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Publication numberUS2535972 A
Publication typeGrant
Publication dateDec 26, 1950
Filing dateApr 26, 1949
Priority dateApr 26, 1949
Publication numberUS 2535972 A, US 2535972A, US-A-2535972, US2535972 A, US2535972A
InventorsEmil A Vitalis
Original AssigneeAmerican Cyanamid Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Alkylbenzenesulfonate detergents containing guanidine salts of inorganic acids
US 2535972 A
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Description  (OCR text may contain errors)

am 2% i950 E. A, vnTALls 2,535,972

ALIHLBENZENESULFONATE DETERGENTS CONTAINING @Mmmm SAMS 0F INORGANIC ACIDS lfftimd April 26. 1949 700,44 No '/wfwjgp/ jyj yNvENmR ATTORNEY Patented Dec. 26, 1950 n coNTArNrNG oRGAmc acms Emil A. Vitalis, Springdale, Conn.,

ican Cyanamid Amer GUANIDINE SALTS F IN- asslgnor to' Company, New York,

N. Y., a corporation of Maine Application April 26, 1949,` Serial No. 89,581

This invention relates to detergent compositions, and more particularly toalkylbenzenesul-L fonate detergents having greatly improved woolscouring properties. n

Synthetic detergents of the alkybenzenesulfonate type are well known and are in wide commercial use. They are the sulfonation products of mononuclear aromatic hydrocarbons containing a` single long alkyl radical, usually of about -16 carbon atoms, with or without one or two additional short chain hydrocarbon substituents on thefbenzene nucleus) The hydrocarbons oi this type are ordinarily prepared by one of two methods; either by condensing an oleiin oi' about 'l0-16 carbon atoms such as a propylene or butylene polymer with benzene, toluene or xylene, or by condensing any one or more of these aromatic hydrocarbons with a chlorinated kerosene fraction of lll-16 carbon atoms, usually with the aid of an aluminum chloride catalyst. 'Ihe resulting alkylbenzene compound is sulfonated by well known sulfonation procedures, usually by employing oleum containing 10% to 30% of free sulfur trioxide at temperatures of about 10`30 C.

The sulfonation of the alkylbenzene compounds is usually carried out with an excess of acid, about 3-4 mois of acid per mol of alkylbenzene compound being used. After the sulfonation is complete the mixture is ordinarily neutralized with a water-soluble alkali such as sodium, potassium or ammonium hydroxide, which produces a mixture of the alkylbenzenesulfonate detergent with `approximately 50-200% of its weight of sodium sulfate, potassium sulfate or ammonium sulfate. It has been proposed to neutralizethe sulfonation product with lime, followed by re` action with sodium or potassium carbonate to remove the calcium and produce a puriiied product containing `only relatively small amounts of alkali metal or ammonium sulfate. However, this procedure is not ordinarily employed in commercial manufacturing processes. It has also been proposed to purify the sulfonated product by extraction with organic solvents, which results in the removal of unsulfonated hydrocarbons and tarry impurities and also removes the alkali metal sulfate.

The alkylbenzenesulfonate detergents of the above-described `class are effective for the washing of cotton cloth and other cotton textiles, but for some unknown reason they are not as good on wool. It is a principal object of the present invention to improve the detergency of this class of compounds for woven and knitted wool or wool-containing textiles by the addition s claims. (C1. cs2-isz) 2 i thereto of a water-soluble guanidine salt. I have found that a mixture of an alkylbenzenel sulfonate detergent of the above-described class with from about 2% to'about 50% of its weight of guanidine salt Vpossesses greatly improved scouring properties for wool and woolen textiles,

l and when the guanidine salts are used in quantities of from about 1li-15% to about 25-40% the detergency on wool is increased some 5 to 6 times.

This discovery is quite surprising, since the guanidine salts themselves possess little or no de` tergency for wool. n

The addition of guanidine carbonate to the alkylbenzeneulfonate, detergents also improves the storage properties of the composition, and

therefore this is the preferred guanidine salt for use `in practicing the invention. Many of the alkylbenzenesulfonates are quite hygroscopic; moreover, `they tend to llquefy 4after absorbing moisture from the atmosphere, and will therefore form a sticky mass unless they are stored in containers which are completely air-tight. A1- though the presence of 50-200% of their weight of sodium sulfate, sodium chloride or other in- 2li organic salt will improve their storage properties the mixtures still have a strong tendency to cake when exposed to a moist atmosphere. I find that the presence of guanidine carbonate will asx sist materially in maintaining the composition 30` above-indicated amounts of inorganic salt are in adry and free-flowing condition. When the present this is accomplished by about 745% or more of guanidine carbonate. based on` the weight of the alkylbenzenesulfonate; a similar result is obtained when about .3D-% of guanidine carbonate is mixed with a puried alkylbenzenesulionate detergent containing little or no sodium sulfate or other inorganic salt.

Although any of the alkylbenzenesulfonate detergents described above may be improved by admixture` with guanidine salts, the preferred compositions of my invention are those in which an alkyltoluenesulfonate is employed. These preierred compounds are best described by the` formula in which R is an alkyl radical of 10-16 carbon atoms, and preferably one of about 12-14 carbon atoms. As will subsequently be shown these alkyltoluenesulfonate detergents, when admixed with 2-50% of their weight of guanidne carbonate orsulfate, possess excellent detergency 3 4 for wool, and also possess good stability on storage.

Any water-soluble guanidine salt may be used to obtain an improved detergency of the alkylbenzenesulfonates on wool, although for most practical purposes the guanidinesalts of inorganic acids are preferred. Typical of these are guanidine nitrate, guanidine hydrochloride, guanidine sulphate, guanidine phosphate, and the guanidine carbonate referred to above. However, the corresponding water-soluble salts of organic acids may be used if desired, and particularly such compounds as guanidine acetate, guanidine benzoate, guanidine phthalate, guanidine carbamate and guanidine anthranilate.

My invention will be described in greater detail by 4the following specific examples, and with reference to the accompanying drawing. In this drawing the single figure is a graph showing the detergency of alkyltoluenesulfonate-guanidine carbonate and guanidine sulfate mixtures on wool.

' Example 1 An alkyltoluenesulfonate prepared by condensing toluene with a propylene polymer fraction and having an average composition of CH3.C6H4.C12H:5 was sulfonated with 20% oleum. The sulfonation was carried out by adding the oleum to the hydrocarbon, using a 4: 1 molar ratio and maintaining the temperature of the mixture at 15-25" C. Under these conditions the formation of the monosulfonate was complete in about 0.5-3 hours.

One portion of the sulfonation mixture was purified by the process described in U. S. Patent No. 2,433,316. A small amount of water was added and the product was then extracted with toluene. The resulting toluene solution of the sulfonic acid was separated from the residue and agitated with 2-3 times its volume of water followed by neutralizing with 40% sodium hydroxide solution and evaporation on a steam bath. This produced a purified sodium alkyltoluenesulfonate containing only a small quantity (about of sodium sulfate.

The remainder of the sulfonaton mixture was neutralized by pouring it into a slight excess of sodium hydroxide solution of -20% concentration. This produced a slurry of approximately 35% solids, of which about 45-50% was sodium the fabric was then air dried at room temperature. The impregnation and drying was repeated for a total of four times after which the alkyltoluenesulfonate and about 50-55 was sodium sulfate: 'I'his slurry was dried to ake form on a steam-heated drum dryer.

Varying amounts of guanidine carbonate and oi' guanidine sulfate were mixed with the alkyltoluenesulfonate-sodium sulfate mixture prepared by the second of 'the two methods described to produce compositions containing from 0.1% to 100% of guanidine carbonate and from 0.1% to of guanidine sulfate, these percentages-being based on the weight of the alkyltoluenesulfonate in the detergent mixture.

The detergency of the products was determined with the aid of a standard soil having the following composition:

Grams Carbon black e 0.75 White mineral oil 3.00 Lard 3.00

Carbon tetrachloride to make 3 liters.

Wool cloth was passed through this solution and held vertically, allowing the excess liquor to drain. During this period the fabric was inverted several times to insure uniform distribufabric was cut into four inch squares. Reflectance measurements were taken o! these squares at 600 millimicrons on a G. E. Recording Spectrophotometer.

Detergency tests were run at 0.1% concentration of sodium alkyltoluenesulfonate in the Launderometer according to A. A. T. C. C. procedure. Into each pint jar were placed 20 onefourth inch glass beads, 200 m1. of the detergent solution under test, and one numbered soiled swatch.` The jars were rotated at 42 R. P. M. in the machine at F. for 20 minutes and this was repeated for a total of 3 times using fresh detergent solution for each wash. The third wash was followed by three ve minute rinses. The cloth pieces were then squeezed, ironed dry, and again measured for reilectance in the spectrophotometer. The percent ofreturn ofthe cloth to its original reflectance. prior to application of the soil, is the measure of detergency.

The results obtained are shown on the attached drawing. When no guanidine salt was added the detergency value was about 8 to 10%. This value increased to about 20% upon adding 2% of the guanidine salt and continued to increase with to that obtained with 2% of the guanidine carbonate or sulfate; therefore, the detergency of the alkyltoluenesulfonate is doubled by adding any' quantity of guanidine salt between 2% and 50% or more and is'increased more than tive times by amounts of from about 10% to about 45%.

Similar tests using 0.25% aqueous solutions of guanidine carbonate and of guanidine sulfate containing no alkyltoluenesulfonate gave detergency values of 2, showing that these salts possess practically no detergency when used alone.

Example 2 Varying quantities of guanidine carbonate were mixed with an alkylbenzene sodium sulfonate prepared by condensing benzene with a propylene polymer fraction ranging from CioHzz to about Cul-Iso and having an average molecular weight of 168 and sulfonating the product as described in Example 1. The sulfonation mixture was neutralized by pouring it into a 20% aqueous sodium hydroxide solution and the guanidine carbonate was added to the resulting slurry which was then drum dried.

The detergency values were determined by the method described in Example 1 and were as follows, the percent of guanidine carbonate being based on the weight of the alkylbenzene sodium sulfonate.

Percent Defer- Guanidine gency on Carbonate Wool 8 l Example 3 Another advantage obtained with guanidine carbonate when admixed with the `alkylated mononuclear arylsulfonate detergents is a marked reduction in hygroscopicity. Many of the detergenis of this class have a tendency to liquefy by reason of moisture absorbed from the air, which is one of the reasons why they are usually sold as a mixture with sodium sulfate. Even the pres-` ence of this salt, however, does not prevent them from caking on storage. I have found that the presence of even small `quantities of guanidine carbonate will maintain a sodium sulfate-containing product in a free-flowing condition under ordinary storage conditions and that larger quantities will protect a puriiied product in similar manner. p Samples of the unpurifled material of Example l, containing about 45% of aikyltoluenesulfonate and 55% of sodium sulfate. were stored in opencontainers under varying conditions of relative humidity. One set of samples was used as a control while 5-12% of guanidine carbonate based on the weight of the alkyltoluenesulfonate (25% on the weight of the mixture) was incorporated uniformly in the others. The compositions were then stored inopen containers under the conditions shown in the following table.

asesora `Alkyltoluenesulfonate 40' ,These samples were tested for detergency on wool by the procedure described in Example 1 with the following results:

Guanidinesllt What I claim is:

1. A composition consisting essentially of a detergent mixture of 98% to 50% by weight of a member of the group consisting of sodium, potassium and ammonium salts of an alkyi fonate containing a single long alkyl radical of 10-16 carbon atoms and 2% to 50% of a watersoluble guanidine salt of an inorganic acid.

2. A composition consisting essentially of a detergent mixture of 98% to 50% by weight of an alkyltoluenesulfonate of the formula GHaCsHaSOxNn Appearance Aitor Storage Additive Per Cent `Room Com 65% R H 90 100% ditions 2 -25 C 2 R. H,30 Months Months C. 4 Days None Gaked--..---- Wet Lumps..-- Liquid. Guanidine Carbonate-- 5 Dry Powder-- Slightly Damp-- Do. Do 7 -do Dry Powder..-- Do. Dn 12 dn do Wet Solid.

A similar test was made on the purified material described in Example 1. Mixtures with guanidine carbonate were prepared and stored in open containers at 65%-relative humidity and 70 F. In the following table the quantities are parts by weight. f

Na Alkyltoluenesulfo- Guanidine Carbonate 5 l5 30 50 Appearance After Stor age Lumped Lumped Dry Dry Powder Powder These results show that the ordinary commercial mixtures containing about equal parts of an alkylbenzenesulfonate detergent and sodium suifate are protected against adverse storage conditions by a content of 542% or more of guanidine carbonate, based on the weight of the alkylbenzenesulfonate, and that ISO-50% or more will give similar protection to a puriiied material.

Example 4 Test samples containing az number of diierent guanidine salts were prepared from an alkyltoluenesulfonate produced from a commercially available alkyltoluene fraction having an A. S. T. M. distillation boiling range (5 to 95%) of 289304 C. and an average molecular weight. (cryoscopic)A of 268. This alkyltoluene was sulfonated and neutralized with aqueous sodium hydroxide solution by the procedure described inExample l.

Mixtures were prepared from this material having the following composition, the parts being by weight:

inwhichRisanalkylmdlcaloflO-lcarbon atoms and 2% to 50% or a water-soluble guaniin which R is an alkyl radical of 10-16 carbon atoms and 2% to 50% of s'uanidine carbonate.

5. A composition of 98 to 50 parts by weight of a member ofthe group co of sodium, potassiumand ammonium salts of an alkylbenzenesulfonate containing a single long alkyl radical ot 10-16 carbon atoms, 2 to y50 parts of guanidine carbonate, and about 200 to 50 parts of sodium sulfate.

6. A composition consisting essentially oi' a de-` tergent mixture of 98% to 50% by weight oi' an alkylarylsulfonate of the formula in which X is a member of the group of hydrogen and the -CBJ radical, M is a mono-` valent salt-forming radical selected from the `group consisting of sodium. potassium and ammesma 7 monium and R is an alkyl radica! o! 10-16 carbon atoms and 2% to 50% ot a. water-soluble guanidine salt of an inorganic acid.


REFERENCES CITED The following references are o! record in the rile oi.' this patent:

UNITED STATES PATENTS Number Dite Name Flett A 24. 1945 Shepard July 27. 1948 Henderson Jan. 25, 1949 Mackay Mar. 15, 1949 Mackay MB! 3. 1949;-

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2374187 *Sep 20, 1941Apr 24, 1945 Detergent composition
US2445975 *May 8, 1946Jul 27, 1948American Cyanamid CoSolubilized alkaryl sulfonate composition
US2459818 *Aug 4, 1944Jan 25, 1949Lever Brothers LtdSoap product containing guanidine stearate
US2464247 *Jan 3, 1947Mar 15, 1949American Cyanamid CoPreparation of guanidine sulfates
US2469338 *Dec 24, 1946May 3, 1949American Cyanamid CoPreparation of guanidine phosphates
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US2832743 *Sep 29, 1949Apr 29, 1958Lever Brothers LtdFree flowing alkyl aryl sulfonate detergent compositions
US2921881 *Nov 13, 1957Jan 19, 1960American Cyanamid CoFungitoxic-bacteriotoxic guanidine compositions
US2967832 *Nov 15, 1954Jan 10, 1961American Cyanamid CoPolyphosphate detergent compositions containing dicyandiamide tarnish inhibitor
US3960782 *Sep 27, 1974Jun 1, 1976The Procter & Gamble CompanySurfactant, urea, dodecyl alcohol, guanidine
U.S. Classification510/357, 510/496, 510/499
Cooperative ClassificationC11D1/22