氢化棕榈酸甲酯磺酸盐的制备

在氯仿体系中,以氢化棕榈酸甲酯为原料、氯磺酸为磺化剂,通过磺化、老化、中和、干燥后制得氢化棕榈酸甲酯磺酸盐。经单因素及正交实验优化得到最佳工艺条件:滴加温度40℃,氯仿与甲酯质量比2.0∶1.0,氯磺酸与甲酯物质的量比1.55∶1.0,磺化时间60 min,老化时间70 min。在最佳工艺条件下,制备的产品颜色呈淡黄色,氢化棕榈酸甲酯磺酸盐的含量为64.36%。

含有棕榈酸甲酯磺酸盐和直链烷基苯磺酸的低密度无磷洗衣粉的性能

本文对含有棕榈酸甲酯磺酸盐（C16MES）和直链烷基苯磺酸（LABsA）两种阴离子表面活性剂的无磷洗衣粉配方进行了小试和中试研究，旨在增加配方中C16MES的含量，降低洗衣粉的密度，且不影响洗涤性和其他特性。小试结果表明，C16MES／LABSA比例为50：50、pH为7～8时，洗衣粉在50℃和85％相对湿度下老化一周，仍具有良好的去污力稳定性。然后，pH保持不变，改变C16MES／LABSA比例，在5kg／h的喷雾干燥器上进行了试验。对不同洗衣粉料浆浓度经喷雾干燥得到的洗衣粉的性能（去污力、泡沫能力和润湿力）进行了评价，确定了C16MES／LABSA比例为40：60的优化配方。环境测试表明，优化配方获得的喷雾干燥洗衣粉易于生物降解、生物毒性低。

氯磺酸制备脂肪酸甲酯磺酸盐的研究

介绍了一种以氯磺酸为磺化剂，在无溶剂下制备棕榈酸甲酯磺酸盐的方法。其方法是：以棕榈酸甲酯为原料，氯磺酸为磺化剂，经无溶剂磺化反应、老化反应，中和、干燥后处理制备得到棕榈酸甲酯磺酸盐。经正交优化试验和重复性试验得到最佳的制备条件为：物质的量之比1：1．2、磺化时间60min、老化时间35min、氮气流量42L／h，得到的活性物含量为62％～65％。

多西他赛注射液在注射液用局部覆聚四氟乙烯膜溴化丁基橡胶塞中棕榈酸及硬脂酸迁移量的测定

目的:建立多西他赛注射液与注射液用局部覆聚四氟乙烯膜溴化丁基橡胶塞相容性研究中棕榈酸及硬脂酸迁移量的气相色谱分析方法。方法:采用DB-FFAP色谱柱,采用程序升温:170℃保持2 min,10℃/min速率升高至240℃,保持11 min,流速:2 ml/min;进样口温度220℃;检测器为FID,温度260℃。结果:棕榈酸甲酯及硬脂酸甲酯分别在0.1959~195.86μg/ml(r=0.9999)、0.1918~191.85μg/ml(r=0.9998)浓度范围内呈良好的线性关系;棕榈酸甲酯及硬脂酸甲酯加样回收率分别为96.66%(RSD为0.42%)和96.53%(RSD为0.45%);棕榈酸甲酯、硬脂酸甲酯的检测限分别为58和98 ng/ml。3批样品5个时间点硬脂酸的迁移量为15.21~26.35μg/ml,棕榈酸的迁移量为12.82~16.26μg/ml。结论:经方法学验证,所建立的方法准确可靠,可用于测定多西他赛注射液在注射液用局部覆聚四氟乙烯膜溴化丁基橡胶塞中棕榈酸和硬脂酸迁移量的测定。

负载的Ni催化剂上植物油脂加氢脱氧制备第二代生物柴油

在半连续反应器中,以棕榈酸甲酯为植物油脂模型化合物,进行了加氢脱氧制取高品质生物柴油燃料的研究。采用浸渍法制备了HY、SiO2、γ-Al2O3及SAPO-11四种载体负载的Ni催化剂,采用XRD、NH3-TPD、H2-TPR、BET、SEM等技术进行催化剂表征。结果表明,Ni/SAPO-11催化剂由于SAPO-11表面呈现的弱酸和中强酸性质,在保持较高的加氢脱氧反应性的同时,抑制了裂解反应的发生,具有较好的催化性能。进一步对SAPO-11上不同的Ni负载量、反应温度、反应压力等进行了研究,发现当Ni负载量为7%,反应温度为220℃,压力为2MPa时,催化剂具有较高的催化性能,棕榈酸甲酯的转化率达到了99.8%,C9～16烷烃的总选择性为92.71%。

丙烯酸-2,4,6-三硝基苯乙酯的合成及热分解

以TNT、甲醛为原料,在弱碱性条件下反应合成得到2,4,6-三硝基苯乙醇(PicCH2CH2OH);PicCH2CH2OH在浓硫酸催化下和丙烯酸在甲苯中回流反应24h,合成得到丙烯酸-2,4,6-三硝基苯乙酯,产率为62%。采用紫外可见光谱(UV-Vis)、核磁共振氢谱(1HNMR)、红外光谱(FTIR)、质谱(MS)以及元素分析等对产物结构进行了表征。利用热重分析(TG)对产物热稳定性进行了研究,采用Kissinger方法和Ozawa方法计算其热分解活化能Ea分别为99.78,102.96kJ·mol-1。

不对称氢化、氢转移反应制备(R)-邻氯扁桃酸甲酯:(S)-氯吡格雷关键中间体的不对称合成

目的用不对称氢化、氢转移方法制备合成(S)-氯吡格雷的关键中间体——(R)-邻氯扁桃酸甲酯。方法以α-邻氯扁桃酮酸甲酯为起始原料,分别用不对称氢化和氢转移方法制备(R)-邻氯扁桃酸甲酯。结果与结论使用不对称氢化方法制备(R)-邻氯扁桃酸甲酯,对映选择性为64.8%,用氢转移方法,优化催化条件后目标产物的ee值高达92.6%,从而为(S)-氯吡格雷的不对称合成奠定了基础。

南美蟛蜞菊根系分泌物中2种化学物质的化感潜力

采用水培法收集南美蟛蜞菊（Wedelia trilobata）根系分泌物,GC-MS分析鉴定得出其根系分泌物中存在邻苯二甲酸二异丁酯、硬脂酸甲酯、棕榈酸甲酯和邻苯二甲酸二异辛酯。采用不同质量浓度硬脂酸甲酯和棕榈酸甲酯对玉米、黄豆、黄瓜、水稻4种农作物种子进行处理,以探究硬脂酸甲酯和棕榈酸甲酯对4种农作物种子萌发和幼苗生长的影响,进而分析这2种物质的化感潜力。结果表明,质量浓度为0-2 000mg/L时,这2种物质均呈现出不同程度的化感作用,均可在一定程度上抑制玉米、黄豆、黄瓜、水稻的发芽势、发芽率、发芽指数和活力指数。其中,硬脂酸甲酯对黄豆的胚根、胚芽的生长无显著的影响,但对玉米、黄瓜、水稻的胚根、胚芽的生长均有显著的抑制作用;棕榈酸甲酯对这4种作物胚根、胚芽的生长均有显著的抑制作用。

Composition Analysis on Intermuscular Fatty Acid of Qinghai Datong Yak

[ Objective] The study aimed to provide a theoretical basis for rational utilization of Datong yak resource. [ Method] By qualitative and quantitative determination with gas chromatograph, the composition and content of intermuscular fatty acid of Datong yak were compared with those of Datong yellow cattle. [ Result] Comparing with Datong yellow cattle, Datong yak had lower saturated fatty acid （SFA） content and higher polyunsaturated fatty acid （PUFA） content at extremely significant level （P 〈0.01 ）, while the difference of monounsaturated fatty acid （MUFA） contents between them was not significant （P〉0.05）. The PUFA/SFA and n-6/n-3 PUFA of Datong yak were in accordance with the recommended proportions. [ Conclusion] The intermuscular fatty acid composition of Datong yak is superior to that of local yellow cattle, which indicates that Datong yak meat has high nutritive value and wide development prospect.

First Asymmetric Synthesis of (-)Methyl 2, 2-dimethyl-3-hydroxychromanyl-6-formate

Aim To synthesize naturally occurring (-) methyl2,2-dimethyl-3-hydroxychromanyl-6-formate. Methods Sharpless' asymmetric dihydroxylation wasemployed to construct the 3-hydroxychroman. Results First asymmetric synthesis of (-) methyl 2,2-dimethyl-3-hydroxychromanyl-6-formate (1) was accomplished starting from methyl 4-hydroxy-benzoate(2), and the absolute configuration was established. Conclusion A useful method for constructingchiral 3-hydroxychroman by employing Sharpless' asymmetric dihydroxylation is achieved.

In_2O_3-modified Cu/SiO_2 as an active and stable catalyst for the hydrogenation of methyl acetate to ethanol

A series of indium oxide‐modified Cu/SiO2catalysts were synthesized and used to produce ethanol via methyl acetate hydrogenation.In‐Cu/SiO2catalyst containing1.0wt%In2O3exhibited the best catalytic activity and stability.The physicochemical properties of the synthesized catalysts were investigated using several characterization methods and the results showed that introducing suitable indium to Cu/SiO2increased the copper dispersion,diminished the copper crystallite size,and enriched the surface Cu+concentration.Furthermore,the Cu/SiO2catalyst gradually deactivated during the stability test,which was mainly attributed to copper sintering and the valence change in surface copper species.In contrast,indium addition can inhibit the thermal transmigration and accumulation of copper nanoparticles to stabilize the catalyst.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.

Epoxidation of Unsaturated Fatty Acid Methyl Esters in the Presence of SO_3H-functional Brφnsted Acidic Ionic Liquid as Catalyst

The epoxidation of unsaturated fatty acid methyl esters(FAMEs)by peroxyacetic acid generated in situ from hydrogen peroxide and acetic acid was studied in the presence of SO3H-functional Brnsted acidic ionic liquid (IL)[C3SO3HMIM][HSO4]as catalyst.The effects of hydrogen peroxide/ethylenic unsaturation ratio,acetic acid concentration,IL concentration,recycling of the IL catalyst,and temperature on the conversion to oxirane were studied.The kinetics and thermodynamics of unsaturated FAMEs epoxidation and the kinetics of oxirane cleavage of the epoxidized FAMEs by acetic acid were also studied.The conversion of ethylenic unsaturation group to oxirane, the reaction rate of the conversion to oxirane,and the rate of hydrolysis(oxirane cleavage)were higher by using the IL catalyst.

Green and efficient epoxidation of methyl oleate over hierarchical TS-1

The epoxidation of methyl oleate(MO)was conducted in the presence of aqueous H2O2 as the oxidant and hierarchical TS-1(HTS-1)as the catalyst;the catalyst was synthesized using polyquaternium-6 as the mesopore template.The effects of various parameters,i.e.,H2O2/C=C molar ratio,oxidant concentration,amount of the catalyst,reaction temperature,and time,were systematically studied.Furthermore,response surface methodology(RSM)was used to optimize the conditions to maximize the yield of epoxy MO and to evaluate the significance and interplay of the factors affecting the epoxy MO production.The H2O2/C=C molar ratio and catalyst amount were the determining factors for MO epoxidation,wherein the maximum yield of epoxy MO reached 94.9%over HTS-1 under the optimal conditions.

Solid base catalysts derived from Ca-M-Al(M = Mg, La, Ce, Y) layered double hydroxides for dimethyl carbonate synthesis by transesterification of methanol with propylene carbonate

Composite solid base catalysts derived from Ca‐M‐Al(M=Mg,La,Ce,Y)layered double hydroxides(LDH)were synthesized,characterized and applied to the transesterification of methanol with propylene carbonate.X‐ray diffraction analyses of the catalysts show that all of the catalysts were in the form of composite oxides.Compared with the Ca‐Al LDH catalyst,the specific surface areas and pore volumes of the catalysts were increased with the introduction of Mg,La or Ce.The catalytic performance of these catalysts increases in the order of Ca‐Y‐Al<Ca‐Al<Ca‐Ce‐Al<Ca‐La‐Al<Ca‐Mg‐Al,which is consistent with the total surface basic amounts of these materials and the formation of especially strong basic sites following modification with Mg and La.The Ca‐Mg‐Al catalyst shows the highest(Ca+Mg):Al atomic ratio,indicating that it likely contains more unsaturated O2?ions,providing it with the highest concentration of very strong basic sites.The recyclability of these catalysts is improved following the addition of Mg,La,Ce or Y,with the Ca‐Mg‐Al maintaining a high level of activity after ten recycling trials.X‐ray diffraction analyses of fresh and used Ca‐Mg‐Al demonstrate that this catalyst is exceptionally stable,which could be of value in practical applications related to heterogeneous catalysis.

Highly efficient Rh(Ⅰ)/tris-H_8-binaphthyl monophosphite catalysts for hydroformylation of dicyclopentadiene to dialdehydes

Novel catalytic systems for the Rh‐catalyzed hydroformylation of dicyclopentadiene have been developed using tris‐H8‐binaphthyl monophosphite as ligands containing different ester substituents at the 2’‐binaphthyl position(OCOMe,OCOPh,OCOAdamantyl and OCOPhCl).The catalysts exhibited high activity(S/C=4000,TON=3286)with good to excellent selectivity towards dialdehydes.Remarkably,the Rh(I)complex bearing the ligands with chlorophenyl ester substituents led to 99.9%conversion and 98.7%selectivity for dialdehydes under relatively mild conditions(6 MPa,120°C).

Closed Loop Recycling of Chlorine for Sustainable Development of Polyurethane Industry

Increasing demand is fueling the booming polyurethane industry worldwide. An impeding issue for poly- urethane industry is how to handle the large quantity of hydrogen chloride byproduct generated from the synthesis of intermediates, i.e., isocyanates. In the meantime, the traditional chloro-alkaline process sufibrs both from the high en- ergy intensity of electrolysis method and the disparity in the chlorine and caustic soda market. To solve these prob- lems, the state-of-the-art chlorine recycling technologies are reviewed and compared. Approaches for cost-effective utilization of chlorine in polyurethane industry are investigated. Chinese academies and enterprises＇ on-going effort on the development of a novel hydrogen chloride oxidation process for the synthesis of chlorine is presented. With this process, the closed loop recycling of chlorine can be realized. Tremendous economic, environmental and social bene- fits can be expected. A wide adoption of this technology will significantly advance the sustainable development of polyurethane industry.

Alumina Supported Vanadium Oxide Catalysts for Residue Hydrotreating

In order to evaluate the role of vanadium in the hydrogenation (HYD) reaction, a series of alumina supported vanadium catalysts were prepared and characterized by SEM, XRD, Raman spectrometry, 51V NMR, XPS, as well as TPR analyses. The catalytic performance of vanadium in HYD of model molecules (naphthalene) and real feedstock (Kuwait atmospheric residue) was studied after sulfidation of the catalysts. It can be concluded that the HYD capabilities of V/Al2O3 catalysts are lower than that of conventional NiMo/Al2O3 catalyst (RefNiMo). The V/Al2O3 catalysts can only facilitate hydrogenation of the first ring of naphthalene, but have little effect on the further hydrogenation of tetralin. Owing to the different forms of metals and sulfur compounds in residue, the weak HYD activity of V/Al2O3 catalysts is able to facilitate the HDM reaction of the residue, albeit with a slight effect on HDS activity.

2-(4-氨基苯基)-6-叔丁基-1H-吡唑[1,5-b][1,2,4]三唑的合成工艺改进

介绍了在碱催化条件下以对硝基苯甲腈为起始原料,醇解生成对硝基苯甲亚胺酸甲酯,继而氨化、肟化一锅反应,并采用氢化还原的方法最终合成2-(4-氨基苯基)-6-叔丁基-1H-吡唑[1,5-b][1,2,4]三唑,总收率达68.6%。