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.     

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.     

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.     

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.     

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: 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 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.     

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.     

Mixed sulfated tallow alkanolamides as lime soap dispersing agents

Sulfated alkanolamides of hydrogenated tallow fatty acids have been shown to possess excellent lime soap dispersing and detergent properties. However the high melting points of the alkanolamides and their relative insolubility in organic solvents such as dichloroethane make sulfation on an industrial scale awk ward. This difficulty has been overcome by the use of a eutectic mixture of the N-(2-hydroxypropyl)amide and N-(2-[2-hydroxyethoxy]ethyl)amide of unhydrogenated tallow fatty acids. The sulfation of such a mixture can be carried out at or slightly above room temperature, and only a small amount of a chlorinated solvent is required in order to keep the sulfation mixture fluid. The resulting sulfated mixed alkanolamide is an excellent lime soap dispersing agent, which is formulated readily with tallow soap and a glassy silicate into an effective heavy duty detergent.     

Soap-based detergent formulations: XIV. Amphoteric derivatives of alkylbenzenesulfonamides

Surface active amphoteric derivatives were prepared from alkylbenzenesulfonyl chlorides. Industrial detergent alkylates, as well as benzene and pure 1-phenylalkanes whose side chains ranged from C₁ to C₁₂, were used as starting materials in this study of chemical structure-physical property relationships. The alkylbenzenes were first converted into the corresponding alkylbenzenesulfonyl chlorides with chlorosulfonic acid, and the sulfonyl chlorides were further treated with N,N-dimethyl-1,3-diaminopropane or N,N-bis-(2-hydroxyethyl)-1,3-diaminopropane. The reaction products were quaternized with propanesultone to produce amphoteric surfactants in high yields. The N,N-dimethyl herivatives of pure phenylalkanes were white crystalline powders, whereas the N,N-bis-(2-hydroxyethyl) derivatives were light , lime soap dispersing requirement, surface tension, wetting ability, and calcium ion stability were determined. The commercial detergent alkylate derivatives showed good detergency by themselves as well as in formulations with soap or with soap and silicate builder. Good lime soap dispersing properties were observed with compounds possessing a side chain of at least 4 carbon atoms. Presented at the AOCS Fall Meeting, Philadelphia, September 1974.     

Soap-based detergent formulations: XXII. Sulfobetaine derivatives ofN-alkylglutaramides and adipamides

The acid chlorides of methyl hydrogen glutarate and methyl hydrogen adipate were allowed to react with various primary fatty amines. The resulting amido esters were converted into the corresponding amino diamides by sodium catalyzed reaction with N,N-dimethylaminoalkylamines. The desired sulfobetaines were obtained by reaction of the resulting N-alkyl-N′-(1,1-dimethylaminoalkyl) glutaramides and adipamides with 1,3-propanesultone. The compouds possess the same excellent lime soap dispersing ability, water solubility, calcium ion stability, and detergency properties as the analogous succinamide derivatives previous reported. This indicates that the spacing between the two amido groups or that between the quaternary nitrogen atom and the nearest amido group does not affect surface active properties.     

The mutual solubilization of soap and lime soap dispersing agents

Krafft point measurements were used to show that lime soap dispersing agents (LSDA) and soaps solu-bilize each other. Addition of as little as 5% soap to amphoteric LSDA of limited water solubility (high Krafft point) brought about a substantial lowering of the Krafft point and thus markedly improved water solubility. On the other hand, addition of 10% amphoteric LSDA to sodium palmitate lowered the Krafft point of the soap by 10 to 14 C. Addition of anionic LSDA to sodium palmitate showed smaller Krafft point depressions. Addition of a builder-type salt, such as sodium metasilicate, had essentially no effect on the Krafft points of soap LSDA mixtures.     

Soap-based detergent formulations: X. Nature of detergent deposits

The cumulative deposition of detergent residue on unsoiled cotton and polyester-cotton permanent press finish cloth was determined for a variety of detergent formulations after washing 25 consecutive times in 300 ppm hard water in a laboratory Tergotometer. Included in this study were: a phosphate-built laundry detergent, two carbonate-built detergents, tallow soap and various tallow soap formulations with anionic and amphoteric lime soap dispersing agents, and a glassy sodium silicate. Sample swatches washed with each formulation were analyzed for calcium, magnesium, and organic acid content. Fabric washed with the carbonate detergents showed the highest calcium and magnesium content, while those washed with the phosphate detergent and the soap-lime soap dispersant-builder formulations had the lowest. Fabric washed with soap alone had a much higher fatty acid residue than those washed with the other detergent formulations. However, the amount of organic acids left on the fabric after washing with a soap-lime soap dispersing agent formulation was no greater than that produced by phosphate- and carbonate-built detergents. The presence or absence of deposits also was verified visually with a scanning electron microscope. Each formulation also was tested for detergency by measuring the soil buildup in a multiwash procedure. Generally, the buildup of soil paralleled the deposit of detergent residue on the unsoiled cloths.     

Surface active properties of combinations of soap and lime soap dispersing agents

Surface tension versus log concentration curves were obtained for combinations of a variety of lime soap dispersing agents (LSDA) with sodium oleate. Salient features of the curves for these mixtures were: (a) criticial micelle concentration (CMC) close to that for LSDA alone; (b) absence of a surface tension minimum or substantial reduction in the minimum, which was often found with LSDA alone; (c) surface tension values above the CMC very close to those found for soap alone above its CMC; and (d) slope below the CMC greater than that for soap alone, more like that for soap with alkali added or lime soap dispersing agent alone. Higher CMC values were confirmed by dye solubilization measurements. The surface tension curves provided further evidence for the mixed micellar nature of soap-LSDA mixtures and suggested that the addition of LSDA to soap increased the surface concentration of surfactant. Presented at the AOCS Meeting, Chicago, September 1976.     

Soap-based detergent formulations: XXI. Amphoteric derivatives of fatty amides of aminoethylethanolamine1

Amides and 2-alkyl-N-(2-hydroxyethyl)-imidazolines were converted into various types of sulfated or sulfonated amphoteric lime soap dispersants. The alkylimidazolines could be readily hydrolyzed to give amidoamines. The cyclized amphoteric surfactants were generally superior in detergency and lime soap dispersing ability to analogous surfactants derived from amidoamines. Some of the cyclized surfactants, when formulated with soap and silicate builder, washed about as well under the test conditions as a control containing 50% sodium tripolyphosphate.     

Soap-based detergent formulations. XVI. Surface active sulfosuccinimides

A series of sodium N-alkylsulfosuccinimides and N-acyloxymethylsulfosuccinimides were prepared by reaction of the corresponding N-alkylmaleimides and N-acyloxymethylmaleimides with sodium bisulfite in aqueous ethanol. The N-alkylmaleimides were prepared by dehydration of N-alkylmaleamic acids with acetic anhydride and fused sodium acetate. The N-acyloxymethylmaleimides were obtained by reaction of an acyl chloride with N-methylolmaleimide in a pyridine-acetone solvent. The surface active properties of the sulfonated derivatives showed them to be efficient lime soap dispersing agents with good calcium ion stability but relatively high Krafft points. The 2 types of compounds exhibited similar detergency characteristics under the conditions employed and were generally comparable to the control on a cotton-polyester blend when used alone and in a ternary formulation with soap and silicate builder on cotton test cloths.     

Soap-based detergent formulations: III. Surface activity of fatty derivatives of 3-hydroxypropanesulfonic acid

Pure 3-sulfopropylesters, ethers and amides were prepared from fatty acids, alcohols and amides by reaction with 1,3-propanesultone. Their solution properties, including Krafft point, critical micelle concentration, lime soap dispersing power and detergency, were compared with those of the analogous 2-sulfoethyl esters. The N-3-sulfopropylamides exhibited superior lime soap dispersing power as well as detergency in soap-based formulations at 300 ppm water hardness. The sulfopropyl ethers and amides displayed excellent stability to acid and alkaline hydrolysis. The sulfopropyl esters were much more stable to alkaline hydrolysis than the sulfoethyl esters, but only slightly more stable to acid hydrolysis. Presented at the AOCS Meeting, Ottawa, Canada, September 1972. E. Market. Nutr. Res. Div.     

Soap-based detergent formulations: XXVI. Hard water detergency of soap-lime soap dispersant combinations with builders and inorganic salts1

Blends of soap and 3 lime soap dispersants—the sulfated tallow alkanolamide (TAM), the coconut-oil-derived amido sulfobetaine (CAHSB) and the cocoamido betaine (CAB)—were formulated with 3 builders—sodium tripolyphosphate (STPP), trisodium nitrilotriacetate (NTA) and trisodium 2-oxa-1,1,3-propane tricarboxylate (OPT). Varying amounts of sodium sulfate were added to these formulations, and the effects of builders and sodium sulfate on detergency at 300 ppm water hardness were studied. At levels below 60%, STPP was not an effective builder for TAM formulations. Dilution of STPP-built TAM formulations with sodium sulfate substantially decreased detergency. Detergency of TAM formulations was improved by incorporation of NTA or OPT and such formulations could tolerate dilution with sodium sulfate without serious loss in detergency. NTA or STPP improved the detergency of CAB formulations but OPT did not. Addition of sodium sulfate caused some loss in detergency in all CAB formulations. Addition of STPP to CAHSB formulations caused a slight loss in detergency, but addition of NTA or OPT had no appreciable effect. Dilution of STPP-built CAHSB formulations with sodium sulfate affected detergency adversely, although not as severely as in STPP-built TAM formulations. Dilution of NTA-or OPT-built CAHSB formulations with sodium sulfate had little effect on detergency. CAB and particularly CAHSB are superior to TAM in dispersing lime soap curd. Therefore, addition of NTA, STPP, or OPT to the amphoteric formulations did not affect detergency to the same extent as in TAM formulations. Further evidence of the superiority of amphoteric lime soap dispersing agents (lsda) in dispersing lime soap curd was provided by the effectiveness of soap, CAHSB, silicate formulations in detergency studies at 1,000 ppm water hardness. Presented at the Annual AOCS Meeting, San Francisco, April 1979. Agricultural Research, Science and Education Administration, U.S. Department of Agriculture.     

Soap-based detergent formulations: XII. Alternate syntheses of surface active sulfobetaines

Sulfopropylated amphoteric surfactants, previously reported in this journal, displayed excellent surface active properties and were good detergents in combination with soap. New synthetic routes were investigated for the preparation of such types of compounds to provide a more economical process and eliminate the hazards due to propanesultone, which was used in the previously reported synthetic procedure. A series of 2-hydroxy-3-sulfopropyl amphoteric surfactants was prepared by reacting sodium 3-chloro-2-hydroxy-1-propanesulfonate (the addition product of sodium bisulfite to epichlorophydrin) with various primary fatty amines as well as with fat derived N,N-dimethylalkylamines. Quaternary sulfobetaines not possessing a hydroxyl group were obtained from tertiary amines by reaction with allyl chloride followed by bisulfite addition. The solubility behavior (Krafft points) of these compounds indicated that they were not identical with the sulfobetaines prepared with the aid of propanesultone. The secondary and quaternary ammonium compounds exhibited limited water solubility but were good lime soap dispersing agents. They displayed good detergency in combination with soap. The quaternary ammonium derivatives were particularly effective on cottonpolyester blend fabrics. Presented at the AOCS Meeting, Philadelphia, September 1974.