US2006309A

US2006309A - Hydroxy sulphonated fatty acid esters and their production

Info

Publication number: US2006309A
Application number: US679217A
Authority: US
Inventors: Charies C Clark
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1933-07-06
Filing date: 1933-07-06
Publication date: 1935-06-25
Anticipated expiration: 1952-06-25

Description

. June 25 1935 PATENT OFFICE j 'HYDBOXY SULPHONATED FA'l'l'Y ACID ES'I'EBS AND THEIR PRODUCTION Charles 0. Clark. St. Bernard, ohimassignor to The Procter d; Gamble Company, Cincinnati,

Ohio, a corporation of Ohio No Drawing. Application July s. 1033, Serial a No. 619,217 7 V momma. (cl. zoo-10c) This invention relates to new foaming, emulsifying, wetting and cleansing agents comprising substances having the general molecular structure of derivatives of glycerol in which one of the .hydroxyls is esterifled with a higher may acid.

one remains unchanged, and the third is replaced by the 80:1! group,'where M may be a-metal or other basic radical. Such compounds may also be considered as salts of sulphonated monoglycerides of fatty acids.

The objects of the invention are to provide new and useful compounds having the desirable properties abovementioned, and to provide means for producing same.

Itis known that foaming, emulsifyin wetting and cleansing properties are possessed by sulphate esters of certain. oils, fats, waxes, fatty acids and fatty alcohols, and that such properties are also possessed by the salts of certain sulphonic acids, such, for example, as those which canbepreparedbyestcrlfyingthealkalimetal salts of isetliionic acid with fatty acids. It is also known that 'compoundawith similar properties can be prepared by combining such products as the sodium salt of 1,2-hydroxy propane sulphonic acid, or thesodium salt of 1,3-hydroxy propanesulphonic acid with fatty acids or fatty acid chlorides. I make no claim to such com-' poimds, which do not contain a free hydroxyl group in the. nucleus of the molecule.

I havefoimd that a new class of compoundsmf different structure from the above, but possessing the above-mentioned desirable properties to a remarkable degree, can be prepared by causing salts of glycerol alpha-sulphonic acid to react with a higher saturated or unsaturated fatty acid or fatty acid halide, thereby obtaining the mono-fatty acid ester. or a mixture of the monoand the div-fatty acidesters, of the said salts of.

glycerol alpha-sulphonic acid. I have also fund that the mono-fatty acid ester of an alpha-glycerol sulphonate, possessing a free hydroxyl group lathe-nucleus of the molecule, has the desirable foaming, emulsifyin wetting, cleansing and dispersing properties to agrea'ter extent than has the di-fatty acid ester or a mixture of the monoand the di-fatty acid esters, and that a separation of the relativelymore desirable mono-fatty acid ester from the relatively less desirable difatty acid ester can be eifected by washing with,

'orfipreferably by crystallization from ethyl alcohol or other low-boiling alcohol. Such separation is sometimes desirable, but is not in all cases essential, and my invention is not limited tothe purified product obtained by such separation.

ized by a molecular nucleus of three carbon T atoms, to one of which a'free hydroxyl group is attached, to another of which ahigher fatty acid radical is attached by an ester linkage, and to the third of which the salt of a sulphonic acid group, 803M, is attached, the sulphur of-this last mentioned group being combined directly with the terminal carbon atom of the said nucleus; The product so obtained is of the general formula: XCHzCHYCHaSOaM, where M may be any alkali metal, alkaline earth metal, heavy metal, ammonium or basic organic radical which, in the above combination, is soluble in water, and where X may be a fatty acid radical, in which case Y is a hydroxyl group, or else X may be'a'hydroxyl group in which case Y is a fatty acid radical. The alkali metals and magnesium form especially useful products, but it should be understood that any metal or basic radical that forms water-soluble compounds may also be used. The fatty acid radical in either case may be any set-- urated or unsaturated fatty acid radical having six or more carbon atoms in the molecule. Products of this type differ from previously used fatty acid esters of sulphonic acids in that they possess an alcoholic hydroxyl group in the nucleus of the been found to add greatly to the solubility of the compound in water and to render it especially useful in hard waters. Thus the replacement of this hydroxylgroup by hydrogen or by a higher. fattyacid group lessens the foaming emulsifying, wetting and cleansing power of the product and its solubility in hard waters. r.

. It is understood that in making the products of my invention, in place of aflsingle fatty acid a mixture of fatty acids may be'used, such for exa'mpleas occurs in any of the natural fats or oils; likewise a mixture of or basic radicals may-housed in place of a single one. The fatty, acids from 'cocoanutoil or' palm. kernel oil are' es'pecially suitable products;

The products'of my invention be made by means of several differentfreactlons depending on the nature of the materials. One method is to start with asolublesalt, such for example as the sodium saltgof glycerol sulphonic acid (sodium 'LZ-dihydroxy' propane-3-suipho-' nate, prepared by alpha' clilorohydrin with aqueous NazSO: solution ahd suhsequent removal o'fwater)v and cause itto combine withthe desired fatty acids. This is by heating one molecular proportion of the aim-ementioned salt with one molecular proportion of the fatty acid in a suitable reacting chamber equipped with a reflux condenser. For the best. yields, the mixture must be heated with stirring to a temperature ranging from about 150 to 225 C. for a period of about 5 to 10 hours.

The water formed in the reaction is allowed to escape while any fatty acids which volatilize are returned to the reacting chamber by the reflux condenser.

A second method is to start with the same form of salt of glycerol sulphonic acid and heat same with a fatty acid chloride instead of a fatty acid itself. In this case again, equal molecular quantitles are used and the process is similar except that it proceeds at a much lower temperature, such as from approximately 75 to 125 C., for a period of about '5 to 10 hours. The hydro- .chloric acid formed in the reaction is allowed to escape, but any acidity still remaining at the end of the reaction should be neutralized with caustic soda or other basic reagent.

' A third method is to start with a soluble salt,

such for example as the sodium salt, of l-chloro- 2-hydroxy propane-3-sulphonic acid and heat same as above with an alkali soap of a fatty acid. In this case, a temperature of about 100 to 200 C. is required with stirring for about 5 to 10 hours.

All three of these methods will yield products of the same chemical structure and properties, differing only in the nature and amount of the impurities which may be present as a result of the method used. The first and second methcds, for example, may result in the presence, as impurities, of fatty acids or of the sodium salt of glycerol sulphonic acid, while the second and third methods may result in the presence, as impurities, of alkali metal soap or of sodium chloride besides unacted-on materials. In the case of the third method, there may also be present unreacted sodium salt of 1-chioro-2-hydroxy propane-3-sulphonic acid. The reaction products may in all cases be purified sufliciently for practical purposes by washing with cold ethyl alcohol or other low-boiling alcohol, or preferably by dissolving in hot ethyl alcohol, filtering to remove insoluble salts and other matters, and crystallizing from the alcoholic solution. The product thus obtained will consist essentially of the mono-fatty acid ester, substantially free from the di-fatty acid ester, and containing variable amounts of other impurities (such as the abovementioned sodium chloride, sodium 1,2-dihydroxy propane- 3-su1phonate, or sodium i-chloro- 2- hydroxy propane-3-sulphonate) depending upon the thoroughness of the purification treatment to which it is subjected. The purified product is a dry powder nearly white in color, stable under all ordinary conditions, and possessing in aqueous solution extraordinary foaming, emulsifying, wetting and cleansing properties, showing these properties strongly even in hard water.

The following examples will illustrate different methods of making the products of my invention, all quantities being by weight.

Example 1 180 parts of the sodium salt of glycerol sulphonic acid (sodium 1,2*dihydroxy propane-3-sulphopate, prepared by heating alpha chlorohydrin with aqueous NazSOs solution and subsequent removal of water) are heated at 150 to 225 C. for 6 hours with stirring with 210 parts of the fatty acids from cocoanut oil, the water evolved in tlie reaction being allowed toescape and the fatty acids being returned to the reacting chamber by suitable reflux condensation. The product of this reaction is then purified by washing with cold ethyl alcohol or other low-boiling alcohol, or preferably by dissolving in hot ethyl alcohol, filtering to remove insoluble inorganic salts. or other insoluble matter and crystallizing from the alcoholic solution. The product thus obtained is a nearly white dry powder, stable under ordinary conditions of use, and possessing in aqueous solution extraordinary foaming, emulsifying, wetting and cleansing properties and can be used advantageously even in hard water.

Example 2 195 parts of the potassium salt of 1,2-dihydroxy propane-3-sulphonic acid are heated at 75 to 125 C. with stirring, for 10 hours with 300 parts of oleic acid chloride. The produce of the reaction is made neutral with NaOH, NazCOa, NH: or other suitable alkali and is then purified as in Example '1. erties described under Example 1.

Example 3 200 parts of the sodium salt of l-chloro-2- hydroxy propane-3-sulphonic acid are heated at to 200 C. with stirring for 5 hours with 300 parts of sodium soap prepared from tallow. The product of the reaction may then be purified as in Example 1, and it then possesses the properties described in Example 1.

Example 4v The triethanolammonium (sometimes called triethanolamine) compound may be formed as follows:

290 parts of the sodium salt of commercial stearic acid are heated at about C., with stirring for 4 hours with 325 parts of the triethanolammonium salt of 1-chloro-2-hydroxy propane-3-sulphonic acid (prepared by heating 1,3dichlorohydrin with triethanolamminium sulphite). The product of the reaction may be purified as in Example 1, and then possesses the properties described in Example 1;

Having thus described my invention, whatI claim as new and desired to secure by letters Patent is:

1. A new composition of matter consisting of monohydric' aliphatic'alcohols derived from a soluble salt of 1,2-dihvdroxy propane-fii-sulphonic acid by e'sterification of one of its hydroxyl groups with a fatty acid containing at least six carbon atoms.

2. The process of preparing foaming, emulsifying, wetting and cleansing agents comprising chemically combining one molecular weight of a soluble salt of 1,2-dihydroxy propane-3-sulphonic acid with one molecular weight of a fatty acid having at least 6 carbon atoms;

3. The process of preparing foaming, emulsifying, wetting and cleansing agents comprising chemically combining one molecular weight of 1 halogen-2-hydroxy propane-3-sulphonic acid with one molecular weight of the alkali metal soap of afatty acid having at least six carbon atoms.

4. Wetting, cleansing and emulsifying agents consisting of compounds of the general formula CHzXCHXCHzSOsM The purified product has the propwhere M may be an equivalent weight of any alkali metal, alkaline earth metal, heavy ammonium or basic organic radical which, in the above combination, is soluble in water and where one X is a hydroxyl group and the other x con- 'sistsofthe groupRCOQinwhichRistheaibl radical'of a fatty acid having at least six carbon atoms.

A new composition of matter consisting of compounds of the general formula CHaXCHXCHaSOaM where M maybe an equivalent weight of any alkali metal, alkaline earth metal, heavy metal,

' ammonium or basic organic radical which in the above combination is soluble in water and where one x is a hydroxyl group and the other x consists of the group RG00, in which it re wts alkyl radicals oi. fatty acids derived from c ut oil. 7

6. The process which comprises causing a compound selected'from the group consisting of 1,2-dihydroxy propane fl-sulphonic acid, 1 halogen-2-hydroxy propane-3-sulphonic acid, and

the soluble salts of these compounds, to react with a compound selected from the group consisting of fatty acids containing at least six carbon atoms per molecule, and their alkali metal salts.

7. The process which comprises causing a compound of the general formula nocmcnoncmsom wherein M stands for an equivalent weight of any alkali metal, alkaline earth metal, heavy metal, ammonium or basic organic radical which in the above combination is soluble in water, to react with a fatty acid whose molecule contains at least six carbon atoms.

. 8; The process which comprises causing a com-- pound of the general formula i XCHsCHOHCHaSOsH.

a,ooe,soo

metal,

wherein 2 stands for a halogen atom and M stands for an equivalent weight of any alkali metal, alkalineearth metal, heavy metal, am-

monium or basic organic radical which in the.

above combination is soluble in water, to react with an alkali metal salt of a fatty acid whose molecule contains at least six; carbon atoms.

9. Wetting, cleansingand emulsifying agents consisting of the products formed by causing a compound of the general formula HOCHsC'HOHCHaSOaM wherein M stands for an equivalent weight of- XCHsCHOHCHrSOsM wherein X stands for a halogen atom and M stands for an equivalent weight ofv any alkali metal, alkaline earth metal, heavy metal, ammonium or basic organic radical which in the above combination is soluble in water, to react with an alkali metal salt of a fatty acid whose molecule contains at least six carbon atoms, said products of reaction great power to water and in soft water;

CHARLES C. CLARK.

I DI SCI-Al M E R 2,006,309.0I|q1-ls 0'. Clark, St. Bernard, Ohio. Hrnnoxr Sunrno'rurnn Fury Acm ddsrnas m Tnmn PRODUCTION. Patent dated June 25, 1935.

V 1 Disclaimer filed DecemberIS, 1935, by the assignee, The Procter d: Gambk Hereby enters this disclaimerto the process of claim 6 insofar as such comprises causing l 2 profpane 3-sulfon ic acid to react with a compound ected from the group consisting-of atty acidscontaim'ng at least six carbon atoms per molecul'e'and their alkah'metal sal ts, and in so far as such process comprises causing the soluble salts of 1 :2 dihydroxy ropane 3 sulphonic acid to react with con [Qflicml Gasefle January 14, 1986.]

e lk limeal tsofthe fft at least six carbon toms per molecule. v m o "d foam,-emulsify, wet, and cleanse, both in hard DISCLAIMER 2,006,309.0Iwrles 0. am, St. Bernard, Ohio. Hrnnoxr SULrnoNa'mn FATTY Acm -Esmns m Tlmm PRODUCTION. Patent dated June 25, 1935. gisclaimer filed December 18 1935, by the assignee 17w Procter (f: Gamble Hereby enters this disclaimer to the process of claim 6 in so far as such process comprises causing 1 :2 dihydroxy pro 0 3-sulfonic acid to react with a compound selected from the group consisting of atty acids containing at least six carbon atoms per molecule'and their alkali metal salts, and in so far as such process comprises causing the soluble salts of 1 2 dihydroxy ropane 3 sulphonic acid to react with a compound selected from the alkali metal ts of the group consisting of fatty acids containing at least six carbon atoms per molecule.

[Qflicull January 14, 1936.]