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Publication numberUS3627822 A
Publication typeGrant
Publication dateDec 14, 1971
Filing dateNov 29, 1968
Priority dateNov 29, 1968
Also published asDE1959103A1, US3609090
Publication numberUS 3627822 A, US 3627822A, US-A-3627822, US3627822 A, US3627822A
InventorsBjorn Sundby
Original AssigneeColgate Palmolive Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Novel compounds with detergency and fabric-softening ability and method of making the same
US 3627822 A
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Description  (OCR text may contain errors)

United States Patent 72] Inventor Bjorn Sundby Highland Park, NJ.

[21] Appl. No. 780,276

122] Filed Nov. 29, 1968 [45] Patented Dec. 14, 1971 [73] Assignee Colgate-Palmolive Company New York, N.Y.

[54] NOVEL COMPOUNDS WITH DETERGENCY AND FABRIC-SOFIENING ABILITY AND METHOD OF MAKING THE SAME 15 Claims, No Drawings 260/501.12, 260/609 F, 260/615 R, 424/70, 424/56, 424/303, 252/161, 117/139.5 CO [51] Int. Cl ..C07c143/l0 [50] Field of Search 260/513 B, 513,615,607 A,513 R [56] References Cited UNITED STATES PATENTS 2,913,324 11/1959 Kosmin 260/513 3,086,043 4/1963 Gaertner 260/513 2,427,577 9/1947 Smith 260/513 3,082,249 3/1963 Gaertner 260/513 8 Swern et al., J. Am. Chem. Soc. 71, 1 1 52 1949).

Primary Examiner- Daniel D. Horwitz Attorneys-Herbert S. Sylvester, Murray M. Grill, Norman Blumenkopf, Ronald S. Cornell, Thomas J. Corum, Richard N. Miller and Robert L. Stone ABS BAQBMYQE WPQHQQ M; fo mu [Rs-Il OH RQJX wherein (1) R is a straight or branched higher alkyl group of C to Q and preferably C to C NOVEL COMPOUNDS WITH DETERGENCY AND FABRIC-SOFTENING ABILITY AND METHOD OF MAKING THE SAME The present invention relates to novel compounds uniquely containing foaming and detergency properties in addition to fabric-softening ability, methods of preparing the same, and novel intermediate compounds useful in their preparation. More particularly, the present invention relates to such novel compounds of the hydroxy ether (including thioether) sulfonate type.

While in recent years various outstanding detergent materials and various outstanding softening agents have been developed, it has still been necessary to provide separate materials for performing these two functions. Thus, until the present invention no successful detergent material possessing softening ability has been discovered.

The most successful detergents developed in recent years are the linear alkyl benzene sulfonates. While such materials possess excellent foaming and detergency characteristics such materials possess little or no softening ability.

The most efi'ective softeners that have been developed in recent years are the quaternary ammonium fabric-softening agents. While these cationic agents are extremely effective in the softening of textile fabrics, it is noted that, because of their cationic nature, such fabric-softening additives cannot be employed in conjunction with conventional anionic detergents, e.g. sulfonates, and therefore, must be added to the wash water during the rinse cycle operation. This is due to the fact that the cationic quaternary ammonium fabric softeners and anionic detergents complex and precipitate thus adversely effecting the operability of each of the materials.

Accordingly, in accordance with previous materials and methods, the use of separate detergents and fabric softeners has been even more complicated by the incompatability of the best detergents and fabric softeners previously available.

Therefore, it has been the long desire of the detergent in- 'dustry to provide a single compound possessing the foaming detergency characteristics of conventional detergents, yet uniquely possessing fabric-softening ability. Such a single compound uniquely possessing both detergency and fabricsoftening ability would of course eliminate the disadvantages of employing two separate materials, and, in addition, would completely eliminate the disadvantages associated with the incompatability of conventional anionic detergents and cationic fabric softeners.

In accordance with the present invention, it has now been discovered that certain hydroxy ether sulfonates possess detergency characteristics substantially equivalent to or better than that of conventional anionic detergents now employed in detergent compositions and, in addition, possess fabric-softening ability substantially equivalent to quaternary ammonium cationic fabric softeners now conventionally employed in the rinse cycle of a washing operation.

It is therefore a principle object of the present invention to provide a detergent compound possessing fabric-softening ability.

It is a further object of the present invention to provide such a novel detergent compound possessing fabric-softening ability which novel compound eliminates the previous deficiencies associated with the employment of separate incompatible detergents and fabric softeners.

A yet further object of the present invention is to provide certain novel hydroxy ether sulfonates which possess detergent and foaming characteristics substantially equivalent to or superior to conventional anionic detergents and fabric-softening ability substantially equivalent to conventional cationic quaternary ammonium softeners.

Still a further object of the present invention is to provide novel methods of producing certain hydroxy ether sulfonates possessing both detergency and fabric-softening ability, such processes including the reaction of an unsaturated alcohol with a long-chain epoxide with subsequent sulfonation of the reaction product.

Yet a further object of the present invention is to provide novel unsaturated hydroxy ethers useful as intermediates in the production of the hydroxy ether sulfonates of the present invention.

Still another further object of the present invention is the provision of novel hydroxy ether sulfonates which are compatible with builder salts and particularly tetrapotassium pyrophosphate in aqueous systems obviating the need for hydrotropic agents.

Still further objects and advantages of the novel compounds and process of the present invention will become more apparent from the following more detailed description thereof.

The novel compounds of the present invention which uniquely possess outstanding foaming and detergency characteristics in addition to fabric-softening ability correspond to the general formula:


l. R, is a straight or branched higher alkyl group of C to C and preferably C to C 2. R, is a straight or branched alkylene of C to C and preferably C to C 3 R to R are, independently, hydrogen or straight or branched alkyl of C to C and preferably hydrogen or lower alkyl of C to C 4. Z is oxygen (-0-) or sulfur (S);

5. x and y have the values 0 or 1 and x-i-y=l and 6. M is a cation such as hydrogen, alkali metal, ammonium, substituted ammonium or amine and preferably a water-solubilizing, salt-forming group.

While the sodium salts of the hydroxy ether sulfonates of the present invention are preferred, it is of course possible to advantageously employ other alkali metals such as potassium or lithium. Additionally, ammonium and amine salts, e.g., trialkanolamine salts such as triethanolamine can be advantageously employed with exceptional results.

The novel hydroxy ether sulfonates of the present invention may be prepared by reacting an epoxy alkane with an unsaturated aliphatic alcohol with subsequent sulfonation of the reaction product. The epoxy alkane reactants that are useful in the preparation of the hydroxy ether sulfonates of the present invention can be any epoxy alkane having a terminal group i.e., an epoxy alkane having the structure:

wherein R, is as defined above. As noted above, R comprises a straight or branchedchain alkyl. radical of from about six to about 30 carbon atoms. Illustrative examples of some suitable alkyl radicals include:

n-hexyl iso-hexyl iso-heptyl n-octyl iso-octyl n-nonyl iso-nonyl n-decyl n-dodecyl tertedodecyl 2-propylheptyl S-ethylnonyl 2-butyloctyl n-undecyl n-tridecyl n-tetradecyl n-pentadecyl tert-octadecyl 2,6,8-trimethylnonyl v 7-ethyl-2-methy1-4-undecyl n-hexadecyl n-octadecyl eicosyl docosyl tricosyl pentacosyl triacontyl etc.

The alkyl radicals may also include unsaturated alkyl radicals such as hexenyl, oleyl, dodecenyl, hexadecenyl, and the like.

Illustrative examples of some epoxy alkanes which can be employed as reactants in the process of the present invention to produce the novel hydroxy ether sulfonates of the present invention include:

1,2 epoxyhexane 1,2 epoxyoctane 1,2 epoxydecane 1,2 epoxyundecane 1.2 epoxydodecane 1,2 epoxytridecane 1,2 epoxytetradecane 1,2 epoxypentadecane 1,2 epoxyhexadecane 1,2 epoxyoxtadecane 7-ethyl-2-methy1- 1 ,2-epoxyundecane 2,6,8-trimethy1-1,2-epoxynonane l,1,2-trimethyl-1.2-epoxy decane 1,1-dimethyl-2-ethy1--epoxy decane -epoxy decane l-methy1-1,2-diethyl-l ,2-epoxy tetradecane 1 l -dimethy1 epoxy undecane 1, l -diethyl epoxy decane 1,1diisopropy1 epoxy octane etc.

Exemplary hydroxy ether sulfonates in accordance with the present invention include:

A. Oxa derivatives 1. wherein v==l and x= 6-hydroxy-4-oxahexadecyl sodium sulfonate 6-hydroxy-4oxaheptadecyl sodium sulfonate 6-hydroxy-4-oxaoctadecyl sodium sulfonate 6-hydroxy-4-oxanonadecyl sodium sulfonate 6-hydroxy-4-oxaeicosyl sodium sulfonate 6-hydroxy-4-oxauncosyl sodium sulfonate 6-hydroxy-4-oxadocosyl sodium sulfonate 6-hydroxy-8-methyl-12-ethyl-4-oxapentadecyl sodium sulfonate 6-hydroxy-7,7-dimethyl-4-oxahexadecyl sodium sulfate 6-hydroxy-4-oxatetracosyl sodium sulfonate 6-hydroxy-4-oxahexadecyl potassium sulfonate 6-hydroxy-4-oxaheptadecyl potassium sulfonate 6-hydroxy-4-oxaoctadecyl potassium sulfonate 6-hydroxy-4-oxanonadecyl potassium sulfonate 6-hydroxy-4-oxaeicosyl potassium sulfonate 6-hydroxy-4-oxauncosyl potassium sulfonate 6-hydroxy-4-oxadocosyl potassium sulfonate 6-hydroxy-8 methyll2-ethyl-4-oxapentadecyl potassium sulfonate 6-hydroxy-7,7-dimethyl-4-oxahexadecyl potassium sulfonate 6-hydroxy-4-oxatetracosyl potassium sulfonate 6-hydroxy-4-oxahexadecyl lithium sulfonate 6-hydroxy-4-oxaoctadecyl lithium sulfonate 6-hydroxy-4-oxanonadecyl lithium sulfonate 6-hydroxy-4-oxadocosyl lithium sulfonate 6-hydroxy-4-oxahexadecyl ammonium sulfonate 6-hydroxy-4-oxaheptadecyl ammonium sulfonate 6-hydroxy-4-oxaeicosy1 ammonium sulfonate 6-hydroxy-4-oxadocosyl ammonium sulfonate 6-hydroxy-8 methyl-l2-ethyl-4-oxapentadecyl ammonium sulfonate triethanol amine salt of 6-hydroxy-4-oxahexadecyl sulfonic acid triethanol amine salt of 6-hydroxy-4-oxaheptadecyl sulfonic acid triethanol amine salt of 6-hydroxy-4-oxaeicosyl sulfonic acid triethanol amine salt of 6-hydroxy-7,7-dimethyl-4-oxahexadecyl sulfonic acid.

8-hydroxy-6-oxahexadecyl sodium sulfonate 8-hydroxy-6-oxaheptadecyl sodium sulfonate 8-hydroxy-6-oxaoctadecyl sodium sulfonate 8-hydroxy-6-oxanonadecyl sodium sulfonate 8-hydroxy-6-oxaeicosyl sodium sulfonate 8-hydroxy-6-oxauncosyl sodium sulfonate 8-hydroxy-6-oxadocosyl sodium sulfonate 8-hydroxy-8 methyl-12-ethyl-6-oxapentadecyl sodium sulfonate 8-hydroxy-1 1,1 1, dimethyl-6-oxahexadecyl sodium sulfonate 8-hydroxy-6-oxatetracosy1 sodium sulfonate 8-hydroxy-6-oxahexadecy1 potassium sulfonate 8-hydroxy-6-oxaheptadecyl potassium sulfonate 8-hydroxy-6-oxaoctadecyl potassium sulfonate 8-hydroxy-6-oxanonadecyl potassium sulfonate 8-hydroxy-6-oxaeicosyl potassium sulfonate 8-hydroxy-6-oxauncosyl potassium sulfonate 8-hydroxy-6-oxadocosyl potassium sulfonate 8-hydroxy-8 methyl-l2-ethyl-6-oxapentadecyl potassium sulfonate 8-hydroxy-1 1,1 l-dimethyl-6-oxahexadecyl potassium sulfonate 8-hydroxy--oxatetracosyl potassium sulfonate 8-hydroxy6-oxahexadecyl lithium sulfonate 8-hydroxy-6-oxaoctadecyl lithium. sulfonate 8-hydroxy-6-oxanonadecyl lithium sulfonate S-hydroxy-fi-oxadocosyl lithium sulfonate 8-hydroxy-6-oxahexadecyl ammonium sulfonate 8-hydroxy-6-oxaheptadecyl ammonium sulfonate 8-hydroxy-6-oxaeicosy1 ammonium sulfonate 8-hydroxy-6-oxadocosyl ammonium sulfonate 8-hydroxy-8 methyl-12-ethy1-6-oxapentadecyl ammonium sulfonate triethanol amine salt of 8-hydroxy-6-oxahexadecy1 sulfonic acid triethanol amine salt of 8-hydroxy 6-oxaheptadecyl sulfonic acid triethanol amine salt of 8-hydroxy-6-oxaeicosyl sulfonic acid triethanol amine salt of 8-hydroxy-9,9-dimethyl-6-oxahexadecyl sulfonic acid 7-hydroxy-5-oxahexadecyl sodium sulfonate 7-hydroxy-5-oxaoctadccyl sodium sulfonate 7-hydroxy-5-oxaeicosyl sodium sulfonate 7-hydroxy-5-oxadocosyl sodium sulfonate 7-hydroxy-9,9-dimethyl-5-oxahexadecyl sodium sulfonate 7-hydroxy-5-oxahexadecyl potassium sulfonate 7-hydroxy-5-oxaoctadecyl potassium sulfonate 7-hydroxy-5-oxaeicosyl potassium sulfonate 7-hydroxy-5-oxadocosyl potassium sulfonate 7-hydroxy-9,Q-dimethyl-5-oxahexadecyl potassium fonate 7-hydroxy-5-oxahexadecyl lithium sulfonate 7-hydroxy-5-oxanondecyl lithium sulfonate 7-hydroxy-5-oxahexadecyl ammonium sulfonate 7-hydroxy-5-oxaeicosyl ammonium sulfonate 7-hydroxy-8 methyl-12-ethy1-5-oxapentadecy1 ammonium sulfonate triethanol amine salt of 7-hydroxy-5-oxaheptadecyl sulfonic acid triethanol amine salt of 7-hydroxy-7,7-dimethyl-5oxahexadecyl sulfonic acid 10-hydroxy-8-oxahexadecyl sodium sulfonate sul- 3,5-dimethyl--hexene-3-thiol 2,3-diemthyl-4-pentene-2-thiol 3-ethyl-5-hexene-3-thiol l-heptene-3-thiol 2-heptene-4-thiol 3-heptenel -thiol 4-hexene-3-thiol 5-hexene-3-thiol 3-methyl-3-butene-2-thiol Z-methyll -heptene-3-thiol 3-methyl-5-hexene-3-thiol 2-methyll -pentene-3-thiol 2-methyl-4-pentene-3-thiol 4-methyll -pentene-3-thiol 4-methyl-3-pentene-2-thiol lO-undecenel -thiol The hydroxy ether or thioether sulfonates of the present invention are prepared, using one technique, by the reaction of long-chain epoxide with an unsaturated alcohol or thioalcohol (Le. mercaptan) with subsequent sulfonation of the intermediate product in accordance with the following equations. illustrating the use of an alcohol:

wherein R is as defined above; and R is C to C which together with CH-CH forms an unsaturated group within the scope of R,,.

Reaction 1 above is preferably catalyzed by the employment of sodium, preferably dissolved in the alcohol reactant. Thus, while it has been established that almost quantitative yields of the unsaturated intermediate product can be produced by the use of sodium as the catalyst in the process of the present invention, it is, of course, obvious that any catalyst material capable of effecting the condensation of the alcohol and longchain epoxide with the opening of the epoxy ring can be successfully employed in the process of the present invention. Such exemplary catalysts include for example BF BF -dialkyl etherate, etc.

The reaction of the long-chain epoxide and alcohol is not critically dependent upon the choice of temperature, pressure or amount of reactants, Thus, while the epoxide and alcohol react in substantially stoichiometric proportions, it is possible to employ a relatively large excess of either the long-chain epoxide or the alcohol reactant without adversely effecting the reaction system. in this respect, it has been shown that the employment of such a relatively large excess of either reactant merely necessitates removal of the excess reactant from the reaction system and does not adversely efiect the product or yield thereof.

Similarly, it has been found that the reaction of the present invention can be suitably run at ambient pressure or under increased pressure conditioi'is, the pressure of the system having relatively little effect upon the yield and purity of the intermediate product and final product produced. For economic purposes however, it has been found most suitable to run the reaction under atmospheric pressure conditions.

Similarly, it has been determined that the temperature at which the reaction is run is not critical with respect to the purity and yield of both the intermediate product and the final product in accordance with the process of the present invention. Thus. temperatures ranging from ambient temperatures up through approximately 150 C. have been found suitable in accordance with the process of the present invention, although any temperature may be used provided the reactants are stable thereat. The selection of any particular temperature will be dependent, inter alia, upon the specific reactants and the selection of catalyst, if any, employed. Suitable catalysts include any basic or acidic material. Illustrative catalysts are alkali metals, alkalihydroxides, Lewis acids such as boron trifluoride, aluminum chloride, etc. The catalyst concentration is not critical, and as little as 0.001 percent may be used; the upper limit may be 10 percent.

It is pointed out that while the above description has been directed primarily to the employment of a single long-chain epoxide in the reaction with alcohol to produce a single unsaturated hydroxy ether intermediate product, it is of course obvious that mixtures of such long-chain epoxides can be suitably employed to produce a mixture of such unsaturated hydroxy ethers. The sulfonation of such mixture of products will produce a mixture of hydroxy ether sulfonates which mixture is exceptionally useful because of its detergency and fabric-softening ability. Accordingly, a suitable reaction mixture of long-chain epoxides has been found to be a mixture of C, C,,, l ,2-epoxy alkanes.

it is within the contemplation of the present invention to carry out the processes for producing the compounds of this invention, including the l2-epoxyalkane-alcohol condensation reaction in the presence of inert diluent or mutual nonreactive solvents such as xylene, toluene, etc., and in the sulfonation phase of the process there may also be used aqueous alcohols e.g., aqueous methanol, ethanol, n-propanol, isopropanol, butanol, pyridine, etc.

The novel unsaturated hydroxy ether intermediate prepared by the reaction of the long-chain epoxide and unsaturated alcohol can be sulfonated to produce the novel detergent and 0 fabric-softening compounds of the present invention in any suitable conventional manner. Thus, it has been found convenient to sulfonate the double bond of the novel intermediate compound with a bisulfite e.g., sodium bisulfite in the presence of an initiator. Suitable initiators include peroxide initiators include for example tertiary butyl perbenzoates, di-tbutyl peroxide, dibenzoyl peroxide, dilauryl peroxide, etc.'(' Another initiator system is the nitrate/oxygen system eg potassium nitrate, lithium nitrate ammonium nitrate, alkaline earth nitrates and others, whichdo not accelerate bisulfite oxidation to sulfate in the presence of oxygen, preferably at a partial pressure of from I to 1.5 psi) Such a process which is conveniently employed in the sulfonation of double bonds is set forth in U.S. Pat. No. 2,504,4l l, the subject matter of which is incorporated herein by reference. While the temperature of the sulfonation reaction is not critical, generally slightly elevated temperatures are employed. Thus, for example, a temperature of from about 40 to C. can be conveniently employed in the sulfonation of the novel unsaturated hydroxy ether compounds of the present invention.

Other synthetic routes may be used. For example, in place of the unsaturated alcohol, one may condense the epoxy alkane with an a, w-halohydroxy compound, dehydrohalogenate and then sulfonate with bisulfite, or alternatively employ sodium sulfite (in lieu of dehydrohalogenation and bisulfite), i.e., Strecker reaction. Further vicinal glycols reacted with sultones yield the instant compounds.

The novel hydroxy ether sulfonates of the present invention, in addition to possessing excellent detergency and fabric-softening properties, have been found to be compatible with the various detergent builders and other additives conventionally employed in detergent compositions. Accordingly, it is possible to formulate a detergent composition based upon the hydroxy ether sulfonate as the detergent and fabric softener. Because of the unusual compatibility of the hydroxy ether sulfonates of the present invention with the various detergent builders, it is possible to prepare both solid-phase detergent compositions and single-phase liquid detergent compositions which could not be suitably prepared with the employment of conventional linear alkyl benzene sulfonates.

The new compounds of this invention and the new mixtures containing such compounds may be employed in a wide variety of detergent compositions, including light-duty liquid detergent formulations and granular compositions such as spray-dried built detergent powders. They may be used in toilet bars for washing the hands, face and body (here, as in other formulations, their unexpected germicidal properties are highly advantageous) or in laundry detergent bars, containing appreciable amounts of builder salts, for washing clothes. They may also be used in hair-shampooing, hair-dyeing or other hair-treating or hair-conditioning compositions. They may also be used in dental creams or other dentifrices and in skin care preparations such as creams and lotions.

The novel detergent compounds of this invention may be used as such or as mixtures with other surface-active detergents. The added surfaceactive detergents may be of the anionic, nonionic, cationic or amphoteric types, or mixtures thereof.

The anionic surface active agents include those surface active or detergent compounds which contain an organic hydrophobic group and an anionic solubilizing group. Typical examples of anionic solubilizing groups are sulfonate, sulfate, carboxylate, phosphonate and phosphate. Examples of suitable anionic detergents which fall within the scope of the invention include the soaps, such as the water-soluble salts of higher fatty acids or rosin acids, such as may be derived from fats, oils and waxes of animal, vegetable or marine origin, eg the sodium soaps of tallow, grease, coconut oil, tall oil and mixtures thereof; and the sulfated and sulfonated synthetic detergents, particularly those having about eight to 26, and preferably about 12 to 22, carbon atoms to the molecule.

As examples of suitable synthetic anionic detergents there may be cited the higher alkyl mononuclear aromatic sulfonates such as the higher alkyl benzene sulfonates containing from to 16 carbon atoms in the alkyl group in a straight or branched chain, e.g., the sodium salts of higher alkyl benzene sulfonates or of the higher alkyl toluene, xylene and phenol sulfonates; alkyl napthalene sulfonate, ammonium diamyl napthalene sulfonate, and sodium dinonyl napthalene sulfonate. In one preferred type of composition there is used a linear alkyl 1 sulfonate having a high content of 3-(or higher) phenyl isomers and a correspondingly low content (well below 50 percent of 2-( or lower) phenyl isomers; in other terminology, the benzene ring is preferably attached in large part at the 3 or higher (e.g. 4, 5, 6 or 7) position of the alkyl group and the content of isomers in which the benzene ring is attached at the the 2 or 1 position is correspondingly low. Particularly preferred materials are set forth in US. Pat. No. 3,320,174, May 16, 1967, OH. Rubinfeld.

The mixtures containing linear alkylbenzene sulfonates and the detergent compounds of this invention have unexpectedly good properties, particularly with respect to softening power. These mixtures are the invention of Harold Wixon.

Other anionic detergents are the olefin sulfonates, including long-chain alkene sulfonates, long-chain hydroxyalkane sulfonates or mixtures of alkenesulfonates and hydroxyalkanesulfonates These olefin sulfonate detergents may be prepared, in known manner, by the reaction of 80;, with long chain olefins (of 8 to 25, preferably 12-21 carbon atoms) of the formula R'CH-CHR", where R is alkyl and R" is alkyl or hydrogen, to produce a mixture of sultones and alkenesulfonic acids, which mixture is then treated to convert the sultones to sulfonates. Examples of other sulfate or sulfonate detergents are paraffin sulfonates, such as the reaction products of alpha olefins and bisulfates (e.g. sodium bisulfate), e.g., primary paraffin sulfonates of about 10-20, preferably about 15-20 carbon atoms; sulfates or higher alcohols; salts of a-sulfofatty esters (e.g. of about 10-20 carbon atoms, such as methyl a-sulfomyristate or a-sulfotallowate).

Examples of sulfates of higher alcohols are sodium lauryl sulfate, sodium tallow alcohol sulfate, Turkey Red Oil or other sulfated oils, or sulfates of monoor diglycerides of fatty acids (e.g. stearic monoglyceride monsulfate), alkyl poly (ethenoxy) ether sulfates such as the sulfates of the condensation products of ethylene oxide and lauryl alcohol (usually having one to five ethenoxy groups per molecule); lauryl or other higher alkyl glyceryl ether sulfonates; aromatic poly (ethenoxy) ether sulfates such as the sulfates of the condensation products of ethylene oxide and nonyl phenol (usually having one to six oxyethylene groups per molecule).

The suitable anionic detergents include also the acyl sarocosinates (e.g. sodium lauroylsarcosinate) the acyl esters (e.g. oleic acid ester) of isethionates, and the acyl N-methyl taurides (e.g. potassium N-methyl lauroylor oleyl tauride).

The most highly preferred water-soluble anionic detergent compounds are the ammonium and substituted ammonium (such as mono-, diand triethanolamine), alkali metal (such as sodium and potassium) and alkaline earth metal (such as calcium and magnesium) salts or the higher alkyl benzene sulfonates, olefin sulfonates, the higher alkyl sulfates, and the higher fatty acid monoglyceride sulfates. The particular salt will be suitably selected depending upon the particular formulation and the proportions therein. Nonionic surface-active agents include those surface-active or detergent compounds which contain an organic hydrophobic group and a hydrophilic group which is a reaction product of a solubilizing group such as carboxylate, hydroxyl, amide or amino with ethylene oxide or with the polyhydration product thereof, polyethylene glycol.

As examples of nonionic surface-active agents which may be used there may be noted the condensation products of alkyl phenols with ethylene oxide, e.g., the reaction product of isooctyl phenol with about six to 30 ethylene oxide units; condensation products of alkyl thiophenols with [0 to 15 ethylene oxide units; condensation products of higher fatty alcohols such as tridecyl alcohol with ethylene oxide; ethylene oxide addends of monoesters of hexahydric alcohols and inner ethers thereof such as sorbitan monolaurate, sorbitol monooleate and mannital monopalmitate, and the condensation products of polypropylene glycol with ethylene oxide.

Cationic surface-active agents may also be employed. Such agents are those surface-active detergent compounds which contain an organic hydrophobic group and a cationic solubilizing group. Typical cationic solubilizing groups are amine and quaternary groups.

As examples of suitable synthetic cationic detergents there may be noted the diamines such as those of the type RNHQl-LNH wherein R is an alkyl group of about l2 to 22 carbon atoms, such as .N-Z-aminoethyl stearyl amine and N-2- aminoethyl myristyl amine; amide-linked amines such as those of the type RCONHC l-LNH where R is an alkyl group of about nine to 20 carbon atoms, such as N-2-amino ethylstearyl amide and N-amino ethyl myristyl amide; quaternary ammonium compounds wherein typically one of the groups linked to the nitrogen atom is an alkyl group of about 12 to l8 carbon atoms and three of the groups linked to the nitrogen atom are alkyl groups which contain one to three carbon atoms, including such one to three carbon alkyl groups bearing inert substituents, such as phenyl groups, and there is present an anion such as halogen, acetate, methosulfate, etc. Typical quaternary ammonium detergents are ethyl-dimethylstearyl ammonium chloride, benzyl-dimethyl-stearyl ammonium chloride, benzyl-dimethyl-stearyl ammonium chloride, trimethyl stearyl ammonium chloride, trimethyl-cetyl ammonium bromide, dimethyl-ethyl dilauryl ammonium chloride, dimethyl-propylmyristyl ammonium chloride, and the corresponding methosulfates and acetates.

Examples of suitable amphoteric detergents are those containing both an anionic and a cationic group and a hydrophobic organic group, which is advantageously a higher aliphatic radical, e.g. of 1020 carbon atoms. Among these are the N- longchain alkyl aminocarboxylic acids (e.g. of the formula the N-long-chain alkyl iminodicarboxylic acids (e.g. of the forwhere R is a long-chain alkyl group, e.g. of about -20 carbons, R is a divalent radical joining the amino and carboxyl portions of an amino acid (e.g. an alkylene radical of one to four carbon atoms), M is hydrogen or a salt-forming metal, R is a hydrogen or another monovalent substituent (e.g. methyl or other lower alkyl), and R and R are monovalent substituents joined to the nitrogen by carbon-to-nitrogen bonds (e.g. methyl or other lower alkyl substituents). Examples of specific amphoteric detergents are N-alkyl-betaaminopropionic acid; N-alkyl-beta-iminodipropionic acid, and N-alkyl, N,N-dimethyl glycine; the alkyl group may be, for example, that derived from coco fatty alcohol, lauryl alcohol, myristyl alcohol (or a lauryl-myristyl mixture), hydrogenated tallow alcohol, cetyl, stearyl, or blends of such alcohols. The substituted aminopropionic and iminodipropionic acids are often supplied in the sodium or other salt forms, which may likewise be used in the practice of this invention. Examples of other amphoteric detergents are the fatty imidazolines such as those made by reacting a long chain fatty acid (e.g. of 10 to carbon atoms) with diethylene triamine and monohalocarboxylic acids having two to six carbon atoms, e.g. l-coco-S- hydroxethyl-S-carboxymethylimidazoline; betaines containing a sulfonic group instead of the carboxylic group; betaines in which the long-chain substituent is joined to the carboxylic group without an intervening nitrogen atom, e.g. inner salts of Z-trimethylamino fatty acids such as Z-trimethylaminolauric acid, and compounds of any of the previously mentioned types but in which the nitrogen atom is replaced by phosphorus.

Water-soluble builder salts may also be present, in the usual proportions, in the detergent formulations when heavy-duty cleaning is desired. These salts include phosphates and particularly condensed phosphates (e.g. pyrophosphates orv tripolyphosphates), as well as organic builders such as salts of nitrilotriacetic acid or ethylene diamine tetracetic acid. Sodium and potassium salts are preferred. Specific examples are sodium tripolyphosphate, potassium pyrophosphate, sodium hexametaphosphate, sodium tetraborate, sodium silicate, salts (e.g. Na salt) of methylene diphosphonic acid, trisodium nitrilotriacetate, or mixtures of such builders, including mix tures of pentasodium tripolyphosphate and trisodium nitrilotriacetate in a ratio, of these two builders, of 1:10 to 10:1, e.g. 1:1. The proportions of builder salt may be, for example, 50 parts or more (e.g. 50 to 1,000 parts) per 100 parts of detergent.

The detergent formulation may also contain other ingredients. Among these are soil-suspending agents such as sodium carboxymethyl cellulose or polyvinyl alcohol, preferably both, or other soluble polymeric materials, such as methyl cellulose (the amount of suspending agent being, for example, in the range of about 1/20 percent to 2 percent); antioxidants such as 2,6-di-tert-butylphenol, or other phenolic antioxidant materials (e.g. in amounts in the range of about 0.001 to 0.1 percent); coloring agents and optical brightening agents or fluorescent dyes in amounts in the range of, for example, about 1.20 percent to 1/2 percent. Among the optical brightening agents are such compounds as the fluorescent dyes of the stilbene type, e.g. sodium 2-sulfo-4-(2-naphtho-1 ,2 triazole) stilbene; disodium 4,4-bis(4-anilino--morpholine-striazin-2-yl-amino) stilbenedisulfonate; or disodium 4,4- bis(4,6-dianilino-s-triazin-Z-yl-amino)2,2'-stilbenedisulfonate; or of the oxazole type, e.g. having a l-phenyl 2 benzoxazole ethylene structure. In preparing aqueous liquid formulations in particular, hydrotropic materials such as lower alkyl aryl sulfonates, e.g. sodium tolueneor xylene-sulfonate, may be used where desired or necessary; in general, these materials are present in minor amounts, usually in the range of about l/2 to 15 percent (e.g. 10 percent) of the total liquid' composition.

One may also add known germicidal ingredients to the detergent compositions. These include halogenated carbanilides, e.g. trichlorocarbanilide, halogenated salicylanilide, e,g. tribromosalicylanilide, bisphenols. e.g. hexachlorophene, halogenated trifluoromethyldiphenyl urea, zinc salt of lhydroxy-Z-pyridinethione and the like (e.g. in amounts in the range of about l/50 percent to 2 percent).

Opacifiers, perfumes, and antitarnishing agents may also be included in the detergent compositions containing the novel products of this invention, as may oxygenand chlorinereleasing bleaches, such as sodium perborate or sodium or potassium dichloroisocyanurate. Heavy-duty detergent compositions containing the new products may also contain sodium bromide (e.g. in amount of 0.1 to 1 percent) to improve the bleaching effect of sodium hypochlorite present in the wash water.

The detergent compositions containing the novel products of this invention may also contain enzymes to assist in the removal of stains. Particularly important among these are the proteolytic enzymes which such materials as pepsin, trypsin, chymotrypsin, papain, bromelin, colleginase, keratinase, carboxylase, amino peptidase, elastase, substilisia and aspergillopepidase A and B. Among commercially available enzymes are Alcalcase and Maxatase. The enzyme is preferably present in powered form and is admixed into the detergent formulation, typically in amount of about 0.001 percent to 4 percent of the total formulation, preferably about 0.05-1 percent. The combination of the novel products of this invention with enzymes yields particularly efficacious results. The enzyme-containing product can be used in cool or tepid water or in hot water.

The manufacture of detergent products in bar form, e.g. toilet bars and laundry bars, from olefin sulfonate detergents is described in Belgian Pat. No. 698,280. The novel hydroxy ether sulfonate compounds of this invention may each be substituted for the olefin sulfonates in the same proportions in each of the general and specific formulations set forth in that patent. The same or similar processing techniques may be used for blending the ingredients and for making the bars.

ln the manufacture of oral preparations, the novel materials of this invention may be incorporated in toothpastes, dental creams, tooth powders, liquid dentifrices, mouth washes or rinses, dental chewing gums, lozenges or troches. Thus, in a tooth paste the composition may comprise some 20-75 percent of dental polishing agent, together with water. a humectant such as glycerol, and a gelling agent such as sodium carboxymethyl cellulose. Fluorides such as stannous fluoride may be present. In general, the novel hydroxy ether sulfonate compounds of this invention may each be substituted for the olefin sulfonates in each of the general and specific formulations set forth in the applications of Bouchal and Salzmann, Ser. No. 579,497 and of Rubinfeld and Levinsky, Ser. No. 579,524 now abandoned, each filed Sept. 15, 1966.

Shampoo formulations may comprise simple dispersions of the new detergent materials of this invention in water, e.g. in the form of alkanolammonium salts thereof, or combinations containing minor proportions of foam-boosting agents such as fatty acid (e.g. lauric/myristic) monoor di-ethanolamides or the corresponding isopropanolamides, or amine oxides such as lauryl dimethylamine oxide. Other surface active detergents such as soaps and sodium lauryl sulfate may also be present.

EXAMPLE 1 Preparation of:

0.3 grams of sodium is dissolved in ml. of allyl alcohol and 48 grams (0.2 moles) of 1,2-hexadecane epoxide is added and the mixture refluxed for 4.5 hours. When the reaction begins, the temperature of the refluxing system is 966 C., the temperature rising slowly during the course of the reaction. After the reaction mixture has refluxed for 2.5 hours the temperature has risen to l00.6 C.; no further rise in temperature is observed. The course of the reaction is followed by means of gas phase chromatography. The column used is a 2-foot Silicon-rubber" column (2 percent SE-30 on Chromosorb W). THe temperature is 100 C. when the sample is injected, followed by a programmed temperature rise of 15 C. per minutes. The original epoxide appears as a peak after 6.6 minutes in the column. After 3.5 hours of reflux the epoxide peak has almost disappeared, while the formation of the product can be seen as a strong peak that appears after 9 minutes in the column. After 4.5 hours of reflux the epoxide peak has disappeared completely.

After neutralization with concentrated hydrochloric acid the excess alcohol is evaporated and the residue is distilled under vacuum. This yields 43.5 g. (73 percent yield) of a colorless liquid, boiling range l55l56 C./O.8 mm. Hg, freezing point 32.5 C.

Elemental analysis of the compound corresponds to the formula: c,,1-i,,,.0

The infrared spectrum has the following characteristic absorptions:

Strong band due to -H of an alcohol Weak hand due to a carbon-carbon double bond.

2.9 microns 6.04 microns 10.05 microns Two strung hands due to a terminal vinyl group. 10.75 microns 8.9-9.2 microns Strong. broad band due to secondary hydroxyl and ether groups.

Sulfonation of C I-I29 CH-CHr O CHz- CH=CH2 The unsaturated hydroxyether produced above is sul-- fonated by dissolving 15 grams of the unsaturated intermediate compound (0.05 moles) in 25 milliliters of methanol, adding 5.2 grams of sodium bisulfite dissolved in milliliters water, and adding 0.5 milliliters of tertiary butyl perbenzoate as a catalyst. This mixture is stirred at 75 C., and the reaction is followed by gas phase chromatography as above, this time by watching the disappearance of the peak at 9 minutes which is due to the unsaturated hydroxyether. After 3 hours at 75 C., most of the unsaturated hydroxyether has reacted. After 5 hours of reaction, the mixture is cooled to room temperature and then stirred into 300 milliliters of acetone. The white solid which precipitates is filtered off and recrystallized from a water/methanol mixture. After drying, 16.0 g. of a white solid is obtained (80 percent yield). A melting point could not be obtained since decomposition occurs around 175 C.

The infrared spectrum and elemental analysis correspond to the following structure:

(])H CuHznCH-CHz-O-CHzCHzCHzS OaNa EXAMPLE ll Sulfonation and isolation is carried out as in example 1 using 1 1.5 g. of sodium bisulfite dissolved in 22 ml. of water and adding the solution to a solution of 30 g. of the above unsaturated hydroxyether in 50 ml. of methanol. One ml. of tertiary butyl perbenzoate is added as a catalyst. The isolated prod uct, by infrared spectrum and elemental analysis, has the structure:

This product decomposes at about 1 75 C.

EXAMPLE lll Example I is again repeated using an equivalent amount of 1,2-dodecane epoxide. The resultant unsaturated ether product has a boiling point of 1 17 C./O.5 mm. Hg and has the formula:

Sulfonation as in example I yields a product of the formula:

EXAMPLE-1V The reaction of hexadecanel ,2-epoxide with allyl alcohol,

using boron trifluoride etherate as catalyst To 1 16 grams allyl alcohol containing 0.5 milliliters boron trifluoride diethyl etherate is added 240 grams 1 mole) of the epoxide dropwise from an addition funnel while stirring rapidly. The addition of the epoxide is complete in 20 minutes; during the reaction the temperature rises from 25 to C. As gas chromatogram performed as described under example I shows that all the epoxide has reacted. After the excess allyl alcohol has been removed by distilling at reduced pressure, a sample of the reaction product is chromatographed on a 6 feet DEGS column (20 percent Diethylene Glycol Succinate on Chromosorb W); temperature 220 C., isothermal.

Two peaks are observed, at 10.6 minutes and at 12.5 minutes. This shows that the reaction had yielded two products, via the reaction:

CHzOH CHzOH EXAMPLE V Example 1V is repeated except that the two isomeric alcohols are separated by the chromatographic procedure described in example 1V and the pure primary unsaturated alcohol product is sulfonated as in example 1V.

EXAMPLE VI The general procedure of example 1V is followed using 8.6 g. (0.1 mole) of l-pentene-S-ol containing 2 drops of boron trifluoride etherate (diethyl), and adding dropwise while stirring, 18.4 g. (0.1 mole) of dodecane-1,2-epoxide. Two main products are formed (Le. a primary and a secondary alcohol) as shown by the gas chromatogram. The products are isomeric and have the structures:

11 CH;(CH2)nCH-O(CH2)3CH=CH2 (30%) GHiOH The relative amounts are determined by calculations based upon the areas under the peaks obtained in the chromatogram. The mixture has a boiling point range of l40146 C. at 0.4 mm. Hg. The infrared spectrum is shown in FIG. 1.

The mixture produced above is sulfonated using g. of

said mixture and a solution of 4.55 g. Nal-lSQ and 0.25 ml. of

tertiary butyl perbenzoate in 10 ml. of methanol and 7.5 ml. of.

water. Stirring is carried out for 1% hours at 135 C. After cooling. 200 ml. of acetone are stirred into the mixture. A white precipitate forms which is filtered and dried. The yield is 12 g. (85 percent).

The sulfonated mixture contains:

OH and 30% CH3(CH2)9CH- 0(CH2) SOJNa CH2 OH EXAMPLE V" 16.3 g. (0.05 moles) of the above mixture of unsaturated a1- cohols, 16 ml. methanol, 0.3 ml. t-butyl perbenzoate, 5.7 g. (0.055 moles) of sodium bisulfite dissolved in 11.5 ml. of water are stirred for 1 hour at 135 C. Then the mixture is poured into acetone and the resultant precipitate is filtered off and dried. Yield is 16.59 g. (77 percent). The product is a mixture of:

70% onnoHzmt ln-cm-ocnms 01m 0H- and 30% CHa(CH2)ta H 0(CH2)s S OsN CH2 OH EXAMPLE V1" The procedures of examples V1 and V11 are repeated insofar as the production of the unsaturated alcohols is concerned. In each case, the mixture is separated into the individual component isomers by a gas phase chromatographic column separation technique. The resultant four products (two isomers of example V1 and two isomers of example V11) are sulfonated in examples V1 and Vll respectively using equivalent amounts of reactants.

EXAMPLE [X The hydroxy ether sulfonates prepared in examples 1 to 111 are tested for their detergency relative to linear tridecyl benzene sulfonate, a commercially available detergent. The detergency of the materials produced in examples 1 to 111 relative to the control is investigated in both soft and hard water and both hot and cold water.

The results of the Spangler soil detergency tests are shown in table 1 below:

TABLE 1 Spangler Soil* Detergency Test Results ARd" (Soil Removal) Temperature and Control Water Hardness Ex. 1 Ex. 2 Ex. 3 LTBS) (linear tridecyl sulfonate) 70 F.,N.B.'"Tap +193 +l9.6 +l7.6 +181 (90 p.p.m.) 70 F.. +160 +l4.9 +1l.2 +9.3 (:00 p.p.m.) 120 F., N.B. Tap +19.7 +201] +174 +193 120 F., +l6.$ +153 +118 +ll.6 (300 p.p.m.)

The Spangler Soil test is carried out using cotton percale swatches (3 inches by 6 inches) soiled with synthetically prepared sebum soil employing 1.5 g. of test detergent and 1 liter of water; the wash cycle is 10 minutes at 100 c.p.m. agitation followed by 5 minutes rinse in same water used in wash. The test detergent is comprised of:

15 percent active sulfonate 35 percent sodium tripolyphosphate The previous example IS repeated using 0.15 moles of the alcohol and 0.1 mole of hexadecane-l,2-epoxide. The isolated unsaturated alcohol mixture has a boiling point range of 178184 C. at 0.6 mm. Hg. The molecular weight is 326. The product is a liquid at room temperature and contains:

50 percent sodium sulfate a value indicates soil removal.

'New Brunswick, New Jersey.

The results shown above indicate an unexpectedly excellent detergency in hard water and soft water, both cold and hot, as compared to the commercial detergent linear tridecyl benzene sulfonate. Accordingly, this exemplifies the unusually good detergency properties of the novel hydroxy ether sulfonates of the present invention.

EXAMPLE X The hydroxy ether sulfonate produced in example 1 is tested for fabric-softening ability in a towel tests. The water employed in the foregoing softening test is l20 F., New Brunswick, N..l., tap water. A controlled detergent composition is prepared by combining 40 grams of sodium tripolyphosphate and I grams of active ingredient of linear dodecyl benzene sulfonate. Ten grams of the hydroxy ether sulfonate produced in example I is also added to 40 grams of the detergent builder sodium tripolyphosphate.

On a scale rating softness from 1 to l0, being maximum softening of the fabric, the control containing the detergent builder and commercial detergent produces a result of 1, while the composition containing the hydroxy ether sulfonate in accordance with the present invention produces a result of 8.

This test, therefore indicates that the hydroxy ether sul-' fonates of the present invention, in addition to possessing excellent detergency, also possess excellent fabric-softening characteristics.

EXAMPLE XI In accordance with the procedure of example "I, the following hydroxy ether sulfonates are prepared:

In all cases. the hydroxy ether sulfonate is prepared by reacting the corresponding long-chain epoxide with allyl alcohol to form the unsaturated hydroxy ether intermediate with sulfonation of the unsaturated intermediate with sodium, potassium, or ammonium bisulfite to produce the desired hydroxy ether sulfonate.

EXAMPLE XII The hydroyether sulfonate products of examples lV, VI and VII are tested as in example lX 'with the following results:

TABLE [I Spangler Soil Detergency Test Results Temperature and ANd (Soil Removal) Control water hardness Ex. VI Ex. Vll (LTBS) Ex. lV

70 F. ma. Tap) 10 F. 300 (p.p.m.) 120 F. (N.B. Tap) 120 F. (300 p.p m.)

Again the outstanding overall performances in both hot and cold water at both hardnesses of these products is demonstrated.


EXAMPLE XlV Example is repeated except that in the sulfonation ammonium bisulfite is used in place of the sodium salt. The corresponding ammonium compound is produced.

EXAMPLE XV Example I is repeated except that the final product is acidified in water, the aqueous solution extracted with alcohol and the acid form neutralized with triethanolamine. Isolation is done similarly as in example I by precipitation with acetone.

While various embodiments of the present invention have been described by reference to the foregoing examples it is to be understood that the present invention is in no way to be deemed as limited thereto but should be construed so as broadly as all or any equivalents thereof.

What is claimed is:

1. Novel compounds which in the free acid form have the formula:



l. R, is a straight or branched higher alkyl group of C to C 2. Rz is a straight or branched alkylene of C,, to C 3. R to R, are, independently, hydrogen, straight or branched alkyl of C, to C,,,;

4. Z is oxygen or sulfur;

5. x and y have the values 0 or 1 and .r-l-y=l; and

6. when x equals 0 the depicted OH group is attached directly to C.

. Compounds of claim 1 wherein Z is oxygen.

. Compounds of claim 1 wherein Z is sulfur.

. Compounds of claim 2 wherein R, is C alkyl.

. Compounds of claim 2 wherein R, is C alkyl.

. Compounds of claim 2 wherein R, is C, alkyl.

. Compound of claim 4 wherein R R and R are hydrogen, and

. R is C, alkylene.

. Compound of claim 5 wherein R,,, R and R, are hydrogen, and

. R is C, alkylene.

. Compound of claim 5 wherein 1. R R, and R are hydrogen, and

2. R is C, alkylene.

10. Compound of claim 9 wherein 1. R R and R are hydrogen, and

2. R is C,, alkylene.

11. A process for producing the compounds of claim 1 which comprises reacting a 1,2-epoxy C to C alkane with a C to C, olefinically unsaturated alcohol or thiol and thereafter sulfonating the resultant product with sodium bisulfite in the presence of a peroxide initiator.

12. A process as defined in claim 11 wherein from 0.00l percent to about 10 percent of a catalyst is employed in the epoxy-alcohol reaction step.

13. A process as defined in claim 12 wherein the said catalyst is sodium.

14. Compounds of claim 1 wherein .-r equals 1.

15. Compounds of claim 1 wherein y equals 1.

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Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4166186 *Mar 4, 1975Aug 28, 1979Bayer AktiengesellschaftDihydroxy carbamates containing sulphonic acid groups
US4245110 *Mar 10, 1975Jan 13, 1981Bayer AktiengesellschaftPolyalkylene oxide-containing urethane polyols with sulphonic acid groups
US4680358 *Nov 8, 1985Jul 14, 1987The B F Goodrich CompanyStyryl terminated macromolecular monomers of polyethers
US5259964 *Feb 19, 1992Nov 9, 1993Colgate-Palmolive Co.Free-flowing powder fabric softening composition and process for its manufacture
US5368755 *Feb 19, 1992Nov 29, 1994Colgate-Palmolive Co.Free-flowing powder fabric softening composition and process for the manufacture of a free-flowing fabric softening composition
US5529710 *Jun 18, 1993Jun 25, 1996The Procter & Gamble CompanyProduction of detergent granules with excellent white appearance
US7153493Jul 30, 2003Dec 26, 2006Warner-Lambert Company LlcClear oral compositions containing potassium salt
US7435409Mar 17, 2006Oct 14, 2008Mcneil-Ppc, Inc.Soluble potassium salt, a sodium (C8-C24) alkylsulfate, polar surfactant, water; free of visible potassium alkyl sulfate precipitates
U.S. Classification562/110, 424/56, 510/495, 568/675, 424/70.24, 568/62
International ClassificationC11D3/00, C11D1/12, C07C33/025, C07C309/08, C11D1/00, B01J8/00
Cooperative ClassificationC07C323/66, C11D1/002, C11D3/001, C07C309/10, B01J8/003, C11D1/12
European ClassificationC07C309/10, C07C323/66, C11D1/00B, C11D3/00B3, C11D1/12, B01J8/00F6