Reaction rates of simultaneous dehydration and hydrogenation of castor oil

The reaction rates of simultaneous dehydration and hydrogenation of castor oil to make tallow-like hard fat were calculated through a simplified procedure which makes use of a new variable derived from the incremental change in hydrodxyl value and iodine value.     

蓖麻油及其衍生物在涂料中的应用

蓖麻油作为一种可再生资源，具有较高工业经济价值。本结合蓖麻油的组成结构与性质，概述了蓖麻油和脱水蓖麻油、氧化蓖麻油等相关衍生物在涂料中的应用现状及其应用前景。     

A process for solid fat from castor oil by simultaneous hydrogénation and dehydration

A single step process has been developed on a pilot plant scale (15 kg/batch) for simultaneous hydrogenation and dehydration of castor oil using nickel catalyst and attapulgite to yield solid fats having a hydroxyl value of 7–33 and an iodine value of 41–56. The polymer and keto fatty acid contents in the products were up to 2% and 3.2%, respectively. The product can be used in the manufacture of soap as the hard fat component and in textile sizing.     

脱水蓖麻油制备聚酰胺/环氧树脂体系的固化行为及固化工艺

采用脱水蓖麻油制得聚酰胺固化剂,并用差示扫描量热法(DSC)研究了该固化剂与环氧树脂体系的固化动力学模型。根据Kissinger方法和Crane方法得到该固化体系的动力学参数:表观活化能Ea为45.81kJ/mol,反应级数n为0.88,频率因子A为3.10×105s-1。由外推法得到体系最佳固化工艺为:起始固化温度为60℃,恒温固化温度为90℃,以及后处理温度为110℃。体系固化前后的红外光谱(FT-IR)进一步验证了该固化工艺的合理性。     

The kinetics of the esterification reaction between castor oil and oleic acid

In this study, esterification of castor oil with oleic acid was investigated in view of the reaction kinetics under various conditions. Potassium hydroxide,p-toluenesulfonic acid and tin chloride (SnCl₂2H₂O) were used as catalysts. Reaction was carried out at 200°C, 225°C and 250° C by using equivalent proportions of the reactants. For tin chloride, experimental data fitted the second-order rate equation, while for the other catalysts the obtained data fitted the third-order rate equation.     

蓖麻油硫酸氢钾催化脱水研究

考察了若干种酸性催化剂对蓖麻油脱水的影响。重点以硫酸氢钾为催化剂,在0.083 MPa真空度下对蓖麻油催化脱水进行了研究。利用正交实验考察了反应温度、反应时间、催化剂用量对脱水反应的影响。得出的最佳工艺条件为:反应温度250℃、反应时间70 m in、催化剂用量1.0%。在该工艺条件下制得的脱水蓖麻油平均碘值可达136,且粘度较小色泽较浅。     

蓖麻油改性环氧聚氨酯防腐蚀涂料的研制

介绍了一种蓖麻油改性的环氧聚氨酯防腐蚀涂料.以蓖麻油改性异氰酸酯预聚物和环氧树脂为基料,以价格较为低廉的滑石粉、钛白粉、沉淀硫酸钡为颜填料制备了成本较低,性能较为优异的防腐蚀涂料.检测了优化条件下制备的涂料的性能.以蓖麻油改性环氧聚氨酯防腐蚀涂料和未经蓖麻油改性的环氧聚氨酯防腐蚀涂料进行防腐蚀性能对比,蓖麻油改性环氧聚氨酯防腐蚀涂料的耐酸、碱、盐水等防腐蚀性能更好.     

Miscibility Studies of Polyesteramides of Linseed Oil and Dehydrated Castor Oil with Poly(vinyl alcohol)

Blends of two polymers have been widely investigated to enhance or modify some of their physical or mechanical characteristics for specific applications. The investigation of miscibility of a pair of polymers is a necessary step in the investigation of the properties of the blends. Poly(vinyl alcohol)(PVA) is a commercial polymer that yields tough films of high tensile strength. They are, however, water soluble, restricting their applications. Vegetable oil constitutes a major resource for several polymeric products, such As alkyds, polyurethanes, polyepoxies, and polyesteramides. Polyesteramides, synthesized from different seed oils, have been used as an anticorrosive material but they fail to form free standing films. They can, therefore, be used for blending with PVA to lower its water sensitivity as well as to obtain free-standing films of a sustainable resource based polymer. In this study, linseed oil polyesteramide (LOPEA) and dehydrated castor oil polyesteramide (DCPEA), the source oils having different unsaturation in their fatty acids chains, were blended with PVA through mixing in solution in the weight ratios LOPEA/DCPEA:PVA: 80:20, 70:30, 60:40, 50:50, 40:60, 30:70, 20:80. In the first phase the miscibility of the two components was investigated in solution by viscosity and ultrasonic measurements and in the solid form through differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). Moisture absorption by the films of different compositions of the blends was studied. The viscosity and ultrasonic studies show that both DCPEA and LOPEA were immiscible with PVA in solution. In solid phase the DCPEA and PVA were found to be partially miscible whereas LOPEA and PVA were found to be completely immiscible. Films of the blend DCPEA:PVA:80:20 were found to be the toughest. Blends of all compositions showed lower absorption of moisture than pure PVA. In view of the toughness of its films, low moisture uptake and high content of sustainable resource based polymer, DCPEA:PVA, 80:20 blend holds potential for commercial application.     

蓖麻油型聚氨酯密封胶

阐述了蓖麻油型聚氨酯密封胶的性能与发展现状 ,分析了各种组分对密封胶性能的影响 ,并预测了此种密封胶的发展方向     

无溶剂蓖麻油聚酯多元醇的合成及应用研究

以蓖麻油、甘油、己二酸和乙二醇为原料,酯化缩聚合成低黏度的蓖麻油聚酯多元醇,并将该蓖麻油聚酯多元醇与HDI聚异氰酸酯制备无溶剂涂料。研究了醇酸比[n(—OH)：n(—COOH)]对蓖麻油聚酯多元醇及其涂层性能的影响。结果表明：在醇酸比为1.32时,蓖麻油聚酯多元醇所制涂层的耐水性、耐冲击性、耐擦伤性、柔韧性等综合性能良好。     

蓖麻油磷酸催化脱水研究

以H3PO4为催化剂,在减压下对蓖麻油催化脱水进行了研究。利用正交实验考察了反应温度、反应时间、催化剂用量、真空度对脱水反应的影响。得出的最佳工艺条件为:反应温度250℃、反应时间90min、催化剂用量1.0%、真空度600×133.3Pa。在该工艺条件下制得的脱水蓖麻油平均碘值达到138,且色泽较浅。     

Ceramer coatings from castor oil or epoxidized castor oil and tetraethoxysilane

New inorganic-organic hybrids were synthesized through the reaction of castor oil (CO) or epoxidized castor oil (ECO) with tetraethoxysilane (TEOS). The mass proportions of ECO/TEOS varied from 90∶10 to 60∶40, and films of the material were thermally cured. An IR spectroscopy analysis was performed, and macro- and microscopic properties such as adhesion, hardness, swelling in toluene, microstructure (scanning electron microscopy), and T _g were investigated as a function of the proportion of their inorganic-organic precursor. Morphologic studies showed that the hybrid films were homogeneous when lower proportions of the inorganic precursors were used. Hardness and tensile strength increased with TEOS concentration, whereas swelling in toluene decreased with TEOS concentration. Good adhesion was observed throughout the hybrid series.     

Characterization of fatty acid isomers in dehydrated castor oil by gas chromatography and gas chromatography-mass spectrometry techniques

Fatty acid isomers present in dehydrated castor oil were analyzed by gas chromatography and gas chromatography-mass spectrometry (GC-MS) of their dimethyl oxazoline derivatives. Conjugated linoleic acid 9,11 and 10,12 isomers were identified by GC based on equivalent chainlengths. Segmental peak analysis of GC-MS total ion chromatogram mass fragmentation pattern revealed the presence of 7,9 and 8,10 conjugated linoleic acids along with 9,11 and 10,12 conjugated linoleic acids. Interestingly, a reverse elution of trans,trans-conjugated linoleic acids was observed, viz. 10,12 was followed by 9,11, which was in turn followed by the 8,10 and 7,9 isomers. The observed reverse order of elution was in contrast to the conventional elution pattern of both nonconjugated and conjugated cis,cis-, cis,trans- and trans,cis-isomers.     

Miscibility behavior of blend of polyesteramides of linseed oil and dehydrated castor oil with poly(methacrylic acid)

Blending of two polymers in solution is a simple and cost‐effective technique to improve upon the physical and mechanical properties of the component polymers through synergism. To obtain maximum synergy in their properties, the component polymers should be miscible with each other on molecular scale. Polymer blends of complex physicomechanical properties are being actively investigated. Poly(methacrylic acid) (PMAA), a commercial polymer, yields transparent, hard, brittle, and water‐sensitive films. It has been blended with natural polymers like dextran, collagen, and gelatin to obtain films with improved physical and mechanical characteristics. Polyesteramides, which are easily synthesized from vegetable seeds oil, a sustainable resource, have found application in surface coatings. These oligomeric products do not make free standing films in the ambient condition. The polyesteramides from vegetable seeds oil can be used to obtain blend with PMMA of improved mechanical and water absorption properties. In this study, linseed oil polyesteramide (LOPEA) and dehydrated castor oil polyesteramide (DCPEA), the source oils with different unsaturation in their fatty acid chains, were blended with PMAA through mixing in solution in the ratio DCPEA/LOPEA: PMAA as 80/20, 70/30, 60/40, 50/50, 40/60, 30/70, and 20/80. In the first instance, the miscibility of the two components was investigated in solution by viscosity and ultrasonic measurements and in solid phase through differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). Moisture absorption by the blend was also studied. DCPEA and LOPEA show immiscibility with PMAA in solution phase while LOPEA with more unsaturation in the fatty acid chain of the oil was found more immiscible than DCPEA. DCPEA shows a narrow miscibility window in the solid phase while LOPEA was found immiscible with PMAA in the solid phase too. Uptake of moisture was found to be markedly reduced in the blends of DCPEA/LOPEA with PMAA. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1367–1374, 2007:     

蓖麻油改性无溶剂型双组分聚氨酯复膜胶

以蓖麻油、苯酐和二甘醇等为原料,经酯化、缩聚后,合成了蓖麻油改性聚酯多元醇,并以此作为复膜胶的固化剂;以MDI-50(二苯基甲烷二异氰酸酯)、PPG-2000/PPG400(聚醚二元醇)为原料,合成了端-NCO基聚氨酯(PU)预聚体,并以此作为复膜胶的主剂;将主剂和固化剂按一定比例混合后,制得无溶剂型双组分PU复膜胶。研究结果表明:当反应温度为45℃、反应时间为3 h和w(-NCO)=18%时,主剂的黏度、流动性相对最好;当双组分中n(-NCO)∶n(-OH)=1.9∶1、固化温度为50℃、固化时间为24 h和w(蓖麻油)=28.3%时,复膜胶的粘接性能相对最好,并且接近于进口同类产品。     

蓖麻油的应用开发

本文介绍了蓖麻油近年来的开发,特别介绍了在表面活性剂和日用化学品等中的应用。     

蓖麻油常压催化氢化的研究

使用混合价态的氧化镁／蛋白质／钯催化剂对蓖麻油的常压催化氢化具有使用寿命长（连续使用３０次仍有较高的活性）、活性高（氢化速度为５１０ｍｌ／ｍｍｏｌ·ｍｉｎ）、氢化彻底（氢化蓖麻油的碘值小于４）等优点，在７０℃用正丙醇作溶剂且与蓖麻油投料比为５．７７ｍｌ／ｇ时氢化活性最高。     

Production of conjugated linoleic acid isomers by dehydration and isomerization of castor bean oil

The possibility of combining dehydration and isomerization of castor bean oil as a means to obtain CLA as TAG forms was studied. First, dehydration was carried out using various catalysts and reaction parameters. Best results were obtained using phosphoric acid (0.1% w/w) at 280°C for 5 h. Under such conditions, satisfactory proportions of CLA were obtained (54% of total FA) with a majority of 9-cis, 11-trans isomer (61% of total CLA). Other catalysts such as bisulfate-bisulfite, sulfuric acid, tungstic and phosphotungstic acids, or resins and zeolites were also tested. With the exception of resins and zeolites, these catalysts also led to CLA production but in limited amounts in comparison with phosphoric acid. In a second step, an isomerization reaction was carried out to transform the residual nonconjugated linoleic acid also produced during dehydration into CLA. Using Wilkinson catalyst [RhCl(PPh₃)₃] in ethanol solvent, dehydrated castor bean oil was isomerized in high yields (>98%), allowing a complete disappearance of nonconjugated linoleic acids. The resulting dehydrated/isomerized oil contained more than 87% CLA with the 9-cis, 11-trans isomer being predominant (40% of CLA fraction). Finally, urea fractionation was also applied on dehydrated/isomerized castor bean oil FA to obtain FFA products containing about 93% CLA.     

海泡石对蓖麻油脱色工艺的研究

通过酸活化海泡石对蓖麻油进行脱色,研究了干燥温度、干燥时间、脱色温度、脱色时间及脱色剂用量等因素对海泡石吸附脱色性能的影响,确定了最佳活化条件及吸附工艺。该研究表明酸活化海泡石对蓖麻油的脱色效果优于其他传统脱色剂,该研究结论为蓖麻油及其他植物油的脱色剂选择提供一种参考。