EP0000125A1 - Esters tensio-actifs de l'acide phosphorique et leur utilisation. - Google Patents

Esters tensio-actifs de l'acide phosphorique et leur utilisation. Download PDF

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Publication number
EP0000125A1
EP0000125A1 EP78100114A EP78100114A EP0000125A1 EP 0000125 A1 EP0000125 A1 EP 0000125A1 EP 78100114 A EP78100114 A EP 78100114A EP 78100114 A EP78100114 A EP 78100114A EP 0000125 A1 EP0000125 A1 EP 0000125A1
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Prior art keywords
acid
phosphoric acid
alcohols
acids
formula
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EP78100114A
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German (de)
English (en)
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EP0000125B1 (fr
Inventor
Gunther Dr. Reitz
Günther Dr. Boehmke
Karlhans Jakobs
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Bayer AG
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Bayer AG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
    • C08G79/04—Phosphorus linked to oxygen or to oxygen and carbon
    • 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
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
    • Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
    • Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents
    • Y10S516/06—Protein or carboxylic compound containing

Definitions

  • the invention also relates to the preparation of the phosphoric acid esters and their use as dispersants, liquefiers, leveling agents, emulsifiers, builders or sequestering agents for detergents.
  • Preferred compounds of group 2 are acids of the formula their anhydrides, acid halides or esters.
  • A stands for Alkylene with 1 to 10 carbon atoms or alkenylene with 2 to 10 carbon atoms, one of the isomeric phenylene or cyclohexylene radicals.
  • the alkylene radicals can be substituted by a sulfonic acid group.
  • Group 1 compounds which may be mentioned are: ethane-1,2-diol, propane-1,2-diol, propane-1,3-diol, butane-1,2-diol, butane-1,3-diol, butane -2,3-diol, butane-1,4-diol., 3-chloropropane-1,2-diol, the individual isomeric pentanediols, hexanediol, for example hexane-1,6-diol, as well as the individual isomeric diols, higher Alkanes.
  • unsaturated diols such as 2-butene-1,4-diol, 2-hydroxy-methyl-2-propen-1-ol and higher alcohols such as glycerol.
  • Trishydroxymethylalkanes such as trishydroxymethylpropane, sugar alcohols, C 1-6 -alkyl diethaolamines, C 1-6 -Alkyldiisopropanol- anine, triethanolamine, triisopropanolamine and Pentraaerythrit called.
  • Aromatic and particularly araliphatic alcohols such as the three isomeric bis (2-hydroxyethoxy) benzenes and bis (2-hydroxypropoxy) benzenes, and further 4,4'-bis (2-hydroxyethoxy) diphenyl sulfone, 4,4'-bis- (2- hydroxypropoxy) diphenyl sulfone, the individual isomeric bis (2-hydroxy-ethoxy) naphthalenes and bis (2-hydroxypropoxy) naphthalenes, the bis (hydroxyethoxy) phenyl alkanes or bis-thydroxypropoxy-phenyl) -alkanes.
  • Cycloaliphatic alcohols may also be mentioned, such as, for example, cyclohexane-1,2-diol, cyclohexane-1,4-diol, 1,4-bis-hydroxymethylcyclohexane: polyglycols are also mentioned; eg diethylene glycol, triethylene glycol, tetraethylene glycol; Pentaethylene glycol, polyethylene glycol, di-propylene glycol, tri-, tetra-, penta- and polypropylene glycol as well as epoxides such as ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin.
  • polyglycols are also mentioned; eg diethylene glycol, triethylene glycol, tetraethylene glycol; Pentaethylene glycol, polyethylene glycol, di-propylene glycol, tri-, tetra-, penta- and polypropylene glycol as well as epoxides such as ethylene oxide, propy
  • ethane-1,2-diol propane-1,2-diol, butane-1,3-diol, butane-1,4-diol, 3-chloropropane pan-1,2-diol, hexane-1,6-diol, glycerin, tris-hydroxymethylpropane, diethanolamine, triethanolamine, bis- (2-hydroxyethoxy) benzene, bis- (2-hydroxyethoxydiphenyl) propane, cyclohexanediol, diethylene glycol, Triethylene glycol, tetraethylene glycol, ethylene oxide, propylene oxide, epichlorohydrin.
  • Group 2 compounds are, for example: malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, methylene malonic acid, ethylidene malonic acid, glutaconic acid, itaconic acid, mesaconic acid, citraconic acid, muconic acid, hexen-2 (or -3) diacid, acetylenedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, biphenyldicarboxylic acid, binaphthyldicarboxylic acid, naphthalenedicarboxylic acids, Cyclohexanedicarboxylic acids, 5-norbornene-2,3-dicarboxylic acid, di-halosuccinic acid, sulfosuccinic acid, phosphonosuccinic acid and their acid anhydride and acid hal
  • maleic anhydride phthalic anhydride, succinic anhydride, maleic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, isophthalic acid, terephthalic acid, terephthalic acid dimethyl ester, cyclohexane-1,4-dicarboxylic acid, sulfosuccinic acid.
  • Group 3 compounds are, for example: phosphoric acid, in aqueous solution, syrupy or crystalline, polyphosphoric acid, metaphosphoric acid, phosphorus pentoxide, POC1 3 , P 2 O 3 Cl 4 , PCl 5 . Of these, preference is given to phosphoric acid, crystalline, syrupy or in aqueous solution, polyphosphoric acid, P 2 O 5 and POC1 3 .
  • the compounds of group 2 can be those of group 3 in a molar ratio (O to 20): 1, preferably in a ratio (0.05 to 10): 1 and particularly preferably in a ratio (0.1 to 4): 1. From this the result is a preferred ratio of compounds of the groups 1: 2: 3 of 1: (0.04 to 1.2): (0.07 to 1.3) and a particularly preferred ratio of 1: (0.07 to 1, 1): (0.15 to 1.25).
  • the molar ratio is preferably that given above.
  • the phosphoric acid esters of the formula (III) are prepared by any combination of the structural elements (1), (2) and (3), which - each individually - can be the same or different, the above provisions applying.
  • the alcohols (I) and the carboxylic acids (II) are reacted with orthophosphoric acid.
  • the orthophosphoric acid can be crystalline, syrupy or in concentrated aqueous solution, e.g. in 40 to 100% solution.
  • the reaction takes place according to methods known per se with acid catalysis of, for example, mineral acids such as H 3 PO 4 , HCl, H 2 SO 4 or of compounds such as p-toluenesulfonic acid, Lewis acids, light metal and heavy metal oxides or salts, such as, for example, halides.
  • mineral acids such as H 3 PO 4 , HCl, H 2 SO 4
  • compounds such as p-toluenesulfonic acid, Lewis acids, light metal and heavy metal oxides or salts, such as, for example, halides.
  • Lewis acids Lewis acids
  • light metal and heavy metal oxides or salts such as, for example, halides
  • the compounds (V) then react with orthophosphoric acid (possibly in the salt form) and / or compounds (IV) and optionally alcohols (I) in a molar ratio of 1: (0.1 to 20): (O, 1 to 20): (O to 20), especially in the molar ratio 1: (0; 25 to 10): (0.25 to 10): (O to 10).
  • the sum of the number of moles of the diol (I) used in the synthesis of compound (V) and of the diol (I) used in the further reaction is 2/3 to 3/2 times, preferably 3/4 to 4 / 3 times the sum of the number of moles of dicarboxylic acid (II) and phosphoric acid used.
  • the reaction takes place at temperatures from 120 to 260 ° C, preferably from 150 to 200 ° C to the esters (III), the water of reaction being distilled off if necessary under vacuum.
  • a preferred procedure also consists in adding orthophosphoric acid, alcohols (I) and carboxylic acids (II) in a molar ratio (0.07 to 1.3): 1: (0.04 to 1.2), preferably - ( 0.15 to 1 , 25): 1: (0.07 to 1.1) to react simultaneously, the sum of the molar numbers of orthophosphoric acid and dicarboxylic acid (II) being 2/3 to 3/2 times, preferably 3 / 4 to 4/3 times the number of moles of alcohol (I).
  • the monoesters or diesters of the type of the compounds (IV) and (V) are first formed by regulating the temperature and pressure so that the compounds (I) and (II) do not boil or decompose, and then later on is preferably heated to 150 to 200 ° C and the esterification is optionally completed under vacuum.
  • All the esterification reactions described are acid-catalyzed, the simplest and preferred case being the orthophosphoric acid participating in the reaction or the compound (IV) as catalyst.
  • Other catalysts can also be used, for example mineral acids such as H 2 S0 4 , HC1, furthermore organic sulfonic acids, for example toluenesulfonic acid or else Lewis acids such as heavy metal and light metal oxides and salts, for example haloenides.
  • the compounds (I), (II), (IV) or (V) themselves are preferably used as the reaction medium, or a solvent is added which does not take part in the reaction, e.g. aliphatic or aromatic hydrocarbon such as petroleum ether, benzene, toluene, xylene.
  • a solvent is added which does not take part in the reaction, e.g. aliphatic or aromatic hydrocarbon such as petroleum ether, benzene, toluene, xylene.
  • a halogenated hydrocarbon such as methylene chloride, chloroform, carbon tetrachloride, trichlorethylene, perchlorethylene, chlorobenzene, dichlorobenzene or chlorotoluene can also be used.
  • Polar, aprotic solvents can also be used as the reaction medium, for example dimethylformamide, acetonitrile, ether or dioxane.
  • the water of reaction is removed either by distillation, if appropriate in vacuo, or by azeotropic distillation, it being possible for one of the abovementioned media to serve as a tug if it is immiscible with water.
  • Xylene, perchlorethylene and dichlorobenzene are preferred.
  • activated forms of these acids can also be used very advantageously instead of the free orthophosphoric acid or the free carboxylic acid (II).
  • the acid anhydrides may be mentioned, for example, all kinds of dehydrated forms of phosphoric acid, ie anhydrous ortho, P yro-, poly-and metaphosphoric acid and phosphorus pentoxide, and various anhydride forms of the carboxylic acids (II), for example, intramolecular or intermolecular anhydrides.
  • a preferred procedure further consists in that the compounds are obtained from the anhydrides of the carboxylic acids (II) and from the alcohols (I), if appropriate with acid catalysis with one of the catalysts mentioned (V) synthesized, in which b is preferably 2, and these compounds (V) further with H 3 PO 4 or the dehydrated forms thereof and optionally with further alcohol (I) to react.
  • the polyesters (III) are formed by applying a vacuum and heating to preferably 150 to 200 ° C.
  • the corresponding phosphoric acid halides for example POC1 3 , P 2 O 3 Cl 4 , PCl 5 , or the carboxylic acid halides, especially the chlorides, can also be used.
  • the phosphoric acid esters (IV) can also be derived from phosphoric acid or one of its primary or secondary salts, e.g. the alkali, alkaline earth or ammonium salt, and alkylene oxides, e.g. Ethylene oxide, propylene oxide, epichlorohydrin, are shown. Such methods are known from the literature (Chem.Phar.-Bull. 5, 121-215; (1957)). Accordingly, it is also possible to prepare the compounds (V) from the carboxylic acids and the alkylene oxides (DT-PS 905 736).
  • Examples of the compounds (IV) which are prepared by one of the processes described above include, in particular, the phosphoric acid mono- and bis-esters of the following alcohols (II): glycol, propane-1,2-diol, butane-1, 4-diol, butane-1,3-diol, 3-chloropropane-1,2-diol, hexane-1,6-diol, glycerin, methyl-diethanolamine, ethyl-diethanolamine, triethanolamine, 1,2-bis-2- (hydroxyethoxy) benzene, 1,4-bis-2- (hydroxyethoxy) benzene, 4,4'-bis (2-hydroxyethoxy) diphenyl sulfone, bis- (2- hydroxyethoxyphenyl) ethane, bis (2-hydroxyethoxyphenyl) propane, cyclohexane-1,4-diol, diethylene glycol, triethylene glycol, tetraethylene
  • Mono- and diesters of the compounds (V), which should be mentioned in particular, are formed from the abovementioned alcohols and the following carboxylic acids (II): malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, phthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, sulfosuccinic acid, phosphonosuccinic acid and cork and sebacic acid.
  • carboxylic acids (II) malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, phthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, sulfosuccinic acid, phosphonosuccinic acid and cork and sebacic acid.
  • the polyesters (III) can also be prepared in the following way: phosphoric acid and / or carboxylic acid (II) are each converted into the corresponding chlorohydrin esters (IV) and / or (V) with epichlorohydrin or its derivatives. These then react further with bases or bases to form the glycidic esters and are reacted directly with further carboxylic acid (II) and / or phosphoric acid to give the polyesters (III).
  • chlorohydrin esters (IV) and / or (V) with the salts, preferably alkali or alkaline earth metal salts Implement carboxylic acids (II) and / or phosphoric acid to the polyesters (III).
  • the two groups Y can be the same or different.
  • One of the groups Y can also be a hydroxyl group.
  • the polyesters (I) can also be prepared by transesterification, the phosphoric acids and / or the carboxylic acids (II) as esters of volatile alcohols, e.g. Methanol, ethanol, isopropanol, propanol or butanol can be used.
  • This transesterification reaction can be catalyzed acidic or alkaline.
  • esters that can be used dimethyl terephthalate is particularly mentioned.
  • the polyesters (III) prepared in the manner described above are obtained as yellowish to brown-colored products which are stirrable or viscous in the heat and solid in the cold. They can be isolated in isolation; For example, by pouring out the hot mass and cooling, or solutions can be places, such as in organic solvents or preferably in water. To dissolve in water, the substances are preferably mixed with one to five times their weight in water and neutralized in such a way with a base or lye, preferably with alkali or alkaline earth lye, that the pH does not rise above 8.
  • the solidified polyester (I) located at the bottom of the reaction vessel with the calculated amount of H 2 O, this water is constantly stirred and concentrated by heating to 20 to 50 ° C. by adding small amounts Sodium hydroxide solution maintains a pH of 5 to 8.
  • the polyester (I) dissolves.
  • the pH is preferably adjusted to 5 to 7, 20 to 50% solutions being obtained.
  • the aqueous solutions can be evaporated to dry powders.
  • the molecular weight of the compounds (III) is 300 to 10,000, preferably 800 to 10,000.
  • the carboxylic acids (II) are generally associated with two moles of the alcohols (I), and a certain proportion of the orthophosphoric acid in two P- OH groups linked with the alcohols (I) to form phosphoric acid esters.
  • a further proportion of the phosphoric acid is present in the monoester structure and only a small proportion possibly as a phosphoric acid triester. Accordingly, the IR spectrum shows the absorption bands at 1730 to 1800 nm corresponding to the carbonic esters and the bands at 1020 to 1120 nm corresponding to the POC bonds of the phosphoric acid esters.
  • a certain small proportion of the phosphoric acid can also be bound pyrophosphate-like or polyphosphate-like via a POP bond be.
  • the polycondensates can consist of alternating structural elements (1) and (3), structural elements (2) can also be condensed in.
  • the compounds of formula (II) or (V) thus perform two functions:
  • the compounds (III) contribute to the action of the compounds (III) by being condensed in, and on the other hand they have a catalytic effect on the esterification of the phosphoric acid groups -P-OH (if these are used in the reaction or are formed in the course of the reaction) the diols of formula (I).
  • This catalysis consists of a transesterification, because the carboxylic acid ester forms the phosphoric acid ester.
  • the dicarboxylic acid escapes from the reaction mixture with increasing reaction, e.g. the sublimation of maleic anhydride or phthalic anhydride.
  • the water solubility of the compounds results from the fact that the phosphoric acid molecules are generally free from one or possibly two P-OH groups, which render the compounds soluble in water either directly or after deprotonation with bases or bases.
  • the discoloration to brown to black that often occurs during esterification with phosphoric acid can be largely prevented by adding reducing agents, preferably low-value phosphorus derivatives, for example H 3 PO 3 or its salts.
  • reducing agents preferably low-value phosphorus derivatives, for example H 3 PO 3 or its salts.
  • the compounds (III) are hydrolysis-resistant in the form of the neutral salts and can be kept in aqueous solutions for several months; after boiling in water at pH 7 for ten hours, they do not lose any noticeable effectiveness. However, the ester bonds are attacked bacterially, so that the compounds (III) are biodegradable.
  • the compounds (III). are used as dispersants for organic and inorganic substances in a preferably aqueous medium. Use as a dispersant for dyes and pigments is preferred.
  • They can be used to produce dye formations or to disperse dyes in the dye bath.
  • They can also be used as emulsifiers for organic substances in water and as leveling agents in dyeing, e.g. when dyeing polyester fibers.
  • the compounds (III) can also be used to "liquefy" concentrated mixtures of oxganic or inorganic solids and water.
  • the "liquefaction” of these mixtures consists in a reduction in the viscosity up to easy stirrability and pourability.
  • Solids include organic dyes, inorganic pigments, e.g. Metal oxides, cement, concrete and sludge.
  • adipic acid and 62 g of glycol are stirred at 90 ° C. for a few minutes, then 58 g of 85% phosphoric acid and 2 g of phosphorous acid are added. Under initially weak, later stronger vacuum, the mixture is slowly heated to 180 to 190 ° C. and held there for a few hours, during which aqueous liquid is distilled off. After cooling, a 20% solution of pH 6 to 7 is prepared with H 2 0 and concentrated sodium hydroxide solution.
  • Disperse Red 106 0.8 g of Disperse Red 106 are poured over with 400 ml of H 2 0 at 50 ° C., which contains 1 g / 1 of the substances prepared in Examples 1 to 25, with stirring and brought to a boil for 10 minutes. Then it is filtered through a round filter under vacuum. The paper filter remains clear and shows no dye agglomeration.
  • 10 g of zinc oxide are gradually mixed with 10 g of a 1.5% solution of one of the substances from Examples 1 to 25. It is constantly stirred well. A milky, viscous mixture is created. Dilution with H 2 O shows that a stable dispersion has formed. If 10 g of zinc oxide are appropriately mixed with 10 g of H 2 0, an irresistible, lumpy mass is formed which does not form a stable dispersion when diluted with H 2 0.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Detergent Compositions (AREA)
EP78100114A 1977-06-15 1978-06-07 Esters tensio-actifs de l'acide phosphorique et leur utilisation. Expired EP0000125B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19772726854 DE2726854A1 (de) 1977-06-15 1977-06-15 Phosphorsaeureester
DE2726854 1977-06-15

Publications (2)

Publication Number Publication Date
EP0000125A1 true EP0000125A1 (fr) 1979-01-10
EP0000125B1 EP0000125B1 (fr) 1981-12-02

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Application Number Title Priority Date Filing Date
EP78100114A Expired EP0000125B1 (fr) 1977-06-15 1978-06-07 Esters tensio-actifs de l'acide phosphorique et leur utilisation.

Country Status (4)

Country Link
US (1) US4258448A (fr)
EP (1) EP0000125B1 (fr)
JP (1) JPS545923A (fr)
DE (2) DE2726854A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0012351A1 (fr) * 1978-12-14 1980-06-25 Bayer Ag Esters d'acides phosphoniques, leur préparation, leur utilisation comme agents émulsionnants et dispersants et leurs compositions aqueuses
EP0133030A2 (fr) * 1983-07-27 1985-02-13 Toyo Seikan Kaisha Limited Agent de refroidissement soluble dans l'eau pour la formation de boîtes étirées et laminées
EP0417490A2 (fr) * 1989-09-14 1991-03-20 Byk-Chemie GmbH Esters phosphoriques, procédÀ© de préparation et utilisation comme agent dispersant
WO2006025738A1 (fr) * 2004-09-02 2006-03-09 Dsm Ip Assets B.V. Polyester prepare a partir de l'acide phosphorique ou ses oligomeres

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JPS55162601A (en) * 1979-06-05 1980-12-18 Nec Corp Sinusoidal wave generating circuit
US4339238A (en) * 1980-01-14 1982-07-13 Ciba-Geigy Corporation Stable aqueous formulations of stilbene fluorescent whitening agents
US4386965A (en) * 1980-07-03 1983-06-07 Ciba-Geigy Corporation Process for obtaining coating compositions of improved whiteness
US4568480A (en) * 1983-11-17 1986-02-04 Basf Wyandotte Corporation Microemulsions
JPS60136459A (ja) * 1983-12-26 1985-07-19 Toshiba Corp Ｄｔｍｆ信号発生装置
JPS60136461A (ja) * 1983-12-26 1985-07-19 Toshiba Corp Ｄｔｍｆ信号発生装置
JPS60136460A (ja) * 1983-12-26 1985-07-19 Toshiba Corp Ｄｔｍｆ信号発生装置
DE3622440A1 (de) * 1986-07-04 1988-01-07 Henkel Kgaa Alkyl-hydroxyalkyl-phosphorsaeureester
US5151218A (en) * 1989-09-14 1992-09-29 Byk-Chemie Gmbh Phosphoric acid esters, method of producing them, and use thereof as dispersants
DE4202720A1 (de) * 1991-05-02 1992-11-05 Henkel Kgaa Verbesserung beim spruehauftrag waessriger behandlungsflotten auf textilmaterial
WO2004099292A1 (fr) * 2003-05-09 2004-11-18 Prometheus Developments Limited Procede de production d'un materiau polymere
CN104231673B (zh) * 2013-06-13 2016-01-13 广东华润涂料有限公司 磷酸酯分散助剂以及包含这种磷酸酯分散助剂的分散体
CN113748171B (zh) 2019-04-26 2022-12-13 毕克化学有限公司 用于制备彩色滤光片的组合物
JP6703653B1 (ja) * 2020-02-04 2020-06-03 国立大学法人佐賀大学 リン酸ジエステルまたはリン酸トリエステルの製造方法
WO2022214502A1 (fr) 2021-04-07 2022-10-13 Byk-Chemie Gmbh Polymère en peigne ayant des groupes de sels

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FR1076808A (fr) * 1952-05-09 1954-10-29 Metallgesellschaft Ag Esters tertiaires à base d'acide phosphorique et d'acides carboxyliques d'alcools polyvalents
DE971212C (de) * 1952-05-10 1958-12-24 Hoechst Ag Verfahren zur Herstellung tertiaerer Phosphorsaeureester partieller Carbonsaeureester mehrwertiger Alkohole
DE1061763B (de) * 1955-06-06 1959-07-23 Union Carbide Corp Verfahren zur Herstellung von kondensierten Polyphosphatestern und deren acylierten Derivaten
FR1401507A (fr) * 1963-05-17 1965-06-04 Lubrizol Corp Procédé de fabrication d'esters contenant du phosphore
FR2139816A1 (fr) * 1971-03-29 1973-01-12 Ppg Industries Inc

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US3022330A (en) * 1956-08-21 1962-02-20 Union Carbide Corp Neutral esters of bicyclo heterocyclic phosphoric acids
BE562150A (fr) * 1956-11-16
US3431223A (en) * 1966-06-10 1969-03-04 Upjohn Co Partial esters as polyols for polyurethane foams
US3544614A (en) * 1967-06-08 1970-12-01 R H Miller Co Inc Complex esters produced by reacting a dicarboxylic acid,a polyhydric alcohol and boric acid
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FR1076808A (fr) * 1952-05-09 1954-10-29 Metallgesellschaft Ag Esters tertiaires à base d'acide phosphorique et d'acides carboxyliques d'alcools polyvalents
DE971212C (de) * 1952-05-10 1958-12-24 Hoechst Ag Verfahren zur Herstellung tertiaerer Phosphorsaeureester partieller Carbonsaeureester mehrwertiger Alkohole
DE1061763B (de) * 1955-06-06 1959-07-23 Union Carbide Corp Verfahren zur Herstellung von kondensierten Polyphosphatestern und deren acylierten Derivaten
FR1401507A (fr) * 1963-05-17 1965-06-04 Lubrizol Corp Procédé de fabrication d'esters contenant du phosphore
FR2139816A1 (fr) * 1971-03-29 1973-01-12 Ppg Industries Inc

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0012351A1 (fr) * 1978-12-14 1980-06-25 Bayer Ag Esters d'acides phosphoniques, leur préparation, leur utilisation comme agents émulsionnants et dispersants et leurs compositions aqueuses
EP0133030A2 (fr) * 1983-07-27 1985-02-13 Toyo Seikan Kaisha Limited Agent de refroidissement soluble dans l'eau pour la formation de boîtes étirées et laminées
EP0133030A3 (fr) * 1983-07-27 1986-11-12 Toyo Seikan Kaisha Limited Agent de refroidissement soluble dans l'eau pour la formation de boítes étirées et laminées
EP0417490A2 (fr) * 1989-09-14 1991-03-20 Byk-Chemie GmbH Esters phosphoriques, procédÀ© de préparation et utilisation comme agent dispersant
EP0417490A3 (en) * 1989-09-14 1991-10-09 Byk-Chemie Gmbh Phosphoric acid esters, process for their preparation and use as dispersing agent
WO2006025738A1 (fr) * 2004-09-02 2006-03-09 Dsm Ip Assets B.V. Polyester prepare a partir de l'acide phosphorique ou ses oligomeres

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EP0000125B1 (fr) 1981-12-02
DE2861394D1 (en) 1982-01-28
US4258448A (en) 1981-03-31
DE2726854A1 (de) 1979-01-11
JPS545923A (en) 1979-01-17

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