Polyesteramides from linseed oil for protective coatings low acid-value polymers

Linseed and soybean diethanolamides, from the sodium alkoxide-catalyzed reaction of the corresponding oil with diethanolamine, were used as diols to prepare a series of polyesteramides. The diols and dibasic acids or anhydrides were heated in refluxing xylene until the theoretical amount of water was collected in a trap. Low acid-value linseed polymers were prepared with 10, 20, and 30 mole percent excess diol over the dibasic acid, and the effect of the excess diol on molecular weight, viscosity, and film properties of the polymers was examined. Polyesteramides which contained 10 mole percent excess fatty diethanolamide were made with 11 dibasic acids or anhydrides. The polymers were brown-orange oils with Gardner viscosities of Z7 to >>Z10. Number-average molecular weights ranged from 2,200 to 5,200. Data on drying characteristics, hardness, and chemical resistance of films were obtained. The better polymers air-dried rapidly to give hard, glossy films (Sward rocker 20–60). Films baked at 190C for 10 min were softer than the corresponding air-dried films. Xylene resistance of soybean and linseed polymer films was generally excellent, and alkali resistance was moderate. Soybean films showed the better alkali resistance. Presented at Division of Organic Coatings and Plastics Chemistry, 153rd ACS meeting, Miami Beach, Fla., April 1967. No. Utiliz. Res. Dev. Div., ARS, USDA.     

Cyclic fatty acid yields from linseed oil

Increased yields of saturated cyclic fatty acids which are fluid at −50C have been obtained from linseed oil. Depending on reaction conditions, yields varied from 20–42 g of cyclic acids per 100 g of linseed oil. Solvent ratios of 6, 3, and 1.5∶1; catalyst concentrations of 10, 30, 60, and 100%; and reaction temps of 225, 275, 295, and 325C were evaluated. Ethylene glycol and diethylene glycol were compared as reaction solvents. In general, high solvent ratios favored high cyclic acid yields at the lower reaction temperature, but as the temperature increased the effect of solvent ratio decreased. Increasing the percentage excess of sodium hydroxide increased the cyclic acid yield. Diethylene glycol gave higher yields than ethylene glycol at comparable conditions. Presented at the AOCS meeting in Chicago, Ill., October, 1961. A laboratory of the No. Utiliz. Res. & Dev. Div., ARS, U.S.D.A.     

Amides ofa-sulfonated palmitic and stearic acids

Summary Carboxylic acid amides of α-sulfopalmitic and α-sulfostearic acids were prepared from ammonia, ethylamine, ethanolamine, isopropylalcoholamine, diethanolamine, and N-methyltaurine, and were isolated as the sodium, ammonium, or ethanolammonium salt. A satisfactory method was found to be the reaction of the sulfocarboxylic acid with an excess of thionyl chloride, and further reaction of the acid chloride with an amine in a chlorinated solvent. More work is needed on the application of direct amidation methods to the preparation of these compounds. The solubility of the α-sulfonated amides increased with substitution of alkyl, hydroxyalkyl, and sulfoalkyl groups at the nitrogen atom. Ethanolammonium N-hydroxyethyl-α-sulfopalmitamide, ethanolammonium N-hydroxyethyl-α-sulfostearamide, sodium N-(2-hydroxypropyl)-α-sulfostearamide, sodium di-(N-hydroxyethyl)-α-sulfostearamide, and disodium N-methyl,N-(2-sulfoethyl)-α-sulfostearamide have aqueous solubility in excess of 10% at room temperature. Most of the sodium salts of the α-sulfonated amides have good or excellent stability to calcium and other divalent ions and are excellent lime soap dispersing agents. Presented at the fall meeting, American Oil Chemists' Society, Los Angeles, Calif., September 28–30, 1959. Enstern Utilization Research and Development Division, Agricultural Research Service, U. S. Department of Agriculture.     

Rigid polyurethane foams from diethanolamides of carboxylated oils and fatty acids

New polyols of high hydroxyl content and reactivity were made from linseed and soybean oils and acids by catalytic carboxylation followed by reaction with diethanolamine. Urethane foams made with these diethanolamides were stronger than those made with castor oil at equivalent polyol wt. Because of their higher hydroxyl content, a larger amount of diethanolamides could be incorporated in foam formulations than is possible with castor oil. The rigid urethane foams prepared with the new polyols meet the requirements of commercial products with respect to density, compressive strength, and dimensional stability. National Flaxseed Processors Association Fellow, 1969–1973. Present address: Avery Products, Technical Center, 325 North Altadena Dr., Pasadena, CA 91107.     

Methods for improving yields of cyclic acid from linseed oil

Liquid C-18 saturated monocarboxylic acids, which are termed “cylic acids” because they contain a ring structure, have been prepared by the action of excess sodium hydroxide on linseed oil in ethylene glycol at elevated temperatures, followed by distillation and hydrogenation of the resulting free fatty acid monomers and by separation of the straight-chain components by low-temperature crystallization from acetone. In a survey of other possible catalysts and reaction conditions, cyclic acid yields were improved from the previously reported 32.4 g to 43.5 g of cyclic acid per 100 g of linseed fatty acids by removing water from the starting materials and using the monosodium derivative of ethylene glycol as catalyst. The corresponding amount of polymer formed decreased because of a decrease in hydroxylation and subsequent polyester formation. Presented at the AOCS meeting, in Chicago, Ill., 1961. A laboratory of the No. Utiliz. Res. & Dev. Div., ARS, U.S.D.A.     

Continuous high temperature preparation of alkylolamides

Lauric diethanolamide was prepared from methyl laurate and diethanolamine in the presence of an alkaline catalyst by a continuous high temperature process. The conventional batch process requires cycle times of 2–6 hr which can lead to undesirable by-products. With a reaction time of about 10 sec, product purity of 91–94% was obtained at 149C for an absolute pressure range of 10–760 mm Hg. When reaction temperature was lowered to 110C, product purity became poorer as the absolute pressure was increased from 30 mm Hg to 760 mm Hg. Two studies for optimum catalyst content of either KOH or sodium methylate showed that maximum product purity of about 97% was obtained at 0.20% catalyst by weight. *** DIRECT SUPPORT *** A03O2184 00003     

Enhanced oil recovery using carboxylate surfactant systems

Oil displacement tests in water wet Berea sandstone cores containing residual crude oil flooded with water have shown that high tertiary oil recoveries can be obtained using the sodium salts of readily available carboxylic acids. Using a 10% pore volume surfactant slug containing 3.0% sodium isostearate and 3.0% isopentyl alcohol followed by a polyacrylamide mobility buffer resulted in a 92% tertiary oil recovery, which compares well with recoveries using petroleum solfonates. Oil recoveries were highly dependent on pH and added base. Aliphatic C18 carboxylates gave higher recoveries at lower pH using sodium bicarbonate as the added base (pH 8.5) rather than sodium hydroxide, sodium carbonate or sodium orthosilicate (pH 11–13). In contrast, aromatic carboxylates e.g., sodium p-(1-pentylnonyl)benzoate, gave higher recoveries at higher pH using sodium carbonate rather than sodium bicarbonate. Carboxylates with branched alkyl groups, e.g., isostearate, gave higher tertiary oil recoveries than unbranched carboxylates, e.g., oleate or stearate. Low cost tall oils and tall-oil fatty acids, when neutralized with base, gave oil recoveries of 60–80%. Carboxylates were found to give good oil recoveries even when significant amounts of calcium ion were present.     

Liquid C-18 saturated acids derived from linseed oil

Liquid C-18 saturated monocarboxylic acids that fail to crystallize at −70°C. have been prepared from linseed oil, linolenic acid, and tung oil. Heating one part of linseed oil in three parts of glycol (weight-volume ratio) at 295°C. for 1 hr. with 25% excess sodium hydroxide, followed by distillation and hydrogenation of the resulting free fatty acid monomers and separation of the straight-chain components by low temperature crystallization from acetone, yielded these liquid acids. The relative proportions of cyclic acids, straight-chain monomeric acids, and polymer varied with the type of starting material and with the conditions employed. Cyclic acids in excess of 30% yields were obtained from linseed oil. Some hydroxylation of the fatty acids apparently takes place during cyclization; the amount increases with ascending temperatures, as evidenced by a rise in polyester content of the polymer fraction. Evidence indicates that the bulk of the unhydrogenated cyclic acids are vicinal disubstituted cyclohexadienes. Gas chromatography of the cyclic acids hydrogenated to an iodine value <1 shows that there are several components. These have not as yet been separated and positively identified. Presented at fall meeting, American Oil Chemists' Society, New York, N.Y., October 17–19, 1960. This is a laboratory of the Northern Utilization Research and Development Division, Agricultural Research Service, U.S. Department of Agriculture.     

Production of structured lipids containing essential fatty acids by immobilizedRhizopus delemar lipase

An attempt was made to produce structured lipids containing essential fatty acid by acidolysis with 1,3-positional specificRhizopus delemar lipase. The lipase was immobilized on a ceramic carrier by coprecipitation with acetone and then was activated by shaking for 2 d at 30°C in a mixture of 5 g safflower or linseed oil, 10 g caprylic acid, 0.3 g water and 0.6 g of the immobilized enzyme. The activated enzyme was transferred into the same amount of oil/caprylic acid mixture without water, and the mixture was shaken under the same conditions as for the activation. By this reaction, 45–50 mol% of the fatty acids in oils were exchanged for caprylic acid, and the immobilized enzyme could be reused 45 and 55 times for safflower and linseed oils, respectively, without any significant loss of activity. The triglycerides were extracted withn-hexane after the acidolysis and then were allowed to react again with caprylic acid under the same conditions as mentioned above. When acidolysis was repeated three times with safflower oil as a starting material, the only products obtained were 1,3-capryloyl-2-linoleoylglycerol and 1,3-capryloyl-2-oleoyl-glycerol, with a ratio of 86∶14 (w/w). Equally, the products from linseed oil were 1,3-capryloyl-2-α-linolenoyl-glycerol, 1,3-caprylol-2-linoleoyl-glycerol, and 1,3-capryloyl-2-oleoly-glycerol (60∶22∶18, w/w/w). All fatty acids at the 1,3-positions in the original oils were exchanged for caprylic acid by the repeated acidolyses, and the positional specificity ofRhizopus lipase was also confirmed to be strict.     

Application of urea complexes in the purification of fatty acids,esters, and alcohols. III. Concentrates of natural linoleic and linolenic acids

Summary Concentrates of natural linoleic acid (linoleic acid content, 85–95%) have been prepared in 50–72% yields from corn oil fatty acids by preferential precipitation of the saturated and monounsaturated fatty acids at room temperature as their urea complexes. By a similar procedure, concentrates of natural linolenic acid (linolenic acid content, 87–89%) have been prepared in 55–61% yields from perilla oil fatty acids by preferential precipitation of the saturated, monounsaturated, and diunsaturated fatty acids. Although concentrates of natural linolenic acid containing only 66–70% linolenic acid were obtained from linseed oil fatty acids, yields were 87–90%. A levelling-off effect has been observed in the use of the preferential precipitation technique in raising the purity of concentrates of linoleic and linolenic acid. This parallels the experience in the purification of these acids by low-temperature crystallization. The preceding papers in this series are references 12 and 13. Presented at the Fall Meeting of the American Oil Chemists' Society, Cincinnati, O., Oct. 20–22, 1952. One of the laboratories of the Bureau of Agricultural and Industrial Chemistry, Agricultural Research Administration, U. S. Department of Agriculture.     

棉籽油酸二乙醇酰胺的合成及应用研究

提出一步法由棉籽油酸甲酯与二乙醇胺缩合高选择性地合成棉籽油酸二乙醇酰胺的工艺。适宜的一步法工艺条件是：０７％ＫＯＨ、７０℃、稍减压（残压约７３ｋＰａ）、反应２ｈ。实验室制备的１∶１６型棉籽油酸二乙醇酰胺接近椰子油酸二乙醇酰胺的去污力,它与ＴＸ １０及烷基苯磺酸钠共用可使０＃柴油形成微乳液,它能使普通碳钢耐５ｍｏｌ／Ｌ盐酸的锈蚀。     

Determination of seventeen elements in edible oils and margarine by instrumental neutron activation analysis

Instrumental neutron activation analysis was used to determine the concentration of As, Ba, Ce, Co, Cr, Cs, Eu, Fe, Hg, K, Na, Rb, Sb, Sc, Se, Sr and Zn in almond, sunflower, peanut, sesame, linseed, soy, corn and olive oils, as well as in three margarine brands. The concentration of As, Ba, Ce, Cs, Eu, Hg, Rb, Se and Sr were below the system detection limit under the experiment conditions. Chromium was detected only in one of the margarine samples (171 μg/g); Sb only in corn oil (18 ng/g) and Sc only in linseed oil (19 ng/g). Cobalt, Fe, K, Na and Zn were detected in all oil and margarine samples investigated. The concentration ranges for Co, Fe, K, Na and Zn in oils were: 0.016–0.053; 4.45–19.1; 5.93–47.2; 2.44–12.9 and 0.48–1.54 μg/g, respectively. For margarine, the concentration ranges for Co, Fe, K, Na and Zn were 0.09–0.012; 4.53–10.6; 58.3–1140; 13.2–9870 and 0.38–0.47 μg/g, respectively. The elemental contents of the analyzed samples are within the ranges reported in the literature for edible oils and fats.     

Gas chromatographic separation of cholesteryl esters of fatty acids of different degrees of unsaturation

Cholesteryl esters prepared from the fatty acid methyl esters of linseed oil, pig liver lipids, and Japanese anchovy oil have been separated on the basis of their chain lengths and number of double bonds by gas lipid chromatography on a cyanosiloxane SILAR 10C column. The equivalent chain lengths of cholesteryl esters having acyl groups with 14–22 carbons and 0–6 double bonds are presented. A significant influence of the column temperature on the equivalent chain lengths of the polyenoic fatty acid cholesteryl esters has been found. Separation of the cholestanyl and epicholestanyl esters of linseed oil fatty acids, respectively, under the same conditions is also described.     

Preparation of Diacylglycerol-Enriched Oil from Free Fatty Acids Using Lecitase Ultra-Catalyzed Esterification

Production of diacylglycerol-enriched oil by esterification of free fatty acids (FFA) with glycerol (GLY) using phospholipase A1 (Lecitase Ultra) was investigated in this work. The variables including reaction time (2–10 h), water content (2–14 wt%, FFA and GLY mass), enzyme load (10–120 U/g, FFA and GLY mass), reaction temperature (30–70 °C) and mole ratio of GLY to FFA (0.5–2.5) were studied. The optimum conditions obtained were as follows: reaction temperature 40 °C, water content 8 wt%, reaction time 6 h, molar ratio of GLY to FFA 2.0, and an enzyme load of 80 U/g. Under these conditions, the esterification efficiency (EE) of free fatty acids was 74.8%. The compositions of the FFA and acylglycerols of the upper oil layer (crude diacylglycerol) of the reaction mixture were determined using a high temperature gas chromatograph (GC). The crude diacylglycerol from the selected conditions was molecularly distilled at 170 °C evaporator temperatures to produce a diacylglycerol-enrich oil (DEO) with a purity of 83.1% and a yield of 42.7%.     

Catalytic carboxylation of fats: Carboxy acids from polyunsaturates

Studies with a palladium chloride-triphenylphosphine catalyst have been extended to the carboxylation of polyunsaturated fats. Linseed, soybean, and safflower oils, acids, and esters were carboxylated catalytically with water-carbon monoxide (4000 psig) at 120–160 C with or without acetone as a solvent. Main products were monocarboxy, 1,3- and 1,4-dicarboxy and tricarboxy acids. Minor products were carbomethoxy esters and disubstituted 2-cyclopentenone. Optimum reaction conditions were determined for the carboxylation of linseed oil and methyl esters by statistically designed experiments. Yields of total carboxy and tricarboxy acids were maximized at low triphenylphosphine and water levels, low temperatures, and high palladium-chloride concentrations. Carboxylated soybean esters were separated by ether extraction of the palladium catalyst from sodium carbonate or hydroxide carboxylate salts. This salt extraction permits catalyst recycling. Presented at the AOCS Spring Meeting, Mexico City, April 1974. Biometrician, North Central Region, USDA. ARS, USDA.     

Further studies on the isomerization of polyunsaturated fatty acids by potassium tertiary butoxide

Summary A temperature and time study revealed that the best conditions for the isomerization and estimation of polyunsaturated acids are heating in a sealed tube for 2 hrs. at 140° with potassium-t-butoxide in t-butanol. Under these conditions conjugation of linolenic and arachidonic acids appears to have attained completion. With linoliec acid a higher degree of conjugation than by other methods and a shift of peak to lower wavelength (231–232 mμ) are observed. Extinction coefficients obtained by this method for isomerized pure linoleic (k₂₃₂, 98.0) and linolenic (k₂₆₈, 138.4) acids are the highest so far reported. Ultraviolet and infrared examination of the conjugated trienes isolated from isomerized linolenic acid concentrate showed that, under these conditions, trienes similar to both alpha- and beta-eleostearic acids are produced. Analyses of samples of oils for component polyunsaturated acids, by this method, compare well with those by other methods. The presence of small amounts of a tetraenoic acid in linseed oil is noted. Postdoctoral Fellow in physiological chemistry. This work was supported in part from funds granted by the Ohio State University Research Foundation to the university for aid in fundamental research. Presented at the 31st Fall Meeting of the American Oil Chemists' Society, Cincinnati, O., September 30 to October 2, 1957.     

Partial hydrogenation of linseed oil by a continuous process

Summary Alkali refined linseed oil was partially hydrogenated, using both continuous and batch processes. The continuous process was carried out in a series of Votator machines, using Rufert nickel catalyst, presures up to 145 psig. and temperatures up to 400°F. The continuous hydrogenation of linseed oil under the most selective conditions possible, using the Votator equipment, shows little selectivity between the linolenic and linoleic acid radicals. A pronounced selectivity is observed between oleic and the more unsaturated acid radicals. Under selective conditions of hydrogenation of linseed oil about 31% of the hydrogenated linolenic acid radical is transformed into 9–15 linoleic acid while the remainder of the linolenic acid goes to oleic acid in either one or two steps. Batch hydrogenation yields oils of superior nonyellowing characteristics over comparable oils prepared by the continuous process. The hydrogenated linseed oils were tested in both clear and pigmented alkyds where they displayed superior non-yellowing characteristics over the original linseed oil and, in many instances, over that of soya bean oil. The yellowing of oils and alkyds appears to be a function of both 1) the quantity of fatty acids more unsaturated than oleic present in the oil and 2) the ratio of the quantity of linolenic acid radicals to linoleic acid radicals present. Presented at 21st fall meeting, American Oil Chemists' Society, Chicago, Oct. 20–22, 1947.     

The elimination of flavor reversion in linseed shortening by heat polymerization and solvent segregation of the oil

Summary The optimum conditions have been established for the high temperature polymerization and solvent segregation of linseed oil to produce a “non-reverting” edible shortening and an improved drying oil. The best oil is obtained by heating at 270–275° C. for 12–15 hours while carbon dioxide is continuously passed through the oil. Under these conditions the polymerized oil has a refractive index of 1.4858 to 1.4861 at 25° C. and yields 60–65% of acetone soluble oil with a refractive index of 1.4830 to 1.4834 at 25° C. and an acid value of less than 1%, calculated as oleic acid. Pie crusts containing shortenings made from the acetone soluble fraction of the oil have been judged to be of good quality. The best shortenings were obtained by hydrogenating to a refractive index of 1.4615-1.4605 (60° C.). Macodonald College Journal Series No. 209. Issued as paper No. 145 of the Canadian Committee on Food Preservation.     

Segregation of fatty acids by preferential neutralization

Summary It has been shown that soybean fatty acids neutralized with a mixture of 40% of sodium hydroxide and 60% of barium hydroxide (on equivalent basis) form about 35% soluble soaps, which after separating from the insoluble soaps and splitting with sulfuric acid, form fatty acids of about 165 iodine number. From these acids a synthetic drying oil was prepared by esterification with glycerol which formed films almost as good as those of linseed oil. It was also shown that the same process applied to fish oil fatty acids, but using in this case 60% of sodium hydroxide and 40% of barium hydroxide, resulted in a yield of about 50% of fatty acids of about 283 iodine number, which when esterified with glycerol gave a very fast drying synthetic drying oil forming tack-free films. Presented at 22nd fall meeting, American oil Chemists' Society, New York City, Nov. 15–17, 1948.     

Urethane foams from animal fats: IX. Polyols based upon tallow and trimethylolpropane; preparation under acidic and basic catalysis

A series of polyols was prepared from epoxidized tallow, by reaction with trimethylolpropane in refluxing toluene, sequentially under basic and acidic catalysis. In preliminary experiments, under catalysis by sodium methoxide alone, the trimethylolpropane reacted rapidly with glyceride linkages and very slowly with oxirane groups. Under catalysis by p-toluenesulfonic acid alone, oxirane was rapidly consumed. Polyols were prepared by the following sequences: (A) reaction under acidic followed by basic catalysis; (B) reaction under basic followed by acidic catalysis; (C) reaction under basic catalysis followed by further treatment with HBr gas to introduce fire retardance; (D) treatment of whole tallow first with trimethylolpropane under basic conditions and secondly with bromine; (E) reaction of epoxidized tallow with diethanolamine under basic catalysis; and (F) treatment of epoxidized tallow first with trimethylolpropane under acidic conditions and then with diethanolamine under basic catalysis. The polyols described were adjusted to equivalent weights of 100 and 120 with added triisopropanolamine and treated with a polymeric isocyanate to give rigid foams. Densities ranged from 1.5–1.8 lb/ft³. Open cell content, for foams made at the equivalent wt of 100, ranged from 14–21%; at the equivalent wt of 120, from 17–27%. Compressive strengths ranged from 14–23 psi, being lower than those of the best previous epoxidized tallow-trimethylolpropane products. Presented at the AOCS Meeting, Mexico City, Mexico, May 1974. ARS, USDA.