Soap-based detergent formulations: II. Oxyethylated fatty amides as lime soap dispersing agents

Nonionic surface active agents with two oxyalkyl chains were prepared from the triethylamine catalyzed reaction of ethylene oxide with diethanolamides of palmitic, stearic and tallow fatty acids. The addition of 4 moles of ethylene oxide was required to render these diethanolamides water soluble, whereas 9 moles were required to make the corresponding monoethanolamide soluble. Efficiency of lime soap dispersion increased as oxyethyl chain length was increased. Best detergency of soap-nonionic combinations was achieved when the oxyethyl chain length was at the minimum required for water solubility. Theγ-hydroxyethanolamides and -diethanolamides were prepared by the uncatalyzed reaction of the corresponding amines withγ-stearolactone. These compounds became water soluble at lower levels of oxyethylation, but the lime soap dispersing power and detergency were not improved over those of corresponding compounds derived from stearic acid. Presented at the AOCS Meeting, Los Angeles, April 1972. E. Market. Nutr. Res. Div., ARS, USDA.     

Soap-based detergent formulations: IX. α-sulfo fatty alkanolamides as lime soap dispersing agents

α-Sulfo fatty alkanolamides were prepared by sodium methylate catalyzed reactions of methyl α-sulfo fatty esters with alkanolamines, such as ethanolamine, N-methyl-2-hydroxyethylamine, diethanolamine, 3-hydroxypropylamine, 2-hydroxypropylamine, and diglycolamine. Pure compounds, such as α-sulfo palmitamides and stearamides, as well as the α-sulfo tallow amides, were prepared and evaluated as surface-active agents. The α-sulfo fatty alkanolamides were found to have excellent stability to alkali. Their stability to acid ranged from excellent in the case of α-sulfo diglycolamides to poor in the case of α-sulfo diethanolamides. Poor stability to acid was related to ease of conversion to ester-amines. Washing tests on standard soil cloths showed that the compounds were good detergents by themselves and were also effective in combination with soap and silicates. Their lime soap dispersant requirements ranged from 7–10. Presented at the AOCS Meeting, September 1973, Chicago. ARS, USDA.     

C-21 dicarboxylic acids in soap and detergent applications

A unique polycarboxylic acid, 5(6)-carboxy-4-hexyl-2-cyclohexene-1-octanoic acid, has been available commercially for over 15 years. A new high-purity (>97%), light-color version of the C-21 dicarboxylic acid has been developed recently. Soaps of the C-21 dicarboxylic acid can be used as hydrotropes to increase the solubility of nonionic surfactants in aqueous solutions containing builders and/or anionic surfactants. Since these soaps are anionic fatty acid derivatives, they reduce the surface tensions of formulations, thus improving detergency. The nontoxic and biodegradable nature of this dicarboxylic acid makes it an attractive formulation component. This paper outlines application evaluations of the soaps prepared from the C-21 dicarboxylic acids. These evaluations demonstrate how the soaps interact with nonionic surfactants or pine oil to provide clear formulations, how they wet cotton skeins in neutral to highly alkaline solutions, and how they inhibit gel formation when preparing high-solids fatty acid soap solutions. Furthermore, the preparation and characterization of the soaps of the C-21 dicarboxylic acid products are discussed. Mass-balance equations describe the preparation of aqueous soap solutions at any given concentration. Characterization of the resulting soap solutions includes acid number, pH, color, color stability, foam stability, surface tension as a function of concentration, and hard-water compatibility.     

Tallow based detergent formulations: Mixtures of alcohol sulfates,salts ofa-sulfo acids and esters,and soap

Saturated (I, ROSO₃Na) and unsaturated (II, R’OSO₃Na) tallow alcohol sulfates, the disodium salt ofa-sulfonated saturated tallow fatty acids (III, RCH(SO₃Na)CO₂Na), the sodium salt of the methyl ester ofa-sulfonated saturated tallow fatty acids (IV, RCH(SO₃Na) CO₂CH₃), and commercial tallow soap flakes (V) were compared, singly and in combinations, as built and unbuilt solutions in soft and hard water, with respect to foam height and detergency, using four different types of standard soiled cotton. Built solutions of combinations of the two most soluble detergents, II and IV, at concentration 0.05% total active ingredient plus 0.20% builder in hard water of 300 ppm, remained perfectly clear on standing for several months. Built solutions containing I or II had the best foaming properties. The presence of soap decreased foam height. Cloths A and B showed the detergency of built solutions to be in the order I=II>IV>III>V, and all combinations containing I or II were superior detergents. With cloth C, detergents ranked in the order I=II=IV>III>V, and many combinations containing I or II with IV were synergistic. Cloth D did not distinguish sharply between detergents in built solutions in hard water. In general, detergent systems containing tallow alcohol sulfates witha-sulfo esters had the most desirable solubility, wetting, foaming, and detergent properties. Presented at the AOCS Meeting, Philadelphia, October 1966. E. Utiliz. Res. Dev. Div., ARS, USDA.     

Soap-based detergent formulations: XV. Amino esters of α-sulfo fatty acids

Amphoteric surfactants were prepared either by direct esterification of α-sulfo fatty acids with various alkanolamines or by rearrangement of the corresponding alkanolamides of the α-sulfo fatty acids to the amino esters with the aid of aqueous hydrochloric acid. The α-sulfo fatty acid monoesters of diethanolamine could be prepared only via the rearrangement method. The amino esters in the C₁₆−C₁₈ range possessed limited water solubility whereas α-sulfolaurate esters were soluble at room temperature. The amino esters were found to be stable to acid hydrolysis; however, they were generally not stable to alkali, by which they were either hydrolyzed or rearranged to the corresponding amide. Only the esters of isopropanolamine and diglycolamine were stable to alkali. Surface active properties of the esters were determined. The lime soap dispersant requirements of the compounds were slightly poorer than those of the corresponding amides. The compounds were good cotton detergents by themselves as well as in combination with soap and a silicate builder. The overall surface active properties of the amino esters were greatly inferior to those of the sulfobetaines previously reported. This indicates that an effective amphoteric lime soap dispersant should have its anionic group located at the very end of the molecule and the cationic group somewhat farther away, instead of the reverse. Presented at the AOCS Meeting, Philadelphia, September 1974.     

Soap-based detergent formulations: VIII. N-Alkylsulfosuccinamates as lime soap dispersants

A series of sodium methyl N-alkylsulfosuccinamates was prepared by the reaction of methyl N-alkylmaleamates with sodium bisulfite in aqueous ethanol. The surface-active properties and detergency of these derivatives were compared with those of a series of disodium N-alkylsulfosuccinamates prepared by the reaction of sodium sulfite with N-alkylmaleamic acid in water. The ester derivatives generally showed good lime soap dispersing requirement and washing ability in combination with soap, where-as the disodium salts were somewhat deficient in these properties and exhibited good washing ability only at 0.2% concentration with the surfactant as the sole component.     

Manufacture of soap from fatty acids

Soap manufacture from fatty acids is a well established precess with some advantages over continuous saponification of neutral fats. These include:

1. Ability to use cheaper fats.
2. Easier glycerol recovery.
3. Better control over by-products.
4. Versatility-fatty acids can be used to make other derivatives than soaps.

     

Soap based detergent formulations. V. Amphoteric lime soap dispersing agents

A series of amphoteric surfactants was prepared by the reaction of 1,3-propanesultone with fat derived primary amines, N-methylalkylamines, N,N-dimethylalkylamines, and N-acyl-N′,N′-dimethyl-1,3-propanediamines. Both mono- and disulfopropylated derivatives of the primary amines were synthesized. All compounds were found to be excellent lime soap dispersing agents. The quaternary sulfobetaines were found to possess the best detergency properties both by themselves and when formulated with tallow soap with or without sodium silicate builder. The detergency performance of such formulations is ca. the same as that of a commercial phosphate-built detergent. Presented at the AOCS Meeting, New Orleands, May 1973. ARS, USDA.     

Soap-based detergent formulations I. Comparison of soap-lime soap dispersing agent formulations with phosphate built detergents

Blends of soap with small amounts of lime soap dispersing agents are efficient detergents in hard water and require little or no tripolyphosphate builder. Lime soap dispersing agents examined include sulfated ethoxylated fatty alcohols, sulfated N-(2-hydroxyethyl) fatty amides, methyl esters of α-sulfo fatty acids, 2-sulfoethyl fatty acid esters and N-methyl-N-(2-sulfoethyl) fatty amides as well as nonionics derived from tallow alcohols. Detergency evaluations were carried out with three commercial soiled cotton cloths as well as by a laboratory multi-wash technique. Formulations containing 80% soap, 10% lime soap dispersing agent and 10% builder gave optimum detergency values. Builder effectiveness was rated tripolyphosphate>silicate (1:1.6)> metasilicate = citrate = oxydiacetate = nitrilotriacetate>carbonate≫sulfate. The detergency of soap-lime soap dispersed combinations compared favorably with a standard brand household heavy duty granular detergent in 50, 150 and 300 ppm hardness water on three soiled cloths. Presented at the AOCS Meeting, Atlantic City, October 1971. East. Market. Nutr. Res. Div., ARS, USDA.     

Alpha sulfo fatty esters in biologically soft detergent formulations

Salts of α-sulfo tallow and coconut esters were subjected to river die-away, activated sludge and Warburg tests, and results show these derivatives to be biologically soft detergents with disappearance curves approximating those of the fatty alcohol sulfates. Selection of the proper fatty acid starting material, alcohol of esterification, and alkali for neutralization provides for a high degree of flexibility in tailor-making biologically soft surface active agents for a wide range of applications. Selected compounds have been found which exhibit remarkable foaming, lime soap dispersing, fabric and hard surface detergency, wetting and related surface-active properties. These properties allow the formulation of a variety of synthetic and soap-synthetic combinations. Primary emphasis is given to the presentation of data on surfactant formulation application studies. Salts of short chain alkyl esters of α-sulfo tallow acid are ideally suited for “combo” soap bar and built heavy-duty detergent applications. Salts of short chain alkyl esters of selected coconut fatty acids are uniquely suitable for light duty liquids, cosmetic and related surfactant applications. An improved process for the manufacture of these sulfo esters has been developed which produces high yield, high purity and light colored products, and which should provide for their acceptance on a large scale in the detergent field. Presented at the 37th Annual AOCS Meeting, Minneapolis, Minn. Oct. 1, 1963.     

Studies in soap crystallization processes. Part III. Acid soap crystallization in the segregation of tall oil fatty acids

Tall oil fatty acids have been fractionated into 80–90% oleic acid, and 60–80% linoleic acid fractions, by precipitation of the oleic acid as acid soap from polar solvents. Sodium and potassium acid soaps are equally effective, but ammonium acid soaps require lower operating temperatures. The choice of solvent is not critical as regards degree of separation, but technically attractive filtration rates have been obtained only with methanol and acetone. Acidulation gives colorless oleic acid of very low rosin acid and unsaponifiable content, but with 5–10% of conjugated linoleic acid.     

Chemical and physical characteristics of soap made from distilled fatty acids of palm oil and palm kernel oil

Manufacture of soaps from distilled fatty acids of palm oil (PO) and palm kernel oil (PK) is a well-established technology in Malaysia. Data on quality and characteristics of various blends of PO/PK fatty acid-based (palm-based) soaps made in Malaysia are not available, however. In view of this, the study described in this paper was undertaken. Eleven blends of palm-based bar soaps were made, and their properties were evaluated. There was an increase in the acid value of blended raw materials with increasing amounts of PK fatty acids. The iodine value and titer (°C) of blended raw materials, however, bear an inverse relationship with the amount of PK fatty acids. As expected, the hardness of the soap bars from the various blends increased with increasing PK fatty acid. Total fatty matter ranged from 76–85%, free caustic content was 0.1%, and sodium chloride content was 0.3–0.4%. Characteristics of soap blends made for this study were comparable with those from other countries. Quality of the soap obtained was comparable to those produced commercially.     

Soap-based detergent formulations: XIX. Amphoteric alkylsuccinamide derivatives as lime soap dispersants

A series of amphoteric surfactants was synthesized by reaction of 1,3-propanesultone with N-alkyl-N′-(ω,ω-dimethylaminoalkyl)succinamides. The intermediate succinamides were prepared by reacting methyl N-alkylsuccinamates, obtained from alkylamines containing 8 to 18 carbon atoms, with N,N-dimethyl-1,3-propylenediamine or N,N-dimethylethylenediamine neat. The amphoterics were isolated as hygroscopic crystalline solids having superior lime soap dispersing ability, water solubility, and calcium ion stability. Detergency studies at 0.2% concentration (300 ppm water hardness) indicated good washing ability when used alone and excellent performance in combination with soap or in soap-silicate formulations. Presented at the AOCS Meeting, Cincinnati, 1975.     

皂基在洗涤剂中的应用

皂基是一种最常用的表面活性剂,常在洗涤行业中被用作洗涤剂的活性组分,同时也是一种常用的控泡剂。通过在洗涤剂中添加几种不同的皂来研究皂的加入是否对体系的使用性能产生影响。结果表明,不同皂的抑制泡沫的性能大不相同,并且在洗涤剂中加入皂能显著减少洗衣后的漂洗次数,极大地节省了水资源。     

Organic acids as builders in linear alkylbenzene sulfonate detergent formulations

Sodium salts of citric, glycolic, diglycolic and three sugar acids, directly derived from D-glucose, were evaluated as builders in a formulation for a linear alkylbenzene sulfonate detergent. Only sodium citrate and diglycolate were at least 60% as effective as sodium tripolyphosphate in building action in hard water. Detergency appeared to be related to calcium sequestration by the salts at pH 10. No. Utillz. Res. Dev. Div., ARS, USDA.     

Soap-based detergent formulations: VI. Alkylaryl sulfonamide derivatives as lime soap dispersing agents

Alkylbenzenes, such as industrial detergent alkylates, as well as pure 1-phenylalkanes whose side chain lengths varied C₈−C₁₂, were converted into the corresponding alkylbenzenensulfonyl chlorides with chlorosulfonic acid. Surface active sulfonamides were obtained from the reaction of the sulfonyl chlorides with various low mol wt aminosulfonic acids, such as N-methyltaurine, or with aminoalkyl esters of sulfuric acid, such as 2-aminoethyl hydrogen sulfate. The hydrolytic stability of the resulting surface active sulfonamide derivatives was investigated. As expected, the sulfonates were quite resistant to acid or alkaline hydrolysis, while the sulfates were more susceptible to hydrolysis. Hydrolytic stability of the sulfonamides was compared with that of the analogous fatty acid amide sulfactants. All of the compounds were excellent lime soap dispersing agents giving Borhetty-Bergman values of 4–10. The compounds were evaluated for detergency either alone or formulated either with tallow soap or with tallow soap and sodium silicate (Na₂O/SiO₂ ratio of 1∶1.6) The derivatives of the pure hydrocarbons which gave the best overall detergency were those of 1-phenyldecane and 1-phenyldodecane, whereas those of 1-phenyloctane exhibited poor detergency. This ranking was observed when the compounds were tested alone as well as when formulated. The sulfonamide derivatives of the detergent alkylate type of alkylbenzenes exhibited excellent detergency characteristics and showed substantial potentiation of detergency when mixed with soap or with a soap-sodium silicate blend. The detergency performance of some of these formulated detergents was equal to that of a commercial household detergent used as a control.     

Soap-based detergent formulations: XX. The physical and chemical nature of lime soap dispersions

Blends of soap and surfactants that possess good lime soap dispersing properties were dispersed in hard water. The turbidity of such dispersions varied depending on the type of dispersant used and also on the soap:dispersant ratio. Differences in coarseness of various dispersions could be measured empirically by filtration through a membrane of intermediate (1.2 μm) porosity. For determinations of the chemical composition of the dispersions a somewhat finer membrane (0.8 μm or less) was chosen, which retained most of the dispersed solids. Filter residues and filtrates were analyzed for sodium, calcium, magnesium and lime soap dispersing agents (LSDA). All of the calcium remained on the filter, whereas sodium was found primarily in the filtrate. Magnesium was held completely on the filter only if sufficient soap was present to tie up all Ca⁺⁺ and Mg⁺⁺. Analysis of the organic portion of the residues indicated that the soap:LSDA ratio found was the same as that used in the preparation of the original dispersion. On filtration through a fine membrane (0.05 μm) virtually all dispersed material was retained on the membrane. The filtrate possessed only slight activity in terms of surface tension and detergency, whereas the resuspended solids possessed high surface activity similar to the unfiltered dispersion. This indicates that the dispersed solids are the major source of surface activity. Presented at the AOCS Meeting, September 1975, Cincinnati.     

Soap-based detergent formulations: XIII. Formulations with alpha-olefin sulfonates as lime soap dispersants

Heavy duty household type detergents were formulated from tallow soap-AOS(α-olefin sulfonate)-builder combinations. Various commercial AOS samples were evaluated. These were derived either from closely fractionated α-olefins such as C₁₄, C₁₆, and C₁₈ or from samples representing broader mol wt ranges such as C₁₄−C₁₆ and C₁₆−C₁₈. The builders incorporated into these combinations were a sodium silicate (Na₂O∶SiO₂=1∶1.6), sodium tripolyphosphate, sodium citrate, sodium carbonate, and trisodium nitrilotriacetate. Detergency evaluations of 0.2% solutions in 300 ppm hard water (as CaCO₃) were determined with three commercial soiled cloths and by a multiwash test in which clean cloth was repeatedly soiled and washed. The relative proportions of soap, AOS, and builder were varied to obtain maximum detergency, and comparisons were made to other soap-LSDA (lime soap dispersing agents)-builder combinations as well as to a commercial high phosphate detergent used as a control. Detergency performance of soap-AOS combinations ranked just below that of the commercial high phosphate detergent control and below that of soap formulations containing sodium methyl α-sulfotallowate. Presented at the AOCS meeting, Philadelphia, September 1974.     

Soap-based detergent formulations: VII. Sodium methyl alkylbenzoylsulfopropionates as lime soap dispersing agents

Research was performed on the development of lime soap dispersing agents derived from alkylbenzenes. The sulfonation with sodium bisulfite of a variety of methyl β-p-alkylbenzoylacrylates (III) produced adducts (I) whose detergent properties were studied. Yields were optimized, model compounds were synthesized, and products characterized by NMR spectroscopy. The sulfonated adduct (I-A) derived from a commercial mixture of alkylbenzenes can be formulated with tallow soap, sodium silicate, and sodium carboxy methylcellulose to give a product that is competitive with a standard linear alkylbenzenesulfonate-phosphate household detergent.