EP0287885A1 - Procédé de préparation de la N,N-dicarboxyméthyl-sérine et de ses dérivés - Google Patents

Procédé de préparation de la N,N-dicarboxyméthyl-sérine et de ses dérivés Download PDF

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Publication number
EP0287885A1
EP0287885A1 EP88105376A EP88105376A EP0287885A1 EP 0287885 A1 EP0287885 A1 EP 0287885A1 EP 88105376 A EP88105376 A EP 88105376A EP 88105376 A EP88105376 A EP 88105376A EP 0287885 A1 EP0287885 A1 EP 0287885A1
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Prior art keywords
acid
serine
formula
salts
sodium
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EP88105376A
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German (de)
English (en)
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EP0287885B1 (fr
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Richard Dr. Baur
Felix Dr. Richter
Stefan Dr. Birnbach
Rolf Dr. Fikentscher
Alfred Dr. Oftring
Ekhard Dr. Winkler
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BASF SE
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BASF SE
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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
    • C11D3/26—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
    • C11D3/39—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 relates to processes for the preparation of serine-N, N-diacetic acid and derivatives, their use in particular as complexing agents and detergents and cleaning agents containing them and the intermediate product serine-N, N-diacetonitrile for the production of serine-N, N-diacetic acid and their salts.
  • Areas of use and uses include, for example, detergents and cleaning agents, technical applications for industrial cleaners, in electroplating, in water treatment and in polymerizations, the photographic industry, the textile industry and the paper industry, and various applications in pharmaceuticals, cosmetics, and food and in plant nutrition.
  • NTA nitrilotriacetic acid
  • EDTA ethylenediaminetetraacetic acid
  • ETMP ethylenediaminetetramethylenephosphonic acid
  • PDTA propylenediamine tetraacetic acid
  • HPDTA hydroxypropylenediamine ethylenediamine acid
  • Diethylenetriaminepentaacetic acid and, for example, diethanolglycine, ethanolglycine, citric acid, glucoheptonic acid or tartaric acid, as described, for example, under the keyword washing agent Ullmann's Encyclopedia of Industrial Chemistry, 4th edition, volume 24, pp. 63-160, in particular pp. 91-96, Verlag Chemie, Weinheim, 1983.
  • NTA works very well as a complexing agent and, in washing and cleaning agents, works quite well as a builder to improve the whitening effect and to prevent deposits that cause incrustations and graying on the fabric.
  • the effect as a bleach stabilizer is only weak.
  • EDTA also shows despite its good complexity compared to heavy metals, only a moderate effect as a bleach stabilizer in detergents and cleaning agents.
  • biodegradability also leaves something to be desired.
  • EDTA proves to be insufficiently biodegradable, as do PDTA or HPDTA and corresponding aminomethylene phosphonates, which are also often undesirable because of their phosphorus content.
  • the object of the present invention is to provide new complexing agents for alkaline earth and heavy metal ions for a wide variety of technical fields, in particular for detergents, which, in addition to good complexing properties, are ecologically harmless, contain no phosphorus if possible and are readily biodegradable.
  • Technically advantageous manufacturing processes are also to be developed for these new complexing agents.
  • serine-N, N-diacetic acid in the form of the free acid or in particular the sodium, potassium, ammonium or organic amine salts is an excellent complexing agent for calcium, magnesium and iron, copper, nickel and manganese ions represent, while the acid derivatives, especially amides, esters and the nitriles are preferred intermediates for the preparation of the acid and its salts.
  • the invention therefore relates to a process for the preparation of compounds of the formula I.
  • Y represents the radical -COOH, which is optionally in the form of an alkali metal, ammonium or substituted ammonium salt, or represents the radical -CN and X is a hydroxyl group, the carboxylic acid group thereby present optionally being in the form of an alkali metal, ammonium or substituted ammonium salt, or a radical -NR3R4, in which R3 and R4 are identical or different and represent a hydrogen atom or an alkyl radical with 1 to 4 C.
  • -Atoms stand, means by 1 mol of serine (3-hydroxy-2-aminopropionic acid), optionally in the form of an alkali salt or acid amide, optionally substituted on the amide nitrogen atom by one or two alkyl radicals having 1 to 4 carbon atoms, in water, an organic solvent or their mixtures with 2.0 to 2.6 mol of formaldehyde and 2.0 to 2.3 mol of liquid hydrocyanic acid at temperatures from 0 to 45 ° C. or with 2.0 to 2.3 mol of alkali metal cyanide at temperatures from 40 to 100 ° C and, if appropriate, hydrolyze the amide and nitrile groups present in the presence of an acid or base and, if appropriate, isolate the free acid or a salt of the formula I.
  • the free serine N, N-diacetic acid and the sodium, potassium and ammonium salts in particular the trisodium, tripotassium and triammonium salt, and organic triamine salts with a tertiary nitrogen atom are to be mentioned in particular.
  • the bases on which the organic amine salts are based are, in particular, tertiary amines, such as trialkylamines having 1 to 4 carbon atoms in the alkyl, such as trimethyl and triethylamine, and trialkanolamines having 2 or 3 carbon atoms in the alkanol radical, preferably triethanolamine and tripropanolamine.
  • tertiary amines such as trialkylamines having 1 to 4 carbon atoms in the alkyl, such as trimethyl and triethylamine, and trialkanolamines having 2 or 3 carbon atoms in the alkanol radical, preferably triethanolamine and tripropanolamine.
  • the preferred starting compound is serine in the form of its racemic mixture and optionally in the form of the sodium, potassium or ammonium salt.
  • Water is preferably used as the solvent, or organic solvents which are miscible with water, such as methanol, ethanol, n-propanol, isopropanol, tertiary butanol, dioxane or tetrahydrofuran. Mixtures of these organic solvents with one another or their mixtures with water can also be used. In the case of aqueous mixtures, 10 to 70% by weight of organic solvent is expediently added to the weight of the water.
  • the concentration of the starting compounds in the respective solvent is advantageously 10 to 80% by weight, preferably 20 to 70% by weight.
  • the sodium or potassium salt of the serine is in one of the above.
  • Solvents or solvent mixtures with an aqueous solution being preferred, are reacted with the formaldehyde in the form of its aqueous, about 30% by weight solution and the liquid hydrocyanic acid at the preferred temperatures of 15 to 25 ° C.
  • reaction with akalicyanide in particular sodium or potassium cyanide, is preferably carried out at 70 to 100 ° C. instead of the liquid hydrocyanic acid.
  • hydrolysis or saponification to give the carboxylic acid is carried out in a conventional manner in an aqueous reaction mixture, if appropriate after adding water in the presence of alkalis, such as sodium or potassium hydroxide, or of acid such as sulfuric or hydrochloric acid.
  • This hydrolysis is expediently carried out at temperatures from 20 to 110 ° C., preferably 40 to 100 ° C., with a slight excess of base or acid, if necessary.
  • the serine-N, N-diacetic acid or an alkali salt is preferably obtained. Then salts with another cation can be prepared without further notice.
  • an acid derivative can also be produced in the usual way from the acid obtained.
  • the compounds of formula I can be isolated in pure form without difficulty. Spray or freeze drying, crystallization or precipitation are particularly suitable for the free acid and the salts. It can be advantageous to use the resulting solution directly for technical use.
  • the compounds of the formula I where the radical —COX additionally denotes a nitrile group, serine-N, N-diacetic acid and its salts, can be prepared by glycolaldehyde with a compound of formula II HN (CH2-Y) 2> II in which Y has the meanings given for formula I and can additionally represent a radical -COOR1, in which R1 is an alkyl radical having 1 to 4 carbon atoms, with liquid hydrocyanic acid or an alkali metal cyanide in water, an organic solvent or their mixtures bie at temperatures of 10 to 100 ° C and optionally hydrolyzed the nitrile groups and amide or ester groups present in the presence of an acid or base and optionally isolated the free acid or a salt according to formula I.
  • R1 is an alkyl radical having 1 to 4 carbon atoms
  • the serine-N, N-diacetic acid and its salts are preferably prepared by this process.
  • the starting compounds of formula II are known or can easily be prepared by known processes.
  • the starting compounds of the formula II are preferably the iminodiacetic acid, if appropriate in the form of the mono- or disodium, potassium or ammonium salt, the iminodiacetonitrile, the methyl and ethyl iminodiacetic acid.
  • a compound of formula II, the glycol aldehyde, liquid hydrocyanic acid, sodium or potassium cyanide are preferably reacted in a molar ratio of 1: 1: 1.
  • reaction is expediently carried out in such a way that a compound of the formula I with a nitrile group for the radical -COX as an intermediate is prepared from glycolaldehyde, liquid hydrocyanic acid and a compound of the formula II, preferably in aqueous solution, that subsequently in the manner indicated above is hydrolyzed or saponified.
  • glycol aldehyde with an alkali metal cyanide and a compound of the formula II, preferably in aqueous solution, in such a way that the nitrile group is saponified during the reaction.
  • hydrolysis of the nitrile group and any amide or ester groups present is expediently carried out as described above, temperatures from 20 to 110 ° C., preferably 40 to 100 ° C., with a slight excess of base or acid.
  • the compounds of the formula I with the meaning nitrile for the radicals Y and -COX, the serine-N, N-diacetic acid and their salts are prepared by preparing nitrilotriacetonitrile with formaldehyde with base catalysis in a pH range from 7.5 to 12 at temperatures of 0 to 100 ° C, optionally hydrolyzed the nitrile groups in the presence of an acid or base and optionally isolated the free acid or a salt of formula I.
  • This process is a conventional base-catalyzed aldol addition of formaldehyde to a CH-acidic compound.
  • Formaldehyde preferably in the form of the aqueous solution of about 30% by weight, and nitrilotriacetonitrile are in a molar ratio of 1: 1 to 5: 1, preferably 1: 1 to 3: 1, in a monohydric alcohol with 1 up to 4 carbon atoms, tetrahydrofuran, dioxane or water or one of their mixtures as solvent.
  • the preferred solvents are a lower alcohol, such as methanol, ethanol or propanol.
  • Useful bases as catalysts are tertiary aliphatic amines, in particular trialkylamines and trialkanolamines, such as triethylamine or triethanolamine, alkaline earth metal hydroxides, in particular calcium and magnesium hydroxide, alkali metal hydroxides, such as sodium and potassium hydroxide, alkali metal carbonates, such as sodium and potassium carbonate, and also strongly basic synthetic resin anions made from synthetic anions the OH form.
  • the reaction is carried out in a pH range from 7.5 to 12, preferably from 8.5 to 11, at temperatures from 0 to 100 ° C. and preferably 25 to 80 ° C.
  • the production processes according to the invention have the advantage over known processes, in particular for the production of serine-N, N-diacetic acid and their salts, that there is practically no inorganic salt load. Due to the easy availability of the starting compounds, extremely inexpensive large-scale processes are made available.
  • the serine-N, N-diacetic acid and its salts produced by the invention are outstandingly suitable for complexing alkaline earth and heavy metal ions, in particular calcium, magnesium and iron, copper, nickel and manganese ions. Because of this ability, they have a variety of technical applications. Since they are biodegradable compounds, they can be used in large quantities wherever the waste water has to be clarified and phosphorus-containing compounds should also be avoided.
  • the complexing agents according to the invention can be used in washing and cleaning agents in order to control the content of free heavy metal ions in the washing agents themselves and in the washing solutions.
  • the amount used as a complexing agent is advantageously 0.1 to 2% based on the total weight of the detergent components.
  • bleach stabilization for example for sodium perborate, in detergents and in 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 sodium perborate.
  • the complexing agents according to the invention 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 new complexing agents 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 new complexing agents prevent metal-catalyzed oxidative decomposition.
  • They can be used to stabilize phosphates in alkaline degreasing baths and prevent the precipitation of lime soaps, thereby preventing "tarnishing" of non-ferrous surfaces and extending the service life of alkaline cleaning baths.
  • the cooling water treatment with the new complex images prevents deposits or dissolves existing ones. Use in an alkaline medium and thus the elimination of corrosion problems is an advantage.
  • the new complexing agents can be used in developer / fixer baths made with hard water to prevent the precipitation of poorly soluble Ca and Mg salts.
  • the precipitations lead to gray haze on films and images, as well as deposits in the tanks, which can thus advantageously be avoided.
  • Iron III complexing agent solutions can advantageously be used in bleach-fix baths, where they can replace the hexacyanoferrate solutions, which are of ecological concern.
  • Various applications include, for example, applications in pharmaceuticals, cosmetics and foodstuffs in order to prevent the metal-catalyzed oxidation of olefinic double bonds and thus the rancidity of the products.
  • Cu, Fe, Mn, Zn complexes are used to remedy heavy metal deficits.
  • the heavy metals are added as chelates to prevent precipitation as biologically inactive, insoluble salts.
  • the complexing agents according to the invention for alkaline earth and heavy metal ions are used as complexing agents in general and very particularly in washing and cleaning agents and dishwashing and washing aids, in particular as complexing agents for heavy metal and / or alkaline earth metal ions, as bleach stabilizers and as builders.
  • the invention accordingly also relates to the corresponding uses and detergents and cleaning agents which contain these compounds in addition to the customary constituents known to the person skilled in the art.
  • the compounds to be used according to the invention are generally used in washing and cleaning formulations in an amount of 0.01 to 20% by weight, preferably 0.05 to 10% by weight, based on the total weight of the detergent formulation.
  • amounts from 1 to 10% by weight are preferred, when used as a bleach stabilizer for perborates, amounts from 0.05 to 1% by weight are particularly preferred.
  • amounts of 0.1 to 2% by weight are preferred.
  • Detergent and cleaning agent formulations which, based on the total weight, contain 0.01 to 20, preferably 0.05 to 10% by weight, of compound to be used according to the invention generally contain 6 to 25 as additional constituents, based on the total weight %
  • surfactants 15 to 50% by weight of builder and optionally co-builder, 5 to 35% by weight of bleach and optionally bleach activators, 3 to 30% by weight of auxiliaries such as enzymes, foam regulators, corrosion inhibitors, optical brighteners, fragrances, dyes , or formulation aids, such as Sodium sulfate.
  • the compounds according to the invention in their capacity as complexing agents, builders and bleach stabilizers, can also be used in washing and cleaning formulations together with other agents of the prior art, the general properties with regard to sequestering, incrustation inhibition, primary washing action and bleaching action being able to be significantly improved under certain circumstances .
  • Suitable surfactants are those which contain at least one hydrophobic organic radical and one water-solubilizing anionic, zwitterionic or nonionic group in the molecule.
  • the hydrophobic radical is usually an aliphatic hydrocarbon radical with 8 to 26, preferably 10 to 22 and in particular 12 to 18 carbon atoms, or an alkyl aromatic radical with 6 to 18, preferably 8 to 16, aliphatic carbon atoms.
  • Suitable synthetic anionic surfactants are in particular those of the sulfonate, sulfate or synthetic carboxylate type.
  • the surfactants of the sulfonate type are alkylbenzenesulfonates with 4 to 15 carbon atoms in alkyl, mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as are obtained, for example, from monoolefins with terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products receives.
  • alkanesulfonates which can be obtained from alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins.
  • esters of ⁇ -sulfo fatty acids e.g. the ⁇ -sulfonic acids from hydrogenated methyl or ethyl esters of coconut, palm kernel or tallow fatty acid.
  • Suitable sulfate type surfactants are the sulfuric acid monoesters of primary alcohols, e.g. from coconut fatty alcohols, tallow fatty alcohols or oleyl alcohol, and those from secondary alcohols. Sulfated fatty acid alkanolamines, fatty acid monoglycerides or reaction products of 1 to 4 moles of ethylene oxide with primary or secondary fatty alcohols or alkylphenols are also suitable.
  • anionic surfactants are the fatty acid esters or amides of hydroxy or aminocarboxylic acids or sulfonic acids, e.g. the fatty acid sarcosides, glycolates, lactates, taurides or isothionates.
  • the anionic surfactants can be in the form of their sodium, potassium and ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the usual soaps, i.e. Salts of natural fatty acids should not go unmentioned.
  • nonionic surfactants are adducts of 3 to 40, preferably 4 to 20, moles of ethylene oxide with 1 mole of fatty alcohol, alkylphenol, fatty acid, fatty amine, fatty acid amide or alkanesulfonamide usable.
  • the addition products of 5 to 16 moles of ethylene oxide with coconut oil or tallow fatty alcohols, with oleyl alcohol or with synthetic alcohols with 8 to 18, preferably 12 to 18 carbon atoms, and with mono- or dialkylphenols with 6 to 14 carbon atoms in are particularly important the alkyl residues.
  • non-fully or not fully water-soluble polyglycol ethers with 1 to 4 ethylene glycol ether residues in the molecule are also of interest, in particular if they are used together with water-soluble nonionic or anionic surfactants.
  • non-ionic surfactants which can be used are the water-soluble adducts of ethylene oxide with 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups with polypropylene glycol ether, alkylene diaminopolypropylene glycol and alkyl polypropylene glycols with 1 to 10 C atoms in the alkyl chain, in which the polypropylene glycol ether chain acts as a hydrophobic residue.
  • Nonionic surfactants of the amine oxide or sulfoxide type can also be used.
  • the foaming power of the surfactants can be increased or decreased by combining suitable types of surfactants. A reduction can also be achieved by adding non-surfactant-like organic substances.
  • Suitable builder substances are, for example: washing alkalis, such as sodium carbonate and sodium silicate, or complexing agents, such as phosphates, or ion exchangers, such as zeolites, and mixtures thereof.
  • These builders and builders have the task of eliminating the hardness ions, which come partly from water, partly from dirt or the textile material, and to support the surfactant effect.
  • co-builders can also be contained in the builder, so-called co-builders.
  • the co-builders have the task of adopting some properties of the phosphates, e.g. Sequestering effect, dirt-carrying capacity, primary and secondary washing effect.
  • water-insoluble silicates as described for example in DE-OS 24 12 837, and / or phosphates may be present in the builder.
  • Pyrophosphate, triphosphate, higher polyphosphates and metaphosphates can be used from the group of phosphates.
  • Organic complexing agents containing phosphorus such as alkane polyphosphonic acids, amino and hydroxyalkane polyphosphonic acids and phosphonocarboxylic acids, also come as further detergent ingredients into consideration.
  • detergent additives are, for example, the following compounds: methane diphosphonic acid, propane-1,2,3-triphosphonic acid, butane-1,2,3,4-tetraphosphonic acid, polyvinylphosphonic acid, 1-aminoethane-1,1-diphosphonic acid, 1-amino-1 -phenyl-1,1-diphosphonic acid, aminotrismethylene triphosphonic acid, methylamino or ethylaminobismethylene diphosphonic acid, ethylenediaminotetramethylene tetraphosphonic acid, diethylene triaminopentamethylene pentaphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, phosphonoacetic and phosphonopropionic acid, and / or polyphosphonate acid, and / or their polymer malpolymer partially or fully neutralized salts.
  • organic compounds which act as complexing agents for calcium and can be present in detergent formulations are polycarboxylic acids, hydroxycarboxylic acids and aminocarboxylic acids, which are mostly used in the form of their water-soluble salts.
  • dicarboxylic acids of the general formula HOOC- (CH2) m -COOH with m 0-8, also maleic acid, methylene malonic acid, citraconic acid, mesaconic acid, itaconic acid, non-cyclic polycarboxylic acids with at least 3 carboxyl groups in the molecule, such as tricarballylic acid, a
  • Hexane hexacarboxylic acid cyclic di- or polycarboxylic acids, such as, for example, cyclopentane tetracarboxylic acid, cyclohexane hexacarboxylic acid, tetrahydrofuran tetracarboxylic acid, phthalic acid, terephthalic acid, benzene tri-, tetra- or pentacarboxylic acid and mellitic acid.
  • hydroxymono- or polycarboxylic acids examples include glycolic acid, lactic acid, malic acid, tartronic acid, methyltartronic acid, gluconic acid, glyceric acid, citric acid, tartaric acid, salicylic acid.
  • aminocarboxylic acids are glycine, glyclglycine, alanine, asparagine, glutamic acid, aminobenzoic acid, iminodi- or triacetic acid, hydroxyethyliminodiacetic acid, ethylenediaminotetraacetic acid, hydroxyethyl-ethylenediamine-triacetic acid, diethylenetriamine-pentaacetic acid and, for example, polymerisation of a carboxylic acid, the acetic acid, the acetic acid, the acetic acid, the acetic acid, the acidic acid, the acid of which is carboxylic acid, the acetic acid, the acidic acid, the acidic acid of which is homologous carboxylic acid , Succinic acid, tricarballylic acid, and subsequent saponification, or by condensation of polyamines with a molecular weight of 500 to 10,000 with chloroacetic or bromoacetic salts.
  • Polymeric carboxylic acids are preferably used as co-builders. These polymeric carboxylic acids include the carboxymethyl ethers of sugar, starch and cellulose.
  • polymeric carboxylic acids e.g. the polymers of acrylic acid, maleic acid, itaconic acid, mesaconic acid, aconitic acid, methylene malonic acid, citraconic acid and the like.
  • copolymers of the abovementioned carboxylic acids with one another e.g.
  • ethylenically unsaturated compounds such as ethylene, propylene, isobutylene, vinyl alcohol, vinyl methyl ether, furan, acrolein, vinyl acetate, acrylamide, acrylonitrile, methacrylic acid, crotonic acid etc., such as e.g. the
  • the co-builders can also contain dirt carriers which keep the dirt detached from the fibers suspended in the liquor and thus inhibit graying.
  • water-soluble colloids usually of an organic nature, are suitable, such as, for example, the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used.
  • Bleaching agents are especially hydrogen peroxide and derivatives or active chlorine-providing compounds.
  • Sodium perborate hydrates such as NaBO2 ⁇ H2O2 ⁇ 3H2O and NaBO2 ⁇ H2O2
  • these compounds can be partially or completely replaced by other active oxygen carriers, in particular by peroxyhydrates, such as peroxycarbonates, peroxyphosphonates, citrate perhydrates, urea-H2O2- or melamine-H2O2-compounds as well as by H2O2-delivering peracid salts, e.g. Caroates, perbenzoates or peroxyphthalates can be replaced.
  • customary water-soluble and / or water-insoluble stabilizers for the peroxy compounds according to the invention can be incorporated together with these in amounts of 0.25 to 10% by weight, based on the peroxy compound.
  • Other alkaline earth metals of appropriate composition can also be used in their place.
  • bleach activators are advantageously incorporated into the detergent, advantageously in an amount of, based on the H2O2-providing compound 5 to 30% by weight.
  • activators for H2O2 delivering per compounds serve certain, with H2O2 organic peracids forming N-acyl, O-acyl compounds, especially acetyl, propionyl or benzoyl compounds, as well as carbonic acid or pyrocarbonate.
  • Useful connections include: N-diacylated and N, N ⁇ -tetraacylated amines, such as N, N, N ⁇ , N ⁇ -tetraacetyl-methylenediamine or -ethylenediamine, N, N-diacetylaniline and N, N-diacetyl-p-toluidine or 1,3-diacylated hydantoins, Alkyl-N-sulfonyl-carbonamides, N-acylated cyclic hydrazides, acylated triazoles or urazoles, such as that Monoacetyl maleic acid hydrazide, O, N, N-trisubstituted hydroxylamines, such as O-benzoyl-N, N-succinyl-hydroxylamine, O-acetyl-N, N-succinyl-hydroxylamine, Op-methoxybenzoyl-N, N-succinylhydroxylamine, Op
  • Benzoic anhydride m-chlorobenzoic anhydride, Phthalic anhydride, 4-chlorophthalic anhydride
  • Sugar esters such as glucose pentaacetate, Imidazolidine derivatives, such as 1,3-diformyl-4,5-diacetoxyimidazolidine, 1,3-diacetyl-4,5-diacetoxy-imidazolidine, 1,3-diacetyl-4,5-di-propionyloxy-imidazolidine, acylated glycolurils, such as Tetrapropionylglycoluril or Diacetyl-dibenzoylglycoluril, dialkylated 2,5-diketopiperazines, such as 1,4-diacetyl-2,5-diketopiperazine, 1,4-dipropionyl-2,5-diketopiperazine, 1,4-dipropionyl-3,6-dimethyl-2,5-diketopiperaz
  • Active chlorine compounds of inorganic or organic nature can also be used as bleaching agents.
  • the inorganic active chlorine compounds include alkali hypochlorites, which can be used in particular in the form of their mixed salts or addition compounds on orthophosphates or condensed phosphates, such as, for example, on pyro- and polyphosphates or on alkali silicates. If the washing and washing aids contain monopersulfates and chlorides, active chlorine is formed in aqueous solution.
  • Suitable organic chlorine compounds are, in particular, the N-chlorine compounds in which one or two chlorine atoms are bonded to a nitrogen atom, the third valence of the nitrogen atoms preferably leading to a negative group, in particular to a CO or SO2 group.
  • These compounds include dichloro- and trichlorocyanuric acid or its salts, chlorinated alkylguanides or alkylbiguanides, chlorinated hydantoins and chlorinated melamines.
  • Suitable foam regulators are, especially when using surfactants of the sulfonate or sulfate type, capillary-active carboxy- or sulfobetaines and the above-mentioned nonionics of the alkylolamide type. Fatty alcohols or higher terminal diols are also suitable for this purpose.
  • a reduced foaming power which is particularly desirable in machine washing, is often achieved by combining different types of surfactants, for example sulfates and / or sulfonates with nonionics and / or with soaps.
  • surfactants for example sulfates and / or sulfonates with nonionics and / or with soaps.
  • foam attenuation increases with the degree of saturation and the C number of the fatty acid ester; Soaps of saturated C20-C24 fatty acids are therefore particularly suitable as foam suppressants.
  • the non-surfactant-like foam inhibitors optionally include chlorine-containing N-alkylated aminotriazines, which are obtained by reacting 1 mol of cyanuric chloride with 2 to 3 mol of a mono- and / or dialkylamine having 6 to 20, preferably 8 to 18, carbon atoms in the alkyl radical.
  • Propoxylated and / or butoxylated aminotriazines e.g. Products obtained by adding 5 to 10 moles of propylene oxide to 1 mole of melamine and further adding 10 to 50 moles of butylene oxide to this propylene oxide derivative.
  • non-surfactant-like foam inhibitors are water-insoluble organic compounds, such as paraffins or halogen paraffins with melting points below 100 ° C., aliphatic C18 to C40 ketones and aliphatic carboxylic acid esters which are present in the acid or alcohol residue, optionally also in each of these two residues, at least Contain 18 carbon atoms (eg triglycerides or fatty acid fatty alcohol esters); they can be used especially with combinations of surfactants of the sulfate and / or sulfonate type with soaps to dampen the foam.
  • water-insoluble organic compounds such as paraffins or halogen paraffins with melting points below 100 ° C., aliphatic C18 to C40 ketones and aliphatic carboxylic acid esters which are present in the acid or alcohol residue, optionally also in each of these two residues, at least Contain 18 carbon atoms (eg triglycerides or fatty acid fatty alcohol esters); they can
  • the detergents can contain optical brighteners for cotton, for polyamide, polyacrylonitrile or polyester fabrics.
  • Suitable optical brighteners are, for example, derivatives of diaminostilbenedisulfonic acid for cotton, derivatives of 1,3-diarylpyrazolines for polyamide, quaternary salts of 7-methoxy-2-benzimidazolyl- (2 ⁇ ) -benzofuran or of derivatives from the compound class of 7- [1 ⁇ , 2 ⁇ , 5 ⁇ -triazolyl- (1 ⁇ )] - 3- [1 ⁇ , 2 ⁇ , 4 ⁇ -triazolyl- (1 ⁇ )] - coumarins for polyacrylonitrile.
  • Brighteners suitable for polyesters are, for example, products from the compound class of substituted styriles, ethylenes, thiophenes, naphthalenedicarboxylic acids or derivatives thereof, stilbenes, coumarins and naphthalimides.
  • auxiliaries e.g. Solubilizers, such as xylene or cumene sulfonates, adjusting agents, such as sodium sulfate, enzymes or perfume oils.
  • the washing and cleaning agents according to the invention can, for example, be powdery or liquid.
  • aqueous formaldehyde solution 100 g (1 mol) of 30% strength by weight aqueous formaldehyde solution are initially introduced, and a solution of 52 g (0.5 mol) of serine in 250 g of water, in which: a pH of 8.5 was previously set with 37 g of 40% NaOH.
  • aqueous solution of serine-N, N-diacetonitrile prepared under 1 is added dropwise to 102 g (1.02 mol) of 40% strength by weight aqueous sodium hydroxide solution at 95 to 110 ° C. in the course of 1 hour. After stirring for a further 3 hours at 100 ° C., no more ammonia development is found (total 0.94 mol).
  • the aqueous solution of serine-N, N-di-acetic acid trisodium salt produced under B is concentrated to about 50% by weight under reduced pressure (water jet pump). A pH of 2 is set with concentrated hydrochloric acid. The solution is then added dropwise to 4 times the volume of methanol. The colorless precipitate which has separated out is filtered off and washed again with methanol. After drying, 98 g ( 86% of theory) Serine-N, N-diacetic acid, mp. 171 to 173 ° C, cf. s. Korman et al., J. Biol. Chem. 221, p. 116 (1956).
  • the solution of hydroxymethylnitrilotriacetonitrile obtained is added dropwise to 300 g (3 mol) of a 40% strength by weight aqueous sodium hydroxide solution heated to 100 ° C. within 30 minutes. For saponification, the mixture is heated at 100 ° C. for 4 hours until no more ammonia escapes.
  • the free acid according to Example 1C is obtained from the solution of serine N, N-di-acetic acid trisodium salt obtained.
  • tripotassium and triammonium salts obtained from the free serine-N, N-diacetic acid each have mp of above 300 ° C.
  • the inhibitory effect of complexing agents on the precipitation of iron (III) hydroxide is determined by turbidity titration.
  • the active substance to be investigated (W.S.) is presented and titrated in an alkaline solution with iron (III) chloride solution until it becomes cloudy.
  • the titration is carried out automatically using a titroprocessor; the light transmittance of the solution is monitored with an optical fiber photometer.
  • the end point of the titration is indicated by the appearance of a turbidity. It indicates the amount of iron bound and is a measure of the strength of the complex formed compared to iron hydroxide.
  • discoloration usually occurs before the end point is reached.
  • the extent of the discoloration (caused by colloidally dispersed iron hydroxide) gives an indication of the tendency of the complex formed to disassociate. A rough measure of this is the slope of the titration curve before the equivalence point is reached. It is measured in% transmission / ml FeCl3 solution. The reciprocal values thus indicate the strength of the complexes.
  • the complexing capacity is expressed as:
  • the hydrogen peroxide responsible for the bleaching action in detergent formulations containing sodium is catalytically decomposed by heavy metal ions (Fe, Cu, Mn). This can be prevented by complexing the heavy metal ions.
  • the peroxide-stabilizing effect of the complexing agents is checked via the residual peroxide content after warm storage of a wash liquor containing heavy metals.
  • the hydrogen peroxide content is determined before and after storage by titration with potassium permanganate in acid solution.
  • composition (in% by weight):
  • the detergent concentration is 6.5 g / l using water at 25 ° dH. Storage is at 80 ° C for 2 hours.
  • composition (in% by weight):
  • the detergent concentration is 8 g / l using water at 25 ° dH. Storage is at 60 ° C for 1 hour.
  • the inhibitory effect of complexing agents or dispersing agents on the precipitation of calcium carbonate is determined by turbidity titration.
  • the substance to be examined is presented and titrated with calcium acetate solution in the presence of sodium carbonate. The end point is indicated by the formation of the calcium carbonate precipitation.
  • the change in light transmittance is monitored using an optical fiber photometer.
  • a light beam directed into the solution via glass fibers is reflected on a mirror and the intensity of the reflected light is measured.
  • Amount mg CaCO3 / g W.S. Consumption of CA (OAc) 2 solution in ml x 25.
  • the 1st breakpoint of the titration curve is the end point.
  • the strength of the complex formed is many times greater than that of the complex of ethylenediaminetetraacetic acid.
  • the particularly surprising effect lies in the excellent perborate stabilization for the N-containing and relatively low molecular weight compound to be used according to the invention.

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  • 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)
EP88105376A 1987-04-11 1988-04-02 Procédé de préparation de la N,N-dicarboxyméthyl-sérine et de ses dérivés Expired - Lifetime EP0287885B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88105376T ATE72229T1 (de) 1987-04-11 1988-04-02 Verfahren zur herstellung von serin-n,ndiessigs|ure und derivaten.

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DE3712329 1987-04-11
DE19873712329 DE3712329A1 (de) 1987-04-11 1987-04-11 Verfahren zur herstellung von serin-n,n-diessigsaeure und derivaten, ihre verwendung insbesondere als komplexbildner und diese enthaltende wasch- und reinigungsmittel

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EP0287885B1 EP0287885B1 (fr) 1992-01-29

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JP (1) JPS63267751A (fr)
AT (1) ATE72229T1 (fr)
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CA (1) CA1313673C (fr)
DE (2) DE3712329A1 (fr)
ES (1) ES2028924T3 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
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EP0356947A2 (fr) * 1988-09-02 1990-03-07 BASF Aktiengesellschaft Procédé pour la préparation du sel trisodique de l'isosérine N,N diacide acétique
EP0379109A2 (fr) * 1989-01-20 1990-07-25 BASF Aktiengesellschaft Glycérineaminocarboxylates, leur préparation et utilisation
WO1994012606A1 (fr) * 1992-12-03 1994-06-09 Basf Aktiengesellschaft Derives d'acide iminodiacetique utilises dans des compositions de nettoyage destinees a l'industrie des boissons et des produits alimentaires, ainsi que pour le nettoyage de surfaces dures en metal, en matiere plastique, vernies ou en verre
US5362412A (en) * 1991-04-17 1994-11-08 Hampshire Chemical Corp. Biodegradable bleach stabilizers for detergents
WO1994026691A1 (fr) * 1993-05-19 1994-11-24 Akzo Nobel N.V. Acide (2-carboxy-3-hydroxy-propyl)-iminodiacetique et derives
EP0745582A2 (fr) * 1995-05-29 1996-12-04 BASF Aktiengesellschaft Procédé pour la préparation de dérivés de glycine-N,N-diacétique par réaction de dérivés de la glycine ou de leurs précurseurs avec le formaldéhyde et l'acide cyanhydrique (ou ...) en milieu acide aqueux
EP0745581A2 (fr) * 1995-05-29 1996-12-04 BASF Aktiengesellschaft Procédé pour la préparation de dérivés de glycine-N,N-diacétique par réaction de dérivés de la glycine ou de leurs précurseurs avec le formaldéhyde et du cyanure de métal alcalin dans un milieu acide aqueux
WO1998059027A1 (fr) * 1997-06-24 1998-12-30 Unilever N.V. Additif de formulation de detergent, formulation de detergent comprenant cet additif et utilisation de cette formulation pour le nettoyage de bouteilles
WO2016180664A1 (fr) * 2015-05-13 2016-11-17 Basf Se Procédé de préparation de mélanges d'agents chélatants

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IT1213029B (it) * 1986-01-30 1989-12-07 Bracco Ind Chimica Spa Chelati di ioni metallici paramagnetici.
DE3914980A1 (de) * 1989-05-06 1990-12-06 Basf Ag 2-methyl- und 2-hydroxymethyl-serin-n,n-diessigsaeure und ihre derivate
US5254290A (en) * 1991-04-25 1993-10-19 Genevieve Blandiaux Hard surface cleaner
US5221496A (en) * 1992-06-02 1993-06-22 Basf Corp. Aqueous prewash stain remover compositions with efficacy on tenacious oily stains
US5186856A (en) * 1992-06-02 1993-02-16 Basf Corp. Aqueous prewash stain remover compositions with efficacy on tenacious oily stains
DE4319935A1 (de) * 1993-06-16 1994-12-22 Basf Ag Verwendung von Glycin-N,N-diessigsäure-Derivaten als Komplexbildner für Erdalkali- und Schwermetallionen
JP2983063B2 (ja) * 1994-10-07 1999-11-29 エカ ケミカルズ アクチェボラーグ 漂白剤
CZ285638B6 (cs) * 1994-10-07 1999-10-13 Eka Chemicals Ab Částice obsahující peroxysloučeninu a prostředek, který je obsahuje
US6034048A (en) * 1995-03-01 2000-03-07 Charvid Limited Liability Co. Non-caustic cleaning composition using an alkali salt
US6194367B1 (en) * 1995-03-01 2001-02-27 Charvid Limited Liability Co. Non-caustic cleaning composition comprising peroxygen compound and specific silicate and method of making the same in free-flowing, particulate form
US5663132A (en) * 1995-03-01 1997-09-02 Charvid Limited Liability Company Non-caustic composition comprising peroxygen compound and metasilicate and cleaning methods for using same
US5488130A (en) * 1995-03-31 1996-01-30 The Dow Chemical Company Amino nitrile intermediate for the preparation of 2-hydroxypropyl iminodiacetic acid
US5481018A (en) * 1995-03-31 1996-01-02 The Dow Chemical Company Amino nitrile intermediate for the preparation of alanine diacetic acid
EP0783034B1 (fr) * 1995-12-22 2010-08-18 Mitsubishi Rayon Co., Ltd. Agent chélateur et détergent le contenant
JPH10168485A (ja) * 1996-12-13 1998-06-23 Kao Corp 高密度洗剤組成物
JP3290382B2 (ja) 1997-07-18 2002-06-10 花王株式会社 粉末洗剤組成物
JPH11217590A (ja) * 1998-02-04 1999-08-10 Kao Corp 漂白洗浄剤組成物
JP2000008099A (ja) * 1998-06-23 2000-01-11 Kao Corp 液体洗浄剤組成物
JP2000008081A (ja) * 1998-06-25 2000-01-11 Kao Corp 洗浄剤組成物
CN1267972C (zh) * 2000-03-21 2006-08-02 和光纯药工业株式会社 半导体基板洗涤剂和洗涤方法
US20100056404A1 (en) * 2008-08-29 2010-03-04 Micro Pure Solutions, Llc Method for treating hydrogen sulfide-containing fluids
CA2917252A1 (fr) * 2013-07-16 2015-01-22 Axel Carstens Nouveaux sels, cristaux, complexes et derives d'acide diacetique de threonine, procede de preparation dudit acide et utilisation associee
RU2712767C2 (ru) * 2015-03-11 2020-01-31 Басф Се Смеси хелатирующих агентов и способ получения таких смесей

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Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0356947A2 (fr) * 1988-09-02 1990-03-07 BASF Aktiengesellschaft Procédé pour la préparation du sel trisodique de l'isosérine N,N diacide acétique
EP0356947A3 (fr) * 1988-09-02 1991-10-02 BASF Aktiengesellschaft Procédé pour la préparation du sel trisodique de l'isosérine N,N diacide acétique
EP0379109A2 (fr) * 1989-01-20 1990-07-25 BASF Aktiengesellschaft Glycérineaminocarboxylates, leur préparation et utilisation
EP0379109A3 (fr) * 1989-01-20 1991-01-09 BASF Aktiengesellschaft Glycérineaminocarboxylates, leur préparation et utilisation
US5025103A (en) * 1989-01-20 1991-06-18 Basf Aktiengesellschaft Glycerol aminocarboxylates and preparation and use thereof
US5362412A (en) * 1991-04-17 1994-11-08 Hampshire Chemical Corp. Biodegradable bleach stabilizers for detergents
WO1994012606A1 (fr) * 1992-12-03 1994-06-09 Basf Aktiengesellschaft Derives d'acide iminodiacetique utilises dans des compositions de nettoyage destinees a l'industrie des boissons et des produits alimentaires, ainsi que pour le nettoyage de surfaces dures en metal, en matiere plastique, vernies ou en verre
WO1994026691A1 (fr) * 1993-05-19 1994-11-24 Akzo Nobel N.V. Acide (2-carboxy-3-hydroxy-propyl)-iminodiacetique et derives
EP0745582A2 (fr) * 1995-05-29 1996-12-04 BASF Aktiengesellschaft Procédé pour la préparation de dérivés de glycine-N,N-diacétique par réaction de dérivés de la glycine ou de leurs précurseurs avec le formaldéhyde et l'acide cyanhydrique (ou ...) en milieu acide aqueux
EP0745581A2 (fr) * 1995-05-29 1996-12-04 BASF Aktiengesellschaft Procédé pour la préparation de dérivés de glycine-N,N-diacétique par réaction de dérivés de la glycine ou de leurs précurseurs avec le formaldéhyde et du cyanure de métal alcalin dans un milieu acide aqueux
EP0745581A3 (fr) * 1995-05-29 1997-12-10 BASF Aktiengesellschaft Procédé pour la préparation de dérivés de glycine-N,N-diacétique par réaction de dérivés de la glycine ou de leurs précurseurs avec le formaldéhyde et du cyanure de métal alcalin dans un milieu acide aqueux
EP0745582A3 (fr) * 1995-05-29 1997-12-10 BASF Aktiengesellschaft Procédé pour la préparation de dérivés de glycine-N,N-diacétique par réaction de dérivés de la glycine ou de leurs précurseurs avec le formaldéhyde et l'acide cyanhydrique (ou ...) en milieu acide aqueux
WO1998059027A1 (fr) * 1997-06-24 1998-12-30 Unilever N.V. Additif de formulation de detergent, formulation de detergent comprenant cet additif et utilisation de cette formulation pour le nettoyage de bouteilles
WO2016180664A1 (fr) * 2015-05-13 2016-11-17 Basf Se Procédé de préparation de mélanges d'agents chélatants
RU2706358C2 (ru) * 2015-05-13 2019-11-18 Басф Се Способ получения смесей хелатообразующих агентов
US10519097B2 (en) 2015-05-13 2019-12-31 Basf Se Process for making mixtures of chelating agents

Also Published As

Publication number Publication date
DE3712329A1 (de) 1988-10-20
US4973730A (en) 1990-11-27
US5019296A (en) 1991-05-28
DE3868118D1 (de) 1992-03-12
AU1446388A (en) 1988-10-13
CA1313673C (fr) 1993-02-16
JPS63267751A (ja) 1988-11-04
ES2028924T3 (es) 1992-07-16
AU608592B2 (en) 1991-04-11
ATE72229T1 (de) 1992-02-15
EP0287885B1 (fr) 1992-01-29

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