Detergent composition
United States Patent 2284086

This Invention relates to wetting, detergeni and emulsifying compositions containing cation. active compounds and to surface active agents contained therein. The invention also includes wettnfg and emulsifying processes employing such compounds, textile oils and lubricants, leather fat licuoring...

Ericks, Walter P.
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209/166, 510/276, 510/490, 516/67, 516/161, 516/DIG.6, 554/104, 562/560, 562/594
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This Invention relates to wetting, detergeni and emulsifying compositions containing cation. active compounds and to surface active agents contained therein. The invention also includes wettnfg and emulsifying processes employing such compounds, textile oils and lubricants, leather fat licuoring compositions, cutting oils, scouring com. positions, foaming agents, emulsified fat and oil compositions, and other types of emulsions prepared therewith as well as demulsifying processes in which petroleum emulsions or similar emulsions of the Wiater-in-oil type are resolved or broken by contact with the eation-active wetting agents.

Most of the wetting agents now in use are of the sulfonic acid or sulfuric ester type; that so say, they are sulfuric acid derivatives of crbon-containing substances. All of the wettiag agents of this class are anion-active, which mens tIha the e se of their- cations is relatively small in comparison with the remaining portion of the molecule which becomes negatively charged in solution. For example such a powerful wetting agent as scduim dioctyl sulfosuccinate is believd to dissociate in aqueous solution in the following manner.

oS - Bdooc r 1 HC-- OOC aN O LS--COO0C Hj from which it is evident that the surface activity is due entirely to the characteristics of the anion.

In contrast to the above, the cation surface active compounds of the present invention have a relatively large cation end a small anion. Tis causes them to have distinctive properties in such processes as, for example, the scouring of wool 2hich is negatively charged.

The wetting, detergent and emulsifying comositions of my invention may be defined as contiuning cation-active compounds of the formula R.CH.COOH NH C-H in which R is an aliphatic radical containing four or more carbon atoms, R, and Rs are hydrogen, aryl radicals such as phenyl, tolyl, xylyl and the llke, or methyl, ethyl, propyl, allyl, butyl, amyl or similar alkyl radicals or hydroxy alkyl radicals such as ethylol, propylol, butylol and the Mkl . These compounds may be present as the sole surface active agent, or they may be used in admixture with fatty acid soaps, sodium sul- f fate or other soluble salts, other wetting agents, alphatic alcohols having more than six carbon atoms, pine oil, alpha pinene, free fatty acids or the glyceride oils thereof, and In general wherever a wetting and emulsifying agent is ret quired that is stable under neutral, acid or alkaline conditions.

S In the above type formula the surface active compounds of my invention have been defined 6 as containing free crboxylic acid groups. This is probably true in most cases where the wetting composition is employed in a neutral medium, and I have found that the compounds are well suited for this purpose. One of the most important features of the invention, however, resides in the characteristic behavior of these com.pounds in the presence of acids and alkalies in which they are readily soluble and to which they are completely resistant. It is probable 1 that this unusual resistance of the compounds of my invention to acids, alkalies and heat is due, at least in some cases, to an intramolecular rearrangement with the formation of a hydantoin structure,. in the following manner R.CH.COOH R.CH. CO NH NHs -- N NH+Hs JIIH 25 However since this has not as yet been definitely proved the compounds will be described and claimed on the assumption that they are free carboxylic acids or salts thereof.

The alpha-guanido fatty acids are preferably 30 Used in the form of the salts which they form with Inorganic or strong organic acids, since the sa8t are in general more soluble than the substituted fatty acid itself. These salts are somewhat unusual since they contain only one mole 3 of a monobasic acid for each two moles of the guanido fatty acid. For example, the hydrochloride has the following empirical formula [R.CH.(CN3H~ ) COOHa.HCI The cation-active agents of my invention may be prepared according to known methods by reacting a fatty acid of more than three carbon atoms with bromine whereby an alpha-brom fatty acid is obtained. One mole of this bromine 5 substituted fatty acid is then reacted with two moles of an unsubstituted or substituted guanidine in alcoholic solution at elevated temperatures to form the alpha-guanido fatty acid by ; the following reaction R.CHBr.COOH+2HsN.C(NNH)N R.CH.COOH H2N NRa.HBr Na + 0 5 \C-N aH Alternatively one mole of the alphabrom fatty acid may be heated with one mole of guanidine 0i the presence of a strong base such as sodium O hydroxide, or with a guanidine salt such as guan[dine nitrate in the presence of sufficent strong alkali to neutralize the acid radical. When two moles of guanidine are used the resulting composition contains an equimolecular mixture of the alpha-guanido fatty acid and guanidine hydrobromide, and is a good wetting and emulsifying agent when used in this form. In many cases, however, it is preferable to separate the alpha-guanido fatty acid and this may be done by crystallization from solvents such as methyl alcohol or in. some cases by extraction of the guanidine salt with hot water. The guanidine and bromine can then be recovered and re-used by treating the guanidine hydrobromide with sodium hydroxide and introducing chlorine into the resulting sodium bromide solution.

Substituted guanidines may be used instead of guanidine itself, as indicated above, whereby the substituted guanidine derivatives are obtained in the same manner. The surface active properties of these substituted guanidine derivatives will vary in accordance with the structure and molecular weight of the substituent or substituents, and in this way a wide variety of wetting, emulsifying and detergent agents can be produced. The surface active properties of the products of my invention are influenced to a considerable extent by the number of carbon atoms in the fatty acid employed as starting material. I have found that such compounds as alpha-guanido in butyric and isobutyric acids possess definite surface activity, but that improved surface active properties are obtained as the length of the carbon chain is increased. Thus, for example, the alpha-guanido derivatives of diethyl acetic acid, methyl-n-proPyl acetic acid and ethyl-npropyl acetic acid are better wetting agents than is the corresponding derivative of secondary butyl acetic acid. When alpha-guanido derivatives of such fatty acids as caprylic acid, pelargonic acid, caproic acid, lauric acid, n-tridecylic acid and nmyristic acid are used the composition has both wetting and emulsifying properties to a high degree. Alpha-guanido derivatives of higher fatty acids such as palmitic acid, stearic acid, penta- 4. decatoic acid, margaric acid, arachidic acid and behenic acid may also be used as both wetting and emulsifying agents, and some of these derivatives are very attractive by reason of the low cost of the acids, which may be obtained by the 5( hydrolysis of fats and oils such as palm oil, olive oil and the like, as well as by hydrogenation of fatty acids from cottonseed oil or from the refining of "talloel," a by-product obtained in the digestion of coniferous wood by the Kraft process. 5 As is indicated above, the surface active agents of the present invention are well suited for the preparation of textile treating compositions of various types. For example the alpha-guanido stearic and palmitic acids and their acid salts a such as the nitrate, hydrochloride or sulfate are well suited for scouring and deliming wool in acid solution, either alone or in admixture with other detergents such as pine oil. They may also be used as emulsifying agents in the preparation of ( wool creams and similar softening agents and lubricants containing, for example, such glyceride oils as teaseed oil, olive oil and the like, or esters such as diethyl or dibutyl phthalate. They may also be incorporated in emulsions of other ma- 7 terials that may be applied to wool such as rubber latex emulsions and the like.

The cation-active agents are also well suited for use in the preparation of paint, wax, lubricating, cosmetic, medicinal and edible fat emulsions, I particularly when employed in conjunction with anion-active agents such as sodium lauryl sulfate, sodium dioctyl sulfosuccinate, isopropyl naphthalene sodium sulfonate, sulfuric esters of secondary aliphatic alcohols and the like. I have found that when the above materials are emulsifled in water with the aid of anion-active emulsifying agents and alpha-guanido fatty acids are then added with stirring until a paste of maximum viscosity is obtained, then an extremely stable emulsion is formed. In similar manner, the above materials may also be emulsified in hot water with ordinary soap, after which the alphaguanido fatty acid is added. Further important applications of this nature will be pointed out in the following examples.

The alpha-guanido fatty acids may also be employed as wetting, dispersing or emulsifying agents in the preparation of printing inks, dye baths, photographic emulsions, bituminous emulsions and the like as well as in the resolution of petroleum emulsions and as frothing agents in the froth flotation of ores.

The invention will be described in further detail by the following specific examples, to which however it is not limited. It is understood that while these examples may illustrate in some detail some of the more specific aspects of the invention, they are given primarily for purposes of illustration and the invention in its broader aspects is not limited thereto.

Example 1 Palm oil was saponified with potassium hydroxide and the soap was decomposed with hydrochloric acid. The resulting aqueous suspension was washed with benzol and then with water until it was neutral to litmus after which the benzol was distilled off and the palmitic acid Scollected separately.

An excess of dry bromine was slowly dropped into 75 parts of the palmitic acid which was intimately mixed with 3.5 parts of red phosphorus, the reaction being carried out in sunlight. After addition of the bromine the mixture was heated until fumes of hydrobromic acid had practically ceased whereupon the mixture was blown with air to expel excess bromine. The reaction products were then extracted with peo troleum ether and the alphabrom-palmitic acid was allowed to crystallize by spontaneous evaporation.

Guanidine was prepared by dissolving 90 parts of guanidine carbonate in 300 parts of 10% sulfuric acid, diluting with 300 parts of water, and addition of barium hydroxide to precipitate the sulfuric acid and sulfate radical. The barium sulfate was filtered off and the solution was concentrated by vacuum evaporation.

SThe concentrated guanidine solution was mixed with 20 parts of brom-palmitic acid and 70 parts of ethyl alcohol were added. The mixture was heated in an autoclave at 100° C. for three hours, after which the crude reaction 5 product wa tanas obtained as an alcoholic solution.

This product was found to possess good wetting and emulsifying properties.

100 parts of raw wool were scoured in a warm bath consisting of 5000 parts water, 36 parts hyr0 drochloric acid and 60 parts of the above described mixed reaction product. It was found that a good lather was obtained, and that the wool could be cleansed in less than 30 minutes.

The dried wool possessed an excellent hand, as r5 some of the detergent remained on the fiber.

Example 2 One mole of alphabrom-isobutyl acetic acid, prepared by the method outlined in Example 1, was mixed with one mole of a hot aqueous guanidine solution containing one mole of sodium hydroxide. The mixture was heated at 60-70* C. for 2Y2 hours, allowed to cool, and the crystalline alpha-guanido isobutyl acetic acid was filtered off and washed with alcohol. It was recrystallized from hot water and dissolved in dilute hydrochloric acid from which the hydrochloride could be obtained in the form of fine, needlelike crystals.

Grey cotton cloth which had been lubricated with sulfonated tallow before weaving was washed in a bath containing 1% caustic soda and 0.5% of the alpha-guanido .isobutyl acetic acid. The lubricant was completely emulsified and removed from the cloth in a short period of time.

Example 3 Alphabrom-stearic acid was prepared by the reaction of bromine on stearic acid as described in Example 1. 363 parts of this material were heated in an autoclave with an alcoholic solution containing 210 parts of dimethyl guanidine for 4 hours at 110° C. The resulting alphadimethyl guanido stearic acid was separated from the dimethyl guanidine hydrobromide by recrystallization from hot methyl alcohol.

A fatliquoring composition for chrome tanned leather was prepared by agitating a mixture of 2 parts of sulfonated and 1 part unsulfonated teaseed oil and slowly addink a 1% solution of the above described emulsifying agent. A clear and stable emulsion was obtained which possessed excellent lubricating properties for the leather.

Example 4 Alpha-quanido lauric acid was prepared from coconut oil by the method outlined in Example 1. A mixture of 5 parts of this material, 10 parts of sodium dioctyl sulfosuccinate and 85 parts of sodium sulfate were dissolved in a 50% water-alcohol solution and the solvent evaporated by contact with hot air in a commercial spray-drying machine.

The resulting spray-dried mixture was a light, fluffy powder constituting an excellent household detergent. When dissolved in hot water it produces copious suds, and the solution was well suited for dishwashing, domestic laundering and the like.

Example Crude "talloel" or black liquor soap was extracted with a sodium sulfate solution to remove the lignin and acidified with sulfuric acid to liberate a mixture of free fatty acids and abletic acid. After filtration the fatty acids were separated from the mixture by selective neutralization with sodium hydroxide and the soaps were extracted with alcohol.

After evaporation of the solvent and acidification there was obtained a mixture containing oleic, linoleic, stearic and palmitic acids which was hydrogenated with nascent hydrogen until the corresponding saturated fatty acids were produced. This product was brominated and heated with a solution containing an equlmolecular quantity of guanidine nitrate and twice as much sodium hydroxide.

The resulting product was separated from inorganic salts, dissolved in toluol and used as a demulsifying agent for the resolution of petroleum emulsions of the water-in-oil type. It was found to be particularly effective in treating emulsions of this type in which the disperse phase was negatively charged, as when the water contained substantial quantities of dissolved salts. Good results were also obtained when the material was used in admixture with phenols, cresols, hydrochloric acid, and other known demulsifying assistants.

What I claim is: 1. A method of cleaning textiles which comprises washing said textiles in an aqueous dispersion of a compound of the formula --CH.COOH aNH C:NH 25 RRsN in which R is an aliphatic radical containing more than three carbon atoms and Ri and Ra are members of the group consisting of hydrogen and aryl, alkyl and hydroxyalkyl radicals.

2. A method of cleaning textiles which comprises washing said textiles in a composition comprising an aqueous dispersion of a compound of the formula R-CH.COOH NH C:NH Sin which R is an aliphatic radical containing more than three carbon atoms and Ri and Ra are members of the group consisting of hydrogen and aryl, alkyl and hydroxyalkyl radicals, and a water-soluble soap.

3. A method of scouring wool which comprises washing the wool in an acidic aqueous dispersion of a compound of the formula R-CH.COOH N H 50 C:NH in which R is an aliphatic radical containing more than three carbon atoms and Ri and Ra are 55 members of the group consisting of hydrogen and aryl, alkyl and hydroxyalkyl radicals.

4. A detergent composition comprising a compound of the formula R-CH.COOH NH C:NH In which R is an aliphatic radical containing 65 more than three carbon atoms and Ri and Ra are members of the group consisting of hydrogen and aryl, alkyl and hydroxyalkyl radicals, and a water-soluble soap.