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US3912663A - Sulfosuccinate derivatives as detergent builders - Google Patents

Sulfosuccinate derivatives as detergent builders Download PDF

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Publication number
US3912663A
US3912663A US401482A US40148273A US3912663A US 3912663 A US3912663 A US 3912663A US 401482 A US401482 A US 401482A US 40148273 A US40148273 A US 40148273A US 3912663 A US3912663 A US 3912663A
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builder
composition
sulfosuccinate
alpha
beta
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US401482A
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Vincent Lamberti
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Lever Brothers Co
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Lever Brothers Co
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Publication date
Priority to DE19722230073 priority Critical patent/DE2230073A1/en
Priority to GB2905772A priority patent/GB1398421A/en
Priority to GB78575A priority patent/GB1398422A/en
Priority to AT542872A priority patent/AT321437B/en
Priority to CH775776A priority patent/CH588452A5/xx
Priority to FR727222899A priority patent/FR2143437B1/fr
Priority to CH942672A priority patent/CH588551A5/xx
Priority to NL7208735A priority patent/NL7208735A/xx
Priority to US394613A priority patent/US3925375A/en
Priority to US401482A priority patent/US3912663A/en
Application filed by Lever Brothers Co filed Critical Lever Brothers Co
Priority to US484919A priority patent/US3917601A/en
Priority to US05/484,918 priority patent/US3950331A/en
Priority to US484744A priority patent/US3922272A/en
Priority to US05/484,916 priority patent/US3936448A/en
Priority to US484741A priority patent/US3922271A/en
Priority to US05/484,920 priority patent/US3957775A/en
Priority to US05/484,917 priority patent/US3935206A/en
Priority to US05/578,705 priority patent/US3984408A/en
Priority to US05/578,703 priority patent/US3968110A/en
Priority to US05/578,704 priority patent/US3976642A/en
Priority to US05/589,959 priority patent/US3989700A/en
Priority to US05/589,960 priority patent/US3970653A/en
Priority to US05/589,961 priority patent/US3987043A/en
Application granted granted Critical
Publication of US3912663A publication Critical patent/US3912663A/en
Priority to US05/647,246 priority patent/USRE29576E/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/349—Organic compounds containing sulfur additionally containing nitrogen atoms, e.g. nitro, nitroso, amino, imino, nitrilo, nitrile groups containing compounds or their derivatives or thio urea
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C291/00—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00
    • C07C291/02—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00 containing nitrogen-oxide bonds
    • C07C291/04—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00 containing nitrogen-oxide bonds containing amino-oxide bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
    • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C309/17—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing carboxyl groups bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
    • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C309/17—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing carboxyl groups bound to the carbon skeleton
    • C07C309/18—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing carboxyl groups bound to the carbon skeleton containing amino groups bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/64—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and sulfur atoms, not being part of thio groups, bound to the same carbon skeleton
    • C07C323/65—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and sulfur atoms, not being part of thio groups, bound to the same carbon skeleton containing sulfur atoms of sulfone or sulfoxide groups bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/64—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and sulfur atoms, not being part of thio groups, bound to the same carbon skeleton
    • C07C323/66—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and sulfur atoms, not being part of thio groups, bound to the same carbon skeleton containing sulfur atoms of sulfo, esterified sulfo or halosulfonyl groups, bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/123—Sulfonic acids or sulfuric acid esters; Salts thereof derived from carboxylic acids, e.g. sulfosuccinates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/755—Sulfoxides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/3427—Organic compounds containing sulfur containing thiol, mercapto or sulfide groups, e.g. thioethers or mercaptales
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/3445—Organic compounds containing sulfur containing sulfino groups, e.g. dimethyl sulfoxide
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/3454—Organic compounds containing sulfur containing sulfone groups, e.g. vinyl sulfones
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/3472—Organic compounds containing sulfur additionally containing -COOH groups or derivatives thereof

Definitions

  • Eutrophication is the process of excessive fertilization of aquatic plants through enrichment of waters with nutrients, such as carbon, nitrogen, phosphorus, potassium, iron, trace metals and vitamins.
  • alkali metal ammonium and substituted ammonium salts of certain sulfoaliphatic dicarboxylic acids can serve as effective detergent builders in detergent compositions.
  • the detergent builders and their acid forms employed in accordance with one embodiment of the present invention can be generally described as tt-substituted-B- sulfosuccinic acids and salts thereof having the general formula:
  • OOH OOH wherein Z is selected from the group consisting of O, S, SO and S R is selected from the group consisting of hydrogen, alkyl containing l-30 carbon atoms, phenyl, carboxyl substituted and monodior tri-alkyl substituted phenyl, wherein the alkyl group or groups contain 1-4 carbon atoms; sulfoand carboxy-alkyl, wherein the alkyl moiety contains 1-4 carbon atoms; and R'Z (CH CH O)n'CH CH wherein R is H or alkyl containing l-24 carbon atoms; Z is as above; and n is 0 or an integer of from l-l5 and the alkali metal, ammonium and substituted ammonium salts thereof.
  • a-hydroxy-B-sulfosuccinic acids a-alkoxy-B-sulfosuccinic acids a-phenoxy-B-sulfosuccinic acids a-carboxyphenoxy-B-sulfosuccinic acids a-alkylphenoxy-B-sulfosuccinic acids a-carboxyalkoxy-B-sulfosuccinic acids a-sulfoalkoxy-B-sulfosuccinic acids a-alkoxyethoxy-B-sulfosuccinic acids a-alkoxypolyethyleneoxyethoxy-B-sulfosuccinic acids a-hydroxyalkoxy-B-sulfosuccinic acids;
  • the alkali metal, ammonium and substituted ammonium salts thereof and the thio, sulfinyl and sulfonyl analogs of all the foregoing compounds wherein the oxygen group attached to the a-carbon of the succinic acid or succinate moiety is replaced by S, SO or -SO respectively, and/or wherein the cases of the a-alkoxyethoxy compounds and the a-alkoxypolyethyleneoxyethoxy compounds the oxygen attached to the alkyl group (R) is replaced by S.
  • SO or In accordance with another embodiment of the present invention are the nitrogen containing a-substituted-B-sulfosuccinic acids and salts thereof having the following general formula:
  • R, and R is hydrogen, C, to C alkyl, C, to C, hydroxyalkyl, carboxymethyl, carboxyethyl, sulfomethyl and sulfoethyl, or R, and R may be joined to form a morpholinyl moiety; with the proviso that both R, and R may not at the same time be hydrogen.
  • a-alkylamino-B-sulfosuccinic acids such as a-methylamino, a-propylamino, a-octylamino and a-laurylamino-B-sulfosuccinic acid
  • a-dialkylamino-B-sulfosuccinic acids such as a-dimethylamino, u-ethylmethylamino, amethylhexylamino and a-dioctylamino-B-sulfosuccinic acid
  • a-hydroxyalkyl-B-sulfosuccinic acids such as a-hydroxyethylamino, a-hydroxybutylamino and a-bis- (hydroxyethyl)amino-B-sulfosuccinic acid;
  • u-carboxyalkylamino-B-sulfosuccinic acids such as oz-carboxymethylamino, a-carboxyethylamino-B- sulfosuccinic acid and the corresponding sulfo analogs;
  • R and R are as is designated in Formula II with the proviso that neither R, nor R, can be hydrogen.
  • the compounds of the invention contain at least two asymmetric carbon atoms and therefore can exist in several optically active forms as well as optically inactive mixtures (racemates).
  • the compounds of the invention contain at least two asymmetric carbon atoms and therefore can exist in several optically active forms as well as optically inactive mixtures (racemates).
  • compounds as defined are intended to include all of the carbons. preferably from about 1 to about 4 carbon atoms, exhibit excellent detergent building properties whereas the higher homologs containing from about 9-30 and more preferably 924 carbon atoms in the alkyl chain, additionally exhibit wetting, foaming and detergency properties.
  • a-alkoxyethoxy and aalkoxypolyethyleneoxyethoxy-B-sulfosuccinic acid compounds containing from about 9-30 and preferably about 9-24 carbon atoms in the alkoxy moiety are also useful as wetting agents. foaming agents and detergents as well as detergent builders.
  • the builders of the present invention may be'utilized as the free acid provided sufficient alkaline additives are included'in the detergent composition to convert the acid forms in situ to the normal salt forms, the alkali metal, ammonium and substituted ammonium salts of the a-substituted-B-sulfosuccinic acids are preferred. Included in the substituted ammonium salts that can be employed are the monoethanolammonium, diethanolammonium, triethanolammonium, methylammonium, dimethylammonium, trimethylammonium, tetramethylammonium, morpholinium, N-methylmonoethanolammonium and N-ethylmonoethanolammonium salts and mixtures thereof.
  • the utility of the compounds of the present invention is not only reflected in terms of excellent buildingand biodegradability properties but also in low cost of preparation, since they are prepared from readily available and inexpensive materials.
  • the compounds contemplated in this invention are derived from sulfomaleic anhydride and readily available alcohols, thiols. hydroxy acids and amines.
  • the compounds contemplated in this invention are reaction products derived at least in part from sulfomaleic acid or sulfomaleic acid with compounds having an active hydrogen atom.
  • Compounds having an active hydrogen and suitable for use in preparing the builders of the present invention are monodior polyhydric alcohols and monodior polyhydroxy. acids and their sulfur-containing analogs.
  • Suitable examples of the aforementioned monohydric alcohols include alkoxyalkanols such as methoxyethanol and the linear primary and secondary alcohols containing up to carbon atoms and their thio analogs; aromatic alcohols particularly the carbocyclic monoand bicyclic aromatic alcohols, such as naphthols and phenols and the monodior tri- C C, alkyl ring substituted derivatives thereof.
  • dihydric alcohols include the glycols such as ethylene glycol, propylene glycol, butylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, heptamethylene glycol, long chain l,2-diols containing from 8 -3.0 carbon atoms and aromatic carbocyclic glycols such as phenylethylene glycocl.
  • suitable polyhydric alcohols include glycerol, pentaerythritol, hexanetriol, sugars and their thio analogs.
  • the hydroxy carboxylic and sulfonic 'acids' may also react with sulfomaleic anhydride and sulfomaleic acid.
  • sulfomaleic anhydride include glycollic. lactic. glyceric. hydroxypropionic. salicyclic and mercapto acetic acid, hydroxymethanesulfonic acid and hydroxyethanesulfonic acid.
  • Still another important class of compounds containing active hydrogens are ethylene oxide adducts of C, to C primary and secondary alcohols with l-l 5 moles of ethylene oxide.
  • the a.-substituted-B-sulfosuccinate salts wherein the oz-substituent is joined to the a-carbon atom of the sulfosuccinate moiety by an O or S linkage.
  • the desired d-oxy or a-thio-B- sulfosuccinate may then be recovered and purified using conventional techniques.
  • a-substituted-B-sulfosuccinate salts wherein the a-substituent is joined to the a-carbon atom of the sulfo-succinatemoiety by an S0 or SO: linkage may be prepared by treating the appropriate ctr-substituted thio-B-sulfosuccinate with hydrogen peroxide according to the methods described on pages 471-472 in the text. Reagents for Organic Synthesis" by Fieser and Fieser, published by John Wiley & Sons, Inc., 1967, incorporated by reference herein.
  • a-substituted-B-sulfosuccinate salts wherein the oz-substituent is joined to the a-carbon atom of the sulfosuccinate moiety by an amino function may be prepared by reacting an appropriately substituted or unsubstituted primary or secondary amine with alkali metal salts of sulfomaleic acid.
  • Typical amines suitable for reaction to form the a-substituted amino-B-sulfosuccinates include:
  • a-amino substituted-B- sulfosuccinates derived from water-soluble amines may be prepared. by reacting in aqueous solution without the aid of heatand those derived from water-insoluble amines (i.e., higher alkylamines) are reacted in a mixed solvent system such as ethanol/water or dioxane/water at temperatures ranging from about 25C to about C; isolation from the reaction medium, and purification if desired, being effected by conventional methods.
  • a mixed solvent system such as ethanol/water or dioxane/water
  • the compounds of Formula lll may be prepared by reacting the tertiary amine compounds of Formula ll with oxidizing agents such as hydrogen peroxide, peroxyacetic and peroxyformic acid in the manner described for oxidizing tertiary amines by Hoh et al., J. Am. Oil Chemists Soc., 40, 268 (1963).
  • oxidizing agents such as hydrogen peroxide, peroxyacetic and peroxyformic acid
  • the amount of base utilized will determine whether the monodior tri-salt is obtained. For example', the use of one mole of base (iLe., sodium hydroxide) per mole of a-hydroxy-B-sulfosuccinic acid yields the monosodium salt; the use of two moles of sodium hydroxide, the disodium salt and the use of three moles of sodium hydroxide, the tri-sodium salt.
  • R is carboxymethyl, carboxyethyl, sulfo-methyl or sulfoethyl, a tetrasalt can also be obtained.
  • other bases such as ammonium hydroxide and organic amines, may be utilized in the same manner to afford the type of salt desired.
  • the builders can be used singularly, in combination with each other as the sole builder in the detergent composition or in combination with other well-known detergent builders such as sodium nitrilotriacetate, sodium ethylenediaminetetraacetate, sodium tripolyphosphate, trisodium orthophosphate, sodium and potassium pyrophosphate, sodium polyacrylate, disodium oxydiacetate, trisodium citrate, trisodium carboxymethyloxysuccinate, salts of oxidized starches and sodium or potassium carbonate, as well as other conventional organic and inorganic builders.
  • detergent builders such as sodium nitrilotriacetate, sodium ethylenediaminetetraacetate, sodium tripolyphosphate, trisodium orthophosphate, sodium and potassium pyrophosphate, sodium polyacrylate, disodium oxydiacetate, trisodium citrate, trisodium carboxymethyloxysuccinate, salts of oxidized starches and sodium or potassium carbonate, as well as other conventional organic and inorganic
  • the wash solutions When using the detergent compositions of the invention to wash clothes, the wash solutions should have a pH from about 7 to 12 and preferably from about 9 to 11 throughout the washing cycle. Therefore, the presence of an alkaline buffer in the detergent composition is usually desirable particularly when the soil to be removed from the clothes has a high content of acidic components.
  • Suitable buffers include any of the common organic and/or inorganic buffers such as monoethanolamine, diethanolamine, triethanolamine, sodium and potassium silicates, sodium and potassium carbonates and bicarbonates and the like.
  • the only essential ingredients are the detergent surface active material and the builder.
  • the weight per cent of the builder present in the detergent composition will range from about 5 to about 90% and preferably from about 20 to about 60% and more preferably 35-50% by weight of the total weight of the composition.
  • the builders used in the instant invention will generally be present in a ratio of about 1:10 to about 1, and preferably 2:1 to 5:1 depending on the end use or whether a heavy-duty or light-duty detergent is desired.
  • the ratio of builder to surfactant is from about 10:1 to about 50:1.
  • the detergent surface active compounds which can be used within the compositions of this invention include anionic, nonionic, zwitterionic, ampholytic detergent compounds and mixtures thereof. These suitable substances are outlined at length below.
  • Anionic detergent compositions which can be used in the compositions of this invention include both soap and non-soap detergent compounds.
  • suitable soaps are the sodium, potassium, ammonium and 6 tallow, i.e., sodium or potassium tallow and coconut soap and tall oil.
  • anionic organic non-soap detergent compounds are the water soluble salts, alkali metal salts of organic sulfuric reaction products having in their 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.
  • Nonionic synthetic detergents may be broadly defined as compounds which do not ionize in water solution.
  • 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 1,500 to 1,800. 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 product is retained up to the point where polyoxyethylene content is about 50% of the total weight of the condensation product.
  • nonionic synthetic detergents include:
  • the polyethylene oxide condensates of alkylphenols e.g., the condensation products of alkylphenols having an alkyl group containing from about 6 to 12 carbon atoms in either a straight chain or branched chain configuration, with ethylene oxide,
  • the alkyl substituent in such compounds may be derived from polymerized propylene, disobutylene, octene, dodecene, or nonene, for example.
  • Those derived from the condensation of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine are satisfactory.
  • compounds containing from about 40% to about 80% polyoxyethylene by weight and having a molecular weight of from about 5,000 to about 1 1,000 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 hydrophobic base having a molecular weight of the order of 2,500 to 3,000 are satisfactory.
  • ethylene oxide e.g., a coconut alcoholethylene oxide condensate having from 6 to 30 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction having from to 14 carbon atoms; a C, C random secondary alcohol derived from n-paraffins and condensed with 7 moles of ethylene oxide per mole of secondary alcohol.
  • R R R N Long chain tertiary amine oxides corresponding to the following .general formula, R R R N 0, wherein R is an alkyl radical of from about 8 to 18 carbon atoms and R and R are each methyl, ethyl or hydroxy ethyl radicals.
  • the arrow in the formula is a conventional representation of a semi-polar bond.
  • amine oxides suitable for use in this invention include dimethyloctylamine oxide, dimethyldecylamine oxide, dimethyldodecylamine oxide, dimethyltetradecylamine oxide and dimethylhexadecylamine oxide, N-bis(hydroxyethyl)- dodecylamine oxide.
  • dimethyltetradecylphosphine oxide dimethyltetradecylphosphine oxide, ethylmethyltetradecylphosphine oxide, cetyldimethylphosphine oxide, dimethylstearylphosphine oxide, cetylethylpropylphosphine oxide, diethyldodecylphosphine oxide, diethyltetradecylphosphine oxide, bis(hydroxymethyl)dodecylphosphine oxide, bis(2-hydroxyethyl)dodecylphopshine oxide,
  • suitable sulfoxide compounds are:
  • Ampholytic synthetic detergents can be broadly described as derivatives of aliphatic secondary and tertiary amines, in which the aliphatic radical may be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic water solubilizing group.
  • Examples of compounds falling within this definition are sodium-3-dodecylaminopropionate and sodium-3-dodecylaminopropanesulfonate and sodium N-2- hydroxydodecyl-N-methyl-taurate.
  • Zwitterionic synthetic detergents can be broadly described as derivatives of aliphatic quaternary ammonium compounds, sulfonium compounds and phosphonium compounds in which the aliphatic radical may be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic water solubilizing group.
  • Examples of compounds falling within this definition are 3-(N,N-dimethyl-N- hexadecylamonio )propanel -sulfonate, 3-( N,N- dimethyl-N-hexadecylammonio)-2-hydroxypropanel sulfonate, 3-(dodecylmethylsulfonium) propane sulfonate, and 3-(cetylmethylphosphonium)ethane sulfonate.
  • compositions of the invention include those conventionally present therein.
  • Typical examples thereof include the well-known soilsuspending agents, hydrotropes, corrosion inhibitors, dyes, perfumes, fillers such as sodium sulfate, optical brighteners, perborates, bleaches, bleach activators, enzymes, suds boosters, suds depressants germicides, fungicides, anti-tarnishing agents, cationic detergents, fabric softening agents and in the case of liquid compositions, opacifiers and organic solvents.
  • the balance of the detergent compositions may be water or inert filler.
  • the detergency of the formulation is significantly enhanced particularly at low form ulation concentration (-0.1%) which are typically used by the US. housewife.
  • the detergent formulation sould contain surfactant levels of about 25% to about 45% by weight and the sulfosuccinate derivative salt levels of about 25% to about by weight in the cases where the surfactants are anionic, ampholytic of switterionic.
  • the surfactant is a nonionic
  • enhanced detergency results are obtained when the level of said nonio nic in the formuation is from about 15% to 30% by weight and the level of sulfosuccinate derivative salt is from about 25% to aboutby weight.
  • the average detergency units (DU) of the formulation is the final reflectance value of the washed cloth (average of 2 runs) minus the initial reflectance of the soiled cloth, the reflectances being obtained by measurement with a Gardner automatic color difference meter, Model AC-3.
  • Table 1 further illustrates the present invention.
  • the detergent formulations set forth in the Table represent detergent compositions containing the builders of the present invention in combination with representative classes of surface active agents compared with control or standard phosphate built detergent compositions.
  • the compositions were prepared by blending together the recited components in the proportions indicated, including an anticorrosive agent and buffer agent (sodium silicate).
  • EXAMPLE 2 a-Thiosubstituted-B-Sulfosuccinates
  • the procedure of Example 1 is repeated except that in place of Ca(OH) the pH is adjusted to 8.6 with NaOH. Then, an aqueous solution containing excess sodium hydrosulfide, sodium methyl mercaptide or sodium ethyl mercaptide is added and the resulting solution allowed to stand overnight. The reaction mixture is then passed through a column of cation exchange resin and the effluent evaporated to low volume. The pH is the adjusted to 8.5 with sodium hydroxide and the solution evaporated to dryness. In this way, there is afforded respectively:
  • Trisodium a-mercapto-B-sulfosuccinate trisodium a-methylthio-B-sulfosuccinate trisodium a-ethylthio-B-sulfosuccinate
  • EXAMPLE 3 Preparation of Trisodium a-Methoxy-B-Sulfosuccinate Sulfomaleic anhydride, 3.9 gm,'was dissolved in 25 ml of methanol and refluxed for hours. Then, 24 gm of 25% sodium methoxide in methanol was added and the solution was refluxed for 2 hours. The methanol was then evaporated and the residue was dissolved in 100 ml of water and heated for 1 hour at 80C.
  • a-ethoxy-B-sulfosuccinate may be prepared by substituting ethanol and sodium ethoxide in the procedure described above.
  • EXAMPLES 6-8 EXAMPLE 9 Preparation of Trisodium a-Hydroxyethoxy-B-Sulfosuccinate Sulfomaleic anhydride (20 gm) is mixed with 37.2 gm (0.6 mole) of ethylene glycol and heated at 80C for 4 hours. A solution of 16 gm (0.4 mole) of sodium hydroxide in ml of water is then added and the mixture heated at C for 4 hours. The mixture is then mixed with acetone to precipitate trisodium a-hydroxyethoxy-B-sulfosuccinate, which is purified by repeated extractions with hot acetone to remove all ethylene glycol and water followediby filtration and drying in an oven.
  • EXAMPLE 10 Preparation of the Tetrasodium Salt of a-Carboxymethyloxy-B-Sulfosuccinic Acid Sulfomaleic anhydride (19.4 gm) is heated to 60C and combined with 76 gm of ethyl glycolate. After heating the mixture at 80C for 5% hours, there is added a solution of 45 gm of sodium hydroxide dissolved in gm of water and heating is continued at 80 for an additional three hours. The mixture is then diluted with water and passed through a column of a cation exchange resin. The resulting eluent is then evaporated in vacuo to a low volume and the concentrate extracted repeatedly with acetone to remove glycolic acid and other impurities.
  • Example 1 Preparation of Trisodium a( 2-Hydroxyethylamino )-B-Sulfosuccinate added slowly and the temperature allowed to rise to I room temperature. After standing overnight, the reaction mixture was poured into 800 ml of acetone. The solvent was then decanted from the resulting syrupy lower layer and the latter reprecipitated three times from water with fresh acetone. The residue was then dried in a dessicator over P 0 to give 38.8 gm of an off-white, granular product containing approximately 88% trisodium a-(2-hydroxyethylamino)-B- a ethanol/water and dioxane/water is used together with temperatures in the range of 2580C.
  • Table 2 indicates the reactants and procedure required to obtain other a-substituted-B-sulfosuccinate salts having the R and Z moieties set forth in Formula I.
  • a detergent composition consisting essentially of a. at least one detergent surface active agent selected from the group consisting of anionic, nonionic. zwitterionic, and ampholytic agents; and,
  • an or ganic detergent builder selected from the group consisting of an alkali metal, ammonium monoethanolammonium, diethanolammonium, triethanolammonium, methylammonium, dimethylammonium, trimethylammonium, tetramethylammonium, morpholinium, N-methylmonoethanolammonium and N-ethylmonoethanolammonium and N-ethylmonoethanolammonium salts and mixtures thereof of an a-substituted-B-sulfosuccinate having the general formula wherein;
  • R is selected from the group consisting of 1. alkyl containing 1 30 carbon atoms,
  • R'Z(CH CH O)nCH CH wherein a. R is hydrogen or alkyl containing l-24 carbon atoms, b. Z is selected from the group consisting of O,
  • n is an integer of 0-15; and Z is as previously defined.
  • composition of claim 1 wherein the builder is an a-alkoxy-B-sulfosuccinate wherein the alkoxy group contains about l-24 carbon atoms.
  • composition of claim 1 wherein the builder is an a-alkoxy-B-sulfosuccinate wherein the alkoxy group contains about 9-24 carbon atoms.
  • composition of claim 1 wherein the builder is an a-alkoxy-B-sulfosuccinate wherein the alkoxy group contains about 1-8 carbon atoms.
  • composition of claim 1 wherein the builder is a-dodecyloxy-B-sulfosuccinate.
  • composition of claim 1 wherein the builder is a-hexadecyloxy-B-sulfosuccinate.
  • composition of claim 1 wherein the builder is a-octadecyloxy-B-sulfosuccinate.
  • composition of claim 1 wherein the builder is a-tetradecyloXy-B-sulfosuccinate.
  • composition of claim 1 wherein the builder is a-hydroxyethoxy-B-sulfosuccinate.
  • composition of claim 1 wherein the builder is a-alkoxyethoxy-B-sulfosuccinate wherein the alkoxy moiety contains about 1-24 carbon atoms.
  • composition of claim 1 wherein the builder is a-dodecyloxyethoxy-B-sulfosuccinate.
  • composition of claim 1 wherein the builder is oz-carboxymethoxy-B-sulfosuccinate.
  • a composition of claim 1 wherein the builder is a salt of an a-substituted-,B-sulfosuccinic acid having the general formula:
  • R is selected from the group consisting of alkyl containing l-30 carbon atoms, phenyl, carboxy substituted and monodior tri-alkyl substituted phenyl wherein the alkyl group or groups contain l-4 carbon atoms, sulfo and carboxy alkyl wherein the alkyl moiety contains 1-4 carbon atoms; and R'Z(CH CH O)- nCh CH wherein R is H or alkyl containing l-24 carbon atoms, n is O or an integer of from l-l5 and Z is O, S, S0 or S0 I 14.
  • the builder is a salt of an a-substituted-B-sulfosuccinic acid having the general formula:
  • R is selected from the group consisting of alkyl containing 1-30 carbon atoms, phenyl substituted phenyl wherein the phenyl ring contains one carboxyl group and one, two or three alkyl groups wherein the alkyl group or groups contain l-4 carbon atoms, sulfo and carboxy alkyl wherein the alkyl moiety contains l-4 carbon atoms; and R'Z(CH CH O )nCH CH wherein R is H or alkyl contaiing 1-24 carbon atoms, n is O or an integer of from 1-15 and Z is O, S, S0 or S0 15.
  • the builder is a salt of an a-substituted-B-sulfosuccinic acid having the general formula:
  • R is selected from the group consisting of hydrogen, alkyl containing l-3O carbon atoms, phenyl, substituted phenyl wherein the phenyl ring contains one carboxyl group and one, two or three alkyl groups wherein the alkyl group or groups contain 1-4 carbon atoms, sulfoand carboxy-alkyl wherein the alkyl moiety contains l-4 carbon atoms; and R'Z(CH CH O)- n-CH CH wherein R is H or alkyl containing l-24 carbon atoms, n is 0 or an integer of from l-l5 and Z is selected from the group consisting of O, S, SO and S0 16.
  • the builder is an a-alkylthio-B-sulfosuccinate containing about l-24 carbon atoms in the alkylthio moiety.
  • composition of claim 15 wherein the builder is an oz-alkylthio-B-sulfosuccinate containing about 1-8 carbon atoms in the alkylthio moiety.
  • composition of claim 15 wherein the builder is an a-alkylthio-B-sulfosuccinate containing about 9-24 carbon atoms in the alkylthio moiety.
  • composition of claim 15 wherein the builder is an a-dodecylthio-B-sulfosuccinate.
  • composition of claim 15 wherein the builder is an a-hexadecylthio-B-sulfosuccinate.
  • a detergent composition consisting essentially of a. at least one detergent surface active agent selected from the group consisting of anionic, nonionic, Zwitterionic and ampholytic agents; and,
  • an organic detergent builder selected from the group consisting of alkali metal, ammonium monocthanolammonium, diethanolammonium, triethanolammonium, methylammonium, dimethylammonium, trimethylammonium, tetramethylammonium, morpholinium, N-methylmonoethanolammonium and N-ethylmonoethanolammonium salts and mixtures thereof of an a-substituted-B-sulfosuccinate having the basic for mula:
  • R is selected from the group consisting of hydrogen, alkyl containing [-30 carbon atoms, phenyl substituted phenyl wherein the phenyl ring contains one carboxyl group and one, two or three alkyl groups wherein the alkyl groups contain [-4 carbon atoms, sulfo and carboxy-alkyl wherein the alkyl moiety contains 1-4 carbon atoms and R'Z(CH CH O) nCH CH wherein R is hydrogen or alkyl containing l24 carbon atoms, n is an integer of 0-15, and z is selected from the group consisting of O, S, SO and S0 or mixtures thereofv 23.
  • the composition of claim 1 wherein the builder is a-hydroxy-B-sulfosuccinate.

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Abstract

Novel salts of Alpha -substituted- Beta -sulfosuccinic acids having the general formula:

wherein R is hydrogen or an organic moiety, Z is selected from the group consisting of O, S, SO, SO2, N and NO and M is an alkali metal, ammonium or substituted ammonium cations, useful as detergents and/or detergent builders and detergent compositions containing same.

Description

United States Patent Lamberti 1 1 Oct. 14, 1975 SULFOSUCCINATE DERIVATIVES AS 3,328,314 6/1967 Marquis 252/383 DETERGENT BUILDERS 3,635,829 l/l972 Yang 252/526 3,635,830 l/l972 Lamberti et a1. 252/89 X [75] Inventor: Vincent Lambem, Upper add 3,706,771 12 1972 Kremers et a1. 260/346.8
River, NJ.
[73] Assignee: Lever Brothers Company, New Primary Examiner Herbert Guynn York Attorney, Agent, or FirmArnold Grant [22] Filed: Sept. 27, .1973
[21] Appl. N0.: 401,482
ABSTRACT Related U.S. Appllcation Data [63] Continuation of Ser. No. 156,933, June 25, 1971, Novel salts of a-substituted-B-sulfosuccinic acids havabandoned. ing the general formula:
[52] US. Cl. 252/542; 252/524; 252/526; 252/538; 252/539; 252/545; 252/546; 252/547; 252/557; 252/558; 260/247.1 E; RZ CH CH SOM 260/247.l R; 260/50l.12; 260/50l.l5; 00M COOM 260/50l.l7; 260/50121; 260/503; 260/513 R [51] Int. Cl. ..C11D l/l2;Cl1D 3/34;
CO7C 143/12 wherein R is hydrogen or an organic moiety, Z is se- [58] Fleld of Search 252/538, 539, 557, 558, lected from the group Consisting of O, S, 50 50 N 252/526, 545, 547, 548; 260/508, and NO and M is an alkali metal, ammonium or sub- 510, 503, 512, 5005 stituted ammonium cations, useful as detergents and- 346-8 /or detergent builders and detergent compositions containing same. [56] References Cited UNITED STATES PATENTS 23 Claims, No Drawings 3,086,043 4/1963 Gaertner 260/485 SULFOSUCCINATE DERIVATIVES AS DETERGENT BUILDERS This is a continuation of application Ser. No. 156,933, filed June 25, 1971, now abandoned.
BACKGROUND OF THE INVENTION Eutrophication is the process of excessive fertilization of aquatic plants through enrichment of waters with nutrients, such as carbon, nitrogen, phosphorus, potassium, iron, trace metals and vitamins.
Although there is no present adequate proof, it has been postulated that the phosphorus-containing builders present in detergent compositions can be a factor in eutrophication. Therefore any substitutes which do not contain phosphorus may decrease to some extent the eutrophication.
It is therefore an object of the present invention to provide novel compounds which are useful as detergent builders. It is another object of the present invention to provide novel compounds which function as surface active agents and as detergent builders. It is still another object of the present invention to provide detergent compositions which are free of phosphorus-containing builders such as the alkali metal condensed phosphates.
DESCRIPTION OF THE INVENTION It has now been discovered that the alkali metal ammonium and substituted ammonium salts of certain sulfoaliphatic dicarboxylic acids can serve as effective detergent builders in detergent compositions. The detergent builders and their acid forms employed in accordance with one embodiment of the present invention can be generally described as tt-substituted-B- sulfosuccinic acids and salts thereof having the general formula:
Formula I RZCHCH-SO,,H
OOH OOH wherein Z is selected from the group consisting of O, S, SO and S R is selected from the group consisting of hydrogen, alkyl containing l-30 carbon atoms, phenyl, carboxyl substituted and monodior tri-alkyl substituted phenyl, wherein the alkyl group or groups contain 1-4 carbon atoms; sulfoand carboxy-alkyl, wherein the alkyl moiety contains 1-4 carbon atoms; and R'Z (CH CH O)n'CH CH wherein R is H or alkyl containing l-24 carbon atoms; Z is as above; and n is 0 or an integer of from l-l5 and the alkali metal, ammonium and substituted ammonium salts thereof.
Thus, specific compounds and classes of compounds embraced by the generic formula above include:
a-hydroxy-B-sulfosuccinic acids a-alkoxy-B-sulfosuccinic acids a-phenoxy-B-sulfosuccinic acids a-carboxyphenoxy-B-sulfosuccinic acids a-alkylphenoxy-B-sulfosuccinic acids a-carboxyalkoxy-B-sulfosuccinic acids a-sulfoalkoxy-B-sulfosuccinic acids a-alkoxyethoxy-B-sulfosuccinic acids a-alkoxypolyethyleneoxyethoxy-B-sulfosuccinic acids a-hydroxyalkoxy-B-sulfosuccinic acids;
the alkali metal, ammonium and substituted ammonium salts thereof; and the thio, sulfinyl and sulfonyl analogs of all the foregoing compounds wherein the oxygen group attached to the a-carbon of the succinic acid or succinate moiety is replaced by S, SO or -SO respectively, and/or wherein the cases of the a-alkoxyethoxy compounds and the a-alkoxypolyethyleneoxyethoxy compounds the oxygen attached to the alkyl group (R) is replaced by S. SO or In accordance with another embodiment of the present invention are the nitrogen containing a-substituted-B-sulfosuccinic acids and salts thereof having the following general formula:
Formula II R,NCHCH-SO;,H
OOH OOH wherein at least one of R, and R is hydrogen, C, to C alkyl, C, to C, hydroxyalkyl, carboxymethyl, carboxyethyl, sulfomethyl and sulfoethyl, or R, and R may be joined to form a morpholinyl moiety; with the proviso that both R, and R may not at the same time be hydrogen.
Thus, broadly the compounds of Formula I differ from the compounds of Formula I] only in the atom represented by Z.
Representative compounds and classes of compounds embraced by generic Formula II above include:
a-alkylamino-B-sulfosuccinic acids such as a-methylamino, a-propylamino, a-octylamino and a-laurylamino-B-sulfosuccinic acid; a-dialkylamino-B-sulfosuccinic acids such as a-dimethylamino, u-ethylmethylamino, amethylhexylamino and a-dioctylamino-B-sulfosuccinic acid;
a-hydroxyalkyl-B-sulfosuccinic acids such as a-hydroxyethylamino, a-hydroxybutylamino and a-bis- (hydroxyethyl)amino-B-sulfosuccinic acid;
u-carboxyalkylamino-B-sulfosuccinic acids such as oz-carboxymethylamino, a-carboxyethylamino-B- sulfosuccinic acid and the corresponding sulfo analogs;
a-morpholinyl-B-sulfosuccinic acid; and the mono or poly salts thereof.
In accordance with still another embodiment of the present invention are the amine oxide derivatives of Formula II, wherein the nitrogen is a tertiary atom, corresponding to the following general formula:
wherein R and R are as is designated in Formula II with the proviso that neither R, nor R, can be hydrogen.
As will be appreciated by those skilled in the art, the compounds of the invention contain at least two asymmetric carbon atoms and therefore can exist in several optically active forms as well as optically inactive mixtures (racemates). For purposes of this invention, the
compounds as defined are intended to include all of the carbons. preferably from about 1 to about 4 carbon atoms, exhibit excellent detergent building properties whereas the higher homologs containing from about 9-30 and more preferably 924 carbon atoms in the alkyl chain, additionally exhibit wetting, foaming and detergency properties.
Similarly, the a-alkoxyethoxy and aalkoxypolyethyleneoxyethoxy-B-sulfosuccinic acid compounds containing from about 9-30 and preferably about 9-24 carbon atoms in the alkoxy moiety are also useful as wetting agents. foaming agents and detergents as well as detergent builders.
Although the builders of the present invention may be'utilized as the free acid provided sufficient alkaline additives are included'in the detergent composition to convert the acid forms in situ to the normal salt forms, the alkali metal, ammonium and substituted ammonium salts of the a-substituted-B-sulfosuccinic acids are preferred. Included in the substituted ammonium salts that can be employed are the monoethanolammonium, diethanolammonium, triethanolammonium, methylammonium, dimethylammonium, trimethylammonium, tetramethylammonium, morpholinium, N-methylmonoethanolammonium and N-ethylmonoethanolammonium salts and mixtures thereof.
The utility of the compounds of the present invention is not only reflected in terms of excellent buildingand biodegradability properties but also in low cost of preparation, since they are prepared from readily available and inexpensive materials. For example, the compounds contemplated in this invention are derived from sulfomaleic anhydride and readily available alcohols, thiols. hydroxy acids and amines.
More specifically, the compounds contemplated in this invention are reaction products derived at least in part from sulfomaleic acid or sulfomaleic acid with compounds having an active hydrogen atom.
Compounds having an active hydrogen and suitable for use in preparing the builders of the present invention are monodior polyhydric alcohols and monodior polyhydroxy. acids and their sulfur-containing analogs. Suitable examples of the aforementioned monohydric alcohols include alkoxyalkanols such as methoxyethanol and the linear primary and secondary alcohols containing up to carbon atoms and their thio analogs; aromatic alcohols particularly the carbocyclic monoand bicyclic aromatic alcohols, such as naphthols and phenols and the monodior tri- C C, alkyl ring substituted derivatives thereof. Suitable examples of dihydric alcohols include the glycols such as ethylene glycol, propylene glycol, butylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, heptamethylene glycol, long chain l,2-diols containing from 8 -3.0 carbon atoms and aromatic carbocyclic glycols such as phenylethylene glycocl. Similarly, suitable polyhydric alcohols include glycerol, pentaerythritol, hexanetriol, sugars and their thio analogs.
In addition tothe alcohols, the hydroxy carboxylic and sulfonic 'acids'(in their ester and acid/salt forms, respectively) may also react with sulfomaleic anhydride and sulfomaleic acid. These include glycollic. lactic. glyceric. hydroxypropionic. salicyclic and mercapto acetic acid, hydroxymethanesulfonic acid and hydroxyethanesulfonic acid.
Still another important class of compounds containing active hydrogens are ethylene oxide adducts of C, to C primary and secondary alcohols with l-l 5 moles of ethylene oxide.
In general. the a.-substituted-B-sulfosuccinate salts. wherein the oz-substituent is joined to the a-carbon atom of the sulfosuccinate moiety by an O or S linkage. may be prepared by heating at a temperature of from about 25 to l2()C, and preferably 60 to 100C, sulfomaleic anhydride with a compound having an active hydrogen followed by further treatment with an alkali metal. hydroxide. The desired d-oxy or a-thio-B- sulfosuccinate may then be recovered and purified using conventional techniques.
The a-substituted-B-sulfosuccinate salts wherein the a-substituent is joined to the a-carbon atom of the sulfo-succinatemoiety by an S0 or SO: linkage may be prepared by treating the appropriate ctr-substituted thio-B-sulfosuccinate with hydrogen peroxide according to the methods described on pages 471-472 in the text. Reagents for Organic Synthesis" by Fieser and Fieser, published by John Wiley & Sons, Inc., 1967, incorporated by reference herein.
The a-substituted-B-sulfosuccinate salts wherein the oz-substituent is joined to the a-carbon atom of the sulfosuccinate moiety by an amino function (Fonnula ll) may be prepared by reacting an appropriately substituted or unsubstituted primary or secondary amine with alkali metal salts of sulfomaleic acid. Typical amines suitable for reaction to form the a-substituted amino-B-sulfosuccinates include:
ethanolamine diethanolamine propanolamine morpholine N-methylethanolamine glycine alanine N-methyl taurine alkylamines containing 1-20 carbons in the alkyl chain, as well as other amines having a replaceable or active hydrogen and a basicity comparable to the aforementioned amines.
In particular the a-amino substituted-B- sulfosuccinates derived from water-soluble amines may be prepared. by reacting in aqueous solution without the aid of heatand those derived from water-insoluble amines (i.e., higher alkylamines) are reacted in a mixed solvent system such as ethanol/water or dioxane/water at temperatures ranging from about 25C to about C; isolation from the reaction medium, and purification if desired, being effected by conventional methods.
The compounds of Formula lll may be prepared by reacting the tertiary amine compounds of Formula ll with oxidizing agents such as hydrogen peroxide, peroxyacetic and peroxyformic acid in the manner described for oxidizing tertiary amines by Hoh et al., J. Am. Oil Chemists Soc., 40, 268 (1963).
In preparing the sulfosuccinate salts from the free acid, the amount of base utilized will determine whether the monodior tri-salt is obtained. For example', the use of one mole of base (iLe., sodium hydroxide) per mole of a-hydroxy-B-sulfosuccinic acid yields the monosodium salt; the use of two moles of sodium hydroxide, the disodium salt and the use of three moles of sodium hydroxide, the tri-sodium salt. When R is carboxymethyl, carboxyethyl, sulfo-methyl or sulfoethyl, a tetrasalt can also be obtained. Similarly, other bases, such as ammonium hydroxide and organic amines, may be utilized in the same manner to afford the type of salt desired.
According to the present invention, excellent cleaning results can be obtained by using the builders described above with a wide range of detergent surface active materials and mixtures thereof in any of the usual physical forms for such compositions such as powders, beads, flakes, bars, tablets, noodles, liquids and the like. The builders can be used singularly, in combination with each other as the sole builder in the detergent composition or in combination with other well-known detergent builders such as sodium nitrilotriacetate, sodium ethylenediaminetetraacetate, sodium tripolyphosphate, trisodium orthophosphate, sodium and potassium pyrophosphate, sodium polyacrylate, disodium oxydiacetate, trisodium citrate, trisodium carboxymethyloxysuccinate, salts of oxidized starches and sodium or potassium carbonate, as well as other conventional organic and inorganic builders.
When using the detergent compositions of the invention to wash clothes, the wash solutions should have a pH from about 7 to 12 and preferably from about 9 to 11 throughout the washing cycle. Therefore, the presence of an alkaline buffer in the detergent composition is usually desirable particularly when the soil to be removed from the clothes has a high content of acidic components. Suitable buffers include any of the common organic and/or inorganic buffers such as monoethanolamine, diethanolamine, triethanolamine, sodium and potassium silicates, sodium and potassium carbonates and bicarbonates and the like.
In the detergent compositions of the present invention, the only essential ingredients are the detergent surface active material and the builder. The weight per cent of the builder present in the detergent composition will range from about 5 to about 90% and preferably from about 20 to about 60% and more preferably 35-50% by weight of the total weight of the composition. When expreseed as a weight ratio of builder to surfactant, the builders used in the instant invention will generally be present in a ratio of about 1:10 to about 1, and preferably 2:1 to 5:1 depending on the end use or whether a heavy-duty or light-duty detergent is desired. When the builders are used in mechanical dishwashing compositions, the ratio of builder to surfactant is from about 10:1 to about 50:1.
The detergent surface active compounds which can be used within the compositions of this invention include anionic, nonionic, zwitterionic, ampholytic detergent compounds and mixtures thereof. These suitable substances are outlined at length below.
a. Anionic detergent compositions which can be used in the compositions of this invention include both soap and non-soap detergent compounds. Examples of suitable soaps are the sodium, potassium, ammonium and 6 tallow, i.e., sodium or potassium tallow and coconut soap and tall oil. Examples of anionic organic non-soap detergent compounds are the water soluble salts, alkali metal salts of organic sulfuric reaction products having in their 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 compositions of the present invention are the sodium or potassium alkyl sulfates especially those obtained by sulfating the higher alcohols (C -C carbon atoms) produced by reducing the glycerides of tallow or coconut oil; sodium or potassium alkyl benzensulfonates in which the alkyl group contains from about 9 to about 20 carbon atoms and in which the alkyl group is attached t0 the benzene ring in either the one position or at the secondary positions such as in LAS,* sodium p- (Z-dodecyl-)benzenesulfonate, sodium p-(2- octadecyl)benzenesulfonates and sodium p-(3- dodecyl)benzenesulfonate; sodium alkyl glyceryl ether sulfonates, especially those ethers of the higher alcohols derived from tallow coconut oil and synthetic alcohols derived from petroleum; sodium coconut oil fatty acid monoglyceride sulfates and sulfonates; sodium or potassium salts of sulfuric acid esters and carboxymethylated derivatives of the reaction product of one mole of a higher fatty alcohol (e.g., tallow or coconut oil alcohols) and about 1 to 6 moles of ethylene oxide per molecule and in which the alkyl radicals contain about 9 to about 18 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 amides of methyl taurine in which the fatty acids, for example, are derived from coconut; alkane sulfonates such as those derived by reacting alpha-olefins containing 8 to 20 carbon atoms with sodium bisulfite and those derived by reacting paraffins with S0 and C1 and then hydrolyzing with a base to produce a random sulfonate; alpha-olefin sulfonates such as those derived by reacting alpha-olefins with $0 and then neutralizing the reaction product; and others known in the art.
*Sodium linear secondary alkyl (Cw-C benzene sulfonate.
b. Nonionic synthetic detergents may be broadly defined as compounds which do not ionize in water solution. 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 1,500 to 1,800. 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 product 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:
1. The polyethylene oxide condensates of alkylphenols, e.g., the condensation products of alkylphenols having an alkyl group 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 to 25 moles of ethylene oxide per mole of alkylphenols. The alkyl substituent in such compounds may be derived from polymerized propylene, disobutylene, octene, dodecene, or nonene, for example.
2. Those derived from the condensation of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine. For example, compounds containing from about 40% to about 80% polyoxyethylene by weight and having a molecular weight of from about 5,000 to about 1 1,000 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 hydrophobic base having a molecular weight of the order of 2,500 to 3,000 are satisfactory.
3. The condensation product of aliphatic alcohols, primary or secondary, having from 8 to 18 carbon atoms, in either straight chain or branched configuration, with ethylene oxide, e.g., a coconut alcoholethylene oxide condensate having from 6 to 30 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction having from to 14 carbon atoms; a C, C random secondary alcohol derived from n-paraffins and condensed with 7 moles of ethylene oxide per mole of secondary alcohol.
4. Long chain tertiary amine oxides corresponding to the following .general formula, R R R N 0, wherein R is an alkyl radical of from about 8 to 18 carbon atoms and R and R are each methyl, ethyl or hydroxy ethyl radicals. The arrow in the formula is a conventional representation of a semi-polar bond. Examples of amine oxides suitable for use in this invention include dimethyloctylamine oxide, dimethyldecylamine oxide, dimethyldodecylamine oxide, dimethyltetradecylamine oxide and dimethylhexadecylamine oxide, N-bis(hydroxyethyl)- dodecylamine oxide.
5. Long chain tertiary phosphine oxides corresponding to the following formula RR'R"P- O, wherein R is an alkyl, alkenyl or monohydroxyalkyl radical ranging from 10 to 18 carbon atoms in chain length and R and R" are each alkyl or monohydroxyalkyl groups containing from 1 to 3 carbon atoms. The arrow in the formula is a conventional representation of a semi-polar bond. Examples of suitable phosphine oxides are:
dimethyldodecylphosphine oxide,
dimethyltetradecylphosphine oxide, ethylmethyltetradecylphosphine oxide, cetyldimethylphosphine oxide, dimethylstearylphosphine oxide, cetylethylpropylphosphine oxide, diethyldodecylphosphine oxide, diethyltetradecylphosphine oxide, bis(hydroxymethyl)dodecylphosphine oxide, bis(2-hydroxyethyl)dodecylphopshine oxide,
Z-hydroxypropylmethyltetradecylphosphine oxide,
dimethyloleylphosphine oxide, and
dimethyl-2-hydroxydodecylphosphine oxide.
6. Dialkyl sulfoxides corresponding to the following formula, RR'S O, wherein R is an alkyl, alkenyl, betaor gamma-monohydroxyalkyl radical or an alkyl or betaor gamma-monohydroxyalkyl radical containing one or two other oxygen atoms in the chain, the R groups ranging from 10 to 18 carbon atoms in chain length. and wherein R is methyl, ethyl or alkylol. Examples of suitable sulfoxide compounds are:
dodecyl methyl sulfoxide tetradecyl methyl sulfoxide 3-hydroxytridecyl methyl sulfoxide 2-hydroxydodecyl methyl sulfoxide 3-hydroxy-4-decyloxybutyl methyl sulfoxide 3-hydroxy-4-dodecylcoxybutyl methyl sulfoxide 2-hydroxy-3-decyloxypropyl methyl sulfoxide 2-hydroxy-3-dodecyloxypropyl methyl sulfoxide dodecyl ethyl sulfoxide 2-hydroxydodecyl ethyl sulfoxide dodecyl-2-hydroxy ethyl sulfoxide c. Ampholytic synthetic detergents can be broadly described as derivatives of aliphatic secondary and tertiary amines, in which the aliphatic radical may be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic water solubilizing group. Examples of compounds falling within this definition are sodium-3-dodecylaminopropionate and sodium-3-dodecylaminopropanesulfonate and sodium N-2- hydroxydodecyl-N-methyl-taurate.
d. Zwitterionic synthetic detergents can be broadly described as derivatives of aliphatic quaternary ammonium compounds, sulfonium compounds and phosphonium compounds in which the aliphatic radical may be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic water solubilizing group. Examples of compounds falling within this definition are 3-(N,N-dimethyl-N- hexadecylamonio )propanel -sulfonate, 3-( N,N- dimethyl-N-hexadecylammonio)-2-hydroxypropanel sulfonate, 3-(dodecylmethylsulfonium) propane sulfonate, and 3-(cetylmethylphosphonium)ethane sulfonate.
Other materials which may be present in the detergent compositions of the invention in generally minor amounts are those conventionally present therein. Typical examples thereof include the well-known soilsuspending agents, hydrotropes, corrosion inhibitors, dyes, perfumes, fillers such as sodium sulfate, optical brighteners, perborates, bleaches, bleach activators, enzymes, suds boosters, suds depressants germicides, fungicides, anti-tarnishing agents, cationic detergents, fabric softening agents and in the case of liquid compositions, opacifiers and organic solvents. The balance of the detergent compositions may be water or inert filler.
It has been discovered that when higher than normal levels of anionic, nonionic, ampholytic or Zwitterionic surfactants are used with the sulfosuccinate derivative salts of this invention, the detergency of the formulation is significantly enhanced particularly at low form ulation concentration (-0.1%) which are typically used by the US. housewife. For enhanced results the detergent formulation sould contain surfactant levels of about 25% to about 45% by weight and the sulfosuccinate derivative salt levels of about 25% to about by weight in the cases where the surfactants are anionic, ampholytic of switterionic. When the surfactant is a nonionic, enhanced detergency results are obtained when the level of said nonio nic in the formuation is from about 15% to 30% by weight and the level of sulfosuccinate derivative salt is from about 25% to aboutby weight.
washing conditions are as indicated and the results reported as detergency units. The average detergency units (DU) of the formulation is the final reflectance value of the washed cloth (average of 2 runs) minus the initial reflectance of the soiled cloth, the reflectances being obtained by measurement with a Gardner automatic color difference meter, Model AC-3.
TABLE 1 Component 7( Composition ahydroxy" 50 a-(2 hydroxyethoxy) a-dodecyloxy" a-methoxy" a-carboxymethoxy" a-dodecyloxyethoxy" a-dodecylthio" Na -,P -,O Sodium silicate (SiO :Na O
2.4:l Anionic" Anionic" Nonionic" Ampholytic" Zwitterionic Water Formulation Concentration, 7: Detergency (DUs) Component ahydroxy" a-(2hydroxyethoxy)" a-dodecyloxy" a-methoxy" a-carboxymethoxy a-dodecyloxyethoxy" a-dodecylthio" Na P o Sodium silicate (siO zNa o 2.431 Anionic Anionic Nonionic" Ampholytic" Zwitterionic Water Formulation Concentration, 7r Detergency (DUs) Controls (7! Composition) l8 bal 0.2 0.2 0.2 0.2 0.2
"Sodium salts of a-substitutcd-B-sulfosuccinutc Sodium linear secondary alkyl (C -C bcnzcnc sulfonatc "C,,C,,, linear secondary alcohols ethoxylatcd with 7 moles ethylene oxide/mole alcohol C -C HAMT (sodium hydroxyalkyl N-mcthyl taurutc) 'Sultobctainc DCH (cododimcthylsull'opropyl bctuinc) Washing conditions 180 ppm (2:1 Ca'VMg): l20F: pH 10 compounds of the invention are excellent metal cleaning compounds.
Table 1 further illustrates the present invention. The detergent formulations set forth in the Table represent detergent compositions containing the builders of the present invention in combination with representative classes of surface active agents compared with control or standard phosphate built detergent compositions. The compositions were prepared by blending together the recited components in the proportions indicated, including an anticorrosive agent and buffer agent (sodium silicate). The compositions were then tested on vacuum cleaner dust soiled cloth for detergency or cleaning ability in the Terg-O-Tometer test; wherein EXAMPLE 1 Preparation of Trisodium a-Hydroxy-B-Sulfosuccinate Sulfomaleic anhydride was prepared by heating a mixture of 1 mole of sulfur trioxide with 1 mole of maleic anhydride first at 60C until the exothermic reaction subsided and then at l 10C for 3 hours. 45 gm of Sulfomaleic anhydride product was then mixed with 45 gm of ice and the resulting solution extracted 25 times with 50 ml portions to ether to remove maleic acid. A 20 ml portion of the resulting aqueous phase was collected, adjusted to pH ll with calcium hydroxide and refluxed for 4 hours. NMR analysis indicated that all of the sulfomaleic acid had hydrated within the first hour of reflux. The reaction mixture was then passed through a column of cation exchange resin. A portion of the effluent was then neutralized to pH 8.5 and evaporated to a white crystalline-residue 19.2 gm), which contained 80.9% of trisodium a-hydroxy-B- sulfosuccinate as determined by. NMR analysis (using D solvent and K biphthalate as an internal standard) and 10.4% water by Karl Fischer analysis.
EXAMPLE 2 a-Thiosubstituted-B-Sulfosuccinates The procedure of Example 1 is repeated except that in place of Ca(OH) the pH is adjusted to 8.6 with NaOH. Then, an aqueous solution containing excess sodium hydrosulfide, sodium methyl mercaptide or sodium ethyl mercaptide is added and the resulting solution allowed to stand overnight. The reaction mixture is then passed through a column of cation exchange resin and the effluent evaporated to low volume. The pH is the adjusted to 8.5 with sodium hydroxide and the solution evaporated to dryness. In this way, there is afforded respectively:
trisodium a-mercapto-B-sulfosuccinate trisodium a-methylthio-B-sulfosuccinate trisodium a-ethylthio-B-sulfosuccinate EXAMPLE 3 Preparation of Trisodium a-Methoxy-B-Sulfosuccinate Sulfomaleic anhydride, 3.9 gm,'was dissolved in 25 ml of methanol and refluxed for hours. Then, 24 gm of 25% sodium methoxide in methanol was added and the solution was refluxed for 2 hours. The methanol was then evaporated and the residue was dissolved in 100 ml of water and heated for 1 hour at 80C. The solution was then decolorized with 5 gm of charcoal, filtered and evaporated. The crude residue of trisodium a-methoxy-B-sulfosuccinate was purified by trituration with acetic acid and then filtered, washed with acetone and dried.
a-ethoxy-B-sulfosuccinate may be prepared by substituting ethanol and sodium ethoxide in the procedure described above.
EXAMPLE 4 Preparation of Trisodium a-Dodecyloxy-B-Sulfosuccinate standard sodium hydroxide: neutralization equivalent:
found 147.0, theory 149.3).
EXAMPLE 5 Preparation of Trisodium a-Dodecyloxyethoxy-B-Sulfosucc inate Using the procedure of Example 4 and substituting 37 gm (0.32 mole) of 2-dodecyloxyethanol in place of the n-dodecanol there is obtained trisodium wdodecyloxyethoxy-B-sulfosuccinate. i
EXAMPLES 6-8 EXAMPLE 9 Preparation of Trisodium a-Hydroxyethoxy-B-Sulfosuccinate Sulfomaleic anhydride (20 gm) is mixed with 37.2 gm (0.6 mole) of ethylene glycol and heated at 80C for 4 hours. A solution of 16 gm (0.4 mole) of sodium hydroxide in ml of water is then added and the mixture heated at C for 4 hours. The mixture is then mixed with acetone to precipitate trisodium a-hydroxyethoxy-B-sulfosuccinate, which is purified by repeated extractions with hot acetone to remove all ethylene glycol and water followediby filtration and drying in an oven.
EXAMPLE 10 Preparation of the Tetrasodium Salt of a-Carboxymethyloxy-B-Sulfosuccinic Acid Sulfomaleic anhydride (19.4 gm) is heated to 60C and combined with 76 gm of ethyl glycolate. After heating the mixture at 80C for 5% hours, there is added a solution of 45 gm of sodium hydroxide dissolved in gm of water and heating is continued at 80 for an additional three hours. The mixture is then diluted with water and passed through a column of a cation exchange resin. The resulting eluent is then evaporated in vacuo to a low volume and the concentrate extracted repeatedly with acetone to remove glycolic acid and other impurities. The resulting extracted residue is then dissolved in water and the pH of the solution adjusted to 8.6 with dilute sodium hydroxide. Evaporation of the solution in vacuo and drying over P 0 gives a residue of the tetrasodium salt of a-carboxymethyloxy-B-sulfosuccinic acid.
Example 1 1 Preparation of Trisodium a( 2-Hydroxyethylamino )-B-Sulfosuccinate added slowly and the temperature allowed to rise to I room temperature. After standing overnight, the reaction mixture was poured into 800 ml of acetone. The solvent was then decanted from the resulting syrupy lower layer and the latter reprecipitated three times from water with fresh acetone. The residue was then dried in a dessicator over P 0 to give 38.8 gm of an off-white, granular product containing approximately 88% trisodium a-(2-hydroxyethylamino)-B- a ethanol/water and dioxane/water is used together with temperatures in the range of 2580C.
Table 2 indicates the reactants and procedure required to obtain other a-substituted-B-sulfosuccinate salts having the R and Z moieties set forth in Formula I.
TABLE 2 Example Reactants (Sulfomaleic Anhydride H Alkyl (C -C Alkyl (c ow) H, cintcuo umcn cmo cmc- "Followed by oxidation to sulloxidc ac Water C or C alcohol C -C primary, secondary or tertiary alcohol Phenol Methyl salicylate Alkylphenol o, m. p cresol. carvacrol, thymol Ethyl glycolate Methyl-Bhydroxypropionate lsethionic acid R'O(CH CH O)"CH CH OH HOCH CH OCH CH OH HO(CH CH O)3CH CH OH HO(CH CH O)|0CH CH OH HO(CH CH O)|5CH CH OH CH CH O(CH CH O) CH CH OH CH (CH UO(CH CH O),,CH CH OH Trimethylene glycol Hexamethylene glycol Sodium hydrosulfide Sodium (C -C alkyl mercaptide C C; alkylmercaptan Thiophenol Methyl Z-mercaptobenzoate Alkylthiophenol Ethyl mercaptoncetatc Methyl B-mercaptopropionate Mercaptoethanesulfonic acid ROtCH CH 0),,CH CH SH HOCH CH OCH CH SNa HO(CH CH O) CH CH SN;1 HO(CH CH O) ,CH CH SNa HO(CH CH O), ,CH .CH SNa CHQCHQOCHQCHQO)3CH2CH2SH CH CH S(CH CH O);,CH CH SH cH,.,c|-|,s(cu cn oncH cn sH Sodium Z-hydroxyethylmercaptide Sodium 3-hydroxypropylmercaptide Sodium o-hydroxyhexylmercaptide C,C alkylmercaptan" C -C alkylmercaptan" Thiophenol" Methyl 2-mercaptobenzoate" alkylthiophenol" Ethylmercaptoacetate" Methyl B-mercaptopropionate" R'O(CH CH O).,CH CH SH" Sodium Z-hydroxyethylmercaptide Sodium 3-hydroxypropylmercaptide Sodium G-hydroxyhexylmercaptide (C -C alkylmercaptan" -C 1m alkylmercaptan" Thiophenol Methyl Z-mercaptobenzoate" Ethyl mercaptoacetate" Methyl Z-mercaptobutyrate" R'O(CH CH ,O),,CH CH SH" wwwtnm U7 U7 UHAUILIIUIUHIHAMZDMVDUHAMOOOQO O OOOOOCOOOOOOOO O00 bb I l NNNlJ-b-l 3 0000 cording to Ficscr reference.
"Followed by oxidation to sulfonc according to Ficscr rclcrcncci What is claimed is:
1. A detergent composition consisting essentially of a. at least one detergent surface active agent selected from the group consisting of anionic, nonionic. zwitterionic, and ampholytic agents; and,
b. from about 5 to about 95 weight percent of an or ganic detergent builder selected from the group consisting of an alkali metal, ammonium monoethanolammonium, diethanolammonium, triethanolammonium, methylammonium, dimethylammonium, trimethylammonium, tetramethylammonium, morpholinium, N-methylmonoethanolammonium and N-ethylmonoethanolammonium and N-ethylmonoethanolammonium salts and mixtures thereof of an a-substituted-B-sulfosuccinate having the general formula wherein;
R is selected from the group consisting of 1. alkyl containing 1 30 carbon atoms,
2. phenyl,
3. carboxy-substituted phenyl further containing mono-, di or tri-alkyl substituents wherein the alkyl groups contain 1-4 carbon atoms,
4. sulfoxyalkyl and carboxyalkyl wherein the alkyl moiety contains l-4 carbon atoms, and
5. R'Z(CH CH O)nCH CH wherein a. R is hydrogen or alkyl containing l-24 carbon atoms, b. Z is selected from the group consisting of O,
S, S0 and SO,
and,
c. n is an integer of 0-15; and Z is as previously defined.
2. The composition of claim 1 wherein the builder is an a-alkoxy-B-sulfosuccinate wherein the alkoxy group contains about l-24 carbon atoms.
3. The composition of claim 1 wherein the builder is an a-alkoxy-B-sulfosuccinate wherein the alkoxy group contains about 9-24 carbon atoms.
4. The composition of claim 1 wherein the builder is an a-alkoxy-B-sulfosuccinate wherein the alkoxy group contains about 1-8 carbon atoms.
5. The composition of claim 1 wherein the builder is a-dodecyloxy-B-sulfosuccinate.
6. The composition of claim 1 wherein the builder is a-hexadecyloxy-B-sulfosuccinate.
7. The composition of claim 1 wherein the builder is a-octadecyloxy-B-sulfosuccinate.
8. The composition of claim 1 wherein the builder is a-tetradecyloXy-B-sulfosuccinate.
9. The composition of claim 1 wherein the builder is a-hydroxyethoxy-B-sulfosuccinate.
10. The composition of claim 1 wherein the builder is a-alkoxyethoxy-B-sulfosuccinate wherein the alkoxy moiety contains about 1-24 carbon atoms.
11. The composition of claim 1 wherein the builder is a-dodecyloxyethoxy-B-sulfosuccinate.
12. The composition of claim 1 wherein the builder is oz-carboxymethoxy-B-sulfosuccinate.
13. A composition of claim 1 wherein the builder is a salt of an a-substituted-,B-sulfosuccinic acid having the general formula:
wherein R is selected from the group consisting of alkyl containing l-30 carbon atoms, phenyl, carboxy substituted and monodior tri-alkyl substituted phenyl wherein the alkyl group or groups contain l-4 carbon atoms, sulfo and carboxy alkyl wherein the alkyl moiety contains 1-4 carbon atoms; and R'Z(CH CH O)- nCh CH wherein R is H or alkyl containing l-24 carbon atoms, n is O or an integer of from l-l5 and Z is O, S, S0 or S0 I 14. A composition of claim 1 wherein the builder is a salt of an a-substituted-B-sulfosuccinic acid having the general formula:
wherein R is selected from the group consisting of alkyl containing 1-30 carbon atoms, phenyl substituted phenyl wherein the phenyl ring contains one carboxyl group and one, two or three alkyl groups wherein the alkyl group or groups contain l-4 carbon atoms, sulfo and carboxy alkyl wherein the alkyl moiety contains l-4 carbon atoms; and R'Z(CH CH O )nCH CH wherein R is H or alkyl contaiing 1-24 carbon atoms, n is O or an integer of from 1-15 and Z is O, S, S0 or S0 15. A composition of claim 1 wherein the builder is a salt of an a-substituted-B-sulfosuccinic acid having the general formula:
wherein R is selected from the group consisting of hydrogen, alkyl containing l-3O carbon atoms, phenyl, substituted phenyl wherein the phenyl ring contains one carboxyl group and one, two or three alkyl groups wherein the alkyl group or groups contain 1-4 carbon atoms, sulfoand carboxy-alkyl wherein the alkyl moiety contains l-4 carbon atoms; and R'Z(CH CH O)- n-CH CH wherein R is H or alkyl containing l-24 carbon atoms, n is 0 or an integer of from l-l5 and Z is selected from the group consisting of O, S, SO and S0 16. The composition of claim 15 wherein the builder is an a-alkylthio-B-sulfosuccinate containing about l-24 carbon atoms in the alkylthio moiety.
17. The composition of claim 15 wherein the builder is an oz-alkylthio-B-sulfosuccinate containing about 1-8 carbon atoms in the alkylthio moiety.
18. The composition of claim 15 wherein the builder is an a-alkylthio-B-sulfosuccinate containing about 9-24 carbon atoms in the alkylthio moiety.
19. The composition of claim 15 wherein the builder is an a-dodecylthio-B-sulfosuccinate.
20. The composition of claim 15 wherein the builder is an a-hexadecylthio-B-sulfosuccinate.
is an a-octadecylthio-B-sulfosuccinate.
22. A detergent composition consisting essentially of a. at least one detergent surface active agent selected from the group consisting of anionic, nonionic, Zwitterionic and ampholytic agents; and,
b. from about 5 to about 95 weight percent of an organic detergent builder selected from the group consisting of alkali metal, ammonium monocthanolammonium, diethanolammonium, triethanolammonium, methylammonium, dimethylammonium, trimethylammonium, tetramethylammonium, morpholinium, N-methylmonoethanolammonium and N-ethylmonoethanolammonium salts and mixtures thereof of an a-substituted-B-sulfosuccinate having the basic for mula:
OOH OOH wherein R is selected from the group consisting of hydrogen, alkyl containing [-30 carbon atoms, phenyl substituted phenyl wherein the phenyl ring contains one carboxyl group and one, two or three alkyl groups wherein the alkyl groups contain [-4 carbon atoms, sulfo and carboxy-alkyl wherein the alkyl moiety contains 1-4 carbon atoms and R'Z(CH CH O) nCH CH wherein R is hydrogen or alkyl containing l24 carbon atoms, n is an integer of 0-15, and z is selected from the group consisting of O, S, SO and S0 or mixtures thereofv 23. The composition of claim 1 wherein the builder is a-hydroxy-B-sulfosuccinate.

Claims (32)

1. ALKYL CONTAINING 1 - 30 CARBON ATOMS,
1. A DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF A. AT LEAST ONE DETERGENT SURFACE ACTIVE AGENT SELECTED FROM THE GROUP CONSISTING OF ANIONIC, NONIONIC, ZWITTERIONIC, AND AMPHOLYTIC AGENTS, AND, B. FROM ABOUT 5 TO ABOUT 95 WEIGHT PERCENT OF AN ORGANIC DETERGENT BUILDER SELECTED FROM THE GROUP CONSISTING OF AN ALKALI METAL, AMMONIUM MONOETHANOLAMMONIUM, DIETHANOLALMMONIUM, TRIETHANOLAMMONIUM, METHYLAMMONIUM, DIMETHYLAMMONIUM, TRIMETHYLAMMONIUM, TETRAMETHYLAMMONIUM, MORPHOLINIUM, N-METHYLMONOETHANOLAMMONIUM AND N-ETHYLMONOETHANOLAMMONIUM AND N-ETHYLMONOETHANOLMMONIUM SALTS AND MIXTURES THEREOF OF AN A-SUBSTITUTED-B-SULFO-SUCCINATE HAVING THE GENERAL FORMULA
2. phenyl,
2. The composition of claim 1 wherein the builder is an Alpha -alkoxy- Beta -sulfosuccinate wherein the alkoxy group contains about 1-24 carbon atoms.
2. PHENYL,
3. The composition of claim 1 wherein the builder is an Alpha -alkoxy- Beta -sulfosuccinate wherein the alkoxy group contains about 9-24 carbon atoms.
3. carboxy-substituted phenyl further containing mono-, di or tri-alkyl substituents wherein the alkyl groups contain 1-4 carbon atoms,
3. CARBOXY-SUBSTITUTED PHENYL FURTHER CONTAINING MONO-, DI OR TRI-ALKYL SUBSTITUENTS WHEREIN THE ALKYL GROUPS CONTAIN 1-4 CARBON ATOMS,
4. SULFOXYALKYL AND CARBOXYALKYL WHEREIN THE ALKYL MOIETY CONTAINS 1-4 CARBON ATOMS, AND
4. sulfoxyalkyl and carboxyalkYl wherein the alkyl moiety contains 1-4 carbon atoms, and
4. The composition of claim 1 wherein the builder is an Alpha -alkoxy- Beta -sulfosuccinate wherein the alkoxy group contains about 1-8 carbon atoms.
5. The composition of claim 1 wherein the builder is Alpha -dodecyloxy- Beta -sulfosuccinate.
5. R''Z(CH2CH2O)n-CH2CH2 wherein a. R'' is hydrogen or alkyl containing 1-24 carbon atoms, b. Z is selected from the group consisting of O, S, SO2 and SO,
5. R''Z(CH2CH2O)N-CH2CH2 WHEREIN A. R'' IS HYDROGEN OR ALKYL CONTAINING 1-24 CARBON ATOMS, B. Z IS SELECTED FROM THE GROUP CONSISTING OF O, S, SO2 AND SO, -O-N(-R1)AND, C. N IS AN INTEGER OF 0-15, AND Z IS AS PREVIOUSLY DEFINED.
6. The composition of claim 1 wherein the builder is Alpha -hexadecyloxy- Beta -sulfosuccinate.
7. The composition of claim 1 wherein the builder is Alpha -octadecyloxy- Beta -sulfosuccinate.
8. The composition of claim 1 wherein the builder is Alpha -tetradecyloxy- Beta -sulfosuccinate.
9. The composition of claim 1 wherein the builder is Alpha -hydroxyethoxy- Beta -sulfosuccinate.
10. The composition of claim 1 wherein the builder is Alpha -alkoxyethoxy- Beta -sulfosuccinate wherein the alkoxy moiety contains about 1- 24 carbon atoms.
11. The composition of claim 1 wherein the builder is Alpha -dodecyloxyethoxy- Beta -sulfosuccinate.
12. The composition of claim 1 wherein the builder is Alpha -carboxymethoxy- Beta -sulfosuccinate.
13. A composition of claim 1 wherein the builder is a salt of an Alpha -substituted- Beta -sulfosuccinic acid having the general formula:
14. A composition of claim 1 wherein the builder is a salt of an Alpha -substituted- Beta -sulfosuccinic acid having the general formula:
15. A composition of claim 1 wherein the builder is a salt of an Alpha -substituted- Beta -sulfosuccinic acid having the general formula:
16. The composition of claim 15 wherein the builder is an Alpha -alkylthio- Beta -sulfosuccinate containing about 1-24 carbon atoms in the alkylthio moiety.
17. The composition of claim 15 wherein the builder is an Alpha -alkylthio- Beta -sulfosuccinate containing about 1- 8 carbon atoms in the alkylthio moiety.
18. The composition of claim 15 wherein the builder is an Alpha -alkylthio- Beta -sulfosuccinate containing about 9-24 carbon atoms in the alkylthio moiety.
19. The composition of claim 15 wherein the builder is an Alpha -dodecylthio- Beta -sulfosuccinate.
20. The composition of claim 15 wherein the builder is an Alpha -hexadecylthio- Beta -sulfosuccinate.
21. The composition of claim 15 wherein the builder is an Alpha -octadecylthio- Beta -sulfosuccinate.
22. A detergent composition consisting essentially of a. at least one detergent surface active agent selected from the group consisting of anionic, nonionic, zwitterionic and ampholytic agents; and, b. from about 5 to about 95 weight percent of an organic detergent builder selected from the group consisting of alkali metal, ammonium monoethanolammonium, diethanolammonium, triethanolammonium, methylammonium, dimethylammonium, trimethylammonium, tetramethylammonium, morpholinium, N-methylmonoethanolammonium and N-ethylmonoethanolammonium salts and mixtures thereof of an Alpha -substituted- Beta -sulfosuccinate having the basic formula:
23. The composition of claim 1 wherein the builder is Alpha -hydroxy- Beta -sulfosuccinate.
US401482A 1971-06-25 1973-09-27 Sulfosuccinate derivatives as detergent builders Expired - Lifetime US3912663A (en)

Priority Applications (24)

Application Number Priority Date Filing Date Title
DE19722230073 DE2230073A1 (en) 1971-06-25 1972-06-20 Alpha-substituted beta-sulfosuccinic acids and their use as builders in detergents
GB2905772A GB1398421A (en) 1971-06-25 1972-06-21 Sulphosuccinate derivatives for use as detergent builders
GB78575A GB1398422A (en) 1971-06-25 1972-06-21 Sulphosuccinate derivatives as detergent builders
AT542872A AT321437B (en) 1971-06-25 1972-06-23 laundry detergent
CH775776A CH588452A5 (en) 1971-06-25 1972-06-23
FR727222899A FR2143437B1 (en) 1971-06-25 1972-06-23
CH942672A CH588551A5 (en) 1971-06-25 1972-06-23
NL7208735A NL7208735A (en) 1971-06-25 1972-06-26
US394613A US3925375A (en) 1971-06-25 1973-09-05 Sulfosuccinate derivatives as detergent builders
US401482A US3912663A (en) 1971-06-25 1973-09-27 Sulfosuccinate derivatives as detergent builders
US05/484,916 US3936448A (en) 1971-06-25 1974-07-01 α-Amino-β-sulfosuccinates
US484744A US3922272A (en) 1971-06-25 1974-07-01 Sulfosuccinate derivatives as detergent builders
US484919A US3917601A (en) 1971-06-25 1974-07-01 Sulfosuccinate derivatives as detergent builders
US484741A US3922271A (en) 1971-06-25 1974-07-01 Sulfosuccinate derivatives as detergent builders
US05/484,920 US3957775A (en) 1971-06-25 1974-07-01 Sulfosuccinate derivatives as detergent builders
US05/484,917 US3935206A (en) 1971-06-25 1974-07-01 Sulfosuccinate derivatives as detergent builders
US05/484,918 US3950331A (en) 1971-06-25 1974-07-01 Sulfosuccinate derivatives as detergent builders
US05/578,703 US3968110A (en) 1971-06-25 1975-05-19 Sulfosuccinate derivatives as detergent builders
US05/578,705 US3984408A (en) 1971-06-25 1975-05-19 Sulfosuccinate derivatives as detergent builders
US05/578,704 US3976642A (en) 1971-06-25 1975-05-19 Sulfosuccinate derivatives as detergent builders
US05/589,959 US3989700A (en) 1971-06-25 1975-06-24 Sulfosuccinate derivatives as detergent builders
US05/589,960 US3970653A (en) 1971-06-25 1975-06-24 Sulfosuccinate derivatives as detergent builders
US05/589,961 US3987043A (en) 1971-06-25 1975-06-24 Sulfosuccinate derivatives as detergent builders
US05/647,246 USRE29576E (en) 1971-06-25 1976-01-07 Sulfosuccinate derivatives as detergent builders

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US15693371A 1971-06-25 1971-06-25
US394613A US3925375A (en) 1971-06-25 1973-09-05 Sulfosuccinate derivatives as detergent builders
US401482A US3912663A (en) 1971-06-25 1973-09-27 Sulfosuccinate derivatives as detergent builders
US484919A US3917601A (en) 1971-06-25 1974-07-01 Sulfosuccinate derivatives as detergent builders
US484744A US3922272A (en) 1971-06-25 1974-07-01 Sulfosuccinate derivatives as detergent builders
US05/484,917 US3935206A (en) 1971-06-25 1974-07-01 Sulfosuccinate derivatives as detergent builders
US05/484,920 US3957775A (en) 1971-06-25 1974-07-01 Sulfosuccinate derivatives as detergent builders
US05/484,916 US3936448A (en) 1971-06-25 1974-07-01 α-Amino-β-sulfosuccinates
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US05/484,917 Expired - Lifetime US3935206A (en) 1971-06-25 1974-07-01 Sulfosuccinate derivatives as detergent builders
US484741A Expired - Lifetime US3922271A (en) 1971-06-25 1974-07-01 Sulfosuccinate derivatives as detergent builders
US484919A Expired - Lifetime US3917601A (en) 1971-06-25 1974-07-01 Sulfosuccinate derivatives as detergent builders
US05/484,920 Expired - Lifetime US3957775A (en) 1971-06-25 1974-07-01 Sulfosuccinate derivatives as detergent builders
US05/484,916 Expired - Lifetime US3936448A (en) 1971-06-25 1974-07-01 α-Amino-β-sulfosuccinates
US484744A Expired - Lifetime US3922272A (en) 1971-06-25 1974-07-01 Sulfosuccinate derivatives as detergent builders
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US484919A Expired - Lifetime US3917601A (en) 1971-06-25 1974-07-01 Sulfosuccinate derivatives as detergent builders
US05/484,920 Expired - Lifetime US3957775A (en) 1971-06-25 1974-07-01 Sulfosuccinate derivatives as detergent builders
US05/484,916 Expired - Lifetime US3936448A (en) 1971-06-25 1974-07-01 α-Amino-β-sulfosuccinates
US484744A Expired - Lifetime US3922272A (en) 1971-06-25 1974-07-01 Sulfosuccinate derivatives as detergent builders
US05/647,246 Expired - Lifetime USRE29576E (en) 1971-06-25 1976-01-07 Sulfosuccinate derivatives as detergent builders

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US (9) US3925375A (en)
AT (1) AT321437B (en)
CH (2) CH588551A5 (en)
DE (1) DE2230073A1 (en)
FR (1) FR2143437B1 (en)
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NL (1) NL7208735A (en)

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US4056491A (en) * 1974-08-05 1977-11-01 Ppg Industries, Inc. Detergent compositions of trisulfosuccinic acid
US5034158A (en) * 1989-10-24 1991-07-23 Shell Oil Company Monionic surfactant based powdered laundry detergent formulation containing an alkenyl or alkyl carboxysulfonate component
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US3328314A (en) * 1964-06-17 1967-06-27 Chevron Res Noncaking straight-chain alkyl aryl sulfonate detergent compositions
US3635830A (en) * 1968-05-24 1972-01-18 Lever Brothers Ltd Detergent compositions containing oxydisuccing acid salts as builders
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US4056491A (en) * 1974-08-05 1977-11-01 Ppg Industries, Inc. Detergent compositions of trisulfosuccinic acid
US3976586A (en) * 1975-10-08 1976-08-24 Gaf Corporation Monoesters derived from ethoxylated higher alcohols and thiodisuccinic acid as detergent builders
US5034158A (en) * 1989-10-24 1991-07-23 Shell Oil Company Monionic surfactant based powdered laundry detergent formulation containing an alkenyl or alkyl carboxysulfonate component
WO2006117070A1 (en) * 2005-05-05 2006-11-09 Unilever Plc Method for bleaching laundry

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CH588551A5 (en) 1977-06-15
GB1398421A (en) 1975-06-18
US3957775A (en) 1976-05-18
USRE29576E (en) 1978-03-14
US3922272A (en) 1975-11-25
NL7208735A (en) 1972-12-28
US3922271A (en) 1975-11-25
US3936448A (en) 1976-02-03
DE2230073A1 (en) 1972-12-28
US3935206A (en) 1976-01-27
AT321437B (en) 1975-03-25
GB1398422A (en) 1975-06-18
US3917601A (en) 1975-11-04
US3925375A (en) 1975-12-09
FR2143437A1 (en) 1973-02-02
FR2143437B1 (en) 1973-07-13
CH588452A5 (en) 1977-06-15

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