WO2000051956A1 - Procede de preparation de composes alcoxyles ayant des atomes d'hydrogene actifs - Google Patents

Procede de preparation de composes alcoxyles ayant des atomes d'hydrogene actifs Download PDF

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Publication number
WO2000051956A1
WO2000051956A1 PCT/EP2000/001503 EP0001503W WO0051956A1 WO 2000051956 A1 WO2000051956 A1 WO 2000051956A1 EP 0001503 W EP0001503 W EP 0001503W WO 0051956 A1 WO0051956 A1 WO 0051956A1
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WO
WIPO (PCT)
Prior art keywords
compounds
active hydrogen
catalysts
hydrogen atoms
acid
Prior art date
Application number
PCT/EP2000/001503
Other languages
German (de)
English (en)
Inventor
Ansgar Behler
Almud Folge
Original Assignee
Cognis Deutschland Gmbh
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Cognis Deutschland Gmbh filed Critical Cognis Deutschland Gmbh
Priority to JP2000602186A priority Critical patent/JP2002538126A/ja
Publication of WO2000051956A1 publication Critical patent/WO2000051956A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/02—Preparation of ethers from oxiranes
    • C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/24—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran
    • C07C67/26—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran with an oxirane ring

Definitions

  • the invention relates to a process for the preparation of alkoxylated compounds with active hydrogen atoms, in which compounds with active hydrogen atoms are reacted with alkylene oxides in the presence of optionally modified hydrotalcite as a catalyst and selected co-catalysts.
  • nonionic surfactants are the addition products of alkylene oxides, in particular ethylene oxide and / or propylene oxide, to compounds with active hydrogen, which are usually prepared by means of homogeneous catalysis in the presence of alkali metal hydroxides or alkali metal alcoholates. Products with a broad homolog distribution are obtained by the homogeneously catalyzed process.
  • the object of the present invention was therefore to provide a process for the preparation of alkoxylated compounds with active hydrogen atoms, which leads on the one hand to products with a restricted homolog distribution, but on the other hand is associated with lower costs.
  • the object of the present invention could be achieved if the hydrotalcite which may have been modified is at least partially replaced by specially selected cocatalysts.
  • the invention includes the finding that such a catalyst mixture also provides products with a restricted homolgen distribution which agrees very well with the homolog distribution of the alkoxylation catalyzed by only hydrotalcite.
  • the total amount of catalyst can be reduced compared to the prior art.
  • significantly shorter reaction times for the alkoxylation can be achieved when using the catalyst mixtures according to the invention.
  • the term “catalytic mixture” is understood to mean a mixture of possibly modified hydrotalcite and the selected cocatalysts.
  • An object of the present invention therefore relates to a process for the preparation of alkoxylated compounds with active hydrogen atoms by reacting compounds with active hydrogen atoms with alkylene oxides in the presence of optionally modified hydrotalcite as a catalyst, characterized in that cocatalysts selected from the group are used Group formed by hydroxides, oxides and / or alkoxides of alkali and / or alkaline earth metals as well as alkali and / or alkaline earth salts, tin salts and mixed metal oxides.
  • al) alcohols with 6 to 22 carbon atoms such as Cappa alcohol, caprylic alcohol, capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, ricinolyl alcohol, eraducyl alcohol alcohol, elaeostol alcohol, elaeostol alcohol as they occur, for example, in the hydrogenation of methyl ester fractions of native origin or of aldehydes from Roelen's oxosynthesis.
  • Fatty alcohols with 12 to 18 carbon atoms are preferred, for example technical coconut or tallow fatty alcohol strains.
  • Guerbet alcohols which are produced by alkali-catalyzed condensation of 2 moles of fatty alcohol and which can contain 12 to 36 carbon atoms, are also suitable as a further group of fatty alcohols.
  • carboxylic acids with 6 to 22 carbon atoms (so-called fatty acids) and hydroxy fatty acids, such as, for example, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid , Elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures, such as those used in the pressure splitting of natural fats and oils occur.
  • Fatty acids with 12 to 18 carbon atoms for example technical coconut or tallow fatty acids, are preferred.
  • alkylphenols a3) alkylphenols, polyglycols, fatty amines, vicinal hydroxy / alkoxy-substituted alkanes, which can be obtained, for example, by ring opening of epoxy compounds with alcohols or carboxylic acids, and secondary alcohols.
  • the alcohols or carboxylic acids with 6 to 22 carbon atoms are preferred.
  • optionally modified hydrotalcites in combination with specially selected cocatalysts are used as alkoxylation catalysts.
  • modified hydrotalcites used are calcined or hydrophobized hydrotalcites, as are known, for example, from German patent applications DE-Al 38 43 713 and DE-Al 40 10 606 (Henkel).
  • the calcined hydrotalcites are particularly preferred.
  • Suitable co-catalysts are compounds from the group formed by hydroxides, oxides and / or alkoxides of alkali and / or alkaline earth metals and of alkali and / or alkaline earth metal salts, tin salts and mixed metal oxides.
  • Particularly suitable hydroxides of alkali and / or alkaline earth hydroxides are lithium hydroxide and / or magnesium hydroxide.
  • the oxides of magnesium are preferred.
  • Preferred alkoxides of the alkali and / or alkaline earth metals are those which are derived from short-chain alcohols, for example from those having 1 to 8 carbon atoms and in particular from methanol, ethanol and / or 2-ethylhexanol.
  • the magnesium and / or barium compounds are particularly preferred.
  • the magnesium and barium salts for example the carbonates such as magnesium carbonate, or the acetates, for example magnesium acetate, are of particular importance.
  • Mixed metal oxides are oxide compounds that contain at least two different metals.
  • One of the metals is preferably magnesium.
  • the other metal can be aluminum, gallium, zircon, indium, thallium, cobalt, scandium, lanthanum and / or manganese.
  • Magnesium / aluminum mixed oxides are particularly preferred.
  • the surface of the mixed oxides can be modified with one or more of the co-catalysts already mentioned, in particular with the hydroxides and / or alkoxides of the alkali and / or alkaline earth metals.
  • Magnesium oxide is particularly preferred as co-catalyst.
  • the optionally modified hydrotalcites can be present in amounts of from 0.01 to 5, preferably from 0.05 to 0.5 and in particular from 0.05 to 0.2% by weight, based on the starting compounds (compounds with active hydrogen atoms and alkylene oxide). - be used.
  • the cocatalysts can be used in amounts of 0.01 to 5, preferably in amounts of 0.05 to 0.5 and in particular in amounts of 0.1 to 0.3% by weight, based on the starting compounds.
  • the ratio between possibly modified hydrotalcite as catalyst and co-catalysts can vary within wide ranges, preferably the weight ratio is between 5: 1 to 1: 5, in particular between 3: 1 and 1: 3 and particularly preferably between 2: 1 and 1 : 2.
  • the reaction of the compounds with active hydrogen atoms with the alkylene oxides can be carried out in a manner known per se at temperatures from 120 to 200, preferably 150 to 180 ° C. and pressures of 1 to 5 bar.
  • the amount of alkylene oxide to be added is not critical and can be, for example, 1 to 100, preferably 2 to 50 and in particular 2 to 20 moles of alkylene oxide per mole of active hydrogen in the compound.
  • alkylene oxides ethylene, propylene and / or butylene oxide can be used, preferably ethylene oxide.
  • At least equimolar amounts of acids - based on the catalyst mixture (hydrotalcite and cocatalyst) - can be added in the process according to the invention in order to decompose the catalyst mixture as completely as possible.
  • Both inorganic and organic acids can be added as acids.
  • Mineral acids such as sulfuric acid, hydrochloric acid and / or phosphoric acid are particularly suitable as inorganic acids.
  • Organic acids include both the so-called fatty acids with 6 to 22 carbon atoms and lower carboxylic acids with 1 to 4 carbon atoms (only the carbon atoms of the hydrocarbon structure are counted, not the carbon atoms of the carboxyl groups), which may have been additionally modified with hydroxyl groups can, used.
  • the lower carboxylic acids such as lactic acid, acetic acid and / or citric acid are preferred as acids.
  • the acids are added as aqueous solutions, preferably as 10 to 90% by weight solutions.
  • the acids are used at least in equimolar amounts, based on hydrotalcite, preferably in molar amounts, in relation to the amount of catalyst, from 1: 1 to 10: 1, in particular from 1: 1 to 4: 1.
  • the acids are added at temperatures above the melting point of the alkoxylated compounds, preferably at temperatures between 70 and 95 ° C. In practice, this is best done carried out that after the alkoxylation, the reaction mixture obtained in this
  • the catalyst can of course be worked up in the usual way, for example by means of filtration, instead of the acid treatment.
  • the alkoxylated compounds obtained by the processes according to the invention have a narrow homolog distribution and can be used without problems as a nonionic surfactant for the production of washing, rinsing and cleaning agents.
  • the alkoxylation is carried out analogously to Example 1, but with 5.0 g (corresponding to 0.5% by weight, based on the starting compounds) of hydrotalcite as a catalyst.
  • the reaction time was 120 minutes.
  • the product had a hydroxyl number of 182.
  • the homolog distributions of the two products are comparable.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un nouveau procédé de préparation de composés alcoxylés ayant des atomes d'hydrogène actifs, selon lequel le catalyseur utilisé est un mélange d'hydrotalcite modifié et de cocatalyseurs, sélectionnés dans le groupe comprenant des hydroxydes, des oxydes et/ou des alcoxydes de métaux alcalins et/ou alcalino-terreux, ainsi que des sels alcalins et/ou alcalino-terreux, des sels stanniques et des oxydes d'alliage de terres rares métalliques.
PCT/EP2000/001503 1999-03-03 2000-02-24 Procede de preparation de composes alcoxyles ayant des atomes d'hydrogene actifs WO2000051956A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2000602186A JP2002538126A (ja) 1999-03-03 2000-02-24 活性水素原子含有アルコキシル化化合物の製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1999109273 DE19909273A1 (de) 1999-03-03 1999-03-03 Verfahren zur Herstellung alkoxylierter Verbindungen mit aktiven Wasserstoffatomen
DE19909273.7 1999-03-03

Publications (1)

Publication Number Publication Date
WO2000051956A1 true WO2000051956A1 (fr) 2000-09-08

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Application Number Title Priority Date Filing Date
PCT/EP2000/001503 WO2000051956A1 (fr) 1999-03-03 2000-02-24 Procede de preparation de composes alcoxyles ayant des atomes d'hydrogene actifs

Country Status (3)

Country Link
JP (1) JP2002538126A (fr)
DE (1) DE19909273A1 (fr)
WO (1) WO2000051956A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103041860A (zh) * 2013-01-24 2013-04-17 凤台精兴生物科技有限公司 用于在壬基酚聚氧乙烯醚合成反应中的碱性复配催化剂

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4302613A (en) * 1980-08-22 1981-11-24 Conoco Inc. Inorganic catalyst for alkoxylation of alcohols
DE3843713A1 (de) * 1988-04-25 1989-11-02 Henkel Kgaa Verwendung von calcinierten hydrotalciten als katalysatoren fuer die ethoxylierung bzw. propoxylierung
DE4010606A1 (de) * 1990-04-02 1991-10-10 Henkel Kgaa Verwendung von hydrophobierten hydrotalciten als katalysatoren fuer die ethoxylierung bzw. propoxylierung
DE19611999C1 (de) * 1996-03-27 1997-07-17 Henkel Kgaa Verfahren zur Herstellung alkoxylierter Fettsäurealkylester

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4302613A (en) * 1980-08-22 1981-11-24 Conoco Inc. Inorganic catalyst for alkoxylation of alcohols
DE3843713A1 (de) * 1988-04-25 1989-11-02 Henkel Kgaa Verwendung von calcinierten hydrotalciten als katalysatoren fuer die ethoxylierung bzw. propoxylierung
DE4010606A1 (de) * 1990-04-02 1991-10-10 Henkel Kgaa Verwendung von hydrophobierten hydrotalciten als katalysatoren fuer die ethoxylierung bzw. propoxylierung
DE19611999C1 (de) * 1996-03-27 1997-07-17 Henkel Kgaa Verfahren zur Herstellung alkoxylierter Fettsäurealkylester

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103041860A (zh) * 2013-01-24 2013-04-17 凤台精兴生物科技有限公司 用于在壬基酚聚氧乙烯醚合成反应中的碱性复配催化剂
CN103041860B (zh) * 2013-01-24 2015-03-25 凤台精兴生物科技有限公司 用于在壬基酚聚氧乙烯醚合成反应中的碱性复配催化剂

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Publication number Publication date
JP2002538126A (ja) 2002-11-12
DE19909273A1 (de) 2000-09-07

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