US3686128A - Washing,bleaching and cleansing agents containing poly - (n-tricarballylic acid)-alkyleneimines - Google Patents

Washing,bleaching and cleansing agents containing poly - (n-tricarballylic acid)-alkyleneimines Download PDF

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US3686128A
US3686128A US881306A US3686128DA US3686128A US 3686128 A US3686128 A US 3686128A US 881306 A US881306 A US 881306A US 3686128D A US3686128D A US 3686128DA US 3686128 A US3686128 A US 3686128A
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washing
acid
bleaching
alkali metal
weight
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Achim Werdehausen
Peter Krings
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Henkel AG and Co KGaA
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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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3937—Stabilising agents
    • C11D3/394—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/0206—Polyalkylene(poly)amines
    • 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
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines

Definitions

  • An object of the present invention is the obtaining WASHING, BLEACHING AND CLEANSING AGENTS CONTAINING POLY (N-TRI- CARBALLYLIC AClD)-ALKYLENEIMINES Achim Werdehausen, Monheim, and Peter Krings, Kre- 5 acids or their salts which i r e stability d cleanfeld, Germany, assignors to Henkel & Cie GmbH, Dus mg properties of the washing agents and stabilize the seldorf-Holthausen, Germany optical brighteners present.
  • Another object of the invention is the obtaining of a Claim! P y, application Germany, May 1 s 1969 washing, bleaching and cleansing agent having a content P 19 24 300-6; July 1969, P 19 33 10 of from 50% to 99.9%, by weight, of customary com- US CL 25% C11!
  • a washing, bleaching and cleansing agent having a have the following formula content of from 50% to 99.9%, by weight, of customary components of washing, bleaching and cleansing agents and from 0.1% to 50%, by weight, of salts of poly-(N- R alkylcar-boxylic y ha g an av g and the remainder of the recurring substituted alkylenemolecular weight of from 430 to 500,000 in which at least i i groups ha the following formula one third of the recurring substituted alkyleneimine groups have the following formula I i Y R wherein, in both formulas, R represents a member selected X R from
  • COOH COOH COOH Y represents a member selected from the group consisting of hydrogen
  • the amino groups present in the polyalkyleneimines can be completely or partially substituted by tricarballylic groups.
  • Completely substituted polyalkyleneimines contain only the recurring groups according to Formula I and have a linear structure of the Formula III XNH-C.Hg(I?H[III-CHT(IJH NHX R x R 1, 111 wherein X and R are defined above and n is an integer from 2 to 130, preferably from 3 to 85, corresponding to a molecular weight of from 430 to 15,000, preferably from 500 to 10,000.
  • Such polymers in which only a part, for example, at least 33%% and less than 100% of the amino groups carry a tricarballylic group are mixed polymers which are built from the groups of the Formulas -I and II. Usually they contain branched chains and are partially illustrated by the following Formula IV wherein X and R are defined above.
  • the branched and/ or mixed polymers have average molecular weights of from 430 to 500,000.
  • alkylcarboxylic acid derivatives of polyethyleneimine or polypropyleneimine are used in which from 50% to 100% of the primary and secondary amino groups in the polyalkylenei'mine molecule carry tricarballylic acid groups.
  • N-tricarballylic acid derivatives of polyetbyleneimines are particularly practical interest.
  • the polymeric(N tricarballylic acid) ethyleneimines are amphoteric substances. They can, therefore, depending upon the alkalinity or acidity of the washing, bleaching, and cleansing agents, be present as salts of alkali metals and ammonium salts, especially salts of sodium and potassium, and as salts of organic ammonium bases, as inner salts, or as salts of strong acids, for example, mineral acids such as sulfuric acid and organic acids such as p-toluene sulfonic acid.
  • the preparation of the polymeric (N-tricarballylic acid)-alkyleneimines can be done according to various known methods.
  • first monomeric ethyleneimine or propyleneimine is alkylated on the nitrogen atom according to the principles of the Michael-Addition, with derivatives of cisor trans-aconitic acids, such as, esters, amides and nitriles.
  • derivatives of cisor trans-aconitic acids such as, esters, amides and nitriles.
  • olefinic-unsaturated carboxylic derivatives also derivatives of halogenated tricarballylic acid can be used for the alkylation on the nitrogen atom.
  • Suitable starting materials are especially the lower alkyl esters, such as the methyl, ethyl, propyl, isopropyl and butyl esters of (N-tricarballylic acid)-aziridine.
  • the plymerization takes place in the presence of Lewis type acids, for example, neutral sulfuric acid esters, preferably di-lower alkyl sulfates, such as dimethyl sulfate, diethyl sulfate, dipropyl sulfate, and dibutyl sulfate, or sulfonic acid esters, preferably lower alkylsulfonates and arylsulfonates, such as the methyl, ethyl, propyl and butyl esters of methanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid.
  • Lewis type acids for example, neutral sulfuric acid esters, preferably di-lower alkyl s
  • the polymerization can also be conducted in the presence of solvents, especially of the lower halogenated hydrocarbons.
  • the polymerization time is usually 2 to 60 hours.
  • the reaction temperature is appropriately held between 30 and C. by cooling.
  • the ester, amide or nitrile derivatives of the polymeric (N tricarballylic acid) alkyleneimines obtained are saponified in a known manner, for example, by heating with an alkali metal hydroxide solution such as aqueous sodium or potassium hydroxide.
  • the alkali metal salts formed can be converted into the free acids by treating with ion-exchange resins.
  • ammonia or organic ammonium bases such as mono-, dior triethanolamine, morpholine, or N-methylmorpholine, the free acids can be converted to the corresponding acid salts.
  • the average molecular weights of the polymeric (N- tricarballylic acid)-alkyleneimines obtained in this way can vary within wide limits depending upon the type and amount of the polymerization catalyst used, the polymerization temperature, and the reaction time. In general, the average molecular weight of such linear polymers is between 500 and 10,000.
  • poymers with varied average molecular weight can be obtained. Since the low molecular components do not disturb, they can remain in the product.
  • the polymerization of the (N-tricarballylic acid)- alkylenimine is conducted in the presence of unsubstituted monomeric ethyleneimine or propyleneimine, mixed polymers are formed which are built from groups of the Formulas I and II, and are more or less highly branched, as indicated in Formula IV.
  • the ratio between substituted and unsubstituted monomeric ethyleneimine or propyleneimine is hereby selected in such a way that at least one third, preferably 50 to of the alkylenimine present 'in the polymerization mixture are substituted by alkylcarboxylic acids, to obtain polymeric (N-tricarballylic acid)-alkyleneimines which are preferably from 50% to 100% substituted on the amino groups.
  • a further method of preparation of the salts of the polymeric(N-tricarballylic acid)-alkyleneimines starts from preformed polyalkyleneirnines having an average molecular weight of from 300 to 150,000.
  • the polyalkyleneimines are then reacted in alkaline aqueous medium with the derivatives or salts, preferably the alkali metal salts, of aconitic acid, or halogenated tricarballylic acids.
  • the amount of carboxylic acid derivative should be selected in order that at least one third, preferably at least 50% of the primary and secondary amino groups in the preformed polyalkyleneimines are substituted.
  • the compounds prepared from performed polyalkyleneimines are usually more or less highly branched.
  • Their average molecular weight depends upon the degree of polymerization of the preformed polyethyleneirnines or polypropyleneimines, and can be from 500 to 500,000. In their performance, particularly in case of their use in washing, bleaching, and cleansing agents there is no essential difference between the linear and the branched polymeric(N-tricarballylic acid)-alkyleneimines.
  • the inner salts of the polymers can be obtained from the aqueous solutions by precipitation with mineral acids at the isoelectric point or by treating with ion-exchange resins.
  • the inner salts are amorphous substances in solid form, which are insoluble in organic solvents and also predominately in water, but are readily soluble in acids and bases.
  • the corresponding ammonium salts can be prepared by neutralization vu'th ammonia or organic ammonium bases, such as, mono-, di-, or triethanolamine, morpholine, or N- methylmorpholine.
  • the washing, bleaching and cleansing agents according to the invention can also contain mixtures of different polymeric (N-tricarballylic acid)- alkyleneimines or their salts.
  • the preferably used poly-(N-carballylic acid)-ethylene imines have an average molecular weight of 430 to 500,000.
  • the agents according to the invention contain at least one other cleaning or bleaching component, such as nonionic, anionic and amphoteric surface-active materials, inorganic or organic builders, oxygen-containing bleaching agents, as well as other conventional washing and cleansing ingredients.
  • the polymeric (N-tricarballylic acid)-alkyleneimines or their salts, particularly the sodium salt, can be added to these ingredients in the form of their solutions or in solid form after previous drying.
  • nonionic compounds such as the polyalkyleneglycolether derivatives of alcohols, fatty acids and alkylphenols which contain 3 to 30 ethyleneglycolether groups and 8 to 20 carbon atoms in the hydrocarbon radical.
  • polyethyleneglycolether derivatives in which the number of oxyethylene groups is from 5 to and whose hydrocarbon radicals are derived from straightchain primary alcohols with 12 to 18 carbon atoms, or from alkylphenols with a straight-chain alkyl chain of 6 to 14 carbon atoms.
  • nonionic basic washing components with low-foaming properties are the water soluble polyethylene oxide adducts, adducted to polypropyleneglycol, ethylenediamine-polypropyleneglycol and alkylpolypropyleneglycol with 1 to 10 carbon atoms in the alkyl chain.
  • these adducts contain from to 250 oxyethylene groups and 10 to 100 oxypropylene groups in the molecule.
  • the named compounds contain usually 1 to 5 oxyethylene units per oxypropylene unit.
  • nonionic compounds of the type of aminooxides and sulfoxides containing at least one hydrocarbon radical with 10 to 20 carbon atoms which, if necessary, can also be ethoxylated, are usable.
  • the washing and cleansing agents can also contain anionic basic washing components of the sulfonate or sulfate type.
  • alkylbenzene sulfonates such as dodecylbenzene sulfonate are suitable.
  • olefin sulfonates such as, are obtained by sulfonation of primary and secondary aliphatic monoolefins with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis, as well as alkylsulfonates obtainable from n-alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis, or neutralization, or by addition of bisulfite to olefins are also suitable.
  • a-sulfo fatty acid esters, primary and secondary alkyl sulfates and the sulfates of ethoxylated or propoxylated higher alcohols are suitable.
  • Other compounds of this class which can be occasionally present in the detergents are the higher molecular weight sulfated partial ethers and partial esters of polyhydric alcohols, such as, the alkali metal salts of the monoalkyl ethers, or mono-fatty acid esters of the glycerine monosulfuric acid esters, or, of 1,2 dihydroxypropane-sulfonic acid.
  • sulfates of ethoxylated or propoxylated fatty acid amides and alkyl phenols as well as fatty acid taurides and fatty acid isethionates are suitable.
  • anionic basic washing components are alkali metal soaps of natural or synthetic fatty acids, such as, sodium soaps of coconut, palm kernel, or tallow fatty acids.
  • amphoteric basic washing components are alkali metal soaps of natural or synthetic fatty acids, such as, sodium soaps of coconut, palm kernel, or tallow fatty acids.
  • alkylbetaines and, particularly, alkylsulfobetaines are suitable, for example, 3-(N,N-dimethyl-N-alkylammonium)-propane-l-sulfonate and 3-(N,N-dimethyl-N-alkylammonium)-2-hydroxy-propane-1 sulfonate, preferably Where alkyl is a lower alkyl such as methyl or ethyl.
  • the anionic basic washing components can be present in the form of the alkali metal salts such as the sodium and potassium salts as well as the ammonium salt, or as salts of organic bases, such as mono, di, and triethanolamine.
  • the named surface-active nonionic, anionic and amphoteric compounds have a long-chain aliphatic hydrocarbon radical, the latter should preferably be straight-chained and should have from 8 to 22 carbon atoms.
  • the preferred straight alkyl chains contain an average of from 6 to 16 carbon atoms.
  • inorganic builders particularly condensed phosphates, such as, pyrophosphates, triphosphates tetraphosphates, trimetaphosphates, tetrametaphosphates as well as more highly condensed phosphates in the form of the neutral or acidic alkali metal salts such as the sodium and potassium salts as well as the ammonium salt.
  • condensed phosphates can also be partly or completely substituted by organic complexing agents containing phosphorus or nitrogen atoms.
  • Such compounds are the alkali metal or ammonium salts of aminopolyphosphonic acids, particularly aminotri-(methylenephosphonic acid), ethylenediaminetetra-(methylenephosphonic acid), l-hydroxyethane-l,l-diphosphonic acid, methylenediphosphonic acid, ethylenediphosphonic acid as well as the higher homologs of the named polyphosphonic acids, as well as the alkali metal or ammonium salts of low-molecular-weight aminopolycarboxylic acids, such as, NTA and EDTA.
  • alkali metal silicates are suitable, particularly sodium silicate in which the ratio Na,O:SiO, is 123.5 to 1:1.
  • mixture ingredients are neutral salts, such as, sodium sulfate and sodium chloride, as well as compounds for adjustment of the pH, such as bicarbonates, carbonates, borates and hydroxides of sodium and potassium and acids, such as, lactic and citric acid.
  • the amount of the alkaline reacting substances should be calculated so that the pH of a serviceable washing liquor for coarse laundry is 9 to 12 and for fine laundry 6 to 9.
  • the washing agents of the invention can contain oxygen-releasing bleaching compounds, such as, hydrogen peroxide, alkali metal perborates, alkali metal percarbonates, alkali metal perphos- .phates, urea hydrogen peroxide and alkali metal persulfates or active-chlorine compounds, such as, alkali metal hypochlorites, chlorinated trisodium phosphate and chlorinated cyanuric acid, or its alkali metal salts.
  • the peroxide compounds can be present in a mixture with bleaching activators and stabilizers, such as, magnesium silicate.
  • Optical brighteners suitable for cellulosic fibers used in the washing agents of the invention are those of the diaminostilbene disulfonic acid type of the formula:
  • i N N -t- N 1 1 is u Y 80; SO;- Y
  • Particularly suitable are those compounds in which X is an anilino and Y a diethanolamino, or a morpholino group.
  • optical brighteners for polyamide fibers suitable for use in the washing agents of the invention are those of the diarylpyrazoline type of the following formula:
  • Ar and Ar are aryl radicals, such as, phenyl, diphenyl, or naphthyl which can have further substituents, such as, hydroxy, alkoxy, hydroxyalkyl, amino, alkylamino, acylamino, carboxyl, sulfonic acid, and sulfonamide groups, or halogen atoms.
  • Preferred is a 1,3 di arylpyrazoline derivative in which the radical Ar is a psulfonarnidophenyl group and the radical Ar is a pchlorophenyl group.
  • whiteners suitable for the brightening of other fiber types can be present, for example, compounds of the type of naphthotriazolestilbene sulfonates, ethylene-bisbenzimidazoles, ethylene-bis-benzoxazoles, thiophene-bis-benzoxazoles, dialkylaminocoumarins, and the cyanoanthracenes.
  • These brighteners or their mixtures can be present in the washing agents in amounts of from 0.01% to 1.5% by weight, preferably from 0.1% to 1% by weight.
  • greying-inhibiting compounds such as sodium celluloseglycolate, as well as the water soluble sodium salts of synthetic polymers which contain free carboxylic groups.
  • these latter include the polyesters or the po'lyamides of triand tetracarboxylic acids and dihydric alcohols or diamines, and also polymeric acrylic acid, methaerylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and aconitic acid as well as the mixed polymerizates of the named unsaturated carboxylic acids, or their mixed polymerizates with olefins.
  • Washing agents intended for the use in drum-washing machines contain appropriately known foam-suppressing substances such as saturated fatty acids with 20 to 24 carbon atoms, or their alkali metal soaps, or triazine derivatives which can be obtained by reacting one mol cyanuric chloride with 2 to 3 mols of aliphatic, straight-chained, branched-chained or cyclic primary monoamines or by propoxylating, or, butoxylating melamine.
  • foam-suppressing substances such as saturated fatty acids with 20 to 24 carbon atoms, or their alkali metal soaps, or triazine derivatives which can be obtained by reacting one mol cyanuric chloride with 2 to 3 mols of aliphatic, straight-chained, branched-chained or cyclic primary monoamines or by propoxylating, or, butoxylating melamine.
  • the washing agents can also contain enzymes from the class of proteases, lipases, or amylases.
  • These enzymes can be of animal or plant origin, for example, those obtained from digestive ferments or yeasts, such as pepsin, pancreatin, trypsin, papain, catalase and diastase.
  • enzymatic active substances obtained from bacterial strains or molds, such as, Bacillus subtilis and Slreptomyces griseus which are relatively stable against alkalis, peroxide compounds and anionic detergents and essentially not inactivated even at temperatures between 45 C. and 70 C.
  • the washing and cleansing agents can be present in liquid, pasty or solid form, as powder, granules or lumps.
  • Liquid preparations may contain water-miscible solvents, particularly lower alkanols such as ethanol and isopropanol, as well as dissolving aids, such as, the alkali metal salts of benzene, toluene, xylene, or ethylbenzene sulfonic acids.
  • dissolving aids such as, the alkali metal salts of benzene, toluene, xylene, or ethylbenzene sulfonic acids.
  • the skin compatibility alkylolamides such as, fatty acid mono, or diethanolamides may, if necessary, be added.
  • the mixture can also contain dyes or odorizing substances, bactericidally-active materials, activators as well as fillers, for example, urea.
  • the preparation of the agents according to the invention can be done in customary manner by mixing, granulating or spray-drying.
  • enzymes it is recommended to mix them with the nonionic basic washing components and, if necessary, odorizing substances, or to disperse them in the melt of a salt containing water of crystallization, such as Glaubers salt, and to combine these premixtures with the other powdery ingredients.
  • the enzymes are cemented with the other powder particles so that the mixtures do not tend to dust or separate.
  • the content of the washing, bleaching and cleansing agents of poly-(N-tricarballylic acid)-alkyleneimine or its alkali metal salts amounts from about 0.1% to 50% preferably 0.2% to 25% by weight, depending upon their use. The difference to 100% is taken up by the previously named detergent and bleaching active substances as well as, if necessary, the additional builders to improve the cleaning power.
  • the qualitative and quantitative composition of these additional ingredients depend widely upon the special use of these agents. It corresponds in the case of the technically particular important washing and cleansing agents to the following recipe: (data in percent by weight) 1% to 40% of at least one compound from the class of the anionic, nonionic, and amphoteric detergents.
  • 0 to preferably 10% to 80% of at least one non-surface-active cleaning intensifying or complexing builder 0 to 50%, preferably 10% to 50% of a percompound, especially sodium perborate, with or without water of crystallization, as well as their mixtures with stabilizers and activators. 0 to 60%, preferably 0.1% to 20% of other auxiliary and supplementary substances.
  • the detergent substances can consist of up to 100%, preferably from 5% to 70%, of compounds of the sulfonate and/or the sulfate type, up to 100%, preferably from 5% to 40% of the nonionic polyglycolether type, and up to 100%, preferably from 10% to 50% of soaps.
  • the builders can consist of up to 100%, preferably from 25% to of alkali metal triphosphates and their mixtures with alkali metal pyrophosphates, up to preferably from 5% to 50%, of an alkali salt of a complexing agent from the class of polyphosphonic acids, nitrilotriacetic acid, ethylene'diaminetetraacetic acid, and up to 100%, preferably from 5% to 75% of at least one compound of the class of alkali metal silicates, alkali metal carbonates and alkali metal borates.
  • foam inhibitors which can be present in the agents according to the invention in an amount of up to 5%, preferably from 0.2% to 3%; also the enzymes which can be present in an amount up to 5%, preferably from 0.2% to 3%; and the greying-inhibitors which can be present in an amount up to 5%, preferably from 0.2% to
  • poly-(N-tricarballylic acid)-ethyleneimine is suitable for the preparation of clear aqueous detergent concentrates without the use of organic solvents or hydrotropic compounds.
  • hydrotropic substances as well as the water mixable solvents have, as it is known, no detergent properties. Since their use makes the preparation of liquid detergents more expensive without any gain in detergent power, there is a special interest for such liquid products in which all ingredients have cleansing properties.
  • a clear liquid concentrate, stable on storage consists essentially of 5% to 40%, preferably 15% to 30%, by weight, of alkali metal salts of poly (N-tricarballylic acid)-ethyleneimine, 3% to 30%, preferably 5% to 15%, of a primary and/or secondary olefinsulfonate with 8 to 24 carbon atoms in the form of its alkali metal, ammonium, or organic ammonium salts, and 50% to 92% by weight of water.
  • such agents can also contain up to 10%, preferably not more than by weight, of anionic or nonionic detergents which have good solubility in water.
  • these detergents are the alkali metal salts of alkanesulfonic acids, and lower alkyl esters of atsulfofatty acids, particularly the methyl, ethyl, propyl and butyl esters of a-sulfonated saturated fatty acids having from 8 to 20 carbon atoms, also the sulfated ethoxylated products of alkanols, alkylphenols, amines, fatty acids and fatty amides which contain a hydrophobic hydrocarbon radical with 8 to 20 carbon atoms and from 1 to oxyethylene units, as well as the corresponding non-sulfated polyglycolether derivatives, in which the ratio of the number of carbon atoms in the hydrophobic hydrocarbon radical to the number of oxyethylene units is between 2:1 and 1:2 as an average.
  • the poly-(N-tricarballylic acid)-alkyleneimines and their salts impart to the washing, cleansing and bleaching agents, according to the invention, a high washing and cleansing power, as well as improved dirt-carrying power. They are effective stabilizers for peroxide compounds and are less attacked by peroxide compounds than known complexing agents. They are, therefore, suitable for the stabilization of liquid bleaching detergents, such as those containing hydrogen peroxide and compounded liquid bleaching agents. The preparation of such agents has failed so far because of the low storage-stability of the peroxide compounds. The new compounds protect, in addition, the oxygen-sensitive ingredients of washing agents, particularly the optical brighteners and enzymes effectively against oxidative destruction.
  • the agents can be easily degraded biologically and have the advantage that they can replace completely or partially the polymeric phosphates which have previously necessarily been present in washing agents, so that because of a lesser amount of phosphate ions in the sewage they do not promote the growth of algae in rivers and lakes.
  • alkylpolyglycolether alkyl C to C or alkylphenolpolyglycolether (alkyl C, to C with 5 to 12 oxyethyene groups 0.2% to 25% of poly-(N-tricarballylic acidhalkyleneimine or its alkali metal salt 0 to 5% of a higher fatty acid ethanolamide or diethanolamide 0 to 20% of sodium tripolyphospate 0 to 1% of a brightener from the class of the diarylpyrazoline derivatives and its mixtures with polyester brighteners 3% to 70% of sodium sulfate (C) Liquid washing agent 0.5% to 10% of a sulfonate basic washing component (potassium salt) 0 to 10% of alkylpolyglycolether sulfate (alkyl C; to C 1 to 5 oxyethylene groups) 0.2% to 25% of poly-(N-tricarballylic acid)-alkyleneimine or its al
  • washing agents cotton cloth which had been soiled with a synthetic soil containing soot, iron oxide and cutaneous fat was washed in a laboratory washing ma chine where the washing liquor was heated from 20 C. to 90 C. within minutes and kept at 90 C. for another 15 minutes.
  • the washing agent concentration was 3 gm./l.
  • the water hardness was 16 dH.
  • the weight ratio of textile to liquor was 1:12.
  • the washed cloth was rinsed with water four times, centrifuged and dried. The percent of whiteness was determined with a photometer (soiled cloth 0%, original cloth 100%) and is shown in the following Table I as well as the composition of the washing agents.
  • the polymeric (N-tricanballylic acid)-ethyleneimine dibutyl aconitate and aziridine in a mol ratio of 1:1 were heated in the persence of 1 mol percent of sodium methylate for 24 hours at 30 to 40 C.
  • the N- (tricarballylic acid tributyl ester)-aziridine formed was polymerized in an inert atmosphere for 5 to 10 hours at a temperature not higher than 40 C.
  • the polymer was dissolved in methanol and then treated with an equivalent amount of sodium hydroxide.
  • the solution was heated to 80 of 85 C., and the methanol removed by distillation. After 5 hours of heating with water being repeatedly added, the saponification was completed.
  • the sodium salt of the polymerizate was isolated by spray drying.
  • Nan-dodecylbenzene sulfonate 5% sodium soap of C to C fatty acids 5% sodium salt of C to C fatty acids 40% pentasodium triphosphate 5% sodium silicate (Na O.3.3SiO
  • EXAMPLE 7 An aqueous solution containing 0.62 gm./l. of sodium perborate was prepared from a bleaching agent consisting of 1 mol (154 gm.) of sodium perborate and one monomeric unit (217 gm.) of a poly-(N-tricarballylic acid)-ethyleneimine having an average molecular weight of 2040. The pH of the solution was adjusted to 10 with dilute sodium hydroxide. Another bleaching solution, also adjusted to a pH of 10 with dilute sodium hydroxide, contained, per liter, 4 millimols (0.136 gm.) of hydrogen peroxide and 4 millimols (0.87 gm.) of complexing agent.
  • EXAMPLES 8 to 10 sodium salts of branched poly-(N-tricarballylic acid)-ethyleneimines were used. These polymers were prepared as follows. Aqueous solutions containing by weight of polyethyleneimines having average molecular weights of 5,000, 25,000, and 70,000 were separately heated to 80 C. to 90 C., each time with 80% of the stoichiometric amount required for complete N-alkylation, of aconitic acid while the pH was adjusted to 10 to 11 by addition of sodium hydroxide. The reaction product was separated by hot spraying. Based on free acid content, the polymers had average molecular weights respectively of 20,000, 100,000, and 280,000.
  • Example 11 10% olefinsulfonate (chain length C C 20% PTE (mol. weight 2040) Residue water
  • Example 12 10% olefinsulfonate (chain length O -C 20% PTE (mol. weight 3500) 0.12% optical brightener Residue water
  • Example 13 15% olefinsulfonate (chain length C 43 15% PTE (mol. weight 1430) 0.1% optical brightener Residue water
  • Example 15 7.5% olefinsulfonate (chain length C C 2.5% salt of methyl a-sulfo-stearate 20% PTE (mol.
  • ethoxylated nonylphenol or, ethoxylated oleyl alcohol with each having 8 oxyethylene units, laurylsulfate, lauryldiglycolether sulfate, methyl u-sulfo-stearate, or secondary alkanesulfonates, whereby the sulfonates and sulfates were used as sodium salts, turbidity and separation occurred within one day.
  • PTE was replaced by other complexing agents, such as, Na nitrilotriacetate, Na ethylenediamiuetetraacetate, pentapotassium triphosphate, or tetrapotassium pyrophosphate.
  • a washing, bleaching and cleansing agent having a content of from 50% to 99.9% by weight, of customary components of washing, bleaching and cleansing agents and from 0.1% to 50% by weight, of a polyalkyleneimine selected from the group consisting of (1) poly-(N-tricarballylic acid)-alkyleneimines having an average molecular weight of from 430 to 500,000 in which at least 33 /s% to 100% of the recurring substituted alkyleneimine groups have the following formula N-CH:CIH-
  • R represents a member selected from the group consisting of hydrogen and methyl
  • X rep resents CH-CHCH2 (IJOOH (10011 00011 and Y represents a member selected from the group consisting of hydrogen
  • Y represents a member selected from the group consisting of hydrogen and NCH2CH- and (2) their alkali metal, ammonium and organic ammonium salts with bases selected from the group consisting of mono-, diand triethanolamine, morpholine and N-methyl morpholine, said customary components or washing, bleaching and cleansing agents consisting essentially of from 0% to 40% by weight of at least one compound selected from the group consisting of anionic, nonionic and amphoteric surface-active basic washing components, from 0% to by weight of at least one builder selected from the group consisting of condensed inorganic phosphate builders, alkali metal silicates, carbonates, bicarbonates, borates, sulfates and chlorides, alkali metal and ammonium salts of aminopolyphosphonic acids and low-molecular-weight aminopolycarboxylic acids, from 0% to by weight of a bleaching compound selected from the group consisting of hydrogen peroxide, urea hydrogen peroxide, alkali metal perborates
  • polyalkyleneimines are branched poly-(N- tricarballylic acid)-alkyleneimines having the formula wherein R represents a member selected from the group consisting of hydrogen and methyl and X represents wherein R represents a member selected from the group consisting of hydrogen and methyl and X represents (?H (1H CH:
  • n is an integer from 3 to 35.
  • a stable, liquid washing and cleansing composition consisting essentially of from 5% to 40% by weight of an alkali metal salt of poly-(N-tricarballylic acid)-ethyleneimine having an average molecular weight of from 430 to 500,000, from 3% to 40% by weight of a sulfonate selected from the group consisting of alkal metal, ammonium and organic ammonium salts of primary and secondary olefinesulfonic acids having from 8 to 24 carbon atoms, and from 50% to 92% by weight of water.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US881306A 1968-12-02 1969-12-01 Washing,bleaching and cleansing agents containing poly - (n-tricarballylic acid)-alkyleneimines Expired - Lifetime US3686128A (en)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
DE19681812166 DE1812166A1 (de) 1968-12-02 1968-12-02 Weisswaschmittel
DE1908728A DE1908728C3 (de) 1968-12-02 1969-02-21 Wasch-, Bleich- und Reinigungsmittel
DE19691915652 DE1915652B2 (de) 1968-12-02 1969-03-27 Wasch-, bleich- und reinigungsmittel
DE19691924300 DE1924300B2 (de) 1968-12-02 1969-05-13 Wasch-, bleich- und reinigungsmittel
DE19691924301 DE1924301A1 (de) 1968-12-02 1969-05-13 Polyaminopolytricarballylsaeuren
DE19691933511 DE1933511A1 (de) 1968-12-02 1969-07-02 Fluessiges Wasch- und Reinigungsmittel

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US3686128A true US3686128A (en) 1972-08-22

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US881306A Expired - Lifetime US3686128A (en) 1968-12-02 1969-12-01 Washing,bleaching and cleansing agents containing poly - (n-tricarballylic acid)-alkyleneimines
US00236158A Expired - Lifetime US3737385A (en) 1968-12-02 1972-03-20 Washing,bleaching and cleansing agents containing poly-(n-alkyl-dicarboxylic acid)-alkyleneimines

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US00236158A Expired - Lifetime US3737385A (en) 1968-12-02 1972-03-20 Washing,bleaching and cleansing agents containing poly-(n-alkyl-dicarboxylic acid)-alkyleneimines

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US (2) US3686128A (cs)
AT (1) AT299876B (cs)
BE (1) BE741124A (cs)
CH (1) CH527898A (cs)
DE (6) DE1812166A1 (cs)
FR (1) FR2024975B1 (cs)
NL (1) NL6913790A (cs)
SE (1) SE376255B (cs)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4551506A (en) * 1982-12-23 1985-11-05 The Procter & Gamble Company Cationic polymers having clay soil removal/anti-redeposition properties useful in detergent compositions
US4597898A (en) * 1982-12-23 1986-07-01 The Proctor & Gamble Company Detergent compositions containing ethoxylated amines having clay soil removal/anti-redeposition properties
US4659802A (en) * 1982-12-23 1987-04-21 The Procter & Gamble Company Cationic compounds having clay soil removal/anti-redeposition properties useful in detergent compositions
US4661288A (en) * 1982-12-23 1987-04-28 The Procter & Gamble Company Zwitterionic compounds having clay soil removal/anti/redeposition properties useful in detergent compositions
US4664848A (en) * 1982-12-23 1987-05-12 The Procter & Gamble Company Detergent compositions containing cationic compounds having clay soil removal/anti-redeposition properties
US5747440A (en) * 1996-01-30 1998-05-05 Procter & Gamble Company Laundry detergents comprising heavy metal ion chelants
US6143713A (en) * 1996-05-03 2000-11-07 The Procter & Gamble Company Polyamines having fabric appearance enhancement benefits
FR2880623A1 (fr) * 2005-01-11 2006-07-14 Ceetal Sa Sa Lab Composition solide, divisee, stable, comprenant du phmbg et un liberateur d'oxygene pour le traitement de l'eau
US20070155646A1 (en) * 2004-01-30 2007-07-05 Basf Aktiengesellschaft Polymer for treating surfaces
US20080194449A1 (en) * 2005-01-26 2008-08-14 Basf Aktiengesellschaft Use of Polymers Based on Modified Polyamines as Additives for Detergents

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2208971B1 (cs) * 1972-12-06 1977-04-08 Colgate Palmolive Co
US4279769A (en) * 1978-03-20 1981-07-21 Kao Soap Co., Ltd. Bleaching composition
US4797221A (en) * 1985-09-12 1989-01-10 S. C. Johnson & Son, Inc. Polymer sheet for delivering laundry care additive and laundry care product formed from same
DE602008006756D1 (de) * 2007-09-24 2011-06-16 Saint Gobain Abrasifs Sa Schleifprodukte mit aktiven füllern

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4551506A (en) * 1982-12-23 1985-11-05 The Procter & Gamble Company Cationic polymers having clay soil removal/anti-redeposition properties useful in detergent compositions
US4597898A (en) * 1982-12-23 1986-07-01 The Proctor & Gamble Company Detergent compositions containing ethoxylated amines having clay soil removal/anti-redeposition properties
US4659802A (en) * 1982-12-23 1987-04-21 The Procter & Gamble Company Cationic compounds having clay soil removal/anti-redeposition properties useful in detergent compositions
US4661288A (en) * 1982-12-23 1987-04-28 The Procter & Gamble Company Zwitterionic compounds having clay soil removal/anti/redeposition properties useful in detergent compositions
US4664848A (en) * 1982-12-23 1987-05-12 The Procter & Gamble Company Detergent compositions containing cationic compounds having clay soil removal/anti-redeposition properties
US5929010A (en) * 1996-01-30 1999-07-27 Procter & Gamble Company Laundry detergents comprising heavy metal ion chelants
US5747440A (en) * 1996-01-30 1998-05-05 Procter & Gamble Company Laundry detergents comprising heavy metal ion chelants
US6143713A (en) * 1996-05-03 2000-11-07 The Procter & Gamble Company Polyamines having fabric appearance enhancement benefits
US20070155646A1 (en) * 2004-01-30 2007-07-05 Basf Aktiengesellschaft Polymer for treating surfaces
US7902141B2 (en) 2004-01-30 2011-03-08 Basf Aktiengesellschaft Polymer for treating surfaces
FR2880623A1 (fr) * 2005-01-11 2006-07-14 Ceetal Sa Sa Lab Composition solide, divisee, stable, comprenant du phmbg et un liberateur d'oxygene pour le traitement de l'eau
WO2006075091A1 (fr) * 2005-01-11 2006-07-20 Laboratoires Ceetal S.A. Composition solide, divisée, stable, comprenant du phmbg et un libérateur d'oxygène pour le traitement de l'eau
US20080194449A1 (en) * 2005-01-26 2008-08-14 Basf Aktiengesellschaft Use of Polymers Based on Modified Polyamines as Additives for Detergents
US7670389B2 (en) 2005-01-26 2010-03-02 Basf Aktiengesellschaft Use of polymers based on modified polyamines as additives for detergents

Also Published As

Publication number Publication date
DE1924300B2 (de) 1977-01-13
DE1915652B2 (de) 1977-05-12
DE1924300A1 (de) 1970-11-19
DE1908728B2 (de) 1977-08-11
FR2024975A1 (cs) 1970-09-04
DE1933511A1 (de) 1971-01-21
BE741124A (cs) 1970-04-30
FR2024975B1 (cs) 1975-11-07
AT299876B (de) 1972-07-10
DE1915652A1 (de) 1970-10-08
SE376255B (cs) 1975-05-12
DE1812166A1 (de) 1970-06-18
DE1908728C3 (de) 1978-04-13
CH527898A (de) 1972-09-15
DE1924301A1 (de) 1970-11-19
NL6913790A (cs) 1970-06-04
US3737385A (en) 1973-06-05
DE1908728A1 (de) 1970-09-10

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