EP0871695A2 - Chelatants degradables derives d'acides polyamino-monosucciniques, leurs utilisations et compositions - Google Patents

Chelatants degradables derives d'acides polyamino-monosucciniques, leurs utilisations et compositions

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Publication number
EP0871695A2
EP0871695A2 EP96929807A EP96929807A EP0871695A2 EP 0871695 A2 EP0871695 A2 EP 0871695A2 EP 96929807 A EP96929807 A EP 96929807A EP 96929807 A EP96929807 A EP 96929807A EP 0871695 A2 EP0871695 A2 EP 0871695A2
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EP
European Patent Office
Prior art keywords
acid
monosuccinic acid
monosuccinic
salt
polyamino
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP96929807A
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German (de)
English (en)
Inventor
Alan D. Strickland
David A. Wilson
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Dow Chemical Co
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Dow Chemical Co
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Publication date
Application filed by Dow Chemical Co filed Critical Dow Chemical Co
Publication of EP0871695A2 publication Critical patent/EP0871695A2/fr
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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
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/52—Hydrogen sulfide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
    • B01D53/56—Nitrogen oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/38—Coating with copper
    • C23C18/40—Coating with copper using reducing agents

Definitions

  • This invention relates to chelants, particularly uses of certain degradable chelants.
  • Chelants or chelating agents are compounds which form coordinate covalent bonds with a metal ion to form chelates.
  • Chelates are coordination compounds in which a central metal atom is bonded to two or more other atoms in at least one other molecule (called ligand) such that at least one heterocyclic ring is formed with the metal atom as part of each ring.
  • Chelants are used in a variety of applications including food processing, soaps, detergents, cleaning products, personal care products, pharmaceuticals, pulp and paper processing, gas conditioning, water treatment, metalworking and metal plating solutions, textile processing solutions, fertilizers, animal feeds, herbicides, rubber and polymer chemistry, photofinishing, and oil field chemistry. Some of these activities result in chelants entering the environment. For instance, agricultural uses or detergent uses may result in measurable quantities of the chelants being present in water. It is, therefore, desirable that chelants degrade after use.
  • Biodegradability that is susceptibility to degradation by microbes, is particularly useful because the microbes are generally naturally present in environments into which the chelants may be introduced.
  • Commonly used chelants like EDTA ethylenediamine tetraacetic acid
  • EDTA ethylenediamine tetraacetic acid
  • Tiedje "Microbial Degradation of Ethylenediaminetetraacetate in Soils and Sediments," Applied Microbiology, Aug. 1 975, pp. 327-329.
  • a chelant useful in areas such as those mentioned above wherein such chelant is greater than about 60 percent biodegradable within less than 28 days according to the OECD 301 B Modified Sturm Test or greater than about 80 percent biodegradable within less than 28 days according to the Semicontinuous Activated Sludge Test (ASTM D 2667 89).
  • the invention includes methods of electroless plating using various metals (especially copper) complexed with a mixture of chelants comprising at least polyamino monosuccinic acids, or salts thereof.
  • the invention includes a method of electroless deposition of copper upon a non-metallic surface receptive to the deposited copper including a step of contacting the non-metallic surface with an aqueous solution comprising a soluble copper salt and a polyamino monosuccinic acid.
  • a method of electroless copper plating which comprises immersing a receptive surface to be plated in an alkaline, autocatalytic copper bath comprising water, a water soluble copper salt, and a polyamino monosuccinic acid complexing agent for cupric ion.
  • the invention includes a bath for the electroless plating of copper which comprises water, a water soluble copper salt, a polyamino monosuccinic acid complexing agent for cupric ions, sufficient alkali metal hydroxide to result in a pH of from 10 to 14, and a reducing agent.
  • Another aspect of the invention includes a method for removing iron oxide deposits or organic stains from a surface including a step of contacting the deposits or stains with a solution comprising a polyamino monosuccinic acid.
  • Yet another aspect of the invention involves gas conditioning.
  • the invention includes a process of removing H2S from a fluid comprising contacting said fluid with an aqueous solution at a pH suitable for removing H2S wherein said solution contains at least one higher valence polyvalent metal chelate of a polyamino monosuccinic acid.
  • Another aspect of the gas conditioning invention includes a process of removing NO x from a fluid comprising contacting the fluid with an aqueous solution of at least one lower valence state polyvalent metal chelate of a polyamino monosuccinic acid.
  • the present invention is also to a laundry detergent composition
  • a laundry detergent composition comprising (a) from 1 % to 80% by weight of a detergent surfactant selected from nonionic, anionic, cationic, zwitterionic, and ampholytic surfactants and mixtures thereof; (b) from 5% to 80% by weight of at least one detergent builder; and (c) from 0.1 % to 15% by weight of at least one polyamino monosuccinic acid or salt thereof.
  • the laundry detergent of the present invention may be a liquid laundry detergent composition comprising (a) from 10% to 50% by weight of a detergent surfactant selected from nonionic, anionic, cationic, zwitterionic, and ampholytic surfactants and mixtures thereof; (b) from 10% to 40% by weight of at least one detergent builder; and (c) from 0.1 % to 10% by weight of at least one polyamino monosuccinic acid or salt thereof.
  • a detergent surfactant selected from nonionic, anionic, cationic, zwitterionic, and ampholytic surfactants and mixtures thereof.
  • the laundry detergent of the present invention may also be a granular laundry composition comprising comprising (a) from 5% to 50% by weight of a detergent surfactant selected from nonionic, anionic, cationic, zwitterionic, and ampholytic surfactants and mixtures thereof; (b) from 10% to 40% by weight of at least one detergency builder; and (c) from 0.1 % to 10% by weight of at least one polyamino monosuccinic acid or salt thereof.
  • a detergent surfactant selected from nonionic, anionic, cationic, zwitterionic, and ampholytic surfactants and mixtures thereof.
  • the present invention is to an automatic dishwashing composition comprising (a) as least one polyamino monosuccinic acid, or salt thereof; and (b) a bleach active salt.
  • the present invention is also to a chelate composition
  • a chelate composition comprising a chelating agent and a metal wherein the chelating agent is a polyamino monosuccinic acid and the metal is iron.
  • polyamino monosuccinic acids are excellent for use in electroless plating of metals, in removing iron oxide stains, in removing organic stains from fabrics, in removing H2S from fluids, and in removing NO x from fluids.
  • the compounds are also biodegradable as measured by the 301 B Modified Sturm Test or the Semicontinuous Activated Sludge Test (ASTM D 2667 89).
  • Polyamino monosuccinic acids are compounds having at least two nitrogen atoms to which a succinic acid (or salt) moiety is attached to one of the nitrogen atoms.
  • succinic acid includes salts thereof.
  • the compounds have at least 2 nitrogen atoms, and due to the commercial availability of the amine, preferably have no more than about 10 nitrogen atoms, more preferably no more than about 6, most preferably 2 nitrogen atoms.
  • the remaining nitrogen atoms may be substituted with hydrogen, an alkyl, an alkylaryl, or an arylalkyl moiety.
  • the alkyl moiety may be linear or branched, saturated or unsaturated and generally contains from 1 to 30 carbon atoms, preferably from 1 to 20 carbon atoms, and more preferably from 1 to 12 carbon atoms.
  • the arylalkyl or alkylaryl moiety generally contains from 6 to 18 carbon atoms and preferably contains from 6 to 12 carbon atoms.
  • the alkyl, arylalkyl, or alkylaryl moieties may also be substituted with from 0 to 12 atoms other than carbon, such as oxygen, sulfur, phosphorus, nitrogen, fluorine, chlorine, bromine, iodine, hydrogen, or combinations thereof.
  • Such substitutions include carboxyalkyl, hydroxyalkyl, sulfonoalkyl, phosphonoalkyl or alkylene hydroxamate groups.
  • the succinic acid moiety may be attached to any of the nitrogens, preferably the succinic acid group is attached to a terminal nitrogen atom.
  • terminal it is meant the first or last nitrogen which is present in the compound, irrespective of other substituents.
  • the remaining bonds on the nitrogen having a succinic acid group are preferably bonded to a second nitrogen through an alkyl or alkylene group and the remaining bond of the nitrogen containing the succinic acid moiety is preferentially filled by a hydrogen or an alkyl group, but most preferably hydrogen.
  • the nitrogen atoms are linked by alkyl or alkylene groups, each of from 2 to 1 2 carbon atoms, preferably from 2 to 1 0 carbon atoms, more preferably from 2 to 8, and most preferably from 2 to 6 carbon atoms.
  • the polyamino monosuccinic acid compound preferably has at least about 6 carbon atoms and preferably has at most about 50, more preferably at most about 40, and most preferably at most about 30 carbon atoms.
  • the polyamino monosuccinic acid when it is desired for the polyamino monosuccinic acid to contain a metal ion binding moiety in addition to the carboxyl groups of the succinic acid, it is desirable to place such a functional group on a nitrogen atom to which the succinic acid moiety is not bound.
  • the polyamino monosuccinic acid when the polyamino monosuccinic acid contains two nitrogen atoms which are joined by an ethylene moiety, it is preferred that the nitrogen atom which is not bound to the succinic acid moiety is substituted with at least one metal ion binding moiety.
  • the nitrogen atom or nitrogen atoms to which the succinic acid moiety is not bound are generally substituted with hydrogen.
  • the nitrogen atom which is not bound to the succinic acid moiety is substituted with two hydrogen atoms.
  • Polyamino monosuccinic acids useful in the present invention include ethylenediamine-N-monosuccinic acid, diethylenetriamine-N- monosuccinic acid, triethylenetetramine-N-monosuccinic acid, 1 ,6- hexamethylenediamine-N-monosuccinic acid, 2-hydroxypropylene-1 ,3- diamine-N-monosuccinic acid, 1 ,2-propylenediamine-N-monosuccinic acid, 1 ,3-propylenediamine-N-monosuccinic acid, cis-cyclohexanediamine-N- monosuccinic acid, trans-cyclohexanediamine-N-monosuccinic acid, ethylene-bis(oxyethylenenitrilo)-N-monosuccinic acid, N-carboxymethyl- ethylenediamine-N'-monosuccinic acid, N-carboxyethyl-ethylened
  • Preferred polyamino monosuccinic acids are those that contain two nitrogen atoms and wherein the nitrogen atom which is bound to the succinic acid moiety is substituted with hydrogen and the nitrogen atom which is not bound to the succinic acid moiety is substituted with at least one hydrogen atom.
  • Polyamino monosuccinic acids can be prepared, for example, by the process of Bersworth et al. in U.S. Patent 2,761 ,874, the disclosure of which is incorporated herein by reference, and as disclosed in Jpn. Kokai Tokkyo Koho JP 57,1 16,031 .
  • Bersworth et al. disclose reacting alkylene diamines and dialkylene triamines with maleic acid esters under mild conditions in an alcohol to yield polyamino monosuccinic acid esters which are then hydrolyzed to the corresponding acids. The reaction yields a mixture of the R and S isomers.
  • Polyamino monosuccinic acids with carboxyalkyl groups can be prepared by reacting the unsubstituted polyamino monosuccinic acids or their esters with the appropriate haloalkyl carboxylic acid or ester followed by hydrolysis of the ester. Polyamino monosuccinic acids with carboxyalkyl groups may also be prepared utilizing the reaction of the unsubstituted polyamino monosuccinic acids or their esters with the appropriate aldehydes and cyanide followed by hydrolysis of the nitrile and ester to the corresponding carboxyalkyl groups.
  • Polyamino monosuccinic acids containing a hydroxyalkyl group may be prepared by reacting the unsubstituted polyamino monosuccinic acids or their esters with the appropriate alkyl oxide followed by the hydrolysis of the ester.
  • Polyamino monosuccinic acids containing hydroxyalkyl or alkyl groups may also be prepared by reaction of the appropriate hydroxyalkylamine or alkylamine with a maleic acid ester followed by hydrolysis of the ester or by reaction of the amine with maleic acid and an alkali metal hydroxide such as sodium hydroxide.
  • Polyamino monosuccinic acids containing phosphonoalkyl groups or sulfonoalkyl groups can be prepared by reacting the unsubstituted polyamino monosuccinic acids or their esters with the appropriate haloalkyl phosphonate or haloalkyl sulfonate, respectively followed by hydrolysis of the ester.
  • Phosphonoalkyl groups may also be introduced by reacting the unsubstituted polyamino monosuccinic acids with the appropriate aldehyde and phosphorous acid.
  • Certain sulfonoalkyl groups may be introduced by reacting the appropriate aldehyde and a bisulfite with the unsubstituted polyamino monosuccinic acids.
  • Hydroxamate groups can be introduced by reacting the appropriate aminocarboxylic acid ester or anhydride with a hydroxylamine compound as described in U.S. 5,256,531 .
  • the invention includes use of iron complexes of polyamino monosuccinic acids such as ethylenediamine-N-monosuccinic acid (EDMS) in abatement of hydrogen sulfide and other acid gases and as a source of iron in plant nutrition.
  • EDMS ethylenediamine-N-monosuccinic acid
  • other metal complexes such as the copper, zinc and manganese complexes supply those trace metals in plant nutrition.
  • the ferrous complexes are also useful in nitrogen oxide abatement.
  • Iron complexes used in the present invention are conveniently formed by mixing an iron compound with an aqueous solution of the monosuccinic acid (or salt).
  • the pH values of the resulting iron chelate solutions are preferably adjusted with an alkaline material such as ammonia solution, sodium carbonate, or dilute caustic (NaOH).
  • Water soluble iron compounds are conveniently used.
  • Exemplary iron compounds include iron nitrate, iron sulfate, and iron chloride.
  • the final pH values of the iron chelate solutions are preferably in the range of 4 to 9, more preferably in the range of 5 to 8.
  • the succinic acid compounds are preferably heated with the insoluble iron source in an aqueous medium at an acidic pH.
  • ammoniated amino succinic acid solutions are particularly effective.
  • Ammoniated amino succinic acid chelants are conveniently formed by combining aqueous ammonia solutions and aqueous solutions or slurries of amino succinic acids in the acid (rather than salt) form.
  • Polyamino monosuccinic acids are effective as chelants especially for metals such as iron and copper. Effectiveness as a chelant is conveniently measured by complexing the chelant with a metal such as copper such as by mixing an aqueous solution of known concentration of the chelant with an aqueous solution containing copper (II) ions of known concentration and measuring chelation capacity by titrating the chelant with copper in the presence of an indicator dye.
  • polyamino monosuccinic acid compounds such as ethylenediamine-N-monosuccinic acid
  • OECD 301 B Modified Sturm Test or the Semicontinuous Activated Sludge Test (ASTM D 2667 89).
  • the polyamino monosuccinic acid compounds are preferably employed in the form of water-soluble salts, notably alkali metal salts, ammonium salts, or alkyl ammonium salts.
  • alkali metal salts can involve one or a mixture of alkali metal salts although the potassium or sodium salts, especially the partial or complete sodium salts of the acids are preferred.
  • Polyamino monosuccinic acids are also useful, for instance, in food products vulnerable to metal-catalyzed spoilage or discoloration; in cleaning products for removing metal ions, that may reduce the effectiveness, appearance, stability, rinsibility, bleaching effectiveness, germicidal effectiveness or other property of the cleaning agents; in personal care products like creams, lotions, deodorants and ointments to avoid metal-catalyzed oxidation and rancidity, turbidity, reduced shelf-life; in pulp and paper processing to enhance or maintain bleaching effectiveness; in pipes, vessels, heat exchangers, evaporators, filters to avoid or remove scaling, in pharmaceuticals; in metal working; in textile preparation, desizing, scouring, bleaching, dyeing; in agriculture as in chelated micronutrients or herbicides; in polymerization or stabilization of polymers; in the oil field such as for drilling, production, recovery, hydrogen sulfide abatement.
  • the chelants can be used in industrial processes whenever metal ions such as iron or copper are a nuisance and are to be prevented.
  • the polyamino monosuccinic acids in the present application may be used in a variety of applications, as is disclosed for the use of disuccinic acid compounds in WO 94/05674 published May 20, 1994. These uses include the use of succinic acid mixtures for the electroless deposition of metals such as nickel and copper; in the polymerization of rubber; in the textile industry; in agriculture to supply micronutrients; and in gas conditioning to remove H 2 S, nitrous oxides (NO x ) and SO 2 .
  • the polyamino monosuccinic acids are also useful in laundry detergents, particularly laundry detergents containing a detergent surfactant and builder.
  • the polyamino monosuccinic acids facilitate the removal of organic stains such as tea stains, grape juice stains and various food stains from fabrics during laundering operations.
  • the stains are believed to contain metals such as copper and iron.
  • the polyamino monosuccinic acids are very effective in chelating these metals and thus aid in the removal of the troublesome stain.
  • compositions comprise from 1 % to 80% by weight of a detergent surfactant, preferably from 10% to 50%, selected from nonionic surfactants, anionic surfactants, cationic surfactants, zwitterionic surfactants, ampholytic surfactants and mixtures thereof; from 5% to 80% by weight of a detergent builder, preferably from 10% to 50%; and from 0.1 % to 15% by weight of a polyamino monosuccinic acid, preferably from 1 % to 10%, or alkali metal, alkaline earth, ammonium or substituted ammonium salt thereof, or mixtures thereof.
  • a detergent surfactant preferably from 10% to 50%, selected from nonionic surfactants, anionic surfactants, cationic surfactants, zwitterionic surfactants, ampholytic surfactants and mixtures thereof.
  • a detergent builder preferably from 10% to 50%
  • a polyamino monosuccinic acid preferably from 1 % to 10%, or alkali metal, alkaline
  • Nonionic surfactants that are suitable for use in the present invention include those that are disclosed in U.S. 3,929,678 (Laughlin et al.), incorporated herein by reference. Included are the condensation products of ethylene oxide with aliphatic alcohols, the condensation of ethylene oxide with the base formed by the condensation of propylene oxide and propylene glycol or the product formed by the condensation of propylene oxide and ethylendiamine. Also included are the various polyethylene oxide condensates of alkyl phenols and various amine oxide surfactants.
  • Anionic surfactants that are suitable for use are described in U.S. 3,929,678. These include sodium and potassium alkyl sulfates; various salts of higher fatty acids, and alkyl polyethoxylate sulfates.
  • Cationic surfactants that may be used are described in U.S. 4,228,044 (Cambre), incorporated herein by reference. Especially preferred cationic surfactants are the quaternary ammonium surfactants.
  • ampholytic and zwitterionic surfactants such as those taught in U.S. 3,929,678 can be used in the present invention.
  • Suitable builder substances are for example: wash alkalis, such as sodium carbonate and sodium silicate, or complexing agents, such as phosphates, or ion exchangers, such as zeolites, and mixtures thereof. These builder substances have as their function to eliminate the hardness ions, which come partially from the water, partially from dirt or textile material, and to support the surfactant action.
  • the builder component may further contain cobuilders. In modern detergents, it is the function of cobuilders to undertake some of the functions of phosphates, for example sequestration, soil antiredeposition and primary and secondary washing action.
  • the builder components may contain for example water-insoluble silicates, as described for example in German Laid-Open Application DE-OS No. 2,412,837, and/or phosphates.
  • phosphate it is possible to use pyrophosphates, triphosphates, higher polyphosphates and metaphosphates.
  • phosphorus-containing organic complexing agents such as alkanepolyphosphonic acids, amino- and hydroxy-alkanepolyphosphonic acids and phosphonocarboxylic acids, are suitable for use as further detergent ingredients generally referred to as stabilizers or phosphonates.
  • detergent additives are the following compounds: methanediphosphonic acid, propane-1 ,2,3-triphosphonic acid, butane-1 ,2,3,4-tetraphosphonic acid, polyvinylphosphonic acid, 1 -aminoethane,-1 , 1 -diphosphonic acid, aminotrismethylenetriphosphonic acid, methylamino- or ethylamino-bismethylenediphosphonic acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriaminopentamethylenephosphonic acid, 1 -hydroxyethane-1 , 1 -diphosphonic acid, phosphonoacetic and phosphonopropionic acid, copolymers of vinylphosphonic acid and acrylic and/or maleic acid and also partially or completely neutralized salts thereof.
  • polycarboxylic acids examples include dicarboxylic acids of the general formula HOOC-(CH ) -COOH where m is 0-8, maleic acid,
  • hydroxymonocarboxylic and hydroxypolycarboxylic acids are glycollic acid, lactic acid, malic acid, tartronic acid, methyltartronic acid, gluconic acid, glyceric acid, citric acid, tartaric acid and salicylic acid.
  • aminocarboxylic acids are glycine, glycylglycine, alanine, asparagine, glutamic acid, aminobenzoic acid, iminodiacetic acid, iminotriacetic acid, hydroxyethyliminodiacetic acid, ethylenediaminetetraacetic acid, ethylenediaminedisuccinic acid, hydroxyethylethylenediaminetriacetic acid, 2-hydroxypropylene-1 ,3- diaminedisuccinic acid, diethylenetriaminepentaacetic acid and higher homologues which are prepared by polymerization of an N-aziridylcarboxylic acid derivative, for example of acetic acid, succinic acid or tricarballylic acid, and subsequent hydrolysis, or by condensation of polyamines having a molecular weight of from 500 to 10,000 with salts of chloroacetic or bromoacetic acid.
  • Preferred cobuilder substances are polymeric carboxylates. These polymeric carboxylic acids include the carboxymethyl ethers of sugars, of starch and of cellulose. Zeolites and phosphates are also useful.
  • Particularly important polymeric carboxylic acids are for example the polymers of acrylic acid, maleic acid, itaconic acid, mesaconic acid, aconitic acid, methylenemalonic acid, citraconic acid, the copolymers between the aforementioned carboxylic acids, for example a copolymer of acrylic acid and maleic acid in a ration of 70:30 and having a molecular weight of 70,000, or copolymers thereof with ethylenically unsaturated compounds, such as ethylene, propylene, isobutylene, vinyl methyl ether, furan, acrolein, vinyl acetate, acrylamide, acrylonitrile methacrylic acid, crotonic acid, for example the 1 :1 copolymers of maleic anhydride and methyl vinyl ether having a molecular weight of 70,000 or the copolymers of maleic anhydride and ethylene and/or propylene and/or furan.
  • the cobuilders may further contain soil antiredeposition agents which keep the dirt detached from the fiber in suspension in the liquid and thus inhibit graying.
  • soil antiredeposition agents which keep the dirt detached from the fiber in suspension in the liquid and thus inhibit graying.
  • water-soluble colloids usually of an organic nature for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ethercarboxylic acids or ethersulfonic acids of starch and of cellulose or salts of acid sulfates of cellulose and of starch.
  • Even water-soluble polyamides containing acid groups are suitable for this purpose.
  • Polyvinylpyrrolidone is also usable.
  • Bleaching agents that can be used are in particular hydrogen peroxide and derivatives thereof or available chlorine compounds.
  • bleaching agent compounds which provide H O in water, sodium perborate hydrates, such as NaBO .H O .3H O and NaBO .H O and
  • peroxyhydrates such as, peroxyphosphonates, citrate perhydrates, urea, H O -providing peracid salts, for example caroates, perbenzoates or peroxyphthalates or other peroxy compounds.
  • customary water-soluble and/or water-insoluble stabilizers for peroxy compounds can be incorporated together with the former in amounts from 0.25 to 10 percent by weight, based on the peroxy compound.
  • Suitable water-insoluble stabilizers are the magnesium silicates MgO:SiO from 4: 1 to 1 :4, preferably from 2:1 to 1 :2, in particular 1 :1 , in composition, usually obtained by precipitation from aqueous solutions.
  • Other alkaline earth metals of corresponding composition are also suitably used.
  • bleach activators in the detergent, advantageously in an amount from 5 to 30 percent by weight, based on the H O -providing compound.
  • Activators for peroxy compounds which provide H O in water are certain N-acyl and O-acyl compounds, in particular acetyl, propionyl or benzyl compounds, which form organic peracids with H O and also carbonic and pyrocarbonic esters.
  • Useful compounds are inter alia: N-diacylated and N,N'-tetraacylated amines, for example
  • 4-chlorophthalic anhydride sugar esters, for example glucose pentaacetate, imidazolidine derivatives, such as 1 ,3 -diformyl -4,5-diacetoxyimidazolidine, 1 ,3-diacetyl-4,5-diacetoxyimidazoline and 1 ,3-diacetyl-4,5-dipropionyloxyimidazolidine, acylated glycolurils, for example tetrapropionylglycoluril or diacetyldibenzoylglycoluril, dialkylated 2,5-diketopiperazines, for example 1 ,4-dipropionyl-2,5-diketopiperazine and 1 ,4-dipropionyl-3,6-dimethyl-2,5-diketopiperazine and 1 ,4-dipropionyl-3,6-2,5-diketopiperazine, acetylation and benzoylation products of
  • the bleaching agents used can also be active chlorine compounds of the inorganic or organic type.
  • Inorganic active chlorine compounds include alkali metal hypochlorites which can be used in particular in the form of their mixed salts and adducts on orthophosphates or condensed phosphates, for example on pyrophosphates and polyphosphates or on alkali metal silicates. If the detergent contains monopersulfates and chlorides, active chlorine will form in aqueous solution.
  • Organic active chlorine compounds are in particular the
  • N-chlorine compounds where one or two chlorine atoms are bonded to a nitrogen atom and where preferably the third valence of the nitrogen atom leads to a negative group, in particular to a CO or SO group.
  • These compounds include dichlorocyanuric and trichlorocyanuric acid and their salts, chlorinated alkylguanides or alkylbiguanides, chlorinated hydantoins and chlorinated melamines.
  • additional assistants are: suitable foam regulants, in particular if surfactants of the sulfonate or sulfate type are used, are surface-active carboxybetaines or sulfobetaines and also the above mentioned nonionics of the alkylolamide type.
  • fatty alcohols or higher terminal diols are also suitable for this purpose.
  • Reduced foaming which is desirable in particular for machine washing, is frequently obtained by combining various 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.
  • soaps In the case of soaps, the foam inhibition increases with the degree of saturation and the number of carbon atoms of the fatty acid ester; soaps of saturated C -C -fatty acids, therefore, are particularly suitable for use
  • the nonsurfactant-like foam inhibitors include optionally chlorine-containing N-alkylated aminotriazines which are obtained by reacting 1 mole of cyanuric chloride with from 2 to 3 moles of a mono- and/or dialkylamine having 6 to 20, preferably 8 to 18, carbon atoms in the alkyl.
  • a similar effect is possessed by propoxylated and/or butoxylated aminotriazines, for example, products obtained by addition of from 5 to 10 moles of propylene oxide onto 1 mole of melamine and further addition of from 10 to 50 moles of butylene oxide onto this propylene oxide derivative.
  • nonsurfactant-like foam inhibitors are water-soluble organic compounds, such as paraffins or haloparaffins having melting points below 100°C, aliphatic C - to C -ketones and also
  • 18 40 aliphatic carboxylic esters which, in the acid or in the alcohol moiety, possibly even both these moieties, contain not less than 18 carbon atoms (for example triglycerides or fatty acid fatty alcohol esters); they can be used in particular in combinations of surfactants of the sulfate and/or sulfonate type with soaps for foam inhibition.
  • the detergents may contain optical brighteners for cotton, for polyamide, for polyacrylonitrile or for polyester fabrics.
  • suitable optical brighteners are derivatives of diaminostilbenedisulfonic acid for cotton, derivatives of 1 ,3-diarylpyrazolines for polyamide, quaternary salts of 7-methoxy-2-benzimidazol-2'-ylbenzofuran or of derivatives form the class of the 7-[1 , f 2',5 , -triazol-1 '-yl]-3-[1 ",2",4"-triazol-1 "-y] coumarins for polyacrylonitrile.
  • Examples of brighteners suitable for polyester are products of the class of the substituted styryls, ethylenes, thiophenes, naphthalenedicarboxylic acids or derivatives thereof, stilbenes, coumarins and naphthalimides.
  • laundry compositions herein also contain enzymes to enhance their through-the-wash cleaning performance on a variety of soils and stains.
  • Amylase and protease enzymes suitable for use in detergents are well known in the art and in commercially available liquid and granular detergents.
  • Commercial detersive enzymes preferably a mixture of amylase and protease are typically used at levels of from 0.001 to 2 weight percent, and higher, in the present cleaning compositions.
  • Detergent formulations of this invention may contain minor amounts of other commonly used materials in order to enhance the effectiveness or attractiveness of the product.
  • exemplary of such materials are soluble sodium carboxymethyl cellulose or other soil redeposition inhibitors; benzotriazoie, ethylene thiourea, or other tarnish inhibitors; perfume; fluorescers; dyes or pigments; brightening agents; enzymes; water; alcohols; other builder additives, such as the water soluble salts of ethylenediaminetetraacetic acid, N-(2-hydroxyethyl)-ethylenediaminetriacetic acid; and pH adjusters, such as sodium hydroxide and potassium hydroxide.
  • Suitable hydrotropes include the water-soluble alkali metal salts of toluene sulfonic acid, benzene sulfonic acid, and xylene sulfonic acid.
  • compositions of this invention may be formulated according to any of the various commercially desirable forms.
  • the formulations of this invention may be provided in granular form, in liquid form, in tablet form of flakes or powders.
  • compositions are prepared using techniques within the skill in the art.
  • Vacuum evaporation removed the water to result in solid 2-aminoethyl-N-aspartic acid (i.e., ethylenediamine- N-monosuccinic acid).
  • a second method for preparing the acid form of 2- aminoethyl-N-aspartic acid from the disodium salt was performed by addition of hydrobromic acid to the disodium 2-aminoethyl-N-aspartate solution until the pH fell to 4. The resulting solution was added to dry methanol which precipitated the 2-aminoethyl-N-aspartic acid. Filtration under a dry nitrogen blanket yielded solid 2-aminoethyl-N-aspartic acid (i.e., ethylenediamine-N-monosuccinic acid).
  • N- methylethylenediamine was dissolved and stirred under a dry atmosphere.
  • Dimethyl maleate (3.40 g, 0.0236 mole) was slowly added while keeping the temperature of the solution below 30°C.
  • the solution was stirred for five days followed by vacuum evaporation of the liquid.
  • the resultant product was weighed (4.27 g, 0.01 96 mole) and dissolved in water.
  • N'-methyl-2-aminoethyl-N-aspartic acid i.e., ethylenediamine-N- methyl-N'-monosuccinic acid
  • N-methyl-2-aminoethyl-N-aspartic acid i.e., ethylenediamine-N-methyl-N-monosuccinic acid
  • EXAMPLE 3 The diethyl ester of 2-aminoethyl-N-aspartic acid (23.23 g, 0.1 mole of diethyl 2-aminoethyl-N-aspartate) was dissolved in water and adjusted with sodium hydroxide to a pH above 12 in a stainless steel vessel and kept above 50°C for one hour. The solution was cooled with an ice bath. An equal molar amount of glycolonitrile (14.33 g of 38.9% solution, 0.1 mole) was slowly added to the solution while maintaining the temperature below 20°C and the pH above 1 2. After 1 2 hours at room temperature, the sodium hydroxide concentration was increased to 25% and the solution was refluxed for two to four hours.
  • glycolonitrile 14.33 g of 38.9% solution, 0.1 mole
  • the acid form(s) of monocarboxymethyl 2-aminoethyl-N-aspartic acid were obtained by either adjusting the pH to 4 by the addition of HBr followed by precipitation in methanol or by passage through a cationic exchange resin (MSC-1 -H) in the acid form.
  • a product was obtained consisting of approximately 85% ethylenediamine-N-carboxymethyl-N-monosuccinic acid and about 15% ethylenediamine-N-carboxymethyl-N'-monosuccinic acid.
  • Dimethyl ester of ethylenediamine-N-monosuccinic acid was prepared as in Example 1 .
  • a quantity of 33.29 g (0.22 mole) methyl bromoacetate was dissolved in acetonitrile or toluene.
  • Anhydrous sodium carbonate (36.20 g, 0.34 mole) was added to the solution.
  • 45.02 g of dimethyl ester of ethylenediamine-N-monosuccinic acid was added.
  • the reaction mixture was refluxed for an hour and allowed to cool.
  • the solids were removed by filtration.
  • the solvent was removed by evaporation under a vacuum resulting in 38.9 g of a thick, pale yellow liquid.
  • a carbon NMR spectrum was consistent with the trimethyl ester of ethylenediamine-N-carboxymethyl-N'-monosuccinic acid.
  • Nanopure water (50 ml) and 10 M NaOH (50 ml) were mixed together and added to the 38.9 g of liquid. The solution was stirred overnight at room temperature.
  • a carbon NMR was consistent with the trisodium salt of ethylenediamine- N-carboxymethyl-N'-monosuccinic acid.
  • the solution was adjusted to pH 5 with HBr. Addition of the solution to a large quantity of dry methanol produced a white precipitate. Filtration of the precipitate beneath a nitrogen blanket resulted in 97.39 g of a white powder.
  • a carbon NMR spectrum was consistent with ethylenediamine-N-carboxymethyl-N'- monosuccinic acid and methanol.
  • the powder was placed into a vacuum oven at 40°C. After 4 days, the material was a dry, slightly yellow powder with a weight of 37.24 g (overall yield 73%).
  • the resulting solution had a pH of 5.2 and precipitated some fumaric acid after standing for three hours.
  • the fumaric acid was removed by maintained at room temperature for three days. Although no precipitate formed, NMR analysis indicated completion of the reaction by the disappearance of the methine carbons of maleate.
  • the solvent was removed by vacuum evaporation resulting in a viscous, clear liquid. This liquid was dissolved in 30 milliliters of water and mixed with 30 milliliters of 10 M sodium hydroxide. The resulting solution was then refluxed for four hours. After refluxing, the solution was passed through a cationic exchange column (MSC-1-H) in the acid form. Fractions from the column were collected and concentrated by vacuum evaporation of the water.
  • MSC-1-H cationic exchange column
  • Example 2 A 1.95 g (0.01 1 mole) quantity of ethylenediamine-N-monosuccinic acid prepared in Example 1 was dissolved in 200 g deionized water. The pH was adjusted from 5.3 to 7.1 by addition of an aqueous ammonium hydroxide solution. Iron nitrate (2.4 g, 0.00507 mole) was then added to the solution with stirring. The resulting pH of 3.1 was adjusted to about 5.0 with aqueous ammonium hydroxide, and the solution was diluted to a final volume of 500 milliliters. Fifty gram aliquots were placed in separate vessels and adjusted to pH 5.0, 6.0, 7.0, 8.0, 9.0, and 10.0 with ammonium hydroxide. After 21 days, the solutions were filtered and analyzed by inductively coupled plasma spectroscopy for soluble iron. The results were as follows:
  • the reduction potential of the material prepared in Example 6 was determined by making the ferric complex.
  • the ferric complex was 0.001 molar iron and 0.001 1 molar ethylenediamine-N-hydroxyethyl-N 1 - monosuccinic acid in 0.1 molar NaCIO4 adjusted to pH 5 with NaOH and HCIO4.
  • the half cell potentials were measured by normal pulse polarography as detailed in Electrochemical Methods. Fundamentals and Applications by A. J. Bard and L. F. Faulkner, 1 980, Wiley.
  • the reduction potential of the material prepared in Example 1 was measured by the same method as in Example 10.
  • the half cell potential of Fe ethylenediamine-N-monosuccinic acid was -140 mV. This redox potential indicates that the ferric complex of ethylenediamine-N- monosuccinic acid was suitable for use in redox applications such as in hydrogen sulfide abatement.
  • EXAMPLE 12 The biodegradability of the material prepared in Example 1 was measured by both the ASTM D 2667-89 (SemiContinuous Activated Sludge) test and the OECD 301 B Modified Sturm test.
  • the ASTM D 2667- 89 test exposes the organisms in sludge to about 33 ppm of the test compound each day for 28 days. After 23 hours of contact with the sludge, the remaining compound was analyzed. In order to pass the test, a minimum of 80% of a compound must be degraded during each 23 hour period for at least 7 consecutive days during the 28 day period.
  • the ethylenediamine-N-monosuccinic acid was more than 80% degraded within the prescribed time for passing the ASTM D 2667-89 test.
  • the OECD 301 B Modified Sturm test measures the CO2 produced by the test compound or standard, which was used as the sole carbon source for the microorganisms.
  • the ethylenediamine-N-monosuccinic acid was tested at a 20 ppm dose level.
  • a vessel containing the test compound a vessel containing acetate as a standard compound, and a vessel containing innoculum as a blank were used as controls.
  • the seed innoculum was obtained from microorganisms previously exposed to ethylenediamine-N- monosuccinic acid in a semi-continuous activated sludge test. To confirm the viability of each seed innoculum, acetic acid was used as the standard at a concentration of 20 ppm. The blank vessel was used to determine the inherent CO2 evolved from each respective innoculum. Carbon dioxide captured in the respective barium hydroxide taps was measured at various times during the 28-day test period. The results from this test indicated that the material was over 75 percent biodegraded within the prescribed time. A value of greater than 60% of the theoretical amount of CO2 produced in this test indicates that a compound was readily biodegradable.
  • Example 3 The material prepared in Example 3 was subjected to biodegradability testing in the ASTM D 2667-89 test as described in Example 12. Results from this test show that the material was greater than 80% biodegraded within the prescribed time.
  • Example 1 The material prepared in Example 1 was titrated with 0.01 M copper solution using murexide as the indicator. The material complexed 1.0 mole of copper per mole of ethylenediamine-N-monosuccinic acid.
  • Example 4 The material prepared in Example 4 was titrated with 0.01 M copper solution using murexide as the indicator. Each mole of the material complexed one mole of copper.
  • Example 6 The material prepared in Example 6 was titrated with 0.01 M copper solution using murexide as the indicator. Each mole of the material complexed 1 .0 mole of copper.

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Abstract

Les acides polyamino-monosucciniques sont des chélatants efficaces utilisés dans le traitement de gaz (l'acide polyamino-monosucciniques se présentant de préférence sous la forme d'un chélate métallique, de préférence un complexe de fer). Du sulfure d'hydrogène peut être éliminé d'un fluide par la mise en contact de ce fluide avec une solution aqueuse à un pH adapté pour l'élimination de sulfure d'hydrogène, la solution contenant au moins un chélate de métal polyvalent de valence plus élevée d'au moins un acide polyamino-monosuccinique. Le NOx peut être éliminé d'un fluide par la mise en contact de ce fluide avec une solution aqueuse d'au moins un chélate de métal de niveau de valence inférieur d'au moins un acide polyamino-monosuccinique. Les chélates de cuivre sont également utiles au dépôt de cuivre chimique. Concernant le dépôt de cuivre chimique, on décrit un procédé de dépôt de cuivre chimique sur une surface non métallique réceptive au cuivre déposé, consistant notamment à mettre en contact la surface non métallique avec une solution aqueuse comportant un sel de cuivre soluble, au moins un acide polyamino-monosuccinique et des bains de plaquage appropriés pour cet usage. L'invention concerne par ailleurs l'utilisation d'acides polyamino-monosucciniques dans des compositions détergentes de blanchissage contenant un tensioactif détergent et un adjuvant.
EP96929807A 1995-08-30 1996-08-29 Chelatants degradables derives d'acides polyamino-monosucciniques, leurs utilisations et compositions Withdrawn EP0871695A2 (fr)

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DE60004502T2 (de) 1999-03-26 2004-02-26 The Dow Chemical Co., Midland Herstellung von bersteinsäure und derivaten mit polyaminofunktionalitäten
EP1638662A2 (fr) * 2003-06-27 2006-03-29 Dynal Biotech ASA Conjuges de particules magnetiques polymeriques et acide aspartique carboxymethyle
EP2784181B1 (fr) * 2013-03-27 2015-12-09 ATOTECH Deutschland GmbH Solution de dépôt de cuivre chimique
CN116422130B (zh) * 2023-04-13 2024-01-23 西安赫立盖斯新能源科技有限公司 一种溶剂、溶剂的生产方法和生产装置

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GB757704A (en) * 1952-04-22 1956-09-26 Dow Chemical Co Improvements in amino derivatives of n-alkyl substituted aspartic acids and their functional derivatives
US2761874A (en) * 1954-09-30 1956-09-04 Dow Chemical Co Amino derivatives of n-alkyl substituted aspartic acids and their functional derivatives
US3773510A (en) * 1971-06-26 1973-11-20 Minnesota Mining & Mfg Additives to bleach/fix baths
US4704233A (en) * 1986-11-10 1987-11-03 The Procter & Gamble Company Detergent compositions containing ethylenediamine-N,N'-disuccinic acid
DE3829001A1 (de) * 1988-08-26 1990-07-05 Trigon Chemie Gmbh Asparaginsaeure-derivate und verfahren zu ihrer herstellung
JP3200465B2 (ja) * 1992-04-24 2001-08-20 富士写真フイルム株式会社 ハロゲン化銀写真感光材料用の処理組成物及びそれを用いた処理方法
GB9216409D0 (en) * 1992-08-01 1992-09-16 Procter & Gamble Detergent compositions
GB2293020B (en) * 1993-05-20 1997-08-27 Dow Chemical Co Succinic acid derivative degradable chelants, uses and compositions thereof
GB9422762D0 (en) * 1994-11-11 1995-01-04 Ass Octel Use of a compound
US5585226A (en) * 1995-08-30 1996-12-17 Eastman Kodak Company Polyamino monoesuccinates for use in photographic processes
US5652085A (en) * 1995-08-30 1997-07-29 Eastman Kodak Company Succinic acid derivative degradable chelants, uses and composition thereof

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