磷钨酸铈催化合成棕榈酸和硬脂酸混合酸甲酯

采用磷钨酸铈作为催化剂,在反应温度67℃合成棕榈酸和硬脂酸混合酸甲酯反应,研究酸醇物质的量比、催化剂用量和反应时间对酯化反应的影响,并在最佳反应条件基础上研究催化剂的循环利用工艺。结果表明,在酸醇物质的量比1∶10、催化剂用量为棕榈酸和硬脂酸混合酸质量的8%、反应时间4 h和催化剂重结晶后循环利用10次条件下,棕榈酸和硬脂酸混合酸转化率均≥96.0%,催化剂反应前后的IR和XRD表征发现,催化剂均为Keggin型结构,未发生变化,表现出良好的催化活性。

第二菊酸类混合含氟苄酯的合成及其杀虫活性

报道了第二菊酸及其2(3)-氟-4-甲氧甲基苄酯和2(3)-氟-4-甲基苄酯的合成,生物活性测试的结果表明这两种新化合物对淡色库蚊四龄孑孓显示出较高的杀虫活性.

乙氧基化脂肪酸甲酯的性能及丙氧基化改性研究

以单碳酸或混合酸甲酯为原料,通过一步法乙氧基化反应合成了不同链长的脂肪酸和不同EO数的乙氧基化脂肪酸甲酯(EFME),测定了EFME的物化性能和应用性能。结果表明,EFME具有低成本、低泡等特殊优点,性能依赖EO加成数变化连续可调整,EFME中的封端甲基是导致其性能不同于AEO的最重要的结构因素。用PO对EFME进行化学改性,先加成PO的产品的起泡力更低、流变性更好,与不改性产品相比起泡力降为原先的29%;稳泡性降为原先的22%;黏度降低为原先的44%。说明PO位于分子的亲水端侧较处于疏水端侧对产品的泡沫性和流变性的影响程度更大,通过PO改性可以进一步开发EFME的新用途。

Extraction of germanium(IV) from acid leaching solution with mixtures of P204 and TBP

Solvent extraction experiments were conducted from acidic solutions containing germanium（IV） and other metal ions, such as Ga3＋, Fe3＋, Zn2＋ and Fe2＋ in hydrometallurgical process of zinc. The purpose of this work was to enhance the efficiency of the extraction and stripping processes and the selectivity of germanium and other metals, while making the method as simple as possible. Germanium was recovered from sulfuric acid, using di-（2-ethylhexyl） phosphoric acid （P2O4） as an extractant, tributyl phosphate （TBP） as modifier diluted in sulfonate kerosene and stripped by NaOH aqueous solution. Extraction studies were carried out under different acid concentrations and solvent concentrations, and optimized conditions were determined. The numbers of stages required for extraction and stripping of metal ions were determined from the McCabe-Thiele plot. The results show that the extracting and stripping efficiencies are 94.3% and 100%, respectively, through two-stage extraction and two-stage strip. Moreover, the synergistic effect of TBP on the system P2O4/kerosense/Ge4＋ is revealed with respect to the extraction of germanium.

Optimization of Propionic Acid Feeding for Production of Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) in Fed-Batch Culture of Ralstonia eutropha

The feeding method of propionic acid for production ofpoly(3-hydroxybutyrate-co-3-hydro xyvalerate) [P(3HB-co-3HV)] by fed-batch culture of Ralstoniaeutropha was optimized to achieve high cell density and high 3HV yield. Effects of different feedingstrategies of propionic acid on the production of P(3HB-co-3HV) were investigated. A decline ofspecific synthesis rate of copolymer and the yield of 3HV unit from propionic acid were observed dueto the propionic acid accumulation in culture broth when the feeding solution with highP/G(propionic acid to glucose) ratio was employed. It was further confirmed by controlling propionicacid concentration at a low level in the separate feeding of propionic acid. An optimal feedingstrategy was demonstrated to reduce the propionic acid accumulation. The cell concentration,P(3HB-co-3HV) productivity and 3HV unit fraction reached to 163.9kg·m^(-3), 1.8kg·m^(-3)·h^(-1),and 10.6%(by mass), respectively, resulting in a yield of 0.33g HV per g propionic acid.

Measurement and modelization of VLE of binary mixtures of propyl acetate,butyl acetate or isobutyl acetate with methanol at pressure of 0.6 MPa

The vapor-liquid equilibrium of binary mixtures of propyl acetate, butyl acetate and isobutyl acetate with meth- anol has been determined at a constant pressure of 0.6 MPa. Results have been modeled with the Peng-Robinson equation, a traditional cubic equation of state widely employed in chemical industries, as well as with the perturbed-chain statistical associating fluid PC-SAFT theory of Gross-Sadowski. By correlation of the binary inter- action parameters of these equations, the measured vapor-liquid equilibrium data can be accurately predicted. Thus, this work shows that these models are able to represent the experimental data for systems with associating comoounds via hydrogen bonding.

Measurement and correlation of solubility of trimethylolethane in different pure solvents and binary mixtures

The solubilities of trimethylolethane in butanol,methyl acetate,ethyl acetate as well as in mixed solvents of(methanol+ethyl acetate) and(ethanol+ethyl acetate) were measured with the gravimetric method in the temperature range from 283.15 K to 318.15 K under atmosphere pressure.The experiment results showed that the solubility of trimethylolethane increased with the temperature,or along with the concentration of methanol or ethanol in the solvents of(methanol+ethyl acetate) and(ethanol + ethyl acetate).In addition,the experiment values were correlated by the van't Hoff equation,Modi fied Apelblat Equation,λh Equation,CNIBS/R-K equation and Jouyban–Acree Model.The Modi fied Apelblat Equation provided the best fitting results of the solubility data of TME in the pure solvents while the CNIBS/R-K model showed the best estimation of the solubility in the binary solvent mixtures.Furthermore,the density functional theory(DFT) calculations showed that solubility in different solvents related to the strength of the interaction between the trimethylolethane and the solvent molecules.Finally,the standard molar enthalpy and molar entropy of trimethylolethane during the dissolving process was also calculated by Modi fied Apelblat equation in this work.

Speeds of Sound and Excess Isentropic Compressibilities of Butyl Acetate＋Aromatic Hydrocarbons

Speed of sound data for butyl acetate＋benzene, or toluene, or o-xylene, or m-xylene, or p-xylene binary mixtures have been measured over the entire range of mole fraction at 308.15 K. The excess isentropic compressibilities （ Ks^E ） were computed from speed of sound and density data, derived from molar excess volume data. The Ks^E values were analyzed by using graph theoretical approach. The Ks^E values evaluated by graph theory compared reasonably well with their corresponding experimental values. The Ks^E data were also expressed in terms of Redlich-Kister polynomial equation to derive the coefficients and the standard deviation.

Cycloaddition of CO_2 with epoxides by using an amino-acid-based Cu(Ⅱ)–tryptophan MOF catalyst

Metal organic frameworks(MOFs)constructed from natural/biological units(amino acids)are prospective candidates as catalysts in CO2chemistry owing to their natural origin and high abundance of Lewis acid/base sites and functional groups.Herein,we report the catalytic efficiency of an amino‐acid‐based Cu‐containing MOF,denoted as CuTrp(Trp=L‐tryptophan).The CuTrp catalyst was synthesized by direct mixing at room temperature using methanol as a solvent-a synthetic route with notable energy efficiency.The catalyst was characterized using various physicochemical techniques,including XRD,FT‐IR,TGA,XPS,ICP‐OES,FE‐SEM,and BET analysis.The catalytic activity of CuTrp was assessed in the synthesis of cyclic carbonates from epoxides and CO2.The CuTrp operated in synergy with the co‐catalyst tetrabutylammonium bromide under solvent‐free conditions.Several reaction parameters were studied to identify the optimal reaction conditions and a reaction mechanism was proposed based on experimental evidence and previous density functional theory studies.The CuTrp also exhibited satisfactory stability in water and could be reused more than three times without any significant loss of activity.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.

Effect of Doping Cerium in the Support of Catalyst Pd-Co/Cu-Co-Mn Mixed Oxides on the Oxidative Carbonylation of Phenol

Effect of doping cerium in the support on the catalytic activity and side product of the reaction in the oxidative carbonylation of phenol to diphenyl carbonate (DPC) over the catalyst Pd-Co/Cu-Co-Mn mixed oxides was studied. The specific surface areas, crystal phase, valency, and content of the element on the surface of the catalysts were determined, and the products were detected by gas chromatograph/mass spectrometry (GC-MS). It is found that the catalyst without Ce shows higher activity than that with Ce, and the yields of DPC for the two cata-lysts can reach 30% and 23%, respectively. However, doping cerium can prevent the formation of 2-hydroxyphenyl benzoate and p-bromophenyl phenyl carbonate.

Separation of arenols from a high-temperature coal tar

A high-temperature coal tar collected from Xuzhou Coking Plant, Saint-Gobain Pipelines （Xuzhou） Co., Ltd. was exhaustively extracted with petroleum ether （PE）. The extract was sequentially eluted through silica gel with PE and PE/ethyl acetate （EA） mixed solvents （volume ratio 2：1 ） to afford two eluted frac- tions. The extract and eluted fractions were analyzed with gas chromatography/mass spectrometry. In total, 14 arenols were detected, including phenol, cresols, xylenols, fluorenols, phenanthren-3-ol and pyren-l-ol.

Excess Molar Volumes and Viscosities of Binary Mixture of Diethyl Carbonate+Ethanol at Different Temperatures

The purpose of this work was to report excess molar volumes and dynamic viscosities of the binary mixture of diethyl carbonate （DEC）+ethanol. Densities and viscosities of the binary mixture of DEC+ethanol at temperatures 293.15 K—343.15 K and atmospheric pressure were determined over the entire composition range. Densities of the binary mixture of DEC+ethanol were measured by using a vibrating U-shaped sample tube densimeter. Viscosities were determined by using Ubbelohde suspended-level viscometer. Densities are accurate to 1.0×10-5 g·cm-3, and viscosities are reproducible within ±0.003 mPa·s. From these data, excess molar volumes and deviations in viscosity were calculated. Positive excess molar volumes and negative deviations in viscosity for DEC+ethanol system are due to the strong specific interactions.All excess molar vo-（lumes） and deviations in viscosity fit to the Redlich-Kister polynomial equation.The fitting parameters were presented,and the average deviations and standard deviations were also calculated.The errors of correlation are very small.It proves that it is valuable for estimating densities and viscosities of the binary mixture by the correlated equation.

Influence of POSS modifier on NLO properties of the hybrid materials

The nonlinear optical （NLO） active chromophore was prepared bv a bridging agent, glyeidyl ether （ AGE）, to connect disperse orange 3 （ DO3 ） and （ γ-Methaerylpropyl）-silsesquioxane （MP-SSO）. A freeradical polymerization was performed to fabricate the methacrylate/Silica hybrid NLO films. Different amounts （ 5-25 wt% ） of （γ-methacrylpropyl） -polyhedral oligomeric silsesquioxanes （POSS） were added as the modifier to improve the degree of cross-linking, density and structure of the NLO matrix. As a result, the modified material properties including coating transmittance, glass transition temperature （ Tg ） , absoption spectra before and after poling, Marker stripes, etc. were presented. The hybrid film containing 15 wt% POSS exhibits the highest T, nonresonant second-order nonlinearity （d33 = 92 pro/V） and temporal stability among the others.

Measurement and Correlation of Solubility of Ethyl Nitrite in Mixed Solvent

An experimental apparatus was used to measure the solubility of ethyl nitrite in mixed solvents under the lower pressure and higher temperature. The solubilities of ethyl nitrite in mixed solvents of ethanol-water at 15℃-40℃ and ethanol-diethyl oxalate at 20℃--40℃ were determined. A Henry constant model has been improved, and the interaction parameters have been fitted from experimental data. The calculation results have been compared with experimental data； the results obtained are satisfactory.

Separation of Acearylenes from High-Temperature Coal Tar

High-temperature coal tar was extracted with petroleum ether （PE） under ultrasonic irradiation and the extracts were analyzed with gas chromatograph/mass spectrometer. The acearylene fractions including acenaphthylene, aceanthrylene and cyclopentapyrene were enriched together and named E, which was then transferred to a car- tridge in Isolera-One flash chromatography. Three groups of compounds were eluted out with ethyl acetate/PE mixed solvent （volume ratio 1：9） and named E1, E2 and E3 according to their main components. Acenaphthylene accounted for 78.2% in El, aceanthrylene 71.6% in E2 and cyclopentapyrene 75.9% in E3, respectively. The three groups of acearylenes were purified by Sephadex LH-20 column chromatography with ethanol/cyclohexane mixed solvent （vol- ume ratio 1：4）, and then confirmed with nuclear magnetic resonance spectrometer. This method indicates that flash chromatography has a good effect on separating the compounds with a similar structnre after extraction under ultrasonic irradiation.

三羟甲基丙烷酯类的制备研究进展

介绍了近期三羟甲基丙烷酯类的合成研究现状,主要包括三羟甲基丙烷的油酸酯、丙烯酸酯、辛酯、聚氨酯、有机酸酯和混合酸酯的合成方法。比较了一步合成法、二步合成法和酯交换合成法。对三羟甲基丙烷酯类按功能应用进行了归类整理。

Hybrid copolymerization of cyclic and vinyl monomers

In this work, we report the hybrid copolymerization of various cyclic monomers and vinyl monomers. Our studies demonstrate that 1-tert-butyl-4,4,4-tris-（dimethylamino）-2,2-bis[tris（dimethylamino） phophoranyliden-amino]-2A5,A5-catenadi（phosphazene） （t-BuP4） can catalyze the hybrid copolymerization of caprolactone （CL）, lactide （LA） or cyclic carbonate ester with acrylate or methyl acrylate. However, the polymerization of cyclosiloxane with vinyl monomers yields two corresponding homopolymers, and the polymerization of lactone with acrylonitrile （AN） produces only polyacrylonitrile. Clearly, the extent of matching of activity between a monomer and an active center determines whether or not there is hybrid copolymerization.

Lubricating properties of polyalkylene glycol and organic phosphate ester mixed aqueous solutions

Till now,water based lubricants,especially aqueous solutions,have not been employed in the elastohydrodynamic lubrication(EHL)due to their poor film forming capability or low wear resistance.In this paper,we proposed a method to develop water based lubricant:employing polyalkylene glycol solution as base stock to improve EHL film forming capability and using organic phosphate ester(DPZ)as anti-wear additive to improve wear resistance property.The lubricating properties of the mixed solutions,including load carrying capability,wear resistance property,friction reduction property,EHL film forming behavior,were investigated.The experimental results indicate that the mixed solution presents excellent lubricating properties,which make it a promising candidate in developing water based lubricants.