EP0411436B1 - Use of derivatives of 2-hydroxy-3-aminopropionic acid as complexants, stabilizer for bleaching compositions and builder for washing and cleaning agents - Google Patents

Description

in der X für Wasserstoff, ein Alkalimetall oder Ammonium, das durch C₁-C₄-Alkylgruppen oder C₁-C₄-Hydroxyalkylgruppen substituiert sein kann, steht, ein Verfahren zu ihrer Herstellung und ihre Verwendung als Komplexbildner, Bleichmittelstabilisatoren und Gerüststoffe in Wasch- und Reinigungsmitteln sowie als Komplexbildner für Schwermetall- oder Erdalkalimetallionen. Außerdem betrifft die Erfindung Wasch- und Reinigungsmittel und Komplexierungsmittel, die die Verbindungen I enthalten.The present invention relates to 2-hydroxy-3-aminopropionic acid derivatives of the general formula I.

in which X represents hydrogen, an alkali metal or ammonium, which can be substituted by C ₁ -C ₄ alkyl groups or C ₁ -C ₄ hydroxyalkyl groups, a process for their preparation and their use as complexing agents, bleach stabilizers and builders in washing - and cleaning agents as well as complexing agents for heavy metal or alkaline earth metal ions. The invention also relates to washing and cleaning agents and complexing agents which contain the compounds I.

in der R³ und R⁴ jeweils einen aliphatischen, cycloaliphatischen oder araliphatischen Rest bedeuten, wobei R³ und R⁴ aber keine Methylgruppe bezeichnen und darüber hinaus unter anderem auch Wasserstoff, Alkylolgruppen oder den Rest -CH₂-CH(OH)-COOH bedeuten. Weiterhin kann einer der Reste R³ oder R⁴ eine zweite substituierte Aminogruppe -NR³R⁴ tragen. Die Verbindungen IV dienen zur Maskierung von Metallionen, insbesondere von Schwermetallkationen, durch Komplexierung in wäßriger Lösung. DE-A 21 03 453 (1) relates to α-hydroxy-β-aminocarboxylic acids of the general formula IV

in which R ³ and R ⁴ each represent an aliphatic, cycloaliphatic or araliphatic radical, but R ³ and R ⁴ do not denote a methyl group and also mean, inter alia, hydrogen, alkylol groups or the radical -CH ₂ -CH (OH) -COOH . Can furthermore one of the radicals R ³ or R ^4, a second substituted amino group -NR ³ R ⁴ carry. The compounds IV serve to mask metal ions, in particular heavy metal cations, by complexing in aqueous solution.

in der Y unter anderem für den Rest -COOX steht und Z die Gruppe -OX, -OR¹ oder -N(R²)₂ bedeutet, wobei R¹ einen C₁-C₄-Alkylrest bezeichnet. Die Verbindungen V werden als Komplexbildner für Schwermetall- und Erdalkalimetallionen sowie als Bleichmittelstabilisatoren und Gerüststoffe in Wasch- und Reinigungsmitteln empfohlen. Allerdings läßt ihre bleichmittelstabilisierende Wirkung zu wünschen übrig.DE-A 37 12 330 (2) describes 2-hydroxy-3-aminopropionic acid-N, N-diacetic acid and its derivatives of the general formula V.

in which Y represents, inter alia, the radical -COOX and Z represents the group -OX, -OR ¹ or -N (R ² ) ₂ , where R ¹ denotes a C ₁ -C ₄ -alkyl radical. The compounds V are recommended as complexing agents for heavy metal and alkaline earth metal ions and as bleach stabilizers and builders in detergents and cleaning agents. However, their bleach stabilizing effect leaves something to be desired.

The object of the present invention was therefore as bleach stabilizers to provide more suitable complexing agents.

Accordingly, the use of the 2-hydroxy-3-aminopropionic acid derivatives defined at the outset I as complexing agents, bleach stabilizers and Builders found in washing and cleaning agents.

The compounds I can occur as free carboxylic acids (X = H) or in a partial or complete salt form. In the latter case, X then stands for alkali metal ions such as lithium or in particular sodium or potassium or for the ammonium ion, which can be partially or completely substituted by C ₁ -C ₄ -alkyl groups or C ₁ -C ₄ -hydroxyalkyl groups. In particular, the salts of tertiary amines should be mentioned here. Preferred tertiary amines are trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine and trialkanolamines such as triethanolamine or triisopropanolamine.

in der Z für die Gruppen -OX, -OR¹ oder -N(R²)₂ steht, wobei R¹ einen C₁-C₄-Alkylrest bezeichnet und die beiden Reste R² Wasserstoff oder C₁-C₄-Alkyl bedeuten und gleich oder verschieden sind, mit einem Amin der allgemeinen Formeln III H₂N-CH₂-COOX und anschließende Hydrolyse noch vorhandener Carbonsäureamid- oder Carbonsäureestergruppen hergestellt.The compounds I are advantageously by reacting a glycidic acid derivative of the general formula II

in which Z represents the groups -OX, -OR ¹ or -N (R ² ) ₂ , where R ¹ denotes a C ₁ -C ₄ alkyl radical and the two radicals R ^{2 are} hydrogen or C ₁ -C ₄ alkyl and are the same or different, with an amine of the general formulas III H ₂ N-CH ₂ COOX and subsequent hydrolysis of carboxylic acid amide or carboxylic ester groups still present.

As glycidic acid derivatives II, for example, glycidic acid, if appropriate in the form of their sodium, potassium or ammonium salt, glycidamide, N-methylglycidamide, N, N-dimethylglycidamide, glycidic acid methyl ester or ethyl glycidate can be used. The best Results are achieved with glycidamide.

The primary amine III is glycine.

The carboxyl group present in the above amine can also in the form of the alkali metal or the optionally substituted Ammonium salts occur.

The reaction of the glycidic acid derivative II with the amine III is usually in water, an organic solvent like Methanol, ethanol, n-propanol, iso-propanol, tert-butanol, Dioxane or tetrahydrofuran or in mixtures of these solvents at temperatures of 10 to 100 ° C, preferably 40 to 80 ° C, and a pH of 4 to 10, preferably 6 to 9, made.

The molar ratio of II to amine is usually 1.8: 1 to 2.7: 1, in particular 2.0: 1 to 2.3: 1.

The reaction is followed by hydrolysis of those still present Carboxamide and carboxylic ester groups to carboxyl groups which, in a manner known per se, in an aqueous reaction medium in the presence of bases such as sodium or potassium hydroxide solution or of acids such as sulfuric or hydrochloric acid usually at temperatures of 20 up to 100 ° C, in particular 40 to 100 ° C, is carried out.

The compounds are obtained in accordance with the reaction conditions I as free carboxylic acids or in the form of salts, usually as alkali metal salts. The free acids can then pass through Neutralization with the appropriate bases, for example amine bases, the desired salts I prepared without difficulty will.

The compounds I can be easily in from their solutions isolate pure form. In particular, spray or freeze drying, crystallization and precipitation. Often the solutions can also be used directly for those according to the invention Use purposes.

The compounds I are outstandingly suitable for or alkaline earth metal ions such as iron, copper, Manganese, zinc, calcium or magnesium or mixtures of such ions complex. Because of this ability, they exhibit a variety of technical applications. Since the compounds I are biodegradable substances, they can be beneficial everywhere are used where wastewater is used in larger Amounts accumulate and must be treated before it is released into the surface water reached.

For example, washing and Household cleaning agents, industrial cleaning agents, electroplating, water treatment and polymerizations, photographic Industry, the textile industry and the paper industry as well various applications in pharmaceuticals, in cosmetics, in food and in plant nutrition.

Their beneficial effect is also in a bleach stabilization, such as sodium perborates as NaBO ₂ · H ₂ O ₂ · 3H ₂ O, peroxycarbonates peroxyphosphonates, citrate, urea and melamine-H ₂ O ₂ adducts, caroates, perbenzoates, Alkandipercarbonsäuren, Peroxyphthalates and alkali metal hypochlorites in detergents and cleaning agents and in the hydrogen peroxide bleaching of textiles, cellulose or paper raw materials. Traces of heavy metals such as iron, copper and manganese occur in the washing powder itself, in the water and in the textile goods and catalyze the decomposition of the per compound or the hydrogen peroxide resulting from it. The complexing agents I bind these metal ions and prevent the undesired decomposition of the bleaching system during storage and in the wash liquor. This increases the efficiency of the bleaching system and fiber damage is suppressed.

In liquid detergent formulations, the compounds I can be used as so-called Preservatives, advantageously in an amount of 0.05 to 1 wt .-%, based on the total weight of the detergent formulation will.

In soaps, the compounds I prevent, for example, metal-catalyzed oxidative decomposition.

They also serve excellently in detergents and cleaning agents as a builder to prevent precipitation and incrustation to prevent the tissue.

They can be used advantageously wherever at technical processes Precipitation of calcium, magnesium and heavy metal salts disturb and should be prevented, for example Prevention of deposits and incrustations in boilers, pipes, on spray nozzles or generally on smooth surfaces.

They can be used to stabilize phosphates in alkaline degreasing baths and prevent the precipitation of lime soaps thereby the "tarnishing" of non-ferrous surfaces and lengthening the service life of alkaline cleaning baths.

They can be used as complexing agents in alkaline rust removal and descaling baths be used as well as in galvanic baths instead of Cyanides.

The cooling water treatment with the compounds I prevents deposits or dissolves existing ones. A particular advantage is that Possible application in alkaline medium and thus the elimination of Corrosion problems.

In the polymerization of rubber, they can be used to manufacture the used redox catalysts are used. They also prevent the precipitation of iron hydroxide in an alkaline polymerization medium.

In the photographic industry, complexing agents I can be used in developer or fixing baths that are prepared with hard water to the precipitation of poorly soluble calcium and magnesium salts to prevent. The precipitations lead to gray veils on films and images as well as deposits in the tanks, which are therefore advantageous can be avoided. They can be used as iron III chelate solutions be used advantageously in bleaching and bleach-fixing baths and so the replace environmentally harmful hexacyanoferrate solutions.

In the textile industry they can be used to remove traces of heavy metals during the manufacturing or dyeing process of natural and synthetic Fibers serve. This prevents many disruptions, for example Stains and streaks on the textile, loss of Gloss, poor wettability, uneven dyeing and color defects.

In the paper industry, they can be used to eliminate heavy metal ions, especially iron ions. The deposition of iron on paper leads to "hot spots" where the oxidative catalytic destruction of cellulose begins. Heavy metal ions also catalyze the decomposition of H ₂ O ₂ , which is used for paper bleaching.

Furthermore, there are applications in pharmaceuticals, cosmetics, for example and food to the metal-catalyzed oxidation of olefinic double bonds and thus the rancidity of the products prevent.

Plant nutrition can help to remedy heavy metal deficits Copper, iron, manganese and zinc complexes with I can be used. This Heavy metals are added as chelates to prevent the precipitation prevent biologically inactive insoluble salts.

Further areas of application for the compounds I are flue gas scrubbing, namely the simultaneous removal of NO _x and SO ₂ from flue gases, desulfurization according to Wellman-Lord, H ₂ S oxidation, metal extraction and applications as catalysts for organic syntheses, for example air oxidation of paraffins and hydroformylation of olefins to alcohols.

The compounds I with their excellent complex-forming properties can be used in a very special degree as Bleach stabilizers and as builders in washing and Detergents are recommended.

The present invention also relates to means for Complexation of heavy metal or alkaline earth metal ions or Mixtures of which, depending on the application, the compounds I in an amount of 0.01 to 99 wt .-%, based on the total amount of the preparations.

The present invention furthermore relates to detergents and cleaning agents, which are 0.01 to 20% by weight, preferably 0.05 to 10% by weight on the total amount of preparation, one or more of the compounds I included. When used as a builder are preferred Amounts of 1 to 10% by weight, preferably when used as a bleach stabilizer, for example for perborates, amounts are from 0.05 to 1% by weight is particularly preferred. When used in particular as Complexing agents in detergents are preferred in amounts of 0.1 to 2% by weight.

The compounds I can function as complexing agents, builders and bleach stabilizer in detergent and cleaning agent formulations also used together with other means of the prior art the general characteristics of sequestration, Incrustation inhibition, graying inhibition, primary washing effect and the bleaching effect can possibly be significantly improved.

Detergent and cleaning agent formulations containing the compounds I contain usually as additional components, based on the total weight, 6 to 25% by weight of surfactants, 15 to 50% by weight of builder and optionally co-builder and 5 to 30% by weight of auxiliaries such as enzymes, foam regulators, Corrosion inhibitors, optical brighteners, fragrances, dyes or Formulation aids such as Sodium sulfate in the usual for this Amounts.

The 2-hydroxy-3-aminopropionic acid derivatives I are excellent complexing agents. In its capacity as a builder in washing and cleaning agents to improve the whitewash effect and to prevent Deposits on the tissue are the compounds I with, for example Ethylenediaminetetraacetic acid or 2-hydroxy-3-aminopropionic acid-N, N-diacetic acid comparable. A significantly superior effect compared to However, the above-mentioned means of the prior art can be seen in the Bleach stabilization.

Manufacturing examples example 1 Nitrilodi (2-hydroxy-3-aminopropionic acid) monoacetic acid trisodium salt

To a solution of 37.5 g (0.5 mol) glycine in 150 g water, with 0.6 g 50% by weight sodium hydroxide solution had been adjusted to a pH of 8, were 478.5 g of a 20 wt .-% at 50 ° C within 1 hour drop of aqueous glycidic acid amide solution (corresponding to 1.1 mol of glycidic acid amide). During the dropping, the pH of the reaction solution was checked Addition of a further 88 g of 50% strength by weight sodium hydroxide solution kept between 8 and 8.5. Then was 30 minutes at 50 ° C and then 3 hours at 80 ° C. stirred. After adding a further 100 g of 50% by weight sodium hydroxide solution the solution then at 80 ° C for 2 hours and then at 100 ° C for 1.5 hours stirred, the resulting ammonia outgassing.

The solution was cooled with three times the volume of methanol transferred. The precipitate formed was filtered off and from a Recrystallized water-methanol mixture. The title compound was obtained in the form of a colorless crystal powder that melted above 300 ° C, in a yield of 66%.

Example 2 (for comparison) Nitrilodi (2-hydroxy-3-aminopropionic acid) monoethanolamine disodium salt

1.0 mol of ethanolamine was mixed with twice the molar amount of glycidamide implemented analogously to Example 1, with the difference that an addition of sodium hydroxide solution only after the reaction for the purpose the hydrolysis of the carboxamide group took place.

The resulting solution was spray dried and this was done Powder obtained recrystallized from a water-methanol mixture. This connection is from the literature reference (1) known.

Example 3 (for comparison) Nitrilo-tri (2-hydroxy-3-aminopropionic acid) trisodium salt

This compound was analogous to Example 2 by reacting Ammonia made with glycidamide. It is from the Literature (1) known.

Application properties Determination of sodium perborate stabilization in wash liquors

That for the bleaching effect in detergent formulations containing sodium perborate Responsible hydrogen peroxide is caused by heavy metal ions (Fe, Cu, Mn) mainly in the wash liquor, but also when it is dry Storage catalytically decomposed. By complexing the heavy metal ions this decomposition process can be prevented or at least delayed. The peroxide stabilizing effect of the complexing agent is determined by the residual peroxide content after leaving a washing solution containing heavy metals tested higher temperature for a certain period of time.

The hydrogen peroxide content was determined immediately after preparation and after leaving the wash liquor at 60 ° C. or 80 ° C. for 2 or 1 hour by titration with potassium permanganate in acid solution. As a result, the percentage of H ₂ O ₂ still present after this period was given in the table below.

(1) Zusammensetzung der phosphatreichen Formulierung: 19,3 % Natrium-C₁₂-Alkylbenzolsulfonat (50 %ige wäßrige Lösung) 15,4 % Natriumperborat-Tetrahydrat 30,8 % Natriumtriphosphat 2,6 % Copolymer aus Maleinsäure und Acrylsäure (Gewichtsverhältnis 50:50, mittlere Molmasse 50.000) 31,0 % wasserfreies Natriumsulfat 0,9 % Komplexbildner I oder Vergleichssubstanz

(2) Zusammensetzung der phosphatarmen Formulierung: 15 % Natrium-C₁₂-Alkylbenzolsulfonat (50 %ige wäßrige Lösung) 5 % Anlagerungsprodukt von 11 Mol Ethylenoxid an 1 Mol Talgfettalkohol 20 % Natriumperborat-Tetrahydrat 6 % Natriummetasilicat·5 H₂O 1,25 % Magnesiumsilicat 20 % Natriumtriphosphat 31,75 % wasserfreies Natriumsulfat 1 % Komplexbildner I oder Vergleichssubstanz

Two detergent formulations (1) and (2) were used to test for perborate stabilization; the following percentages relate to the weight.

(1) Composition of the high-phosphate formulation: 19.3% Sodium C ₁₂ alkyl benzene sulfonate (50% aqueous solution) 15.4% Sodium perborate tetrahydrate 30.8% Sodium triphosphate 2.6% Copolymer of maleic acid and acrylic acid (weight ratio 50:50, average molecular weight 50,000) 31.0% anhydrous sodium sulfate 0.9% Complexing agent I or reference substance

(2) Composition of the low-phosphate formulation: 15% Sodium C ₁₂ alkyl benzene sulfonate (50% aqueous solution) 5% Addition product of 11 moles of ethylene oxide with 1 mole of tallow fatty alcohol 20% Sodium perborate tetrahydrate 6% Sodium metasilicate · 5 H ₂ O 1.25% Magnesium silicate 20% Sodium triphosphate 31.75% anhydrous sodium sulfate 1 % Complexing agent I or reference substance

The test was carried out in such a way that a solution of 6.5 g / l of formulation (1) in water of 25 ° dH hardness was heated to 80 ° C. and, for test purposes, with 2.5 ppm of a mixture of the ions Fe ³⁺ , Cu ²⁺ and Mn ²⁺ in a ratio of 8: 1: 1, used in the form of their sulfates. The H ₂ O ₂ content was measured by titration with KMnO ₄ in acidic solution before the heavy metal addition and after leaving the wash liquor at 80 ° C. for ₂ hours.

Similarly, a solution of 8 g / l of formulation (2) in water hardness 25 ° dH was heated to 60 ° C and treated analogously to the process described above. The residual H ₂ O ₂ content was determined after leaving the washing liquor at 60 ° C. for 1 hour.

The following table shows the results of the tests, the 2-hydroxy-3-aminopropionic acid derivative I in its sodium salt form from Example 1 with Examples 2 and 3 according to reference (1) and ethylenediaminetetraacetic acid tetrasodium salt (EDTA-Na ₄ ) as well as 2-hydroxy-3-aminopropionic acid-N, N-diacetic acid trisodium salt (ISDA-Na ₃ ) according to reference (2). The values illustrate the superior effect of compound I. Bleach stabilizer Sodium perborate stabilization [residual% H ₂ O ₂ ] Wording (1) Wording (2) example 1 60.6 90.0 for comparison: Example 2 25.5 57.4 Example 3 51.8 80.7 EDTA-Na ₄ 20.0 34.0 ISDA-Na ₃ 43.4 82.0 without 20.0 28.0

Claims (8)

1. 2-Hydroxy-3-aminopropionic acid derivatives of the general formula I

   

   where X is hydrogen, an alkali metal, or ammonium which can be substituted by C₁-C₄-alkyl groups or C₁-C₄-hydroxyalkyl groups.
2. Nitrilodi(2-hydroxy-3-aminopropionic acid)monoacetic acid, trisodium salt.
3. A process for preparing 2-hydroxy-3-aminopropionic acid derivatives I as set forth in claim 1 or 2, characterized in that a glycidic acid derivative of the general formula II

   

   where Z is -OX, -OR¹ or -N(R²)₂, where R¹ is a C₁-C₄-alkyl radical and the two R² radicals denote hydrogen or C₁-C₄-alkyl and are identical or different, is reacted with an amine of the general formula III H₂N-CH₂-COOX and then any carboxamide or carboxylic ester groups still present are hydrolyzed.
4. A process as claimed in claim 3, characterized in that the glycidic acid derivative II is glycidamide.
5. The use of 2-hydroxy-3-aminopropionic acid derivatives I as set forth in claim 1 or 2 as complexing agents, bleaching agent stabilizers and builders in laundry and cleaning detergent compositions.
6. The use of 2-hydroxy-3-aminopropionic acid derivatives I as set forth in claim 1 or 2 as complexing agents for heavy metal or alkaline earth metal ions.
7. A composition for complexing heavy or alkaline earth metal ions, comprising from 0.01 to 99% by weight, based on the total amount of the preparation, of one or more compounds I as set forth in claim 1 or 2.
8. Laundry and cleaning detergent compositions comprising from 0.01 to 20% by weight, based on the total amount of the preparation, of one or more compounds I as set forth in claim 1 or 2.