US3922271A - Sulfosuccinate derivatives as detergent builders - Google Patents

Sulfosuccinate derivatives as detergent builders Download PDF

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Publication number
US3922271A
US3922271A US484741A US48474174A US3922271A US 3922271 A US3922271 A US 3922271A US 484741 A US484741 A US 484741A US 48474174 A US48474174 A US 48474174A US 3922271 A US3922271 A US 3922271A
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sodium
compounds
acid
sulfosuccinate
detergent
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US484741A
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Vincent Lamberti
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Lever Brothers Co
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Lever Brothers Co
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Priority to DE19722230073 priority Critical patent/DE2230073A1/en
Priority to GB78575A priority patent/GB1398422A/en
Priority to GB2905772A priority patent/GB1398421A/en
Priority to AT542872A priority patent/AT321437B/en
Priority to CH942672A priority patent/CH588551A5/xx
Priority to FR727222899A priority patent/FR2143437B1/fr
Priority to CH775776A priority patent/CH588452A5/xx
Priority to NL7208735A priority patent/NL7208735A/xx
Priority to US394613A priority patent/US3925375A/en
Priority to US401482A priority patent/US3912663A/en
Priority to US05/484,920 priority patent/US3957775A/en
Priority to US05/484,916 priority patent/US3936448A/en
Priority to US484741A priority patent/US3922271A/en
Priority to US05/484,918 priority patent/US3950331A/en
Application filed by Lever Brothers Co filed Critical Lever Brothers Co
Priority to US484744A priority patent/US3922272A/en
Priority to US05/484,917 priority patent/US3935206A/en
Priority to US484919A priority patent/US3917601A/en
Priority to US05/578,704 priority patent/US3976642A/en
Priority to US05/578,705 priority patent/US3984408A/en
Priority to US05/578,703 priority patent/US3968110A/en
Priority to US05/589,960 priority patent/US3970653A/en
Priority to US05/589,959 priority patent/US3989700A/en
Priority to US05/589,961 priority patent/US3987043A/en
Application granted granted Critical
Publication of US3922271A publication Critical patent/US3922271A/en
Priority to US05/647,246 priority patent/USRE29576E/en
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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

  • DETERGENT BUILDERS [75] inventor: Vincent Lamberti, Upper Saddle River, NJ.
  • R is hydrogen or an organic moiety
  • Z is selected from the group consisting of O, S, SO, S0 N and NO
  • M is an alkali metal, ammonium or substituted ammonium cations, useful as detergents and- /or detergent builders and detergent compositions containing same.
  • 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.
  • Formula I C 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-3O carbon atoms, phenyl, carboxyl substituted and monodior tri-alkyl substituted phenyl, wherein the alkyl group or groups contain l-4 carbon atoms; sulfoand carboxy-alkyl, wherein the alkyl moiety contains l-4 carbon atoms; and RZ(CH CH O)n-CH CH wherein R is N or alkyl containing l-24 carbon atoms; Z is as above; and n is O or an integer of from land the alkali metal, ammonium and substituted ammonium salts thereof.
  • a-hydroxy-B-sulfosuccinic acids a-alkoxy-B-sulfosuccinic acids a-phenoxyB-sulfosuccinic acids a-carboxyphenoxy-B-sulfosuccinic acids a-alkylphenoxy-B-sulfosuccinic acids a-carboxyalkoxy-fi-sulfosuccinic acids a-sulfoalkoxy-B-sulfosuccinic acids a-alkoxyethoxy-B-sulfosuccinic acids a-alkoxypo]yethyleneoxyethoxy-B-sulfosuccinic acids a-hydroxyalkoxy-B-sulfosuccinic acids;
  • R COOH COOH 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.
  • a-alkylamino-B-sulfosuccinic acids such as amethylamino, a-propylamino, a-octylamino and alaurylamino-B-sulfosuccinic acid;
  • a-dialkylamino-B-sulfosuccinic acids such as a-dimethylamino, a-ethylmethylamino, a-methylhexylamino and a-dioctylamino-B-sulfosuccinic acid;
  • oz-hydroxyalkyl-B-sulfosuccinic acids such as ahydroxyethylamino, oz-hydroxybutylamino and a-bis(- hydroxyethyl)amino-B-sulfosuccinic acid;
  • a-carboxyalkylaminoB-sulfosuccinic acids such as a-carboxymethylamino, a-carboxyethylamino-B-sulfosuccinic acid and the corresponding sulfo analogs;
  • 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 as defined are intended to include all of the stereoisomeric forms and mixtures thereof.
  • certain select members also exhibit properties whichmake them useful as wetting and foaming agents and thus constitute a class of novel surface active agents.
  • the a-alkoxy-B-sulfosuccinic acids and the thio analogs containing from about 1-8 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 9-24 carbon atoms in the alkyl chain, additionally exhibit wetting, foaming and detergency properties.
  • a-alkoxyethoxy and walkoxypolyethyleneoxyethoxy-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 oz-substituted-B-sulfosuccinic acids are preferred. Included in the substituted ammonium salts that can be employed are the monoethanolammonium, diethanolammoniurn, triethanolammonium, methylammonium, dimethylammonium, trimethylammonium, tetramethylamrnoniurn, 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 building and biodegradability properties but also in low costof 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 1,2-diols containing from 8-30 carbon atoms and aromatic carbocyclic glycols such as phenylethylene glycol.
  • suitable polyhydric alcohols include glycerol, pentacrythritol, hexanetriol, sugars and their thio analogs.
  • the hydroxy carboxylic and sulfonic acids may also react with sulfomaleic anhydride and sulfomaleic acid.
  • sulfomaleic anhydride includeglycollic, lactic, glyceric, hydroxypropionic, salicyclic andmercapto acetic acid, hydroxymethanesulfonic acidfand.
  • Still another important class of compounds containing active hydrogens are ethylene oxide adducts of Cr '1 I moles, a of ethylene oxide.
  • the desired u-oxy or athio-Bsul-' g fosuccinate may. then be recovered and purified using conventional techniques.
  • the oz-substituted-B-sulfosuccinate salts wherein the. oz-substituent is joined to the a-carbon atom of the sul-i s fosuccinate moiety by an S0 or SO linkage may be prepared by treating the appropriate a-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, lnc., 1967, incorporated by reference herein.
  • the zx-substituted-B-sulfosuccinate salts wherein the I a-substituent is joined to the a-carbon atom of the sul-f I fosuccinate moiety, by an amino function may be prepared by reacting an appropriately substituted or unsubstituted primary or secondaryamine with'alkali metal salts of sulfomaleic acid.
  • the oz-amino.substituted-,B-sulfosuccinates derived from water-soluble amines may be pre-I I pared by reacting in aqueous solution without the aid of t heat and 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 tem- V peratures ranging from about 25C to about C; isolation from the reaction medium, andpurification if desired, being effected by conventional methods.
  • a mixed solvent system such as ethanol/water or dioxane/water
  • the compounds of Formula III may be prepared by reacting the tertiary amine compounds of Formula II ,7 with oxidizing agents such as hydrogen peroxide, per- 7 oxyacetic and peroxyformic acid in the manner def scribed, for oxidizing tertiary amines by Hohet al., J.
  • the amount of base utilized will determine 1 whether the monodior tri-salt is obtained.
  • base i.e., sodium hydroxide
  • the use of one mole of base (i.e., sodium hydroxide) per mole of oz-hydroxy-/3sulfosuccinic acid yields the monosodium salt, the use of two moles of sodium the alkyl chain, as well as other amines having a replaceable hydroxide, the disodium salt and the use of three moles of sodium hydroxide, the trisodium salt.
  • R is carboxymethyl, carboxyethyl, sulfomethyl or sulfoethyl
  • 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 l l 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 percent of the builder-present in thedetergent 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 toabout :1, and preferably 2:] 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 alkylolammonium salts of higher fatty acids (C 10"C20).
  • Particularly useful are the sodium or potassium salts of the mixtures of fatty acids derived from coconut oil and 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 5 sulfuric acid esterradicals.
  • Important examples of the synthetic detergentswhich 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 glyceridesof 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 to the benzene ring in either the one position or at the secondary positions such as in LAS,* sodium p- (2-dodec yl- )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 s
  • Nonionic synthetic detergents maybe 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 chainor branched chain configuration, withethylene oxide, the said ethylene oxide being present in amounts equal to S to 25 moles of ethylene oxide per mole of alkylphenols.
  • 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 alcohol-ethylene oxide condensate having from 6 to 30 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction having from 10 to 14 carbon atoms; a C,,-C, random secondary. alcohol derived from n-paraffins and condensed with 7 moles of ethyl ene oxide per mole of secondary alcohol.
  • amine oxides corresponding to the following general formula, R,R R l ⁇ l 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.
  • Long chain tertiary phosphine oxides correspond. ing to the following formula RRRP 0, 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 semipolar bond. Examples of suitable phosphine oxides are:
  • dimethyltetradecylphosphine oxide dimethyltetradecylphosphine oxide, ethylmethyltetradecylphosphine oxide, ethyldimethylphosphine oxide, dimethylstearylphosphine oxide, cetylethylpropylphosphine oxide, diethyldodecylphosphine oxide, diethyltetradecylphosphine oxide, bis(hydroxymethyl)dodecylphosphine oxide, bis(2-hydroxyethyl)dodecylphosphine oxide, 2-hydroxypropylmethyltetradecylphosphine oxide, dimethyloleylphosphine oxide, and dimethyl-Z-hydroxydodecylphosphine oxide.
  • Dialkyl sulfoxides corresponding to the following formula, RRS -+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.
  • RRS -+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.
  • suitable sulfoxide compounds are:
  • Ampholytic synthetic detergents can be broadly de- I scribed as derivatives of aliphatic secondary and, tertiary amines, in which the aliphatic radical may be. straight chain or branched and wherein one ofthe aliphatic substituents contains from about 8 to l8carbon atoms and one contains an anionic water solubilizing.
  • 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 ali phatic substituents contains from about 8 to l8carbon atoms and one contains an anionic water solubilizing group.
  • Examples of compounds falling within this defi nition are 3-(N,N-dimethyl-N-hexadecylamm0nio)pro- 3'( N,Ndimethyl-N-hexadecylammonio)-2-hydroxypropane-l-sulfonate, 3-(dodecylmethylsulfonium) propane sulfonate, and 3-(cetylmethylphosphonium )ethane t su lfonate.
  • compositions of the invention include those conventionally present therein.
  • Typ 5 ical examples thereof include the well-known soil-sus.- pending agents, hydrotropes, corrosion inhibitors, dyes, perfumes, fillers such as sodium sulfate, optical brighteners, perborates, bleaches, bleach activators, enzynes, suds boosters, suds depressants, germicides, fungicides, anti-tarnishing agents, cationic detergents,
  • the balance of i the detergent compositions may be water or inert filler.
  • the deter-' gent formulation should contain surfactant levels of about 25% to about 45% by weight and the sulfosuccinate derivative salt levelsof about 25% toabout by weight in the cases where the surfactantsare anionic, ampholytic or zwitterionic.
  • the surfactant is a nonionic
  • enhanced detergency results are obtained 1 i when the level of said nonionic in the formulation is from about 15% to 30% by weight and the level of sulfosuccinate derivative salt isfrom about 25% to about by weight.
  • compositions were then tested on hydroxlde and refluxed for 4 i NMR analysls 1nd]- vacuum cleaner dust s d 1 th f d t 15 cated that all of the sulfomalelc acid had hydrated cleanin abilit in the 9 3. i i 9 within the first hour of reflux.
  • the reaction mixture was washin g condiiions are as i dicatet i and th e 6:112: 1 then passed through a column of cation exchange resin' portedgas detergency units
  • the avera e deter e C A portion of the effluent was then neutralized to pH n i units (DU) of the formulation is the fin al refleiancg f to a White cry-stan-me resldue w value of the washed cloth (average of 2 runs) minus the 20 contained of msodlum a hyqrOXy-B initial reflectance of the soiled cloth th n t sulfosuccmate as determlned by NMR analysis (usmg being Obtained y measurement with a ggf f i 232 D 0 solvent and K biphthalate as an internal standard) matic color difference meter Model AC-3 and 104% water by Karl Escher analysls' TABLE -I
  • Trisodiuma-mercapto-B-sulfosuccinate trisodiuma-methylthio-B-sulfosuc'cinate trisodiumoz-ethylthio-B-sulfosuccinate EXAMPLES Preparation of Trisodium a-Methoxy-B- Sulfosucciriate Sulfomalcic anhydride, 3.9 gm, was dissolved in 25 ml of methanol and refluxed for hours. Then, 24 gm of 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.
  • oz-cthoxy-B-sulfosuccinate may be prepared by substituting ethanol and sodium ethoxide in the procedure described above.
  • EXAM PLE 4 Preparation of Trisodium oz-Dcdecyloxy-B-Sulfosuccinate Sulfomaleic anhydride 10 gm) are mixed with 80 gm (0.45 mole) of n-dodecanol and heated at 100C for 14 hours. A solution of 7.04 gm of sodium hydroxide in 50 ml water is then added and the mixture heated at 60C for 2 hours.
  • a mixedsolvent system such as ethanol/water and dioxane/water isused together with i 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 methylmonoethanolammonium or 14 methylammonium, dimethylammonium, trimethylammoni'umf tetrametliylammonium; morpholinium, N- N ethylmonoethanolamn ionium salt thereof, wherein n'is an integer TABLE 2
  • R Z Example Reactants (Sulfomalcic Anhydride h 0 1 Water Alkyl (C -C O 3 C or C alcohol Alkyl (C -C 0 4-8 C C primary, secondary or tertiary alcohol Phenyl 0 48 Phenol Carboxyphenyl 0 l0 Methyl salicylatc Alkylphenyl 0 4-8 Alkylphenol o.

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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 [1 1 [111 3,922,271 Lamberti 1 Nov. 25, 1975 [541 SULFOSUCCINATE DERIVATIVES AS 3,706,771 12/1972 Kremers et al. 260/346.8
DETERGENT BUILDERS [75] inventor: Vincent Lamberti, Upper Saddle River, NJ.
[73] Assignee: Lever Brothers Company, New
York, N.Y.
[22] Filed: July 1, 1974 [21] Appl. No.: 484,741
Related U.S. Application Data [62] Division of Ser. No. 394,613, Sept. 5, 1973, which is a division of Ser. No. 156,933, June 25, 1971, abandoned.
[52] U.S. Cl. 260/247.1 E; 260/501.12; 260/501.15; 260/501.19; 260/501.2l; 260/513 R; 260/513 N; 252/546; 252/547; 252/552 [51] Int. CL C07D 295/00; C07C 143/00 [58] Field of Search 260/513 R, 513 B, 513 H, 260/513 N, 501.15, 501.19, 501.21, 247.1 E
[56] References Cited UNITED STATES PATENTS 3,635,829 l/l972 Yang 252/526 Primary Examiner-James 0. Thomas, Jr. Assistant ExaminerNicky Chan Attorney, Agent, or FirmArnold Grant, Esq.
[57] ABSTRACT Novel salts of ot-substituted-B-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, S0 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.
8 Claims, No Drawings SULFOSUCCINATE DERIVATIVES AS DETERGENT BUILDERS This is a division of application Ser. No. 394,613, filed Sept. 5, 1973, which in turn is a division of 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 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 a-substituted-B-sulfosuccinic acids and salts thereof having the general formula:
Formula I C 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-3O carbon atoms, phenyl, carboxyl substituted and monodior tri-alkyl substituted phenyl, wherein the alkyl group or groups contain l-4 carbon atoms; sulfoand carboxy-alkyl, wherein the alkyl moiety contains l-4 carbon atoms; and RZ(CH CH O)n-CH CH wherein R is N or alkyl containing l-24 carbon atoms; Z is as above; and n is O or an integer of from land the alkali metal, ammonium and substituted ammonium salts thereof.
Thus, specific compoundsand classes of compounds embraced by the generic formula above include:
a-hydroxy-B-sulfosuccinic acids a-alkoxy-B-sulfosuccinic acids a-phenoxyB-sulfosuccinic acids a-carboxyphenoxy-B-sulfosuccinic acids a-alkylphenoxy-B-sulfosuccinic acids a-carboxyalkoxy-fi-sulfosuccinic acids a-sulfoalkoxy-B-sulfosuccinic acids a-alkoxyethoxy-B-sulfosuccinic acids a-alkoxypo]yethyleneoxyethoxy-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 SO2.
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, COOH COOH 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 II 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 amethylamino, a-propylamino, a-octylamino and alaurylamino-B-sulfosuccinic acid;
a-dialkylamino-B-sulfosuccinic acids such as a-dimethylamino, a-ethylmethylamino, a-methylhexylamino and a-dioctylamino-B-sulfosuccinic acid;
oz-hydroxyalkyl-B-sulfosuccinic acids such as ahydroxyethylamino, oz-hydroxybutylamino and a-bis(- hydroxyethyl)amino-B-sulfosuccinic acid;
a-carboxyalkylaminoB-sulfosuccinic acids such as a-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:
Formula III 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 stereoisomeric forms and mixtures thereof.
In addition to the detergent building properties exhibited by the entire class of compounds described above, certain select members also exhibit properties whichmake them useful as wetting and foaming agents and thus constitute a class of novel surface active agents. For example, the a-alkoxy-B-sulfosuccinic acids and the thio analogs, containing from about 1-8 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 9-24 carbon atoms in the alkyl chain, additionally exhibit wetting, foaming and detergency properties.
Similarly, the a-alkoxyethoxy and walkoxypolyethyleneoxyethoxy-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 oz-substituted-B-sulfosuccinic acids are preferred. Included in the substituted ammonium salts that can be employed are the monoethanolammonium, diethanolammoniurn, triethanolammonium, methylammonium, dimethylammonium, trimethylammonium, tetramethylamrnoniurn, 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 building and biodegradability properties but also in low costof 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. v
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 1,2-diols containing from 8-30 carbon atoms and aromatic carbocyclic glycols such as phenylethylene glycol. Similarly, suitable polyhydric alcohols include glycerol, pentacrythritol, hexanetriol, sugars and their thio analogs.
In addition to the 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 includeglycollic, lactic, glyceric, hydroxypropionic, salicyclic andmercapto acetic acid, hydroxymethanesulfonic acidfand.
hydroxyethanesulfonic acid.
Still another important class of compounds containing active hydrogens are ethylene oxide adducts of Cr '1 I moles, a of ethylene oxide.
to C primary and secondary alcohols with 1-15 Inzgeneral, the a-substituted-B-sulfosuccinate salts,
wherein the a-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 120C, and preferably 60 to 100C, sulfomaleic anhydride with a compound having an active hydrogen followed by further'treatment with an alkali; I 2 metal hydroxide. The desired u-oxy or athio-Bsul-' g fosuccinate may. then be recovered and purified using conventional techniques.
The oz-substituted-B-sulfosuccinate salts wherein the. oz-substituent is joined to the a-carbon atom of the sul-i s fosuccinate moiety by an S0 or SO linkage may be prepared by treating the appropriate a-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, lnc., 1967, incorporated by reference herein.
The zx-substituted-B-sulfosuccinate salts wherein the I a-substituent is joined to the a-carbon atom of the sul-f I fosuccinate moiety, by an amino function (Formula II) may be prepared by reacting an appropriately substituted or unsubstituted primary or secondaryamine with'alkali metal salts of sulfomaleic acid. Typical amines suitable for reaction to form the rat-substituted I or active hydrogen and a basicity comparable to the aforementioned amines. In particular, the oz-amino.substituted-,B-sulfosuccinates derived from water-soluble amines may be pre-I I pared by reacting in aqueous solution without the aid of t heat and 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 tem- V peratures ranging from about 25C to about C; isolation from the reaction medium, andpurification if desired, being effected by conventional methods. s
The compounds of Formula III may be prepared by reacting the tertiary amine compounds of Formula II ,7 with oxidizing agents such as hydrogen peroxide, per- 7 oxyacetic and peroxyformic acid in the manner def scribed, for oxidizing tertiary amines by Hohet 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 1 whether the monodior tri-salt is obtained. For exam ple, the use of one mole of base (i.e., sodium hydroxide) per mole of oz-hydroxy-/3sulfosuccinic acid yields the monosodium salt, the use of two moles of sodium the alkyl chain, as well as other amines having a replaceable hydroxide, the disodium salt and the use of three moles of sodium hydroxide, the trisodium salt. When R is carboxymethyl, carboxyethyl, sulfomethyl 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 l l 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 percent of the builder-present in thedetergent 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 expressed as a weight ratio of builderto surfactant, the builders used in the instant invention will generally be present in a ratio of about 1:10 toabout :1, and preferably 2:] 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.
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 alkylolammonium salts of higher fatty acids (C 10"C20). Particularly useful are the sodium or potassium salts of the mixtures of fatty acids derived from coconut oil and 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 5 sulfuric acid esterradicals. Important examples of the synthetic detergentswhich 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 glyceridesof 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 to the benzene ring in either the one position or at the secondary positions such as in LAS,* sodium p- (2-dodec yl- )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 potassiumsalts 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 l8 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 fattyacid amides of methyl taurine in which the fatty acids, for example, are derived from c0- conut; 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 and then neutralizing the reaction product; and
others known in the "art; *Sodium linearsecondary alkyl (C -C benzene sulfonatc.
Nonionic synthetic detergents maybe 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 chainor branched chain configuration, withethylene oxide, the said ethylene oxide being present in amounts equal to S to 25 moles of ethylene oxide per mole of alkylphenols. The
7 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, havingfrom 8 to 18 carbon atoms, in either straight chain or branched configuration, with ethylene oxide, e.g., a coconut alcohol-ethylene oxide condensate having from 6 to 30 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction having from 10 to 14 carbon atoms; a C,,-C, random secondary. alcohol derived from n-paraffins and condensed with 7 moles of ethyl ene oxide per mole of secondary alcohol.
4. Long chain tertiary amine oxides corresponding to the following general formula, R,R R l\l 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 correspond. ing to the following formula RRRP 0, 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 semipolar bond. Examples of suitable phosphine oxides are:
dimethyldodecylphosphine oxide,
dimethyltetradecylphosphine oxide, ethylmethyltetradecylphosphine oxide, ethyldimethylphosphine oxide, dimethylstearylphosphine oxide, cetylethylpropylphosphine oxide, diethyldodecylphosphine oxide, diethyltetradecylphosphine oxide, bis(hydroxymethyl)dodecylphosphine oxide, bis(2-hydroxyethyl)dodecylphosphine oxide, 2-hydroxypropylmethyltetradecylphosphine oxide, dimethyloleylphosphine oxide, and dimethyl-Z-hydroxydodecylphosphine oxide.
6. Dialkyl sulfoxides corresponding to the following formula, RRS -+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 panel -sulfonate,
Ampholytic synthetic detergents can be broadly de- I scribed as derivatives of aliphatic secondary and, tertiary amines, in which the aliphatic radical may be. straight chain or branched and wherein one ofthe aliphatic substituents contains from about 8 to l8carbon 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 ali phatic substituents contains from about 8 to l8carbon atoms and one contains an anionic water solubilizing group. Examples of compounds falling within this defi nition are 3-(N,N-dimethyl-N-hexadecylamm0nio)pro- 3'( N,Ndimethyl-N-hexadecylammonio)-2-hydroxypropane-l-sulfonate, 3-(dodecylmethylsulfonium) propane sulfonate, and 3-(cetylmethylphosphonium )ethane t su lfonate.
Other materials which may be present in the detergent compositions of the invention in generally minor amounts are those conventionally present therein. Typ 5 ical examples thereof include the well-known soil-sus.- pending agents, hydrotropes, corrosion inhibitors, dyes, perfumes, fillers such as sodium sulfate, optical brighteners, perborates, bleaches, bleach activators, enzynes, 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 i the detergent compositions may be water or inert filler.
It has beendiscovered 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 formula-;
tion is significantly enhanced particularly at low formulation concentration (-O. 1%) which are typically used I by the U.S. housewife. For enhanced results the deter-' gent formulation should contain surfactant levels of about 25% to about 45% by weight and the sulfosuccinate derivative salt levelsof about 25% toabout by weight in the cases where the surfactantsare anionic, ampholytic or zwitterionic. When the surfactant is a nonionic, enhanced detergency results are obtained 1 i when the level of said nonionic in the formulation is from about 15% to 30% by weight and the level of sulfosuccinate derivative salt isfrom about 25% to about by weight.
In addition to their use in general household detergent compositions, the builders of the present invention.
find utility as boiler scale removers, stain removers and general cholating agents. When used at pHs of about 2 to about 5 as partially neutralized alkali metal, ammo-j nium or substituted ammonium salts, especially in combination with wetting agents and surfactants, the com pounds of the invention are excellent metal cleaning compounds.
EXAMPLE 1 Preparation of Trisodium a-hydroxy-B-Sulfosuccinate Sulfomaleic anhydride was prepared by heating a Table 1 further illustrates the present invention. The mixture of 1 mole of sulfur trioxide with 1 mole of detergent formulations set forth in the Table represent 1 h d f o h deter em Com h b e1c an y r1 e 1rst at 60 C unt l the exot ermlc reacg posltlons comammg t e m ders of the tion subsided and then at lO0-l C for 3 hours Forresent inve ti i of gm of or standard phosphate built detergent compositions. 10 mlxed Wlthgm-Oflcc and resultmg Solunon ex- The Com Sitions were re ared b blendin to ether tracted 25 t1mes w1th ml portlons of ether to remove the gg' onentspin 3 y f t d maleic acid. A 20 ml portion of the resulting aqueous including an antiizorrosive ageiit a b iifigj :eift o phase was collected adjusted to pH 2 l l with cakTiur-n dium silicate). The compositions were then tested on hydroxlde and refluxed for 4 i NMR analysls 1nd]- vacuum cleaner dust s d 1 th f d t 15 cated that all of the sulfomalelc acid had hydrated cleanin abilit in the 9 3. i i 9 within the first hour of reflux. The reaction mixture was washin g condiiions are as i dicatet i and th e 6:112: 1 then passed through a column of cation exchange resin' portedgas detergency units The avera e deter e C A portion of the effluent was then neutralized to pH n i units (DU) of the formulation is the fin al refleiancg f to a White cry-stan-me resldue w value of the washed cloth (average of 2 runs) minus the 20 contained of msodlum a hyqrOXy-B initial reflectance of the soiled cloth th n t sulfosuccmate as determlned by NMR analysis (usmg being Obtained y measurement with a ggf f i 232 D 0 solvent and K biphthalate as an internal standard) matic color difference meter Model AC-3 and 104% water by Karl Escher analysls' TABLE -I Component 7! Composition a-hydroxy 50 5O 5O 5O 50 cz-(Z-hydroxy- 50 5O ethoxy)" a-dodecyloxy 50 mmethoxy" 50 a-carboxymethoxy" 50 a-dodecyloxyethoxy 50 u-dodecylthio" 50 M113 0... Sodium silicate 10 10 10 10 10 10 10 10 10 10 10 10 (SiOgNzuO 2.411 Anionic 18 18 36 I8 18 I8 18 18 Anionic" l8 Nonionic" 2O Ampholytic" l8 Zwitterionic l 8 Water bal Formulation 0. 0.2 0. 0.2 0.2 0.2 0.1 0.2 0.2 0.2 0.2 0.2 Concentration. '71 Detergency (DUS 24.6 24.4 26.5 23.1 25.6 26.1 24.7 27.1 23.0 24.2 15.4 22.3
Component Controls (Z Composition) a-hydroxy" z1-( Z-hydroxyethoxy)" a-doclecyloxy" a-methoxy" a-carboxymethoxy" mdodecyloxyethoxy oedodccylthio" s rt lu 50 50 50 Sodium silicate 10 10 10 10 10 10 10 10 10 (SiO :Na O= 2.4.1 Anionic l8 l8 Anionic 18 18 Nonionic" 20 20 Ampholytic l8 l8 Zwitterionic l8 Water bu] Formulation 0.1 0.2 0.2 0. 0.2 0.2 0. 0.2 0.2 Concentration. '71 Detergency (DUS 4.8 6.4 16.1 19.9 18.8 20.1 28.7 29.4 28.5
"Sodium salts of asubs!ilu1ed-B-sulfosuccinutc "Sodium linear secondary ulkyl (C -C benzene sulfonate "Sodium -C zx-olefin sulfonate "C -C, linear secondnry alcohols elhoxylated with 7 moles ethylene oxide/mole alcohol "C -C HAMT (sodium hydroxyalkyl N-mcthyl mutate) 'Sult'obetaine DCH (cododiniclhylsultopropyl butninc) Washing conditions lSU ppm (2:1 CaflMg"): F: pH ll) EXAMPLE 2 d-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 tolow 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: I
trisodiuma-mercapto-B-sulfosuccinate trisodiuma-methylthio-B-sulfosuc'cinate trisodiumoz-ethylthio-B-sulfosuccinate EXAMPLES Preparation of Trisodium a-Methoxy-B- Sulfosucciriate Sulfomalcic anhydride, 3.9 gm, was dissolved in 25 ml of methanol and refluxed for hours. Then, 24 gm of 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, f11- tered 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.
oz-cthoxy-B-sulfosuccinate may be prepared by substituting ethanol and sodium ethoxide in the procedure described above.
EXAM PLE 4 Preparation of Trisodium oz-Dcdecyloxy-B-Sulfosuccinate Sulfomaleic anhydride 10 gm) are mixed with 80 gm (0.45 mole) of n-dodecanol and heated at 100C for 14 hours. A solution of 7.04 gm of sodium hydroxide in 50 ml water is then added and the mixture heated at 60C for 2 hours. The heated mixture is then extracted 3 times with 300 cc portions of acetone (at reflux) and the acetone insoluble fraction is then filtered, washed with additional acetone and dried to give 16.2 gm of the title compound (structure confirmed by NMR and ion exchange of a sample followed by titration with standard sodium hydroxide: neutralization equivalent: found 147.0, theory 149.3).
EXAMPLE 5 Preparation of Trisodiuma-Dodecyloxyethoxy-B-Sulfosuccinate Using the procedure of Example 4 and substituting 37 gm (0.32 mole) of 2-dodecy1oxyethanol in place of the n-dodecanol there is obtained trisodiumadodecyloxyethoxy-l3-sulfosuccinate.
EXAMPLES 6-8 Using n-tetradecanol in place of n-dodecanol in the procedure of Example 4 and carrying out the hydrolysis step with 10% excess aqueous sodium hydroxide at 80C for 4 hours instead of 60C at 2 hours, there is obtained trisodiuma-tetradecyloxy-B-sulfosuccinate (Example 6). Similarly, using n-hexadecanol in place of n- 'dodecanol, there is obtained trisodiuma-hexadecyloxy- B-sulfosuccinate' (Example 7); using n-octadecanol, there is obtained trisodium a-octadecyloxy-B-sulfosuccinate (Example 8).
EXAMPLEQ for 4 hours. A solution of 16 gm (0.4 mole) of sodium hydroxide iiiml of water is then added and the mixture heated at C for 4 hours. The mixture is then. mixed withacetone to precipitate trisodium a-hydroxyethoxy-B-sulfosuccinate, which is purified by repeated f.
extractionswith hot acetone to remove all ethylene glycol and water followed by filtration and drying in an oven.
EXAMPLE 10 Preparation of the Tetrasodium Salt of oz-Carboxymethyloxy-B-Sulfosuccinic Acid Sulfomaleic anhydride (19.4 gm) is heated to 60C and combined with 76 gm of ethyl glycolate. After heating the mixtureat 80C for 5 /2 hours, there is:
added a solution of 45 gm of sodium hydroxide dis-. solved in 135 gm of water and heating is continued at C 80 for an additional 3 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 1 I and other impurities. The resulting extracted residue is I then dissolved in water and the pH of the solution ad-. justed to 8.6 with dilute sodium hydroxide. Evaporation of the solution in vacuo and drying overP O gives, a residue of the tetrasodium salt or a-carboxymethyloxy-B-sulfosuccinic acid.
I V 1 Example 11 Preparation of Trisodiuma-(2-l-lydroxyethylamin0)-B-Sulfosuccinate Sulfomaleic anhydride (prepared from a 1/1 mole ratio of SO /maleic anhydride by heating the mixture at -1 10C for 3 hours; active content, 86%), 20.7 gm
(0.1 mole), was added to 100 gm of ice. The resulting solution was kept at l015C and neutralized to pH 8.6 by slowly adding 28.4 gm of 50% sodium hydroxi ide. Monoethanolamine, 6.1 gm (0.1 mole), was next I I added slowly and the temperature allowed to rise to 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 3 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% triso-pdium a-(Z-hydroxyethylamino)-B-sulfosuccinate by titratiori with perchloric acid. The structure was confirmed by NMR analysis. I
The above method is satisfactory for reacting water soluble amino compounds with sulfomaleic anhydride.
For water insoluble amino compounds such as the. 5 I g higher alkyl amines, a mixedsolvent system such as ethanol/water and dioxane/water isused together with i 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 methylmonoethanolammonium or 14 methylammonium, dimethylammonium, trimethylammoni'umf tetrametliylammonium; morpholinium, N- N ethylmonoethanolamn ionium salt thereof, wherein n'is an integer TABLE 2 R Z Example Reactants (Sulfomalcic Anhydride h 0 1 Water Alkyl (C -C O 3 C or C alcohol Alkyl (C -C 0 4-8 C C primary, secondary or tertiary alcohol Phenyl 0 48 Phenol Carboxyphenyl 0 l0 Methyl salicylatc Alkylphenyl 0 4-8 Alkylphenol o. m. p methylphenyl 0 4-8 0. m. p cresol carvacrol, thymol HOOCCH 0 l0 Ethyl gylcolate Phenyl Sodium 3-hydroxypropylmercaptide Sodium fi-hydroxyhexylmercaptide C,C alkylmercaptan" C -C alkylmercaptan" Thiophenyl" Methyl 2-'mercaptobenzoate" Alkylthiophenol Ethylmercaptoacetate Methyl B-mercaptopropionate" RO(CH CH O),,CH CH SH" Sodium Z-hydroxyethylmercaptide Sodium 3-hydroxypropylmercaptide Sodium 6-hydroxyhexvlmercaptide C -C alkylmercaptan C -C alkylmercaptan Thiophenol Methyl Z-mercaptobenzoate" Ethyl mercaptoacetate" Methyl Z-mercaptobutyrate RO(CH CH 0)CH CH SH 'Followed by oxidation to sulfoxide according to Fieser reference Followed by oxidation to sulfone according to Fieser reference.
What is claimed is:
1. An a-hydroxyalkoxy-B-sulfosuccinic acid having the general formula:
HOCH (CH ),,O CH
COOH COOH and the alkali metal, ammonium, monoethanolammonium, diethanolammonium, triethanolammonium,
6. The a-hydroxyalkoxy-B-sulfosuccinic acid and salt The h d lk B 1f i j id d l 2 thereof of claim 1 wherein n is 5.
7. The a-hydroxyalkoxy-B-sulfosuccinic acid and salt thereof of claim 1 wherein H is thereof of claim 1 wherein n is 6.

Claims (8)

1. AN A-HYDROXYALKOXY-B-SULFOSUCCINIC ACID HAVING THE GENERAL FORMULA
2. The Alpha -hydroxyalkoxy- Beta -sulfosuccinic acid and salt thereof of claim 1 wherein n is 1.
3. The Alpha -hydroxyalkoxy- Beta -sulfosuccinic acid and salt thereof of claim 1 wherein n is 2.
4. The Alpha -hydroxyalkoxy- Beta -sulfosuccinic acid and salt thereof of claim 1 wherein n is 3.
5. The Alpha -hydroxyalkoxy- Beta -sulfosuccinic acid and salt thereof of claim 1 wherein n is 4.
6. The Alpha -hydroxyalkoxy- Beta -sulfosuccinic acid and salt thereof of claim 1 wherein n is 5.
7. The Alpha -hydroxyalkoxy- Beta -sulfosuccinic acid and salt thereof of claim 1 wherein n is 6.
8. The Alpha -hydroxyalkoxy- Beta -sulfosuccinic acid and salt thereof of claim 1 wherein n is 7.
US484741A 1971-06-25 1974-07-01 Sulfosuccinate derivatives as detergent builders Expired - Lifetime US3922271A (en)

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DE19722230073 DE2230073A1 (en) 1971-06-25 1972-06-20 Alpha-substituted beta-sulfosuccinic acids and their use as builders in detergents
GB78575A GB1398422A (en) 1971-06-25 1972-06-21 Sulphosuccinate derivatives as detergent builders
GB2905772A GB1398421A (en) 1971-06-25 1972-06-21 Sulphosuccinate derivatives for use as detergent builders
AT542872A AT321437B (en) 1971-06-25 1972-06-23 laundry detergent
CH942672A CH588551A5 (en) 1971-06-25 1972-06-23
FR727222899A FR2143437B1 (en) 1971-06-25 1972-06-23
CH775776A CH588452A5 (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
US484741A US3922271A (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
US05/484,920 US3957775A (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
US484919A US3917601A (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
US05/578,704 US3976642A (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
US05/578,703 US3968110A (en) 1971-06-25 1975-05-19 Sulfosuccinate derivatives as detergent builders
US05/589,960 US3970653A (en) 1971-06-25 1975-06-24 Sulfosuccinate derivatives as detergent builders
US05/589,959 US3989700A (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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US401482A US3912663A (en) 1971-06-25 1973-09-27 Sulfosuccinate derivatives as detergent builders
US05/484,917 US3935206A (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
US484744A US3922272A (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
US484919A US3917601A (en) 1971-06-25 1974-07-01 Sulfosuccinate derivatives as detergent builders
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US484741A Expired - Lifetime US3922271A (en) 1971-06-25 1974-07-01 Sulfosuccinate derivatives as detergent builders
US05/484,917 Expired - Lifetime US3935206A (en) 1971-06-25 1974-07-01 Sulfosuccinate derivatives as detergent builders
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US484744A Expired - Lifetime US3922272A (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
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US484744A Expired - Lifetime US3922272A (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
US484919A Expired - Lifetime US3917601A (en) 1971-06-25 1974-07-01 Sulfosuccinate derivatives as detergent builders
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US3922272A (en) 1975-11-25
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CH588551A5 (en) 1977-06-15
US3957775A (en) 1976-05-18
CH588452A5 (en) 1977-06-15
US3935206A (en) 1976-01-27
USRE29576E (en) 1978-03-14

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