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WO2003053898A1 - Procede de production de composes alcoxyles - Google Patents

Procede de production de composes alcoxyles Download PDF

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Publication number
WO2003053898A1
WO2003053898A1 PCT/EP2002/013692 EP0213692W WO03053898A1 WO 2003053898 A1 WO2003053898 A1 WO 2003053898A1 EP 0213692 W EP0213692 W EP 0213692W WO 03053898 A1 WO03053898 A1 WO 03053898A1
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WO
WIPO (PCT)
Prior art keywords
acid
compounds
reaction mixture
catalysts
alcohol
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.)
Ceased
Application number
PCT/EP2002/013692
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German (de)
English (en)
Inventor
Ansgar Behler
Almud Folge
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Personal Care and Nutrition GmbH
Original Assignee
Cognis Deutschland GmbH and Co KG
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 and Co KG filed Critical Cognis Deutschland GmbH and Co KG
Publication of WO2003053898A1 publication Critical patent/WO2003053898A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2615—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen the other compounds containing carboxylic acid, ester or anhydride groups
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • the invention relates to a process for the production of alkoxylated compounds, in which compounds with active hydrogen atoms or carboxylic acid esters with alkylene oxides in the presence of solid catalysts which are not soluble in the reaction mixture, for example modified hydrotalcites or solid, salt-like Mg / Al compounds as catalyst and, if appropriate implemented further selected co-catalysts and then filtered through a cellulose-containing filter aid.
  • solid catalysts which are not soluble in the reaction mixture, for example modified hydrotalcites or solid, salt-like Mg / Al compounds as catalyst and, if appropriate implemented further selected co-catalysts and then filtered through a cellulose-containing filter aid.
  • 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.
  • Products with a restricted homolog distribution can be obtained if the reaction is carried out in the presence of solid catalysts, for example in the presence of optionally modified hydrotalcites, for example in accordance with German published patent application DE-A-3833076 or in the presence of solid, salt-like Mg / Al compounds.
  • WO 92/12951 describes a process for the preparation of fatty alcohol polyalkylene glycol ethers, in which fatty alcohols are reacted in the presence of layered compounds with an average of 1 to 20 moles of ethylene oxide or propylene oxide per mole of fatty alcohol, the reaction product is treated with a coagulant and, if appropriate, a base, and that from Layer compound and the coagulant formed coagulate is separated, if appropriate, in the presence of a filter aid. Products based on diatomaceous earth, wood flour or cellulose are mentioned as filter aids.
  • the problem with the described method is that the use of coagulants is required to achieve acceptable filterability.
  • the filtration times that can be achieved according to the process specified in the publication are often too long for an economical process.
  • the object of the present invention was therefore to provide a process for the preparation of alkoxylated compounds which no longer has the disadvantages of a complex and time-consuming filtration known from the prior art.
  • the object of the present invention was achieved by adjusting the reaction mixture containing at least one catalyst which is not soluble in the reaction mixture to a certain water content and then filtering through a cellulose-containing filter aid.
  • the present invention therefore relates to a process for the preparation of alkoxylated compounds by reacting compounds having active hydrogen atoms or carboxylic acid esters with alkylene oxides in the presence of catalysts which are not soluble in the reaction mixture, in which the reaction mixture is filtered through a filter aid after the alkoxylation, the filter aid being cellulose contains and the reaction mixture has a water content of at least 1.5 wt .-%.
  • 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 Mixtures such as those obtained 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 cuts.
  • Guerbet alcohols which are produced by alkali-catalyzed condensation of 2 mol 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, e.g. 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, ricinoleic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid, and gemenic acid, as well as their and erucic acid for example in the pressure splitting of natural fats and oils.
  • Fatty acids with 12 to 18 carbon atoms are preferred, for example technical coconut or tallow fatty acids.
  • alkylphenols a3) alkylphenols, polyglycols, fatty amines, vicinal hydroxy / alkoxy-substituted alkanes, which can be obtained, for example, by ring opening epoxy compounds with alcohols or carboxylic acids, and secondary alcohols.
  • the alcohols or carboxylic acids with 6 to 22 carbon atoms are preferred.
  • carboxylic acid esters are used as starting materials. There are two basic types:
  • R CO represents an aliphatic acyl radical having 6 to 22 carbon atoms and R represents a linear or branched alkyl radical having 1 to 4 carbon atoms.
  • Methyl esters of fatty acids with 12 to 18 carbon atoms and in particular technical coconut or tallow fatty acid methyl esters are preferably used.
  • R and R independently of one another represent hydrogen or likewise an aliphatic acyl radical having 6 to 22 carbon atoms.
  • Typical examples of this are synthetic, but preferably natural triglycerides, such as palm oil, palm kernel oil, coconut oil, rapeseed oil, olive oil, sunflower oil, cottonseed oil, peanut oil, linseed oil, lard oil, beef tallow and lard. Castor oil or hardened castor oil is preferably used.
  • fatty acid partial glycerides in particular monoglycerides of fatty acids having 12 to 18 carbon atoms, can also be used instead of the full esters.
  • Technical coconut fatty acid monoglycerides are particularly preferred here.
  • carboxylic acid lower alkyl esters in particular the methyl esters of carboxylic acids having 6 to 22 carbon atoms, are preferred for carrying out the process according to the invention, alkyl ester ethoxylates, in particular methyl ester ethoxylates, being obtained as reaction products.
  • compounds which are not soluble in the reaction mixture itself are present as alkoxylation catalysts in the process according to the invention. All such catalysts which are not soluble in the reaction mixture are suitable in principle within the scope of the process according to the invention.
  • hydrotalcites which may have been modified as catalysts are present alone or in a mixture with selected co-catalysts in the reaction mixture. According to one embodiment of the present invention, only modified hydrotalcite is used as catalyst in the process according to the invention.
  • the modified hydrotalcites are calcined or hydrophobized hydrotalcites, such as those from the German patent applications DE-Al 38 43 713 and DE-Al 40 10 606 (Henkel) are known. Reference is expressly made to the cited documents and the disclosure of the cited documents with regard to hydrotalcites is regarded as part of the disclosure of the present text.
  • the calcined hydrotalcites are particularly preferably used in the process according to the invention.
  • modified hydrotalcites and selected cocatalysts are optionally used as catalysts together as alkoxylation catalysts.
  • 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 metal 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.
  • 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.
  • Such mixed metal oxides and their modification options are described, for example, in German Offenlegungsschrift DE-A-44 46 064, reference being expressly made to the publication mentioned and the disclosure thereof with regard to mixed metal oxides and their modification options being regarded as part of the disclosure of the present text ,
  • Magnesium oxide is particularly preferably used as cocatalyst in the context of the present invention.
  • the optionally modified hydrotalcites are the sole catalysts, they are usually used in amounts of 0.1 to 5, preferably in amounts of 0.5 to 1.5,% by weight, based on starting compounds (compounds with active hydrogen or carboxylic acid esters and alkylene oxide) are used.
  • the optionally modified hydrotalcites are used together with the selected cocatalysts, they are usually used in amounts of from 0.05 to 2.5 and in particular from 0.1 to 0.5% by weight, based on the starting compounds - used.
  • the cocatalysts can be used in amounts of 0.05 to 5, preferably in amounts of 0.1 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 or the carboxylic acid esters with the alkylene oxides can be carried out in a manner known per se at temperatures from 120 to 200 ° C., preferably 150 to 180 ° C. and pressures from 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 H-active compound or carboxylic acid ester.
  • alkylene oxides ethylene, propylene and / or butylene oxide can be used, preferably ethylene oxide.
  • the catalysts used which are insoluble in the reaction mixture, for example the possibly modified hydrotalcite, are separated from the reaction mixture obtained by a filtration process.
  • the water content of the reaction mixture is adjusted to a value of at least 1.5% by weight, but preferably above, for example at least 2% by weight, before carrying out the filtration.
  • Particularly suitable ranges for the water content are approximately 2.5 to approximately 30% by weight, in particular approximately 3 to approximately 15 or approximately 5 to approximately 12% by weight. If a water content of about 30% by weight is exceeded, this results in excellent filterability, but the economics of the process decrease significantly.
  • cellulose-containing materials commonly used for filtration processes are suitable as filtration aids.
  • wood flour, finely divided cellulose or Cellulose acetate used.
  • Suitable products are commercially available under the names Arbocel ®, Lignocell® or Primisil ® in various types.
  • the filtration aids are used in concentrations of about 0.1 to about 5, for example about 0.5 to about 2% by weight, based on the reaction product.
  • the filtration is carried out at temperatures above the cloud point of the alkoxylated compounds, preferably at temperatures of more than 50 ° C., for example at temperatures between 60 and 95 ° C. or between about 65 and about 80 ° C.
  • the process according to the invention can be followed by workup of the reaction product, for example removal of the water from the filtered reaction mixture.
  • alkoxylated compounds obtained by the processes according to the invention can be used without further purification. They are therefore suitable, for example, as nonionic surfactants for the production of washing, rinsing and cleaning agents and for the production of cleaning cosmetics, in particular of liquid products such as liquid textile detergents, hair shampoos and the like.
  • Example 2 1245 grams of a reaction product obtained in Example 1 were adjusted to a water content of 10% by weight and a temperature of 80 ° C. Subsequently, over 1% by weight (based on the total amount of reaction product) of Hyflo®, a filtration aid based on silicate, was filtered. The filtration time was 16 minutes and 40 seconds.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de production de tensioactifs alcoxylés non ioniques, qui consiste à faire réagir des composés contenant des atomes d'hydrogène actifs ou des esters d'acide carboxylique avec des oxydes d'alkylène en présence d'hydrotalcite éventuellement modifiée en tant que catalyseur et éventuellement de cocatalyseurs puis à effectuer un post-traitement aux acides.
PCT/EP2002/013692 2001-12-13 2002-12-04 Procede de production de composes alcoxyles Ceased WO2003053898A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10161350A DE10161350A1 (de) 2001-12-13 2001-12-13 Verfahren zur Herstellung alkoxylierter Verbindungen
DE10161350.4 2001-12-13

Publications (1)

Publication Number Publication Date
WO2003053898A1 true WO2003053898A1 (fr) 2003-07-03

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Application Number Title Priority Date Filing Date
PCT/EP2002/013692 Ceased WO2003053898A1 (fr) 2001-12-13 2002-12-04 Procede de production de composes alcoxyles

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DE (1) DE10161350A1 (fr)
WO (1) WO2003053898A1 (fr)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4101742A1 (de) * 1991-01-22 1992-07-23 Henkel Kgaa Verfahren zur herstellung von fettalkoholpolyalkylenglycolethern
DE4101740A1 (de) * 1991-01-22 1992-07-23 Henkel Kgaa Verfahren zur herstellung von fettalkoholpolyalkylenglycolethern
WO1992012951A1 (fr) * 1991-01-22 1992-08-06 Henkel Kommanditgesellschaft Auf Aktien Procede de preparation d'ethers de polyalkyleneglycol d'alcool gras
DE4110834A1 (de) * 1991-04-04 1992-10-08 Henkel Kgaa Verfahren zur herstellung von fettalkoholpolyalkylenglycolethern
DE4115149A1 (de) * 1991-05-08 1992-11-12 Henkel Kgaa Verfahren zur herstellung von fettalkoholpolyalkylenglycolethern
DE19505037A1 (de) * 1995-02-15 1996-08-22 Basf Ag Verfahren zur Herstellung von Alkoxylierungsprodukten mit verbesserter Filtrierbarkeit
US5723698A (en) * 1995-12-18 1998-03-03 Huntsman Specialty Chemicals Corporation Catalytic decomposition of formate impurities in tertiary butyl alcohol and methyl tertiary butyl ether streams
DE19909272A1 (de) * 1999-03-03 2000-09-07 Cognis Deutschland Gmbh Verfahren zur Herstellung alkoxylierter nichtionischer Tenside

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4101742A1 (de) * 1991-01-22 1992-07-23 Henkel Kgaa Verfahren zur herstellung von fettalkoholpolyalkylenglycolethern
DE4101740A1 (de) * 1991-01-22 1992-07-23 Henkel Kgaa Verfahren zur herstellung von fettalkoholpolyalkylenglycolethern
WO1992012951A1 (fr) * 1991-01-22 1992-08-06 Henkel Kommanditgesellschaft Auf Aktien Procede de preparation d'ethers de polyalkyleneglycol d'alcool gras
DE4110834A1 (de) * 1991-04-04 1992-10-08 Henkel Kgaa Verfahren zur herstellung von fettalkoholpolyalkylenglycolethern
DE4115149A1 (de) * 1991-05-08 1992-11-12 Henkel Kgaa Verfahren zur herstellung von fettalkoholpolyalkylenglycolethern
DE19505037A1 (de) * 1995-02-15 1996-08-22 Basf Ag Verfahren zur Herstellung von Alkoxylierungsprodukten mit verbesserter Filtrierbarkeit
US5723698A (en) * 1995-12-18 1998-03-03 Huntsman Specialty Chemicals Corporation Catalytic decomposition of formate impurities in tertiary butyl alcohol and methyl tertiary butyl ether streams
DE19909272A1 (de) * 1999-03-03 2000-09-07 Cognis Deutschland Gmbh Verfahren zur Herstellung alkoxylierter nichtionischer Tenside

Also Published As

Publication number Publication date
DE10161350A1 (de) 2003-06-26

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