Enzymatic esterification of dihydroxystearic acid

Dihydroxystearic acid (DHSA) ester was synthesized enzymatically to overcome the problems associated with chemical processes. Immobilized enzyme, Lipozyme IM and Novozym 435, were employed as catalysts in the esterification reaction between DHSA and monohydric alcohol. Various factors that may affect the esterification reaction were studied, such as initial water content (a _w ), organic solvent, substrate concentration and the influence of alcohol chain length. It was found that the percent conversion was higher in organic solvents with log P (the logarithm of the partition coefficient of solvent in octanol/water system) from 2.0 to 4.0. The reaction was not affected by a _w from 0.09 to 0.96. Increasing the mole ratio of alcohol to acid above 2.0 did not increase the percent converions of ester. The ester was identified by Fourier transform infrared and ¹³C nuclear magnetic resonance spectroscopy.     

Performance of palm oil‐based dihydroxystearic acid as ionizable molecule in waterborne polyurethane dispersions

Waterborne polyurethane dispersions (WPUDs) containing a renewable palm oil‐based 9,10‐dihydroxystearic acid (DHSA) as an isocyanate‐reactive compound bearing ionizable carboxylic group to incorporate hydrophilic groups into the polymer chain have been successfully prepared. The WPUDs were prepared by using polyether and polyester polyols of 2000 molecular weight, DHSA and its traditional petroleum‐based counterpart 2,2‐bis(hydroxymethyl)‐propionic acid (DMPA), and an aliphatic diisocyanate (isophorone diisocyanate, IPDI). A comparison was made between the properties of WPUDs obtained using blends of DHSA and DMPA at different molar ratios and a reference WPUD based on DMPA. The particle size of polyester type WPUDs containing DHSA was reduced at a 0.5 to 0.5 molar ratio of DMPA to DHSA. A lower initial temperature was used in the preparation of NCO‐prepolymers with DHSA as compared to DMPA and this eased the preparation of WPUDs. The effect of molar ratio of DMPA to DHSA on the properties of films and coatings prepared with WPUDs was evaluated. The best properties were obtained with WPUDs prepared with a 0.5 to 0.5 molar ratio of DMPA to DHSA. The incorporation of renewable palm oil‐based DHSA into WPUDs improved water resistance (lower water uptake) and exhibited good combination of properties including hardness, adhesion strength, tensile strength, and elasticity. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43614.     

氨基磺酸催化合成柠檬酸三戊酯的工艺研究

以柠檬酸和正戊醇为原料,氨基磺酸为催化剂,合成了柠檬酸三戊酯,采用活性炭脱色,通过单因素和正交实验考察了各反应因素对产品收率的影响。当柠檬酸与正戊醇摩尔比为1∶5,氨基磺酸用量为柠檬酸质量1%,反应温度135~145℃,反应时间4 h时,柠檬酸三戊酯收率可达90%以上,经气相色谱分析纯度大于99.0%,产品经红外光谱进行定性分析。     

对叔丁基苯甲酸甲酯的合成研究

以对叔丁基苯甲酸、无水甲醇为原料,对甲苯磺酸为催化剂,合成对叔丁基苯甲酸甲酯,应用正交设计探讨了催化酯化的影响因素。结果表明,最佳工艺条件为:醇酸摩尔比为6∶1,催化剂用量占物质总质量的13.3%,反应时间为6 h,反应温度是65℃,环己烷用量占液体总体积的37.5%,酯化率达97%,产品结构经沸点、折光率和IR确证。     

硼酸三甲酯无“三废”合成工艺

以硼酸、甲醇为原料,用甲酰胺对产物进行萃取提纯,来合成硼酸三甲酯,并探索最佳工艺条件。结果利用气相色谱、色谱-质谱联用、红外光谱等分析表征手段,鉴定反应产物确实是硼酸三甲酯。并摸索最佳工艺条件为:n(硼酸)∶n(甲醇)=1∶3.5;回流时间为4h。此工艺实现了无"三废"的排放,有利于工业化的生产。     

叔丁醇常压羰基化合成三甲基乙酸

以甲酸为CO来源,常压下浓硫酸催化将叔丁醇羰基化得到三甲基乙酸。考察了醇酸配比、硫酸用量、反应温度、反应时间对三甲基乙酸收率的影响。结果表明,反应最优工艺条件为:n(叔丁醇)∶n(甲酸)∶n(浓硫酸)摩尔比=1∶1.5∶6.6,反应温度为30℃,反应时间为180 m in,三甲基乙酸的平均收率高达75.04%。     

对甲苯磺酸催化合成硬脂酸甲酯

以对甲苯磺酸催化硬脂酸和甲醇的酯化反应,合成了硬脂酸甲酯,研究结果表明,对甲苯磺酸对酯化反应具有较高的催化活性。考察了反应时间、酸醇摩尔比、催化剂用量对酯化反应的影响。当硬脂酸与甲醇的摩尔比为1∶3.5,对甲苯磺酸用量为硬脂酸质量的1.2%,于回流温度反应4 h,硬脂酸的转化率大于98.5%,产品酸值小于3.0 mg KOH/g。     

磺化硅胶催化合成2,4-滴丁酯

以2,4-二氯苯氧乙酸和正丁醇为原料,磺化硅胶为催化剂,催化合成除草剂2,4-二氯苯氧乙酸正丁酯(2,4-滴丁酯)。考察催化剂用量、原料配比及回流时间对反应的影响。结果表明,最佳反应条件为:催化剂用量为2,4-二氯苯氧乙酸质量的1.4%,n(正丁醇):n(2,4-二氯苯氧乙酸)=10:1,回流时间为1.0 h,2,4-二氯苯氧乙酸正丁酯的收率为98.7%。     

十二碳二元酸的重结晶精制工艺研究

采用有机溶剂重结晶法对十二碳二元酸粗品进行精制,讨论了溶剂种类、溶剂浓度对重结晶效果的影响;采用正交实验设计方法优选了重结晶工艺。结果表明:二元酸与乙酸粗品的固液比(质量体积比)为1.0:12.5,乙酸体积分数为100%,溶解温度为90℃,脱色剂的加入量为1%,脱色时间为60min时,用毛细气相色谱(GC)测定产品纯度为99.62%,用气质联用测定产品中所含的杂质为十三碳二元酸,用热分析仪(TG-DSC)测定产品熔点为130℃。     

The preparation of lauryl alcohol and 6-hydroxycaproic acid from petroselinic acid

Lauryl alcohol and 6-hydroxycaproic acid have been prepared from the ozonolysis products from both petroselinic acid and its ethyl ester by reduction with sodium borohydride. Satisfactory conversion of the ozonolysis product from ethyl petroselinate to lauryl alcohol and ethyl 6-hydroxycaproate was also achieved by catalytic hydrogenation, but the hydrogenation product was contaminated with small amounts of diethyl adipate and ethyl laurate as indicated by gas liquid chromatography. A procedure has been devised using ion exchange resin for the conversion of sodium 6-hydroxycaproate to 6-hydroxycaproic acid without the concomitant formation of lactones or polyesters. Presented at the AOCS Meeting, St. Louis, Mo., 1961. One of the laboratories of the Southern Utilization Research and Development Division, Agricultural Research Service, U.S.D.A. An erratum to this article is available at .     

氢溴酸-浓硫酸法合成1-溴代丁烷

以工业废氢溴酸与正丁醇为原料，在浓硫酸存在的条件下合成1-溴代丁烷。考察了反应条件对产率的影响，比较合适的反应条件为：正丁醇、氢溴酸和浓硫酸物质的量比为1：1．13：1．37，反应时间5h。分离产率达到93．8％。粗产品经气相色谱分析证明无副产物，产品经IR和折光率进行表征。     

硼酸三甲酯无“三废”合成工艺

以硼酸、甲醇为原料,用甲酰胺对产物进行萃取提纯,合成硼酸三甲酯,探索了最佳工艺条件。利用气相色谱、色谱-质谱联用、红外光谱等分析表征手段,鉴定反应产物,最佳工艺条件：n硼酸：n甲醇=1∶3.5;回流时间为4 h。此工艺无＂三废＂排放,有利于工业化生产。     

活性炭负载磷钨酸催化合成烷基多苷

用活性炭负载磷钨酸为催化剂,用二步法合成了十二烷基多苷(APG)。丁苷化反应的最优工艺条件是:磷钨酸负载量20%,用量为葡萄糖的5%,n(葡萄糖)∶n(丁醇)为5∶1,温度120℃,反应时间2 h。催化剂可以重复使用。在n(十二醇)∶n(葡萄糖)为2.5∶1时,可以用水萃取分离APG,得到的产品色浅且稳定。APG在水溶液中的临界胶束浓度为65.5 mg/L,表面张力为25.2 mN/m,泡沫力为160 mm,5 min后泡沫高度为158 mm。     

气相色谱法测定乙醛酸含量

建立了气相色谱法测定乙醛酸含量的新方法。乙醛酸水溶液在80～90℃下烘干2.5h,以酸性树脂为催化剂,80℃下甲酯化1h,采用15%的EGA色谱柱,该法测定的回归曲线为Y=3290X-4.5,相关系数R=0.9987。对用乙二醛硝酸氧化法自制样品进行测定的相对标准偏差为2.32%。标准品测定的回收率97.4%以上。     

对甲苯磺酸催化合成草酸二异戊酯的研究

以草酸和异戊醇为原料,对甲苯磺酸为催化剂,环己烷为带水剂,合成了新型柴油十六烷值改进剂草酸二异戊酯。考察了酸醇的物质的量比、反应时间、催化剂用量和带水剂用量等因素对酯收率的影响。结果表明:当反应温度为回流温度(85~100℃),n(草酸)∶n(异戊醇)=1∶3.5,催化剂用量为草酸质量的1.5%,带水剂用量为10mL/0.1 mol草酸,反应时间110~120 m in时,草酸二异戊酯的收率大于88%。与现有工艺相比,采用对甲苯磺酸为催化剂,环己烷为带水剂,具有反应温度低、反应时间短、带水剂的毒性较小、草酸二异戊酯的收率和纯度较高等优点。产物经红外光谱和气相色谱分析,证明确为草酸二异戊酯且纯度大于98%。     

Synthesis and properties of erucic acid triacylglycerols

The chemical synthesis of high-erucic acid triacylglycerols by a direct esterification approach was investigated in this study. A two-stage process was adopted in which reactants (without any catalyst) were heated at 160±5°C for 4 h, followed by heating at 250±10°C for 8 h. Purification of the esterified product was achieved by alkali refining, followed by alumina column chromatography. A greater than 85% yield of pure triacylglycerols was obtained, which contained ≈90% erucic acid, by using a 5% molar excess of erucic acid in the reaction. Oils containing erucic acid ranging from 45 to 91% were prepared by chemically interesterifying native high-erucic acid rapeseed (HEAR) oil and the synthetic high-erucic acid triacylglycerols. The melting point, cloud point, pour point, titer and viscosity of all oils exhibited positive correlations with the erucic acid content, whereas saponification value, iodine value and refractive index showed negative correlations. Randomization of native HEAR oil resulted in an increase in the melting point, cloud point and pour point.     

尼龙酸二丁酯的合成及其性能

以尼龙酸和丁醇为原料,浓硫酸为催化剂,环己烷为带水剂,合成出了3种尼龙酸二丁酯.以正丁醇和异丁醇为原料时反应速率最快,仲丁醇为原料时反应速率最慢.考察了反应的醇酸物质的量比对酯化反应的影响,n（醇）∶n（酸）=1.1∶1是最适宜的反应条件.测试了3种产品的性能,其中尼龙酸二正丁酯性能最佳,适合作为润滑油添加剂和耐寒型增塑剂.     

β-溴代乙基苯的合成

以氢溴酸代替溴化氢在浓硫酸存在下与 β 苯乙醇反应合成 β 溴代乙基苯。考察了用料比、反应温度对产物收率的影响 ,结果表明 :V(HBr)∶V(H2 SO4) =2 .2 0∶1.0 0 ,反应温度 12 0℃为最适宜条件 ,在该条件下 ,产物收率达 90 %。采用柱洗脱的方法分离提纯产物 ,产物纯度经气相色谱分析无杂质峰 ,产物结构经红外、核磁表征。采用液体氢溴酸代替气体溴化氢与苯乙醇反应合成 β 溴代乙基苯 ,原料均为液体 ,与工业上采用溴化氢与苯乙醇反应制备 β 溴代乙基苯相比 ,反应更易控制 ,工艺有所简化且安全性好 ,而采用柱洗脱的方法分离提纯产物 ,与工业上所采用的减压蒸馏方法相比分离更彻底。     

辛酰羟肟酸的制备方法以及防腐效能研究

通过以硫酸羟胺和正辛酸乙酯为原料,以羟基乙叉二膦酸为稳定剂,以乙醇钠乙醇溶液为催化剂,采用水和乙醇混合溶剂作为重结晶溶剂,制备得到辛酰羟肟酸的产品,同时采用高效液相色谱法对合成产品进行了纯度分析,利用微生物挑战性实验对合成产品进行防腐效能评价。结果表明,辛酰羟肟酸制备方法的较佳反应条件为:n(正辛酸乙酯)∶n(硫酸羟胺)=2.3∶1,n(羟基乙叉二膦酸)∶n(硫酸羟胺)=0.0014∶1,n(乙醇钠)∶n(硫酸羟胺)=2.5∶1,重结晶溶剂m(水)∶m(乙醇)=6∶1,在此条件下产品的收率可达94.4%,纯度可达99.8%,具有良好的防腐抑菌能力。     

硅钨杂多酸催化合成己二酸二丁酯的研究

以硅钨杂多酸为催化剂,以己二酸和正丁醇为原料合成了己二酸二丁酯。通过正交实验考察了影响酯化率的各种因素,确定了最佳反应条件为:己二酸用量0.05 mol时,正丁醇与己二酸的物质的量比为2.6,催化剂0.3 g,15 mL甲苯作带水剂,回流温度下反应30 m in,酯化率达99%以上。