US2562155A - Wetting and detergent composition - Google Patents

Description

gent properties.

Patented July 24, 1951 2,552,155 WETTING AND DETERGENT COMPOSITION.

Emil A. Vitalis, Springdale, Conn., assignor to a corporation of Maine American Cyanamid Company, New York, N. Y.,

No Drawing. Application November 3, 1949, Serial No. 125,396

2 Claims. 1

This invention relates to wetting and detergent compositions containing monoalkyl sulfosuccinates together with solubilizin agents therefor. The invention includes the compositions themselves, their methods of preparation, and wetting and detergent processes in which these compositions are used.

It is known that the higher monoalkyl sulfosuccinates, when used in the form of their salts with monovalent salt-forming compounds, possess good wetting and particularly good deter- However, the salts of monesters oi sulfosuccinic acid with alcohols of 12 or more carbon atoms, which is the minimum chain length for good detergency, possess relatively low solubility in water, which is a serious disadvantage. It is a principal object of the present invention to provide for this class of compounds solubilizin agents which improve their water solubility and thus increase their usefulness as wetting agents and detergents. A further object resides in the provision of readily soluble pastes or powders containing the higher monoalkyl sulfosuccinates in a solubilized and therefore water-dispersible condition. Still further objects 25 Solubility, Monoslkyl Disodium sulfosuccinate gms./l cc. of Solution 4. 0.05 EexadecyL 0. 2 0ctadecyl. 0. 05

Additional monoalkyl sulfosuccinates which have desirable qualities as wetting agents comprise the sodium, potassium, ammonium, etc. salts of mixed ester of sulfosuccinic acid obtained from a mixture of higher aliphatic alcohols that is available commercially and which contains about 40-45 myristyl alcohol (tetracontains about 40-45% myristyl alcohol (tetradecanol-l), about 3-5% capryl alcohol (octanol-2), about -15% of non-alcoholic substances of hydrocarbon nature boiling at 39 C. to 96 C. at 0.3 mm. of mercury pressure and therefore containing about 14-16 carbon atoms, and about 5-8% of higher boiling materials, possibly higher alcohols. This mixture is hereinafter designated as Ammecol, which is its commercial name. I

Attempts have been made to solubilize these and similar compounds by addin water-soluble alcohols, ethers of ethylene glycol and other agents which are known to solubilize the highu dialkyl sulfosuccinates. However, it was foumthat these alcohols and ethers actually reduce the water solubility of the alkali metal and ammonium salts of higher monoalkyl sulfosuccinates.

I have now discovered that water-soluble magnesium and beryllium salts such as magnesium sulfate, magnesium chloride, magnesium bro-' mide, magnesium nitrate, magnesium acetate, magnesium formate, and the like, and the corresponding beryllium salts, are excellent solubilizing agents for the higher monoalkyl sulfosuccinate salts. This is a remarkable discovery, for the addition of the corresponding salts of alkali metals such as sodium or potassium sulfate or chloride causes precipitation of the higher monoalkyl sulfosuccinate salts instead of solubilizing them. I have found, however, that I can prepare stable aqueous solutions containing from about 1% to about 30% of the wetting agents, depending on the particular alcohol present in the sulfosuccinate ester, as well as water-soluble concentrated aqueous pastes containing about 30 70% of the wetting agents, and even watersoluble dry powders containing the higher monoalkyl sulfosuccinate salts together with inorganic salts of the type of sodium sulfate, sodium chloride and the like by incorporating therein suitable quantities of magnesium or beryllium salts which ionize in aqueous solution.

The monoalkyl sulfosuccinate salts which are solubilized by magnesium and beryllium salts in accordance with the present invention have the following formula H MOiS.C.COOM

COOR

in which M is a monovalent salt-formin group such as sodium, potassium, ammonium, ethanolamine and the like, and R is an alkyl radical, of at least 12 carbon atoms and preferably 12-18 carbon atoms which may be saturated 0! unsaturated, or a mixture of such alkyl radicals.

The compounds defined by the above formula are .preferably prepared by esterifying maleic anhydride or maleic acid with dodecyl, tetradecyl, octadecyl, octadecenyl or other alcohols containing 12 or more carbon atoms atabout 100-110 C. to form the monoester, followed by sulfonating this ester to form the sulfosuccinate. Preferably the sulfonation is carried out by heating the ester with an aqueous solution of sodium sulflte, or sodium metabisulflte, or of the corresponding potassium or ammonium compounds. By this method the alkali metal and ammonium salts of the monoalkyl suli'osuccinic acid esters are obtained directly.

The corresponding salts of ethanolamine and other bases are preferably produced by first acidifying an alcoholic solution of the alkali metal or ammonium sulfosuccinates, whereby the free sulfosuccinic acid monoester is obtained, I

filtering off the inorganic salt of the acid used and reacting the sulfosuccinicacid ester with the desired base. Salts of other metals such as calcium, barium, zinc, chromium, tin, lead and the like are prepared by adding stoichiometric quantitles of their oxides or hydroxides to the alcoholic sulfosuccinic acid monoester followed by stirring until the salt formation is complete. Salts of organic bases such as methylamine, ethylamine, ethanolamine and the like may also be prepared by the same method.

salts. However, it has been found that while the upper limit of diluent which may be employed depends entirely on the desired concentration of wettin agent in the dry mixture, the lower limit of diluent is not substantially less than of the mixture. For example, when a dry mix is prepared containing more than about 60% of the monoalkyl sulfosuccinate, the material is not easily soluble in cold water; for this reason dry mixtures containing in excess of about 60% of monoalkyl sulfosuccinate are not included within the purview of this invention.

In practicing the invention, the amounts of magnesium or beryllium salts to be employed vary according to the original water solubility of the various monoalkyl sulfosuccinate salts. It will be readily apparent that dodecyl disodium sulfosuccinate, having a water solubility of 4.5 grams per 100 00., will require the addition of less magnesium or beryllium salt than will disodium hexadecyl suli'osuccinate, for example, having a water solubility of 0.2 gram per 100 cc., in the preparation of aqueous solutions of 10% wetting agent content. The following table sets forth the increase in aqueous solubility of various sulfosuccinate salts induced by optimum molar addition of magnesium and beryllium salts. M01, as

expressed in the description of the present invention, may be defined as the gram ionic equivalent of the salt employed.

Monoalkyl Disodium Bulfosuocinates Dodecyl Dodecyl Tetradecyl Hexsdecyl Mixture l Octsdecyl Per Cent Bolubiii gms .1100 cc. at 30 C. N 0 salt add'n.-- 4. 5 4. 6 0. 06 0. 2 0. 2 0, 05 Per Cent sensing, gum/100 cc. at 30 cj MZSO|.7H20---. 10 2a 9 14 14 4, Molarratio,Mgtosuocinate salt M 1 1:1 111 1:1 1:1 1%;1 Per Cent Solubility, gull/100 cc. at 30 0., B9804 added.... 8 26 8. 6 17 12 3 Molar ratio, beryllium to succinato salt 34H 1:1 1:1 1:1 1:1 15:1

1 The sullosuccinato mixturehbove referred to is that preparedlfrom Ammeo'ol.

texture to ordinary soap. The compounds are precipitated from their aqueous solutions by the addition of ammonium, sodium or potassium salts, and therefore the addition of sodium or potassium sulfate or chloride to form a dry, freeflowing powder could not be resorted to.

Another important feature of the present invention is the discovery that the solubilizin action of water-soluble magnesium and beryllium salts persists even in the presence of sodium sulfate, sodium chloride and other salts which would ordinarily precipitate the higher monalkyl sulfosuccinate salts from their water solutions. This discovery has enabled me to prepare dry, free-flowing powders containing the higher monoalkyl sulfosuccinate salts in admixture with water-soluble alkali metal compounds other than magnesium and beryllium compounds, or in admixture with water-soluble ammonium compounds, which powders are readily soluble in cold water. No material change in the ratio of magnesium or beryllium salt to monoalkyl sulfosuccinate salt need be made when other water-soluble salts are added, 1. e., the solubilizing action of the magnesium and beryllium salts is the same in the presence of sodium sulfate, sodium chloride and the like as it is in the absence of these As is common in the case of the solubility of salts, higher solution temperatures result in an increase of the solubility'of the various salts. In the case of the present invention, such variations in solution temperatures permit the use of smaller amounts of the solubilizing magnesium or beryllium salts. For this reason, the lower limits of such salt additions may in some cases and for some purposes be within the range of from 0.25 mol to 0.5 mol per mol of sulfosuccinate salt employed. 0n the other hand, while there is no absolute upper limit of magnesium or beryllium salt addition since the solubilizing agent does not interfere with the wetting and detergent prop-' erties of the monoalkyl sulfosuccinates, for most commercial applications not more than about 7 to 10 mols of magnesium or beryllium salt should be employed for 'each mol of sulfosuccinate. Moreover, I have found that the most preferable quantity of magnesium or beryllium salt to be employed is from 0.25 mol to 1.5 mols for each mol of the sulfosuccinate depending on its water solubility.

Conversely, in preparing aqueous pastes and dry powders containing water-soluble inorganic salts of monovalent metals such as sodium and potassium, larger amounts of magnesium or beryllium salts may of course be used, although amounts of substantially larger than those given in the above table are not usually necessary.

It is evident, therefore, that the invention in its broader aspects is not limited to the use of large quantities of the magnesium and beryllium salts but that relatively small proportions 01' these salts may. be used if desired.

The invention will now be illustrated in greater detail by the following specific examples. It should be understood, however, that although these examples may describe in detail certain specific features of the invention, they are given primarily for purposes of illustration and the invention in its broader aspects is not limited thereto. All parts given are by weight.

Example 1 A paste was prepared by mixin together 92 parts of a 30% aqueous gel of a disodium monoalkyl sulfosuccinate pre ared from Ammecol, and 8 parts of MgSO4.7H2O. The paste was used to prepare an aqueous solution containing 10% oi a salt of the sulfosuccinate mixture. The material was completely soluble, and remained clear at temperatures of from about 6-10 0., whereas the same sulfosuccinate salt is normally only 0.2% soluble at temperatures of or less than 35 C.

Example 2 A paste was made similarly to that of Example 1, employing 4 parts of BeSO4 and 96 parts of the disodium monoalkyl sulfosuccinate mixture. when made up into a 10% aqueous solution, the solubility and stability of this mixture compared very favorably with the paste of Example 1.

Example 3 A dry, free-flowing powder was obtained by drying to 100 parts an aqueous mixture consisting of 116 parts of a 30% aqueous gel of a disodium monoalkyl sulfosuccinate mixture prepared from Ammecol, 10 parts of MgSO4.7H2O, and 65 parts of Na2SO4. The dried powder formed clear solutions with water when used in concentrations up to 10%.

Example 4 Using 6 parts of 38804, 116 parts of the sulfosuccinate mixture employed in Example 3, and 69 parts of NazSO4, a powder was made similar to that of Example 3. Clear aqueous solutions were obtained using the dried powder in concentrations up to 10%.

Example 5 To 100 cc. of a 2% aqueous dispersion of dipotassium cetyl sulfosuccinate was added 3.8 cc. of a aqueous MgClz solution 1:1 molar ratio). The initially cloudy dispersion immediately became clear, indicating that a true solution of the sulfosuccinate had been obtained.

Other magnesium halides which have been found to give similar results are magnesium iodide and magnesium bromide.

Example 6 To 100 cc. of a 2% aqueous dispersion of diammonium cetyl sulfosuccinate was added 11.2 cc. of a 10% Mg(NOa)2 solution (1:1 molar ratio). The initially cloudy dispersion immediately became clear indicating that a true solution of the sulfosuccinate had been obtained.

Example 7 To 100 cc. of a 5% aqueous dispersion of disodium oleyl sulfosuccinate was added 9.7 cc. of a 10% aqueous MgClz solution 1:1 molar ratio). The initially cloudy dispersion immediately became clear indicating that a true solution of the sulfosuccinate had been obtained.

6. Example 8 To 'cc. of a 2% aqueous dispersion of dipotassium cttyl sulfosuccinate was added 3.2 cc. of a 10% aqueous solution of BeCla (1:1 molar ratio) The initially cloudy dispersion immediately became clearindicating that a true solution oi the sulfosuccinate had been obtained.

Example 9 To 100 cc. of a 2% aqueous dispersion of diammonium cetyl sulfosuccinate was added 8.1 cc.

or a 10% aqueous solution of Be(NOa)a. Theihitially' cloudy dispersidn immediately became clear indicating that a, true solution of the sulfosuccinate had been obtained.

Example 10 To 100 cc. of a. 5% aqueous dispersion of disodium oleyl sulfosuccinate was added 8.3 cc. of a 10% aqueous BeCl: solution (1:1 molar-ratio). The initially cloudy dispersion immediately became clear indicating that a true solution of the sulfosuccinate had been obtained.

Example 11 A dry, free-flowing powder was prepared by drying to 100 parts an aqueous mixture consisting of '10 parts of a 30% gel of a monoalkyl sulfosuccinate mixture prepared from Ammecol, 20 parts of MgSO i, parts'pf NazSO4, and 10 parts of NazCOa. The dried powder formed clear solutions with water when used in concentrations up to 10%.

Example 12 in which M is a member or the group consisting of alkali metal and ammonium radicals and both M's are the same, a.nd R is an alkyl radical of from 12 to 18 carbon atoms, and a member of the group consisting of water=soluble magnesium and beryllium salts which are capable of increasing the water solubility oi the monoalkyl sulfosuccinate. said salt being presentinan amount the minimum range of which is from 0.25 mol to 1.5 mols and the maximum amount of 10 mols for each mol of the sulfosuccinate.

2. A wetting and detergent composition comprising essentially a surface active material which is a mixture of monoalkyl sulfosuccinates having the formula in which M is a. member of the group consisting REFERENCES CITED of alkali metal and ammonium radicals and both M's are the same, and R is an alkyl radical of 'ghg, erences are of record m the from 12 to 18 carbon atoms, and a member of the group consisting of water'soluble magnesium and 5 V UNITED STATES PATENTS beryllium salts which vare capable ot'increasing Number Name Date the water solubility oi the mixture of monoalkyl 2,181,087 Caryl at 21, 1939' sulfosuccinates, said salt being present in an 2,29 Harris Oct. 13, 1942 am nt he minimumrange of which is from 2, 1 Flett APR 13, 1943 0.25 mol to 1.5 mols and the maximum amount 10 2,419,805 Wegst et al. Apr. 29, 1947 th of 10 mols for each mol of e sulfosucclnates OTHER RE ENCES EMIL A. vrrALIs. Aerosol Wetting Agents, Pub. of Amer. Cyanamid and Chem. Corp., N. Y. (1941), PP. 8-13.

Claims (1)

1. A WETTING AND DETERGENT COMPOSITION COMPRISING ESSENTIALLY A SURFACE ACTIVE MATERIAL WHICH IS A MONOALKYL SULFOSUCCINATE HAVING THE FORMULA