Synthetic detergents from animal fats. VI. Polymerizable esters of alpha-sulfonated fatty acids

Summary Sodium allyl α-sulfopalmitate and sodium allyl α-sulfostearate, prepared by esterification of an α-sulfonated fatty acid with allyl alcohol, resemble sodium alkyl α-sulfopalmitates and stearates in surface-active and detergent properties and stability to hydrolysis. The allyl esters are easily converted to a new type of water-soluble polymer. The polymers may be thickening and emulsifying agents and may have other uses yet to be discovered. Presented at the meeting of American Oil Chemists’ Society, Philadelphia, Pa., October 10–12, 1955. A laboratory of the Eastern Utilization Research Branch, Agricultural Research Service, U. S. Department of Agriculture.     

Reactions of polyunsaturated fatty alcohols. IX. Molecular-weight distribution of some conjugated soybean vinyl ether homopolymers

The molecular-weight distributions of several conjugated soybean vinyl ether homopolymers were studied by means of the integral fractionation technique. Polymers having number average molecular weights of 2,200, 4,800 and 10,000 prepared with stannic chloride as catalyst as well as a polymer having a molecular weight of 3,400 prepared with boron trifluoride as catalyst were included in the study. The observed distributions for all the polymers were found to approximate the socalled “most probable” distributions expected theoretically for polymers obtained by simple difunctional polymerization. Presented at annual meeting. American Oil Chemists' Society, New Orleans, La., April 20–22, 1959. This is a laboratory of the Northern Utilization Research and Development Division, Agricultural Research Service, U. S. Department of Agriculture.     

Search for new industrial oils. VII

Seed oils from 37 plant species in 18 families have been analyzed for fatty acid composition by the isomerization method. The variability encountered is evidenced by the range in content of component acids: from 0–23% for apparent linolenic acid, from 8–74% for apparent linoleic acid, and from 2–88% for apparent oleic acid. Dimorphecolic acid has been found to the extent of approximately 60% in a second species ofDimorphotheca, D. pluvialis (L.) Moench, and in the closely related species,Osteospermum ecklonis (DC.) T. Norl.O. spinescens Thunb. contained instead 30% of a conjugated triene, presumably the same as the 8,10,12-octadecatrienoic reported from the relatedCalendula officinalis L. Oils rich in monoenoic acids are mostly in the Umbelliferae and Araliaceae and presumably contain petroselinic acid as well as oleic. Presented at the AOCS meeting in St. Louis, Mo., May 1–3, 1961. A laboratory of the Northern Utilization Research and Development Division, Agricultural Research Service, U.S.D.A. Agricultural Research Service, U.S.D.A.     

Fractionation of animal fat glycerides by crystallization from acetone. Am improved lard oil

Summary Various edible and inedible grades of animal fats, such as lard, grease, tallow, and selectively hydrogenated lard, grease and tallow were separated into “oils” and “stearins” by crystallization from acetone. The chemical and physical properties as well as the yields of oils and stearins obtained by this method are described. Antioxidants and metal deactivators are much more effective in stabilizing lard and grease oils produced from partially hydrogenated fats than in stabilizing corresponding products from unhydrogenated fats. Report of a study certain phases of which were made under the Research and Marketing Act of 1946. One of the laboratories of the Bureau of Agricultural and Industrial Chemistry, Agricultural Research Administration, United States Department of Agriculture.     

Synthetic detergents from animal fats. V. Esters from alpha-sulfonated fatty acids and sodium isethionate

Summary Disodium 2-sulfoethyl α-sulfopalmitate, disodium 2-sulfoethyl α-sulfostearate, and disodium 2-sulfoethyl α-sulfobehenate were prepared by esterification of the corresponding α-sulfonated acid with sodium isethionate. Disodium 1-methyl-2-sulfoethyl α-sulfostearate was made from sodium 2-hydroxypropanesulfonate. The esters were found to be readily soluble surface-active agents and detergents, very responsive to building with inorganic phosphates and sulfates. Compared to sodium 2-sulfoethyl oleate the esters were readily prepared without the necessity of making the acid chloride; they were considerably more resistant to acid or alkaline hydrolysis; they were about equal in their excellent lime soap dispersing power, but inferior in foaming properties, producing a less permanent foam. The esters were easily soluble because of the presence of two sulfo groups and were improved detergents in the presence of inorganic builders. Mixtures of the palmitic and stearic acid derivatives, such as might be obtained from the saturated acids of tallow, containing a total of 20% active ingredient, were effective detergents in hard water. Disodium 1-methyl-2-sulfoethyl α-sulfostearate, an ester of a secondary alcohol, was even more resistant to alkaline hydrolysis than the esters from sodium isethionate. Presented at the meeting of the American Oil Chemists’ Society, New Orleans, April, 1955. A laboratory of the Eastern Utilization Research Branch, Agricultural Research Service, U. S. Department of Agriculture.     

Hydrogenation of linolenate. VI. Survey of commercial catalysts

A survey of commercially available hydrogenation catalysts has been made in a search for high-selectivity and low-isomerizing characteristics. Selectivity—the ratio of hydrogenation rates for linolenate to linoleate—was determined on a linoleate-linolenate equimixture under standardized conditions. Ratios of reaction rate constants for nickel catalysts at 140C ranged between 1.48 and 2.71; for palladium catalysts at 25C, 1.68 to 1.99; and for platinum catalysts at 25C, 1.33 to 1.61.Trans contents of ester mixtures reduced with these three metal catalysts ranged from 18.0 to 22.8, 16.7 to 20.5, and 6.3 to 8.4%, respectively. Although platinum catalysts produced the lowest isomerization, their selectivities were also low. Presented at Spring meeting, American Oil Chemists' Society, 1961. A laboratory of the Northern Utilization Research and Development Division. Agricultural Research Service, U.S.D.A.     

Glyceride structure of vegetable oils by countercurrent distribution. V. Comparison of natural,interesterified, and synthetic cocoa butter

The glyceride structure of cocoa butter is of considerable practical importance and of particular theoretical interest Countereurrent distribution, gas chromatography, and isotopic dilution methods are employed in its study. The observed fractionation of glycerides is acounted for by assuming that palmitie and stearic acids are randomly esterified on the 1 and 3 positions of glycerol and that oleic is on the 2 position, as demonstrated by other workers. Complete randomization of the specifie structure of cocoa butter through the application of interesterification eatalysts greatly alters its physical A glyceride synthesized according to the “1,3 random palmitostearo-2-olein” concept has properties similar to natural cocoa butter. Presented before Division of Agricultural and Food Chemistry, American Chemical Society Meeting, Cleveland, O., April 5–14, 1960. This is a laboratory of the Northern Utilization Research and Development Division, Agricultural Research Service, U.S. Department of Agriculture.     

Ozonization of soybean oil. The preparation and some properties of aldehyde oils

A polyaldehydie product called aldehyde oil was prepared by the ozonization of soybean oil, followed by reductive decomposition of the ozonolysis products. Reductive decomposition by chemical means gave 85–90% yields of carbonyl in the aldehyde oil. Catalytic reduction gave 75–80% yields. Partially-hydrogenated soybean oil gave more efficient results than did unhydrogenated oil. The polyfunctional aldehyde oil was found to undergo condensation reactions with phenolic compounds, urea, amines, and polyols to give cross-linked polymers. Presented at annual meeting, American Oil Chemists' Society, St. Louis, Mo., May 1–3, 1961. This is a laboratory of the Northern Utilization Research and Development Division, Agricultural Research Service, U.S. Department of Agriculture.     

Reactions of fatty materials with oxygen. XVII. Some observations on the secondary products of autoxidation of methyl oleate

Summary Methyl oleate, autoxidized for short and long periods of time, has been fractionated with urea. Up to a peroxide content of about 15% the autoxidation mixture can be cleanly separated into a peroxide concentrate containing 90% peroxide and unoxidized methyl oleate. From about 15% peroxide to the maximum peroxide content (35–40%) concentration to only about 70% peroxide can be obtained, and the remaining material is largely a mixture of oxygenated compounds and residual methyl oleate. If the autoxidation is conducted beyond the peak value in peroxide content, little, if any, concentration of peroxide can be obtained. Also, beyond the peak in peroxide value and in the range of 30–20% peroxide, methyl oleate is substantially absent and the autoxidation mixture consists almost entirely of oxygenated compounds containing only one functional group in the chain. Evidence is presented which shows that in the autoxidation of methyl oleate substantially all of it undergoes single attack by oxygen (or peroxides) before any significant quantity of multiple attack occurs. α,β-Unsaturated carbonyl compounds are among the important secondary products of autoxidation. Paper XVI is reference 14. Presented at the Fall Meeting of the American Oil Chemists' Society, Minneapolis, Minn., Oct. 11–13, 1954. A labortory of the Eastern Utilization Research Branch, Agricultural Research Service, U. S. Department of Agriculture.     

Synthetic detergents from animal fats. VII. Detergent combinations

Summary Laboratory measurements of detergency were made on mixtures of sodium salts of sulfated hydrogenated tallow alcohol (X), disodium salts of α-sulfonated hydrogenated tallow acids (Y), sodium dodecylbenzenesulfonate (Z), and a builder (B) using three different kinds of standard soiled cotton. Component X was the most important, and mixtures not containing X were generally inferior detergents. Built XY mixtures were better than XZ mixtures with one kind of soiled cotton (cloth I). Built XZ mixtures were better than XY mixtures with another soiled cotton (cloth III). The results, based on laboratory measurements of detergency using standard soiled cotton, are suggestive rather than conclusive. Partial substitution of X by Y or Z, or by both Y and Z, may be possible without loss in detergency. Presented at the meeting of the American Oil Chemists’ Society, Houston, Tex., April 1956. A laboratory of the Eastern Utilization Research Branch, Agricultural Research Service, U. S. Department of Agriculture.     

Hydrogenation of linolenate. V. Procedure of evaluating hydrogenation catalysts for selectivity

Equations for determining the ratio of hydrogenation rates for linolenate and linoleate acyl groups are derived from kinetic theory. They are based upon the analysis for linolenate after absorption of 0.5 mole of hydrogen by an equal mixture of linoleate and linolenate. This method finds routine application in the evaluation of hydrogenation catalysts for selectivity. Presented at spring meeting, American Oil Chemists' Society, May 1–3, 1961, St. Louis, Mo. This is a laboratory of the Northern Utilization Research and Development Division, Agricultural Research Service, U. S. Department of Agriculture.     

Differential utilization of long chain fatty acids during triacylglycerol depletion. I. Rat heart after ischemic perfusion

Rat hearts were perfused with Krebs-Henseleit buffer for 90 min according to the Langendorff procedure. Normoxic perfusion for 90 min resulted in minor changes in fatty acid composition and a decrease in residual heart triacylglycerol to 60% of preperfusion values. When the protocol included 30 min of slow perfusion-induced ischemia, the hearts were observed to be depleted of 89% of their initial triacylglycerol content. The triacylglycerol fatty acid composition (mg %) remained similar after compared to before perfusion except for a 121 mg % increase in stearic acid and a 225 mg % increase in arachidonic acid. The percentage composition of both fatty acids was significantly inversely correlated with the amount of triacylglycerol remaining in the heart after perfusion. Postperfusion, arachidonic acid and stearic acids were present at nearly 1∶1 in the residual heart triacylglycerol, suggesting that a common mechanism may be involved in the selective retention of these fatty acids by the heart. This paper was presented in part at the annual meeting of the Canadian Federation of Biological Societies, Guelph, Ontario, June 16–22, 1986. S.C.C. was the recipient of an Industrial Research Fellowship from the National Science and Engineering Research Council of Canada (1982–1986).     

Conjoined crystals. II. Applications

Mixed crystals of glycerol monostearate and 1,2-propanediol monostearate (propylene glycol monostearate) (a useful composition of Conjoined Crystals, see Part 1) disperse readily in water, retaining this property for long periods of time. The effect of composition on retention of the α-crystalline form of the glycerol monoester in such dispersions is discussed. The water dispersions foam when shaken or when air is blown through the dispersion, a property which appears to be associated with the superior activity of the mixed crystals as a food emulsifier. A test method for measuring foam retention is described. The crystals, or their water dispersions, are useful in the preparation of low-calorie, fruit “fluffs,” such as whipped applesauce. Sponge cakes with fine grain, improved volume, and texture were prepared with the water dispersions. The crystals are effective emulsifiers in cake mixes and bread. These tests are described. Communication no. 294 from the Research Laboratories of Distillation Products Industires, Division of Eastman Kodak Co.     

Reactions of fatty materials with oxygen. XX. Recent developments in the autoxidation of methyl oleate and other monounsaturated fatty materials

Summary Some significant developments since 1947 in the autoxidation of methyl oleate and other monounsaturated fatty materials have been reviewed and critically evaluated. Subjects discussed are preparation and characterization of hydroperoxides, and mechanism, kinetics, and secondary products of autoxidation. Major developments in the field have resulted largely from the use of newer instruments (polarograph, infrared spectrophotometer) and separation techniques (urea complexes, molecular distillation, countercurrent distribution). Direct experimental evidence is now available which demonstrates that a) hydroperoxides are the predominating, but not the exclusive, primary products of autoxidation; b) the hydroperoxides obtained from methyl oleate are mostly, if not entirely,trans; c) substantially all the methyl oleate undergoes single attack in the chain before any significant amount of multiple attack occurs, and d) α,β-unsaturated carbonyl compounds are among the most important secondary products of autoxidation. Paper XIX is reference 66a. Presented at the Fall Meeting of the American Oil Chemists' Society, Philadelphia, Pa., October 10–12, 1955. A laboratory of the Eastern Utilization Research Branch, Agricultural Research Service, U. S. Department of Agriculture.     

Glycidyl esters. II. Synthesis of esters of commercial and pure fatty acids

The reaction of salts of earboxylic acids with epichlorohydrin in the presence of quaternary ammonium halides to form glycidyl esters has been demonstrated to be applieable to a variety of acids derived from fats, including commercial mixtures. The glycidyl esters of pelargonic, lauric, oleic, dimerized linoleic, ricinoleic, behenic, and sebacic acids as well as those of the fatty acids derived from tallow, wool wax, and soya oil have been prepared in 80–95% yields and purities. Eastern Utilization Research and Development Division, Agricultural Research Service, U.S. Department of Agriculture.     

Combustion regimes of magnesium in carbon oxides. 2. Combustion in CO

The oxidation and combustion of solitary magnesium particles in a CO medium in the range of ambient temperatures 898–1323 K are studied experimentally. Various regimes of interaction between magnesium and CO are revealed: low- and high-temperature regimes of slow heterogeneous combustion, low- and high-temperature regimes of vapor-phase combustion, and pulse combustion. The possible reasons for the existence of various regimes are discussed on the basis of an analysis of the processes in the surface film and in the gas phase with allowance for the thermodynamic features of the Mg CO system. Translated fromFizika Goreniya i Vzryva, Vol. 36, No. 2, pp. 67–73, March–April, 2000. This work was supported by the Russian Foundation for Fundamental Research (Grant No. 95-03-09829).     

Rice bran oil. IV. Storage of the bran as it affects hydrolysis of the oil

Summary and Conclusions The oil, contained in bran from regularly milled rice, when stored at prevailing atmospheric temperature, humidity, and natural moisture content is subject to rapid hydrolysis which increases the free fatty acid content of the oil to a point where it cannot be economically refined. Data have been presented showing the effects of a) temperature, b) drying at temperatures of 70°, 85°, 100°, and 110°C. for various periods of time up to 5 hours, c) different relative humidities before and after drying, and d) added moisture on the rate of formation of free fatty acids during storage in bran from both regular and “Converted” rice. Decreasing the storage temperature tends to retard the formation of free fatty acids. In the case of regular rice bran deterioration during storage occurred at a fairly rapid rate even at 3°C. whereas bran from “Converted” rice was fairly stable when stored at this temperature. The investigation of the effect of heating or drying and the effect of different relative humidities on the storage of rice bran have shown that bran from both regular and “Converted” rice can be stored for periods of at least four months without excessive increase in the content of free fatty acids, provided the bran is dried sufficiently and is maintained at a low moisture content. An increase in the moisture content of predried bran causes a rapid increase in the free fatty acid content of the oil in the bran. Investigations of the effect of chemical inhibitors and of inert atmosphere on the rate of free fatty acid formation of regular rice bran indicated that these were ineffective in preventing deterioration. Presented at the 40th Annual Meeting of the American Oil Chemists’ Society, New Orleans, La., May 10–12, 1949; Report of a Study Made Under the Research and Marketing Act of 1946. One of the laboratories of the Bureau of Agricultural and Industrial Chemistry, Agricultural Research Administration, U. S. Department of Agriculture.     

Fatty acid morpholides as plasticizers for vinyl chloride resins. II. The morpholides of selectively hydrogenated and of epoxidized cottonseed fatty acids

The morpholides of selectively hydrogenated cottonseed acids and of epoxidized cottonseed acids have been prepared and shown to be good primary plasticizers for vinyl chloride homopolymer and copolymer resins. They are also acceptable plasticizers for cellulose triacetate and possibly also as Buna A softeners. The degree of hydrogenation or partial epoxidation was approximately that equivalent to the conversion of all the polyunsaturated acyls to monounsaturated acyls. Presented at the 52nd Annual Meeting. American Oil Chemists’ Society, St. Louis, Mo., May 1–3, 1961. One of the laboratories of the Southern Utilization Research and Development Division, Agricultural Research Service, U.S. Department of Agriculture.     

Synthetic detergents from animal fats. Disodium alpha-sulfopalmitate and sodium oleyl sulfate

Summary Disodium α-sulfopalmitate and homologous compounds were prepared by sulfonation of the fat acid with liquid sulfur trioxide. Sodium oleyl sulfate was prepared in an estimated 95% purity by sulfation of oleyl alcohol with pyridine-sulfur trioxide. The solubility, surface tension, wetting, foaming, and detergent properties of these and related compounds were measured. Disodium α-sulfopalmitate is potentially inexpensive, has adequate surface active properties, is a good detergent in hard and soft water, but has limited solubility at room temperature (0.25% at 25°C.). The lauric and myristic homologs are less surface active, but more soluble. Disodium α-sulfostearate is less soluble. Sodium oleyl sulfate has excellent solubility, and surface active properties and is an excellent detergent in soft water. It is not quite so efficient in hard water although no insoluble calcium salts are formed. The future of the two compounds will depend upon successful formulation with builders or combinations with soap or other detergents. Report of a study in which certain phases were made under the Research and Marketing Act of 1946. One of the laboratories of the Bureau of Agricultural and Industrial Chemistry, Agricultural Research Administration, United States Department of Agriculture. Presented at the meeting of the American Oil Chemists’ Society, Chicago, Ill., in October 1951.     

Hydrogenation of linolenate. II. Hydrazine reduction

Observations by Aylward and Rao that hydrazine is a reducing agent for a number of unsaturated fatty acids were extended. The hydrazine reaction on linolenic acid was followed by periodic sampling until methyl esters prepared from the reduced acids had an iodine value of 162. These esters were shown by countercurrent distribution to consist of 26% triene, 43% diene, 26% monoene, and 5% stearate and by infrared analysis to contain notrans bonds. Oxidation of the separated monoene and diene fractions by permanganate-periodate mixtures and gas chromatography of the dibasic acids showed that the double bonds were in the original 9, 12, and 15 positions and that the double bonds farthest from the carboxyl were reduced at a slightly faster rate. Gas chromatography of the monoene fraction indicated three components that were identified in the order of elution from the column as 9, 12, and 15 monoenes; in the diene fraction three components were identified in the order of elution as 9,12; 9,15; and 12,15 dienes. After alkali isomerization of this diene fraction, the conjugated material was reacted with maleic anhydride; the unreacted 9,15 diene isomer was separated by distillation. Presented at fall meeting, American Oil Chemists’ Society, New York, October 17–19, 1960. This is a laboratory of the Northern Utilization Research and Development Division, Agricultural Research Service, U.S. Department of Agriculture.