Production,chemistry, and commercial applications of various chemicals from castor oil

The presence of a hydroxyl group, in addition to an olefinic linkage, in the predominating fatty acid of castor oil gives this vegetable oil many unique and interesting properties. Castor oil consists largely of glycerides of ricinoleic acid or 12-hydroxy octadecenoic acid. The chemical reactions of castor oil, undecylenic acid, 12-hydroxylstearic acid, sebacic acid, and nylon 11, depict the uniqueness of this agricultural oil. By dehydration, castor oil is converted to a conjugated acid oil similar to tung or oiticica oil. The catalytic dehydration results in the formation of a new double bond in the fatty acid chain. The dehydrated castor oil imparts good flexibility, rapid dry, excellent color retention, and water resistance to protective coatings. The pyrolysis of castor oil cleaves the molecule to produce undecylenic acid and heptaldehyde. The pyrolysis of the methyl ester at 450–550 C results in the formation of methyl 10-undecylenate. Hydrolysis of the methyl ester gives 10-undecylenic acid. Hydrogen bromide is added to form 11-bromo undecanoic, which is ammoniated and condensed to form a nylon polymer. When castor oil is added slowly to an 80% caustic solution, the sodium ricinoleate formed splits to form sodium sebacate and capryl alcohol. Sebacic acid is condensed with hexamethylene diamine to form nylon 6,10. The commercial application of castor oil derivatives in urethanes, starch gel modifiers, medium chain triglycerides, and thixotropic additives is reviewed briefly. One of 12 papers presented in the symposium “Novel Uses of Agricultural Oils” at the AOCS Spring Meeting, New Orleans, April 1973.     

有机膦酸钡负载的新型固体超强碱催化合成γ-十一内酯的研究

对以十一烯酸为原料,通过转位、内酯化合成γ-十一内酯的工艺进行了改进。采用多乙烯多氨基乙基膦酸钡载体,载体用5%KOH处理后,用苯基钾处理得固体超强碱,用于γ-十一内酯的合成。对催化剂用量、反应物与溶剂的量比、反应温度的影响进行了研究。结果表明,最佳工艺条件为:n(十一烯酸)∶n(二氧六环)=1.0∶1.0,催化剂用量为十一烯酸质量的3%,反应近终点时在(60±2℃)再保温反应2 h,γ-十一内酯收率可达78%以上。该催化剂具有较高的催化活性,易于再生,可重复使用5次以上,是一种环境友好的催化剂。     

Structural Analysis of Partial and Total Esters of Glycerol Undecenoate and Diglycerol Undecenoate

The direct esterification reaction between glycerol and undecylenic acid or between diglycerol and undecylenic acid generates all the possible types of glycerol or diglycerol esters. Purification by silica gel chromatography resulted in the isolation of each of these types of ester in a pure form. The molecular structures of the compounds isolated were characterized and identified by mass spectrometry, ¹H NMR, ¹³C NMR and DEPT‐135. We then studied the composition of esters of undecylenic acid formed with glycerol or diglycerol as a function of their reaction conditions, which constitute a highly complex system. We purified undecylenic acid esters from each polyol family to allow the structural identification of each ester of glycerol and each ester of diglycerol with undecylenic acid. We found that the polarity of these non‐ionic amphiphilic esters directly affected their affinity for organic and inorganic solvents and that these esters behaved very differently from anionic amphiphilic molecules, such as undecylenic acid.     

庚醛催化加氢制庚醇新型催化剂的性能研究

研制了一种新的庚醛催化加氢催化剂,并用于进行庚醛催化加氢合成庚醇试验,以活性炭为载体时,最佳反应条件为:反应温度为250℃,压力2.0MPa,空速0.5h-1,H2与C7H14O的体积比为1000。通过100mL单管放大试验及500h的稳定运转,庚醛转化率达90%以上,庚醇的选择性达到91%。     

硫酸氢钠催化合成庚醛二乙缩醛研究

研究了以硫酸氢钠为催化剂 ,庚醛和乙醇为原料来制备庚醛二乙缩醛。实验结果表明 :最佳工艺条件为反应温度 6 8℃ ,庚醛与乙醇的摩尔比为 1∶8,催化剂用量为 2 0 % ,反应时间为 15h ,庚醛二乙缩醛的收率达 85 %以上     

Grafting of long‐chain unsaturated carboxylic acids onto acrylonitrile–butadiene–styrene terpolymer

The graft copolymerization of undecylenic acid, oleic acid, and crotonic acid onto acrylonitrile–butadiene–styrene terpolymer (ABS) was initiated by benzoyl peroxide (BPO) in 1,2‐dichloroethane solution. The infrared spectra confirmed that undecylenic acid, oleic acid, and crotonic acid were successfully grafted onto the ABS backbone. The grafting occurred at the butadiene region of the ABS. The grafting degree increased with increasing monomer concentration, but it decreased after monomer concentration, reaching 0.30 mol/L in undecylenic acid and oleic acid systems. The grafting degree increased rapidly with increasing initiator concentration, but slowed down at about 0.012 mol/L of initiator concentration. The grafting degree decreased considerably with increasing ABS concentration; however, the total amount of grafted monomer increased. Increasing reaction time and temperature led to an increase in grafting degree. The chain length of the monomer has a great influence on grafting. The grafting degree decreases with increasing the chain length due to a steric hindrance and monomer cage effect, which is in agreement with activation energy calculation. The overall activation energy of crotonic acid, undecylenic acid, and oleic acid systems are 118, 122, and 134 kJ/mol, respectively. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1934–1939, 2002     

蓖麻油酸甲酯合成和高温裂解反应条件优化

先用蓖麻油和甲醇酯交换合成蓖麻油酸甲酯,再对蓖麻油酸甲酯进行高温裂解制备十一碳烯酸,探讨各种因素对蓖麻油酸甲酯合成和裂解的影响,得到较为适宜的反应条件。合成蓖麻油酸甲酯适宜的条件为:系统真空度0.095 MPa,反应时间4 h,甲醇钠催化剂质量为蓖麻油质量的3.00%,反应温度35 ℃,醇油物质的量比18∶1,该条件下,蓖麻油酸甲酯收率为86.4%;550 ℃裂解蓖麻油酸甲酯为最佳温度,十一碳烯酸收率为44.15%。     

Fe_3O_4/P(St/ACPA)磁性高分子纳米球的制备与磁性能研究

采用化学共沉淀方法制备Fe_3O_4磁性粒子,并使用油酸和十一烯酸对其进行表面改性,然后采用一步细乳液聚合法制备含有羧基官能团的Fe_3O_4/P(St/ACPA)磁性高分子纳米球,对磁流体和磁性高分子纳米球进行性能表征。结果表明,改性的Fe_3O_4磁流体分散性好,粒径均一,在室温下呈超顺磁性,磁含量为68.5%(w),饱和磁化强度为51.3emu/g;Fe_3O_4/P(St/ACPA)磁性高分子纳米球成球性好,粒径为70 nm,磁含量为39%(w),饱和磁化强度为27.9 emu/g。     

KF/Al_2O_3催化下茉莉醛的合成

以苯甲醛和正庚醛为原料,氟化钾／氧化铝作催化剂合成了茉莉醛。通过正交试验得到了影响反应的５种主要因素的大小顺序：苯甲醛＞催化剂＞反应温度＞正庚醛的滴加速度＞反应时间;最佳工艺条件：苯甲醛∶正庚醛∶催化剂为１２∶１０∶０．０６（摩尔比）,正庚醛的滴加速度为６ｈ,反应温度６０℃,反应时间２ｈ。平均摩尔收率可达９２１％。     

庚醛低压催化加氢催化剂的制备

研究了一种新的庚醛低压催化加氢催化剂的制备方法 ,同时进行了催化剂活性检验。并通过实验证明 ,在催化剂用量为 2 % (wt)时 ,庚醛转化率达 92 %以上 ,产率为 90 %左右 ,催化剂的选择性为 80 % ,且该催化剂可回收利用。     

Thermally promoted addition of undecylenic acid on thermally hydrocarbonized porous silicon optical reflectors

Thermally promoted addition of undecylenic acid is studied as a method for modifying porous silicon optical reflectors that have been pre-treated with thermal hydrocarbonization. Successful derivatization of undecylenic acid is demonstrated and confirmed with Fourier transform infrared and X-ray photoelectron spectroscopies. The results indicate that the hydrocarbonization pre-treatment considerably improves stability against oxidation and chemical dissolution in basic environments. The two-step treatment also does not cause an appreciable change on sample reflectance spectra, which enables the use of the functionalized structures in optical sensing applications.     

Hydrogenation of heptaldehyde to heptyl alcohol with nickel catalysts

Hydrogenation of heptaldehyde to heptyl alcohol was studied with W2 Raney nickel catalyst, prepared in the laboratory, commercial Raney nickel catalyst and Rufert nickel catalyst by varying temperature, catalyst concentration, hydrogen pressure and reaction time. The products were analyzed by gas-liquid chromatography on SE-30 column. The optimum conditions found for quantitative conversion (99.6%) of heptaldehyde to heptyl alcohol were: temperature, 100°C, W2 Raney nickel catalyst concentration, 2% based on heptaldehyde (w/w), hydrogen pressure, 145 psig and reaction time, 1 h. IICT Communication No. 3085.     

蓖麻油催化裂解制十一烯酸研究

采用减压催化的方式 ,对蓖麻油直接裂解制备十一烯酸的方法进行了研究。结果表明 :使用N型催化剂 ,在温度 40 0°C,压力 2 3.3k Pa,物料流量 70 0 g/ h的条件下 ,十一烯酸收率达 2 4 .6% ,庚醛 1 8.3%。该法降低了解裂温度 ,简化了工艺 ,节省了原料 ,且催化剂可反复再生使用。     

十一烯酸及其衍生物的应用

介绍了十一烯酸及其衍生物在医药中间体、香料、表面活性剂及高分子材料中的应用。     

蓖麻油裂解物中十一碳烯酸和庚醛的气相色谱分析

采用气相色谱法对蓖麻油热裂解物中的庚醛（ Ⅰ） 、十一碳烯酸（ Ⅱ） 进行分析。结果表明,本研究提供的方法快捷、简便,结果准确。     

十一烯酸基乳化剂制备及应用研究

利用十二醇(DA)与十一烯酸(UA)/马来酸酐(MAH)共聚物通过酯化反应制备了UMA-DA聚合物，并将聚合物作为乳化剂用于UA与甲基丙烯酸甲酯(MMA)的乳液聚合中。FT-IR分析表明：DA中的羟基与UMA共聚物中的酸酐发生了反应。¹H NMR结果表明：在δ 3.2~3.4处有明显的—O—CH₂—质子信号，表明成功制备了UMA-DA共聚物。通过表面张力法对UMA皂化物的临界胶束浓度(CMC)值进行了测定，UMA-DA的CMC值为9.6 g/L，此时表面张力γ_CMC为23.04 mN/m, UMA-DA的γ_CMC值要远低于纯水(71.97 mN/m)。在乳液聚合时，随UMA-DA用量的不断增加，乳液粒径和粒径分散系数(PDI)增大，凝胶率逐渐减小。当自制乳化剂UMA-DA用量为总单体的10%且UA与MMA质量比10 : 90时乳液较为稳定，总单体转化率为98.1%。     

Epoxides of unsaturated fatty acids as anti-rust additives in water-based cutting fluids

Epoxides from a variety of unsaturated fatty acids were prepared, and corrosion tests for these products as water-based cutting fluid additives were performed. The triethanolamine salt of an epoxide of undecylenic acid showed very effective rust-inhibiting properties in a water-based cutting fluid.     

生物素中间体:四氢-7-乙氧羰基-3,3-五亚甲基-5-硫代-1-戊基-3H,5H-咪唑并[1,5c]噻唑的合成

以正庚醛为起始原料 ,α 溴化后与环己酮、氨、硫氢化钠反应合成 2 ,2 五亚甲基 5 戊基 3 噻唑啉 ,再用三氟化硼催化后 ,与异硫氰基乙酸乙酯的锂衍生物反应合成生物素中间体四氢 7 乙氧羰基 3 ,3 五亚甲基 5 硫代 1 戊基 3H ,5H 咪唑并 [1,5c]噻唑 ,收率达 17 1% ,通过 3步反应建立了生物素的立体化学骨架     

Oxidation of unsaturated fatty acids with ruthenium and osmium tetroxide

The oxidation of the alkali metal salts of oleic and undecylenic acid with ruthenium and osmium tetroxides is reported. The oxidants are used in catalytic amounts in conjunction with an excess of the in-expensive cooxidant sodium hypochlorite. Ruthenium tetroxide cleaves the carbon-carbon double bond of potassium oleate, to give pelargonic and gives sebacic acid. With osmium tetroxide, hydroxylation of the double bond of potassium oleate gives a 95% yield oferythro-9,10-dihydroxystearic acid. The osmium tetroxide oxidation of sodium undecylenate results in the formation of 10,11-dihydroxyundecanoic acid and the cleavage product sebacic acid in varying yields.     

Preparation and surface- active properties of polyoxyethylene-glycol (600) monoesters of fatty acids

Polyoxyethyleneglycol (PEG-600) monoesters of undecylenic, lauric, myristic, palmitic, stearic, oleic, ricinoleic and 12-hydroxystearic acids were prepared in 80-85% yield by reacting PEG with boric acid, esterifying the resultant borate with fatty acid, and selectively hydrolyzing the borate ester; their surface active properties were evaluated. Increase in acyl chain length increased the surface tension. The presence of a double bond or hydroxyl group in C₁₈ series improved the wetting and emulsifying proper-ties. Unsaturation in the fatty acid chain reduced the foaming power.