Sodium salts of alkyl esters ofa-sulfo fatty acids. Wetting,lime soap dispersion,and related properties

A series of esters of the general formula RCH(SO₃Na)-CO₂R′ of 14–19 carbon atoms prepared by the α-sulfonation of propionic, butyric, pelargonic, lauric, myristic, palmitie, and stearic acids and esterification with normal primary alcohols were compared for critical micelle concentration, surface and interfacial tension, Ca⁺⁺ stability, wetting properties, foam height, detergency, and lime soap dispersing properties. Comparison of position isomers showed that as the hydrophilic portion moved from the center toward either end, cmc and wetting efficiency decreased, surface and interfacial tension increased, and Ca⁺⁺ stability and lime soap dispersing properties improved. A coconut oil fatty acid forerun sulfonated with SO₃ vapor and esterified with 2-ethylhexanol gave a product with useful wetting properties in soft and hard water. Presented at the fall meeting, American Oil Chemists' Society, Chicago, October 30–November 1, 1961. Eastern Utilization Research and Development Division, Agricultural Research Service, U. S. Department of Agriculture.     

Benzyl,cyclohexyl, and phenyl esters ofalpha-sulfo fatty acids

Sodium salts of benzyl, cyclohexyl, and phenyl esters of α-sulfopelargonic, α-sulfopalmitic, and α-sulfostearic acids were prepared by reaction of the α-sulfo acid with excess of the alcohol or phenol, in the presence of methylene chloride, carbon tetrachloride, benzene, or toluene. Synthesis from the acid chloride of the α-sulfo acid gave lower yields of a less pure product. Melting point, surface and interfacial tension, critical micelle concentration, rate of hydrolysis and wetting, foaming and detergent properties were measured. The ring esters have properties similar to the corresponding propyl, butyl, or amyl esters. Presented at the AOCS Meeting, New Orleans, May 1967. E. Util. Res. Dev. Div., ARS, USDA.     

Sulfonated branched chain fatty acids and esters

In continuation of work reported a year ago describing branched chain fatty acids, a series of monosodium methyl 2-sulfo-2-alkylalkanoates [RR'C (SO₃Na) CO₂CH₃] were synthesized. The surface active properties of these compounds were evaluated and compared with the corresponding disodium 2-sulfo-2-alkylalkanoates [RR'C (SO₃Na)CO₂Na]. Alkaline hydrolysis rates show that the sodium methyl esters are stable. Relative to the disodium salts, these compounds exhibit better wetting properties and more stable foams. Presented at the AOCS Meeting, Cincinnati, October 1965. E. Utiliz. Res. Dev. Div., ARS, USDA.     

Surface-active properties of salts of alpha-sulfonated acids and esters

Summary In a comparison of the solubility, detergency, and surface-active properties of the mono- and disodium salts ofa-sulfonated lauric, myristic, palmitic, and stearic acids, it has been shown that the less solublea-sulfopalmitates anda-sulfostearates, and sodiuma-sulfomyristic acid as well, are the best detergents. The easily soluble disodiuma-sulfolaurate resembles a simple electrolyte with little evidence of surface-active properties. Ammoniuma-sulfopalmitic acid and triethanolammoniuma-sulfopalmitic acid are more soluble surface-active agents and detergents than the sodium salts. Triethanolammoniuma-sulfopalmitic acid is exceedingly soluble in water at room temperature. The sodium salts of alkyla-sulfopalmitates anda-sulfostearates are easily prepared from the isolated crude diacid. The esters of primary alcohols containing from one to six carbon atoms are readily soluble in water and quite stable to hydrolysis, especially in acid solution. Salts ofa-sulfonated esters of secondary alcohols are stable both to acid and to alkaline hydrolysis. This behavior extends the range of possible application. Presented at the Fall Meeting of the American Oil Chemists’ Society, Chicago, Ill., November 2–4, 1953. One of the laboratories of the Bureau of Agricultural and Industrial Chemistry, Agricultural Research Administration, U. S. Department of Agriculture.     

Autoxidation kinetics for fatty acids and their esters

The autoxidation kinetics for n-3 and n-6 polyunsaturated fatty acids and their esters, which are collectively referred to as polyunsaturated fatty acids (PUFA), were investigated. Changes in the amounts of unreacted n-6 PUFA during the entire period of autoxidation could be expressed by dY/dt−k ₁ Y(1 −Y), wereY was the fraction of unreacted PUFA,t was the time, andk ₁ was the rate constant. For n-3 PUFA, autoxidation had to be separated into two parts. The first half of autoxidation (Y ≥ 0.5) was expressed by the same equation as above, while the latter half (Y<0.5) relates to dY/dt=−k ₂ Y, wherek ₂ was the rate constant. The apparent activation energies and the frequency factors ofk ₁ andk ₂ were evaluated. The apparent activation energies were in a range of 50 to 60 kJ/mol for bothk ₁ andk ₂. The frequency factor became large as the number of double bonds of PUFA increased.     

脂肪酰氧乙基磺酸盐类表面活性剂的研究进展

综述了脂肪酰氧乙基磺酸盐类表而活性剂的合成、性能及应用,重点讨论了其合成方法,分别介绍了以脂肪酸为原料、以酰氯为原料和酯交换等方法.对其研究趋势进行了展望.因原料来源于天然脂肪酸,其性能温和,易生物降解,可广泛应用于日用化学品配方.     

Fatty acids,fatty alcohols,wax esters,and methyl esters fromCrambe abyssinica andLunaria annua seed oils

Crambe abyssinica andLunaria annua, members of the Cruciferae family, have seed oil glycerides containing ca. 55–65% of C₂₂ and C₂₄ unsaturated fatty acids. Fatty acids were prepared by saponification; fatty alcohols, by sodium reduction of glycerides; liquid wax esters, byp-toluenesulfonic acid-catalyzed reaction of fatty acids with fatty alcohols; and methyl esters, by reaction of fatty acids with diazomethane. Solid hydrogenated glyceride oils and wax esters were compared with several commercial waxes. Chemical and physical constants were determined for the seed oils and their derivatives. Position of unsaturation in theCrambe fatty acids was determined by gas chromatographic analysis of the permanganate-periodate degradation products. The major dicarboxylic acid was brassylic (C₁₃), proving the docosenoic acid to be erucic. Presented in part at the AOCS meeting in New Orleans, La., 1962. A laboratory of the No. Utiliz. Res. & Dev. Div., ARS, U.S.D.A.     

Addition of chlorine to unsaturated fatty acids and esters

Summary Methyl oleate, oleic acid, and ethyl linoleate were chlorinated with elemental chlorine at temperatures near −20°C. Approximately quantitative yields of the addition products were obtained, with little or no concurrent substitution. The products prepared in this manner had not previously been reported in the pure state. Two new compounds, ethyl tetrachlorostearate and tetrachlorostearic acid, were prepared. Methyl dichlorostearate was found to distil with no apparent decomposition at 190–200°C. under pressures below 1 mm. Removal of the chlorine atoms required more drastic conditions that removal of bromine atoms from the same positions and was accompanied by complicating side reactions. Journal Paper No. 755 of the Purdue University Agricultural Experiment Station, Lafayette, Ind.     

Hexitol and sucrose esters of α-sulfo fatty acids

Use of the α-sulfo acid, the acid chloride and the methyl ester was explored in the preparation of mannitol, sorbitol and sucrose esters of α-sulfopalmitic and α-sulfostearic acids. The products were difficult to purify because of solubilization of reactants. The α-sulfo esters are more soluble and more resistant to hydrolysis than hexitol and sucrose palmitates and stearates. Presented at the AOCS Meeting, New York, October 1968. ARS, USDA.     

Characterization of esters of fatty acids and dicarboxylic acids with Guerbet alcohols

Esters of some common fatty acids and diacids with Guerbet alcohols were prepared by p-toluenesulfonic acid-catalyzed esterification. Such materials are of interest in applications such as additives in various industrial products. Gas chromatography-mass spectrometry with chemical ionization using methane as ionization gas is an efficient characterization method for these Guerbet esters and diesters. Under these conditions, structural features such as molecular weight and site of branching are easily determined. The spectra of the present compounds were compared to those of di-Guerbet esters reported earlier and differences noted. The compounds were also characterized by ¹³C nuclear magnetic resonance spectroscopy.     

Efficient synthesis of fatty monoglyceride sulfates from fatty acids and fatty acid methyl esters

An efficient high yield synthesis of fatty monoglyceride sulfates from fatty acids or fatty acid methyl esters, glycerine and chlorosulfuric acid in chloroform using stoichiometric amounts of reagents was developed. Sodium coco monoglyceride sulfate was prepared in 79% yield with 93% purity from coco fatty acids. Similarly, sodium palm kernel monoglyceride sulfate in 57% yield and sodium palm monoglyceride sulfate in 71% yield were obtained from palm kernel fatty acid methyl esters and palm fatty acids, respectively. This new synthetic method produced better quality products with higher active ingredients and improved yields without having to use such cost prohibitive, high purity, fatty acid monoglycerides, and it reduced the undesirable aqueous sodium sulfate by-product by 60% over a current commercial process. The product’s composition and purity were confirmed by cationic titration, infrared and C-13 NMR spectroscopy.     

α-Sulfonated fatty acids and esters: Manufacturing process,properties, and applications

α-Sulfonated fatty acid esters, because of their wide-range of application and biological properties, represent an interesting class of surfactants. A technical method for the preparation of α-sulfonated fatty acid esters is described. By using special reaction conditions it is possible to α-sulfonate saturated fatty esters directly without the use of solvents. The use of gaseous SO₃ gives the product in greater than 97% yield. A process for the bleaching of the α-sulfonated fatty esters has been developed, whereby a product of faultless color is produced without the necessity of further purification or separation techniques. The sulfonation and bleaching processes operate continuously. The process has been tried successfully on a commercial scale using the methyl esters of technical fatty acids. Methods for the preparation of α-sulfonated fatty acids are given. The chemical, technical, and biological properties of the α-sulfonated fatty acids and their esters are discussed. α-Sulfonated fatty esters possess good washing and foaming properties, have good biological degradability, possess good skin compatibility and low acute toxicity. They can be considered as surfactant components for phosphate-free or low-phosphate detergents. α-Sulfonated fatty acids and esters also possess other favorable technical properties which allow them to be used in cosmetics, as auxiliary agents in the production of fibers, plastics, and rubber, and in leather manufacture.     

Maleyl esters of monoglycerides of saturated fatty acids

Esterification between maleic anhydride and monoglycerides of saturated fatty acid has been studied. The nature of reaction vessels, temperature and reaction time have been evaluated in view of the product distribution in the final product. Concentration of monoesters (half-esters) diesters and dimers has been calculated and related to the reactants’ ratio, time and temperature of the esterification.     

Polyhydric alcohol esters of α-sulfo fatty acids

Direct esterification of α-sulfopalmitic and α-sulfostearic acids with excess ethylene glycol, glycerol, pentaerythritol and 2-methoxyethanol was carried out in carbon tetrachloride to give products containing essentially monoesters. Surface active properties of these compounds were measured with emphasis on washing ability in combination with soap. The detergency of these esters was compared with those of hexitol and sucrose α-sulfo fatty acid esters. Although the esters had moderate lime soap dispersing ability, their detergency showed synergism when combined with soap. Deceased. East. Market. Nutr. Res. Div., ARS, USDA.     

Autoxidation of methyl esters of cyclopentenyl fatty acids

The early stages of the autoxidation of methyl hydnocarpate, chaulmoograte and gorlate in air have been examined at 40, 60 and 80 C, and the initial products have been compared by several methods with those derived from methyl oleate and linoleate autoxidized at 60 C. To supplement information about oxygen absorption and peroxide development in relation to time, other information about the early products, and some information about the reduced products, have been obtained by ultraviolet (UV) and infrared (IR) spectrophotometry, and by thin layer chromatography (TLC). The kinetic and other data presented in this study strongly support the conclusion that the methyl esters of cyclopentenyl fatty acids yield initial autoxidation products that, although they are primarily peroxides, differ in some ways (as expected) in the kinetics of their formation and their chemical nature, compared to those of oleate and linoleate. Nevertheless, all the data obtained strongly support the surmise that the peroxides are formed autocatalytically by a chain mechanism, and that secondary products not derived from peroxide decomposition, are formed pari passu in lesser, but increasing amounts with increasing temperature, probably from free radical intermediates. The autoxidation of esters of cyclopentenyl fatty acids has potential importance in several ways, 3 of which are mentioned briefly.     

Stability ofd-a-tocopherol alone,in solvents,and in methyl esters of fatty acids

Summary The stability ofd-a-tocopherol in stable solvents and in methyl esters of fatty acids varied with the stability of the medium and with the concentration of tocopherol. Pure tocopherol was less stable than tocopherol in solvents. The concentrations of tocopherol that were most effective in delaying rapid oxidation of the esters were also best for stability of tocopherol itself. The rate of destruction of tocopherol could not be described by simple kinetics. N.R.C. No. 4429 Contribution from the Division of Applied Biology, National Research Laboratories, Ottawa, Canada.     

Selective hydrogenation of fatty acids and methyl esters of fatty acids to obtain fatty alcohols–a review

In this paper, a review is presented of the evolution of different catalytic systems and operating conditions used in the selective hydrogenation of acids and esters of fatty acids to obtain fatty alcohols, which have broad industrial applications in the oleochemical industry. In addition, the current status of the different technologies used industrially (Lurgi, Davy and Henkel) for obtaining fatty alcohols, as well as major global sources of raw materials for the oleochemical industry are put forward. Finally, the reaction mechanisms of the selective hydrogenation process of oleic acid and methyl oleate to obtain the corresponding unsaturated alcohol as well as the new catalysts proposed by researchers are described. © 2016 Society of Chemical Industry