US3384595A - Detergent compositions containing gamma-hydroxy organic sulfonate type compounds - Google Patents

Description

United States Patent DETERGENT COMPOSITIONS CONTAINING GAM- MA HYDROXY ORGANIC SULFONATE TYPE COMPOUNDS George L. Broussalian, St. Louis, Mo., assignor to Monsanto Company, St. Louis, Mo., a corporation of Delaware No Drawing. Filed Dec. 15, 1964, Ser. No. 418,567

11 Claims. (Cl. 252161) ABSTRACT OF THE DISCLOSURE Detergent compositions containing in addition to conventional detergent ingredients from about 5 to 50% by weight of a gamma-hydroxy sulfonate type compound. The gamma-hydroxy organic sulfonate type compound acts as a supplemental detergent active material and results in the production of large quantities of foam or lather which is extremely stable in the presence of greases.

This invention relates to new and useful detergent compositions and to processes for preparing them. More particularly, this invention relates to both aqueous and nonaqueous compositions which contain significant amounts of gamma-hydroxy organic sulfonate type compounds that can be represented by Formula 1:

o B H l I; S'oat wherein R and R are hydrophobic organic radicals containing from 1 to about 21 carbon atoms or hydrogen and the sum of the total number of carbon atoms in R plus R is from about 7 to about 21; A and B are selected from the group consisting of lower alkyl, halogen, hydrogen, and halogen-substituted lower alkyl radicals; and M is either hydrogen, an alkali metal cation, an alkaline earth metal cation, or an ammonium cation; and to processes for preparing these materials.

The swifty increasing consumption of high foaming household hand dishwashing compositions over the past several years both in this country and abroad is conclusive evidence of the increasing value of this type of product both to manufacturers of such dishwashing compositions and to manufacturers of surface active agents (surfactants) that can be utilized in the formulation of such compositions. In view of the importance of this end use, a search for new and improved hand dishwashing detergents is being conducted practically continuously by many surfactant manufacturers.

In order to qualify as a useful hand dishwashing surfactant, a material must have the ability to cause the formation of large quantities of foam or lather when aqueous solutions of the materials are agitated, which lather is stable when greases or greasy soils are also dissolved or dispersed therein. It has been discovered that when the above-described gamma-hydroxy sulfonate-type compounds are utilized in sufiicient amounts or proportions, either with or without other surfactants, in hand dishwashing compositions, for example, unexpectedly large quantities of foam or lather which is extremely stable in the presence of dissolved greases or greasy soils results therefrom. While extremely small amounts of some ICC of the gamma-hydroxy sulfonates described above may inadvertently have been produced heretofore (in processes, for example, in which other types of surfactants were manufactured in very large quantities or proportions) the valuable benefits that result from using larger amounts were not appreciated heretofore.

It has now been discovered that not only are the abovedescribed ga'mmahydroxy organic sulfonate-type compounds of this invention useful as general purpose surface active agents in aqueous solutions, but they are particularly useful as agents which produce unexpectedly large quantities of foam or lather when they are dissolved in water, which foam or lather is extremely stable in the presence of dissolved and/or dispersed greases. Thus, the compositions of this invention represent particularly useful laundry and dishwashing detergent compositions.

Ordinarily the organic radicals (designated by R and R" in Formula 1, above) that are present in the gammahydroxy organic sulfonate-type compounds of the present invention can be branched or unbranched to practically any degree without substantially eliminating all of the benefits that can result from the invention. It is generally preferred, however, that the organic radical(s) be straight-chain in nature. It is still further preferred that the sum of the total number of carbon atoms in R and R be between about 9 and about 17. Although organic radicals R and R can contain heterocyclic, monocyclic hydrocarbyl and polycyclic hydrocarbyl 'radials (whether the rings are saturated or not), and can also contain substituents such as halides (including for example, fluoride, chloride, bromide and iodide), ester groups, ether groups, thioether groups, amine groups, nitrile groups, amide groups, and the like, in their otherwise aliphatic or alicyclic radicals, it is preferred that R and/ or R be either hydrocarbyl in nature or that they contain only halide substituents in their otherwise hydrocarbyl radicals. Also, it is particularly preferred that the sulfonate group (in the above-described gamma-hydroxy organic sulfonate type compounds that are contemplated for use in the practice of this invention) be attached to the carbon atom which is at an end of a long chain hydrophobic organic radical (preferably alkyl), and that the single hydroxy group appear attached to the third carbon atom in the same long chain. For example, these particularly preferred compounds just described include those having a structure such as that illustrated in Formula 2:

( H H H -CC--CH l (i) S 0 3M H wherein R is a higher alkyl radical, preferably containing from about 9 to about 17 carbon atoms, and M is an alkali metal cation. Of these compounds, those having straight chain alkyl groups are even further preferred.

While from the above discussion it can be seen that the alkali metal sulfonate salts are preferred forms of the above-described gamma-hydroxy sulfonate-type compounds, it is nevertheless :a fact that ammonium salts, as well as alkaline earth metal salts (where, for example, M in 'Formulas 1 and 2, above, represents /zCa /2Mg++, /2Ba++, /zSr++ or /2Ra++) can be used in the practice of this invention. Of the preferred alkali 3 metal salts (including Li, Na, K, Rb, Cs, Fr) the sodium and potassium salts are particularly preferred, especially from the standpoint of cost.

Typical, but non-limiting examples of the gammahydroxy organic sulfonate-type compounds that are useful in the practice of the present invention include ammonium 2-methyl-3-hydroxy-l-octadecanesulfonate,

sodium 3-hydroxy-l-pentadecanesulfonate,

potassium 4-(branched) dodecyl-4-hydroxy-2-butanesulfonate,

ammonium 5-hydroxy-3-octadecanesulfonate,

sodium 3-(branched) pentadecyl-3-hydroxy-l-propanesulfonate,

ammonium 1-isopropyl-3-(9, lO-dichloroheptadecyl) -3- hydroxy-1-propanesulfonate,

potassium 3-hydroxy-l-dodecanesulfonate,

sodium l-phenyl-3-hydroxy-l-hexadecenesulfonate,

sodium '2-brom-o-3-hydroxy-l-hexadecanesulfonate,

potassium 1- 3-pyridyl l-hydroxy-3-hexadecanesulfonate sodium 3-hydroxy-l-hexadecanesulfonate,

magnesium 3,3-dioctyl-3-hydroxy-l-propanesulfonate,

sodium 3-methyl-3-hydroxy-l-octadecanesulfonate,

sodium 3-(branched) dodecyl-S-hydroxy-l-propanesulfonate,

calcium l-hydroxy-3-tetradecanesulfonate,

sodium l-trichlorometbyl-1-hydroxy-3-hexadecanesulfonate,

sodium l-carbamido-l-hydroxy-3-pentadecanesulfonate potassium 4-autoxy-5-hydroxy-3-nonadecanesulfonate,

sodium 1-hydroxy-3-octadecanesulfonate,

sodium 3-(branched dodecylphenyl)-3-hydroxy-l-propane sulfonate,

magnesium 2-hydroxy-4-pentadecanesulfonate,

sodium l-hydroxy-2-cyano-3-pentadecanesulfonate,

strontium 3-hydroxy-l-tetradecanesulfonate,

sodium l-amino-2-hydroxy-4-hexadecanesulfonate, and

ammonium 1-methoxy-4-hydroxy2-heptadecanesulfonate.

The gamma-hydroxy organic sulfonates of the present invention can be manufactured by one of several methods. One method is to react an appropriate Grignard with beta-chloropropionaldehyde followed by sulfitation with sulfite ion. Another method is to react an appropriate acid chloride and olefin in the presence of a Friedel-Crafts catalyst to yield an alpha,beta-unsaturated ketone followed by free radical addition of bisulfite ion and their reduction with hydrogen, either catalytically or chemically. Still another method is to hydrolyze the corresponding gamma-sultone with water or base, preferably in basic methanol.

The gamma-hydroxy sulfonate-type compounds that are useful in the practice of the present invention can be utilized advantageously as general purpose detergent active ingredientseither alone or in combination with practically any material that can be employed in combination with known organic detergent anionic and nonionic surface active agents, such as soap, the alkali metal fatty alcohol sulfates, the alkali metal, ammonium, and alkaline earth metal alkylaryl sulfonates; higher alcoholethylene oxide condensates, alkylphenol ethylene oxide condensation products, fatty acid-ethylene oxide condensation products, for example, sodium dodecylbenzene sulfonates, vicinal acylamido alkane sulfonates, vicinal amino alkane sulfonates, olefin sulfonates; and other similar surfactants. The types of materials that can 'be employed in the formulation of so-called polyphosphate built detergents, flake and powdered compositions (presuming the usual conditions of compatibility are applied) include such materials as other organic anionic 'and/or nonionic and/or ampholytic surface active agents or materials, polyphosphate complexing agents and other inorganic and organic builders, anti-redeposition agents, optical brighteners, bleaching agents, and the like; all of which are well-known in the detergent art and need not be detailed here. It is interesting to note that the gammahydroxysulfonatetype materials of this invention can be utilized advantageously in practically any of the compositions in which the alkylaryl sulfonates, for example, can be utilized. It should be noted, however, that whenever these gamma-hydroxy sulfonates are utilized in combination with other organic surface-active agents such as the higher alkyl benzene sulfonates, for example, generally in order for the unexpectedly desirable properties of the gamma-hydroxy sulfonate to become readily apparent when the mixture or combination of organic surfactants is ultimately dissolved in Water, the amount of the gamma-hydroxy sulfonate in the organic surfactant combination should be at least about 10 weight percent, based on the total combined weight of the organic surfactants in the combination. Preferably, this proportion of the gamma-hydroxy sulfonate should be at least about 15 weight percent of the total amount of organic detergent surface active ingredients in any aqueous or nonaqueous composition in which they are utilized.

The gamma-hydroxy sulfonates described above are particularly useful when they are formulated into socalled built detergent compositions and used as such, for example, as light duty or heavy duty laundering detergents. Built detergents are those that contain, in addition to the detergent active material, at least one water-soluble inorganic builder salt such as an alkali metal pyrophosphate, tripolyphosphate, carbonate, sulfate, or the like. In such built detergent compositions, the outstanding properties of the sulfonates of the present invention can readily be appreciated when the composition contains at least about 5 Weight percent, and up to about weight percent or more; preferably from about 10 to about 35 weight percent, of these gamma-hydroxy sulfonate(s).

As it was stated hereinbefore, the gamma-hydroxy sulfonates described above can advantageously be utilized along with any other anionic, nonionic, or ampholytic detergent active materials (surfactants) or mixtures thereof in the proportions specified above. The term anionic surfactants, encompasses such materials as the alkali metal salts of fatty acids and fatty acid derivatives, commonly known as soaps (such as sodium la-urate, sodium palmitate, and the potassium salts of coconut fatty acids); the alkali metal salts of sulfuric esters [such as sodium lauryl alcohol sulfate, potassium hexadecanol sulfate, lithium petroleum alcohol (average C chain length) sulfate as well as the alkali metal sulfates of condensation products of alcohols containing from about 10 to about 30 carbon atoms with from about 2 to about 40 moles of a lower alkylene oxide such as ethylene oxide, propylene oxide, or mixtures thereof]; the alkali metal salts of alkanesulfonates, preferably straight-chain alkanesulfonates (such as those prepared by sulfonating certain petroleum fractions with S03); the alkali metal and alkaline earth metal salts of esterand ether-linked sulfonates [such as the sodium dialkyl sulfosuecinates (wherein alkyl contains from about 4 to about 20 carbon atoms), the potassium lauryl diester of 2,3-dihydroxypropane-lsulfonate]; amide-linked sulfonates (such as sodium oleylmethyltaurate, sodium 4-acyl-aminobutane-l-sulfonates, and sodium myristyl sulfomethylamide); alkylarylsulfonates wherein the single alkyl group preferably contains from about 10 to about 20 carbon atoms (such as sodium dodecylbenzene sulfonate); mahogany and petroleum sulfonates; vicinal acylamido alkane sulfonates; vicinal amino alkane sulfonates; olefin sulfonates; and the like. The term nonionic surfactants encompasses such materials as the condensation products of several moles of a lower alkylene oxide such as ethylene-, propylene-, or butylene-oxide with a mole of a higher alkyl alcohol, alkylphenol, fatty acid, and the like (wherein the alkyl group contains from about 10 to about 20 or more carbon atoms); the fatty alkanolamides (such as the diethanolamide of tall oil fatty acids and the diethanolamide of lauric acid); and the polyhydroxy nonionic surfactants (such as sorbitol monolaurate, and the reaction products of fatty primary amines with deltagluconolactone). The ampholytic surfactants contain both acidic and basic functional groups in their individual molecules, and include such materials as dodecyl-beta-alanine, sodium N- dodecyl taurate, and the products from reacting benzene amino sulfonic acid, for example, with n-hexadecylchloride. Other examples of organic anionic, nonionic and ampholytic surfactants that can also be present in compositions containing the gamma hydroxy sulfonate materials described above can be found in Surface Active Agents and Detergents, by Schwartz et :al., Interscience Publishers, Inc., New York (1958), volume II.

The pure gamma-hydroxy sulfonate compounds of this invention as well as compositions containing them such as those described above, have physical and chemical properties that make them particularly outstanding detergents for use in the form of aqueous solutions (containing them) to clean various solid substrates in the presence of dissolved and dispersed greases, for example, as a hand dishwashing detergent composition. In a standard test designed to closely examine the suitability of various water-soluble surface active agents for use in the for-mulation of high foaming hand dishwashing detergents, sodium B-hydroxy-l-n-pentadecane sulfonate cleaned 18 plates before the foam or lather on the surface of the test solution broke, while sodium dodecylbenzene sulfonate (made from a tetrapropylene olefin) effectively washed only about 7 plates before the lather broke when it was used in the same test under practically identical conditions. These high-foaming beneficial properties of the gamma-hydroxy sulfonates of this invention can be readily appreciated when these materials are present (dissolved) in water at a level of at least about 0.005 weight percent (so that they represent at least about 10 weight percent of the total surfactant therein). For optimum results, this level should be generally between about 0.010 and about 20 weight percent, and preferably between about 0.015 and about 10 weight percent of the total aqueous solution weight.

In the following example, which is illustrative of one of the preferred embodiments of this invention, all parts are by weight unless otherwise specified.

EXAMPLE I Process To cold C.) Grignard material prepared by reacting 125 parts of n-l-bromododecane with 14 parts of magnesium (powder) in anhydrous ethyl ether is added slowly, with stirring, a cold C.) solution of 53 parts of beta-chloropropionaldehyde (prepared according to the procedure of Jacobs and Weinstein, J. Org. Chem., vol. 11, p. 225, 1946) in 200 parts of ethyl ether. The resulting mixture is warmed slowly (over 1 hour) to room temperature. After stirring for about 3 hours at room temperature the mixture is permitted to stand for 15 minutes. Two layers separate. The top (ether) layer contains 140 parts of crude S-hydroxy-l-chloropentadecane. Treatment of this material (after evaporation of the ether) with 700 parts of potassium sulfite, 1000 parts of water and 750 parts of methanol by heating the mixture at reflux for 16 hours, followed 'by cooling to 0 C., and filtering, yields 155 parts of practically pure potassium 3-hydroxy-l-pentadecanesulfonate.

The residue (after removal of the solvent mixture) from Example I is itself an excellent very high foaming surfactant; yielding an extremely high volume of foam when it is dissolved in water at a level of about 0.1 weight percent and the water is subsequently agitated, which foam is unexpectedly stable in the presence of dissolved greases, as for example, after many greasy dishes are washed in the aqueous solution.

A procedure such as that described in either Example I, above, or in the literature referred to hereinbefore, can be utilized to manufacture any of the gammahydroxy sulfonates useful in the practice of the present invention.

For the sake of convenience and more ready understanding of the aforementioned fundamentals of the present invention, the gamma-hydroxy organic sulfonate-type compounds of this invention have generally been referred to as though they were pure components, containing for example hydrophobic radicals, alkyl groups, and the like [as R and R in Formulae 1 and 2] which are all identical. It is well known by those skilled in the art, however, that a high degree of purity in such compounds is very rarely if ever attainable in practical commercial operations for manufacturing detergents. Thus, in practice when a particular chain length such as dodecyl, hexadecane, octadecene, and the like are referred to, almost invariably these terms mean that these are the average chain lengths in the particular surfactant materials being described, and that, in addition to dodecyl, for example, some chain lengths varying to some extent from C in length can be (and generally are) present therein. Similarly, where terms are utilized herein referring to a particular chain length such as hexadecane, tetradecane, and the like, it is intended that this be about the average chain length, and that the term encompasses mixtures of materials having chain lengths varying to some extent from the named average chain length. It is generally preferred, however, that such mixtures of materials contain at most about 10 weight percent of materials varying more than about 3 carbon atoms on either side of the named average. For example, the term sodium 3-hydroxy-l-hexadecanesulfonate includes not only the pure hexadecane material but also mixtures containing from about tridecane to about nonadecane wherein the average chain length of the mixture is C and less than a total of 10 weight percent of the materials in the mixtures have chain lengths less than C or more than C Generally, in such mixtures, material containing the named average number of carbon atoms will be the largest single component in the mixtures.

Table 1, below, illustrates the valuable benefits which can be obtained when the preferred gamma-hydroxy sulfonates of this invention are utilized as laundering detergents.

TABLE 1.DETERGENCY LDATA Compound: Detergency Sodium 2-bromo-3-hydroxy- 1 hexadecanesulfonate 115 Sodium 3-hydroxy-1 hexadecansesulfonate 117 Sodium 3-hydroxy-l-mntadecanesulfonate 118 Potassium 4-(branched) dodecyl 4-hydroxy-2- butanesufonate 110 Potassium 3-hydroxy-l-dodecanesulfonate Sodium 1-hydroxy-3-octadecanesulfonate Potassium 4-autoxy-5-hydroxy 3 nonadecanesulfonate Strontium 3-hydroxy-l-tetradecanesulfonate 110 60 Sodium 3-(branched) pentadecyl-3-hydroxy 1- propanesulfonate Sodium 1-phenyl-3-hydroxy 1 hexadecenesulfonate 112 Ammonium 2-methyl-3-hydroxy-1 octadecane- 65 sulfonate 113 Magnesium 3,3-dioctyl-3-hydroxy-l-propanesulfonate 98 Standard Na DDBSA (from tetrapropylene) 103 1 p .p.m. hard water. Test described by Jay C. Harris in 70 lgElrlluatron of Surface Active Agents ASTM Bulletin, May

Table 2, below, illustrates the very valuable benefits that can be obtained by utilizing these materials as hand dishwashing detergents both alone and in combination with other surface active agents. Details on the test procedure for evaluating hand dishwashing detergents are described after Table 2.

TABLE 2.EVALUA'J]ION AS HAND DISHVVASHI NG 1 Sodium dodecylbenzene sulfonate made from tetrapropylene; average C12 alkyl group.

This hand dishwashing test involves the washing; by hand of nineinch dinner plates which are pre-soiled with one teaspoonful each of a synthetic soil mixture consisting of 75 weight percent of shortening and 25 weight percent of flour. Washing of the plates is performed (using a dishcloth to remove the synthetic soil) in 4 liters of water having an initial temperature of about 50 C. and containing 0.075 weight percent of the surfactant or surfactant mixture being tested. The number of plates washed cleaned in the formal fashion by the time the lather of the dishpan has broken to the extent that less than half of the surface remains covered with lather. The manipulative procedures of this test are described in greater detail in the Proceedings of the,43rd Annual Meeting of the Chemical Specialties Manufacturers Association, December 1956; Procedure No. 3, page 191.

In the following Table 3 are tabulated data showing some typical surfactant properties of one of the outstanding preferred gamma-hydroxy sulfonates of the present invention (practically pure sodium B-hydrOXy-I-npentadecane sulfonate).

TABLE 3.SURFACTANT EVALUATION DATA Test Concentration Results (wt. percent) D etergency 1 Ross-Miles Lather Z 1 In 150 p.p.1n. hard water. Test described by Jay C. Harris in Evalu ation of Surface Active Agents ASTM Bulletin, May, 1946.

1 50 0. Values taken 5 minutes after lather was formed.

3 Room temperature, in distilled water.

What is claimed is:

1. A detergent composition consisting essentially of at least one material selected from the group consisting essentially of anionic detergent active materials, nonionic detergent active materials and ampholytic detergent active materials, and additionally containing, as a supplemental detergent material, from about 5 to about 50 weight percent of a gamma-hydroxy sul fonate-type compound having the formula wherein R and R are selected from the group consisting of saturated and monoethylenically' unsaturated hydrophobic hydrocarbon radicals containing from 1 to 21 carbon atoms, halogen substituted saturated hydrocarbon radicals containing from 1 to 21 carbon atoms and hydrogen, the sum of the total number of carbon atoms in is determined by the number of plates which can be' 8 R plus R is from about 7 to about 21; A and B are selected from the group consisting of lower alkyl, halogen, hydrogen, and halogen-substituted lower alkyl radicals; and M is a cation selected from the group consisting of alkali metal, ammonium, alkaline earth metal and hydrogen'cations.

2. A composition as in claim 1, wherein said composition contains between about 10 and about 50 weight percent of said sulfonate-type compound, R is an alkyl radical containing from about 9 toabout 17 carbon atoms, R is hydrogen, A and B are hydrogen, and M is an alkali metal cation.

3. A detergent composition as in claim 1 wherein R and R in each instance represent a member selected from the group consisting of hydrogen and alkyl radicals and wherein A and B in each instance represent a member selected from the group consisting of hydrogen and lower alkyl radicals.

4. A composition as in claim 2 containing an inorganic detergency builder salt.

5. A detergent composition consisting essentially of a first detergent active material selected from the group consisting of organic anionic and nonionic surface active agents and at least about 10 weight percent, based on the total weight of organic detergent active materials in said composition, of a second detergent active material; said second detergent active material being a sodium 3- hydroxy-l-sulfonate having the formula wherein R is an alkyl group containing from about 7 to about 21 carbon atoms.

6. A composition as in claim 5, wherein said sodium 3-hydroxy-l-sulfonate is a mixture of sulfonates having single alkyl groups containing from about 12 to about 20 carbon atoms, wherein the average chain length of said alkyl groups is from about 12 to about 17 carbon atoms, and wherein said detergent composition contains an inorganic detergency builder salt.

7. A built detergent composition consisting essentially of at least one inorganic detergency builder salt, and, as an organic detergent active from about 5 to about 50 weight percent of a gamma-hydroxy sulfonate having the formula wherein R and R are selected from the group consisting of saturated and monoethylenically unsaturated hydrophobic hydrocarbon radicals containing from 1 to 21 carbon atoms and hydrogen, the sum of the total number of carbon atoms in R plus R is from 7 to 21, and M is an alkali metal cation.

8. A built detergent composition as in claim 7, wherein said hydrophobic hydrocarbon radicals are alkyl radicals.

9. A built detergent composition as in claim 8, where in said alkali metal cation is sodium and said sulfonate is a mixture of sulfonates having from about 10 to about 24 carbon atoms in their alkyl groups and the average chain length of said alkyl groups is from about 12 to about 20 carbon atoms.

10. A built detergent composition as in claim 8, wherein R is hydrogen and the average number of carbon atoms in R is about 12.

11. A detergent composition consisting essentially of an inorganic detergency builder salt and from about 5 to about 50 weight percent of a gamma hydroxy sulfonate type compound having the formula:

wherein R and R are selected from the group consisting of saturated and monoethylenically unsaturated hydrophobic hydrocarbon radicals containing from 1 to 21 carbon atoms, halogen substituted saturated hydrocarbon radicals containing from 1 to 21 carbon atoms, and hydrogen, the sum of the total number of carbon atoms in R plus R is from about 7 to about 21; A and B are selected from the group consisting of lower alkyl, halogen, hydrogen, and halogen-substituted lower alkyl radicals; and M is a cation selected from the group consisting of alkali metal, ammonium, alkaline earth metal and hydrogen cations.

References Cited UNITED STATES PATENTS 2,793,229 5/ 1957 laser.

3,115,501 12/1963 Finch et al. 260-613 3,164,608 1/1965 Blaser.

3,164,609 1/1965 VOss et al.

LEON D. ROSDOL, Primary Examiner.

P. E. WILLIS, S. D. SCHNEIDER, S. DARDEN,

Assistant Examiners.