Chemical epoxidation of a natural unsaturated epoxy seed oil fromVernonia galamensis and a look at epoxy oil markets

Since 1963, production of all epoxy esters has ranged from 60 to 150 million lb annually, a steady 7% of the 1 to 2 billion lb of annual plasticizer production. Growth rates in production averaged 4.3% for all plasticizers, 3.8% for all epoxy esters and 5.0% for epoxidized soybean oil (ESBO). ESBO accounted for 70–76% of total epoxy ester production (1963–1982). The natural liquid epoxy oil fromVernonia galamensis seed, with oxirane value (4.1%) and viscosity (100 cps) similar to some commercial epoxy fatty esters but with molecular weight similar to epoxidized vegetable oils, combines some of the properties of both commercial types. Chemical epoxidation ofVernonia oil raises the oxirane content to 8.2, intermediate between ESBO and epoxidized linseed oil (ELSO), while consuming less of the costly epoxidizing reagents. Epoxidation proceeds in stepwise fashion through partially epoxidized products, which are converted to final product. Since the major fatty components ofVernonia oil arecis-12,13-epoxy-9-octadecenoic (75%) and linoleic (13%) acids, further epoxidation produces fatty acids that are specifically epoxidized at the 9,10- and 12,13-positions, and the major product has 6 epoxy units per triglyceride molecule. The resulting mixture of products has compositional and physical properties distinctly different from commercial samples of ESBO and ELSO.     

Industrial uses of high erucic oils

Vegetable oils rich in erucic acid have desirable properties for a variety of applications. At present, only a fraction of the potential that exists for commercial exploitation of high erucic oils in the United States is fulfilled with 10 million pounds of rapeseed oil imported annually. Though rape is not a crop in the United States, another member of the mustard family, crambe, has been recommended by the USDA as a practical crop for domestic cultivation. Compared to rapessed oil, crambe oil is more suitable for industrial use because it consistently contains a higher percentage of erucic acid. High erucic oils, as examplified by crambe, can be employed as lubricants in continuous steel casting, in formulated lubricants and in the manufacture of rubber additives. Both the hydrogenated oil and derived wax esters have properties comparable to commercial waxes. Useful nitrogen derivatives can be prepared from either the erucic acid or mixed acids from the oil; behenyl amine is used in a corrosion inhibitor, disubstituted amides are effective plasticizers and erucamide is an excellent slip and antiblocking agent for plastic films. Oxidative ozonolysis of erucic acid produces the dibasic acid, brassylic, and the monoacid, pelargonic. Mixed diacids, mainly brassylic and azelaic, can be obtained by ozonolysis of fatty acids from the oil. Alkyl diesters of brassylic, or of the mixed diacids, are excellent low temperature plasticizers. Two new nylons (13 and 1313), which are derived from C-13 difunctional products of erucic acid ozonolysis, contain repeating units that have longer uninterrupted polymethylene chains than other nylons. Moderate melting points and exceptionally low water absorption are a consequence of this structure. The low-melting characteristic is an advantage in adhesive uses and facilitates fluidized-bed coating, molding and extrusion; low moisture affinity contributes to excellent electrical properties and dimensional stability. One of 9 papers presented at the Symposium, “Cruciferous Oil-seeds”. ISF-AOCS World Congress. Chicago, September 1970. No. and Eastern Utilliz. Rev. Div., ARS, USDA.     

Search for new industrial oils,IX.Cuphea,a versatile source of fatty acids

Seed oils from five species ofCuphea show three distinct patterns of fatty acid composition.C. hookeriana andC. painteri oils contain ca. 70% caprylic acid,C. ignea and C.llavea oils have over 80% capric acid, andC. carthagenensis oil contains 57% lauric and 18% capric acids. No. Utiliz. Res. and Dev. Div., ARS, USDA ARS, USDA     

Sulfurized vegetable oil products as lubricant additives

Sulfurized products based on hog fat and its derivatives have extensive commercial use as additives for metalworking and industrial oils, but only relatively small quantities of vegetable oils find such application in North America. Products were made by sulfurization of soybean, sunflower, cottonseed, high erucic rapeseed, canola,Limnanthes (meadowfoam) and prime lard oils. Unlike products from the wax ester jojoba oil, the sulfurized vegetable triglycerides alone had physical properties generally undesirable for lubricant additives. When the oils were sulfurized in the presence of methyl lardate, however, the products had potential practical application. High-sulfur (active) products were made using a 50:50 ratio of triglyceride to methyl lardate, and low-sulfur (inactive) products were made using a 70:30 ratio. Compared to the other sulfurized vegetable triglyceride products,Limnanthes products showed the best solubility in high viscosity-index paraffinic oil. For solutions, measurements of extreme pressure, friction and wear were compared. Whereas products from jojoba were best, of the triglyceride group theLimnanthes-containing products generally gave the best performance. Although this oil had much promise, it is only in its early stage of commercial development. The other vegetable oils also have potential depending on cost and applications. However, overall competition with the well-established, usually lower-cost products from hog fat or greases would appear to be difficult.     

New crop developments for industrial oils

Traditional industrial fats and oils are derived from inedible tallow or lard, fish and whale oil, and a small group of plant oils, including linseed, soybean, castor, tung, tall, and rapeseed oil. A group of new crops and prospective new crops is available to be utilized advantageously for the production of renewable industrial resources. Some of these plants have been studied extensively from germplasm variation through crop production and processing to evaluation of the final oil and meal products. Others are not developed that far yet. Case histories onCramble, Limnanthes, Lunaria (long chain acids),Lesquerella (hydroxy acids),Stokesia andVernonia (epoxy acids),Calendula (conjugated unsaturation),Cuphea (short chain acids), jojoba (liquid wax esters), andFoeniculum (petroselenic acid) indicate that many obstacles must be overcome to arrive at success.     

Nutritional and toxicological evaluation ofHibiscus sabdariffa oil andCleome viscosa oil

Mesta seed oil (Hibiscus sabdariffa), like cottonseed oil, contains cyclopropenoid fatty acids (2.9%) and epoxy fatty acids (2.6%) in addition to normal fatty acids found in vegetable oils.Cleome viscosa (Capparidaceae) seed oil is rich in linoleic acid (70%) and free from any abnormal chemical constituents. Nutritional and toxicological evaluations of these two oils were done by multigeneration breeding studies by feeding the respective oils and groundnut oil as control at 10% level in a 20% protein diet with adequate vitamins and minerals. These studies revealed that rats fed mesta oil had inferior growth and reproductive performance and also had altered liver metabolism. Rats fedC. viscosa oil did not show any abnormal growth or reproductive performance or altered liver lipid levels. Thus, these studies indicate that raw or refined mesta oil may not be suitable for human consumption whereasC. viscosa oil can be used safely by humans.     

Density and viscosity of vegetable oils

A generalized method was developed to estimate the liquid density of vegetable oils and fatty acids. The correlation for vegetable oils was based on fatty acid critical properties and composition of the oil. The correlations predicted the density of vegetable oils and fatty acids with an average absolute deviation of 0.21 and 0.77%, respectively. The present method is slightly more accurate in predicting vegetable oil density and simpler than the method of Halvorsen et al. Also, a method is introduced that predicts viscosity from density data, thus relating two key properties of vegetable oils.     

Industrial chemical uses of polyunsaturated fatty acids

Production of vegetable, animal and marine oils containing more than about 40% unsaturated fatty acids totaled 15,000 million pounds in 1968, almost on the scale of petrochemical production. The greater share (64%) of this nonfossil oil production was directed toward food uses, the remainder toward industrial and animal feed uses. The variety of chemical reactions carried out on these unsaturated fatty acid products include hydrogenation, interesterification, dimerization, sulfation, formation of nitrogen compounds, epoxidation, alkaline cleavage and oxidative ozonolysis. Some of these reactions have been developed at Utilization Research and Development Divisions of the Agricultural Research Service, U.S. Department of Agriculture. Research is continuing in developing new reactions for potential industrial application. An example is reductive ozonolysis of unsaturated fatty esters to produce monofunctional aldehydes and bifunctional aldehyde esters. Presented at the ISF-AOCS World Congress, Chicago, September 1970. No. Market. Nutr. Res. Div., ARS, USDA.     

Place of rapeseed in the edible oil market

The potential for rapeseed oil in the world edible oil market is evident in the statistics of net exports of the principal vegetable oilseeds from primary producing countries. The last complete year for which figures are available is 1970, and in that year soybeans accounted for some 52% and rapeseed only 7.5% in oil equivalent. Since soybeans have only ca. 50% of the oil content of rapeseed, they are bought mainly for their yield of high protein meal. Conversely, rapeseed is bought for its oil content and produces a meal that is not only lower in protein but up to this time has been less acceptable as an ingredient in animal feed formulations. Fortunately for rapeseed, these problems are being tackled diligently and should be overcome in the near future. When this point has been reached, rapeseed will be a much stronger competitor in world markets for protein meal. The trend in the use of rapeseed oil in the Canadian domestic market is an indicator of the potential in world markets. It is displacing other edible oils that have dominated the Canadian market in the past. In the 1971 calendar year, 35.6% or 160.5 million pounds, i.e., 73,000 metric tons, of vegetable oil used in the manufacture of margarine, shortening and salad oils was rapeseed oil. Rapeseed oil is competing keenly with soybean oil in the Canadian market and in the future should be able to greatly enlarge its share of world trade. One of six papers presented in the symposium “Rapeseed Marketing and Breeding,” AOCS Meeting, Ottawa, September 1972.     

The development and application of novel vegetable oils tailor‐made for specific human dietary needs

Conventional edible oils, such as sunflower, safflower, soya bean, rapeseed (canola) oils, were modified to obtain high‐oleic, low‐linoleic or even low‐linolenic oils. The aim was to develop salad, cooking and frying oils, that are very stable against lipid peroxidation. They are also suitable for margarine blends, as additives to cheeses and sausages, or even as feed components. Oils containing higher amounts of medium‐chain length or long‐chain polyunsaturated fish oil fatty acids are suitable as special dietetic oils or as nutraceuticals. High‐stearic oils are designed as trans‐fatty acid‐free substitutes for hydrogenated oils. New tailor‐made (designer) oils are thus a new series of vegetable oils suitable for edible purposes, where conventional oils are not suitable.     

Studies of Oils of Unusual Fatty Acids

Studies of linseed, castor seed and Vernonia anthelmintica seed oils have been undertaken together keeping in view their industrial importance. Linseed oil contains the highest percentage of linolenic acid (69.1%) whereas the highest percentage of hydroxy fatty acid (85.6%) and epoxy fatty acids (76.8%) has been found out in castor seed and Vernonia anthelmintica seed oils respectively as determined by the application of thin-layer and gas liquid chromatography.     

滇产植物油理化指标测定

研究滇产食用植物油的理化特征与储藏期品质变化规律。以两种特色植物油为对照,对云南出产的五种植物油脂的理化指标进行评价和对比。同时使用过氧化值和酸价,对所研究的油脂的储藏期品质变化进行初步探索。结果表明:云南产植物油质量均满足国标要求。但由于其加工工艺原因,植物油级别较低。含有不饱和脂肪酸的植物油在光照情况下过氧化值和酸价明显改变,可作为质量变化的主要指标。云南出产的四种特色植物油脂不饱和脂肪酸含量较高,是良好的食用油产品;但仍需改善加工工艺以提高其级别。葡萄籽油、红花籽油需添加额外抗氧化剂稳定其品质;过氧化值是最适于进行日常油品质量控制的指标。     

木本油料脂肪酸组成、提纯及其应用研究进展

木本油料是我国传统工业油料,应用领域广泛,可作为优质的食用植物油的来源,也可作为生产生物柴油的原料,并且还被用于饲料添加剂和化妆品行业。木本油料中C12~C18不饱和脂肪酸含量高,易被人体吸收,不同提取技术(压榨法、水酶法、超声波辅助法、浸出法等)对木本油料的脂肪酸组成及含量的影响较小。本文对橡胶籽油、核桃油、椰子油、山苍子核仁油、牡丹籽油、油茶籽油和棕榈油等7种木本油料的资源量、应用情况做了简单介绍,并综述了7种木本油料的脂肪酸组成及其提取纯化技术,重点介绍了木本油料中的中长碳链不饱和脂肪酸的提纯技术,并对提纯后的月桂酸、油酸、亚油酸、亚麻酸的应用进行了综述和展望。     

Agricultural and genetic potentials of cruciferous oilseed crops

Oilseed crops of the Cruciferae are widely adapted and are of particular importance to countries in the northern latitudes. Cruciferous seed oils from the crops, rapeseed, mustard, Camelina, oilseed radish and Crambe, enter edible or industrial markets, or both. The oil-seed meal can be used either as a high protein feed supplement or as an organic fertilizer. The spring and winter forms of the two species of rapeseed,Brassica napus andB. campestris, are commercially the most important. Advances in crop management and plant breeding have resulted in a 40% to 50% increase in seed yield over the past 25 years. In the next 10 to 15 years, application of newer plant-breeding techniques will result in varieties even higher in yield and seed with improved oil and meal quality. Some of the quality improvements will be new patterns in fatty acid composition, higher oil and protein content, lower fiber content, and removal of the undesirable glucosinolate compounds from the meal. The mustard cropsBrassica juncea andB. hirta are important condiment crops which have considerable potential as edible oil sources. Oilseed radish,Raphanus sativus, yields significantly less seed and oil than other cruciferous oil crops but its oil, which contains a low level of erucic acid (3.7%) and a relatively high content of 16-carbon fatty acids (9.3%), may be useful in blending with normal or zero erucic acid rapeseed oils.Camelina sativa or false flax has many desirable agronomic characteristics but the oil of camelina seed contains too high a level of linolenic acid (36%) to penetrate the edible oil market and too low to compete industrially with linseed oil.Crambe abyssinica andC. hispanica are potentially important producers of high erucic acid industrial oils. Factors limiting Crambe development are the high cost of seed transportation due to the high volume to weight ratio of the threshed seed and the need for extra seed processing steps to render the meal suitable as a high protein feed supplement for livestock and poultry. One of 9 papers presented at the Symposium, “Cruciferous Oilseeds,” ISF-AOCS World Congress, Chicago, September 1970. Contribution No. 425, Research Station, Canada Department of Agriculture, Saskatoon, Saskatchewan, Canada.     

Rubber-toughening epoxy thermosets with epoxidized crambe oil

Epoxidized crambe oil and rapeseed oil were synthesized by reaction of the oils with m-chloroperoxybenzoic acid. Formulating the neat epoxidized oils with epoxy-amine systems gave two-phase thermosets with epoxidized crambe oil, but not with epoxidized rapeseed oil. Glass transition temperature, mechanical properties, and fracture toughness of the epoxidized crambe oil thermoset specimen were measured. Fracture toughness values of the epoxy thermosets were increased approximately 100% by both 5 and 10% epoxidized crambe oil. Glass transition temperature and mechanical properties were affected only modestly.     

Fatty Acids,Tocopherols and Sterols of <Emphasis Type="Italic">Cephalocroton cordofanus</Emphasis> in Comparison with Sesame,Cotton, and Groundnut Oils

Cephalocroton cordofanus, a perennial much-branched shrub, is dominant in the eastern and western states of Sudan. The seeds of C. cordofanus sesame, groundnut, and cotton were compared for their oil and protein content as well as for fatty acids, tocopherols, and sterols. Fatty acids and sterols were analyzed by GC while tocopherols were analyzed by HPLC. The oil of C. cordofanus showed low levels of saturated fatty acids in comparison with the other three oils. The other reported fatty acids of C. cordofanus were 8.60 % oleic, 17.2% linoleic, 64.2% vernolic, and 2.0% coronaric acids. Neutral lipids, glycolipids, and phospholipids of C. cordofanus oil accounted for 77.5, 14.4, and 8.1% of the total lipid fraction, respectively. The oil of C. cordofanus showed higher levels of tocopherols (113.53 mg/100 g) in comparison to sesame, groundnut, and cottonseed oils, with 64.74, 27.96, and 77.83 mg/100 g, respectively. The primary tocopherol of C. cordofanus was γ-tocopherol (106.21 mg/100 g), which amounted to 93.8% of the total tocopherols. β- and δ-tocopherol were present at levels below 5.0 mg/100 g. In comparison to sesame, groundnut, and cottonseed oils, C. cordofanus oil contains more (304.4 mg/100 g) total sterols than ground nut (294.0 mg/100 g), but less than sesame (774.9 mg/100 g) and cotton seed (492.4) oils. Due to its high level of epoxy fatty acids, C. cordofanus oil is used for industrial rather than edible applications.     

Fats and oils as feedstocks for oleochemicals

The approximate quantity of 3 million tons estimated to be required at present for the production of oleochemicals is to be covered from a total production of more than 60 million tons of vegetable and animal fats. While the quantity of eleochemicals produced has nearly doubled in recent years, vegetable oil production alone has increased from 25 to 40 million tons in the same period. More than half the feedstocks required for oleochemicals are acid oils and other fats and oils which are unsuitable for human food. The demand for fats and oils for oleochemicals will certainly grow for price and technological reasons, but only the use of large quantities of oils and fats for diesel engines could shift this balance drastically and endanger the world supply of edible fats. A bottleneck may arise in the supply of fatty acids of medium chain length, although the use of coconut and palm kernel oil by the food industry in the highly developed countries has been on the decline. The green revolution goes on and the fat supply grows faster than the population. In addition, new approaches to plant breeding and agriculture, and biochemical processes as well, might help circumvent any conceivable shortage in the supply of oils and fats in general, and in the supply of special fatty acids in particular.     

Chemical evaluation of egyptian citrus seeds as potential sources of vegetable oils

Seeds of the citrus fruits orange, mandarin, lime and grapefruit were analyzed. Petroleum ether-extracted oils of such seeds amounted to more than 40% of each. Physical and chemical properties of the extracted oils are presented. Samples of the extracted oils were saponified and the unsaponifiables and fatty acid fractions isolated. The isolated unsaponifiables and fatty acids were analyzed by GLC. GLC analysis of the unsaponifiables revealed compositional patterns differ-ent in number, type and relative concentration of fractions according to type of citrus seed oil, depending on the solvent system used for oil extraction and unsaponifiable matter isolation. The compositional patterns of the unsaponifiables were similar to that of cottonseed oil. Mandarin and grapefruit oils are free of cholesterol. The data demonstrate that the fatty acid compositional patterns of the oils differ; Mandarin seed oil contains the largest number of fatty acids, and grapefruit seed oil contains the lowest. The total amounts of volatile fatty acids in these oils are generally higher than those of other edible oils. Lime seed oil is similar, in the degree of unsaturation, to soybean oil. The orange oil pattern is similar to cottonseed oil. The amount of total essential fatty acids in lime seed oil is the highest of the oils studied.     

Optimization of biodiesel production from edible and non-edible vegetable oils

The non-edible vegetable oils such as Jatropha curcas and Pongamia glabra (karanja) and edible oils such as corn and canola were found to be good viable sources for producing biodiesel. Biodiesel production from different edible and non-edible vegetable oils was compared in order to optimize the biodiesel production process. The analysis of different oil properties, fuel properties and process parameter optimization of non-edible and edible vegetable oils were investigated in detail. A two-step and single-step transesterification process was used to produce biodiesel from high free fatty acid (FFA) non-edible oils and edible vegetable oils, respectively. This process gives yields of about 90-95% for J. curcas, 80-85% for P. glabra, 80-95% for canola, and 85-96% for corn using potassium hydroxide (KOH) as a catalyst. The fuel properties of biodiesel produced were compared with ASTM standards for biodiesel.     

Substitutability of fractionated beef tallow for other fats and oils in the food and confectionery industries: An economic evaluation

The United States is the most important beef tallow producer in the world, supplying ca. 5.5 billion pounds annually. Approximately half of this beef tallow is exported at relatively low prices when compared to other fats and oils. Only ca. 10% of the total is used in domestic edible products. On the other hand, cocoa butter, coconut oil, palm oil, and palmkernel oil are imported oils whose demand for use in food and confectionery products has been increasing over the past few years. The first of these is the most expensive fat in the world. Beef tallow contains specific triglycerides which are also contained in these imported fats and oils. Through modern technology, beef tallow has been fractionated into products which are compatible with or superior to the imported fats and oils. It is visualized that products from fractionated beef tallow can be used as substitutes and extenders to cocoa butter, palm oil, and other fats and oils in the food and confectionery industries. The economic evaluation in this paper, analyzed through time series data and multiple regression techniques, established the past relationships between per capita consumption of confectionery food fat, beef tallow, cocoa butter, adjusted per capita disposable income, and adjusted costs of confectionery, beef tallow, and cocoa butter from 1956 to 1973. The substitutability of fats and oils was evaluated and the potential uses of fractionated beef tallow investigated. Presented in part at the AOCS meeting in Cincinnati, September 1975.