EP0000061A1 - Dérivés d'acide carboxylique contenant du phosphore, procédé pour leur préparation et leur utilisation - Google Patents

Dérivés d'acide carboxylique contenant du phosphore, procédé pour leur préparation et leur utilisation Download PDF

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Publication number
EP0000061A1
EP0000061A1 EP78100104A EP78100104A EP0000061A1 EP 0000061 A1 EP0000061 A1 EP 0000061A1 EP 78100104 A EP78100104 A EP 78100104A EP 78100104 A EP78100104 A EP 78100104A EP 0000061 A1 EP0000061 A1 EP 0000061A1
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EP
European Patent Office
Prior art keywords
alkyl
radicals
optionally
group
acid
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.)
Granted
Application number
EP78100104A
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German (de)
English (en)
Other versions
EP0000061B1 (fr
Inventor
Horst Dieter Dr. Thamm
Fritz Dr. Linke
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Hoechst AG
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Hoechst AG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4025—Esters of poly(thio)phosphonic acids
    • C07F9/4046—Esters of poly(thio)phosphonic acids containing carboxylic acid or carboxylic acid derivative substituents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • C02F5/14—Treatment 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
    • C07F9/305—Poly(thio)phosphinic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
    • C07F9/32—Esters thereof
    • C07F9/3205—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/3235—Esters of poly(thio)phosphinic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
    • C07F9/3839—Polyphosphonic acids
    • C07F9/3869—Polyphosphonic acids containing carboxylic acid or carboxylic acid derivative substituents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
    • C07F9/5304—Acyclic saturated phosphine oxides or thioxides
    • C07F9/5308—Acyclic saturated phosphine oxides or thioxides substituted by B, Si, P or a metal
    • C07F9/5312—Acyclic saturated phosphine oxides or thioxides substituted by B, Si, P or a metal substituted by a phosphorus atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
    • C07F9/5329—Polyphosphine oxides or thioxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5393—Phosphonous compounds, e.g. R—P(OR')2
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
    • D06M13/288—Phosphonic or phosphonous acids or derivatives thereof

Definitions

  • Ln adduct is said to have been obtained from 1 mol of methane diphosphonic acid tetraethyl ester and 2 mol of crylonitrile; with other olefinically unsaturated compounds such as, for example, the vinylphosphonic acid diethyl starch and the acrylic acid methyl ester, only the monoaddition product, ie the product from 1 mol of methane diphosphonic acid tetraethyl ester and 1 mol of the unsaturated compound, is said to have arisen. It is not clear from the Russian work which connections are used.
  • esters of 3,3-diphosphano-pimelic acid ie those di-adducts of the formula given for this, in which A only denotes the - optionally halogen-substituted-alkyl radicals, but not H and the alkali metal or ammonium ions.
  • the esters can be transesterified to other esters in a known manner.
  • the free acid as well as the alkali and ammonium salts are obtained from the esters in a likewise known manner by acidic or alkaline saponification.
  • R, R 4 , R 5 , R 6 H or alkyl groups are preferred.
  • 3 Preferred among the alkyl groups mentioned for the radicals R to R 6 are those with 1-4 C atoms, in particular methyl and ethyl and Cl-ethyl.
  • Preferred radicals R 2 and R ' 2 are CN, CONH 2 and CONH 2-x (CH 2 OH) x .
  • the products obtained in this way are obtained in a suitable unit or can be easily cleaned by distillation after by-products have been removed.
  • the olefinically unsaturated compounds of the general formula III to be used in carrying out the reaction are known and are in some cases used. manufactured on an industrial scale. The following are three examples:
  • Strong bases such as e.g. Alkaline alcoholates, hydrides, amides, quaternary ammonium hydroxides used.
  • Alkali alcoholates, alkali hydrides and amides are particularly preferred.
  • the Na and K compounds are particularly preferred.
  • a solvent or diluent are all organic solvents which are inert under the reaction conditions, such as aliphatic and aromatic hydrocarbons, e.g. n-pentane, n-hexane, decane, toluene, xylene, ether such as e.g. Tetrahydrofuran, dieth
  • the reaction temperatures can be varied within a wide range; generally one works between about + 20 ° and + 100 ° C, especially between about + 40 ° and + 80 ° C. Since the addition reaction is exothermic, good cooling may be required.
  • An excess of component III up to about 10% is possible; Larger quantities are possible, but without advantage.
  • the basic catalyst e.g. sodium methylate in methanolic solution
  • the basic catalyst generally about 0.01 to 0.25 mol per mol of compound II, is added.
  • the reaction temperature or the reaction rate can be regulated both by external cooling and by the metering rate of the catalyst.
  • the adducts I are formed in sufficient purity in accordance with the process according to the invention, so that they can be directly processed further after volatile components have been distilled off in vacuo.
  • the substituted carboxylic acids according to the invention are also present when acidolysis has ended and can be carried out by distilling off water and / or hydrochloric acid in vacuo and at temperatures up to about + 150 ° C. Shape are preserved. Acidolysis can also be particularly advantageously analogous to that in P 2719415.6 proposed method by with lower aliphatic. Carboxylic acids (HCOOH, CH 3 COOH, C 2 H 5 COOH .) or with benzoic acid.
  • the (substituted) carboxamides of the formula I can be obtained in a technically simple manner under gentle conditions by known processes from the analogous carboxylic acid nitriles by reaction with hydrogen peroxide / sodium hydroxide solution. Likewise, the conversion results of the substituted Carbonklareester with ammonia or substituted amines at 20 ° - 100 ° C, optionally under pressure, to the unsubstituted or substituted carboxamides.
  • the compounds of the formula I are valuable products which can be used in a variety of ways.
  • the acids and salts of the formula I can be used as gypsum binders or complexing agents, in particular for metal ions such as iron or alkaline earth metal ions. They can therefore be used for water softening. Compounds with m + n + p + q 2 2 are preferred for this.
  • the compounds of the formula I also have favorable properties as flame retardants, especially in the primer of pile carpets.
  • a cotton fabric, twill-wrapped, with a weight per square meter of 240 g, is treated on a two-roll pad with the following impregnation solution:
  • the squeezing effect is approx. 75%. After predrying at 100 ° - 110 ° C, the mixture is condensed at 170 ° C for 4 minutes. It is then washed with 2.3 g / l of soda for 5 minutes at 90 ° C and rinsed very well warm and cold until free of alkali and dried again at 100 ° C.
  • the cotton fabric treated in this way shows very good flame-retardant properties, which are retained even after three further machine washings with 3 g / l of a commercially available detergent.
  • the untreated cotton fabric continues to burn after the flame has been removed.
  • the treated fabric shows a burn-in length of 6 cm after washing and 8 cm after a three-time machine wash.
  • the handle After washing, the handle is soft and flowing.
  • the treated cotton fabric shows a very good flame retardant effect according to DIN 53 906.
  • the burn-in length is 5 cm.
  • the flame retardant effect lasts 5 chemical cleanings. You get equally good effects when you
  • a needle punched fabric made of a polyester fiber core and a polyamide tread in a mixing ratio of 65:35 is treated on a two-roll pad (squeezing effect approx. 105%) with an aqueous solution of the following composition:
  • the needle punched fabric treated in this way is then dried at 145 ° C. for 30 minutes.
  • the needle punched fabric shows good dimensional stability and good unrolling ability.
  • the needle fleece shows very good flame retardant properties according to DIN 54 333.
  • test piece of the needle felt described above with a weight of 750 g per square meter is only treated with 300 g / l of the 40% plastic dispersion, it will continue to burn in a broad direction after the flame has been removed.
  • the flame front runs through the test section of 10 cm in a time of 2 minutes and 55 seconds.
  • the needle-punched non-woven fabric equipped according to the invention does not continue to burn after the test flame has been removed. Outside the test section, only an after-flame of 8-10 seconds could be detected. After 3 shampoos, the flame retardant properties of the needle fleece are fully retained. The afterflame time has increased to only 1 minute and 15 seconds.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Textile Engineering (AREA)
  • Fireproofing Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP78100104A 1977-06-14 1978-06-06 Dérivés d'acide carboxylique contenant du phosphore, procédé pour leur préparation et leur utilisation Expired EP0000061B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH7299/77 1977-06-14
CH729977 1977-06-14

Publications (2)

Publication Number Publication Date
EP0000061A1 true EP0000061A1 (fr) 1978-12-20
EP0000061B1 EP0000061B1 (fr) 1980-10-15

Family

ID=4322957

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78100104A Expired EP0000061B1 (fr) 1977-06-14 1978-06-06 Dérivés d'acide carboxylique contenant du phosphore, procédé pour leur préparation et leur utilisation

Country Status (4)

Country Link
EP (1) EP0000061B1 (fr)
JP (1) JPS545922A (fr)
DE (1) DE2860216D1 (fr)
IT (1) IT1096642B (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0044470A1 (fr) * 1980-07-17 1982-01-27 Hoechst Aktiengesellschaft Acides diméthyl-phosphinyl-alcanephosphoniques, procédé pour les préparer et leur utilisation comme retardateurs de prise de ciments
GB2122999A (en) * 1982-07-05 1984-01-25 Schering Ag Novel disphosphonic acid derivatives and their manufacture and use
US4666895A (en) * 1985-04-06 1987-05-19 Boehringer Mannheim Gmbh Diphosphonic acid derivatives
US6254651B1 (en) 1996-07-24 2001-07-03 Exxon Chemical Patents Inc. Materials for use in oils and processes for their manufacture
WO2003021031A1 (fr) * 2001-09-01 2003-03-13 Rhodia Consumer Specialties Limited Composes phosphores

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1768759A1 (de) * 1968-06-27 1972-01-13 Procter & Gamble Zinnsalze von Phosphonsaeuren
FR2338948A1 (fr) * 1976-01-21 1977-08-19 Henkel & Cie Gmbh Acides diphosphonoalcanecarboxyliques
FR2368496A1 (fr) * 1976-10-19 1978-05-19 Hoechst Ag Derives d'acides phosphono-carboxyliques utilisables notamment comme plastifiants de hauts polymeres

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1768759A1 (de) * 1968-06-27 1972-01-13 Procter & Gamble Zinnsalze von Phosphonsaeuren
FR2338948A1 (fr) * 1976-01-21 1977-08-19 Henkel & Cie Gmbh Acides diphosphonoalcanecarboxyliques
FR2368496A1 (fr) * 1976-10-19 1978-05-19 Hoechst Ag Derives d'acides phosphono-carboxyliques utilisables notamment comme plastifiants de hauts polymeres

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
RUSSIAN CHEMICAL REVIEWS 44(6). 1975 Seiten 468-480 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0044470A1 (fr) * 1980-07-17 1982-01-27 Hoechst Aktiengesellschaft Acides diméthyl-phosphinyl-alcanephosphoniques, procédé pour les préparer et leur utilisation comme retardateurs de prise de ciments
GB2122999A (en) * 1982-07-05 1984-01-25 Schering Ag Novel disphosphonic acid derivatives and their manufacture and use
US4666895A (en) * 1985-04-06 1987-05-19 Boehringer Mannheim Gmbh Diphosphonic acid derivatives
US6254651B1 (en) 1996-07-24 2001-07-03 Exxon Chemical Patents Inc. Materials for use in oils and processes for their manufacture
WO2003021031A1 (fr) * 2001-09-01 2003-03-13 Rhodia Consumer Specialties Limited Composes phosphores

Also Published As

Publication number Publication date
IT7824481A0 (it) 1978-06-12
DE2860216D1 (en) 1981-01-22
IT1096642B (it) 1985-08-26
EP0000061B1 (fr) 1980-10-15
JPS545922A (en) 1979-01-17

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