Thermal analysis and calorimetry of some fatty acid sodium soaps

Transition temperatures and enthalpies and some phase diagrams of pure odd and even sodium soaps have been determined by means of dif-ferential thermal analysis and scanning calorim-etry. Branched sodium soaps have been added for comparison. No essential difference has been found between the number, type, and enthalpy of the transitions of the neighboring odd and even soaps. The total enthalpy and entropy of transition are consider-ably lower than those of the corresponding par-affins and fatty acids. The entropy of the subneat-neat and perhaps of the neat isotropic transition has an alternating character, which suggests a different methyl end-group packing for even and odd soap. These two facts suggest that the melted soap is still in an organized state. Presented at the AOCS Meeting, New Orleans, May 1967.     

The separation of solid fatty acids from liquid fatty acids by the formation of acid soaps. I. Tallow soaps

The formation of acid soaps has been used successfully for the separation of a mixture of fatty acids into high and low iodine value fractions. The acid soaps of saturated acid can be made to crystallize from water leaving their unsaturated counter parts in solution. Acid soaps of saturated fatty acids are well characterized compounds with the formula R-COOM.R-COOH, where R is a straight alkyl chain, and M is sodium, potassium or ammonium. Optimum crystallization conditions involve a soap concentration of 2–5%, pH adjustment to between 7.0 and 8.0, an initial crystallization temperature not below 25C, and a crystallization period of at least 4 hr during which time cooling to a final temperature of 5–10C must be gradual, and agitation gentle.     

Effect of tallow-coconut fatty acid ratios on properties of bar soaps

In this study, blends of tallow and coconut fatty acids prepared at ratios ranging from 95:5 to 75:25 were converted to sodium soaps, and were processed into soap bars through conventional milling and pressing techniques. Other minor ingredients were included in the bar to protect against rancidity and to provide color. The resulting bars were tested for lather, solubility, penetration, swell, slushing tendency, moisture and cracking. According to one mechanical method, the 85:15 tallow/coconut fatty acid blend yields optimum lather quickness. This does not agree with lather preference by an expert panel which preferred bars with increasing sodium cocoate content or with increasing levels of sodium laurate. Coincident with these effects was an increase in aqueous solubility. However, certain deleterious effects were observed with increase of sodium cocoate, namely: increased slushing and a higher erosion rate.     

Applications of fatty acids in metallic soaps

Summary In this discussion we have attempted to cover pertinent factors concerning the production and applications of solid fatty acid soaps, with particular emphasis on how the fatty acid characteristics come into play. We have avoided reference to specific formulations because these must be kept in the realm of metallic soap manufacturers’ “know how.” Those interested in modifiers and their effect on metallic soaps can find reference material in past issues of the Journal of American Oil Chemists’ Society (for example, reference 9) and in the patent literature. Reference to theoretical considerations of metallic soap structure has also been avoided as in this area the reader can again find reference material in the Journal of American Oil Chemists’ Society (for example, reference 10).     

Foaming properties of rosin soap and their comparison with those of fatty acid soaps

Summary The foam production of soaps made from rosin, modified rosins, and rosin acids were evaluated. The foam production of rosin soaps was compared with soaps made from the individual fatty acids. There was no difference in the foaming properties of soaps made from longleaf and slash pine rosin. Oxidation of the unstable rosin acids in rosin caused the foaming properties of the rosin soap to become more nearly proportional to the concentration. The more hydrogen present in the rosin acid molecule the greater were the foaming properties of the rosin soap. At temperatures between 200° C. and 275° C., the lower the temperature employed for producing pyroabietic acid catalytically, the greater were the foaming properties of the pyroabietic acid soap. There was a difference in the foaming properties of commercial stabilized rosins. In foaming properties the soaps made from rosins, modified rosins, and rosin acids were more like sodium laurate than the other individual fatty acid soaps tested. The author wishes to express his indebtedness to to Dr. G. S. Jamieson and W. G. Rose of the Agricultural Chemical Research Division for the pure lauric, myristic, palmitic and stearic acid used in this study.     

The solubilization of calcium soaps by fatty acids

The solubilization of the calcium soaps of long chain fatty acids by liquid fatty acids was observed. The solubilities of calcium palmitate, calcium laurate, and calcium oleate were 15.6, 22.8, and 53.3 wt%, respectively, in oleic acid at 40°C. The formation of an acid-calcium soap complex was demonstrated by x-ray diffraction studies of calcium laurate, lauric acid, and a mixture of these compounds that had been heated. Similar evidence was obtained for a calcium oleate-oleic acid complex. The solubility of calcium oleate in a bile salt micellar system was enhanced by obeic acid. The solubilization of calcium soaps by liquid fatty acids may explain the unexpectedly high bioavailability of some calcium soaps.     

Gas-liquid chromatography of triglyceride mixtures containing both odd and even carbon number fatty acids

Quantitative GLC of triglycerides has been extended to natural fats containing both odd and even carbon number fatty acids. A 1.83-m glass column containing 3.0% JXR silicone on 100/120 mesh Gas-Chrom Q resolved triglycerides differing by only one carbon number. Peak resolution was significantly improved by hydrogenating each triglyceride sample prior to GLC analysis. The triglycerides of four fish oils (mullet, tuna, menhaden, and pilchard) and one seed fat (Acanthosyris spinescens) containing odd carbon number fatty acids were analyzed by this technique. The method was also useful for determining the triglyceride composition of the cyclopentene fatty acid oil fromHydnocarpus wightiana seeds. Presented at the AOCS meeting, New Orleans, May, 1967     

The function of fatty acids in metallic soaps

Conclusion The above consideration of metallic soaps has been conducted from the point of view of the fatty acid used. It is evident that the fatty acid does play an important function in determining the method of preparation, the physical properties, and ultimately the use of metallic soaps. Presented at the annual Fall Meeting, American Oil Chemists’ Society, Nov. 2–4, 1953, Chicago, Ill.     

Isovaleric acid as a precursor of odd numbered iso fatty acids in Tetrahymena

Tris isovalerate-supplementedTetrahymena pyriformis W showed no qualitative change in fatty acid composition; however, an increase in polar lipids that contain odd numbered iso acids (C₁₃, C₁₅, C₁₇, C₁₉) occurred. This change was accompanied by a decrease in the proportional amount of even numbered normal acids (C₁₄, C₁₆, C₁₈). The neutral and polar lipids from cells incubated with [1-¹⁴C] isovaleric acid were found to contain radioactivity. The methyl esters of the saturated fatty acids obtained from the polar lipids by alkaline methanolysis were separated by reversed phase chromatography, the identities confirmed by gas chromatography-mass spectrometry, and the specific activities determined. Iso acids were found to be the most heavily labeled materials. In addition to ceramide, two sphingolipid components were detected. One yielded saturated fatty acids after acidic methanolysis, while the other contained >93% α-hydroxy fatty acids. Radioactivity was noted in the long chain base fraction derived from the sphingolipids. Progressive growth inhibition occurred as the isovalerate concentration was increased in the culture medium; however, the ciliates were morphologically indistinguishable from unsupplemented cells.     

肥皂和表面活性剂的配方与性质

将表面活性剂添加到以肥皂为基剂的配方中,可有效降低体系的pH值,如选择合适的中和试剂和表面活性剂还可使溶液呈透明状.同时,专业小组的研究表明：某些表面活性剂的加入可有效提高肥皂配方的许多其他表观特性.     

The separation of solid fatty acids from liquid fatty acids by the formation of acid soaps. II. Pilot plant studies

On contemplating pilot plant scale-up of the acid soap process for separating fatty acid mixtures into low and high iodine value fractions, improvements were desirable in acidifying agent used, and the method of separating the solid acid soaps. A further objective was to determine the range of applicability of the process. Studies indicated that CO₂ can be replaced by mineral acids, or by the fatty acids themselves. A continuous precoat vacuum filter is suitable for the separation of the solid acid soaps. The process is applicable to refinery foots as well as to distilled and undistilled fatty acids.     

Thia fatty acids with the sulfur atom in even or odd positions have opposite effects on fatty acid catabolism

As tools for mechanistic studies on lipid metabolism, with the long-term goal of developing a drug for the treatment of lipid disorders, thia FA with the sulfur atom inserted at positions 3–9 from the carboxyl group were fed to male Wistar rats for 1 wk to determine their impact on key parameters in lipid metabolism and hepatic levels of thia FA metabolites. Thia FA with the sulfur atom in even positions decreased hepatic and cardiac mitochondrial β-oxidation and profoundly increased hepatic and cardiac TAG levels. The plasma TAG level was unchanged and the hepatic acyl-CoA oxidase activity increased. In contrast, thia FA with the sulfur atom in odd positions, especially 3-thia FA, tended to increase hepatic and cardiac FA oxidation and acyl-CoA oxidase and carnitine palmitoyltransferase-II activities, and decreased the plasma TAG levels. The effects seem to be related to differences in the catabolic rate of the thia FA. Differences between the two groups of acids were also observed with respect to the regulation of genes involved in FA transport and catabolism. Feeding experiments with 3- and 4-thia FA in combination indicated that the 4-thia FA partly attenuated the effects of the 3-thia FA on mitochondrial FA oxidation and the hepatic TAG level. In summary, the position of the sulfur atom in the alkyl chain, especially whether it is placed in the even or odd position, is crucial for the biological effect of the thia FA. The first and second authors contributed equally to the work.     

Polymorphism of mixed triglycerides containing odd fatty acids

Paris of C _n C_(n+1)C _n (i.e., C₁₆C₁₇C₁₆ and C₁₈C₁₉C₁₈) and C _n C_(n-1)C _n triglycerides (C ₁₆ C ₁₅ C ₁₆ and C ₁₈ C ₁₇ C ₁₈ ) triglycerides,n even, were prepared to compare with C _n C_(n+2)C _n and C _n C_(n-2)C _n glycerides, respectively, in polymorphic behavior. It was found that C _n C_(n+1)C _n compounds were β′ tending and C _n C_(n-1)C _n compounds β tending in line with their all-even counterparts. The glyceride C₁₁C₁₃C₁₁ is β′ stable, like C₁₀C₁₂C₁₀ and C₁₆C₁₈C₁₆, and seems closely related to them in physical behavior and diffraction characteristics.     

Foam separation of active carbon

An experimental investigation is presented of the foam separation of powdered active carbon, equilibriated with an aqueous, synthetic waste water containing phenol and a cationic (ethylhexadecyldimethylammonium bromide (EHDA-Br)), anionic (dodecyl sodium sulphate), or non-ionic (alkyl phenoxy polyethoxy ethanol) surfactant. The effect of surfactant, of pH, of initial carbon concentration, and of initial surfactant concentration on the flotation of carbon is investigated. At pH 3, 7, and 10, the cationic surfactant yields the best flotation of carbon, which increases with increasing pH. At pH 7, a suspension containing 800 mg/1 carbon can be reduced to 24 mg/1 in 10 min. with 0·37 mM EHDA-Br. The relative concentrations of carbon and of surfactant must be controlled carefully to yield sufficient free surfactant to obtain a foam but not excessive free surfactant to impair the foam separation process. Foam volumes are controlled by free (non-adsorbed) surfactant.     

Production of odd chain polyunsaturated fatty acids byMortierella fungi

A soil isolate,Mortierella alpina 1S-4, was found to show high production of odd chain polyunsaturated fatty acids (PUFAs) among various arachidonic acid-producingMortierella strains tested. The fungus mainly accumulated 5,8,11,M-cis-nonadecatetraenoic acid. With 5%n-hepta-decane and 1% yeast extract as growth substrates, the amount of C_19:4:4 acid accumulated reached 44.4 mg/g dry mycelia (0.68 mg/mL of culture broth). This value accounted for 11.2% of the total fatty acids in the extracted lipids from mycelia, and odd chain fatty acids comprised over 95% of the total mycelial fatty acids. The addition of sesamin, a specific inhibitor of A5 desaturation, caused an increase in C_19:3 acid and an accompanying decrease in C_19:4 acid. On the other hand, species ofMortierella that could not produce C-20 PUFAs accumulated C-17 acids, but no C-19 PUFAs, when grown with fatty substrates with an odd chain skeleton. The odd chain PUFAs were distributed in both neutral and polar lipids. The biosynthetic route to C_19:4 acid was presumed to mimic the n-6 route to arachidonic acid as follows: C_17:0 → C_17:1→ C_17:2→ C_17:3 → C_19:3 → C_19:4 acids. On leave from Suntory Ltd.     

皂氨型洁面的开发及性能研究

根据皂氨型洁面的开发需求,首先筛选合适的皂基型表面活性剂和氨基酸型表面活性剂;然后对皂基型表面活性剂和氨基酸型表面活性剂的配比进行优化,得出最优配比;最后将制得的复配皂氨型洁面与市售单一的皂基型洁面和单一的氨基酸型洁面的性能进行对比测试。结果表明,皂氨复配的皂氨型洁面对皮肤刺激性比单一皂基型洁面和单一氨基酸型洁面都小;皂氨复配的皂氨型洁面对油脂的清除率介于单一的皂基型和单一的氨基酸型洁面之间,为90.2%;皂氨型洁面在使用感方面整体上优于单一皂基型洁面和单一氨基酸型洁面。     

Effect of molecular weights of fatty acid esters on cetane numbers as diesel fuels

Cetane numbers for various esters of the saturated fatty acids from C8 to C18 have been determined according to ASTM D-613. For the methyl esters the cetane numbers were found to increase in a non-linear relationship with the chain length of the fatty acid. Cetane numbers of esters in which the fatty acid is kept constant while the alcohol esterified is altered also increased with the molecular weight of the ester. However, increases in the molecular weight of the fatty acid portion of the ester produce greater increases in cetane number than the same change in molecular weight in the alcohol portion of the ester. Except for the esters of octanoic acid, all of the esters tested had cetane numbers above the value of 40, which is specified as the minimum cetane number for commercial diesel fuel.     

X-Ray diffraction study of sodium soaps of monounsaturated and polyunsaturated fatty acids

X-Ray powder diffraction patterns of the sodium soaps of 14 monounsaturated and polyunsaturated fatty acids were obtained at room temperature. The patterns of the soaps of 9,12-trans,trans-octadecadienoic acid, 11,14-cis,cis-eicosadienoic acid 11,14,17-allcis-eicosatrienoic acid and 5 monounsaturated fatty acids were typical of the crystalline lamellar phase. The patterns of the soaps of 9,12-cis,cis-octadecadienoic, allcis-9,12,15-octadecatrienoic, allcis-8,11,14-eicostrienoic, allcis-5,8,11,14-eicosatetraenoic, allcis-5,8,11,14,17-eicosapentaenoic and allcis-4,7,10,13,16,19-docosahexaenoic acids were indicative of the less ordered forms reported for sodium oleate at elevated temperature. The diffraction data from the less ordered soaps are consistent with the melted form of the hydrocarbon chains of the unsaturated acids at room temperature.     

蔗糖脂肪酸酯的合成与性能研究

在酸催化作用下乙醇与硬脂酸反应合成了硬脂酸乙酯.以硬脂酸乙酯和蔗糖为原料,采用DMF溶剂法,在碱性条件下通过酯交换反应合成了硬脂酸蔗糖酯.采用正交实验设计对反应条件进行优化,在最佳工艺条件下产率可高达95.8%.测定了产品的表面化学性能.结果显示,产品的临界胶束浓度(cmc)为2.228×10-4 mol/L,此时的表面张力为39.88 mN/m,其钙皂分散、乳化、增溶等表面化学性能优良.     

High performance liquid chromatographic separation of sucrose fatty acid esters

The synthesis of sucrose fatty acid esters always results in complex mixtures. Two procedures for quantitative analysis of sucrose monoesters, respectively sucrose diesters, by means of high performance liquid chromatography on reversed-phase columns, are described. A mixture of methanol and water (85:15, v/v) was used for the separation of the monoesters, while methanol, ethyl acetate and water (65:25:10, v/v/v) was used for the separation of diesters. These methods gave information about the amount of monoesters and diesters in the product; the ratio between sucrose monopalmitate and sucrose monostearate, and the number of the most important structure isomers. A complete separation of all the possible diester products seemed to be impossible, due to the presence of more complex structure isomers. The described procedures can give important support during preparative work on sucrose fatty acid esters and also in the evaluation of these products for application purposes.