催化环氧脂肪酸甲酯制备9(10)-羟基-10(9)-甲氧基脂肪酸甲酯

采用强酸性离子交换树脂(D002-H)催化环氧脂肪酸甲酯合成9(10)-羟基-10(9)-甲氧基脂肪酸甲酯。首先,以油酸甲酯在甲酸催化下制备中间体环氧脂肪酸甲酯,考察了反应时间、反应温度、甲酸和双氧水加入量对产物环氧值的影响。其次,以D002-H为催化剂,以环氧脂肪酸甲酯和甲醇为原料,通过开环醚化制备9(10)-羟基-10(9)-甲氧基脂肪酸甲酯,考察了反应时间、反应温度、醇油质量比和催化剂加入量对转化率的影响,并通过IR以及GC-MS对产物进行了表征。结果表明,反应时间12 h,反应温度65℃,催化剂加入量为环氧脂肪酸甲酯质量的6%,甲醇加入量为100%,在该条件下其转化率高达99%以上。     

固体酸催化制备环氧脂肪酸甲酯

氨基磺酸催化下,环氧脂肪酸甘油酯与甲醇进行酯交换反应制备环氧脂肪酸甲酯。考察了醇油摩尔比、催化剂用量、反应温度和反应时间对反应收率的影响。结果表明,醇油摩尔比为8∶1,催化剂用量为原料油总质量的2.5%,反应温度70℃,反应时间为2.0h,反应收率高达85.6%。采用气相色谱分析了产物的纯度,红外光谱表征了产物分子的官能团结构。     

环保增塑剂环氧脂肪酸甲酯催化合成工艺优化

以甲酸、过氧化氢和脂肪酸甲酯为原料,通过改变工艺条件合成环氧脂肪酸甲酯。考察过氧化氢浓度、甲酸用量、反应温度、反应时间、过氧化氢滴加时间以及过氧化氢用量对环氧化产品环氧值和碘值的影响。经单因素实验得到最佳工艺条件：甲酸用量为脂肪酸甲酯质量的6%,反应温度80 ℃,反应时间4 h,过氧化氢滴加时间30 min,50%过氧化氢用量为脂肪酸甲酯质量的32%。与传统工艺相比,新工艺条件降低了甲酸用量,提高了过氧化氢浓度与反应温度,缩短了反应时间。     

微通道中合成环氧脂肪酸甲酯

采用盐酸H2O2/HCOOH法,在微通道反应器内对不饱和脂肪酸甲酯进行环氧化反应。考察了双氧水用量、甲酸用量、反应温度及催化剂用量对反应的影响,得到最优的反应条件为:m(脂肪酸甲酯):m(甲酸):m(双氧水)=1:1.5:2,反应温度40℃,催化剂浓盐酸质量分数为3%(即浓盐酸质量占原料脂肪酸甲酯质量的百分数,下同),反应时间为110 s。在该条件下,产品环氧值为4.32%。     

管道反应器中合成环氧脂肪酸甲酯

研究在管道反应器中采用连续化工艺方法,以质量分数70%的双氧水进行环氧化反应合成环氧脂肪酸甲酯,其改善了传统的间歇工艺方法、釜式反应器中生产环氧脂肪酸甲酯产品所存在的诸多弊端。考察了双氧水用量、甲酸用量、反应时间、反应温度等工艺参数对产品环氧值的影响,确定了最佳工艺参数:m(脂肪酸甲酯)∶m(双氧水)∶m(甲酸)=1∶0.6∶0.05、反应时间15 min、反应温度90℃,在该条件下,所得产品的环氧值高达6.0%。     

铜铬催化剂催化脂肪酸甲酯加氢制备脂肪醇的研究

采用共沉淀法制备了铜铬催化剂并用于催化脂肪酸甲酯加氢反应制备脂肪醇。考察了催化剂种类和用量、反应温度、反应时间和反应压力等因素对反应结果的影响。确定了最佳实验条件,脂肪酸甲酯2.5g,m(铜铬催化剂)∶m(原料)=3∶200,反应温度230℃,氢气压力6MPa,反应时间6h。在该条件下,产物脂肪醇羟值186mgKOH/g,碘值22I2g/100g。另外,该催化剂回收重复利用5次后,脂肪醇的羟基值没有明显降低,具有较好的重复使用性能。     

利用废弃油脂制备环氧脂肪酸甲酯

以废弃油脂为原料,经预处理得到甘油酯,在碱催化作用下与甲醇发生酯交换反应得到脂肪酸甲酯,再与过氧化氢和甲酸的反应产物—过氧有机酸,发生环氧化反应,得到环氧脂肪酸甲酯增塑剂。实验表明最佳合成配比为:(1)甘油酯:甲醇:氢氧化钠=1:0.24:0.0004,(2)脂肪酸甲酯:过氧化氢(35%):甲酸=1:0.3:0.14,反应温度为65℃。     

β-(3,4-环氧环己基)乙基三甲氧基硅烷的合成

以4-乙烯基环氧环己烷(VCHO)、三甲氧基硅烷(TMSH)为原料,氯铂酸-三苯基膦为催化剂,采用硅氢加成法一步合成出β-(3,4-环氧环己基)乙基三甲氧基硅烷(A-186)。讨论了影响合成反应的主要因素,得到了最佳合成条件:反应时间4 h、反应温度为90℃、催化剂质量分数为10×10-6、VCHO与TMSH的量之比为1.2∶1,在此条件下目标产物收率为99%。     

膨润土催化脂肪酸甲酯合成二聚酸甲酯的工艺优化

利用响应面方法优化膨润土催化脂肪酸甲酯合成二聚酸甲酯的工艺参数,得到最优参数为:催化剂加入量10%,催化助剂LiCl 0.8%,反应温度220℃,反应时间6 h。在最优条件下,二聚体收率为64.8%,产物的理化特性分析显示各项性能指标优良。     

环保增塑剂环氧脂肪酸甲酯的合成

对环氧脂肪酸甲酯的现有生产工艺进行了改进研究,得出优化的工艺条件为:脂肪酸甲酯:甲酸:过氧化氢=1:0.1:0.6,对甲苯磺酸的加入量为1.5%,复合表面活性剂的加入量为0.2%,反应温度60℃,反应时间4 h。在此条件下产品的环氧值可达4.62%,产品结构经过红外表征得到确认。     

9(10)-Carboxyoctadecylamine and 9(10)-aminomethyloctadecanoic acid: Synthesis and polymerization to polyamides with lateral substitution

9(10)-Carboxyoctadecylamine (I) and 9(10)-aminomethyloctadecanoic acid (II) have been prepared from selectively hydroformylated oleonitrile and oleic acid, respectively. Polymerization of I gave a transparent hard, somewhat brittle, polyamide, whereas polymerization of II gave a soft, rubbery polymer that flowed slowly at room temperature. Copolymers of I with II had properties reflecting those of the component homopolymers, although II exercised a disproportionate softening effect. The same was generally true of copolymers of I or II with nylon-66 salt, caprolactam, and 9-aminononanoic acid. The copolymer of I with 25 mole % nylon-66 salt was transparent, was also elastic, and could be either drawn into fibers or made into a coherent film. The properties of the two amino acids and of their polymers agreed with those expected from simpler alkyl-substituted amino acids.     

Synthesis and Characterization of 9(10)-Bromo-9-octadecenoic Acids

9(10)-Bromo-cis-9-octadecenoic acid, m. p. 36.7° C, was prepared by dehydrobromination of threo-9,10-dibromo-stearic acid with bases and by polar addition of hydrogen bromide to stearolic acid. The trans isomer, m. p. 6°–8° C, was obtained from the corresponding erythro-dibromide. Both compounds were characterized by IR and NMR spectroscopies and a reaction scheme for their formation by dehydrobromination is suggested.     

Catalytic autoxidation of 9(10)-formylstearic acid

A procedure has been developed for the preparation of carboxystearic acid by catalytic autoxidation of hydroformylated oleic acid. This autoxidation is catalyzed effectively with Ca, Cu, Co, Fe, Mn and Ce naphthenates in either acetone or glacial acetic acid at 20 C. With the exception of Ca, all these catalysts produce from 2 to 10% keto- and hydroxystearic acids as by products. Yields of up to 95% 9(10)-carboxystearic acid are obtained by autoxidation for 24 hr with Ca naphthenate (0.5% Ca based on formylstearate). This autoxidation period was shortened to 7 hr by using a binary catalyst (0.5% Ca and 0.05% Mn), which affords a minimum of side products.     

合成10-硝基蒽酮的一种新方法

在醋酸、相转移催化剂聚乙二醇存在下,蒽与硝酸铈铵反应生成10-硝基蒽酮。聚乙二醇作为相转移催化剂,可以提高反应的选择性。最佳反应条件为:n蒽∶n硝酸铈铵为1∶1.05,反应温度50℃,反应时间1.4h。10-硝基蒽酮的产率达74.1%。     

Germinal hydroxymethyl compounds from 9(10)-formylstearic acid

9(10)-Formylstearic acid and methyl 9(10)-formylstearate reacted with formaldehyde in basic methanolic or aqueous medium to undergo the Tollens condensation, followed by a crossed Cannizzaro reaction to give 9,9(10,10)-bis(hydroxymethyl)-octadecanoic acid in essentially quantitative yield. This 2,2-disubstituted-1,3-propanediol has been esterified on the carboxyl group and the hydroxymethyl groups have been acetylated and acetalated with acetone to give a series of stable liquids boiling at ca. 200 C/0.005 mm and freezing at <−70 C.     

Conversion of methyl 9(10)-formylstearate to carboxymethylstearate

Methyl 9(10)-formylstearate was converted to methyl 9(10)-carboxymethylstearate. The reactions to prepare the intermediates methyl 9(10)-hydroxymethyl-, 9(10)-ace toxymethyl-, 9(10)-methylene-, and 9(10)-formylmethylstearate are described. Methyl 9(10)-hydroxy methylstearate readily loses methanol and forms a trimeric polymer. The acetate of the primary alcohol when pyrolyzed gives 59% yield of methyl 9(10)-methylenestearate. Hydroformylation of the methylene compound followed by permanganate oxidation gave methyl carboxymethylstearate. Evidence is presented to show that pyrolysis of the acetate ester and hydroformylation of the pyrolysis product produce, respectively, only the methylene and formylmethylstearates. Rates of esterification-transes terification of methyl 9(10)-carboxymethyl sterate show that the carboxymethyl group is 2–3 times as active as the carboxyl group in methyl 9(10)-carboxystearate and that the terminal carboxyl group is about 10 times more active towards esterification than the branched carboxymethyl group.     

20(S)-9-硝基-10-羟基喜树碱的制备研究

以 9-硝基喜树碱为原料 ,经过过氧化氢氧化成氮氧化物 ,再经光化重排反应制得 9-硝基 - 10羟基喜树碱 ,该方法合成收率略高于文献值 ,且成本价格远低于文献方法。     

Low temperature and pressure hydrogenation of methyl-9-(hydroxyimino)-octadecanoate and derivatives to their corresponding amino derivatives

A two step, one pot procedure, for the preparation of methyl-9-(or 12)-aminooctadecanoate and 1-hydroxy-9-(or 12)-aminooctadecane was developed. This procedure is based on the oximation followed by hydrogenation of methyl-9-oxooctadecanoate, 1-hydroxy-9-oxooctadecane and the C-12-oxo isomers. For the oximation of the keto compounds ( 1a – d ) two methods were used. In the first method NH₂OH.HCl as aminodonor and Et₃N as HCl-acceptor has been used. One of the major problems in this reaction sequence is the formation of Et₃N.HCl. Experimentally it became clear that in an one pot reaction without separation of the Et₃N.HCl, the catalytic reduction of the oximes ( 2a – d ) to their corresponding amines was inhibited. This problem could be solved by using free NH₂OH. In the second method free NH₂OH was used for the oximation. For the catalytic reduction of the oxime derivatives mild (room temperature and 40 psi), and therefore industrial interesting, hydrogenation conditions were used.     

10-(异丙基-2-醇)-9,10-二氢-9-氧杂-10-膦杂菲-10-氧化物的合成

以9,10-二氢-9-氧杂-10-膦杂菲-10-氧化物(DOPO)和丙酮为原料,合成10-(异丙基-2-醇)-9,10-二氢-9-氧杂-10-膦杂菲-10-氧化物。考察了原料摩尔比、反应温度和反应时间对产物收率的影响。结果表明,较优工艺条件为:n(丙酮)∶n(DOPO)=12∶1,反应温度为50℃,反应时间为30 min时,DOPO的转化率为99%,目标产物收率为90%。