Search Images Maps Play YouTube News Gmail Drive More »
Sign in
Screen reader users: click this link for accessible mode. Accessible mode has the same essential features but works better with your reader.

Patents

  1. Advanced Patent Search
Publication numberUS3303138 A
Publication typeGrant
Publication dateFeb 7, 1967
Filing dateMar 5, 1965
Priority dateMar 5, 1965
Publication numberUS 3303138 A, US 3303138A, US-A-3303138, US3303138 A, US3303138A
InventorsDe Witt William J, Taylor Robert C
Original AssigneeAtlantic Refining Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Triethanolamine straight chain secondary alkylbenzene sulfonate liquid detergent compositions containing degelling agents
US 3303138 A
Abstract  available in
Images(7)
Previous page
Next page
Claims  available in
Description  (OCR text may contain errors)

United States Patent Pennsylvania No Drawing. Filed Mar; 5, 1965, Ser. No. 437,577

26 Claims. (Cl. 252-152) This invention relates to, anionic detergent compositions which contain triethanolamine salts of alkylbenzene sulfonic acids. More particularly this invention relates to non-gelling, aqueous solutions containing triethyanolamine salts of straight chain secondary alkylbenzene sulfonic acids.

Aqueous detergent solutions containing triethanolamine salts of alkylbenzene sulfonic acids are widely used in the home and industry in applications where it is required that the detergent formulation have the properties of high water solubility and mildness, such as in shampoo formulations. The triethanolamine salts of alkylbenzene sulfonic acids are more water soluble and less irritating than the corresponding alkali or alkaline-earth metal salts, such as the sodium and magnesium salts. Whereas the concentration of the triethanolamine alkylbenzene sulfonates normally ranges from weight percent to about 35 weight percent in the end-use product, it is expedient for the manufacturer of the detergent sulfonates to prepare concentrated aqueous solutions containing from about 45 weight percent to about 70 weight percent of the triethanolamine alkylbenzene sulfonates during the manufacturing process thereof. This concentrated solution is diluted to the extent desired at the time convenient for the preparation of the end-use product. The advantage of working with a concentrated solution is an economic one, in that the greater the amount of detergent per volume of water that can be stored or transported, the cheaper the attendant costs will be. The cost savings are substantial in view of the fact that in the detergent industry the manufacturer of the detergent sulfonate is not generally the manufacturer of the end-use product and the detergent sulfonate, consequently, must be conveyed, sometimes over long distances, from the one manufacturer to the other.

The manufacturer of the end-use product who, in addition to preparing the detergent formulation which the consumer buys, prepares concentrated specialty formulations for commercial establishments, also realizes an advantage in being able to purchase concentrated sulfonate solutions. For example, it is not uncommon for the manufacturer of the end-use product to sell concentrated shampoo formulations which contain additional ingredients along with the sulfonate to beauty salons. The large amounts of shampoo which the beauty salon operators use dictate that they buy concentrated shampoo formulations for the same reasons the manufacturer of the sulfonate prepares concentrated sulfonate solutions: If

the manufacturers of the end-use product received a dilute sulfonate solution from the manufacturer of the sulfonate they would incur an additional expense by having to further concentrate the solution. However, by receiving concentrated sulfonate solutions they may add additional ingredients, that may also be dissolved in water, to the sulfonate solution without having to resort to evaporation of the water to attain the desired high solids content in the final shampoo formulation.

Presently the bulk of the triethanolamine alkylbenzene sulfonates that are marketed commercially are mixtures of compounds that are derived from propylene polymer detergent formulations.

, above.

3,303,138 Patented Feb. 7, 1967 wherein the alkyl side chain is highly branched and contains approximately 10 to 15 carbon atoms with an average of about 12 carbon atoms. Aqueous solutions containing 1 to 62 weight percent or more of these compounds are clear, free-flowing liquids which can be stored and transported very conveniently. However, as this class of detergents is not biodegradable and since the detergent industry is striving to market only biodegradable detergents as a means of eliminating detergent pollution, these compounds are no longer desirableingredients in As it is known that straight chain secondary alkylbenzene sulfonates are biodegradable, it would seem to be a simple expedient to substitute these compounds for the corresponding branched chain compounds for use in the applications described However, when this substitution is made, it has been found that as the concentration of triethanolamine straight chain secondary alkylbenzene sulfonates in water is increased beyond about 40 weight percent, viscous gellike slurries are obtained and when the concentration of thestraight chain sulfonates is increased to 45 and higher weight percent, non-flowing, solid gels are formed. These gel-like slurries and non-flowing, solid gels are virtually impossible to pour and pump and generally create handling problems. Although aqueous solutions containing lower concentrations of triethanolamine straight chain secondary alkylbenzene sulfonates are nongelling and free-flowing, their high water content makes them uneconomical to store, transport, and formulate for certain applications. It, therefore, would -be extremely desirable to provide non-gelling, aqueous solutions containing in excess of about 45 weight percent triethanolamine straight chain secondary alkylbenzene sulfonates.

It is therefore an object of this invention to provide non-gelling, aqueous solutions which contain triethanolamine straight chain secondary alkylbenzene sulfonates in an amount exceeding about 45 weight percent. It is a further object of this invention to provide a method for producing non-gelling, aqueous solutions which contain triethanolamine straight chain secondary alkylbenzene sulfonates in an amount exceeding about 45 weight percent.

Other objects will become apparent from the description of the invention and from the claims.

In accordance with the instant invention, it has been found that about 45 to about 70 weight percent aqueous solutions of triethanolamine straight chain secondary alkylbenzene sulfonates that contain compounds selected from the group consisting of glycols, polyglycols, hydroxy diamines, certain derivatives of cycloimidine, and N-alkyl substituted beta-amino propionic acids and salts thereof are non-gelling compositions. It has also been found that these compounds, hereinafter described more particularly and referred to as degelling agents, are effective in increasing the solubility and decreasing the viscosity of the gel-like slurries. It should be understood that the term solution as used herein and in the claims includes homogeneous clear solutions and non-gelling slurries wherein some solid sulfonate particles are in equilibrium with the solution. The degelling agentor mixtures thereof may be incorporated into aqueous solutions of triethanolamine straight chain secondary alkylbenzene sulfonates in minimum amounts, that is in amounts just suflicient to prevent said sulfonate solution from forming a gel, or additional amounts of the degelling agent may be added to increase the solubility and decrease the viscosity of the slurry to the extent desired. The effective amounts of degelling agent will vary depending on the particular compound used and the concentration of the triethanolamine straight chain secondary alkylbenzene sulfonates in aqueous solution in that more concentrated solutions will require higher amounts of the degelling agent. Theamount of degelling agent required will also depend upon the degree of water solubility of the particular triethanolamine straight chain secondary alkylbenzene sulfonates being utilized. For instance, those compounds with the shorter side chain will require less degelling agent. .Generally there will be required the presence of about 2 weight percent degelling agent, although the more highly concentrated sulfonate solutions may require as much as weight percent degelling agent. In instances where it is also desired to increase the solubility and decrease the viscosity of the gel-like sulfonate slurry, slightly higher amounts of degelling agent are necessary.

The triethanolamine alkylbenzene sulfonates which form gels in concentrated aqueous solutions as hereinabove described are characterized by having a straight alkyl side chain containing 9 to carbon atoms wherein the alkyl side chain is attached to a carbon atom of the benzene nucleus at a secondary carbon atom of the chain. Normally detergent formulations are prepared from mixtures of the, above compounds wherein the average number of carbon atoms in the alkyl side chain ranges from 10 to 13. The carbon number spread of the alkyl side chain may range as high as 7, as in mixtures which contain 9 to 15 carbon atoms in the alkyl side chain, or as low as 2. The preferred mixture is triethanolamine straight chain secondary alkylbenzene sulfonates that has a carbon number spread of three or four wherein the average number of carbon atoms in the alkyl side chain is 1-1 to 12. These blends of compounds have excellent overall surface active properties.

The triethan-olamine straight chain secondary alkylbenzene sulfonates used in this invention may be prepared by any one of a number of well-known methods. For example, a halogenated normal paraffin which contains from 9 to 15 carbon atoms and which is obtained by mono-chlorinating the corresponding paraffin can be treated with an excess of benzene in the presence of a suitable alkylation catalyst of the Friedel-Crafts type, such as aluminum chloride, to obtain substantial yields of secondary straight chain alkylated benzene. These alkylated benzene compounds may also be prepared by alkylating benzene with a normal alcohol or a normal mono-olefin containing 9 to 15 carbon atoms in the presence of a Friedel-Crafts catalyst. The alkylated benzenes having a straight chain alkyl group containing from 9 to 15 carbon atoms or a mixture of alkylated benzenes within this carbon number range is then subjected to sulfonation. This may be accomplished with oleum, sulfuric acid or sulfur trioxide. If sulfur trioxide is used, the sulfonic acids may be directly neutralized with triethanolamine in the presence of a suitable amount -of water to obtain the desired solids concentration for the final product. If sulfuric acid or oleum is used for sulfonation, spent acid must first be settled out. This may be rendered faster and more complete by dilution of the reaction mixture with a solvent such as benzene or hexane or mixtures there-of. The sulfonic acids may then be extracted from the benzene or hexane solvent With water and methanol or other low molecular weight alcohol solution, to purify the sulfonic acids of any unreacted hydrocarbon or any hydrocarbon soluble by-products such as sulfones. The sulfonic acids in the aqueous alcohol solution are then neutralized with triethanolamine. The alcohol is removed from the neutralized sulfonate solution by stripping and a concentrated aqueous solution of the triethanol-amine sulfonate is prepared by evaporation of a suitable amount of water.

The glycols suitable for use in the practice of this invention are those which are highly soluble in water and are characterized by the general formula:

n zn 2 4 wherein n ranges from 2 to 7. These glyvcols may be straight or branched chain in structure. Examples of appropriate glycols are ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butane diol, 2,4-penta-ne diol, 1,6-hexane diol, 2-methyl-2,4-pentane diol, 2,3-dimethyl- 2,3-butane diol, 2,4-heptane diol, and 2,2-diethyl-1,3- propane diol. It should be understood that only those glycols which are highly water soluble are useful and preferred as ingredients for the composition of this invention and that glycols of relatively low water solubility such as 2-methyl-1,3-pentane diol are obviously not preferred for practicing this invention. Glycols are well known commercial compounds and may be prepared in a variety of ways which have been described both in the technical literature and patented art.

The polyglycols suitable for use in the practice of this invention are the highly water soluble polyethylene and polypropylene glycols characterized by the general formu a:

wherein R is an alkylene radical having from 2 to 3 carbon atoms and n is an integer rangingfrom 2 to about when R contains 2 carbon atoms and wherein n ranges from 2 to about 9 when R contains 3 carbon atoms. Only those polyglycols which are highly water soluble are suitable as components in the composition of this invention. Thus, polyethylene glycols ranging in molecular weight up to about 6,000 and polypropylene glycols ranging in molecular weight up to about 600 may be successfully utilized. The higher molecular weight polyethylene and polypropylene glycols that are most readily available commercially are mixtures of a number of ethylene oxide polymers. These mixtures, which are identified by their average molecular weight, are also effective as degelling additives. Exemplary polyethylene glycols are diethylene glycol, triethylene glycol, and the higher molecular weight polyethylene glycols whose average molecular weight ranges from 190 to 210, 570 to 630, 1300 to 1600, and 3000 to 3700. Exemplary polypropylene glycols are d-ipropylene glycol, tripropylene glycol, and the higher molecular weight polypropylene glycols whose average molecular weight ranges for example from to and 400 to 450. The polyglycols may be prepared by polymerizing the corresponding alkylene oxide in the presence of an acid or alkaline catalyst.

The hydroxy diamines suitable for use in the practice of this invention are characterized by the formula:

wherein R is an alkyl radical containing from 2 to 10 carbon atoms, R is an alkylene radical containing from 2 to 10 carbon atoms and wherein the sum of the car-bon atoms in the R and R groups ranges from 8 to about 18, and R is selected from the group consisting of hydrogen and an alkyl radical containing from 1 to. about 5 carbon atoms. The compounds are normally derived from suitable chain length mono-olefinic monocarboxylic acids which are converted to the corresponding unsaturated amine by reaction with ammonia and hydrogen. The mono-olefinic primary amine is then epoxidized and the hydroxy diamines described above are obtained by reacting the epoxy linkage with ammonia or suitable derivatives of ammonia such as methyl amine, dimethyl amine, ethyl amine, diethyl amine, and the like. Exemplary hydroxy diamines suitable for practicing this invention are -9-a-mino IO-hydroxy stearylamine, 3-dimethylamino 4-hydroxy octylamine, and 8-propylamine 9-'hydroxy dodecylamine.

The N-alkyl substituted beta-amino propionic acids and salts thereof which are suitable for practicing this invention are characterized by the general formula:

wheren R is an alkyl radical containing from 8 to about 18 carbon atoms, R is selected from the group consisting of hydrogen and the radical and X is selected from the group consisting of hydrogen and an alkali metal.

When R is hydrogen the compounds are N-alkyl betaamino propionic acids or the corresponding alkali metal salts. These compounds may be most conveniently derived by appropriate conversion steps from a suitable chain length fatty acid such as octanoic, lauric, tetradecanoic, and mixtures of organic acids such as those derived from coconut oil and tallow. The selected acid is reacted with ammonia to prepare a fatty nitrile which is then hydrogenated to the primary amine. An ester of acrylic acid such as methyl acrylate is condensed with the primary amine to obtain the corresponding alkyl substituted betaamino propionate ester which is then hydrolyzed to the free acid or converted to the alkali salt. Exemplary compounds are N-decyl beta-amino propionic acid, sodium N-dodecyl beta-amino propionate, potassium N-pentadecyl beta-amino propionate, and N-lauryl myristyl beta-amino propionic acid which is derived from a mixture of lauric and myristic acid.

When R in the above described formula is the radical wherein X is as defined above, the compounds'are N- alkyl beta-iminodipropionic acids or their corresponding alkali metal salts. Preparation of these compounds is also well known to those skilled in the art. For example, an alkyl substituted beta-amino propionate ester, the preparation of which isdescribed above rnay be condensed with additional amounts of an ester of acrylic acid to obtain the corresponding dipropionate ester which can then be hydrolyzed to the corresponding free acid or converted to the partial or complete alkali salt. Exemplary compounds are N-undecyl beta-iminodipropionic acid, the partial sodium salt of N-octyl beta-iminodipropionic acid and disodium N-alkyl beta-iminodipropionic acid wherein the alkyl group is derived from tallow acid.

The derivatives of cycloimidine which are useful in the practice of this invention are characterized by the formula:

wherein R is an alkyl radical containing 4 to 18 carbon atoms, X is an alkali metal, and n is the integer -1 or 2.

When n is 1, these compounds may be referred to generally as the alkali metal salt of a substituted quaternary hydroxy cycloimidinic acid alkali metal alcoholate. These compounds are produced by reacting an organic acid or a mixture of organic acids containing 4 to 18 carbon atoms with aminoethylethanolamine to produce a cycloimidine. Exemplary organic acids are hexanoic acid, decanoic acid, tetradecanoic acid, octadecanoic acid, and the natural occurring acids such as the coconut and tallow acids. The cycloimidine is then reacted with an equal molar quantity of a monohalocarboxylic acid such as monochloroacetic acid in the presence of 2.7 to 3 moles of alkali such as caustic soda to produce the alkali metal salt of substituted quaternary hydroxy cycloimidinic acid alkali metal alcoholate. Preparation of these compounds is described in US. Patent No. 2,528,378 to Mannheimer. These compounds may be moreiparticularly referred to as alkyl ethyl cycloimidinium l-hydroxy 3-et-hyl alkali metal alcoholate, Z-methyl alkali metal carboxylates.

"When n is 2 in the above described formula, the compounds are the dicarboxylic analogues of the alkali metal salts of the substituted quaternary hydroxy cycloimidinic acid alkali metal alcoholates. These compounds may be produced by making a cycloimidine as described above but thereafter reacting the cycloimidine with an excess molar quantity of a monohalo-carboxylic acid such as monochloroacetic acid, and larger amounts of alkali. Preparation of these compounds is particularly described in US. Patent No. 2,773,068 to Mannheimer. These compounds may be referred to as alkyl ethyl cycloimidinium l-hydroxy ethoxyethanoic acid-2, ethanoic acid alkali metal salt.

The compositions of this invention may be prepared in various ways, the choice of which depends on the method used to sulfonate the alkylated benzene. When the alkylated benzene is sulfonated with sulfuric acid or oleum, and a hydrocarbon solvent and an alcohol-water extraction is used to aid in separating spent acid, and in purifying the sulfonic acids, the triethanolamine sulfonate solution resulting from neutralization is usually less than 40 weight percent solids. The degelling agent can be added at any time before or during concentration by distillation or evaporation to the desired high solids content of about 45 to 70 weight percent. For practical ease in mixing and concentrating, the degelling agent is preferably added at any time before the gel-like slurry forms.

When the alkylated benzene is sulfonated with sulfur trioxide or with sulfuric acid or oleum without the use of solvents to aid in separating spent acid or unreacted hydrocarbons, common practice is to neutralize the alkylbenzene sulfonic acids with triethanolamine in the presence of the necessary amount of water to give directly the desired solids content of the final product. In this case, an aqueous solution containing triethanolamine and degelling agent should be prepared. The alkylbenzene sulfonic acids are then admixed with this aqueous solution for reaction to form the non-gelling triethanolamine alkylbenzene sulfonate.

The examples included in Table 1 below serve to illustrate and compare the gelling properties of aqueous solutions of triethanolamine salts of branched chain and straight chain alkylbenzene sulfonic acids. The triethanolamine branched chain alkylbenzene su'lfonates are a mixture of compounds containing from 9 to 15 carbon atoms in the alkyl side chain with an average of about 12 carbon atoms and are derived from the sulfonation by sulfuric acid of alkylate produced from propylene tetramer and benzene using AlCl 1 catalyst. The triethanolamine straight chain secondary alkylbenzene sulfonates are a mixture of compounds containing 9 to 14 carbon atoms in the side chain with an average of about 12 carbon atoms and are derived from the sulfonation by sulfuric acid of alkylate produced from alpha olefins and benzene using AlCl catalyst. The numbers which appear under the column headed Amount of Detergent in Weight Per-- cent refer to the total weight percent solids present in the aqueous composition. The solids, in addition to the alkylbenzene sulfonates, contain the normal amounts of bY-iPIOdUClLS such as triethanolamine sulfate, and triethanolamine, which are present in a commercially manufactured product. The alkylbenzene sulfonates comprise about weight percent of the total solids present.

7 TABLE I Aqueous Composition The table illustrates the unexpected difierence in the gelling properties of triethanolamine branched and straight chain alkylbenzene sulfonates. Moreover, it was surprising to find that the monoand diethanolamine salts of straight chain secondary alkylbenzene sulfonates do not form a solid gel in concentrated aqueous solutions. They form flowable slurries and as such behave similarly to their corresponding branched chain sulfonates.

It was also surprising to find that the triethanolamine straight chain secondary alkylbenzene sulfonates are only about 40 weight percent water soluble. The fact that the triethanolamine branched chain alkylbenzene sulfonates are about three times more water soluble than the corresponding sodium sulfonates (about 60 weight percent vs. 20 weight percent) coupled with the fact that the sodium salts of straight chain secondary alkylbenzene sulfonic acids are almost twice as soluble as the sodium salts of branched chain alkylbenzene sulfonic acid (about 35 weight percent vs. 20 weight percent) would lead one to expect that the triethanolamine straight chain secondary alkylbenzene sulfonates would be much more water soluble than the corresponding sodium sulfonates and consequently have a water solubility much in excess of 40 weight percent. However, it should be understood that it is not primarily lack of water solubility that creates the practical problems associated with triethanolamine straight chain secondary alkylbenzene sulfonates because the corresponding sodium sulfonates which are slightly less soluble can be concentrated up to 60 weight percent in water and still remain a fiowable gel-like slurry at room temperature that can be pumped andhandled albeit with some difficulty. It is the fact that the triethanolamine straight chain secondary alkylbenzene sulfonates at concentrations in excess of about 45 weight percent in water are a solid gel that prevents their use in commerce.

The examples included in Table II below serve to describe specific compositions of this invention, the effectiveness of the degelling agents hereinabove described, and the approximate range of amounts of degelling agents required to produce non-gelling compositions. The triethanolamine straight chain secondary alkylbenzene sulfonate is the same as that used in the examples presented in Table I. The compositions represented by Examples 9 to 16 were prepared simply by admixing the degelling additives with aqueous solutions of the sulfonate compounds and evaporating a sufficient amount of water to obtain the stated concentrated products. However because of the volatility of 2-methyl-2,4-pentane diol at the temperature of evaporation, the compositionsv represented by Examples 7 and 8 were prepared by adding this glycol to the sulfonate after evaporation of the water to the stated concentration ie. the glycol was added to the gel and admixed therewith until the gel was broken and a homogeneous solution was obtained.

TABLE II Aqueous composition TEA straight Descrip- Degelling chain tion* of Ex. additive secondary composi- N o Degelling additive in Weight alkylbention percent zene sulfonate in weight percent 7 Z-methyl-ZA-pentanediol 10. 0 60 1 8 do 7. 5 60 2 9 Polyethylene glycol, aver- 1. 0 59 4 age molecular weight 1,300l,600. 10 --do 3.0 57 3 11.... Q-diethylamino l0- 3. 0 57 1 hydroxy stearyl amine. 12 Partial sodium salt of 5. O 55 1 N -lauryl betaiminodipropionic acid. l3 N-lauryl, myristyl beta- 5.0 55 2 amino propionic acid. 14...- Undecyl ethyl cyclo- 5. 0 55 1 imidinium l-hydroxy ethoxyethanoic acid-2 ethanoic acid disodium s 15 Coconut ethyl cyclo- 3. 0 57 2 imidiniurn l-liydroxy 3-ethyl sodium alcoholate 2-methyl sodium carboxylate. 16".. do 1.8 58.2 4

*1Clear, free-flowing liquid.

2Haz-y liquid.

3I-Iazy gel, slight flow when inverted.

4Gel, no flow when inverted.

Although the gelling of triethanolamine straight chain secondary alkylbenzene sulfonates may be considered at least partly a solubility problem, several difierent types of solubilizing agents and hydrotropes were not effective in preventing the gel from forming as illustrated by the compositions represented by Examples 17 and 18 in Table III below. The compositions included in Table III also serve to illustrate that compounds containing functional groups similar to those in compounds successfully used as degelling agents were ineffective in preventing gel formation. The triethanolamine straight chain secondary alkylbenzene sulfonate included in Table III is the same as that used in the examples presented in Tables I and II.

TABLE III Aqueous composition TEA straight Descripchain tion of Ex. additive secondary composi- No. addltlve in weight alkylbention percent zene sulfonate in weight percent 17 Triethanolamine salts of 10. 0 50. 4

xylene sulfonic acids. 18.. Dimethyl naphthalene 5. 0 55 4 sodium sulfonate. 19..-- Polymerizcd sodium salts 5. 0 55 4 of short chain alkyl naphthalene sulfonic acid. 20..-. Laurie acid diethanol- 5. 0 55 4 amine condensate. 21...- Mixed polyethylene- 3.0 57 4 propylene glycol, 1750 mol. wt. of polypropylene oxide hydrophobe base, 40% polyethylene oxide. 22 Ethylene glycol mono- 3. 0 57 4 stearate.

*4-Gel, no flow when inverted.

The phenomenon of gel formation of concentrated aqueous compositions of triethanolamine straight chain secondary alkylbenzene sulfonate and the behavior of the degelling agents is not completely understood. However it is generally accepted that the triethanolamine straight chain secondary alkylbenzene sulfonate molecules form micelles with the hydrophobic end of each molecule oriented toward the center of the micelle and the hydrophilic end oriented away from the center. It is theorized that the hydrogen in the OH group of the triethanolamine salt hydrogen bonds to adjacent molecules in the same micelle giving a rigid structure to the micelle and, consequently a gel is formed. It is also theorized that the effective degelling agents are structures of particular molecular shape and functionality that sandwich themselves between the triethanolamine straight chain secondary alkylbenzene sulfonate molecules in the micelle to increase the distance sufiiciently between the OH groups of the triethanolamine salt to prevent hydrogen bonding and therefore prevent rigid gel structures from being formed. It is also thought that concentrated aqueous compositions of triethanolamine branched chain alkylbenzene sulfonates do not gel because the branching in the alkyl side chain keeps the individual molecules in the micelle a distance far enough apart to prevent hydrogen bonding and hence gel structures.

It is understood that the above explanation should in no way be construed to limit the claimed compositions of this invention.

The compositions of this invention are useful as bubble bath detergents or fine fabric detergents. When so used, small amounts of additional ingredients, such as perfumes and dyes, may be added to the compositions for aesthetic reasons. On the other hand, the compositions of this invention may be diluted with water or formulated with additional ingredients to prepare detergents suitable for use in other applications, such as shampoos.

We claim:

- 1. A non-gelling aqueous solution consisting essentially of an amount in excess of about 40 weight percent and ranging up to about 70 weight percent of triethanolamine straight chain secondary alkylbenzene sulfonates, said sulfonates having a straight alkyl side chain length of 9 to 15 carbon atoms, and an organic degelling compound in amounts at least sufiicient to prevent the gelling in aqueous solution of said sulfonates, said compound being selected from the group consisting of glycols, polyglycols, hydroxy diamines, N-alkyl substituted beta-amino propionic acids and salts thereof and derivatives of cycloimidine, wherein:

(a) said glycols are highly water soluble glycols characterized by the formula C H (OH) wherein n ranges from 2 to 7, and wherein,

(b) said polyglycols are highly water soluble polyglycols characterized by the formula wherein R is an alkylene radical having from 2 to 3 carbon atoms and n is an integer ranging from 2 to about 135 when R contains 2 carbon atoms and wherein n ranges from about 2 to about 9 when R contains 3 carbon atoms and wherein,

(c) said hydroxy diamines are characterized by the formula wherein R is an alkyl radical containing from 2 to 10 carbon atoms, R is an alkylene radical containing from 2 to 10 carbon atoms, and wherein the sum of the carbon atoms in the R and R groups ranges from 8 to about 18, and R" is selected from the group consisting of hydrogen and an alkyl radical containing from 1 to about carbon atoms, and wherein,

(d) the alkyl substituted beta-amino propionic acids and salts thereof are characterized by the general formula:

wherein R is analkyl radical containing from 8 to about 18 carbon atoms, R is selected from the group consisting of hydrogen and the radical and X is selected from the group consisting of hydrogen and an alkali metal and wherein, (e) the derivatives of cycloimidine are characterized by the formula:

CH2 O N CH2 CH2CH2O(CH2- C)n-1X Rt il l i O I H OH OHz-C-OX wherein R is an alkyl radical containing 4 to about 18 carbon atoms, X is an alkali metal, and n is an integer selected from the group consisting of 1 and 2.

2. A composition according to claim 1 wherein said organic degelling compound is a glycol.

3. A composition according to claim 2 wherein said glycol is Z-methyl 2,4-pentane diol.

4. A composition according to claim 1 wherein said organic degelling compound is a polyglycol.

5. A composition according to claim 4 wherein said polyglycol is polyethylene glycol having an average molecular weight ranging from 1300 to 1600.

6. A composition according to claim 1 wherein said organic degelling compound is a hydroxy diamine.

7. A composition according to claim 6 wherein said hydroxy diamine is 9-diethylamino IO-hydroxystearyl amine.

8. A composition according to claim 1 wherein said organic degelling compound is an alkyl substituted betaamino propionic acid and salts thereof.

9. A composition according to claim 8 wherein said propionate is the partial sodium salt of N-lauryl betaimino dipropionic acid.

10. A composition according to claim 8 wherein said propionic acid is N-lauryl, myristyl beta-amino propionic acid.

11. A composition according to claim 1 wherein said organic degelling compound is a derivative of cycloimidine.

12. A composition according to claim 11 wherein said cycloimidine is coconut ethyl cyclo-imidinium l-hydroxy 3-ethyl sodium alcoholate 2-methyl sodium carboxylate.

13. A composition according to claim 11 wherein said cycloimidine is undecyl ethyl cycloimidinium l-hydroxy ethoxyethanoic acid-2 ethanoic acid disodium salt.

14. A non-gelling aqueous solution consisting essentially of about 60 weight percent triethanolamine straight chain secondary alkylbenzene sulfonates, said sulfonates having .a straight alkyl side chain length of 9 to 15 carbon atoms and an organic degelling compound in amounts at least sufiicient to prevent the gelling in aqueous solution of said sulfonates, said compounds being selected from the group consisting of glycols, polyglycols, hydroxy diamines, N-alkyl substituted beta-amino propionic acids and salts thereof and derivatives of cycloimidine, wherein:

(a) said glycols are highly water soluble glycols characterized by the formula C H (OH) wherein n ranges from 2 to 7, and wherein,

(b) said polyglycols are highly water soluble polyglycols characterized by the formula wherein R is an alkylene radical having from 2 to 3 carbon atoms and n is an integer ranging from 2 to about 135 when R contains 2 carbon atoms and wherein n ranges from about 2 to about 9 when R contains 3 carbon atoms and wherein,

(c) said hydroxy diamines are characterized by the formula wherein R is an alkyl radical containing from 8 to about 18 carbon atoms, R is selected from the group consisting of hydrogen and the radical and X is selected from the group consisting of hydrogen and an alkali metal and wherein, (e) the derivatives of cycloimidine are characterized 'by the formula:

CH2 CHrOHr-O(CHgCO)n-1X RC N 12 wherein R is an alkyl radical containing 4 to about 18 carbon atoms, X is an alkali metal, and n is an integer selected from the group consisting of 1 and 2.

15. A composition according to claim 14 wherein said organic degelling compound is a glycol. v

16. A composition according to claim 15 wherein said glycol is Z-methyl 2,4-pentanediol.

17. A composition according to claim 14 wherein said organic degelling compound is a polyglycol.

18. A composition according to claim 17 wherein'said polyglycol is a polyethylene glycol having an average molecular weight ranging from 1300 to 1600.

19. A composition according to claim 14 wherein said organic degelling compound is a hydroxy diamine.

20. A composition according to claim 19 wherein said diamine is 9-diethylamino IO-hydroxy stearylamine.

21. A composition according to claim 14 wherein said organic degelling compound is an alkyl substituted betaamino propionic acid and salts thereof.

22. A composition according to claim 21 wherein said propionate is a partial sodium salt of N-lauryl beta-imino dipropionic acid.

23. A composition according to claim 21 wherein said propionic acid is N-lauryl myristyl beta-imino propionic acid.

24. A composition according to claim 14 wherein said organic degelling compound is a derivative of cycloimidine.

25. A composition according to claim 24 wherein said cycloimidine is undecyl ethyl cycloimidinium l-hydroxy ethoxyethanoic acid-2 ethanoic acid disodium salt.

26. A composition according to claim 24 wherein said cycloimidine is coconut ethyl cycloimidinium l-hydroxy 3-ethyl sodium alcoholate Z-methyl sodium carboxylate.

References Cited by the Applicant UNITED STATES PATENTS 2,679,482 5/1954 Ross. 3,005,777 10/1961 Terry.

LEON D. ROSDOL, Primary Examiner.

SAMUEL H. BLECH, Examiner.

S. E. DARDEN, Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,303,138 February 7, 1967 William J. De Witt et al.

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 10, lines 20 to 24, the formula should appear as shown, below instead of as in the patent;

Signed and sealed this 17th day of October 1967.

(SEAL) Attest:

EDWARD J. BRENNER

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2679482 *Oct 8, 1949May 25, 1954Colgate Palmolive CoSynthetic detergent compositions
US3005777 *Nov 2, 1959Oct 24, 1961Continental Oil CoManufacture of surface-active compositions
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3463736 *Mar 4, 1966Aug 26, 1969Atlantic Richfield CoAqueous slurries of triethanolamine salts of linear alkylbenzene sulfonic acids
US3920807 *Jan 22, 1975Nov 18, 1975Lever Brothers LtdAntiperspirant and deodorant compositions
US3925227 *Sep 28, 1973Dec 9, 1975American Home ProdNovel laundering compositions
US3935130 *Jul 12, 1973Jan 27, 1976Kabushiki Kaisha Tsumura JuntendoDetergent composition for cleaning bathtubs
US4107095 *Apr 11, 1973Aug 15, 1978Colgate-Palmolive CompanyLiquid olefin sulfonate detergent compositions containing anti-gelling agents
US4880569 *Jan 5, 1988Nov 14, 1989Lever Brothers CompanyConcentrated liquid detergent composition containing anionic surfactants having non-terminal sulfonate groups
US20100317522 *Dec 12, 2008Dec 16, 2010Cognis Ip Management GmbhAdjuvants for Agrochemical Applications
WO2009080225A2 *Dec 12, 2008Jul 2, 2009Cognis Ip Management GmbhAdjuvants for agrochemical applications
WO2009080225A3 *Dec 12, 2008Jun 17, 2010Cognis Ip Management GmbhAdjuvants for agrochemical applications
Classifications
U.S. Classification510/426, 562/571, 510/432, 510/490, 562/553, 510/499, 510/135, 510/500, 510/292, 510/428
International ClassificationC11D3/16, C11D17/00, C11D1/02, C11D1/22
Cooperative ClassificationC11D3/16, C11D1/22, C11D17/0008
European ClassificationC11D1/22, C11D3/16, C11D17/00B