DC-Trennung von Ricinusölfettsäure-Estoliden

TLC Separation of Estolides of Castor Oil Fatty Acids Estolides of castor oil fatty acids (polyricinoleic acids) with varying degrees of condensation were synthesized by heating the castor oil fatty acids at 120° C–240° C under vacuum and CO₂ circulation. These products were analyzed by chemical constants and fractionated by TLC on silicagel 60 precoated plates into ricinoleic acid and di-, tri- as well as tetra-ricinoleic acids. Furthermore, the estolides were separated by two-dimensional TLC into two series of estolides, i.e. estolides containing only ricinoleic acid and those which contain fatty acids other than ricinoleic acid at the chain terminal. Hydrogenated castor oil fatty acids (technical 12-hydroxystearic acid) also form estolides which can be fractionated in a similar manner. Thus, TLC provides information on the oligomeric and polymeric character of the estolides of castor oil fatty acids and permits separation even of the decamers.     

蓖麻油基聚酯多元醇的制备及表征

以可再生资源蓖麻油、苯酐和小分子醇为原料,钛酸正丁酯为催化剂,经酯化、缩聚合成蓖麻油基聚酯多元醇,考察了反应时间对聚酯多元醇酸值的影响以及不同官能度的小分子醇对醇解蓖麻油结构和羟值的影响。采用红外光谱仪（FT—IR）、凝胶色谱（GPC）、热失重仪（TGA）对醇解蓖麻油、蓖麻油基聚酯多元醇的相对分子质量、热稳定性进行了表征。结果表明,随着小分子醇官能度的增加,醇解体系中单酯和二酯含量明显减少,转化率也相应减小;甘油醇解蓖麻油和蓖麻油基聚酯多元醇较普通聚醚多元醇635具有更高的热稳定性。     

Oleochemical products as building blocks for polymers

The use of oleochemical derivatives is dominated by applications in the field of surfactants and emulsifiers. There also is a remarkable amount of highly specialised uses, for example in lubricants and as additives to modify the characteristics of polymers. Besides this, some products have been developed on the basis of oleochemical building blocks in the polymer backbone. Starting with oleic acid, the difunctional azelaic acid (C-9) is produced by ozonolysis for application in high-value polyesters and polyamides. Pyrolysis of castor oil or ricinoleic acid is the commercial route to sebacic acid (C-10). Castor oil itself is used as a polyol for the production of polyurethanes. Similar polyols with modified viscosity and application characteristics are made by epoxidation and ring-opening reactions of unsaturated fatty acid derivatives. Dimer acid (C-36) is obtained by a double bond reaction of C₁₈ unsaturated fatty acids. By using hydrogenation technology, which is wellknown in the oleochemical industry to produce fatty alcohols, dimerdiols can be prepared from dimer acid. This dimerdiol is of great interest in polyurethane application fields in general, because it is a liquid, hydrophobic, long-chain raw material with two primary hydroxyl groups. By condensation of dimerdiol to building blocks with a molecular weight around 2,000 it is possible to prepare soft segments, that allow the production of thermoplastic polyurethanes (TPU) with modified application characteristics. Two different soft segments based on dimerdiol, ethers, and carbonates are discussed. The advantages for TPUs prepared from these building blocks are hydrolytic and oxidative stability and resistance to saponification and polar solvents.     

Assessment of Variation in Castor Genetic Resources for Oil Characteristics

Castor (Ricinus communis L.) oil is used in production of wide range of industrial products because of the presence of nearly 85% of ricinoleic acid in it. Any increase in the ricinoleic acid level would be great benefit to industry. None of the existing castor cultivars possess ≥90% ricinoleic acid because donors with this level of ricinoleic acid are not available to develop high ricinoleic type cultivars. In order to search for high ricinoleic acid genotypes, the present investigation was under taken. Fatty acid and oil content were assayed in 392 castor genotypes comprising 335 Indian and 57 non-Indian collections. Great variation was observed among the collections for oil content and fatty acid composition. Oil content ranged from 38.5 to 53.5% while ricinoleic acid was between 71.15 and 93.68%. Diversity analysis was done using K-means clustering which clustered the entire collection into 30 diverse groups by minimizing the dissimilarity within each cluster while maximizing the dissimilarity between clusters. Finally, 15 accessions having high oil (52–54%), high ricinoleic acid (91.12–93.68%) and high monounsaturates (92.8–94.95%) levels were identified. These would be of great value as donors to develop high oil, high ricinoleic type castor cultivars.     

溴化蓖麻油多元醇合成及其制备的阻燃聚氨酯硬泡性能

采用可再生的醇解蓖麻油多元醇为原料,与液溴进行加成反应制备溴化蓖麻油多元醇,通过红外光谱证实发生了溴化反应,并测定了产物粘度、羟值、酸值.通过发泡实验和氧指数、烟密度、水平燃烧等测试手段,考察了溴化蓖麻油基聚氨酯硬泡发泡参数和阻燃性质,并与工业级阻燃荆雅保RB-79制备的聚氨酯硬泡进行比较.结果表明,由溴化蓖麻油多元醇...     

Characteristic properties of cutting fluid additives derived from the reaction products of hydroxyl fatty acids with some acid anhydrides

Several adducts were prepared from the thermal reaction of hydroxyl fatty acids (ricinoleic acid oligomers, 12-hydroxystearic acid oligomers, oleyl alcohol, dehydrated castor oil fatty acids, and dimer acid) with maleic anhydride and screened as water-soluble cutting fluids. For example, aqueous solutions of triethanolamine salts with the products of ricinoleic acid oligomers, 12-hydroxystearic acid dimer, and 12-hydroxysteric acid hexamer showed good antirust properties for waterbased cutting fluids. Various half esters of hydroxyl fatty compounds with acid anhydrides were prepared. Aqueous solutions of triethanolamine salts of half esters of maleic anhydride and succinic anhydride and phthalic anhydride with hydroxyl fatty acids gave good antirust and antiwear properties for waterbased cutting fluids.     

DC-Trennung von Ricinusölfettsäure-Partialglyceriden

Thin-Layer Chromatographic Separation of Partial Glycerides of Castor Oil Fatty Acids Partial glycerides of castor oil fatty acids and hydrogenated castor oil fatty acids were prepared by esterification or glycerolysis and fractionated, together with commercial products, by TLC (especially by two-dimensional technique) on silicagel 60 precoated plates. By comparison of the two-dimensional chromatograms of the partial esters of castor oil fatty acids with synthetic standards, such as partial glycerides of ricinoleic, di- and tri-ricinoleic acids, estolides of castor oil fatty acids esterified to partial glycerides, and partial esters of castor oil fatty acids with 1,3-propanediol, the substances that could be identified were partial glycerides of ricinoleic, diricinoleic and triricinoleic and tetraricinoleic acids as well as partial glycerides, which contained, in addition to ricinoleic, diricinoleic and triricinoleic acids, fatty acids without hydroxyl groups as terminal estolide chain. The TLC enables an insight into the complex character of the glyceride composition of partial glycerides of castor oil fatty acids.     

Preparation and characterization of modified castor oil via photo-click chemistry for UV-curable waterborne polyurethane with enhanced water resistance and low conductive percolation threshold

A castor oil (CO) was modified via thiol-ene click chemistry reaction between CO and 3-mercaptopropyl trimethoxysilane, with the conversion of CC bonds of CO over 99% based on ¹HNMR spectra. The obtained modified castor oil (MCO) was used as a biobased polyol to prepare waterborne polyurethane (WPU) dispersions. The modification of CO exhibited a great effect on the properties of WPU dispersions and coatings, and an obvious change is the improvement of the water resistance of WPU coatings. WPU dispersions with MCO had good storage stability. A WPU coating with 7% MCO had high surface hydrophobicity, and its water absorption was as low as 3.2%. Conductive carbon black filled WPU coatings with MCO were cured by efficient UV radiation, and their conductive percolation threshold could decrease to 0.76%, which could be attributed to the well filler dispersion and strong filler-polymer interaction. The WPU dispersions are ecofriendly, and can be used to produce biobased WPU coatings with a great application potential in antistatic coating fields.     

Synthesis and characterization of hyperbranched and air drying fatty acid based resins

In this research four hyperbranched resins having fatty acid residues were synthesized. Dipentaerythritol, which was used as the core molecule of the resins, was twice esterified with dimethylol propionic acid. This resin was then esterified with the castor oil fatty acids. The hydroxyl group present in the ricinoleic acid which constitutes almost 87% of the castor oil fatty acids was then reacted with linseed oil fatty acids and benzoic acid. The linseed fatty acids were incorporated into the structure to esterify 0, 15, and 70% of the ricinoleic acid on mole basis. These resins were named as HBR-1, 2, and 3. A fourth resin (e.g. HBR-4) was synthesized by the incorporation of ‘15% linseed fatty acids + 55% benzoic acid’. The chemical characterization of the resins was achieved by FTIR spectroscopy and the thermal properties were determined by DSC. The physical and the mechanical properties of the resins were determined. The hardness value of the resins was measured as 24, 27, 25, and 68 Persoz for HBR-1, 2, 3, and 4, respectively. The viscosity of the resins was measured as 17.3, 9.7, 5.8, and 17.5 Pa·s at a shear rate of 200 s⁻¹. The increase in the amount of the linseed fatty acids increased the hardness, and decreased the viscosity of the resins. All resins showed excellent adhesion, gloss, and flexibility.     

Enzymatic preparation of polyethylene glycol esters of castor oil fatty acids and their surface-active properties

This study concerns the preparation and evaluation of nonionic surfactants prepared from polyethylene glycol (PEG) esters of castor oil fatty acid, a source of hydroxy fatty acid. A lipase-catalyzed esterification reaction has been employed to prepare PEG esters of hydroxy acid to overcome problems associated with chemical processes. Castor oil fatty acid (85% ricinoleic acid) was mixed with PEG of different molecular weight. Rhizomucor miehei lipase was added as catalyst (10% level) and the reaction was continued at 60°C under 2 mm Hg pressure for 360 min. Conversion of PEG to esters was in the range of 86–94%, depending on the molecular size of PEG. The products were isolated and examined for surface activity by surface tension measurement. Surface tension values measured at 25°C were about 36–37 dynes/cm.     

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.     

Features of the enzymatic hydrolysis of castor oil

Ricinoleic acid, which is used in medicine and veterinary science and is the initial material in the organic synthesis of various valuable products, is obtained via the hydrolysis of castor oil. The enzymatic hydrolysis of castor oil, which allows us to conduct the process under mild conditions (in the temperature range of 35–45°C and without high pressures) is a promising method for obtaining ricinoleic acid. This work demonstrates the feasibility of the enzymatic hydrolysis of castor oil with lipase from Candida rugosa in oil-water systems without an emulsifier. We propose a method for hydrolysis without emulsifiers, simplifying the process of isolating the target product (a mixture of free fatty acids in which ricinoleic acid predominates) and thus the relevant technology. The catalyst that we use ensures the environmental friendliness of the process. Our selection of the experimental conditions for hydrolysis resulted in a 47% yield of fatty acids.     

蓖麻油基热稳定剂制备及其在聚氯乙烯制品中的作用行为研究

将蓖麻油酸与马来酸酐、六氢苯酐分别制备了2种蓖麻油基二元酸,并合成出相应的新型蓖麻油基钙/锌(Ca/Zn)盐。通过刚果红法、电导率法和热重分析等方法研究了蓖麻油基Ca/Zn盐与传统的石油基异辛酸Ca/Zn盐分别在聚氯乙烯制品中的热稳定性能。结果表明,改性蓖麻油基二元酸锌不易“锌烧”,锌离子含量为2 %时,静态热稳定时间分别为9.8、9.2 min,异辛酸钙/蓖麻油基二元酸锌盐之间协同效应较为显著,且热稳定效果随Ca/Zn离子含量比的变化而变化。     

高固体分自干型苯乙烯改性醇酸树脂

选用蓖麻油、豆油或亚麻油、多元醇、多元酸、苯乙烯及助剂合成了一种高固体分（７０％）、低苯乙烯游离单体量（≤０７质量％）的改性醇酸树脂。该树脂及其涂料性能相当于或优于同类进口树脂     

Rigid polyurethane foam prepared from a rape seed oil based polyol

A new kind of polyol based on rape seed oil for use in rigid polyurethane foam was synthesized and characterized. The synthesis of such a polyol was divided into two steps. The first step was the hydroxylation of the double bonds existing in the long chains of the unsaturated aliphatic hydrocarbon of rape seed oil with peroxy acid. The second step was use of the alcoholysis of the hydroxylated rape seed oil with triethanolamine to increase the hydroxyl value of the product. The reaction process was monitored by means of a novel on‐line infrared spectrometer. Rigid polyurethane foam was produced with this rape seed oil based polyol and some physical properties of the foam were examined and compared with a reference foam. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 591–597, 2002; DOI 10.1002/app.10311     

Reduction of unsaturated fatty acids and fatty alcohols with diimide from hydroxylamine-ethyl acetate

Hydroxylamine has been recently found to react with ethyl acetate to generate diimide in situ. This reaction was used to reduce 10-undecenoic, oleic, linoleic, stearolic, concentrates of ricinoleic, cyclopentene and cyclopropene fatty acids (FA), dehydrated castor oil FA, 10-undecen-1-ol, oleyl alcohol and castor fatty alcohols. Unsaturated FA and their corresponding alcohols reacted in a similar manner. Terminally unsaturated, cyclopropene and cyclopentene FA were more reactive than oleic acid, which, in turn, was more reactive than hydroxymonoenoic acids. Conjugated dienoic FA reduced faster than nonconjugated dienoic acids. Partial hydrogenation using this reagent is particularly advantageous in determining geometry and the position of double bonds in the polyunsaturated FA, as it can be carried out in the absence of oxygen or oxidizing agents unlike hydrazine reductions.     

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.     

Insight on Castor Oil Based Polyurethane and Nanocomposites: Recent Trends and Development

Castor oil has gained momentous attention as a valuable bio-based monomer and a potential alternative to the current petrobased polyol for synthesizing polyurethane due to the presence of inherent hydroxyl group. In spite of its huge potentiality very little has been reviewed regarding the development of polyurethane from castor oil. This review thus highlights the recent trends and development in the field of polyurethane and its nanocomposite based on castor oil including its biodegradability and weatherability studies. Further, this review also provides an insight regarding the utilization of castor oil based polyurethane and its nanocomposite for coating application.     

Selectivity of lipases: isolation of fatty acids from castor,coriander, and meadowfoam oils

The lipase‐catalyzed hydrolysis of castor, coriander, and meadowfoam oils was studied in a two‐phase water/oil system. The lipases from Candida rugosa and Pseudomonas cepacia released all fatty acids from the triglycerides randomly, with the exception of castor oil. In the latter case, the P. cepacia lipase discriminated against ricinoleic acid. The lipase from Geotrichum candidum discriminated against unsaturated acids having the double bond located at the Δ‐6 (petroselinic acid in coriander oil) and Δ‐5 (meadowfoam oil) position or with a hydroxy substituent (ricinoleic acid). The expression of the selectivities of the G. candidum lipase was most pronounced in lipase‐catalyzed esterification reactions, which was exploited as part of a two‐step process to prepare highly concentrated fractions of the acids. In the first step the oils were hydrolyzed to their respective free fatty acids, in the second step a selective lipase was used to catalyze esterification of the acids with 1‐butanol. This resulted in an enrichment of the targeted acids to approximately 95—98% in the unesterified acid fractions compared to the 70—90% content in the starting acid fractions.     

A simple and rapid polarimetric method for quantitative determination of castor oil

A simple and rapid polarimetric method is developed for quantitation of adulteration of castor oil in edible oils such as cottonseed, coconut, mustard, olive, palm, peanut, rice bran, safflower, soybean, and sunflower. The method is based on the optical activity of ricinoleic acid (12-hydroxy octadecenoic acid), a major constituent of castor oil. There is a good correlation between optical rotation and castor oil content in admixtures above 5%. Highly colored and viscous oils interfere in the measurement of optical activity. The method is highly specific and cost-effective. No solvents and chemicals are required for the analysis because no sample processing is involved in the present method.