US3382180A

US3382180A - Detergent compositions containing sulfoxide as a suds-stabilizing agent

Info

Publication number: US3382180A
Application number: US634897A
Authority: US
Inventors: Hill M Priestley; James H Wilson
Original assignee: Lever Brothers Co
Current assignee: Lever Brothers Co
Priority date: 1958-04-01
Filing date: 1967-05-01
Publication date: 1968-05-07
Anticipated expiration: 1985-05-07

Description

United States Patent Office 3,382,180 DETERGENT COMPOSITIONS CONTAIN- ING SULFOXIDE AS A SUBS-STABILIZ- ING AGENT Hill M. Priestley, North Bergen, and James H. Wilson, Demarest, N.J., assignors to Lever Brothers Company, New York, N.Y., a corporation of Maine No Drawing. Continuation-in-part of application Ser. No. 725,505, Apr. 1, 1958. This application May 1, 1967, Ser. No. 634,897

41 Claims. (Cl. 252-152) ABSTRACT OF THE DISCLOSURE Detergent compositions comprising suds-producing organic non-soap detergent compounds of the anionic, ampholytic and nonionic type and, as suds-stabilizing materials, at least 0.1% of an alkyl monosulfoxide of the class described. The sulfoxide is present in minor amounts, and within the certain critical ranges of proportions set forth. A method of stabilizing foam is also described.

This invention relates to detergent compositions having improved foam stability in the presence of greasy soil. More particularly, the invention relates to the use of certain sulfoxides as foam stabilizing additives in detergent compositions, containing, as the major active ingredient thereof, a suds-producing organic synthetic detergent.

This application is a continuation-in-part of United States applications Ser. Nos. 725,505, filed Apr. 1, 1958, and 60,546, filed Oct. 5, 1960, both now abandoned. This application is also a continuation-in-part of United States application Ser. No. 365,487, filed May 6, 1964.

It is common practice in the industry to include foam stabilizers in detergent compositions to improve the persistence and stability of the foam produced by agitation of the washing solution containing the detergent composition. These foam stabilizers are particularly useful in detergent compositions based upon organic non-soap synthetic detergent compounds.

The present invention is concerned with the problem of stabilizing the foam produced on agitation of an aqueous washing solution containing a suds-producing organic synthetic detergent. Foam persistence is generally used by the housewife as an index of the cleansing abilityof the solution. Once the foam has collapsed and disappeared, the housewife believes that the fat emulsifying and other cleansing abilities of the solution have been used up. This is not necessarily true, however, as the foam may collapse before the cleansing ability of the solution has been consumed. The problem of stabilizing the foam of aqueous solutions of detergent compositions is thus an important one and is one which has received considera-ble attention by workers in the field.

In addition to stability, several other characteristics of the foam are involved. The original amount of foam produced on agitation of the aqueous solution is an important consideration. Furthermore, the texture of the foam, i.e., whether it is open and coarse, or of a very fine, dense character, and the ability of the foam to rinse cleanly and quickly from the articles being washed are factors which must be taken into consideration.

The prior art compounds which function as foam stabilizers in detergent systems depend upon Well known foam stabilizing functional linkages, such as amide, and alcoholic and phenolic hydroxy groups. Examples of these materials include fatty alcohols such as lauric alcohol and fatty acid substituted amides such as lauric diethanol amide and lauric isopropanol amide. Parahydroxy laurophenone is an example of a foam stabilizing compound containing a phenolic hydroxyl group.

, 3,382,180 Patented May 7, 1868 These prior art foam stabilizers have some degree of specificity, i.e., they are suitable for use in stabilizing the foams produced in aqueous solutions of certain suds-producing organic detergent compounds. For example, parahydroxy laurophenone is effective only with sodium lauryl sulfate or mixtures of this with other compatible active detergents. Also, the above-mentioned amides are generally suitable for use with alkyl aryl sulfonates, and lauryl alcohol is generally limited to use with alkyl sulfates.

Another deficiency of some of the foam stabilizers known in the prior art is their instability and ineffectiveness in the presence of household bleaching agents. In heavy duty laundry detergents where bleach is often added to the washing solution during the first stages of the washing operation, stability of the additives to bleach is an important characteristic.

Still another deficiency of prior art foam stabilizers is that while they are effective in experimentalsystems based on pure water, their effectiveness is considerably diminished or non-existent in the presence of soil or fatty materials.

Alkyl sulfoxides having a long chain fatty acid residue are known to have surface active properties. US. Patent No. 2,787,595 to Webb discloses the use of alkyl sulfoxides as the essential active ingredient in detergent compositions. Compounds including methyl heXyl sulfoxide, methyl dodecyl sulfoxide, and ethyl decyl sulfoxide, are among those disclosed. According to Webb, the sulfoxides may be employed per se as the essential active ingredient in detergent compositions, but preferably are employed in combination with inorganic builder salts. It is also stated in the patent that other synthetic detergents may be employed as detergency supplements in combination with the sulfoxides and that foam stabilizers may be added. According to the patent, the sulfoxides are employed at a level of above about 5% in the detergent composition.

Quite surprisingly, it has now been found that the presence of small amounts of certain sulfoxides improves the stability of the foam produced by agitating aqueous solutions of suds-producing materials selected from the group consisting of anionic, ampholytic and nonionic organic synthetic detergents. The sulfoxides found useful according to this invention are those having the formula wherein R is an alkyl or hydroxyalkyl radical having from 8 to 18 carbon atoms; X is a divalent radical selected from the class consisting of benzyl, phenyl, (lower) oxyalkylene, and a lower) polyoxyalkylene from the group consisting of polyethylene and polypropylene wherein the total number of carbon atoms is 4-6; a is 0 or 1; R' is a radical selected from the class consisting of mononuclear aryl, 2-dimethylamino(lower)alkyl, 2 diethanolarnino(lower) alkyl, 2-morpholino(lower)alkyl, 2-piperidino(lower)alkyl, lower alkyl, hydroxy(lower)alkyl of 2 to 5 carbon atoms, acetonyl, and ethers and thio ethers of the formula AY-B, wherein Y is S or O, A is a saturated alkylene group having from 2 to 5 carbon atoms, B is selected from the group consisting of alkyl groups having 1-5 carbon atoms, alkene groups having 2-5 carbon atoms and hydroxy alkyl groups having from 2-5 carbon atoms, and wherein A and B taken together have from 3 to 7 carbon atoms.

R in the above formula may be a straight chain radical having from 8 to 18 carbon atoms. Examples include octyl, C H1r; octadecyl, C f-I dodecyl, C H and hexadecyl, C H groups. R may also be a hydroxy alkyl group, as in the compound C H CHOHCH SOCH a hydroxylated C methyl sulfoxide. Some of these radi- C H OCH CH CH CH SOCH As indicated above, X can also be a (lower)polyoxyalkylene selected from the group consisting of polyethylene and polypropylene wherein the total number of carbon atoms in the radical is from 4 to 6. The compound dodecyloxyethoxyethyl methyl sulfoxide,

is one compound of this type. Others which are suitable include dodecyloxypropoxypropyl methyl sulfoxide,

C H OCH CI-I CH OCH CH CH SOCH and dodecyloxyethoxyethoxyethyl methyl sulfoxide, C H OCH CH OCH CH OCH CH SOCH Dodecylbenzyl methyl sulfoxide, C H C H CH SOCH is an example of a compound where X is an arylene radical. Each of these compounds is useful according to this invention.

R in the above formula, when a (lower)alkyl group, may be either straight or branched, saturated or unsaturated. Thus, R may be a pentyl, heptyl, octyl, methyl, ethyl or butyl group. Dodecyl isopropyl sulfoxide,

is an example of a suitable sulfoxide having a branched chain (lower)alkyl radical. R may also be a hydroxy (lower)alkyl group, dodecyl glyceryl sulfoxide,

dodecyl Z-hydroxyethyl sulfoxide, n-C H SOCH CH OH and dodecyl-3-hydroxypropyl sulfoxide,

C H SOCH CH CH OH being suitable examples. Dodecyl vinyl sulfoxide,

CHHZSSOCHZCHZ is an example of an unsaturated compound useful according to this invention.

R may contain other functional groups which do not interfere with the suds stabilizing characteristics of the compound. For example, R may be a Z-dimethylamino (lower)alkyl group, as in dodecyl Z-dimethylaminoethyl sulfoxide, C H SOCH CH N(CH dodecyl Z-dimethylaminoisopropyl sulfoxide,

C H SOCHCH CH N (CH 2 dodecyl Z-dimethylaminopropyl sulfoxide,

C H SOCH CH CH N CH 2 and dodecyl Z-dimethylaminobutyl sulfoxide,

C H SOCH CH CH CH N (CH 2 R' may also be 2-diethanolamino(lower)alkyl, as in dodecyl Z-diethanolaminoethyl sulfoxide,

C H SOCH CH N(CH CH OH) dodecyl Z-diethanolaminoisopropyl sulfoxide,

C H SOCHCH CH N (CH OH OH 2 dodecyl Z-diethanolaminopropyl sulfoxide,

C H SOCH CH CH N (CH CH OH) 2 and dodecyl Z-diethanolaminobutyl sulfoxide,

C H SOCH CH CH CH N (CH CH OH 2 4 R may also be a 2-morpholino(lower)alkyl, as in dodecyl 2-morpholinoethyl sulfoxide,

CHz-CH: CnHzrSOOHzCHzN CHz-Cfir Other suitable compounds of this type include dodecyl Z-morpholinoisopropyl sulfoxide,

CHz-CII2 C rzHuS 0 CII CIIzN on; CHr-cfiz dodecyl 2-morpholinopropyl sulfoxide,

CHr-CH:

CuHz SO CHzCHzCHzN CHr-C: and dodecyl 2-morpholinobutyl sulfoxide,

CHz-CH: OuHuSOCHaCHzCHzCHzN OHr-CI B R may also be a Z-piperidino (lower)alky1 group, as in dodecyl Z-piperidinoethyl sulfoxide,

CHr-CH:

CH2 0111-0142 Other suitable compounds of this type include dodecyl Z-piperidinoisopropyl sulfoxide,

CH2-OH2 CnHuSOC-OHzN CH2 CH3 \CH2C I: dodecyl 2-piperidinopropyl sulfoxide,

CHz-CH:

CH: (ma-C6: and dodecyl 2-piperidinobutyl sulfoxide,

GHQ-C112 CH1 CH2Cfiz Furthermore, R may be an ether or thioether of the formula AYB, where Y is sulfur or oxygen, and A and B are as defined above.

Suitable compounds with ethers of the type described above include dodecyl Z-methoxyethyl sulfoxide,

C H SOCH CH OCH dodecyl 2-ethoxyethyl sulfoxide,

C H SOCH CH OCH CH dodecyl 2-allyloxyethyl sulfoxide,

C H SOCH CH OCH CH CH dodecyl 2-allyloxybutyl sulfoxide,

C12H25SOCH2CH2CH2CH2OCH2CH 1 CH2 dodecyl(Z-hydroxybutoxy-n-propyl)sulfoxide,

C H SOCH CH CH OCH CH CHOHCH and dodecyl 2- 2-hydroxy ethoxyethyl] sulfoxide,

C H SOCH CH OCH CH OH Suitable compounds with thioethers of the type described include dodecyl 2-thiomethylethyl sulfoxide,

C H SOCH CH SCH dodecyl 2-thioethylpentyl sulfoxide,

C H SOCH CH CH CH CH SCH CH dodecyl 2-thioallylbutyl sulfoxide,

C12H25SOCH2CH2CH2CH2SCH2CH 1 CH2 and dodecyl 2-thiohydroxybutylpropyl sulfoxide,

12 2580 CHzCHzCHzN CrzHnaSO CHzCHzCHzCIIzN In addition, R may contain a keto group, as in dodecyl acetonyl sulfoxide, C H SOCH COCH Where R is a mononuclear aryl group, the phenyl, benzyl and tolyl radicals may be employed. The suitable alkyl heterocyclic groups include morpholinoethyl and piperidinoethyl groups.

Further examples of specific compounds which may be used according to this invention include octyl heptyl sulfoxide,

dodecyl pentyl sulfoxide,

12 25 5 11 dodecyl phenyl sulfoxide,

C12H25S0C6H5 dodecyl benzyl sulfoxide,

C H SOCH C H dodecyl octyl sulfoxide,

C12H25SOC8H17 hexadecyl methyl sulfoxide,

C H SOCH octadecyl methyl sulfoxide,

- C H SOCH octyl methyl sulfoxide,

C H SOCH dodecyl ethyl sulfoxide,

C H SOCH CH dodecyl n-propyl sulfoxide,

C H SOCH CH CH dodecyl-n-butyl sulfoxide,

C H S0CH CH CH CH and dodecyl isobutyl sulfoxide,

C H SOCH CH(CH The preferred compounds for use according to this invention are those where R contains from to 14 carbon atoms and R is a methyl, ethyl, propyl, isopropyl or vinyl group.

A preferred compound of the above-described sulfoxides is dodecyl methyl sulfoxide. This compound is odorless and is effective as a foam stabilizing additive in a wide range of detergent compositions. It can replace lauric diethanolamide in liquid detergents based on ammonium dodecyl benzene sulfonate and lauryl alcohol in formulations containing sodium lauryl sulfate. In both instances, the foam stabilizing effect of the sulfoxide is greatly improved over that obtained with the prior art stabilizer.

A further preferred class within the above-described sulfoxides includes dodecyl glyceryl sulfoxide,

C H SOCH CHOHCH OH dodecyloxyethyl methyl sulfoxide,

C H OCH CH SOCH 2-hydroxy-n-dodecyl methyl sulfoxide,

C H CHOHCH SOCH and dodecyloxyethoxyethyl methyl sulfoxide,

C H OCH CH OCH CH SOCH These materials are exceptionally stable in the presence of household bleach.

The term suds-producing materials selected from the group consisting of anionic, ampholytic and nonionic organic synthetic detergents, as employed herein and in the claims, is intended to include those anionic, ampholytic and nonionic compounds which are commonly employed as the essential active ingredient of suds-producing detergent compositions.

Suitable anionic suds-producing organic synthetic detergents include the alkyl aryl sulfonates, such as sodium dodecyl benzene sulfonatc or ammonium pentadecyl benzene sulfonate, and the methyl taurates, such as Igepon TK-32, a sodium N-methyl-N-tall oil acid taurate, and Igepon TE-42, an N-methyl acyl taurate derived from tallow. Also included are the sulfated fatty alcohols, such as sodium lauryl sulfate and ammonium lauryl alcohol sulfate; the sulfated polyethylene oxide esters of resins or fatty acids, such as the ammonium salt of sulfated nonyl phenol condensed with four moles of ethylene oxide; and Sipon LT-6, a triethanolamine lauryl alcohol sulfate.

Suitable nonionic suds-producing organic synthetic detergents which may be employed according to this invention include Oronite NI8589, a dodecyl phenol con densed with more than 10, Le, 20 to 30 moles of ethylene oxide; Triton X100, an alkyl aryl polyether alcohol, i.e., octylphenol condensed with 10 moles of ethylene oxide; and Tergitol NP14, an alkyl phenol polyethylene glycol ether; Neutronyx 600, an aromatic polyglycol ether condensate; and Sterox A], a tridecyl alcohol condensed with 10 moles of ethylene oxide, and Sterox CD, a tall oil condensed with 10 moles of ethylene oxide.

Also suitable are Deriphat No. 154, a tallow disodium betaimino dipropionate, and sodium cocoglycinate. These are ampholytic substances.

Conventional soaps and inorganic builder salts, such as the phosphates, silicates, sulfates and the like, are not included within the term suds-producing materials selected from the group consisting of anionic, ampholytic and nonionic organic synthetic detergents used herein, although these materials can be used as auxiliary agents in the compositions of this invention. Also excluded from this class are the sulfoxides described in the aforementioned Webb patent as an essential active ingredient in detergent compositions. The benefits of this invention are not obtained by merely increasing the concentration of dialkyl sulfoxide in the detergent composition.

In the detergent compositions of this invention, the level of sulfoxide required .to provide optimum foam stability depends upon the particular organic synthetic detergent employed and upon the nature of the sulfoxide. Generally speaking, the sulfoxides are effective at levels above about 0.1% in detergent compositions containing operable levels of suds-producing organic synthetic detergents. At levels below this range, little if any benefit is obtained. This is shown clearly in Table I, below, which gives data obtained by evaluating light duty liquid detergents in terms of their suds stability in the presence of foam destroying agents.

TABLE I.-DISHPAN SUDS STABILITY TEST Detergent Compositions, Time for Suds to Break (Seconds) Percent 17.14% 29.01% 29.01% Ammonium Dodecyl Ethyl Water Ammonium Sodium Dodecyl Methyl Alcohol and Dodoeyl Lauryl Benzene Sull'oxide Misc. Benzene Sulfate Sult'onate Sulfouate plus 11.87%

Alipal* None 14. 8 56. 19 100 5 50 125 14. 8 56. 065 125 5 50 25 14. 8 55. 94 180 10 50 5O 14. 8 55. 69 250 25 110 1. 00 14. 8 55. 19 360 255 290 2. 00 14. 8 54. 19 610 600 3. 00 14. 8 53. 19 640 70 680 4. 00 14. 8 52. 19 660 65 (180 5. 00 14. 8 51. 19 660 65 660 5. 00 None 65. 99 680 70 6. 00 14. 8 50. 19 680 (i5 080 Laurie Diethanolamide Ammonium salt of sulfated nonyl phenol condensed with 4 moles of ethylene oxide.

The Dishpan Suds Stability Test is a standard test for determining the stability of suds in the presence of sudsdestroying agents. In conducting the test, 10 grams of the detergent sample are dissolved in six quarts of tap water at 120 F. in a dishpan of standard size. 20 grams of tallow containing of free fatty acids are added and the solution is agitated for 30 seconds. The time for the suds to completely disappear is then determined in secends, and these are the values given above. It is noted that fatty acids are particularly effective in destroying foam and that for this reason, the test employs a tallow having a high free fatty acid content.

From the above table it can be seen that when dodecyl methyl sulfoxide is employed with ammonium dodecyl benzene sulfonate, the stability of the suds reaches a peak at a concentration of about 4% and that the use of additional amounts of stabilizer does not provide a large In conducting the test set forth in Table H above, 11 grams of the detergent sample were dissolved in six quarts of tap water at 116 F. in a dishpan of standard size. grams of tallow containing 15% of free fatty acids are added and the solution is agitated for seconds. The time for the suds to completely disappear is determined in seconds.

It will be noted from Table II that sulfoxide to detergent ratios of more than about 1:3.5 do not improve foam stability, and at the higher ratios, actually destroy the foam.

The following table illustrates the improved foam stability obtained in the presence of lime soaps through the use of the foam stabilizing agents of this invention.

TABLE IIL-FOAM STABILITY OF AQUEOUS DETERGENT SOLUTIONS IN THE PRESENCE OF LIME SOAPS measure of improvement. On the other hand, where the sulfoxide is employed with sodium lauryl sulfate, the optimum improvement in suds stability is obtained at about 1% concentration.

Furthermore, an important and critical factor of this invention is the ratio of sulfoxide to organic synthetic detergent. In the ease of the anionic and nonionic sudsproducing organic synthetic detergents, the proportions of these two ingredients should be adjusted so that the sulfoxide is present in a minor amount, and the sulfoxide to detergent ratio should be no higher than about 1:35. A range of ratios of sulfoxide to detergent of from about 1:14 to about 123.5 is preferred in some instances, as illustrated in the following Table H. In some instances, even lesser amounts of sulfoxides, relative to the detergent level, may be used to advantage. In Table I above, ratios of 1:300 are shown to be useful, and a ratio of 1:30 is preferred in one instance. Ampholytic detergents are useful at sulfoxide to detergent ratios of from about 1:1 to above 1:50.

TABLE II.DISHPAN SUDS STABILITY TEST Detergent Compositions, Percent Time for Ratio Suds to Sodium Hexadeeyl Sulfoxide Break Dodeeyl Methyl Sodium Water, to (Seconds) Benzene Sulfoxide Sulfate etc. Detergent (Dupli- Sulionate cate Runs) The data of Table III shows that the addition of a very small amount of dodecyl methyl sulfoxide to a 0.1% solution of sodium dodecyl sulfate more than doubles the initial foam volume and that the foam thus produced remains completely stable for 30"minutes. It is also noted that the results are more than additive, as evidenced by a comparison of the results obtained by each compound separately. The prior art amide foam stabilizer in combination with the sodium dodecyl sulfate is included for the purposes of comparison. The amide actually depresses the initial volume of foam, but retards somewhat the subsequent collapse of the foam.

Another important factor to consider in preparing the compositions of this invention is that the sulfoxides themselves are not easily dispersible in water at temperatures below F. It is necessary, therefore, that the sulfoxidc be made dispersible in aqueous solutions at room temperature by providing for the presence of a dispersant. Many suds-producing organic synthetic detergents satisfactorily perform this function. Thus, for example, a composition containing 29% ammonium dodecyl benzene sulfonate and 4% dodecyl methyl sulfoxide disperses in water at room temperature without having the sulfoxide precipitate. This is a definite advantage in washing solutions. Where the sulfoxide is not accompanied by a dispersant such as an organic detergent, the sulfoxide precipitates below 120 F., thus allowing objectionable deposition of the sulfoxides on fabrics, dishes, etc.

The sulfoxide of the present invention must be as pure as possible. Sulfoxides prepared according to certain processes must be employed at levels substantially higher than those set forth herein. It has been found that dodecyl methyl sulfoxide may be prepared in a particularly pure state by reacting dodecyl bromide and methyl mercaptan in alkaline solution followed by oxidation of the dodecyl methyl thioether with hydrogen peroxide in acetone solution to dodecyl methyl sulfoxide. Another process, suitable for use on a commercial scale involves the preparation of the compound from l-dodecene and methyl mercaptan in the presence of peroxides or disulfides followed by air oxidation in the liquid phase with the oxides of nitrogen as catalysts. A further general type of reaction which may be employed in preparing the sulfoxides is described in detail in US. Patent 2,787,595.

The following examples illustrate methods of preparing suitably pure sulfoxides for use according to the present invention.

EXAMPLE 1 16.4 grams of metallic sodium were dissolved in 300 ml. of alcohol in a 3-neck flask, provided with a stirrer, reflux condenser, and dropping funnel. The mixture was cooled with Dry Ice to 20 C. and 27.55 grams of methyl mercaptan, previously cooled to 20 C., were added to the sodium alcoholate solution. 145 grams of dodecyl bromide were then added and the mixture was refluxed, with stirring, in a water bath for 3 hours. About 700 ml. of ether were added to the cooled mixture and the sodium bromide filtered off. The solvent was distilled and the residue fractionated. The dodecyl methyl sulfide passed over at 160 C./22 mm. (bath temperature 210 C.). The yield was 116 grams (92% of theory). A- 50 gram portion was redistilled over 2 grams of metallic sodium, yielding 47 grams of the product, B.P. 159 C./ 21 mm.

grams of the dodecyl methyl sulfide were dissolved in 40 ml. of acetone and 10 grams of 19% hydrogen peroxide were added thereto. The addition of the aqueous peroxide caused the formation of two layers in the reaction mixture. The mixture was refluxed on the water bath until a homogeneous solution was obtained. This solution was then poured into ice water where the oil quickly solidified. The solidified oil was separated by filtration, the efficiency of which was improved by allowing the mixture to stand on ice for several hours. After filtration, the sulfoxide was dried in a vacuum desiccator and recrystallized from a suitable solvent. The yield in this case was 6.6 grams of a sulfoxide having a melting point of 65 C.

EXAMPLE 2 Dodecyl acetonyl sulfoxide was prepared from dodecyl acetonyl sulfide according to the following procedure.

A solution of 5.0 grams dodecyl acetonyl sulfide in 30 ml. acetone was treated with 1.75 ml. of 30% hydrogen peroxide. The solution was refluxed for minutes on a water bath kept at 60 C. The reaction was freed of the solvent by vacuum evaporation with a water pump on a water bath at 40 C. The solid residue was triturated with 50 ml. Skellysolve B is a mortar and filtered by suction. The material on the filter was washed with 10 ml. light petroleum ether. The yield of the sulfoxide was 4.1 grams, 75% of theory, and had a melting point of 84 C. One gram, after recrystallization from 40 ml. Skellysolve B, yielded 0.85 gram of a product having a melting point of 84 C.; phenylhydrazone, melting point 73 C.

EXAMPLE 3 Dodecyl vinyl sulfoxide was prepared from dodecyl 2- hydroxyethyl sulfide. The preparation is summarized by the following equations:

The intermediate chlorosulfinate C H SCH CH OSOCl is quite stable and was heated at 200 C. under reduced pressure to drive out all of the sulfur dioxide, leaving the dodecyl 2-chloroethyl sulfide. The latter, by oxidation with sodium hypochlorite solution or concentrated nitric acid, gave dodecyl 2-chloroethyl sulfoxide. This was converted to dodecyl 2-iodoethyl sulfoxide by action of sodium iodine in acetone solution. Dodecyl vinyl sulfoxide, M.P. 42, was formed by heating 2-iodoethyl sulfoxide With 10% aqueous sodium hydroxide for 2 hours at C., with mechanical stirring.

The intermediates found in this reaction may also be used to form other sulfoxides which are useful according to this invention. For example, dodecyl Z-methoxyethyl sulfoxide, C H SOCH CH OCH M.P. 58 C., is formed by treating dodecyl 2-chloroethyl sulfoxide with sodium methylate. Also, the thioether linkage can be introduced by treating dodecyl .2-chl-oroethyl sulfoxide with sodium methyl mercaptide, NaSCH thus forming dodecyl Z-mercaptomethylethyl sulfoxide.

Further, amino sulfoxides may be prepared from these intermediates. For example, dodecyl Z-dimethylaminoethyl sulfoxide is prepared by mixing 8 grams of dodecyl 2-chloroethyl sulfoxide, 16 ml. of a 45% dimethylamine solution in methanol, and 32 ml. of methanol and keeping the mixture in a magnesium citrate bottle for 3 hours at 50 C. and at room temperature overnight. The reaction product is added to 50 ml. of 1:1 HCl and the volume made up to 200 ml. with distilled water. The hydrochloride is filtered and washed with 50 ml. of 1:4 HCl, and dried. The dry hydrochloride was then washed with a little ethyl acetate. The yield was 9.1 grams of dodecyl 2-dimethylaminoethyl sulfoxide hydrochloride, M.P. 162-4 C. Dodecyl Z-diethanolaminoethyl sulfoxide.

(3 21 12550 2 dodecyl 2-morpholinoethyl sulfoxide,

C Hr- C H:

012111580 CHzCHzN o o H2C 2 and dodecyl 2- piperidinoethyl,

CmHzaSO CHzCHzN C H2CH2 were also prepared by this method, from diethanol amine, morpholine and piperidine, respectively.

EXAMPLE 4 A C -hydroxylated sulfoxide, specifically Z-hydroxydodecyl methyl sulfoxide, was prepared by treating dodecylene chlorohydrin, C H -CHOHCH Cl with methyl mercaptan in sodium ethylate solution. The sulfide thus formed was oxidized with nitric acid to the 'hydroxylated sulfoxide, C H CHOHCH SOC-H EXAMPLE 5 mg them.

TABLE IV Compound Melting Melting Formula Point, Method of Point of No. Name 0. Preparation Sirligne,

1 Dodccylglyoeryl sulioxide 012111580CIIZCIIOIIOHZOII 83 See below 93 2 Dodocyloxyethyl methyl sulfoxide CrzlI OCIIzSOCII; 43 do 66 3.. Z-hydro dodecyl methylsulioxidenu 01 11 1CHOIICH SOCH; See Example4 4... Dodecyl acotonyl sulloxide CizlImSOCHzCOCIIs 84 bee Example 5 Dodecyl 2dimcthylaminocthyl sulioxit C1:IIzsSOCIIgCHgNKlHsM 59 See Example .5 ti Dodecylil-dicthanolaminoethylsulioxidc C111] JSOCH CH N(CH CHgOU); 26 do CH -CH 7 Dodecyl .Z-morpholinoothylsulioxido C12II25SOCII2CH1N 67 ....do 00 Oll -CH,

GH -CH 8 Dodecyl2'pipcridinoethy1sultoxide C12HZSOCII7CI12N\ GHQ 57 ..do 42 CHr-Cfig 9 Dodecyl2-chloroethyl sulioxide CnHzsSOCHnCHaCl .do G2 10 Dodecyl 2-hydroxyethyl sull'oxide CrzHzsSOCHaCHzOH 71 See below. ll Dodecyloxyethoxyethylrnethyl sulfoxide C1zHzsOCII CHzOCHQCHgSOCHf; 43 d0 44 12 Dodecyl 2-iodoethy1 sulfoxide CuHzsSOCIIgCEIzI 74 See Example 3 100 13 Dodecyl 2-mercaptomethylethyl sull'oxid CHH SOOIIgCH SOILt 68 d0 l 71 14 Dodeeyl-2-(2-hydroxy)ethoxy-ethyl sull'oxide. CizI-InSOOHzCH OOH CHgOH 54 See below 60 M.P. oi disulioue, 171 C.

Dodecyl glyceryl sulfoxide, compound No. 1 in Table IV, was prepared from dodecyl thioglyceryl ether,

The latter compound was in turn prepared according to a modification of the teachings of U.S. Patent No. 1,987,- 526. To a solution of 5.2 grams metallic sodium in 130 ml. of ethyl alcohol, 95%, there were added 45.0 grams dodecyl mercaptan followed by 24.6 grams glyceryl alphamonochlorohydrin. The mixture was refluxed for one hour on a water bath, and then poured into water. The product was extracted with 400 ml. of diethyl ether, washed with a sodium chloride solution and dried over anhydrous sodium sulfate. The ether was distilled off. The residue amounted to 54 grams and had a melting point of 4748 C. A solution of 26 grams of the crude thioglyceryl ether in 2 60 ml. of diethyl ether was cooled in ice. The crystals were filtered and washed with 50 ml. cold ether. The yield of pure dodecyl thioglyceryl ether, melting point 52 C., was 15.3 grams. The above reaction is represented by the equation:

C H Br+NaOCH CH OH The thioether was then oxidized with cold concentrated nitric acid to form the corresponding sulfoxide.

Dodecyloxyethyl methyl sulfoxide, compound No. 2 in Table IV, was prepared according to the following series of equations:

The following examples illustrate several preferred embodiments of detergents of this invention.

EXAMPLE 6 Percent 20.0

Ingredient:

Ammonium dodecyl benzene sulfonate Ammonium salt of sulfated nonyl phenol condensed with 4 moles of ethylene oxide 10.0 Dodecyl methyl sulfoxide 2.0 Denatured ethyl alcohol 15.0 Perfume 0.2 Water and miscellaneous ingredients 52.8

100.0 EXAMPLE 7 Ingredient:

Ammonium dodecyl benzene sulfonate 20.0

Ammonium salt of sulfated dodecyl phenol condensed with 4 moles of ethylene oxide 10.0 Dodecyl methyl sulfoxide 2.0 Denatured ethyl alcohol (100%) 15.0 Perfume 0.2 Water and miscellaneous ingredients 52.8

EXAMPLE 8 Ingredient:

Ammonium dodecyl benzene sulfonate 20.0 Sodium lauryl sulfate 10.0 Dodecyl methyl sulfoxide 2.0 Denatured ethyl alcohol (100%) 15.0 Perfume 0.2 Water and miscellaneous ingredients 52.8

Examples 6, 7 and 8 are light duty liquid detergents and represent preferred compositions of this invention. Their performance in dish washing and light duty laundering was exceptional. The foam produced during agitation of a washing solution containing the usual level of these detergents was of medium finc open texture and remained stable in the presence of soil until the fat emulsifying and cleansing ability of the solution was exhausted. It is EXAMPLE 9 Table V below, shows a series of detergent compositions and their evaluation in a standard dish washing test and a standard dishpan suds stability test. The standard dish washing test measures the number of artificially soiled dinner plates washed with the detergent under standard conditions. The standard soil employed is a uniform blend of 9 parts by weight of emulsifier-free vegetable shortening, 8 parts by Weight of bread flour and green color. A teaspoontul of the standard soil is spread evenly over each plate. Six quarts of water of the desired hardness is adjusted to 116 F. and a measured amount of detergent is added. The number of standardly soiled plates Washed in this solution according to a standardized washing technique gives an indication of the effectiveness of the solution. The end point is reached when the foam no longer completely covers the surf-ace of the washing solution.

The standard dishpan suds stability test is conducted by dissolving grams of the detergent and grams of tallow containing 15% free fatty acids in 6 quarts of tap water at 120 -F. with agitation for seconds. The results are expressed in the time required for the suds to break, in seconds.

TABLE V Light Duty Liquid Detergent Indgredients 1 2 3 4 Sultonic acid (dodecyl) 18.20 18. 20 Alipal* (active) 11.87 11.87 Laurie diethanol amiden" 6.00 Dodecyl methyl sulfoxide- 6.00 6.00 Ethyl alcohol 12. 00 12.00 12. 00 12.00 Water, ammonium hydroxide, etc 51. 93 51. 93 57. 93 82.00

Standard Dishwashing Test Data Number of plates washed in 120 p.p.m.

hardness water at 3 grams 19, 19 19, 20 13, 14 1 6 grams 32, 34 33, 36 24, 24 2 (Duplicate runs.)

Standard Dishpau Suds Stability Test Time for suds to break (seconds) 900 112 *Ammonium salt of sulfated nonyl phenol condensed with 4 moles of ethylene oxide.

Ingredient: Percent Dodecyl benzene sulfonic acid (90% active) 7.0 Sodium xylene sul-fonate (37% active) 24.0 Sodium silicate (37.5% solids) 7.0 Potassium hydroxide 2.4 Dodecyl methyl sulfoxide 3.7 Tetrapotassium pyrophosphate 19.1 Water and miscellaneous ingredients 36.8

1 4 EXAMPLE 11 Ingredient: Percent Dodecyl benzene sulfonic acid active) 7.0 Sodium xylene sulfonate (37% active) 18.9 Sodium silicate (37.5% solids) 7.0 Potassium hydroxide 2.4 Dodecyl methyl sulfoxide 2.0 Laurie isopropanol amide 1.7 Tetrapota-ssium pyroph-osph-ate 19.1 Water and miscellaneous ingredient-s 41.9

Examples 10 and 11 represent heavy duty liquid detergents prepared according to this invention. These materials are exceptionally useful in dish washing and in heavy duty laundering. Example 11 uses a combination of lauric isopro-panol amide and dodecyl methyl sulfoxide as the foam stabilizing additive. The sulfoxide is not stable in the presence of a bleaching agent while the amide is. By employing the combination of additives, a detergent composition is provided which has the advantages of a sultoxide stabilized composition in situations where bleach is not employed and at the same time has the required action in the presence of a bleaching agent.

This example is a powdered detergent composition containing dodecyl methyl sulfoxide as a foam stabilizing additive. The volume of foam produced in aqueous solutions of this composition is equal or superior to that obtained with prior art foam stabilizers. In addition, the foam produced remains stable for a much longer period than the foams heretofore obtained.

EXAMPLE 13 Dodecyl glyceryl sulfoxide, a C -hydroxylated methyl sulf-oxide of the formula C H CHOHCH SOCH dodecyloxyethyl methyl sulfoxide, dodecyloxyethoxyet'hyl methyl sulfioxide, dodecyl Z-dimethylaminoet-hyl sulfoxide, dodecyl Z-diethanolaminoethyl sulfoxide, dodecyl 2-imorpholinoethyl sulfoxide, dodecyl 2-piperidinoethyl sulfoxide, dodecyl vinyl .sulf-oxide, dodecyl ethyl sulfoxide, dodecyl n-propyl sulfoxide, dodecyl isopropyl sulf-oxi-de, dodecyl Z-mercaptomethylethyl sulfioxide, and dodecyl acet-onyl sulf-oXide were each substituted for the dodecyl methyl sulfoxide of Example 11 at 3.5% level. In each instance, the resulting powedered detergent produced an exceptionally stable foam in aqueous solution.

EXAMPLE 14 Dodecyl benzyl methyl sulfoxide, octadecyl methyl sulfoxide, cetyl methyl sulfoxide, dodecyl phenyl sulfoxide, dodecyl benzyl sulfoxide, dodecyl pentyl sulfoxide and octyl methyl sulfoxi-de were each substituted for the dodecyl methyl sulfoxide in the liquid detergent formula of Example 5 above. The foam produced in each instance had exceptional stability in the presence of greasy soil.

EXAMPLE 15 The sulfoxides of this invention are useful in stabilizing the foam of a large number of suds-producing organic 15 synthetic detergents, including anionic, ampholytic and noni-onic species. A respresentative number of synthetic detergents were evaluated in a liquid detergent composition which contained, in addition to the detergent, 3% of dodecyl methyl sulfoxide, 15% of ethyl alcohol, and water to make a total of 100%. Controls were prepared in the same manner as the test products, the omitted sulfoxide being replaced by an additional 3% water. Table VI below shows the suds stability obtained with a number of suds-producing organic synthetic detergents. The level of detergent used is expressed in the table as grams contained in a 100 gram portion of mixture. In the Dishpan Suds Sta'bility Test described, 100 grams of the mixture were added to 6 quarts of 90 ppm. hardness water. The

Dodecyl methyl suh'oxide not completely dissolved in aqueous solution.

In the above series, the Deriphat No. 154 and the test was otherwise conducted as described above in the sodium cocoglycinate are ampholytic, and the range of specification. ratios is from about 1:1 to about 1:50.

TABLE VI Time for Suds to Gms. of Percent of Break, in Seconds Detergent Product Product Used Active Test Control Product Igepon TE-42 (N -methyl acyl taurate derived from tallow) 15 24 140 Neutronyx 600 (Aromatic polyglyeol ether condensate 100 100 20 Sipon L-22 (am um lau sulfate) 40 430 60 Sipon LS (sodium lauryl alcohol sulfate). 4O 30 440 00 Sipon LT-6 (triethanolamine lauryl alcohol sulfate) 30 50 600 60 Sterox .AJ (trideeyl alcohol condensed with 10 moles of ethylene oxide) 100 80 10 Stcrox CD (tall oil condensed with 10 moles of ethylene oxide (n nouioni 40 100 80 10 Triton X-100 (octylphenol condensed with 10 moles of ethylene oxide (a nonionie)) 40 100 180 30 Triethanoiaminc dodecyl benzene sultonate. 35 30 370 25 Potassium dodecyl benzene sulionate 35 30 360 30 Control-3 gm. dodecylmethyl sulioxide only Less than 10 EXAMPLE l6 EXAMPLE 17 An additional series of synthetic detergents were evaluated and the results are given in Table VII below. The indicated amounts of detergent and sulfoxide were dissolved in 75 grams of water and the solution was employed in the Dishpan Suds Stability Test. The sample detergent solution, cOntaining 75 grams of water and the indicated amounts of detergent and sulfoxide was added to 6 quarts of water along with 20 grams of tallow containing 16% free fatty acids. The aqueous solution was agitated for 30 seconds. The end point was the time required, in seconds, for the suds to break. Where the data give :two numbers separated by a dash, duplicate determinations are indicated.

The study was made to determine the operating range for pure dodecyl methyl suit-oxide combined with the following detergents.

(a) Deriphat No. 154 (100% active): An ampholytic surfactant, disodium betaiminodipropionate.

(b) Sodium cocoglycinate (spray-dried, 100% active): S-476150.

TABLE VII Deriphat No. 154

A series of tests were conducted to determine the effect of varying the ratio of a sulfoxide and Triton X- (octyl phenol condensed with about 10 moles of ethylene oxide). The effect of adding Na SO was also investigated. The Suds Stability Test was conducted at 116 F., using water and 20 grams of tallow. The results are given in Table VIII below, numbers separated by a dash indicating duplicate determinations.

Gms. Gms. Ratio; Sult- Suds Triton Dodeeyl Gms. Gms. oxide to Stability X-lOO Methyl N 32504 Water Detergent (sees) Sulfoxide gent being within the range of from about 1:300 to about 1:3.5 where the detergent is selected from the group consisting of non-soap anionic and nonionic detergents, and the ratio being within the range of from about 1:50 to about s1:1 when the detergent is ampholytic, the sudsproducing synthetic detergent being capable of dispersing sulfoxides and aqueous solution and being present in an amount suflicient to disperse the sulfoxide in an aqueous solution at room temperature.

2. A detergent composition consisting essentially of a suds-producing material selected from the group consisting of non-soap anionic, ampholytic and sulfoxide-free nonionic organic synthetic detergent and at least about 0.1% based on the weight of the composition of dodecyl ethyl sulfoxide, the weight ratio of sulfoxide to detergent being within the range of from about 1:300 to about 1:35 where the detergent is selected from the group consisting of non-soap anionic and nonionic detergents, and the ratio being within the range of from about 1:50 to about 1:1 when the detergent is ampholytic, the suds-producing synthetic detergent being capable of dispersing sulfoxides in aqueous solution and being present in an amount suflicient to disperse the sulfoxide in an aqueous solution at room temperature.

3. A detergent composition consisting essentially of a suds-producing alkyl aryl sulfonate detergent and dodecyl methyl sulfoxide, the weight ratio of sulfoxide to sulfonate being in the range of from about 1:300 to about 123.5.

4. A detergent composition consisting essentially of a suds-producing alkyl aryl sulfonate detergent and dodecyl glyceryl sulfoxide, the weight ratio of sulfoxide to sulfonate being in the range of from about 1:300 to about 1:3.5.

5. A detergent composition consisting essentially of a sudsproducing alkyl aryl sulfonate detergent and dodecyloxyethyl methyl sulfoxide, the weight ratio of sulfoxide to sulfonate being in the range of from about 1:300 to about 1:3.5.

6. A detergent composition consisting essentially of a suds-producing alkyl aryl sulfonate detergent and dodecyloxyethoxyethyl methyl sulfoxide, the weight ratio of sulfoxide to sulfonate being in the range of from about 1:300 to about 1:3.5.

7. A detergent composition consisting essentially of a fatty alcohol sulfate and dodecyl methyl sulfoxide, the weight ratio of sulfoxide to fatty alcohol sulfate being in the range of from about 1:300 to about 123.5.

8. The detergent composition of claim 7 wherein the fatty alcohol sulfate is present in an amount suflicient to disperse the dodecyl methyl sulfoxide in aqueous washing solutions at room temperature.

9. A detergent composition consisting essentially of an ampholytic suds-producing organic synthetic detergent and dodecyl methyl sulfoxide, the weight ratio of sulfoxide to detergent being in the range of from about 1:50 to about 1: l.

10. A detergent composition consisting essentially of sodium cocoglycinate and dodecyl methyl sulfoxide, the weight ratio of sulfoxide to sodium cocoglycinate being within the range of from about 1:50 to about 1:1.

11. A detergent composition consisting essentially of a suds-producing material selected from the group consisting of nonsoap anionic, ampholytic and sulfoxide-free nonionic organic synthetic detergents and at least about 0.1% based on the weight of the composition of a sulfoxide of the formula R-Xa s=o R! wherein R is a member of the group consisting of alkyl and hydroxyalkyl radicals having from 8 to 18 carbon atoms; X is a divalent radical selected from the class consisting of benzyl, phenyl, (lower)oxyalkylene, and a (lower) polyoxyalkylene from the group consisting of polyethylene and polypropylene wherein the total number of carbon atoms is 4-6; a is 0 or 1; R is a radical selected from the class consisting of mononuclear aryl, 2- dimethylaminoflower)alkyl, 2 diethanolamino (lower)alkyl, 2-morpholino(lower)alkyl, Z-piperidino(lower)alkyl, (lower)all yl, hydroxy(lower)alkyl of 2 to 5 carbon atoms, acetonyl, and ethers and thioethers of the formula --AYB, wherein Y is S, or O, A is a saturated alkylene group having from 2 to 5 carbon atoms, B is selected from the group consisting of alkyl groups having 1-5 carbon atoms, alkene groups having 2-5 carbon atoms and hydroxy alkyl groups having from 25 carbon atoms, and wherein A and B taken together have from 3 to 7 carbon atoms, the weight ratio of sulfoxide to detergent being within the range of from about 1:300 to about 1:35 Where the detergent is selected from the group consisting of nonsoap anionic and nonionic detergents and the ratio being Within the range of from about 1:50 to about 1:1 When the detergent is ampholytic.

12. The detergent composition of claim 11, wherein the suds-producing material is a nonsoap anionic sudsproducing organic detergent, wherein the sulfoXide is present at a level of at least 0.1% by weight of the composition, and wherein the weight ratio of sulfoxide to synthetic detergent is within the range of from about 1:300 to about 123.5.

13. The detergent composition of claim 11, wherein the detergent is a sulfoXide-free nonionic suds-producing organic synthetic detergent, wherein the sulfoxide is present at a level of at least 0.1% by weigh-t of the composition and the weight ratio of sulfoxide to synthetic detergent is within the range of from about 1:300 to about 1:35.

14. The detergent composition of claim 11, wherein the detergent is an ampholytic suds-producing organic, synthetic detergent, wherein the sulfoxide is present at a level of at least 0.1% by weight of the composition and the weight ratio of sulfoxide to synthetic detergent is within the range of from about 1:50 to about 1:1.

15. The detergent composition of claim 11, wherein the sulfoxide is 2-hydroxydodecyl methyl sulfoxide.

16. The detergent composition of claim 11, wherein the sulfoxide is dodecyl 2morpholinoethyl sulfoxide.

17. The detergent composition of claim 11, wherein the sulfoxide is dodecyl Z-piperidinoethyl sulfoxide.

18. A detergent composition consisting essentially of a suds-producing alkyl aryl sulfonate detergent and 2- hydroxydodecyl methyl sulfoxide, the Weight ratio of sulfoxide to alkyl aryl sulfonate being within the range of from about 1:300 to about 123.5.

19. A detergent composition consisting essentially of a suds-producing alkyl aryl sulfonate detergent and dodecyl 2-morpholinoethyl sulfoxide, the weight ratio of sulfoxide to alkyl aryl sulfonate being within the range of from about 1:300 to about 123.5.

20. A detergent composition consisting essentially of a suds-producing alkyl aryl sulfonate detergent and dodecyl Z-piperidinoethyl sulfoxide, the weight ratio of sulfoxide to alkyl aryl sulfonate being within the range of from about 1:300 to about 113.5.

21. A detergent composition consisting essentially of a fatty alcohol sulfate and Z-hydroxydodecyl methyl sulfoxide, the weight ratio of sulfoxide to fatty alcohol sulfate being in the range from about 1:300 to about 1:35.

22. A detergent composition consisting essentially of a fatty alcohol sulfate and dodecyl 2-morpholinoethyl sulfoxide, the weight ratio of sulfoxide to fatty alcohol sulfate being in the range from about 1:300 to about 1:35.

23. A detergent composition consisting essentially of a fatty alcohol sulfate and dodecyl Z-piperidinoethyl sulfoxide, the weight ratio of sulfoxide to fatty alcohol sulfate being in the range from about 1:300 to about 1:3.5.

24. A detergent composition consisting essentially of 19 sodium cocoglycinate and Z-hydroxydodecyl methyl sulfoxide, the weight ratio of sulfoxide to detergent being in the range of from about 1:50 to about 1:1.

25. A detergent composition consisting essentially of sodium cocoglycinate and dodecyl Z-morpholinoethyl sulfoxide, the weight ratio of sulfoxide to sodium cocoglycinate being in the range from about 1:50 to about 1: l.

26. A detergent composition consisting essentially of sodium cocoglycinate and dodecyl Z-piperidinoethyl sulfoxide, the weight ratio of sulfoxide to sodium cocoglycinate being in the range from about 1:50 to about 1:1.

27. The detergent composition of claim 11, wherein the sulfoxide is dodecyl glyceryl sulfoxide.

28. The detergent composition of claim 11, wherein the sulfoxide is dodecyloxyethyl methyl sulfoxide.

29. The detergent composition of claim 11, wherein the sulfoxide is dodecyl acetonyl sulfoxide.

30. The detergent composition of claim 11, wherein the sulfoxide is dodecyl Z-dimethylaminoethyl sulfoxide.

31. The detergent composition of claim 11, wherein the sulfoxide is dodecyl Z-diethanolaminoethyl sulfoxide.

32. The detergent composition of claim 11, wherein the sulfoxide is dodecyl 2-hydroxyethyl sulfoxide.

33. The detergent composition of claim 11, wherein the sulfoxide is dodecylethoxyethyl methyl sulfoxide.

34. The detergent composition of claim 11, wherein the sulfoxide is dodecyl 2-thiomethylethyl sulfoxide.

35. The detergent composition of claim 11, wherein the sulfoxide is dodecyl-2-(2-hydroxy)ethoxyethyl sulfoxide.

36. A method of stabilizing foams produced by agitating a solution consisting essentially of an anionic sudsproducing organic synthetic detergent comprising adding dodecyl methyl sulfoxide in a minor amount to said solution, the ratio of the sulfoxide to said detergent in said solution being no gretaer than 1:35.

37. A method of stabilizing foams produced by agitating a solution consisting essentially of a suds-producing material selected from the group consisting of nonsoap anionic, ampholytic, and sulfoxide-free nonionic organic synthetic detergents comprising adding to said solution at least about 0.1% based on the weight of the composition of a sulfoxide of the formula R-Xa s-0 Rl wherein R is a member of the group consisting of alkyl and hydroxyalkyl radicals having from 8 to 18 carbon atoms; X is a divalent radical selected from the class consisting of benzyl, phenyl, (lower)oxyalkylene, and a (lower)polyoxyalkylene from the group consisting of polyethylene and polypropylene wherein the total number of carbon atoms is 4-6; a is 0 or 1; R is a radical selected from the class consisting of mononuclear aryl, 2- dimethylamino(lower)alkyl, 2-diethanolamino(lower)alkyl, 2-morpholino(lower)alkyl, 2-piperidino(lower)alkyl, (lower)alkyl, hydroxy(lower)alkyl of 2 to 5 carbon atoms, acetonyl, and ethers and thioethers of the formula AYB, wherein Y is S or O, A is a saturated alkylone group having from 2 to 5 carbon atoms, B is selected from the group consisting of alkyl groups having 1-5 carbon atoms, alkene groups having 2 to 5 carbon atoms and hydroxy alkyl groups having from 2 to 5 carbon atoms, and wherein A and B taken together have from 3 to 7 carbon atoms, the weight ratio of sulfoxide to detergent being within the range of from about 1:300 to about 123.5 where the detergent is selected from the group consisting of nonsoap anionic and nonionic detergents and the ratio being within the range of from about 1:50 to about 1:1 when the detergent is ampholytic.

38. The method of claim 37, wherein the suds-producing material is a nonsoap anionic suds-producing organic detergent, wherein the sulfoxide is present at a level of at least 0.1% by weight of the composition, and wherein the weight ratio of sulfoxide to synthetic detergent is within the range of from about 1:300 to about 1:35.

39. The method of claim 37, wherein the detergent is a sulfoxide-free nonionic suds-producing organic synthetic detergent, wherein the sulfoxide is present at a level of at least 0.1% by weight of the composition and the weight ratio of sulfoxide to synthetic detergent is within the range of from about 1:300 to about 1:3.5.

40. The method of claim 37, wherein the detergent is an ampholytic suds-producing organic synthetic detergent, wherein the sulfoxide is present at a level of at least 0.1% by weight of the composition and the Weight ratio of sulfoxide to synthetic detergent is within the range of from about 1:50 to about 1:1.

41. The method of claim 37, wherein the sulfoxide is selected from the group consisting of dodecyl glyceryl sulfoxide, dodecyloxyethyl methyl sulfoxide, Z-hydroxyn-dodecyl methyl sulfoxide and dodecyl oxyethoxyethyl methyl sulfoxide.

References Cited UNITED STATES PATENTS 2,787,595 4/1957 Webb 252-l38 LEON D. ROSDOL, Primary Examiner.

S. D. SCHNEIDER, Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No 3 ,38 2,180 May 7 1968 Hill M. Priestley et a1.

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 3 line 11 "C H OCH CH CH CH SOCH should read C H OCH CH CH CH CH SOCH Columns 7 and 8,

TABLE III, third column, line 1 thereof, "60(20 min.)" should read 40(20 min.) Column 10, line 39, "4 C." should read' 4 C. Column 11, line 46, "C H Br+NaOCH CH OH" 12 25 Z 2 should read C H SNa+ClCH CH0HCH OH line 54,

clzHlsBr Signed and sealed this 11th day of November 1969.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. WILLIAM E. SCHUYLER, JR. Attesting Officer Commissioner of Patents