US3414593A - Alpha-sulfo peroxy fatty acid detergent compounds - Google Patents

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United States Patent 0 3,414,593 ALlHA-SULFO PEROXY FATTY ACID DETERGENT COM J.

Peter Robson, Whitley Bay, Northumberlaud, England,

assignor to The Procter & Gamble Company, Cmcinnati, Ohio, a corporation of Ohio No Drawing. Filed Aug. 16, 1965, Ser. No. 480,135

Claims priority, application Great Britain, Aug. 20, 1964,

34,074/64 3 Claims. (Cl. 260-400) ABSTRACT OF THE DISCLOSURE Novel alpha-sulfo peroxy fatty acid compounds as detergents and bleaching agents; and detergent compositions containing said alpha-sulfo peroxy fatty acid compounds.

This invention relates to wetting and detergent compounds which are not only detergents, but also bleaching wherein R is an alkyl group of from about 8 to about 18 carbon atoms, and wherein X and Y are each selected from the group of cations consisting of hydrogen, sodium, potassium, ammonium and substituted ammonium cations and by providing detergent compositions containing such compounds as hereinafter more fully described. The compounds of this invention comprise the alpha-sulfo peroxy fatty acids which are necessary intermediates in the production of the corresponding salts.

The alpha-sulfo peroxy fatty acids of this invention are obtained from the corresponding alpha-sulfo fatty acids or their mono methyl esters by reaction with a suitable peroxide, but preferably hydrogen peroxide, in methanesulfonic acid which serves as both solvent and catalyst. The alpha-sulfa fatty acids used as starting materials may be obtained by sulfonation of the corresponding decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, and eicosanoic acid by the action of stabilized sulfur trioxide in carbon tetrachloride solution.

By using the corresponding saturated fatty acids in this way, each of the compounds of this invention, namely alpha-sulfo peroxy decanoic acid, alpha-sulfo peroxy undecanoic acid, alpha-sulfo peroxy dodecanoic acid, alphasulfo peroxy tridecanoic acid, alpha-sulfa peroxy tetradecanoic acid, alpha-sulfo peroxy pentadecanoic acid, alphasulfo peroxy hexadccanoic acid, alpha-sulfo peroxy heptadecanoic acid, alpha-sulfo peroxy octadecanoic acid, alpha-sulfo nonadecanoic acid, and alpha-sulfo eicosanoic acid can be prepared. The sodium, potassium, ammonium, or substituted ammonium salts of each of these acids can be obtained by reaction with an appropriate base. Substituted ammonium cations include monoethanolammonium, diethanolammonium and triethanolammonium cations.

The new compounds in which R is an alkyl group of from 8 to 18 carbon atoms, particularly in the form of ice their water soluble salts, have both detergent and bleaching properties and are, therefore, useful ingredients of washing and bleaching compositions. Alpha-sulfo peroxy hexadecanoic monosodium salt was found to be an especially good bleaching detergent and is therefore especially preferred. The alpha-sulfo fatty acid salts which are formed by the release of oxygen during the bleaching process have detergent properties, so that the detergency of such compositions persists after the bleaching power has been exhausted.

In detergent compositions, any of the water soluble salts of the new compounds can be used as the only detergent ingredient since they are all useful per se as detergents and surface active agents, or they can be used in admixture with each other, or they can be used in admixture with other detergents.

Examples of such other suitable detergents which can be used in conjunction with these novel detergent compounds are:

(1) Soap wherein the fatty acids contain from about 8 to about 22 carbon atoms and wherein the cation is selected from the group consisting of sodium, potassium, ammonium and substituted ammonium cations. Specific examples are the ordinary alkali metal soaps such as the sodium and potassium salts of the higher fatty acids of naturally occurring plant or animal esters (e.g., palm oil, coconut oil, babassu oil, soybean oil, castor oil, tallow, whale and fish oils, grease and lard, and mixtures thereof) or of synthetically produced fatty acids (e.g., by the oxidation of petroleum, or by hydrogenation of carbon monoxide by the Fisc'her-Tropsch process), of resin acid (e.g., rosin and those resin acids in tall oil) and/ or of napthenic acids. Sodium and potassium soaps can be made by direct saponification of the fats and oils or by the neutralization of the free fatty acids which are prepared in a separate manufacturing process.

(2) Synthetic organic detergents characterized by their high solubility in Water, their resistance to precipitation by the constituents of hard water and their surface active and effective detergent propreties, including:

(a) Anionic synthetic detergents (excluding true soaps): This class of synthetic detergents can be broadly described as the water-soluble salts, particularly the alkali metal salts, or organic sulfuric reaction product having in the molecular structure an alkyl radical containing from about 8 to about 22 carbon atoms and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals. Important examples of the synthetic detergents which form a part of the preferred compositions of the present invention are the sodium or potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols produced by reducing the glycerides of tallow or coconut oil; sodium or potassiumalkyl benzene sulfonates, in which the alkyl group contains from about 9 to about 15 carbon atoms, especially those of the types described in United States Letters Patent Nos. 2,220,099 and 2,477,383; sodium alkyl glyceryl ether sulfonates, especially those ethers of the higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfates and sulfonates; sodium or potassium salts of sulfuric acid esters of the reaction product of one mole of a higher fatty alcohol (e.g., tallow or coconutoil alcohols) and from 1 to about 10 moles of ethylene oxide; sodium or potassium salts of alkyl phenol ethylene oxide ether sulfate with 1 to about 15 units of ethylene oxide per molecule and in which the alkyl radicals contain from about 9 to about 15 carbon atoms; the reaction product of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide where, for example, the fatty acids are derived from coconut oil; sodium or potassium salts of fatty acid amide of a methyl taurine in which the fatty acids, for example, are

derived from coconut oil; and others known in the art, a number being specifically set forth in United States Letters Patent Nos. 2,486,921, 2,486,922 and 2,396,278.

(b) Nonionic synthetic detergents: This class of syn thetic detergents may be broadly defined as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, 'which may be aliphatic or alkyl aromatic in nature. The length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophobic group can be readily adjusted to yield a watersoluble compound having the desired degree of balance between hydrophlic and hydrophobic elements.

For example, a well known class of nonionic synthetic detergents is made available on the market under the trade name of Pluronic. These compounds are formed by condensing ethylene oxide with an hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The hydrophobic portion of the molecule which, of course, exhibits water insolubility has a molecular weight of from about 1500 to 1800. The addition of polyoxyethylene radicals to this hydrophobic portion tends to increase the water solubility of the molecule as a whole and the liquid character of the products is retained up to the point where polyoxyethylene content is about 50% of the total weight of the condensation product.

Other suitable nonionic synthetic detergents include:

(i) The polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl radical containing from about 6 to 12 carbon atoms in either a straight chain or branched chain configuration, with ethylene oxide, the said ethylene oxide being present in amounts equal to 10 to 25 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such compounds may be derived from polymerized propylene, diisobutylene, octane, or nonane, for example.

(ii) Those derived from the condensation of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamineproducts which may be varied in composition depending upon the balance between the hydrophobic and hydrophilic elements which is desired. For example, compounds containing from about 40% to about 80% polyoxyethylene by weight and having a molecular weight of from about 5000 to about 11,000, resulting from the reaction of ethylene oxide groups with a hydrophobic base, constituted of the reaction product of ethylene diamine and excess propylene oxide, said base having a molecular weight of the order of 2500 to 3000, are satisfactory.

(iii) The condensation product of aliphatic alcohols having from 8 to 18 carbon atoms, in either straight chain or branched chain configuration, with the ethylene oxide, e.g., a coconut alcohol ethylene oxide condensate having from 10 to 30 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction having from 10 to 14 carbon atoms.

(iv) 'Trialkyl amine oxides and trialkyl phosphine oxides wherein one alkyl radical contains from about 10 to about 18 carbon atoms, from to about ether linkages, and from 0 to about 2 hydroxy groups and wherein the other two alkyl radicals each contain from 1 to about 3 carbon atoms, from 0 to about 2 ether linkages, and from 0 to about 2 hydroxy groups. Specific examples are dedocyl diethanol amine oxide and tetradecyl dimethyl phosphine oxide.

(v) Dialkyl sulfoxide detergents having the formula wherein R is a hydrocarbon group containing from about to about 20 carbon atoms, from about 0 to 5 ether linkages, and from about 0 to about 3 hydroxy groups, there being at least one moiety of R which constitutes a carbon chain containing no ether linkages and containing about 10 to about 18 carbon atoms, and wherein R is a short alkyl chain containing from about 1 to about 3 carbon atoms having 0-2 hydroxyl groups attached to said short alkyl chain. Specific examples of such sulfoxides are octadecyl methyl sulfoxide, dodecyl methyl sulfoxide, tetradecyl methyl sulfoxide, S-hydroxytridecyl methyl sulfoxide, B-methoxytridecyl methyl sulfoxide, 3- hydroxy-4-dodecoxybutyl methyl sulfoxide, 2-hydroxyundecyl methyl sulfoxide, 2-hydroxydecyl methyl sulfoxide, and 2-decoxyethyl-2-hydroxyethyl sulfoxide.

(c) Zwitterionic detergents such as betaine and betainelike detergents wherein the molecule contains both basic and acidic groups which form an inner salt giving the molecule both cationic and anionic hydrophilic groups over a board range of wash water pH values. For example, suitable zwitterionic detergents include those having the formula wherein R contains from about 10 to about 18 carbon atoms and from about 0 to about 5 ether linkages, wherein R and R are each selected from the group consisting of alkyl groups containing from one to about three carbon atoms and hydroxy alkyl groups containing from one to about three carbon atoms, wherein R is selected from the group consisting of alkylene and hydroxy substituted alkylene groups containing from one'to about four carbon atoms, and wherein Z is selected from the group consisting of groups. Specific examples of such compounds are l-(hexadecyldimethylammonio) propane-3-sulfonate, l-(dodecyldimethylammonio) butane-3-sulfonate, and l-(dodecyldimethylammonio) acetate. Some other common examples of these detergents are described in US. Patents 2,082,- 275; 2,129,264; 2,217,846; 2,255,082; 2,702,279.

(d) Amphoteric and ampholytic detergents which can be either cationic or anionic depending upon the pH of the system and which are represented by detergents such as dodecylbeta-alanine, N-alkyltaurines such as the one prepared by reacting dodecylamine with sodium isethionate according to the teaching of US. 2,658,072, N- higher alkylaspartic acids such as those produced according to the teaching of US. 2,438,091, and the products sold under the trade name Miranol and described in US. Patent 2,528,378.

The detergent compositions of this invention contain from about 0% to preferably from 10% to 90%, of water soluble alkaline detergency builder salts, either of the organic or inorganic types, and should provide a washing solution pH of from about 9 to about 12. The ratio of builder salts to organic detergent is preferably from about 1:4 to about 20:1, more preferably from about 0.7:1 to about 9:1. Examples of suitable water soluble inorganic alkaline detergency builder salts are alkali metal carbonates, borates, phosphates, polyphosphates, bicarbonates and silicates. Specific examples of such salts are sodium and potassium tetraborates, bicarbonates, carbonates, tripolyphosphates, pyrophosphates, orthophosphates, and hexametaphosphates. Examples of suitable organic alkaline detergency builder salts are: (1) Watersoluble aminopolycarboxylates [e.g., sodium and potassium ethylenediaminetetraacetates, nitrilo triacetates, and N-(Z-hydroxyethyl)-nitrilo diacetates]; (2) Water-soluble salts of phytic acid (e.g., sodium and potassium phytatessee US. Patent 2,739,942); (3) Water-soluble salts of ethane-l-hydroxy-l,l-diphosphonate (e.g., the trisodium and tripotassium saltssee US. Patent 3,159,581; (4) Water-soluble salts of methylene diphosphonic acid (e.g., trisodium and tripotassium methylene diphosphonate and the other salts described in the copending application of Francis L. Diehl, Ser. No. 266,025, filed Mar. 18, 1963, now US. Patent 3,213,030); (5) Water-soluble salts of substituted methylene diphosphonic acids (e.g., trisodium and tripotassium ethylidene, isopropylidene, benzylmethylidene, and halomethylidene diphosphonates and the other substituted methylene diphosphonates disclosed in the copending application of Clarence H. Roy, Ser. No. 266,055, filed Mar. 18, 1963); (6) Water-soluble salts of polycarboxylate polymers and copolymers as described in the copending application of Francis L. Diehl, Ser. No. 269,359, filed Apr. 1, 1963, now US. Patent 3,260,153. (Specifically, a polyelectrolyte builder material comprising a water soluble salt of a polymeric alphatic polycarboxylic acid having the following structural relationships as to the position of the carboxylate groups and possessing the following prescribed physical characteristics: (a) a minimum molecular weight of about 350 calculated as to the acid form; (b) an equivalent weight of about 50 to about 80 calculated as to acid form; (c) at least 45 mole percent of the monomeric species having at least two carboxyl radicals separated from each other by not more than two carbon atoms; (d) the site of attachment to the polymer chain of any carboxyl-containing radical being separated by not more than three carbon atoms along the polymer chain from the site of attachment of the next carboxyl containing radical. Specific examples are polymers of itaconic acd, aconitic acid, maleic acid, mesaconic acid, fumaric acid, methylene malonic acid, and citraconic acid and copolymers with themselves and other compatible monomers such as ethylene), and (7) mixtures thereof.

Mixtures of organic and/or inorganic builders can be used and are generally desirable. Especially preferred are the mixtures of builders disclosed in the copending application of Burton H. Gedge, Ser. No. 398,705, filed Sept. 23, 1964, e.g., ternary mixtures of sodium tripolyphosphate, sodium nitrilotriacetate, and trisodium ethane-1- hydroxy-l,ldiphosphonate.

The detergent compositions of this invention can contain any of the usual adjuvants, diluents and additives, for example, perfumes, anti-tarnishing agents (e.g., sodium and potassium silicates and benzotriazole), anti-redeposition agents (e.g., alkali metal and ammonium salts of carboxymethyl cellulose), bacteriostatic agents, dyes or pigments (including optical brighteners), suds builders, suds depressors, and the like, without detracting from the advantageous properties of the composition.

Normally the organic detergent components, the builders and the minor ingredients are incorporated into the composition prior to conversion into final product form, e.g., detergent granules, flakes, etc., but they can also be added individually in the form of particles or as liquids.

All percentages, ratios and parts herein are by weight unless otherwise specified.

The following are examples which illustrate the preparation of alpha-sulfo peroxy fatty acid compounds and compositions of this invention. The following examples are not to be considered limiting, but are merely to serve to more fully describe my invention.

Example I Sixty grams of liquid sulfur trioxide were added dropwise to a vigorously stirred solution of 120 grams of hexadecanoic acid in 800 ml. of carbon tetrachloride cooled externally by an ice bath. When the addition was complete the mixture was heated to 60 C. and held at that temperature for one hour with continuous stirring. The carbon tetrachloride solvent and excess sulfur trioxide were evaporated ofi at reduced pressure and the residue carefully poured into 300 ml. of water with stirring and cooling. The pH of the solution was adjusted to 4.5 and the solution was allowed to stand overnight in a refrigerator. Filtration gave 114.5 grams of alpha-sulfo hexadecanoic acid mono sodlum salt. This was dried at 50-60 C. and further purified by recrystallization from ethanol.

A solution of 48.7 grams of the said mono sodium salt in 700 ml. of 50% v./v. aqueous alcohol was stirred with 400 ml. of ion exchange resin (Amberlite IR. 120 H) at 55 C. for eight hours. The resin was removed by filtration and the filtrate cooled overnight in a refrigerator. Unchanged sodium salt was filtered off and the filtrate was evaporated to dryness to give 39.6 grams of alpha-sulfo hexadecanoic acid.

Four grams of hydrogen peroxide was added dropwise to a vigorously stirred mixture of 16 grams of methanesulfonic acid and 11.4 grams of the alpha-sulfo hexadecanoic acid maintained at 40 C. by a thermostatted oil bath. If the temperature of the reaction mixture rose to 45 C. during the addition the mixture was immediately cooled to 40 C. with an ice bath. When the addition of hydrogen peroxide was complete the solution was stirred for a further hour at 40 C. and was then cooled to 15 C. and about 30 grams of chopped ice were added. The pH of the solution (monitored with a glass electrode) was raised to 1.5 by the addition of caustic soda with continuous cooling. The precipitated alpha-sulfo peroxy hexadecanoic acid mono sodium salt was filtered 01f, washed twice with ice-cold water and dried over phosphorus pentoxide to give 9.2 grams of a product which, by iodometric titration, was estimated at 89% pure alphasulfo peroxy hexadecanoic acid mono sodium salt.

Example II When in the above example decanoic acid,undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, eicosanoic acid, or the methyl esters of these acids, or mixtures thereof in, for example, 1:1 ratios, are substituted either wholly or in part for hexadecanoic acid substantially the same results are obtained in that the corresponding alpha-sulfo peroxy decanoic acid, alpha-sulfo peroxy undecanoic acid, alphasulfo peroxy dodecanoic acid, alpha-sulfo peroxy tridecanoic acid, alpha-sulfo peroxy tetradecanoic acid, alphasulfo peroxy pentadecanoic acid, alpha-sulfo peroxy heptadecanoic acid, alpha-sulfo peroxy octadecanoic acid, alpha-sulfo peroxy nonadecanoic acid, and alpha-sulfo peroxy eicosanoic acid are obtained.

Example III A suitable formulation for a washing composition containing the new alpha-sulfo peroxy fatty acids is:

Percent Alpha-sulfo peroxy hexadecanoic acid (monosodium salt) 30 Sodium tripolyphosphate 40 Sodium silicate 10 Sodium sulfate 20 Example IV When in the composition of Example III the following alpha-sulfo peroxy fatty acid salts are substituted, either wholly or in part, for the monosodium salt of alpha-sulfo peroxy hexadecanoic acid substantially the same results are obtained in that a good bleaching detergent composition is obtained:

The mono or di-sodium, potassium, ammonium, monoethanol ammonium, diethanol ammonium, and triethanol ammonium salts of alpha-sulfo peroxy decanoic acid, alpha-sulfo peroxy undecanoic acid, alpha-sulfo peroxy tridecanoic acid, alpha-sulfo peroxy tetradecanoic acid, alpha-sulfo peroxy pentadecanoic acid, alpha-sulfo peroxy hexadecanoic acid, alpha-sulfo peroxy heptadecanoic acid, alpha-sulfo peroxy octadecanoic acid, alpha-sulfo peroxy nonadecanoic acid, alpha-sulfa peroxy eicosanoic acid, or mixtures thereof.

7 Example V When in the composition of Example III the following builders are substituted for the sodium tripolyphosphate, and/or sodium silicate, and/or sodium sulfate, either wholly or in part, substantially the same results are obtained in that a good bleaching detergent composition is obtained:

Sodium or potassium carbonates, bicarbonates, pyrophosphate, orthophosphates, hexametaphosphates, ethylenediaminetetraacetates, nitrilo triacetates, phytates, ethane-l-hydroxy-l,l-diphosphonates, water soluble methylene diphosphonates, benzylidene diphosphonate, poly (itaconate-acrylate) (4:1 on a molar basis) (specific viscosity of 1% by weight, in dimethyl formamide at room temperature .40; equivalent weight 65.8), polyitaconate (specific viscosity of 1% by weight in dimethylformamide at room temperature .13; equivalent weight 65), poly (itaconate-aconitate) (1:1 on molar basis) (specific viscosity of 1% by weight in dimethylformamide at room temperature .12; equivalent weight 60.8), poly(ethylenemaleate) (1:1 on molar basis) (specific viscosity of 1% by weight in dimethyl formamide at room temperature 1.58; equivalent weight 72), poly(itaconate-acrylamide) (:1) (specific viscosity of 1% by weight of dimethylformamide at room temperature .92; equivalent weight 72.1).

Example VI When in the composition of Example III a 1:1 ratio of alpha-sulfo peroxy hexadecanoic acid monosodium salt and the following detergents, or mixtures thereof in, for

example, 1:1 ratios are used in place of alpha-sulfo peroxy hexadecanoic acid monosodium salt substantially the same results are obtained in that a good bleaching detergent composition is obtained:

Sodium stearate, potassium hexadecyl sulfate, sodium hexadecyl sulfonate, sodium dodecylbenzene sulfonate, glyceryl ether sulfonate, sodium coconut oil fatty acid monoglyceride sulfonate, sodium coconut oil fatty acid monoglyceride sulfate, the sodium salt of the sulfuric acid ester of the reaction product of one mole of tetradecanol with 3 moles of ethylene oxide, sodium nonyl phenol ethylene oxide ether sulfate (containing about 4 units of ethylene oxide per molecule), the sodium salt of hexadecanoic acid esterified with isethionic acid, stearyl methyl taurine, the product formed by the condensation of ethylene oxide with the product formed by the condensation of propylene oxide with propylene glycol and known as Pluronic F38, the condensation product of alkyl phenol having alkyl groups containing from about 6 to about 12 carbon atoms in either straight or branched chain configuration with about 15 moles of ethylene oxide per mole of phenol, the condensation product of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine having about polyoxyethylene by weight and having a molecular weight of about 8000, the condensation product of one mole of coconut alcohol with about 20 moles of ethylene oxide, dodecyl diethanol amine oxide, tetradecyl dimethyl phosphine oxide, 3-hydroxy-tetradecyl methyl sulfoxide, 1- (hexadecyldimethylammonio)propane 3 sulfonate, 1- (dodecyldimethylammonio)acetate, dodecyl-beta-alanine.

Example VII Another suitable formulation for a washing composition containing the new alpha-sulfo peroxy fatty acids is:

presented describing certain operable and preferred embodiments. It is not intended that the invention should be so limited since variations and modifications thereof will be obvious to those skilled in the art, all of which are within the spirit and scope of this invention.

Having thus described my invention, what I claim is:

1. A compound having the formula:

wherein R is alkyl of from 8 to 18 carbon atoms, and

wherein X and Y are each selected from the group of cations consisting of hydrogen, sodium, potassium, ammonium, monoethanol ammonium, diethanol ammonium, and triethanol ammonium cations.

2. Alpha-sulfa peroxy hexadecanoic acid. 3. Alpha-sulfo peroxy hexadecanoic acid monosodium salt.

References Cited UNITED STATES PATENTS 2,813,885 11/1957 Swern et a1. 260406 NICHOLAS S. RIZZO, Primary Examiner.

I. H. TURNIPSEED, Assistant Examiner.

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