Ether alcohol sulfates from oleyl alcohol

Oleyl alcohol was caused to react with ethylene oxide, propylene oxide, and 1,2-butylene oxide in the presence of an alkaline catalyst. The first and second derivatives from each reaction were isolated by fractional distillation. Sulfation with dioxane-SO₃ gave high-purity oleyl ether sulfates, easily soluble, with good detergent and lime soap-dispersing properties. The use of chlorosulfonic acid or sulfuric acid as the sulfating agent for oleyl ether alcohols resulted in about 60% retention of the double bond, compared with oleyl alcohol, which under the same conditions retained only about 25% unsaturation. Oleyl ether alcohols sulfated with chlorosulfuric acid or sulfuric acid are easily sobuble and have good lime soap-dispersing properties. They are able to solubilize less soluble soaps and saturated ether alcohol sulfates. Presented at the AOCS Meeting, New Orleans, May 1967 E. Utiliz. Res. Dev. Div., ARS, USDA     

Chlorinated alcohols: II. The chlorination of oleyl alcohol

Chlorination of oleyl alcohol gives mainly 9,10-dichlorostearyl alcohol but a variety of other products are also formed. By-products include 9(10)-(9,10-dichlorostearoxy)-10(9)-chlorostearyl alcohol (14%) and 9,10-dichlorostearyl 9,10-dichlorostearate (3–4%) in addition to three or four less clearly defined products (12%). One group of products is apparently derived from participation of the hydroxyl group in the chlorine addition step while the other products formed by the reaction of the hydroxyl group with chlorine or chlorine and hydrogen chloride.     

Experiments in the formulation of heavy duty liquid detergents from tallow

Several tallow-based detergents were investigated in simplified formulations comprising ca. 10~15% active ingredient, 4% foam stabilizer, 10% isopropyl alcohol, 20% K₄P₂O₇ and 50~55% water, 1% with respect to carboxymethylcellulose. Disodium 2-sulfoethyl α-sulfostearate or sodium oleate could be used as the only active ingredient or in blends with other tallow-based compounds. The presence of a soluble form of the tallow alcohol sulfates, sodium 9,10-dichlorooctadecyl sulfate, gave maximum detergency in hard water. Presented at the AOCS Meeting, Minneapolis, 1963. E. Utiliz. Res. and Dev. Div., ARS, USDA.     

Properties and uses of some unsaturated fatty alcohols and their derivatives

A number of unsaturated fatty alcohols are known, but only those of the C₁₆ and C₁₈ chain lengths are of much importance. In particular, oleyl alcohol., 9,10-octadecenol-1, is by far the most important. A variety of grades of oleyl alcohols is produced and used in the USA ranging from high purity material having iodine values (IV) of 90–95 to those having IV of 45–55, with the other components being primarily cetyl (hexadecanol-1) and stearyl (octadecanol-1) alcohols. This paper takes a brief look at the various grades of unsaturated alcohols used in the USA, methods of preparation, and the change in physical and chemical properties as the octadecanol-1 content and IV decline. Uses of these alcohols industrially and in cosmetic and pharmaceutical preparations are also discussed. Unsaturated alcohols are useful chemical intermediates since they have two reactive sites, the hydroxyl group and the carbon-carbon double bond. Particular attention is paid to the properties, uses and potential uses of some of their sulfates, ether sulfates, ethylene oxide adducts and ethylene/propylene oxide adducts as detergents and emulsifiers for ultimate use in cosmetics and light-duty and heavy-duty systems. Current estimated consumption of unsaturated alcohols in the USA is discussed.     

The a-sulfonation of pelargonic,stearic, and substituted stearic acids

Direct sulfonation of higher fatty acids with sulfur trioxide or chlorosulfonic acid, without use of solvent, is possible, but the product must then be isolated as the sodium salt. Use of a chlorinated solvent permits isolation of the α-sulfo acid. Sulfonation with dioxane sulfur trioxide in place of sulfur trioxide gave a nearly colorless α-sulfostearic acid. Substituted stearic acids derived from oleic or elaidic acids (phenyl-, 9,10-dichloro-, and 9,10-dihydroxystearic acids) were α-sulfonated with dioxane sulfur trioxide. Solubility, detergent, and surface-active properties were examined and related to structure. The surface-active properties of sodium α-sulfopelargonic acid are not very evident, but the octyl ester, with a much lower critical micelle concentration (0.08% compared to 1.00%), was found to be a very efficient wetting agent. Presented at the fall meeting, American Oil Chemists’ Society, New York, N. Y., October 17–19, 1960. Eastern Utilization Research and Development Division, Agricultural Research Service, U. S. Department of Agriculture.     

Synthetic detergents from animal fats. The sulfation of tallow alcohols

Summary Sodium oleyl sulfate (or the trans isomer) is a desirable component in a mixture of sulfated tallow alcohols, principally because of its ready solubility in water at room temperature. The use of moderate sulfating agents, which can be thought of as complexes formed with either sulfur trioxide, chlorosulfonic acid, or sulfuric acid, has been shown to give products having good detergent and surface-active properties. Desirable properties are generally related to the purity of the product and to the extent to which side reactions at the double bond are minimized or avoided. Presented at the annual meeting of the American Oil Chemists’ Society, in San Antonio, Tex., April 12–14, 1954.     

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.     

Octadecylsulfuric acid. Properties of the acid,amine salts,and salts of amino acids

Summary Octadecanol, hexadecanol, tetradecanol, and dodecanol were sulfated with chlorosulfonic acid, and the corresponding alkylsulfuric acids were isolated in a pure state as white crystalline solids with definite melting points. Octadecylsulfuric acid resembles sodium octadecyl sulfate in detergent and surface-active properties and in stability to hydrolysis at equal concentrations of hydrogen ion. It is more soluble in water than sodium octadecyl sulfate and readily soluble in organic solvents. The critical micelle concentration (0.0387 millimoles/I.) is only about one-third that of the sodium salt. Isolation of octadecylsulfuric acid as a useful chemical intermediate made possible the preparation of a number of salts with amines and amino acids and their rapid screening for useful properties. Presented at the spring meeting, American Oil Chemists' Society, New Orleans, La., April 20–22, 1959. Eastern Utilization Research and Development Division, Agricultural Research Service, U. S. Department of Agriculture.     

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.     

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.     

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.     

Nuclear magnetic resonance studies on hydrolysis kinetics and micellar growth in solutions of surface-active betaine esters

A series of surface-active betaine esters of medium- to long-chain alcohols has been synthesized. The hydrophobic parts used were decyl, dodecyl, tetradecyl, and oleyl chains. Ethyl betainate was prepared as a non-surface-active reference compound. The surfactants were characterized by critical micellization concentration (CMC), and base-catalyzed hydrolysis was studied by using ¹H nuclear magnetic resonance (NMR). Micellar catalysis was shown to have a strong influence on the hydrolysis. This means that the hydrolysis rates are concentration dependent. For dodecyl betainate, the effect of the degradation products (dodecanol and betaine) on the micellar shape was investigated by NMR diffusion experiments. The degradation products were shown to induce micellar growth.     

Reactions of dimethyl sulfoxide with sulfonate esters of fatty alcohols. I. Synthesis of higher saturated and unsaturated fatty aldehydes

Long-chain saturated fatty aldehydes (C₁₀ to C₁₈), as well as the C₁₈ unsaturated aldehydes (oleyl, linoleyl, and linolenyl), were synthesized in good yields by the selective oxidation of the sulfonate esters of the corresponding alcohols with dimethyl sulfoxide in the presence of sodium bicarbonate. Chromatographic procedures for the isolation of the pure aldehydes from the reaction mixtures are described. The purity of the aldehydes was ascertained by thin-layer chromatography, melting points of their 2,4-dinitrophenyl hydrazones, infrared spectra and other physical methods. Presented at the AOCS Meeting in Houston, April, 1965.     

A study of the surface activity of tertiary alcohol sulfates

A number of tertiary alcohols were prepared by the action of a series of Grignard reagents on ethyl oleate. The tertiary alcohols were converted to alkyl sulfates by reaction with sodium chlorosulfonate. The surface active properties of the prepared sodium alkyl sulfates were studied in relation to the length of the branched chain and the bulkiness of the charged head of the surfactants.     

Preparation of some ethyl higher-alkyl acetals and their conversion to vinyl ethers

Unsymmetrical acetals were prepared from stearyl, oleyl, and the mixed alcohols, derived from linseed oil, by the acid-catalyzed addition of each alcohol to ethyl vinyl ether. Stearyl, oleyl, and linseed-alkyl vinyl ethers were obtained by cleavage of ethanol from the respective unsymmetrical acetals over alkali-metal bisulfates, sulfanilic acid, or aniline sulfate-sulfuric acid. Yields of the higher alkyl vinyl ethers were moderate due to disproportionation and formation of ethyl vinyl ether from the acetals. Presented at fall meeting. American Oil Chemists' Society, Los Angeles, Calif., September 28–30, 1959. Paper Number 11 of a series. “Reactions of Unsaturated Fatty Alcohols”. This is a laboratory of the Northern Utilization Research and Development Division, Agricultural Research Service, U.S. Department of Agriculture.     

Soap—Based detergent formulations: XXV. Synthesis and surface active properties of higher molecular weight betaine lime soap dispersants

A series of surface active betaines have been prepared via the quaternization of a tertiary amine with drolysis. The betaines possessed a hydrophobic (C₁₂-C₁₆) alkyl side chain, and the anionic and cationic sites were separated by one, two, or three methylene groups or a benzyl group. The betaines were more water soluble and were poorer lime soap dispersants than analogous sulfobetaines. Detergency of most soap-based detergent formulations containing the betaine lime soap dispersants was good and generally close to that of a commercial control detergent containing 50% sodium tripolyphosphate in screening tests conducted in water of 300 ppm hardness. Fats and Proteins Research Foundation fellow stationed at Eastern Regional Research Center. Federal Research, Science and Education Administration, U.S. Department of Agriculture.     

Synthetic detergents from animal fats. X. Sulfated,ethenoxylated tallow alcohols

Summary Sulfated ethenoxylated tallow alcohols of average composition corresponding to the formulas C₁₆H₃₃(OC₂H₄)₂OSO₃Na, C₁₈H₃₇(OC₂H₄)₂OSO₃Na, and C₁₈H₃₇(OC₂H₄)₁₀OSO₃Na, were prepared by ethenoxylation and sulfation of hexadecanol and octadecanol. The incorporation of two ethenoxy groups improved solubility without loss in detergency compared to the corresponding sodium hexadecyl and octadecyl sulfates. With consideration also of economy in the number of ethenoxy groups, two appear to be near the optimum. The product with 10 ethenoxy groups was an even more readily soluble but less effective detergent. Of the sulfated ethenoxylated tallow alcohols, sodium hexadecyloxyethoxyethyl sulfate [C₁₆H₃₃(OC₂H₄)₂OSO₃Na] had the lowest surface-tension and the best foaming properties; sodium octadecyloxyethoxyethyl sulfate [C₁₈H₃₇(OC₂H₄)₂OSO₃Na] was the best emulsifying agent; and the product with 10 ethenoxy groups [C₁₈H₃₇(OC₂H₄)₁₀OSO₃Na] had the greatest stability in regard to metallic ions and to acid hydrolysis. All three were excellent lime-soap dispersing agents with good or excellent emulsifying properties and stability in regard to metallic ions. Presented at the meeting of the American Oil Chemists' Society, New Orleans, April 29–May 1, 1957. For number IX in this series see reference (18). A laboratoryof the Utilization Research and Development Division, Agricultural Research Service, U. S. Department of Agriculture.     

The oxyethylation of 9, 10-octadecanediols and 9, 10-dihydroxystearonitrile. Nonionic soaps

The alkali-catalyzed reaction of ethylene oxide with themeso- anddl-forms of 9,10-octadecanediol and withthreo-9,10-dihydroxystearonitrile was carried out in an apparatus that was equipped with automatic controls for temperature and pressure. The earlier consumption found for thedl-form compared to themeso is attributed to intramolecular hydrogen bonding. A characteristic constant for the distribution of products is calculated. The products formed are nonionic surface-active agents with the hydrophilic portion at the middle rather than at the end of the hydrophobic chain. Properties were primarily determined by the value of n, the average number of oxyethyl groups. Optimum emulsifying properties were found at n=4; optimum wetting at n=12. The oxyethylated nitriles were hydrolyzed to the corresponding “nonionic soaps”, which have typical nonionic characteristics; unlike soap they are not easily precipitated by hard water or various metal ions. Presented at the Annual Meeting, American Oil Chemists' Society, St. Louis, Mo., May 1–3, 1961. Eastern Utilization Research and Development Division, Agricultural Research Service, U. S. Department of Agriculture.     

Chlorine-stable machine dishwashing products

The increasing use of active chlorinecontaining compounds in machine dishwashing has led to the need for chlorine-stable, low foaming detergent formulations. To avoid oxidative degradation of nonionic surfactant and simultaneous loss of available chlorine, a new basic formulation process has been devised. This obviates the need for modifying nonionic surfactants. The process requires a preferred order of addition and the use of tetrasodium pyrophosphate builder as an integral part of the composition. The detergent product is free-flowing, granular, readily soluble and exhibits no tendency to cake on storage. A suggested machine dishwashing formulation is given, and data are presented which show good chlorine stability and excellent dishwashing performance. Presented at the AOCS-AACC Joint Meeting, Washington, D.C., April 1968.     

Fatty alcohols

“Fatty” or higher alcohols are mostly C₁₁ to C₂₀ monohydric compounds. In probably no other homologous aliphatic series is the current balance between natural and synthetic products so vividly evident. Natural sources, such as plant or animal esters (waxes), can be made to yield straight chain (normal) alcohols with a terminal (primary) hydroxyl, along with varying degrees of unsaturation. In the past, socalled fatty alcohols were prepared commercially by three general processes from fatty acids or methyl esters, occasionally triglycerides. Fatty acids add hydrogen in the carboxyl group to form fatty alcohols when treated with hydrogen under high pressure and suitable metal catalysts. By a similar reaction, fatty alcohols are prepared by the hydrogenation of glycerides or methyl esters. Fatty alcohols are also prepared by the sodium reduction of esters of fatty acids in a lower molecular weight alcohol. The sodium reduction method was ordinarily too expensive; it was displaced early by the other methods; finally most unsaturated alcohols made by this route were largely replaced. Methyl ester reduction continues to provide perhaps 20% of the saturated fatty alcohols, and selective hydrogenation with the use of special catalysts such as copper or cadmium oxides was developed for the production of oleyl alcohol. Synthetic or petroleum technology for long chain alcohols include the Ziegler process, useful for straight chain, even-numbered saturated products. A second is the carbonylation and reduction of olefins affording medium or highly branched chain alcohols. Paraffin oxidation affords mixed primary alcohols. Fatty alcohols undergo the usual reactions of alcohols. They may be reacted with ethylene oxide to yield a series of polymeric polyoxyethylene alcohols or with acetylene under pressure to yield vinyl ethers or with vinyl acetate to give vinyl ethers.