DE1045373B - Use of phosphonic acids - Google Patents

Use of phosphonic acids

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Publication number
DE1045373B
DE1045373B DEF22912A DEF0022912A DE1045373B DE 1045373 B DE1045373 B DE 1045373B DE F22912 A DEF22912 A DE F22912A DE F0022912 A DEF0022912 A DE F0022912A DE 1045373 B DE1045373 B DE 1045373B
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Prior art keywords
phosphonic acids
acid
ions
phosphonates
dyes
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Pending
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DEF22912A
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German (de)
Inventor
Dr Ludwig Orthner
Dr Martin Reuter
Dr Erhard Wolf
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Hoechst AG
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Hoechst AG
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Priority to DEF22912A priority Critical patent/DE1045373B/en
Publication of DE1045373B publication Critical patent/DE1045373B/en
Pending legal-status Critical Current

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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00Medicinal preparations containing organic active ingredients
    • A61K31/70Carbohydrates; Sugars; Derivatives thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/55Phosphorus compounds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/08Preparations for bleaching the hair
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • C02F5/14Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02Phosphorus compounds
    • C07F9/28Phosphorus compounds with one or more P—C bonds
    • C07F9/38Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/3804Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
    • C07F9/3808Acyclic saturated acids which can have further substituents on alkyl
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02Phosphorus compounds
    • C07F9/28Phosphorus compounds with one or more P—C bonds
    • C07F9/38Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/3804Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
    • C07F9/3839Polyphosphonic acids
    • C07F9/3843Polyphosphonic acids containing no further substituents than -PO3H2 groups
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/36Organic compounds containing phosphorus
    • C11D3/361Phosphonates, phosphinates or phosphonites
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/36Organic compounds containing phosphorus
    • C11D3/365Organic compounds containing phosphorus containing carboxyl groups
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3902Organic or inorganic per-compounds combined with specific additives
    • C11D3/3937Stabilising agents
    • C11D3/394Organic compounds
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/29Development processes or agents therefor
    • G03C5/305Additives other than developers
    • G03C5/3053Tensio-active agents or sequestering agents, e.g. water-softening or wetting agents
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/51Chelating agents

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Molecular Biology (AREA)
  • Wood Science & Technology (AREA)
  • Animal Behavior & Ethology (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Epidemiology (AREA)
  • Biochemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Medicinal Chemistry (AREA)
  • Birds (AREA)
  • General Chemical & Material Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)

Description

Verwendung von Phosphonsäuren Es ist bereits bekannt, daß sich Pyro- und Polvphosphate als Komplexbildnngsmittel für mdrwertige Metalle eignen. Diese Phosphate haben jedoch den Nachteil, daß sie bei steigenden p-Werten und Temperaturen zu unwirksamer o-Phospho,rsäure hydrolysiert werden. Sie sind deshalb nur sehr beschränkt anwendbar.Use of phosphonic acids It is already known that pyro- and poly phosphates are suitable as complexing agents for low-grade metals. These However, phosphates have the disadvantage that with increasing p-values and temperatures hydrolyzed to ineffective o-phosphorous acid. They are therefore only very limited applicable.

Es ist fernerbekannt, Poiyphosphonate - hergestellt aus z. B. Äthulendiamin oder seinen N-Alkylverbindungen oder seiner N-,N'-Diessigsäure und 2 Mol Chlormetltylphosphonsäure - als Komplexbildner zu verwenden. Entscheidend für die Wirksamkeit dieser Verbindungen ist die Kombination einer Phosphonatmit einer Aminogruppe. Erst die Einführung dieser Aminogruppe mit den freien Elektronenpaaren ermöglicht die Komplexbildung. It is also known to use polyphosphonates - made from e.g. B. Ethulene diamine or its N-alkyl compounds or its N-, N'-diacetic acid and 2 moles of chloromethylphosphonic acid - to be used as a complexing agent. Critical to the effectiveness of these compounds is the combination of a phosphonate with an amino group. Only the introduction of this Amino group with the free electron pairs enables complex formation.

Demgegenfiber sind stickstofffreie Polyphosphonate in der Regel keine Komplexbildner, wie beispielsweise die Verbindungen lithan-1,2-diphosphonsäure und Propan-1,3-diphosphonsäure zeigen. In contrast, nitrogen-free polyphosphonates are usually not Complexing agents, such as, for example, the compounds lithane-1,2-diphosphonic acid and Show propane-1,3-diphosphonic acid.

Es wurde gefunden, daß Diphosphonsäuren und Phosphoncarbonsäuren, deren funktionelle Gruppen nur durch eine C H2-Gruppe verbunden sind. bzw. ihre Alkalisalze sich vorzüglich als Komplexbildner eignen. It has been found that diphosphonic acids and phosphonic carboxylic acids, whose functional groups are only linked by a C H2 group. or their Alkali salts are particularly suitable as complexing agents.

Die Phosphonsäuren lassen sich nach verschiedenen, an sich bekannten Verfahren herstellen. Beispielsweise kann man aus Chloressigsäurealkylestern durch Umsatz mit Trialkylphosphiten den Phosphonessigsäure-trialkylester erhalten, der bei der Verseifung in glatter Reaktion die Phosphonessigsäure gibt. Man kann ferner Halogenester, wie z. B. Chlofmethylphosphonsäure-dialkylester, mit Alkali-dialkylphosphiten zu Diphosphon- bzw. Phosphoncarhonsäureestern kondensieren und diese in üblicher Weise zu den Säuren verseifen. The phosphonic acids can be classified according to various known per se Process. For example, you can from chloroacetic acid alkyl esters by Sales with trialkyl phosphites obtained the trialkyl phosphonoacetate, the in the saponification the phosphonoacetic acid gives in a smooth reaction. One can also Halogen esters, such as. B. Chlofmethylphosphonsäure dialkyl ester, with alkali dialkyl phosphites Condense to diphosphonic or phosphonic acid esters and these in the usual way Way to saponify the acids.

Die stickstoffhaltigen Polyphospbonate haben gegenüber den erfindungsgemäßen Phosphonsäuren den Nachteil, daß sie schwerer zugänglich sind. Nachteilig für die stickstoffhaltigen Phosphonate ist es auch, daß sie z. B. in Gegenwart von Säuren bei etwa Pn 2 ausfallen und völlig unwirksam werden. The nitrogen-containing polyphosphonates have compared to the invention Phosphonic acids have the disadvantage that they are more difficult to access. Detrimental to the nitrogen-containing phosphonates, it is also that they z. B. in the presence of acids fail at about Pn 2 and become completely ineffective.

Die vorliegenden Phosphonsäuren, insbesondere die Methylen-diphosphonsäure, vermögen als solche oder in Form ihrer Alkalisalze Kationen außer denen der Alkalimetalle hervorragend komplex zu binden. Die Ionen sind in den Komplexen so stark maskiert, daß sie zahlreiche chemische Reaktionen nicht mehr geben. The phosphonic acids present, in particular methylene-diphosphonic acid, as such or in the form of their alkali metal salts, they have cations other than those of the alkali metals excellent to bind complex. The ions are so strongly masked in the complexes, that they no longer give numerous chemical reactions.

Zum Beispiel gibt der Fe3+-Komplex der Methylendiphosphonsäure mit Rhodanid keine Rotfärbung, der entsprechende Caldumkomplex mit Ammoninmoxalat keine Fällung. Von besonderer Bedeutung ist, daß die erfindungsgemäß genannten Phosphonsäuren in wäßriger Lösung vollkommen temperatur- und p-be- ständig sind, also in dieser Beziehung keinen Einschränkungen in ihrer Anwendung unterliegen wie Pyro- oder Polyphosphate. Gegenüber letzteren besitzen sie außerdem noch den großen Vorteil des stärkeren Komplexbildungsvermögens. weshalb man in der Praxis viel weniger Phosphonate als Phosphate einzusetzen braucht. Das Calciumbindevermögen wurde in der Weise bestimmt, daß 10 g Komplexbildner in wäßriger Lösung mit 0,5 n Calciumchlorid lösung titriert wurden unter Verwendung von Ammon-oxalat als Indikator bis zum Auftreten einer Trübung durch Calcium-oxalat.For example, the Fe3 + complex gives the methylenediphosphonic acid with Rhodanide no red color, the corresponding Caldum complex with ammonine moxalate none Precipitation. It is of particular importance that the phosphonic acids mentioned according to the invention in aqueous solution completely temperature and p-loading are constantly, so in this one Relationship are not subject to any restrictions in their application such as pyro- or polyphosphates. Compared to the latter, they also have the great advantage of being stronger Complexing ability. which is why in practice much less phosphonates than Needs to use phosphates. The calcium binding capacity was determined in the way that 10 g of complexing agent in aqueous solution is titrated with 0.5 N calcium chloride solution were using ammonium oxalate as an indicator until turbidity appeared by calcium oxalate.

1 g Na-pyrophosphat bindet 18,6 mg Calciumionen; 1 g Na-tripolyphosphat bindet 61,0 mg Calciumionen; 1 g Dinatrium-methylen-diphosphonat bindet 99 mg Calciumionen. 1 g Na pyrophosphate binds 18.6 mg calcium ions; 1 g sodium tripolyphosphate binds 61.0 mg calcium ions; 1 g of disodium methylene diphosphonate binds 99 mg of calcium ions.

Man kommt im allgemeinen mit Konzentrationen von etwa 0,01 bis 1 ovo aus. Die Diphosphon und Phosphoncarbonsäuren bzw. ihre Salze können überall bei industriellen Prozessen in wäßrigem Medium mit Vorteil verwendet werden, wo durch Fremdionen Störungen verursacht werden. Sie können als temperatur- und p-beständige Wasserenthärter verwendet werden. Als Zusatz zu festen und flüssigen Seifen, Waschmitteln, kosmetischen Artikeln, Haar-Shampoos und anderen Reinigungsmitteln unterbinden sie in genügender Konzentration die Bildung schwerlöslicher Metallseifen, Verfärbungen und Ranzigwerden und wirken gleichzeitig als Antioxydans und Stabilisatoren des Schaumes. In der photographischen Praxis können alle durch Verwendung von hartem Wasser bedingten Störungen beseitigt werden, z. B. können Entwicklerlösungen stabilisiert werden. Auf Grund ihrer Fähigkeit, Schwermetailsalze zu binden, eignen sich die erfindungsgemäß genannten Diphosphonate und Phosphoncarboxylate zum Stabilisieren von Peroxyverbindungen, wie sie für Reinigungs- und Bleichzwecke gebraucht werden, zum Stabilisieren von Latices aus natürlichem Kautschuk oder auch synthetischer Produkte aus Polystyrol, Butadien u. a. Aus demselben Grund vermögen sie Autoxydationen zu hemmen, wie z. B. von Sulfit (Haarbleichen), Fetten, Ölen, Proteinen, Gummen, Kunststoffen u. a. Bei der Darstellung und zur Stabilisierung von Antibiotika, wie Penicillin, lassen sie sich vorteilhaft anwenden. In der Lederindustrie lassen sich mit ihrer Hilfe Lederverfärbungen (z. B. durch Eisen) und Fäulnis der Häute vermeiden. Bei der Hydrazindarstellung wirken sie wie Leimzusatz ausbeuteverbessernd. Bei der elektrolytischen Reindarstellung von Metallen wifit sich der Zusatz der genannten Phosphonate wegen ihrer Fäligkeit, Fremdionen zu binden, günstig aus. Bei Galvanisierprozessen zeigen sie sich den Alkalicyaniden überlegen, weil sie physiologisch unbedenklich sind und nicht die Verwendung destillierten Wassers erfordern. Als Zusatz zu alkalischen Bädern beim »Finish« von Metallgegenständen sowie beim Polieren von Metallteilen lassen sich mit ihrer Hilfe gute Glanzeffekte erzielen, da sie die Entstehung schwerlöslicher Salze und Seifen verhindern. Auch für agrikulturchemische Zwecke lassen sie sich in zahlreichen Fällen mit Vorteil anwenden. So können dem Boden fehlende Spurenelemente besonders wirksam als Phosphonatkomplexe zugeführt werden. Wuchsstoffiösungen und Unkrautvertilgungsmittel, wie a-Naphthylessigsäure und Dichlorphenoxyessigsäure, die durch hartes Wasser ausgefällt werden, können durch die genannten Phosphonate in Lösung gehalten werden. Auf Grund ihres Calciumbindungsvermögens vermögen sie wie Zitronensäure die Blutgerinnung zu hemmen. Bei der Papierherstellung lassen sich mit ihrer Hilfe leicht sehr weiße und leicht zu bleichende Papiere herstellen. In der Färberei und bei der Farbstoffdarstellung können die Phosphonate mit Vorteil verwendet werden, um Calcium-, Magnesium- und Schwermetallionen zu binden. Das hat bei all den Farbstoffen, z. B. Küpenfarbstoffen, Eisfarben und Azofarbstoffen mit zur Azogruppe oder Carboxylgruppe orthoständigen Oxygruppen, Bedeutung, die mit den genannten Ionen meist schwerlösliche Salze bilden, wodurch Ausbeuteverminderung und Echtheitsverluste, z. B. der Reib- und Waschechtheit, eintreten können. Auch die katalytische Zersetzung diazotierter Amine durch Spuren von Eisen- und Kupferionen läßt sich mit den genannten Phosphonaten unterbinden. Bei der Darstellung von Chromierungsfarbstoffen können sie dazu dienen, um Spuren störender Schwermetallionen, wie vor allem Kupfer-und Eisenionen, zu binden. Auch beim Abziehen mancher Farbstoffe, wie z. B. einiger Schwefelfarbstoffe, und zum Entkupfern von Kupferfarbstoffen können sie mit Erfolg verwendet werden. Bei der Stärkedarstellung verhindern sie das Stockigwerden, soweit es durch hartes Wasser oder Metalle bedingt ist. Bei der Rayondarstellung lassen sich die durch Blejionen bedingten Störungen mit den genannten Phosphonaten beheben. Bei der Tieftemperaturpolymerisation von Kunststoffen eignen sich die FeS+-Komplexe der erfindungsgemäß genannten Phosphonate in Kombination mit Fe2l+-Salzen vorzüglich zur Polymerisationsauslösung. In general, concentrations of about 0.01 to 1 are used ovo off. The diphosphonic and phosphonic carboxylic acids or their salts can be used anywhere be used with advantage in industrial processes in aqueous medium, where interference is caused by foreign ions. They can be used as temperature and p-resistant Water softeners can be used. As an additive to solid and liquid soaps, detergents, Cosmetic items, hair shampoos and other cleaning products stop them in sufficient concentration, the formation of sparingly soluble metal soaps, discoloration and becoming rancid and at the same time act as antioxidants and stabilizers of the Foam. In photographic practice, all can be achieved by using hard Water related disturbances are eliminated, e.g. B. developer solutions can be stabilized will. on Because of their ability to bind heavy metal salts, the diphosphonates and phosphonic carboxylates mentioned according to the invention are suitable for stabilizing peroxy compounds such as those used for cleaning and bleaching purposes are used to stabilize latices made of natural rubber or also synthetic products made from polystyrene, butadiene and others Ability for the same reason to inhibit autoxidation, such as B. of sulfite (hair bleaching), fats, oils, Proteins, gums, plastics, etc. In the display and for stabilization antibiotics such as penicillin can be used to advantage. In the leather industry With their help, leather discolouration (e.g. due to iron) and decay of the Avoid skins. In the hydrazine preparation, they have the effect of improving the yield like an additive of glue. In the electrolytic preparation of metals, the addition of called phosphonates because of their ability to bind foreign ions, favorable. In electroplating processes, they are superior to alkali cyanides because they are physiologically harmless and do not require the use of distilled water. As an additive to alkaline baths for the »finish« of metal objects as well as for Polishing of metal parts can be used to achieve good gloss effects, as they prevent the formation of sparingly soluble salts and soaps. Also for agricultural chemicals They can be used to advantage in numerous cases. So can that Soil missing trace elements particularly effectively supplied as phosphonate complexes will. Growth solutions and weedkillers, such as a-naphthylacetic acid and dichlorophenoxyacetic acid, which can be precipitated by hard water are kept in solution by the phosphonates mentioned. Because of their calcium binding capacity Like citric acid, they can inhibit blood clotting. In papermaking With their help, very white and easy-to-bleach papers can easily be produced. The phosphonates can be used to advantage in dyeing and in the preparation of dyes used to bind calcium, magnesium and heavy metal ions. That has with all the dyes, e.g. B. vat dyes, ice colors and azo dyes with the azo group or carboxyl group ortho-position oxy groups, meaning those with the ones mentioned Ions usually form poorly soluble salts, which leads to a reduction in yield and loss of authenticity, z. B. the rub and wash fastness can occur. Catalytic decomposition too Diazotized amines by traces of iron and copper ions can be with the mentioned Stop phosphonates. In the representation of chromating dyes they serve to remove traces of disruptive heavy metal ions, such as especially copper and Iron ions, to bind. Even when peeling off some dyes, such as. B. some You can use sulfur dyes and copper dyes to decopper with success be used. With the representation of strength, they prevent the foxing, so far it is caused by hard water or metals. Leave at the rayon display the disorders caused by lead ions can be remedied with the above-mentioned phosphonates. The FeS + complexes are suitable for the low-temperature polymerisation of plastics of the phosphonates mentioned according to the invention in combination with Fe2l + salts are excellent to initiate polymerization.

Claims (1)

PATENTANSPRUCH Verwendung von Phosphonsäuren der allgemeinen Formel X-CH2-PO3 H2, worin X -P OsH, oder -CO2H bedeutet, und ihrer Alkalisalze als Komplexbildungsmittel zur Bindung mehrwertiger Metallionen in wäßrigem Medium. ~~~~~~~ In Betracht gezogene Druckschriften: Britische Patentschriften Nr. 703180, 703181, 744633. PATENT CLAIM Use of phosphonic acids of the general formula X-CH2-PO3 H2, where X is -P OsH, or -CO2H, and their alkali salts as complexing agents for binding polyvalent metal ions in an aqueous medium. ~~~~~~~ Considered Publications: British Patent Nos. 703180, 703181, 744633.
DEF22912A 1957-04-26 1957-04-26 Use of phosphonic acids Pending DE1045373B (en)

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Cited By (24)

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DE1163114B (en) * 1962-02-13 1964-02-13 Dehydag Gmbh Galvanic metal baths
DE1192021B (en) * 1963-01-12 1965-04-29 Dehydag Gmbh Galvanic baths
US3201246A (en) * 1961-04-10 1965-08-17 Eastman Kodak Co Photographic developers containing calcium precipitation inhibitors
US3213030A (en) * 1963-03-18 1965-10-19 Procter & Gamble Cleansing and laundering compositions
DE1217928B (en) * 1962-10-18 1966-06-02 Monsanto Co Process for preventing the separation of heavy metal ions from an aqueous solution
US3271306A (en) * 1963-11-06 1966-09-06 Monsanto Co Method for preventing the formation of insoluble iron compounds
US3297578A (en) * 1963-07-26 1967-01-10 Monsanto Co Bleaching, sterilizing, disinfecting, and deterging compositions
US3348613A (en) * 1965-05-19 1967-10-24 Monsanto Co Novel acidizing composition and method
US3368978A (en) * 1964-12-28 1968-02-13 Monsanto Co Builder compositions and detergent compositions using same
US3422021A (en) * 1963-03-18 1969-01-14 Procter & Gamble Detergent composition
US3488707A (en) * 1964-07-02 1970-01-06 Agfa Gevaert Nv Light-sensitive silver halide elements containing phosphonic acids
US4083723A (en) * 1976-02-24 1978-04-11 Fuji Photo Film Co., Ltd. Process for color photographic processing
US4146397A (en) * 1976-08-06 1979-03-27 Fuji Photo Film Co., Ltd. Method of forming a photographic image
US4162161A (en) * 1976-08-06 1979-07-24 Fuji Photo Film Co., Ltd. Reversal color photographic process
USRE30064E (en) * 1976-02-24 1979-08-07 Fuji Photo Film Co., Ltd. Process for color photographic processing
EP0008640A1 (en) * 1978-07-21 1980-03-19 Ciba-Geigy Ag Method for the removal of hydrogen sulfide from gases or liquid hydrocarbons and gases or liquid hydrocarbons thus purified
US4277556A (en) * 1976-08-18 1981-07-07 Konishiroku Photo Industry Co., Ltd. Process for treating light-sensitive silver halide color photographic materials
US4689200A (en) * 1981-09-04 1987-08-25 Ciba-Geigy Corporation Systems inhibited against corrosion and/or scale deposition
EP0375615A2 (en) * 1988-12-21 1990-06-27 Ciba-Geigy Ag Method of treating water containing fertilisers
WO1997011148A1 (en) * 1995-09-19 1997-03-27 Colgate-Palmolive Company Personal cleansing composition
EP1974950A1 (en) 2007-03-30 2008-10-01 FUJIFILM Corporation Thermal transfer image-receiving sheet and method for producing it
EP1974945A2 (en) 2007-03-28 2008-10-01 FUJIFILM Corporation Heat-sensitive transfer image-receiving sheet
EP1974949A1 (en) 2007-03-28 2008-10-01 FUJIFILM Corporation Heat-sensitive transfer image-receiving sheet and production method thereof
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GB703181A (en) * 1950-06-01 1954-01-27 Frederick Charles Bersworth Alkylene diamine methylene phosphonic acids
GB744633A (en) * 1952-06-06 1956-02-08 Dow Chemical Co N-alkyl-(or-aralkyl-) substituted alkylene polyamine methylene phosphonic acid compounds

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US3201246A (en) * 1961-04-10 1965-08-17 Eastman Kodak Co Photographic developers containing calcium precipitation inhibitors
DE1168208B (en) * 1962-02-13 1964-04-16 Dehydag Gmbh Galvanic metal baths
DE1163114B (en) * 1962-02-13 1964-02-13 Dehydag Gmbh Galvanic metal baths
DE1217928B (en) * 1962-10-18 1966-06-02 Monsanto Co Process for preventing the separation of heavy metal ions from an aqueous solution
DE1192021B (en) * 1963-01-12 1965-04-29 Dehydag Gmbh Galvanic baths
DE1196464B (en) * 1963-01-12 1965-07-08 Dehydag Gmbh Galvanic baths
DE1201152B (en) * 1963-01-12 1965-09-16 Dehydag Gmbh Galvanic baths
US3422021A (en) * 1963-03-18 1969-01-14 Procter & Gamble Detergent composition
US3213030A (en) * 1963-03-18 1965-10-19 Procter & Gamble Cleansing and laundering compositions
US3297578A (en) * 1963-07-26 1967-01-10 Monsanto Co Bleaching, sterilizing, disinfecting, and deterging compositions
US3271306A (en) * 1963-11-06 1966-09-06 Monsanto Co Method for preventing the formation of insoluble iron compounds
US3488707A (en) * 1964-07-02 1970-01-06 Agfa Gevaert Nv Light-sensitive silver halide elements containing phosphonic acids
US3368978A (en) * 1964-12-28 1968-02-13 Monsanto Co Builder compositions and detergent compositions using same
US3348613A (en) * 1965-05-19 1967-10-24 Monsanto Co Novel acidizing composition and method
US4083723A (en) * 1976-02-24 1978-04-11 Fuji Photo Film Co., Ltd. Process for color photographic processing
USRE30064E (en) * 1976-02-24 1979-08-07 Fuji Photo Film Co., Ltd. Process for color photographic processing
US4162161A (en) * 1976-08-06 1979-07-24 Fuji Photo Film Co., Ltd. Reversal color photographic process
US4146397A (en) * 1976-08-06 1979-03-27 Fuji Photo Film Co., Ltd. Method of forming a photographic image
US4277556A (en) * 1976-08-18 1981-07-07 Konishiroku Photo Industry Co., Ltd. Process for treating light-sensitive silver halide color photographic materials
US4251492A (en) 1978-06-07 1981-02-17 Ciba-Geigy Corporation Purification process
EP0008640A1 (en) * 1978-07-21 1980-03-19 Ciba-Geigy Ag Method for the removal of hydrogen sulfide from gases or liquid hydrocarbons and gases or liquid hydrocarbons thus purified
US4689200A (en) * 1981-09-04 1987-08-25 Ciba-Geigy Corporation Systems inhibited against corrosion and/or scale deposition
US4828795A (en) * 1981-09-04 1989-05-09 Ciba-Geigy Corporation Systems inhibited against corrosion and/or scale deposition
EP0375615A2 (en) * 1988-12-21 1990-06-27 Ciba-Geigy Ag Method of treating water containing fertilisers
EP0375615A3 (en) * 1988-12-21 1990-09-12 Ciba-Geigy Ag Method of treating water containing fertilisers
AU630396B2 (en) * 1988-12-21 1992-10-29 Ciba-Geigy Ag Method of treating water containing fertilisers
WO1997011148A1 (en) * 1995-09-19 1997-03-27 Colgate-Palmolive Company Personal cleansing composition
US5891834A (en) * 1995-09-19 1999-04-06 Colgate Palmolive Company Composition
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