Bio-Based Polyurethanes from Microbially Converted Castor Oil

Bio-based new polyurethanes (PU) were synthesized from microbially converted castor oil. Castor oil was used as a raw material to synthesize 7,10,12-trihydroxy-8(E)-octadecenoic acid (TOD) by the strain Pseudomonas aeruginosa PR3. Subsequently, hexamethylene diisocyanate (HMDI) was used in different ratios and reacted with TOD to produce new PU. Fourier transform-infrared spectroscopy, nuclear magnetic resonance spectroscopy, and gas chromatography/mass spectrometry were used to confirm the identity of TOD. Differential scanning calorimetry, thermogravimetric analysis, and tensile property testing were used to investigate the thermal and mechanical properties of PU. PU synthesized based on TOD had a tensile strength of 45.4 MPa with low elongation at break of 8.16% at an isocyanate/hydroxyl ratio of 2.0. To modify the properties of PU, TOD was blended separately with polyethylene glycol or polycaprolactone diol at different weight ratios before reacting with HMDI. The modified polymer showed improved thermal stability and comparatively higher elongation at break. This is the first study demonstrating the conversion of castor oil into TOD that can be used stand alone or as a blend for PU synthesis.     

Trifunctional Acids Derived from Dehydrated Hardened Castor Oil

Dehydration and splitting of hydrogenated castor oil produces a mixture of fatty acids containing about 80% of the iso-oleic acids having the double bond in 11 and 12 positions in approximately equal proportions (as demonstrated by periodate/permanganate scission) and largely in the trans configuration. This technical iso-oleic acid reacts as expected with maleic anhydride to produce a mixture of isomeric iso-oleyl succinic anhydrides. When the oleate is reacted as the methyl ester the crude product can be distilled to produce methyl iso-oleyl succinic anhydride (M. O. S. A.) free from polymeric material. The yields of product under different conditions of time, temperature and ratio of maleic anhydride to fatty esters have been studied.     

由蓖麻油制备的UV光固化涂料

由蓖麻油甘油酯、环氧树脂UVR6100、光引发剂UV16900制得的涂料具有良好的光泽、优良的柔韧性、良好的附着力与硬度,且当蓖麻油甘油酯含量为40％时,漆膜综合性能较佳。     

蓖麻油裂解制癸二酸生产工艺研究进展

论述了近年来蓖麻油裂解制癸二酸生产工艺的研究进展,重点介绍了生产工艺的改进、含酚废水的治理、癸二酸的提纯等方面的最新研究成果,并指出目前癸二酸生产中仍存在的问题和进一步研究的方向.特别提出了回收游离碱的新观点.     

改性硅藻土固定化脂肪酶催化蓖麻油制备生物柴油

采用改性硅藻土做为载体,用吸附法对脂肪酶进行固定化,对固定条件进行优化,利用固定化脂肪酶催化蓖麻油制备生物柴油,考察反应时间、温度、醇油比及酶用量对转化率的影响和固定化脂肪酶催化合成生物柴油的稳定性。研究表明,硅烷化试剂添加量0.4%、温度30℃和时间4~6 h时固定化脂肪酶的活性最高,在醇油比为9:1,固定化酶用量为蓖麻油质量的4%,温度为60℃,反应时间为10 h的条件下,生物柴油的产率最高,经过3个批次的反应后,其产率都在40%以上,该固定化酶催化合成生物柴油有良好的工业化前景。     

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。     

蓖麻油磺酸钠的制备

用浓硫酸磺化蓖麻油酸,得到磺化蓖麻油酸,进行洗涤加碱中和得到蓖麻油磺酸钠。用正交试验初步优化磺化反应的工艺条件,可知物料配比n(蓖麻油)∶n(浓硫酸)对反应的影响较大,其次是反应时间、反应温度、硫酸浓度,硫酸滴加时间对反应的影响最小。在正交试验的基础上,进行单因素实验,得到最优工艺条件:硫酸浓度96%,n(蓖麻油)∶n(浓硫酸)=1∶2.2,硫酸滴加时间85min,反应时间6 h,反应温度46℃。最优条件下磺化率可达39%以上。     

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。     

Preparation of Sebacic Acid via Alkali Fusion of Castor Oil and its Several Derivatives

Castor oil and its three derivatives including methyl ricinoleate, sodium ricinoleate and ricinoleic acid were used as the raw material for alkali fusion to prepare sebacic acid. The reaction parameters including catalyst, ratio of oleochemicals/NaOH, reaction time and reaction temperature were optimized. It was found that Pb₃O₄ (1%) showed the best catalytic performance, and 553 K was considered as the most suitable reaction temperature. The oleochemicals/NaOH ratios of 15:14, 15:14, 15:12 and 15:14 were determined as the optimal ratio for alkali fusion of castor oil, methyl ricinoleate, sodium ricinoleate and ricinoleic acid, respectively. In addition, the optimal reaction time of alkali fusion of castor oil was 5 hours, and that of its derivatives was 3 hours. The maximum yield in sebacic acid of 68.8%, 77.7%, 80.1%, 78.6% can be obtained by using castor oil, methyl ricinoleate, sodium ricinoleate and ricinoleic acid as the raw material, respectively. High purity of sebacic acid was confirmed by GC and melting point analysis. ICP-OES results illustrated that the content of Pb in sebcic acid was less than 1 mg kg⁻¹. Separating glycerol from castor oil was beneficial for alkali fusion, by which, the yield of sebacic acid was increased of approximately 10%, and the reaction time was reduced from 5 to 3 hours. This study provided guiding significance for the future industrial production of sebacic acid.     

Hydrotreating Model Comparison of Raw Castor Oil and its Methyl Esters for Biofuel Production

Some of the main problems during vegetable oil hydrotreating are the high heat of reaction released, the huge quantity of expensive hydrogen required, and the high corrosion rates in the equipment. Some insights into the advantages and disadvantages of processing raw vegetable oils or their respective fatty acid methyl esters are given. The ASPEN Plus process simulator was used for the simulation of a hydrotreating process, with two different feedstocks coming from the same plant: raw castor oil and castor oil methyl esters. That process was modeled with two stoichiometric reactors in series. The technical viability of using methyl esters as hydrotreating feedstock for the production of biofuels such as green gasoline and diesel is demonstrated.     

蓖麻油制癸二酸裂解工艺研究

通过间歇工艺实验和几种创新方法研究了这个裂解反应。考察了温度、时间、水分和甲酚对产物收率的影响。发现了关于水、连串反应、催化、第二反应平衡和制约癸二酸收率等方面的反应特征。确定了双温工艺条件,癸二酸收率达51.3%,2-辛醇收率达33.2%。特别指出甲酚的催化作用,为寻找新物质代替甲酚指明了方向。     

蓖麻油的精炼与开发利用

介绍了ＩＣＯＡ－１号蓖麻油的精炼工艺，综述了国内外蓖麻油在各领域中的开发应用情况。笔者认为，大力发展蓖麻油的深度加工业，具有很好的应用前景。     

有机硅改性磷酸化蓖麻油的合成

以蓖麻油为主要原料,经醇解反应、与有机硅接枝、磷酸化反应合成了加脂剂含硅磷酸化酯交换蓖麻油。通过红外光谱、凝胶渗透色谱等确定了合成产物的结构、组成和相对分子质量,并对各步反应条件进行了优化实验:当蓖麻油与丁醇的摩尔比为1(∶3-4)时,蓖麻油的酯交换深度比较理想;反应温度在80-90℃时,接枝率可达85%以上;在较低的温度下,蓖麻油接枝产物可以发生磷酸化反应,生成的磷酸化蓖麻油平均相对分子质量为1 200左右,乳液稳定。     

蓖麻油的单官能团反应

蓖麻油是具有独特性能的植物油类,分子中含有羟基、酯基、烯键等官能团,这些官能团可以单独进行反应得到蓖麻油衍生物,也可以其中两个或三个基团组合先后进行不同反应得到特殊用途的蓖麻油衍生物。主要对三种官能团单独进行化学反应综述归类,系统地介绍蓖麻油中各官能团所能发生的反应,简述不同反应产物的用途,较全面地介绍了蓖麻油基础化学反应知识,便于新反应和多官能团反应的设计和新产品的开发,提高蓖麻油深加工技术水平。     

马来酸酐改性蓖麻油制备交联型水性聚氨酯

以马来酸酐与蓖麻油制备含碳碳双键的三羧基蓖麻油(MACO)作为内交联剂,合成改性蓖麻油水性聚氨酯乳液(MACO-WPU)。采用FT-IR和XRD对改性聚氨酯的结构进行表征,证实MACO被成功引入到聚氨酯大分子链中且分子链呈现无序状态。通过对力学性能、吸水率、粒径、热重分析等研究了MACO用量对聚氨酯乳液及胶膜性能的影响,结果表明:当w(MACO)=3%时,乳液外观和稳定性好,平均粒径为48.45 nm; 胶膜的拉伸强度和断裂伸长率分别为13.15 MPa、195%;与未改性WPU相比热稳定性略有提高。     

Cast Polyurethanes Based on Castor Oil and Fluorescein

Cast polyurethanes based on castor oil, fluorescein and tolylene diisocyanate have been synthesized. The polyurethanes were characterized by Fourier transform infrared spectroscopy. The thermal stabilities of the polymers were determined using a thermogravimetric analyser. From the differential scanning calorimetric analysis, change in the glass transition temperature of the soft segment was observed as the molar ratio and feed composition of the fluorescein were varied. © 1997 SCI.     

The Component Fatty Acids and Glycerides of Castor Oil

Gas-liquid chromatographic analysis of methyl esters of two samples of castor oil gave the following (as wt %): palmitate 1.2, 0.9; stearate 0.7, 1.2; arachidate 0.3, 0.2; hexadecenoate 0.2, 0.2; oleate 3.2, 3.3; linoleate 3.4, 3.7; linolenate 0.2, 0.2; ricinolE'ate 89.4, 89.0; and dihydroxystearate 1.4, 1.3. Oxidative cleavage of purified methyl ricinoleate indicated that the double bond was exclusively in the 9舑10 position. Castor oil glycerides were fractionated in a 100-tube CCD apparatus using 90% ethanol and commercial hexane as solvents. Analysis of pooled fractions showed (as mole %) triricinolein 68.2, diricinoleins 28.0, mono-ricinoleins 2.9 and nonricinoleins 0.9. These results coupled with lipase hydrolysis of the whole oil and of the fractions agree well with the distribution pattern proposed by Vander Wal.     

Salt Mixture and in vivo Digestibility of Groundnut Oil in Rats

Coefficient of true digestibility of refined groundnut oil in rats, fed a diet containing 4% Hawk and Oser's salt mixture which is stoichiometrically equivalent to Osborne-Mendel's salt mixture and which provides 473.4 mg calcium and 71.6 mg magnesium per 100 g diet was found to be 96.6. Corresponding figure with a similar diet but containing 2% salt mixture-351 of Hubbel et al. providing 434.2 mg calcium and 20.9 mg magnesium per 100 g diet was only 90.0. Higher digestibility of the oil with the Hawk-Oser's salt mixture was due to lesser excretion of soap (in the main) and neutral fat, compared to that obtained with the diet containing the other salt mixture. In Hawk and Oser's salt mixture, the sources of calcium are citrate, hydrogen phosphate and carbonate of calcium whereas in the other salt mixture, it is exclusively derived from calcium carbonate. It seems that source of calcium in a diet has profound effect on the digestibility of a fat.     

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。