Oleic acid products

Brevib. thiogenitalis oleic acid production from acetic acid and Cu " is effective 66, 50% ... 

The obtained results showed that total fatty acids, triacylglycerols and oleic acid accumulation during olive fruit ripening decreased when NaCl concentrations augmented in Irrigation water. This oleic acid synthesis decrease could be explained by a photosynthetic acitivity inhibition because the chloroplast is an important site of oleic acid production in plant cells (Stumpf and al,, 1980). 

Colourless liquid. B.p. 286 C/100 mm., insoluble in water. Oleic acid occurs naturally in larger quantities than any other fatty acid, being present as glycerides in most fats and oils. It forms one third of the total fatty acids of cow s milk. A crude grade from inedible tallow is used in the production of lubricants, detergents, resins and other products. 

Multiply unsaturated linolenic and linoleic acid residues make triglycerides more vulnerable to oxidative degradation than oleic acid which is relatively stable. It is therefore desirable to hydrogenate the most unsaturated residues selectively without production of large quantities of stearic (fully saturated) acid. The stepwise reduction of an unsaturated oil may be visualized as ... 

Typically, soHd stabilizers utilize natural saturated fatty acid ligands with chain lengths of Cg—C g. Ziac stearate [557-05-1/, ziac neodecanoate [27253-29-8] calcium stearate [1592-23-0] barium stearate [6865-35-6] and cadmium laurate [2605-44-9] are some examples. To complete the package, the soHd products also contain other soHd additives such as polyols, antioxidants, and lubricants. Liquid stabilizers can make use of metal soaps of oleic acid, tall oil acids, 2-ethyl-hexanoic acid, octylphenol, and nonylphenol. Barium bis(nonylphenate) [41157-58-8] ziac 2-ethyIhexanoate [136-53-8], cadmium 2-ethyIhexanoate [2420-98-6], and overbased barium tallate [68855-79-8] are normally used ia the Hquid formulations along with solubilizers such as plasticizers, phosphites, and/or epoxidized oils. The majority of the Hquid barium—cadmium formulations rely on barium nonylphenate as the source of that metal. There are even some mixed metal stabilizers suppHed as pastes. The U.S. FDA approved calcium—zinc stabilizers are good examples because they contain a mixture of calcium stearate and ziac stearate suspended ia epoxidized soya oil. Table 4 shows examples of typical mixed metal stabilizers. 

Cyanide Wastes. Ozone is employed as a selective oxidant in laboratory-scale synthesis (7) and in commercial-scale production of specialty organic chemicals and intermediates such as fragrances, perfumes (qv), flavors, antibiotics (qv), hormones (qv), and vitamins (qv). In Japan, several metric tons per day (t/d) of piperonal [120-57-0] (3,4-methylenedioxybenzaldehyde) is manufactured in 87% yield via ozonolysis and reduction of isosafrole [93-16-3], Piperonal (or heHotropine [120-57-0]) has a pleasant odor and is used in perfumery. Oleic acid [112-80-1/, CH3(CH2 )7CH—CH(CH2 ). C02H, from tall oil (qv) is ozonated on a t/d scale to produce pelargonic, GgH2yG02H, and azelaic, H02G(GH2)yG02H, acids. Oleic acid also is ozonated in Japan... 

The most commonly used emulsifiers are sodium, potassium, or ammonium salts of oleic acid, stearic acid, or rosin acids, or disproportionate rosin acids, either singly or in mixture. An aLkylsulfate or aLkylarenesulfonate can also be used or be present as a stabilizer. A useful stabilizer of this class is the condensation product of formaldehyde with the sodium salt of P-naphthalenesulfonic acid. AH these primary emulsifiers and stabilizers are anionic and on adsorption they confer a negative charge to the polymer particles. Latices stabilized with cationic or nonionic surfactants have been developed for special apphcations. Despite the high concentration of emulsifiers in most synthetic latices, only a small proportion is present in the aqueous phase nearly all of it is adsorbed on the polymer particles. 

Four columns are needed to produce the desired products. Considering the Sharp Distillation Sequencing heuristics, heuristic (/) does not apply, as there is more than one product in this mixture. Fatty acids are moderately corrosive, but none is particularly more so than the others, so heuristic (2) does not apply. The most volatile product, the caproic and capryflc mixture, is a small (10 mol %) fraction of the feed, so heuristic (3) does not apply. The least volatile product, the oleic—stearic acids, is 27% of the feed, but is not nearly as large as the capric—lauric acid product, so heuristic (4) does not apply. The spht between lauric and myristic acids is closest to equimolar (55 45) and is easy. Therefore, by heuristic (5) it should be performed first. The boiling point list implies that the distillate of the first column contains caproic, capryflc, capric, and lauric acids. This stream requires only one further separation, which by heuristic (/) is between the caproic—capryflc acids and capric—lauric acids. 

The most volatile product (myristic acid) is a small fraction of the feed, whereas the least volatile product (oleic—stearic acids) is most of the feed, and the palmitic—oleic acid split has a good relative volatility. The palmitic—oleic acid split therefore is selected by heuristic (4) for the third column. This would also be the separation suggested by heuristic (5). After splitting myristic and palmitic acid, the final distillation sequence is pictured in Figure 1. Detailed simulations of the separation flow sheet confirm that the capital cost of this design is about 7% less than the straightforward direct sequence. 

Sulfated Natural Oils and Fats. Sulfated natural triglycerides were the first nonsoap commercial surfactants introduced in the middle of the nineteenth century. Since then sulfates of many vegetable, animal, and fish oils have been investigated (see also Fats AND FATTY oils). With its hydroxyl group and a double bond, ricinoleic acid (12-hydroxy-9,10-octadecenoic acid) is an oil constituent particularly suited for sulfation. Its sulfate is known as turkey-red oil. Oleic acid is also suited for sulfation. Esters of these acids can be sulfated with a minimum of hydrolysis of the glyceride group. Polyunsaturated acids, with several double bonds, lead to dark-colored sulfation products. The reaction with sulfuric acid proceeds through either the hydroxyl or the double bond. The sulfuric acid half ester thus formed is neutralized with caustic soda ... 

The physical properties of the fatty acid ethoxylates depend on the nature of the fatty acid and even more on ethylene oxide content. As the latter increases, consistencies of the products change from free-flowing Hquids to slurries to firm waxes (qv). At the same time, odor, which is characteristic of the fatty acid, decreases in intensity. Odor and color stabiUty are important commercial properties, particularly in textile appHcations. Oleic acid esters, though possessing good functional properties, cannot be used because they tend to yellow on exposure to heat and air. 

When tallow fatty acids are the feed, stearic acid (actually 60/40 C16/C18) and oleic acids are the products. Solvent separation is also used to separate stearic acid from isostearic acid when hydrogenated monomer is the feed, and oleic acid from linoleic acid when using tall oil fatty acids as feed. 

Rhodium catalyst is used to convert linear alpha-olefins to heptanoic and pelargonic acids (see Carboxylic acids, manufacture). These acids can also be made from the ozonolysis of oleic acid, as done by the Henkel Corp. Emery Group, or by steam cracking methyl ricinoleate, a by-product of the manufacture of nylon-11, an Atochem process in France (4). Neoacids are derived from isobutylene and nonene (4) (see Carboxylic acids, trialkylacetic acids). 

Unhardeaed whole cut tallow and palm acids contain 40—45% oleic acid, which is derived by separation technology. This used to be done by a pressing technique thereby the terminology pressed stearics. In the 1990s the separation is done usiag solvents and/or refrigeration techniques. Oleic and pressed stearics account for about one-third of all U.S. acid production. 

Tall oil fatty acids (TOFA) consist primarily of oleic andlinoleic acids and are obtained by the distillation of crude tall oil. Crude tall oil, a by-product of the kraft pulping process, is a mixture of fatty acids, rosin acids, and unsaponiftables (1). These components are separated from one another by a series of distillations (2). Several grades of TOFA are available depending on rosin, unsap oniftable content, color, and color stabiUty. Typical compositions of tall oil fatty acid products are shown in Table 1 (see Tall oil). 

G-19 Dicarboxylic Acids. The C-19 dicarboxyhc acids are generally mixtures of isomers formed by the reaction of carbon monoxide on oleic acid. Since the reaction produces a mixture of isomers, no single chemical name can be used to describe them. Names that have been used include 2-nonyldecanedioic acid, 2-octylundecanedioic acid, l,8-(9)-heptadecanedicarboxyhc acid, and 9-(10)-carboxystearic acid. The name 9-(10)-carboxystearic acid can be used correctiy if the product is made with no double bond isomerization (rhodium triphenylphosphine catalyst system). 

C-21 dicarboxyhc acids are produced by Westvaco Corporation in Charleston, South Carolina in multimillion kg quantities. The process involves reaction of tall oil fatty acids (TOFA) (containing about 50% oleic acid and 50% hnoleic acid) with acryhc acid [79-10-7] and iodine at 220—250°C for about 2 hours (90). A yield of C-21 as high as 42% was reported. The function of the iodine is apparendy to conjugate the double bond in linoleic acid, after which the acryhc acid adds via a Diels-Alder type reaction to form the cycHc reaction product. Other catalysts have been described and include clay (91), palladium, and sulfur dioxide (92). After the reaction is complete, the unreacted oleic acid is removed by distillation, and the cmde C-21 diacid can be further purified by thin film distillation or molecular distillation. 

The dimer acids [61788-89-4] 9- and 10-carboxystearic acids, and C-21 dicarboxylic acids are products resulting from three different reactions of C-18 unsaturated fatty acids. These reactions are, respectively, self-condensation, reaction with carbon monoxide followed by oxidation of the resulting 9- or 10-formylstearic acid (or, alternatively, by hydrocarboxylation of the unsaturated fatty acid), and Diels-Alder reaction with acryUc acid. The starting materials for these reactions have been almost exclusively tall oil fatty acids or, to a lesser degree, oleic acid, although other unsaturated fatty acid feedstocks can be used (see Carboxylic acids. Fatty acids from tall oil Tall oil). 

Most of the products Hsted in Tables 1—3 are based on manufacture from tall oil fatty acids. Dimer acids based on other feedstocks (eg, oleic acid) may have different properties. A European manufacturer recently announced availabiUty of a 44-carbon dimer acid, presumably made from an emcic acid feedstock (7). 

Examples are given of common operations such as absorption of ammonia to make fertihzers and of carbon dioxide to make soda ash. Also of recoveiy of phosphine from offgases of phosphorous plants recoveiy of HE oxidation, halogenation, and hydrogenation of various organics hydration of olefins to alcohols oxo reaction for higher aldehydes and alcohols ozonolysis of oleic acid absorption of carbon monoxide to make sodium formate alkylation of acetic acid with isobutylene to make teti-h ty acetate, absorption of olefins to make various products HCl and HBr plus higher alcohols to make alkyl hahdes and so on. 

Azelaic acid is made by the ozonolysis of another natural product, oleic acid ... 

There has been only one major use for ozone today in the field of chemical synthesis the ozonation of oleic acid to produce azelaic acid. Oleic acid is obtained from either tallow, a by-product of meat-packing plants, or from tall oil, a byproduct of making paper from wood. Oleic acid is dissolved in about half its weight of pelargonic acid and is ozonized continuously in a reactor with approximately 2 percent ozone in oxygen it is oxidized for several hours. The pelargonic and azelaic acids are recovered by vacuum distillation. The acids are then esterified to yield a plasticizer for vinyl compounds or for the production of lubricants. Azelaic acid is also a starting material in the production of a nylon type of polymer. 

Polyunsaturated fatty acids pose a slightly more complicated situation for the cell. Consider, for example, the case of linoleic acid shown in Figure 24.24. As with oleic acid, /3-oxidation proceeds through three cycles, and enoyl-CoA isomerase converts the cA-A double bond to a trans-b double bond to permit one more round of /3-oxidation. What results this time, however, is a cA-A enoyl-CoA, which is converted normally by acyl-CoA dehydrogenase to a trans-b, cis-b species. This, however, is a poor substrate for the enoyl-CoA hydratase. This problem is solved by 2,4-dienoyl-CoA reductase, the product of which depends on the organism. The mammalian form of this enzyme produces a trans-b enoyl product, as shown in Figure 24.24, which can be converted by an enoyl-CoA isomerase to the trans-b enoyl-CoA, which can then proceed normally through the /3-oxidation pathway. Escherichia coli possesses a... 

Fats can be either optically active or optically inactive, depending on their structure. Draw the structure of an optically active fat that yields 2 equivalents of stearic acid and 1 equivalent of oleic acid on hydrolysis. Draw the structure of an optically inactive fat that yields the same products. 

Even today renewable resources play a dominant role as raw materials for surfactants, but only because of the great contribution made by soaps to the production of surfactants. If the soaps are left out of consideration as native surfactants, petrochemistry holds 65-70% of the production of synthetic surfactants [2]. But for the future a further increase of renewable raw materials is expected in surfactant production [3]. The main reason for this development is the superior digestibility in the environment of products produced from natural materials. The future importance of the renewable raw materials becomes evident from the fact that even now new plants are cultivated or plants are modified to obtain an improved yield. A new type of sunflower has been cultivated to obtain a higher proportion of monounsaturated oleic acid compared with doubly unsaturated linoleic acid [4],... 

Sulfosuccinates are not only less irritating to skin and mucus membranes than other surfactants, but it was also found that they reduce skin irritation of other surfactants used in skin and hair care products. In particular, the effect on sodium lauryl ether sulfate was found to be most pronounced [103]. Figure 14 shows the mollifying effect of disodium oleic acid monoethanol amide sulfo-succinate when blended with anionic surfactant at a total concentration of 15%. 

The production of fatty acid-capped silver nanoparticles by a heating method has been reported [115]. Heating of the silver salts of fatty acids (tetradecanoic, stearic, and oleic) under a nitrogen atmosphere at 250°C resulted in the formation of 5-20-nm-diameter silver particles. Monolayers of the capped particles were spread from toluene and transferred onto TEM grids. An ordered two-dimensional array of particles was observed. The oleic acid-capped particle arrays had some void regions not present for the other two fatty acids. 

Dimerization of unsaturated fatty acids, to. so-called dimer acids, is widely practised in industry, where acid-treated clays are invariably used as a catalyst. In the case of oleic acid the major products are dimers, trimers, and isosteric acid. Koster et al. (1998) have investigated the relative importance of the various acid sites as well as structural and textural parameters of montmorrilonite. The interlamellar space dominates the oleic acid dimerization and the active site is the tetrahedrol substitution site. 

Separation of fatty acids (Ruthven, 1997). Tall oil from the pulp and paper industry is subjected to separation of rosin acid, linoleic acid, oleic acid, and neutral compounds. Distillation at reduced pressure is u.sed, but this leads to degradation of products. A Sorbex process eliminates this problem. 

The first example of a heterogeneously catalyzed hydroamination of an alkene appeared in a 1929 patent in which it is claimed that NHj reacts with ethylene (450°C, 20 bar) over a reduced ammonium molybdate to give EtNH2 [24]. An intriguing reaction was also reported by Bersworth, who reacted oleic acid with NH3 in the presence of catalysts like palladium or platinum black or copper chromite to give the hydroamination product in quantitative yields [25]. However, this result could not be reproduced [26]. 

E. A. Konovalov, Y. A. Ivanov, T. N. Shumilina, V. F. Pichugin, and N. N. Komarova. Lubricating reagent for drilling solutions—contains agent based on spent sunflower oil, water, vat residue from production of oleic acid, and additionally water glass. Patent SU 1808861-A, 1993. 

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