Classifications

• • 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
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
  • C11D3/3773—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in liquid compositions
• • 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
  • C11D3/26—Organic compounds containing nitrogen
  • C11D3/33—Amino carboxylic acids
• • 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
• • 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
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or 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
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
  • C11D3/3937—Stabilising agents
  • C11D3/394—Organic compounds

Definitions

• the invention further relates to these new compounds, a process for their preparation, their use as complexing agents for heavy metal or alkaline earth metal ions and the complexing agents containing them.
• DE-A 21 03 453 (1) relates to ⁇ -hydroxy- ⁇ -aminocarboxylic acids of the general formula IV in which R7 and R8 each represent an aliphatic, cycloaliphatic or araliphatic radical, but R7 and R8 denote no methyl group and also mean, inter alia, hydrogen, alkylol groups or the radical -CH2-CH (OH) -COOH. Furthermore, one of the radicals R7 or R8 can carry a second substituted amino group -NR7R8.
• the compounds IV serve to mask metal ions, in particular heavy metal cations, by complexing in aqueous solution.
• the object of the present invention was therefore to provide complexing agents which are more suitable as bleach stabilizers.
• X 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 C1-C4-alkyl groups or C1-C4-hydroxyalkyl groups.
• 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.
• the compounds Ia which are a subgroup of the compounds I, are new.
• the compounds I and especially the compounds Ia are expediently reacted by reacting a glycidic acid derivative of the general formula II in which Z represents the groups -OX, -OR6 or -N (R2) 2, where R6 denotes a C1-C4-alkyl radical and the two radicals R2 are the same or different, with ammonia or one of the amines of the general formulas IIIa or IIIb and subsequent hydrolysis of carboxylic acid amide or carboxylic ester groups still present.
• Glycidic acid derivatives II which can be used are, for example, glycidic acid, optionally in the form of its sodium, potassium or ammonium salt, glycidic acid amide, N-methylglycidic acid amide, N, N-dimethylglycidic acid amide, glycidic acid methyl ester or glycidic acid ethyl ester. The best results are achieved with glycidamide.
• Examples of primary amines IIIa are glycine, aspartic acid, serine, 2-methylserine, 2- (hydroxymethyl) serine, 1-amino-2-hydroxysuccinic acid, ethanolamine, ethanolamine methyl ether, ethanolamine (2-hydroxyethyl) ether, sorbitylamine, glycopyranosylamine, glusofuranosylamine, polyvinylamine , 1,2-ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine and 2-hydroxypropane-1,3-diamine.
• secondary amines IIIb examples include sarcosine, iminodisuccinic acid, iminodi (2-hydroxysuccinic acid), ethanolaminoacetic acid, diethanolamine, disorbitylamine and polyethyleneimine.
• glycine aspartic acid, ethanolamine, ethanolaminoacetic acid, diethanolamine and sarcosine are preferred.
• Polyamines with primary and secondary amino functions such as diethylenetriamine and triethylenetetramine can also be used.
• the carboxyl groups present in part in the amines mentioned above can also occur in the form of the alkali metal or the optionally substituted ammonium salts.
• the reaction of the glycidic acid derivative II with ammonia or an amine IIIa or IIIb is generally carried out in water, an organic solvent such as methanol, ethanol, n-propanol, isopropanol, tert-butanol, dioxane or tetrahydrofuran or in mixtures of these solvents at temperatures from 10 to 100 ° C, preferably 40 to 80 o C, and a pH value of 4 to 10, preferably 6 to 9, carried out.
• an organic solvent such as methanol, ethanol, n-propanol, isopropanol, tert-butanol, dioxane or tetrahydrofuran or in mixtures of these solvents at temperatures from 10 to 100 ° C, preferably 40 to 80 o C, and a pH value of 4 to 10, preferably 6 to 9, carried out.
• the molar ratio of II to ammonia or amine is usually 2.8: 1 to 3.7: 1, in particular 3.0. : 1 to 3.3: 1, for ammonia, 1.8: 1 to 2.7: 1, in particular 2.0: 1 to 2.3: 1, for primary amines IIIa and 0.8: 1 to 1, 5: 1, in particular 1.0: 1 to 1.2: 1, in the case of secondary amines IIIb; the ratios given each relate to an amino group in the compound IIIa or IIIb.
• the reaction is followed by hydrolysis of carboxylic acid amide and carboxylic ester groups still present to give 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, generally at temperatures of 20 up to 110 ° C, in particular 40 to 100 o C, is carried out.
• bases such as sodium or potassium hydroxide solution or of acids such as sulfuric or hydrochloric acid
• compounds I and Ia are obtained as free carboxylic acids or in the form of salts, usually as alkali metal salts.
• the desired salts I or Ia can then be prepared from the free acids without difficulty by neutralization with the appropriate bases, for example amine bases.
• the compounds I and Ia can be isolated from their solutions in pure form without any problems. Spray or freeze drying, crystallization and precipitation are particularly suitable for this. The solutions can often also be used directly for the purposes of the invention.
• the compounds I are outstandingly suitable for complexing heavy metal or alkaline earth metal ions such as iron, copper, manganese, zinc, calcium or magnesium or mixtures of such ions. Because of this ability, they have a variety of technical applications. Since the compounds I are biodegradable substances, they can be used advantageously wherever wastewater is produced in large quantities during use and must first be treated before it reaches the surface waters.
• Areas of use and uses include, for example, detergents and cleaning agents for the household, industrial cleaning agents, electroplating technology, water treatment and polymerizations, the photographic industry, the textile industry and the paper industry, and various applications in pharmaceuticals, cosmetics, foodstuffs and in Plant nutrition into consideration.
• a bleach stabilization for example for sodium perborates such as NaBO2 ⁇ H2O2 ⁇ 3 H2O, peroxycarbonates, peroxyphosphonates, citrate perhydrates, urea and melamine-H2O2 adducts, caroates, perbenzoates, alkane dipercarboxylic acids, peroxyphthalates and detergents and alkali metal acetates and detergents 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.
• the compounds I can be used as so-called preservatives, advantageously in an amount of 0.05 to 1% by weight, based on the total weight of the detergent formulation.
• the compounds I prevent, for example, metal-catalyzed oxidative decomposition.
• They can be used to stabilize phosphates in alkaline degreasing baths and prevent the precipitation of lime soaps and thereby prevent the "tarnishing" of non-ferrous surfaces and extend the service life of alkaline cleaning baths.
• the cooling water treatment with the compounds I prevents deposits or dissolves existing ones.
• a particular advantage is the possibility of application in an alkaline medium and thus the elimination of corrosion problems.
• the complexing agents I can be used in developer or fixing baths which are prepared with hard water in order to prevent the precipitation of poorly soluble calcium and magnesium salts.
• the precipitations lead to gray haze on films and images, as well as deposits in the tanks, which can thus advantageously be avoided.
• They can be used as iron III chelate solutions can be used advantageously in bleaching and bleach-fixing baths and thus replace the hexacyanoferrate solutions, which are questionable for ecological reasons.
• copper, iron, manganese and zinc complexes with I can be used to remedy heavy metal deficits. These heavy metals are added as chelates to prevent precipitation as biologically inactive insoluble salts.
• flue gas scrubbing namely the simultaneous removal of NO x and SO2 from flue gases, desulfurization according to Wellman-Lord, H2S 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 recommended to a very special extent as bleach stabilizers and as builders in detergents and cleaning agents in the fields of application mentioned.
• the present invention also relates to compositions for complexing heavy metal or alkaline earth metal ions or mixtures thereof which, depending on the intended use, contain the compounds Ia in an amount of 0.01 to 99% by weight, 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 referred to the total amount of preparation, one or more of the compounds I included.
• detergents and cleaning agents which are 0.01 to 20% by weight, preferably 0.05 to 10% by weight referred to the total amount of preparation, one or more of the compounds I included.
• amounts from 1 to 10% by weight are preferred
• amounts from 0.05 to 1% by weight are particularly preferred.
• amounts of 0.1 to 2% by weight are preferred.
• the compounds I in their capacity as complexing agents, builders and bleach stabilizers in detergent and cleaning agent formulations, can also be used together with other agents of the prior art, the general properties with respect to sequestration, incrustation inhibition, graying inhibition, primary washing action and bleaching action, under certain circumstances, significantly improved can be.
• Detergent and cleaning agent formulations with the compounds I generally contain, as additional constituents, based on the total weight, 6 to 25% by weight of surfactants, 15 to 50% by weight of builders and optionally co-builders and 5 to 30% by weight. % Auxiliaries such as enzymes, foam regulators, corrosion inhibitors, optical brighteners, fragrances, dyes or formulation aids such as Sodium sulfate in the usual amounts for this.
• the 2-hydroxy-3-aminopropionic acid derivatives I are excellent complexing agents. In their capacity as builders in sweeteners and cleaning agents to improve the whitening effect and to prevent deposits on the fabric, the compounds I are comparable to, for example, ethylenediaminetetraacetic acid or 2-hydroxy-3-aminopropionic acid-N, N-diacetic acid. However, bleach stabilization shows a clearly superior effect compared to the prior art agents mentioned.
• the pH of the reaction solution was kept between 8 and 8.5 by adding a further 88 g of 50% strength by weight sodium hydroxide solution. Then was 30 minutes at 50 ° C and then 3 hours at 80 ° C. stirred. After adding a further 100 g of 50% strength by weight sodium hydroxide solution, the solution was then stirred at 80 ° C. for 2 hours and then at 100 ° C. for 1.5 hours, during which the ammonia formed outgassed.
• the resulting solution was spray-dried and the light brown powder thus obtained was recrystallized from a water-methanol mixture.
• the title compound was obtained in the form of a colorless crystal powder with a melting point> 280 ° C. in a yield of 74%.
• This compound was prepared analogously to Example 1 by reacting aspartic acid with glycidamide in a molar ratio of 1: 2.2 in a yield of 55%. After recrystallization, it had a melting point of 125 ° C. (with decomposition).
• This compound was prepared analogously to Example 1 by reacting serine with glycidamide in a molar ratio of 1: 2.2 in a yield of 57%. After recrystallization, it had a melting point of 120 ° C. (with decomposition).
• This compound was prepared analogously to Example 2 by reacting ethanolamine with glycidamide. It is known from the literature reference (1).
• This compound was prepared analogously to Example 2 by reacting ammonia with glycidamide. It is known from the literature reference (1).
• This compound was prepared analogously to Example 1 by reacting equimolar amounts of sarcosine with glycidamide in a yield of 94%. After recrystallization, it had a melting point of> 310 o C.
• the hydrogen peroxide responsible for the bleaching effect in detergent formulations containing sodium peroxide is catalytically decomposed by heavy metal ions (Fe, Cu, Mn) primarily in the wash liquor, but also when stored dry. This decomposition process can be prevented or at least delayed by complexing the heavy metal ions.
• the peroxide-stabilizing effect of the complexing agents is checked for a certain period of time via the residual peroxide content after leaving a wash liquor containing heavy metals at a higher temperature.
• 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 H2O2 still present after this period was given in the table below.
• the test was carried out in such a way that a solution of 6.5 g / l of the formulation (1) in water of hardness 25 ° dH was heated to 80 ° C. and for test purposes with 2.5 ppm of a mixture of the ions Fe3+, Cu2+ and Mn2+ in the ratio 8: 1: 1, used in the form of their sulfates, was added.
• a solution of 6.5 g / l of the formulation (1) in water of hardness 25 ° dH was heated to 80 ° C. and for test purposes with 2.5 ppm of a mixture of the ions Fe3+, Cu2+ and Mn2+ in the ratio 8: 1: 1, used in the form of their sulfates, was added.
• the H2O2 content was measured before adding heavy metals and after leaving the wash liquor at 80 ° C for 2 hours.
• the following table shows the results of the tests, the 2-hydroxy-3-aminopropionic acid derivatives I in their sodium salt form from Examples 1 to 6 having ethylenediaminetetraacetic acid tetrasodium salt (EDTA-Na4) and 2-hydroxy-3-aminopropionic acid N, N-diacetic acid trisodium salt (ISDA-Na3) according to reference (2) were compared.
• the values illustrate the superior effect of compounds I.

Landscapes

• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Detergent Compositions (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Applications Claiming Priority (2)

Publications (3)

Family

ID=6386462

Family Applications (1)

Country Status (4)

Cited By (6)

Families Citing this family (3)

Citations (2)

Family Cites Families (9)

• 1989
  • 1989-08-03 DE DE3925727A patent/DE3925727A1/de not_active Withdrawn
• 1990
  • 1990-07-13 US US07/552,098 patent/US5112530A/en not_active Expired - Fee Related
  • 1990-07-24 DE DE59010804T patent/DE59010804D1/de not_active Expired - Lifetime
  • 1990-07-24 EP EP90114141A patent/EP0411436B1/fr not_active Expired - Lifetime
  • 1990-08-03 JP JP2205289A patent/JPH03148243A/ja active Pending

Patent Citations (2)

Also Published As

Similar Documents

Legal Events