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WO2003053898A1 - Method for producing alkoxylated compounds - Google Patents

Method for producing alkoxylated compounds 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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Prior art keywords
acid
compounds
reaction mixture
catalysts
alcohol
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PCT/EP2002/013692
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German (de)
French (fr)
Inventor
Ansgar Behler
Almud Folge
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Cognis Deutschland Gmbh & Co. Kg
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Publication of WO2003053898A1 publication Critical patent/WO2003053898A1/en

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    • 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

The invention relates to a method for producing alkoxylated, non-ionic surfactants according to which compounds having active hydrogen atoms or carboxylic acid esters are reacted with alkylene oxides in the presence of optionally modified hydrotalcite serving as a catalyst and optionally of co-catalysts and, afterwards, undergo a subsequent treatment with acids.

Description

Verfahren zur Herstellung alkoxylierter VerbindungenProcess for the preparation of alkoxylated compounds
Die Erfindung betrifft ein Nerfahren zur Herstellung alkoxylierter Verbindungen, bei dem man Verbindungen mit aktiven Wasserstoffatomen oder Carbonsäureester mit Alkylenoxiden in Gegenwart von festen, im Reaktionsgemisch nicht löslichen Katalysatoren, beispielsweise ggf. modifizierten Hydrotalciten oder festen, salzartigen Mg/ AI- Verbindungen als Katalysator sowie ggf. weiteren ausgewählten Co-Katalysatoren umsetzt und anschließend über ein cellulosehaltiges Filterhilfsmittel filtriert.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.
Eine wichtige Gruppe der nichtionischen Tenside stellen Anlagerungsprodukte von Alkylenoxiden, insbesondere Ethylenoxid und/oder Propylenoxid an Verbindungen mit aktivem Wasserstoff dar, die üblicherweise mittels homogener Katalyse in Gegenwart von Alkali- metallhydroxiden oder Alkalimetallalkoholaten hergestellt werden. Nach dem homogen katalysierten Verfahren werden Produkte mit einer breiten Homologenverteilung erhalten. Produkte mit eingeschränkter Homologenverteilung können erhalten werden, wenn die Umsetzung in Gegenwart fester Katalysatoren, beispielsweise in Gegenwart von ggf. modifizierten Hydrotalciten, beispielsweise gemäß der deutschen Offenlegungsschrift DE- A-3833076 oder in Gegenwart fester, salzartiger Mg/ AI- Verbindungen erfolgt. Auch die Alkoxylierung von Carbonsäureestem erfolgt mit besseren Erfolgen in Gegenwart von Hydrotalciten, wobei die Alkylenoxide in die Carbonylesterbindung eingelagert (Insertion) werden, beispielsweise gemäß den beiden Patentschriften EP-Bl- 0 339 425 und EP-Bl- 0 523 089.An important group of nonionic surfactants is 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. The alkoxylation of carboxylic acid esters also takes place with better success in the presence of hydrotalcites, the alkylene oxides being incorporated (insertion) into the carbonyl ester bond, for example according to the two patents EP-Bl-0 339 425 and EP-Bl-0 523 089.
Nach Durchfuhrung der eigentlichen Alkoxylierung unter Einsatz von ggf. modifiziertem Hydrotalcit bereitet jedoch die Abtrennung des Katalysators vom Reaktionsprodukt technische Schwierigkeiten, da der ggf. modifizierte Hydrotalcit oft so feinteilig ist, daß die Filtration nur über spezielle Filterkerzen gelingt. Ein Verbleiben des Katalysators im Reaktionsendprodukt ist indes auch nicht möglich, da es sonst zu Austrübungen und zu Sedimentationen kommen kann. Aus dem Stand der Technik sind verschiedene Verfahren bekannt, welche die Abtrennung eines festen, im Reaktionsgemisch nicht löslichen Katalysators aus dem Reaktionsgemisch betreffen.After carrying out the actual alkoxylation using possibly modified hydrotalcite, however, the separation of the catalyst from the reaction product presents technical difficulties, since the possibly modified hydrotalcite is often so finely divided that the filtration is only possible using special filter candles. However, it is also not possible for the catalyst to remain in the end product of the reaction, since otherwise clouding and sedimentation may occur. Various processes are known from the prior art which relate to the separation of a solid catalyst which is insoluble in the reaction mixture from the reaction mixture.
So beschreibt beispielsweise die WO 92/12951 ein Verfahren zur Herstellung von Fettalkoholpolyalkylenglykolethem, bei dem Fettalkohole in Gegenwart von Schichtverbindungen mit durchschnittlich 1 bis 20 Mol Ethylenoxid oder Propylenoxid pro Mol Fettalkohol umgesetzt, das Reaktionsprodukt mit einem Koagulierungsmittel und gegebenenfalls einer Base behandelt und das aus der Schichtverbindung und dem Koagulierungsmittel gebildete Koagulat gegebenenfalls in Gegenwart eines Filterhilfsmittels abgetrennt wird. Als Filterhilfsmittel werden Produkte auf Basis von Kieselgur, Holzmehl oder Cellulose genannt. Problematisch wirkt sich bei dem beschriebene Verfahren aus, daß zum Erreichen einer annehmbaren Filtrierbarkeit der Einsatz von Koagulierungsmitteln erforderlich ist. Darüber hinaus sind die gemäß dem in der Druckschrift angegebenen Verfahren erzielbaren Filtrationszeiten häufig für ein wirtschaftliches Verfahren zu lange.For example, 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. In addition, the filtration times that can be achieved according to the process specified in the publication are often too long for an economical process.
Die Aufgabe der vorliegenden Erfindung hat somit darin bestanden, ein Verfahren zur Herstellung von alkoxylierten Verbindungen zur Verfügung zu stellen, welches die aus dem Stand der Technik bekannten Nachteile einer aufwendigen und zeitraubenden Filtration nicht mehr aufweist.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.
Überraschenderweise konnte die Aufgabe der vorliegenden Erfindung dadurch gelöst werden, daß man das mindestens einen nicht im Reaktionsgemisch löslichen Katalysator enthaltende Reaktionsgemisch auf einen bestimmten Wassergehalt einstellt und anschließend über ein cellulosehaltiges Filterhilfsmittel filtriert.Surprisingly, 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.
Ein Gegenstand der vorliegenden Erfindung betrifft daher ein Verfahren zur Herstellung alkoxylierter Verbindungen durch Umsetzung von Verbindungen mit aktiven Wasserstoffatomen oder Carbonsäureestem mit Alkylenoxiden in Gegenwart von nicht im Reaktionsgemisch löslichen Katalysatoren, bei dem das Reaktionsgemisch nach der Alkoxylierung über ein Filterhilfsmittel filtriert wird, wobei das Filterhilfsmittel Cellulose enthält und das Reaktionsgemisch einen Wassergehalt von mindestens 1,5 Gew.-% aufweist.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 .-%.
Als Verbindungen mit aktiven Wasserstoffatomen kommen beispielsweise die folgenden Stoffklassen in Betracht:The following classes of substances are suitable as compounds with active hydrogen atoms:
al) Alkohole mit 6 bis 22 Kohlenstoffatomen (sogenannte Fettalkohole), wie z.B. Ca- pronalkohol, Caprylalkohol, Caprinalkohol, Laurylalkohol, Myristylalkohol, Cetyl- alkohol, Palmoleylalkohol, Stearylalkohol, Isostearylalkohol, Oleylalkohol, Elai- dylalkohol, Petroselinylalkohol, Linolylalkohol, Linolenylalkohol, Ricinolylalko- hol, Elaeostearylalkohol, Arachylalkohol, Gadoleylalkohol, Behenylalkohol, Erucylalkohol sowie deren technische Gemische, wie sie beispielsweise bei der Hydrierung von Methylesterfraktionen nativer Herkunft oder von Aldehyden aus der Roelen'schen Oxosynthese anfallen. Bevorzugt sind Fettalkohole mit 12 bis 18 Kohlenstoffatomen, beispielsweise technische Kokos- bzw. Talgfettalkoholschnitte.al) alcohols with 6 to 22 carbon atoms (so-called fatty alcohols), 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.
Als weitere Gruppe von Fettalkoholen kommen femer auch die sogenannten Guer- betalkohole in Betracht, die durch alkalisch katalysierte Kondensation von 2 Mol Fettalkohol hergestellt werden und 12 bis 36 Kohlenstoffatome enthalten können.The so-called 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.
a2) __ Carbonsäuren mit 6 bis 22 Kohlenstoffatomen (sogenannte Fettsäuren) und Hy- droxyfettsäuren, wie z.B. Capronsäure, Caprylsäure, Caprinsäure, Laurinsäure, My- ristinsäure, Palmitinsäure, Palmoleinsäure, Stearinsäure, Isostearinsäure, Ölsäure, Elaidinsäure, Petroselinsäure, Linolsäure, Linolensäure, Ricinolsäure, Elaeostearin- säure, Arachinsäure, Gadoleinsäure, Behensäure und Erucasäure sowie deren technische Gemische, wie sie beispielsweise bei der Druckspaltung von natürlichen Fetten und Ölen anfallen. Bevorzugt sind Fettsäuren mit 12 bis 18 Kohlenstoffatomen, beispielsweise technische Kokos- bzw. Taigfettsäuren.a2) __ 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.
a3) Alkylphenole, Polyglycole, Fettamine, vicinale hydroxy/alkoxysubstituierte Al- kane, die man beispielsweise durch Ringöffhung von Epoxyverbindungen mit Alkoholen oder Carbonsäuren erhalten kann, sowie sekundäre Alkohole. Innerhalb der Gruppe der Verbindungen mit aktiven Wasserstoffatomen werden die Alkohole oder Carbonsäuren mit 6 bis 22 Kohlenstoffatomen bevorzugt.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. Within the group of compounds with active hydrogen atoms, the alcohols or carboxylic acids with 6 to 22 carbon atoms are preferred.
Im Rahmen einer bevorzugten Ausführungsform des erfmdungsgemäßen Verfahrens werden als Ausgangsstoffe Carbonsäureester eingesetzt. Auch hier können grundsätzlich zwei Typen unterschieden werden:In a preferred embodiment of the process according to the invention, carboxylic acid esters are used as starting materials. There are two basic types:
bl) Carbonsäureniedrigalkylester der Formel (I),bl) carboxylic acid lower alkyl esters of the formula (I),
R^O-OR2 (I)R ^ O-OR 2 (I)
in der R CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen und R für einen linearen oder verzweigten Alkylrest mit 1 bis 4 Kohlenstoffatomen steht.in which 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.
Typische Beispiele sind Ester der Capronsäure, Caprylsäure, Caprinsäure, Laurinsäure, Myristinsäure, Palmitinsäure, Palmoleinsäure, Stearinsäure, Isostearinsäure, Ölsäure, Elaidinsäure, Petroselinsäure, Linolsäure, Linolensäure, Ricinolsäure, Elaeostearinsäure, Arachinsäure, Gadoleinsäure, Behensäure und Erucasäure sowie deren technische Gemische mit Methanol, Ethanol, Propanol oder Butanol. Vorzugsweise werden Methylester von Fettsäuren mit 12 bis 18 Kohlenstoffatomen und insbesondere technische Kokos- bzw. Talgfettsäuremethylester eingesetzt.Typical examples are esters of 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, arachic acid, and technical grade erasic acid, with behenic acid, with behenic acid, methanol , Ethanol, propanol or butanol. 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.
b2) Carbonsäureglycerinester der Formel (II),b2) carboxylic acid glycerol esters of the formula (II),
CH O-COR-CH O-COR
CH-O-R4 (π) CH-OR 4 (π)
CHoO-R~ in der R CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen undChoo-R ~ in the R CO for an aliphatic acyl radical having 6 to 22 carbon atoms and
R und R unabhängig voneinander für Wasserstoff oder ebenfalls einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen stehen.R and R independently of one another represent hydrogen or likewise an aliphatic acyl radical having 6 to 22 carbon atoms.
Typische Beispiele hierfür sind synthetische, vorzugsweise jedoch natürliche Triglyceride, wie Palmöl, Palmkernöl, Kokosöl, Rapsöl, Olivenöl, Sonnenblumenöl, Baumwollsaatöl, Erdnußöl, Leinöl, Lardöl, Rindertalg und Schweineschmalz. Vorzugsweise wird Ricinusöl bzw. gehärtetes Rizinusöl eingesetzt.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.
Im Rahmen des erfindungsgemäßen Verfahrens können anstelle der Vollester auch Fettsäurepartialglyceride, insbesondere Monoglyceride von Fettsäuren mit 12 bis 18 Kohlenstoffatomen eingesetzt. Besonders bevorzugt sind hier technische Ko- kosfettsäuremonoglyceride.In the process according to the invention, 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.
Innerhalb der Gruppe der Carbonsäureester werden zur Durchführung des erfindungsgemäßen Verfahrens Carbonsäureniedrigalkylester, insbesondere die Methylester der Carbonsäuren mit 6 bis 22 Kohlenstoffatomen bevorzugt, wobei als Reaktionsprodukte Alkylesterethoxylate, insbesondere Methylesterethoxylate erhalten werden.Within the group of carboxylic acid esters, 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.
Gemäß dem erfmdungsgemäßen Verfahren liegen im Rahmen des erfindungsgemäßen Verfahrens als Alkoxylierungskatalysatoren Verbindungen im Reaktionsgemisch vor, die im Reaktionsgemisch selbst nicht löslich sind. Dabei sind im Rahmen des erfmdungsgemäßen Verfahrens grundsätzlich alle derartigen, im Reaktionsgemisch nicht löslichen Katalysatoren geeignet. Im Rahmen einer bevorzugten Ausführungsform des erfmdungsgemäßen Verfahrens liegen im Reaktionsgemisch als Katalysatoren ggf. modifizierte Hydrotalcite alleine oder in Mischung mit ausgewählten Co-Katalysatoren vor. Einer Ausführungsform der vorliegenden Erfindung entsprechend wird ausschließlich ggf. modifizierter Hydrotalcit im Rahmen des erfindungsgemäßen Verfahrens als Katalysator eingesetzt. Als modifizierte Hydrotalcite werden calcinierte oder hydrophobierte Hydrotalcite, wie sie beispielsweise aus den deutschen Patentanmeldungen DE-Al 38 43 713 und DE-Al 40 10 606 (Henkel) bekannt sind, eingesetzt. Auf die genannten Druckschriften wird ausdrücklich Bezug genommen und die Offenbarung der genannten Druckschriften im Hinblick auf Hydrotalcite wird als Bestandteil der Offenbarung des vorliegenden Textes angesehen. Besonders bevorzugt werden im Rahmen des erfmdungsgemäßen Verfahrens die calcinierten Hydrotalcite eingesetzt.According to the process according to the invention, 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. In the context of a preferred embodiment 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.
Einer weiteren Ausführungsform der vorliegenden Erfindung entsprechend werden als Katalysatoren ggf. modifizierte Hydrotalcite und ausgewählte Co-Katalysatoren zusammen als Alkoxylierungskatalysatoren eingesetzt. Als Co-Katalysatoren eignen sich Ver- bindungen aus der Gruppe, die gebildet wird von Hydroxiden, Oxiden und/oder Alkoxiden von Alkali- und/oder Erdalkalimetallen sowie von Alkali- und/oder Erdalkalisalzen, Zinnsalzen und von Mischmetalloxiden.According to a further embodiment of the present 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.
Als Hydroxide von Alkali- und/oder Erdalkalihydroxiden eignen sich insbesondere Lithi- umhydroxid und/oder Magnesiumhydroxid.Particularly suitable hydroxides of alkali and / or alkaline earth metal hydroxides are lithium hydroxide and / or magnesium hydroxide.
Innerhalb der Gruppe der Oxide von Alkali- und/oder Erdalkalioxiden werden die Oxide des Magnesiums bevorzugt.Within the group of oxides of alkali and / or alkaline earth oxides, the oxides of magnesium are preferred.
Bevorzugte Alkoxide der Alkali- und/oder Erdalkalimetalle sind solche, die sich von kurz- kettigen Alkoholen, beispielsweise von solchen mit 1 bis 8 Kohlenstoffatomen und insbesondere von Methanol, Ethanol und/oder 2-Ethylhexanol ableiten. Hierbei sind die Magnesium- und/oder Bariumverbindungen besonders bevorzugt.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.
Innerhalb der Gmppe der Alkali- und/oder Erdalkalisalze sind die Magnesium- und Bariumsalze, beispielsweise die Carbonate wie Magnesiumcarbonat, oder die Acetate, beispielsweise Magnesiumacetat von besonderer Bedeutung.Within the group of alkali and / or alkaline earth salts, the magnesium and barium salts, for example the carbonates such as magnesium carbonate, or the acetates, for example magnesium acetate, are of particular importance.
Als Mischmetalloxide werden solche Oxidverbindungen bezeichnet, die mindestens zwei verschiedene Metalle enthalten. Bevorzugt ist eines der Metalle Magnesium. Das andereMixed metal oxides are oxide compounds that contain at least two different metals. One of the metals is preferably magnesium. The other
Metall kann Aluminium, Gallium, Zirkon, Indium, Thallium, Kobalt, Scandium, Lanthan und/oder Mangan sein. Besonders bevorzugt werden Magnesium/ Aluminiummischoxide. Die Mischoxide können oberflächlich modifiziert sein mit einem oder mehreren der bereits genannten Co-Katalysatoren, insbesondere mit den Hydroxiden und/oder Alkoxiden der Alkali- und/oder Erdalkalimetalle. Derartige Mischmetalloxide und deren Modifizie- rungsmöglichkeiten werden beispielsweise in der deutschen Offenlegungsschrift DE-A- 44 46 064 beschrieben, wobei auf die genannte Druckschrift ausdrücklich Bezug genommen wird und deren Offenbarung im Hinblick auf Mischmetalloxide und deren Modifizierungsmöglichkeiten als Bestandteil der Offenbarung des vorliegenden Textes betrachtet wird.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 ,
Besonders bevorzugt wird im Rahmen der vorliegenden Erfindung als Co-Katalysator Magnesiumoxid eingesetzt.Magnesium oxide is particularly preferably used as cocatalyst in the context of the present invention.
Sofern die ggf. modifizierten Hydrotalcite alleinige Katalysatoren sind, werden sie üblicherweise in Mengen von 0,1 bis 5, vorzugsweise in Mengen von 0,5 bis 1,5 Gew.% - be- zogen auf Ausgangsverbindungen (Verbindungen mit aktivem Wasserstoff bzw. Carbonsäureester und Alkylenoxid) eingesetzt.If 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.
Sofern die ggf. modifizierten Hydrotalcite zusammen mit den ausgewählten Co-Katalysatoren eingesetzt werden, werden sie üblicherweise in Mengen von 0,05 bis 2,5 und ins- besondere von 0,1 bis 0,5 Gew.-% - bezogen auf die Ausgangsverbindungen - eingesetzt. Die Co-Katalysatoren können in Mengen von 0,05 bis 5, vorzugsweise in Mengen von 0,1 bis 0,5 und insbesondere in Mengen von 0,1 bis 0,3 Gew.-% - bezogen auf die Ausgangsverbindungen - eingesetzt werden.If 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.
Aufgrund des synergistischen Effektes in der Aktivität als Katalysator zwischen ggf. modifiziertem Hydrotalcit und den Co-Katalysatoren ist es im Sinne der vorliegenden Erfindung sogar möglich, bei einer Gesamtmenge an Hydrotalcit und Co-Katalysatoren unter 0,5 Gew.-%, vorzugsweise bei Mengen zwischen 0,1 und 0,4 und insbesondere zwischen 0,2 und 0,3 Gew.-% - bezogen auf die Ausgangsverbindungen - sehr gute Ergebnisse zu erzielen. Das Verhältnis zwischen ggf. modifiziertem Hydrotalcit als Katalysator und Co-Katalysatoren kann in weiten Bereichen schwanken, vorzugsweise liegt das Gewichtsverhältnis zwischen 5 : 1 bis 1 : 5, insbesondere zwischen 3 : 1 und 1 : 3 und insbesondere bevorzugt zwischen 2 : 1 und 1 : 2.Because of the synergistic effect in the activity as a catalyst between possibly modified hydrotalcite and the co-catalysts, it is even possible in the sense of the present invention, with a total amount of hydrotalcite and co-catalysts below 0.5% by weight, preferably in amounts to achieve very good results between 0.1 and 0.4 and in particular between 0.2 and 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.
Die Umsetzung der Verbindungen mit aktiven Wasserstoffatomen bzw. der Carbonsäureester mit den Alkylenoxiden kann in an sich bekannter Weise bei Temperaturen von 120 bis 200 °C, vorzugsweise 150 bis 180 °C und Drücken von 1 bis 5 bar durchgeführt werden. Die Menge des anzulagernden Alkylenoxids ist dabei unkritisch und kann beispiels- weise 1 bis 100, vorzugsweise 2 bis 50 und insbesondere 2 bis 20 Mol Alkylenoxid pro Mol H-aktiver Verbindung bzw. Carbonsäureester betragen.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.
Als Alkylenoxide können Ethylen-, Propylen- und/oder Butylenoxid eingesetzt werden, vorzugsweise Ethylenoxid.As alkylene oxides, ethylene, propylene and / or butylene oxide can be used, preferably ethylene oxide.
Erfindungswesentlich ist nun, daß im Anschluß an die eigentliche Alkoxylierung die eingesetzten , im Reaktionsgemisch nicht löslichen Katalysatoren, beispielsweise der ggf. modifizierte Hydrotalcit, aus der erhaltenen Reaktionsmischung durch ein Filtrationsverfahren abgetrennt werden.It is essential to the invention that, after the actual alkoxylation, 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.
Für das erfindungsgemäße Verfahren wesentlich, daß vor der Durchführung der Filtration der Wassergehalt des Reaktionsgemischs auf einen Wert von mindestens 1,5 Gew.-%, vorzugsweise jedoch darüber, beispielsweise mindestens 2 Gew.-%, eingestellt wird. Besonders geeignete Bereiche für den Wassergehalt liegen bei etwa 2,5 bis etwa 30 Gew.- %, insbesondere bei etwa 3 bis etwa 15 oder etwa 5 bis etwa 12 Gew.-%. Wird ein Wassergehalt von etwa 30 Gew.-% überschritten, so resultiert daraus zwar eine ausgezeichnete Filtrierbarkeit, die Wirtschaftlichkeit des Verfahrens nimmt jedoch deutlich ab.It is essential for the process according to the invention that 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.
Als Filtrationshilfsmittel eignen sich grundsätzlich alle üblicherweise zu Filtrationsverfahren eingesetzten, cellulosehaltigen Materialien. Im Rahmen einer bevorzugten Ausführungsform wird insbesondere Holzmehl, feinteilige Cellulose oder Celluloseacetat eingesetzt. Geeignet Produkte sind unter den Namen Arbocel ®, Lignocell® oder Primisil ® in verschiedenen Typen kommerziell erhältlich. Die Filtrationshilfsmittel werden dabei in Konzentrationen von etwa 0,1 bis etwa 5, beispielsweise etwa 0,5 bis etwa 2 Gew.-%, bezogen auf das Reaktionsprodukt, eingesetzt.In principle, all cellulose-containing materials commonly used for filtration processes are suitable as filtration aids. In a preferred embodiment, in particular 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.
Es hat sich im Rahmen des erfindungsgemäßen Verfahrens darüber hinaus als vorteilhaft erwiesen, wenn die Filtration bei Temperaturen oberhalb des Trübungspunktes der alkoxylierten Verbindungen erfolgt, vorzugsweise bei Temperaturen von mehr als 50 °C, beispielsweise bei Temperaturen zwischen 60 und 95 °C oder zwischen etwa 65 und etwa 80 °C.In the process according to the invention, it has also proven to be advantageous if 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.
Falls gewünscht kann sich dem erfindungsgemäßen Verfahren eine Aufarbeitung des Reaktionsprodukts anschließen, beispielsweise eine Abtrennung des Wassers aus dem filtrierten Reaktionsgemisch.If desired, 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.
Die nach den erfindungsgemäßen Verfahren erhaltenen alkoxylierten Verbindungen sind ohne weitere Reinigung einsetzbar. Sie eignen sich daher beispielsweise als nichtionische Tenside zur Herstellung von Wasch-, Spül und Reinigungsmitteln und zur Herstellung von reinigender Kosmetika, insbesondere von flüssigen Produkten wie flüssigen Textilwaschmitteln, Haarshampoos und dergleichen.The 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.
Die Erfindung wird nachfolgend durch Beispiele näher erläutert.The invention is explained in more detail below by examples.
B e i s p i e l eB e i s p i e l e
Beispiel 1 (erfindungsgemäß)Example 1
300,9 g (entsprechend 1,06 Mol) eines Cl 6/18 -Methylesters wurden zusammen mit 3,0 g (entsprechend 1,0 Gew.-% - bezogen auf Ausgangsverbindungen) calciniertem Hydrotalcit in einem Druckbehälter vorgelegt. Der Behälter wurde 30 Minuten bei 100 °C evakuiert und anschließend mit Stickstoff belüftet. Bei max. 180 °C und max. 5 bar Druck erfolgte portionsweise die Zudosierung von 699,1 g (entsprechend 15,89 Mol) Ethylenoxid. Die Reaktionszeit betrag 120 Minuten. Nach Beendigung der Alkoxylierung wurde 30 min bei 120 °C nachreagiert und nochmals 30 Minuten bei 120 °C die Apparatur evakuiert. Der Reaktionsprodukt wurde anschließend durch Zugäbe von Wasser auf einen Wassergehalt von 10 Gew.-% eingestellt.300.9 g (corresponding to 1.06 mol) of a Cl 6/18 methyl ester together with 3.0 g (corresponding to 1.0% by weight, based on the starting compounds) of calcined hydrotalcite were placed in a pressure vessel. The container was evacuated at 100 ° C for 30 minutes and then vented with nitrogen. At max. 180 ° C and max. 5 bar pressure took place portions of 699.1 g (corresponding to 15.89 mol) of ethylene oxide are metered in. The response time was 120 minutes. After the alkoxylation had ended, the reaction was continued at 120 ° C. for 30 minutes and the apparatus was evacuated again at 120 ° C. for 30 minutes. The reaction product was then adjusted to a water content of 10% by weight by adding water.
1245 g des so eingestellte Reaktionsprodukts wurden anschließend auf eine Temperatur von 80 °C gebracht und über 1 Gew.-% (bezogen auf die Gesamtmenge an Reaktionsprodukt) Arbocel ® BC 200 filtriert. Die Filtrationszeit betrag 45 Sekunden.1245 g of the reaction product thus set were then brought to a temperature of 80 ° C. and Arbocel® BC 200 was filtered over 1% by weight (based on the total amount of reaction product). The filtration time was 45 seconds.
Beispiel 2 (nicht erfindungsgemäß)Example 2 (not according to the invention)
1245 Gramm eines gemäß Beispiel 1 erhaltenen Reaktionsprodukts wurden auf einen Wassergehalt von 10 Gew.-% und eine Temperatur von 80 °C eingestellt. Anschließend wurde über 1 Gew.-% (bezogen auf die Gesamtmenge an Reaktionsprodukt) Hyflo ®, ein Filtrationshilfsmittel auf Silikatbasis, filtriert. Die Filtrationszeit betrag 16 Minuten und 40 Sekunden.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.
Beispiel 3 (nicht erfindungsgemäfiExample 3 (not according to the invention
1245 Gramm eines gemäß Beispiel 1 erhaltenen Reaktionsprodukts wurden ohne Veränderung des Wassergehalts (Wassergehalt = 1 Gew..-%) auf eine Temperatur von 80 °C eingestellt. Anschließend wurde über 1 Gew.-% (bezogen auf die Gesamtmenge an Reaktionsprodukt) Arbocel®, ein Filtrationshilfsmittel auf Silikatbasis, filtriert. Die Filtrationszeit betrag 6 Minuten. 1245 grams of a reaction product obtained according to Example 1 were adjusted to a temperature of 80 ° C. without changing the water content (water content = 1% by weight). Then over 1% by weight (based on the total amount of reaction product) Arbocel®, a filtration aid based on silicate, was filtered. The filtration time was 6 minutes.

Claims

Patentansprüche claims
1. Verfahren zur Herstellung alkoxylierter Verbindungen durch Umsetzung von Verbindungen mit aktiven Wasserstoffatomen oder Carbonsäureestem mit Alkylenoxiden in Gegenwart von nicht im Reaktionsgemisch löslichen Katalysatoren, bei dem das Reaktionsgemisch nach der Alkoxylierung über ein Filterhilfsmittel filtriert wird, wobei das Filterhilfsmittel Cellulose enthält und das Reaktionsgemisch einen Wassergehalt von mindestens 1,5 Gew.-% aufweist.1. A process for the preparation of alkoxylated compounds by reacting compounds with active hydrogen atoms or carboxylic esters with alkylene oxides in the presence of catalysts which are not soluble in the reaction mixture, in which the reaction mixture is filtered after the alkoxylation through a filter aid, the filter aid containing cellulose and the reaction mixture having a water content of at least 1.5% by weight.
2. Verfahren nach Ansprach 1, dadurch gekennzeichnet, daß die Filtration bei einer Temperatur oberhalb des Trübungspunkts des entstandenen Produkts durchgeführt wird.2. The method according spoke 1, characterized in that the filtration is carried out at a temperature above the cloud point of the product formed.
3. Verfahren nach Ansprach 1, dadurch gekennzeichnet, daß das Reaktionsprodukt bei der Filtration einen Wassergehalt von 2 bis 15 Gew.-% aufweist.3. The method according spoke 1, characterized in that the reaction product in the filtration has a water content of 2 to 15 wt .-%.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß das Reaktionsgemisch als Katalysator einen Hydrotalcit oder ein Gemisch aus zwei oder mehr Hydrotalciten enthält.4. The method according to any one of claims 1 to 3, characterized in that the reaction mixture contains as a catalyst a hydrotalcite or a mixture of two or more hydrotalcites.
5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß es sich bei dem Reaktionsprodukt um ein Alkylesterethoxylat handelt.5. The method according to any one of claims 1 to 4, characterized in that the reaction product is an alkyl ester ethoxylate.
6. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß es sich bei dem Reaktionsprodukt um ein Methylesterethoxylat handelt. 6. The method according to any one of claims 1 to 4, characterized in that the reaction product is a methyl ester ethoxylate.
PCT/EP2002/013692 2001-12-13 2002-12-04 Method for producing alkoxylated compounds WO2003053898A1 (en)

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