCL) and the amorphous layer thickness (4.4 nm for pure PCL), is formed after the supercritical CO₂ treatment. The size of this heterogeneity is found to enhance from 21.7 nm for pure PCL to 29.8 and 34.9 nm for the PCL samples containing 10 and 25 wt % PVC, respectively. These big heterogeneities in the PCL/PVC blends formed during CO₂ depressurization might arise from the segregated PVC‐rich amorphous domains that are located between bundles of the lamellar stacks, possibly as a result of the molecular dragging on PCL during depressurization of the PCL‐interacted CO₂. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 85–93, 2006     

Effect of supercritical CO2 on the copolymerization behavior of cyclohexene oxide/CO2 and copolymer properties with DMC/Salen‐Co(III) catalyst system

The copolymerization of cyclohexene oxide (CHO) and carbon dioxide (CO₂) was carried out under supercritical CO₂ (scCO₂) conditions to afford poly (cyclohexene carbonate) (PCHC) in high yield. The scCO₂ provided not only the C1 feedstock but also proved to be a very efficient solvent and processing aid for this copolymerization system. Double metal cyanide (DMC) and salen‐Co(III) catalysts were employed, demonstrating excellent CO₂/CHO copolymerization with high yield and high selectivity. Surprisingly, our use of scCO₂ was found to significantly enhance the copolymerization efficiency and the quality of the final polymer product. Thermally stable and high molecular weight (MW) copolymers were successfully obtained. Optimization led to excellent catalyst yield (656 wt/wt, polymer/catalyst) and selectivity (over 96% toward polycarbonate) that were significantly beyond what could be achieved in conventional solvents. Moreover, detailed thermal analyses demonstrated that the PCHC copolymer produced in scCO₂ exhibited higher glass transition temperatures (T_g ～ 114 °C) compared to polymer formed in dense phase CO₂ (T_g ～ 77 °C), and hence good thermal stability. Additionally, residual catalyst could be removed from the final polymer using scCO₂, pointing toward a green method that avoids the use of conventional volatile organic‐based solvents for both synthesis and work‐up. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2785–2793     

New CO2-philic Compounds： Design, Synthesis and Solubility in Supercritical Carbon Dioxide

Liquid and supercritical carbon dioxide (scCO2) have attracted much attention as “green” replacement for organic solvents, offering economical and environmental benefits due to its favorable physical and chemical properties, such as recyclability, ease …     

Accurate Interaction Energies of CO2 with the 20 Naturally Occurring Amino Acids

We have performed a series of highly accurate calculations between CO₂ and the 20 naturally occurring amino acids for the investigation of the attractive noncovalent interactions. Different nucleophilic groups present in the amino acid structures were considered (α-NH₂, COOH, side groups), and the stronger binding sites were identified. A database of accurate reference interactions energies was compiled as computed by explicitly-correlated coupled-cluster singles-and-doubles, together with perturbative triples extrapolated to the complete-basis-set limit. The CCSD(F12)(T)/CBS reference values were used for comparing a variety of popular density functionals with different basis sets. Our results show that most density functionals with the triple-zeta basis set def2-TZVPP align with the CCSD(F12)(T)/CBS reference values, but errors range from 0.1 kcal/mol up to 1.0 kcal/mol.