The plasticizing characteristics of some fatty acid morpholides and morpholide-hydrocarbon extender blends

The preparation and plasticizing characteristics in poly (vinyl chloride-vinyl acetate) copolymer resin of 14 morpholides of unsubstituted and substituted C₁₈ fatty acids are reported, as well as the plasticizing performance of blends of the morpliolide of hydrogenated cottonseed acids with such hydrocarbon extenders as Conoco H-35, Amoco BN-1, and Monsanto HB-20 and 40. Up to 50% of some of these extenders can be blended with the morpholide of hydrogenated cottonseed acids without loss of compatibility. Economics excepted, such blends are of questionable merit with respect to performance. Although substituent groups such as oxirane, benzyl, and carbonyl improve the compatibility, volatility, and soapy water extractability characteristics of the fatty acid morpholide plasticizers, they are almost invariably detrimental to low-temperature performance and efficiency. The dimorpholides of the dimer acids exhibit no measurable volatility loss in plasticized stock and mixtures with a monomeric morpholide exhibit unusually low volatility losses. Ternary composition-compatibility diagrams are described for two systems involving the morpholides of linoleic, epoxyoctadecenoic, and palmitic acid in one instance and oleic, dimer, and palmitic acid in the other. These diagrams delineate the fatty acyl compositional limitations consonant with compatibility of these two sys-tems in poly (vinyl chloride-vinyl acetate) copolymer. So. Utiliz. Res. Dev. Div., ARS, USDA. Use of a company and/or product named by the Department does not imply approval or recommendation of the product to the exclusion of others which may also be suitable.     

Nitrogenous derivatives of cyclic fatty acids

A number of nitrogenous derivatives of cyclized acids derived from C-18, triene-containing fatty acid sources, were prepared. Mixed amides (mp 33C), nitriles (fp −25C), and amines (fp −34C), prepared from the hydrogenated cyclic acids, have uniquely low mp for fat-derived substances of their mol wt. Compatibility with synthetic resins and solubility in organic solvents of the mixed amides are high compared to common fatty-amide mixtures. The nitriles and morpholides are compatible with polyvinyl chloride and may have potential as plasticizers for it. The hydrogenated cyclic fatty acid amines have an approximate fp of −34C. The diethanolamides, ethenoxylated amides, and quaternary amines were prepared and their surface-active properties compared with similar fat-derived substances. Presented at AOCS meeting in St. Louis, Mo., 1961. A laboratory of the Northern Utilization Research and Development Division, Agricultural Research Service, U.S.D.A.     

Spectrophotometric estimation of soybean oil in admixture with cottonseed and peanut oils

Conclusion A spectrophotometric method has been described for the determination of soybean oil in admixture with cottonseed oil. The method provides a simple and rapid means of detecting gross adulteration of one oil with another and permits an accurate determination of linolenic acid for use as a criterion of the economic value of an oil mixture and as a guide in oil processing. The factor limiting the precision of the method is variation in composition of the cottonseed and soybean oils in the mixtures to be analyzed. Variations in composition affect the proportion of measured triene conjugation, due to the linolenic acid content of the soybean oil and the apparent linolenic acid content of the cottonseed oil. Thus, for unknown mixtures only average value corrections can be made for apparent linolenic acid content and the accuracy of a particular analysis will depend upon how well the composition of the oils in the particular mixture follows those of the average mixture. The method described can be extended to mixtures other than those of soybean and cottonseed oils. Thus, soybean oil may be determined in admixture with a peanut oil. In general, any oil which has an unsaturated fatty acid capable of producing triene conjugation upon alkali isomerization can be determined in the presence of any other oil containing no appreciable quantity of unsaturated fatty acids which can produce triene conjugation by such treatment. Presented before The American Oil Chemists’ Society, New Orleans, Louisiana, May 10–12, 1944. One of the laboratories of the Bureau of Agricultural and Industrial Chemistry, Agricultural Research Administration, U. S. Department of Agriculture.     

Preparation of pure palmitic acid and a by-product plasticizer from cottonseed oil

Summary A laboratory process has been developed which permits the isolation of a highly purified palmitic acid from cottonseed acids through the recrystallization of its cyclohexylamine salt from acetone and subsequent regeneration of the acid. The by-product, predominantly cyclohexylamine salts of the unsaturated fatty acids, can be modified and converted to morpholides which have shown promise as vinyl plasticizers. The morpholine salts can be obtained as a direct byproduct by the use of an appropriate mixture of cyclohexylamine and morpholine with the composite acid. By using an amount of cyclohexylamine closely equivalent to the saturated fatty acid content and sufficient morpholine to make up the residual neutralization equivalent of the composite cottonseed acids, the saturated acids can be isolated as cyclohexylamine salts. The stripped mother liquor will consist essentially of the morpholine salts of the unsaturated acids. Pure palmitic acid is obtained by recrystallization of the cyclohexylamine salts. The complete process is applicable to fatty acids from other natural glyceridic oils in which the dominant saturated acid bears a ratio to the other saturated acids closely paralleling that in cottonseed oil. The process is not operable with partially hydrogenated oils. Presented at the 49th Annual Meeting of the American Oil Chemists’ Society, Memphis, Tenn., April 21–23, 1958. One of the laboratories of the Southern Utilization Research and Development Division, Agricultural Research Service, U. S. Department of Agriculture.     

A method for the determination of linoleic acid and conjugated dienoic acids in materials containing eleostearic acids

Summary A procedure has been described which extends the scope of the spectrophotometric method for polyun-saturated acids to the determination of linoleic and conjugated acids in the presence of large quantities of conjugated trienoic acids. Basis for the proposed method rests on equations which are offered to correct the “end” or “back-ground” absorption of the highly absorbing triene conjugated acids at 233 mμ, the position of maximum absorption of conjugated dienoic acids and alkali isomerized linoleic acids. The method is limited to samples which do not contain nonconjugated trienoic acids (linolenic acids). The method has been tested by the analysis of several mixtures of cottonseed and dehydrated castor oils of known composition, to which varying amounts of alpha, beta, and mixtures of alpha- and beta-eleostearic acids have been added. These samples have been used to demonstrate the application of the proposed method for the determination of dienoic conjugated acids, alpha-eleostearic acid, beta-eleostearic acid linoleic acid, oleic acid, and total saturated fatty acids. Comparisons of the results obtained with similar values, calculated from the known composition of the mixtures, prove that the proposed method gives reasonable results. Standard deviations between determined and calculated results vary from 0.36 for diene conjugated acids to 1.40 for oleic acid. The method has been applied to the analysis of foreign and domestic tung oils. Presented before 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.     

Nomographs for calculating the fatty acid composition of oils and fats from iodine values and either extinction coefficients or thiocyanogen values

Summary Very few alignment charts are available which can be used for routine calculations in fat analysis and processing. Three alignment charts are presented in this communication for determining the fatty acid composition of a fatty acid mixture consisting variously of linolenic, linoleic, oleic, and saturated fatty acids or glycerides, incorporating for accuracy, data based on ultraviolet extinction coefficients. In two of the charts triangular diagrams have been used as a novel feature in nomography to give directly the fatty acid composition.     

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).     

Quantitative estimation of esters by thin-layer chromatography

A method for the analysis of fatty esters employing separation by thin-layer chromatography and quantitative determinationvia their hydroxamic acids has been developed. Esters of different types are separated on silica gel plates, the spots or zones are scraped from the plates, the esters are extracted from the silica gel, and the iron hydroxamic acid complexes are formed. The latter are then measured by colorimetry. The method is suitable for analysis of mixtures of ordinary, epoxy, monohydroxy, and dihydroxy fatty esters as well as for mixtures of mono-, di-, and triglycerides. Used in conjunction with gas chromatography this method permits the fatty acid composition of seed oils containing oxygenated fatty acids to be measured in about 3 hours. The amount required for the total analysis is 1 to 10 mg. per determination, depending upon composition. Presented at the Spring Meeting, American Oil Chemists' Society, St. Louis, May, 1–3, 1961. Supported by the Hormel Foundation, the National Institutes of Health (Research Grant H-3559), and the National Dairy Council. Appointment supported by the International Cooperation Administration under the Visiting Research Scientists Program of the U.S.A.     

Fractionation of tallow fatty acids. Preparation of purified oleic acid and an inedible olive oil substitute

Summary Tallow fatty acids have been fractionally crystallized from acetone at temperatures ranging from 0° to −60° C. By crystallizing at 0° to −20° C., a saturated acid fraction which amounts to 40 to 50% by weight of the starting material has been obtained. This fraction corresponds to “double- or triple-pressed stearic acid.” The filtrate acids from the crystallization at −20° C. contain over 90% of the oleic acid present in the starting material, and in fatty acid composition this mixture is similar to olive oil. From this fraction. which amounts to about 50% by weight of the starting material, a synthetic triglyceride with, properties approximating those of olive oil has been prepared. By low-temperature crystallization of this oleic-acid-rich fraction at −50° to −60° C., followed by fractional distillation, a good yield of purified oleic acid (oleic acid content, over 95%) has been obtained. One of the laboratories of the Bureau of Agricultural and Industrial Chemistry, Agricultural Research Administration, United States 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.     

Rapid synthesis of fatty acid esters for use as potential food flavors

Lipase-catalyzed esterification has been performed in hexane to generate novel mixtures of fatty acid esters from specially chosen combinations of fatty acids and alcohols. By varying the alcohol and enzyme compositions in the enzymatic reactions, different ester mixtures were produced, which were further purified and analyzed for ester composition by gas chromatography-mass spectrometry. Depending on the combination of alcohols and enzymes used, the final ester mixture exhibited significant compositional variation. These mixtures could be manipulated at the synthesis step, thereby enabling a high degree of product control. Such manipulation over enzyme-catalyzed ester synthesis in mixtures may be useful in the preparation of ester flavors for use in the food industry.     

Rapid synthesis of fatty acid esters for use as potential food flavors

Lipase-catalyzed esterification has been performed in hexane to generate novel mixtures of fatty acid esters from specially chosen combinations of fatty acids and alcohols. By varying the alcohol and enzyme compositions in the enzymatic reactions, different ester mixtures were produced, which were further purified and analyzed for ester composition by gas chromatography-mass spectrometry. Depending on the combination of alcohols and enzymes used, the final ester mixture exhibited significant compositional variation. These mixtures could be manipulated at the synthesis step, thereby enabling a high degree of product control. Such manipulation over enzyme-catalyzed ester synthesis in mixtures may be useful in the preparation of ester flavors for use in the food industry.     

Low temperature solubilities of fatty acids in selected organic solvents

Summary A number of highly purified fatty acids have been prepared and their solubilities determined in six common organic solvents within the temperature range from 10° to −70°. The acids studied were palmitic, stearic, oleic, elaidic, petroselinic, petroselaidic, linoleic, stearolic, arachidic, eicosenoic, behenic, erucic, and brassidic. The solvents used were methanol, ethyl acetate, diethyl ether, acetone, toluene, and n-heptane, representing six different solvent types. A limited study was also made with a series of hydrocarbon solvents in order to note any effects of solvent structure on fatty acid solubility. Data are discussed with respect to their application in separating various fatty acid mixtures by low temperature crystallization. From a dissertation submitted by Doris Kolb to The Ohio State University in partial fulfillment of the requirements for the Ph.D. degree, August, 1953. This work was supported in part from funds granted by the Ohio State University Research Foundation to the university for aid in fundamental research.     

Separation of fatty acids from binary melts using physical vapour deposition (PVD)

BACKGROUND: The use of fatty acid mixtures, natural biochemical compounds, will be extended to various chemical industries for the production of a wide variety of products, and various mixtures of fatty acids are necessary for production. Separation of a binary fatty acid mixture of lauric acid and myristic acid using physical vapour deposition (PVD) on a cold quartz crystal resonator is examined. The extremely small amount of deposits can be measured with the quartz crystal resonator. The vapour phase is prepared by vaporizing a calculated composition of melt according to the vapour‐liquid equilibrium (VLE). RESULTS: The composition of lauric acid in the melt and the melt temperature were utilized as operating variables in the PVD. The growth rate of deposit increases when melt temperature and the composition of lauric acid in the melt are increased. The composition of lauric acid in the deposit is significantly lower than that of the melt of 19% lauric acid, but the composition of lauric acid in the deposit is much higher than that of the melts of 50% and 75% lauric acid. CONCLUSION: The distribution coefficient of lauric acid between solid and vapour phases can be correlated as a function of the growth rate of deposit. The possibility of separation of fatty acid mixtures by PVD is suggested experimentally and theoretically. Copyright © 2008 Society of Chemical Industry     

The lipids of the common house cricket,Acheta domesticus L. I. Lipid classes and fatty acid distribution

The lipids of the common house cricket,Acheta domesticus L., have been examined with the following results. The fatty acids associated with the lipid extracts do not change significantly from the third through the eleventh week of the crickets' postembryonic life. The major fatty acids are linoleic (30–40%), oleic (23–27%), palmitic (24–30%), and stearic acids (7–11%). There are smaller amounts of palmitoleic (3–4%), myristic (∼1%), and linolenic acids (<1%). The fatty acid composition of the cricket lipids reflects but is not identical to the fatty acids of the dietary lipids: linoleic (53%), oleic (24%), palmitic (15%), stearic (3%), myristic (2%), and linolenic acid (2%). The amount of triglycerides present in the crickets increases steadily from the second through the seventh or eighth week of postembryonic life, then drops sharply. Other lipid classes, such as hydrocarbons, simple esters, diglycerides, monoglycerides, sterols, and free fatty acids remain about constant. The composition of the fatty acids associated with the tri-, di-, and monoglycerides and the free fatty acid fraction are all about the same. The fatty acids associated with the simple esters are high in stearic acid. Postdoctoral Research Associate, Department of Chemistry, University of Michigan, 1965–1967.     

Modification of vegetable oils

Summary 1. An investigation has been made of low-temperature crystallization from organic solvents as a means of effecting practical separations of the solid and liquid acids of unhydrogenated and hydrogenated cottonseed oils. 2. At any fixed temperature the most efficient separations were obtained in the highly polar solvents, acetone and methyl acetate. However, it was possible in any case to make nonpolar petroleum naphtha (Skellysolve B) fully equivalent to the polar solvents simply by conducting the crystallization at a temperature approximately 10° F. lower than that employed with the polar solvents. Ethyl acetate and methyl ethyl ketone were intermediate between petroleum naphtha and acetone or methyl acetate in their effectiveness. 3. By employing a solvent-fatty acid ratio of 4 to 1 by weight and conducting crystallizations at 5° F. or lower from acetone and −5° F. or lower from petroleum naphtha, the liquid fatty acids from unhydrogenated cottonseed oil could be reduced to below −2° C. in titer and to below about 3 per cent in saturated acid content. Under these conditions there was no appreciable crystallization of oleic acid. 4. At a solvent-fatty acid ratio of 6 to 1 and the same temperatures (5° F. for acetone and − 5° F. for petroleum naphtha) equally good separations could be made of the saturated fatty acids present in the mixed acids from hydrogenated cottonseed oil (I.V.=70). Separation of “iso-oleic” acids from the fatty acids of the hydrogenated oil took place over a wide range of temperatures, beginning at 35° F. in acetone and at 25° F. in petroleum naptha, and being incomplete (according to Twitchell analyses of the liquid acids) in either solvent at −15° F. However, the bulk of the higher melting iso-oleic acids was precipitated as the temperature approached −5° F. in acetone and −15° F. in petroleum naphtha. One of the laboratories of the Bureau of Agricultural and Industrial Chemistry, Agricultural Research Administration, U. S. Department of Agriculture.     

Breeding for lipid composition in corn

Large genetic diversity is available in corn (Zea mays L.) for alteration of its lipid composition. Mass selection has produced strains ranging from 0.4–17% oil with genetic variability still existing in the high oil version. High oil hybrids (7–8% oil) with yields equal to those of commercial hybrids (4% oil) have recently been developed. In feeding trials at the University of Minnesota, pigs made more efficient gains on high oil corn. Oleic and linoleic acids usually make up 80–90% of the fatty acids of corn oil. Screening of corn lines has revealed a range for linoleic acid of 25–71% and for oleic acid of 20–60%. Although the genetics of fattya cid synthesis have not been completely elucidated, breeding of corn with selected unsaturation should be possible. Fatty acid placement within the triglyceride molecule also may be subject to genetic modification in corn.     

Synthesis of Chloroalkoxy eicosanoic and docosanoic acids from meadowfoam fatty acids by oxidation with aqueous sodium hypochlorite

Chloroalkoxy substituted C₂₀ and C₂₂ fatty acids can be synthesized from the unsaturated fatty acids in meadow-foam oil by reaction of the fatty acids with primary or secondary alcohols and an aqueous sodium hypochlorite solution (commercial bleach). The reactions are conducted at room temperature for 3 h. Chlorohydroxy fatty acid derivatives are formed as by-products owing to the presence of water in the reaction mixture. Chlorinated δ-lactones are also produced by direct reaction of sodium hypochlorite with the Δ5 unsaturated fatty acids present in meadowfoam or by ring closure of the 6-chloro-5-hydroxy fatty acids. The product yield of chloroalkoxy fatty acids is dependent on the nature and volume of the alcohol used in the reaction, as well as the concentration and pH of the sodium hypochlorite solution. Primary alcohols such as methanol and butanol produce maximal yields (50–60%) of chloroalkoxy fatty acids whereas the secondary alcohol 2-propanol gives a 30% yield. Chloroalkoxy fatty acid yields can be increased to 75–80% by elimination of water from the reaction mixture through a procedure that partitions sodium hypochlorite from water into hexane/ethyl acetate mixtures. All of the reaction products were fully characterized using nuclear magnetic resonance and gas chromatography-mass spectrometry.     

Nutritional and toxicological evaluation of rubber seed oil

Rubber (Hevea brasiliensis) seed oil (RSO) is available in India (Ca. 4500 tons per year) and is used mainly as a drying oil. The oil does not contain any unusual fatty acids, and it is a rich source of essential fatty acids C_18∶2 and C_18∶3 that make up 52% of its total fatty acid composition. Acute toxic potential in rats and the systemic effects and nutritional quality were assessed in a 13 week feeding study in weanling albino rats using a diet containing RSO or groundnut oil (GNO) (as the control) at a 10% level as the sole source of dietary fat. RSO did not manifest any acute toxic potential. Food consumption, growth rate and feed efficiency ratio of rats fed RSO were similar to those fed GNO. The digestibility of this oil was found to be 97%, as compared to 94% for GNO. There were no macroscopic or microscopic lesions in any of the organs which could be ascribed to the RSO incroporation in the diet. Thus the current data show that RSO could be used for edible purposes. However, it will be necessary to process the oil to achieve deodorization and to remove free fatty acids to make it organoleptically acceptable.     

Antagonistic effects ofMyxococcus xanthus on fungi: II. Isolation and characterization of inhibitory lipid factors

The chemical composition of the lipophilic excretion ofMyxococcus xanthus inhibitory to the germination of fungal spores and growth has been investigated. The inhibitory effect was attributed to a mixture of fungistatically acting fatty acids and a component of antibiotic character. The fatty acid mixture has been fully characterized and found to constitute a mixture of saturated (68%) and unsaturated (32%) structures in the C₁₃–C₁₇ range. The major part is methylbranched of theiso-type, with 13-methyltetradecanoic acid being the main component (33% of the total). The fungistatic activity of the fatty acid mixture on spore germination is attributed to the structures withiso-configuration. The presence of unsaturation is of minor importance. Observed morphological changes of the spores and hyphae in the presence ofiso-fatty acids suggest that they act on the plasma membrane.