EP1534426A1 - Multi-metal cyanide compounds - Google Patents

Multi-metal cyanide compounds

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Publication number
EP1534426A1
EP1534426A1 EP03790833A EP03790833A EP1534426A1 EP 1534426 A1 EP1534426 A1 EP 1534426A1 EP 03790833 A EP03790833 A EP 03790833A EP 03790833 A EP03790833 A EP 03790833A EP 1534426 A1 EP1534426 A1 EP 1534426A1
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EP
European Patent Office
Prior art keywords
multimetal cyanide
poly
catalysts
weight
cyanide compound
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.)
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Application number
EP03790833A
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German (de)
French (fr)
Inventor
Georg Heinrich Grosch
Edward Bohres
Raimund Ruppel
Kathrin Harre
Eva Baum
Michael Stösser
Jeffery T. Miller
Richard B. Prager
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BASF SE
Original Assignee
BASF SE
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Publication of EP1534426A1 publication Critical patent/EP1534426A1/en
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Classifications

    • B01J35/30—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B01J27/26—Cyanides
    • 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
    • C08G65/2642—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 characterised by the catalyst used
    • C08G65/2645—Metals or compounds thereof, e.g. salts
    • C08G65/2663—Metal cyanide catalysts, i.e. DMC's

Definitions

  • the invention relates to multimetal cyanide compounds which can be used in particular as catalysts for the ring-opening polymerization of alkylene oxides, a process for their preparation and their use as catalysts for the polymerization of alkylene oxides.
  • Multimetal cyanide catalysts also known as DMC catalysts, are effective catalysts for the production of polyetherols by ring-opening polymerization of alkylene oxides. Products of this type are used in industry, for example, as starting materials for the production of polyurethanes by reaction with polyisocyanates, as surface-active compounds or as carrier oils.
  • the DMC catalysts also have disadvantages. This can delay the start of the reaction when the reaction starts. This delay is often referred to as the induction period. Another disadvantage is the formation of very high molecular weight fractions in the polyether alcohol. These high molecular weight components can have a very disadvantageous effect on further processing into polyurethanes.
  • WO 99/16775 describes crystalline monoclinic DMC catalysts which have a higher catalytic activity than the previously preferred amorphous DMC catalysts. However, it has been shown that these catalysts also have an induction period that is still too long.
  • the object of the present invention was to provide crystalline DMC catalysts which are distinguished by an increased catalytic activity and, when used for the polymerization of alkylene oxides, the induction period is clearly suppressed
  • DMC catalysts which consist of at least 10% by weight of a crystalline monoclinic multimetal cyanide compound, have an X-ray diffractogram with sharp reflections at at least the d values
  • the invention accordingly relates to DMC catalysts which consist of at least 10% by weight, based on the weight of the DMC catalysts, of a crystalline multimetal cyanide compound whose X-ray diffractogram shows sharp reflections at at least the d values
  • the invention further relates to a process for the preparation of the DMC catalysts according to the invention and their use as catalysts for the polymerization of alkylene oxides.
  • the X-ray diffractograms were determined at a wavelength non 1.5406 A at room temperature.
  • the other multimetal cyanide compounds of the DMC catalysts according to the invention can be crystalline or amorphous, preferably crystalline.
  • they are multimetal cyanide compounds with the same empirical formula as the multimetal cyanide compounds with the structure described above.
  • the other multimetal cyanide compounds are crystalline and monoclinic.
  • the DMC catalyst can also consist entirely of the multimetal cyanide compound described in more detail above. With a content of less than 10% by weight of the multimetal cyanide compound characterized in more detail above, the positive effect of the compound on the catalytic properties of the DMC catalysts can only be demonstrated to a very small extent.
  • the multimetal cyanide compound characterized in more detail above has a monoclinic crystal system.
  • the unit cell of this monoclinic crystal system preferably has the following lattice parameters:
  • the monoclinic multimetal cyanide compound shows the following reflections:
  • the multimetal cyanide compounds according to the invention preferably have the general formula (I)
  • M 1 is a metal ion selected from the group containing Zn 2+ ,
  • M 2 is a metal ion selected from the group containing Fe 2+ , Fe 3+ , Co 2+ , Co 3+ , Mn 2+ , Mn 3+ , Ni 2+ V 4+ , V 5+ , Cr 2+ , Cr 3+ , Rh 3+ , Ru 2+ , Ir 3+ ,
  • A is an anion selected from the group consisting of halide, hydroxide, sulfate, carbonate, cyanide, thiocyanate, isocyanate, cyanate, carboxylate, oxalate or nitrate,
  • X is an anion selected from the group consisting of halide, hydroxide, sulfate, carbonate, cyanide, thiocyanate, isocyanate, cyanate, carboxylate, oxalate, nitrate or nitrite (N0 2 ⁇ ), and the uncharged species CO, H0 and NO,
  • a water-miscible ligand selected from the group comprising alcohols aldehydes, ketones, ethers, polyethers, esters, polyesters, polycarbonate, ureas, amides, nitriles and sulfides or mixtures thereof,
  • P is an organic additive selected from the group consisting of polyethers, polyesters, polycarbonates, polyalkylene glycol sorbitan esters, polyalkylene glycol glycidyl ethers, polyacrylamide, poly (acrylamide-co-acrylic acid), polyacrylic acid, poly (acrylamide-co-maleic acid), polyacrylonitrile, polyalkyl - acrylates, polyalkyl methacrylates, polyvinyl methyl ether, poly vinyl ethyl ether, polyvinyl acetate, polyvinyl alcohol, poly-N- vinyl pyrrolidone, poly (N-vinyl pyrrolidone-co-acrylic acid), poly-vinyl methyl ketone, poly (4-vinyl phenol), poly (acrylic acid-co-styrene), oxazoline polymers, polyalkyleneimines, maleic acid and maleic anhydride copolymer, hydroxyethyl cellulose, polyacetates, ionic surfaces
  • a, b, d, g and n are integer or fractional numbers greater than zero
  • c, f, e, h and k are integer or fractional numbers greater than zero
  • f and k may only be zero if c is non-zero and A is exclusively carboxylate, oxalate or nitrate.
  • an aqueous solution of a cyanometalate compound in particular a cyanometalate hydrogen acid or a cyanometalate salt
  • a metal salt of the general formula M ⁇ fXJ n the symbols having the meaning explained above, united.
  • a stoichiometric excess of the metal salt is used.
  • the molar ratio of the metal ion to the cyanometalate component is preferably from 1.1 to 7.0, preferably from 1.2 to 5.0 and particularly preferably from 1.3 to 3.0. It is advantageous to present the metal salt solution and add the cyanometalate compound, but the procedure can also be reversed. Thorough mixing, for example by stirring, is required during and after the starting material solutions have been combined.
  • the content of the cyanometalate compound in the aqueous solution is 0.1 to 30% by weight, preferably 0.1 to 20% by weight, in particular 0.2 to 10% by weight. %.
  • the content of the metal salt component in the metal salt solution is 0.1 to 50% by weight, preferably 0.2 to 40% by weight, in particular 0.5 to 30% by weight.
  • At least one of the aqueous solutions of the starting materials preferably contains a ligand containing heteroatoms, as it is designated and explained as L in the general formula (I).
  • the ligands containing heteroatoms can also be added to the resulting suspension only after the two starting material solutions have been combined, and here too thorough mixing must be ensured.
  • the content of the ligands containing heteroatoms, if such compounds are used, in the suspension formed after the precipitation should be 1 to 60% by weight, preferably 5 to 40% by weight, in particular 10 to 30% by weight.
  • the surface-active substances are already introduced in at least one of the two solutions.
  • the surface-active substances are preferably added to the solution which is initially introduced during the precipitation.
  • the content of surface-active substances in the precipitation solution is preferably between 0.01 and 40% by weight, in particular between 0.05 and 30% by weight.
  • Another preferred embodiment provides that the surface-active substances are distributed proportionally to both educt solutions.
  • the metal salt is reacted with the cyanometalate compound in two stages.
  • a catalytically inactive phase of the multimetal cyanide compound is first produced and this is subsequently converted into a catalytically active phase of the multimetal cyanide compound by recrystallization.
  • the recrystallization can be carried out by various measures. It is thus possible to add further reactant solutions, in particular the solution of the metal salt, to the suspension formed after the reaction. Another possibility is to change the temperature of the precipitation suspension after the precipitation has ended, in particular to heat the suspension. Another possibility is to add further heteroatoms containing ligands and / or surface-active substances to the precipitation suspension after the precipitation has ended. Another possibility is to change the pH of the precipitation suspension.
  • an in particular crystalline multimetal cyanide compound is first prepared, for example described in WO 99/16775. This can then be converted into the multimetal cyanide compound according to the invention in a further step, for example by thermal treatment, preferably in the presence of an inert gas.
  • the multimetal cyanide compound can be separated off from the precipitation suspension and dried.
  • the multimetal cyanide compound can also be subjected to the temperature treatment in the precipitation suspension.
  • the multimetal cyanide compound prepared by conventional processes can be added to the starter substance used for the production of the polyether alcohols and this mixture can be subjected to the temperature treatment, if appropriate under vacuum and / or by passing an inert gas through it.
  • the temperature treatment is preferably carried out at a temperature in the range between 90 and 200 ° C., in particular between 100 and 160 ° C.
  • polyether alcohols according to the invention takes place, as stated, by adding alkylene oxides to H-functional starter substances using the catalysts described.
  • alkylene oxides can be used as alkylene oxides, for example ethylene oxide, propylene oxide, butylene oxide, styrene oxide.
  • ethylene oxide, propylene oxide and mixtures of the compounds mentioned are used as alkylene oxides.
  • H-functional compounds are used as starting substances.
  • alcohols with a functionality of 1 to 8, preferably 2 to 8, are used.
  • the starting substances used are, in particular, alcohols with a functionality of 2 to 4, in particular 2 and 3.
  • examples are ethylene glycol, propylene glycol, glycerin, trimethylolpropane, pentaerythritol.
  • alkylene oxides are added by means of DMC catalysts, it is advantageous to use their reaction products with alkylene oxides, in particular propylene oxide, together with or instead of the alcohols mentioned.
  • Such compounds preferably have a molecular weight of up to 500 g / mol.
  • the addition of the alkylene oxides in the production of these reaction products can take place with any catalysts, for example with basic catalysts.
  • the polyether alcohols for the production of poly Flexible urethane foams mostly have a hydroxyl number in the range between 20 and 100 mgKOH / g.
  • the entire starter substance is introduced and the alkylene oxide is metered in after activation.
  • difunctional alcohols in particular are used as starter substances.
  • the starting substances used are, in particular, monofunctional alcohols having 5 to 20 carbon atoms in the main chain.
  • the addition of the alkylene oxides in the preparation of the polyether alcohols can be carried out by the known processes. It is possible that the polyether alcohols contain only one alkylene oxide. When using several alkylene oxides, a so-called blockwise addition, in which the alkylene oxides are added individually one after the other, or a so-called statistical addition, in which the alkylene oxides are metered in together, is possible. It is also possible to incorporate both block-by-block and statistical sections into the polyether chain in the production of the polyether alcohols. To produce surface-active compounds and carrier oils, the alkylene oxides are usually added in blocks.
  • Polyether alcohols with a high content of secondary hydroxyl groups and a content of ethylene oxide units in the polyether chain of at most 30% by weight, based on the weight of the polyether alcohol are preferably used for the production of flexible polyurethane foams.
  • These polyether alcohols preferably have a propylene oxide block at the chain end.
  • polyether alcohols with a high content of primary hydroxyl groups and an ethylene oxide end block in an amount of ⁇ 20% by weight, based on the weight of the polyether alcohol are used for the production of flexible molded polyurethane foams.
  • the alkylene oxides are added under the usual conditions, at temperatures in the range from 60 to 180 ° C., preferably between 90 to 140 ° C., in particular between 100 to 130 ° C. and pressures in the range from 0 to 20 bar, preferably in the range from 0 to 10 bar and especially in the range of 0 to 5 bar.
  • the mixture of starter substance and DMC catalyst can be pretreated by stripping before the start of the alkoxylation according to the teaching of WO 98/52689.
  • the polyether alcohol is worked up by customary processes in that the unreacted alkylene oxides and volatile constituents are removed, usually by distillation, steam or gas stripping and or other methods of deodorization. If necessary, filtration can also be carried out.
  • the polyether alcohols thus produced can be used, for example, for the production of polyurethanes, as surfactants or as carrier oils.
  • aqueous hexacyanocobaltoic acid (cobalt content: 9 g / 1 cobalt) were placed in a 2-1 reactor equipped with an inclined-blade turbine, dip tube for metering, pH electrode, conductivity measuring cell and scattered light probe and the mixture was brought to 50 with stirring ° C warmed. Then 588 g of aqueous zinc acetate dihydrate solution (zinc content:
  • a surface-active compound (Pluronic® PE 6200 from BASF Aktiengesellschaft) were added. The mixture was heated to 55 ° C. and further stirred at this temperature for twenty minutes. Then 189 g of aqueous zinc acetate Dihydrate solution (zinc content: 2.6% by weight) is metered in with stirring at 55 ° C. within 20 min. After a few minutes, the conductivity started to drop. The suspension was stirred at this temperature until the pH of the suspension had dropped from 4.03 to 3.41 and remained constant. The precipitate suspension thus obtained was filtered off and washed with about 600 ml of water. The catalyst obtained was then dried at 50 ° C. overnight.
  • a surface-active compound Pluronic® PE 6200 from BASF Aktiengesellschaft
  • the solid was heated from room temperature to 100 ° C. in the course of 2 hours, where it was heated at 100 ° C. for 1 hour. The temperature was then raised to 150 ° C. over a further hour and the solid was annealed at 150 ° C. for 3 hours. After the tempering was completed, the solid was cooled at a rate of 2 ° C./min.
  • the solid produced in this way was stored under an argon atmosphere.
  • the XRD spectrum of this catalyst recorded under a nitrogen atmosphere shows the formation of the new phase according to the invention as described above.
  • Example 2 0.225 g of dried DMC catalyst from Example 1 were introduced into a dry, 20-1 autoclave ventilated with nitrogen using Schlenk technology. Furthermore, 2796 g of dried tridekanol N stored in dry nitrogen were metered into the reactor via a metering line. The stirred autoclave was then heated to 120 ° C. with stirring and, using a vacuum pump, to an internal pressure of less than 20 mbar abs. evacuated. The autoclave was kept at these conditions for 1 h. The vacuum was then broken with nitrogen and the internal pressure in the autoclave to 1.2 bar abs. set.
  • the stirred autoclave was then heated to 150 ° C. 100 g of propylene oxide were metered in at a temperature of 150 ° C. and the reaction started. After 30 minutes, the start of the reaction was detected by the drop in pressure in the reactor. 10586 g of propylene oxide were then added at a temperature of 150 ° C. in the course of 7 hours. The catalyst fell asleep towards the end of the reaction. The unreacted propylene oxide was removed from the autoclave by means of vacuum.
  • the product produced had a viscosity of 40 mm 2 / s at a temperature of 40 ° C.
  • Example 2 0.225 g of dried DMC catalyst from Example 2 were introduced into a dry, 20-1 autoclave ventilated with nitrogen using Schlenk technology. Furthermore, 2796 g of dried tridekanol N stored in dry nitrogen were metered into the reactor via a metering line.
  • the stirred autoclave was then heated to 120 ° C. with stirring and, using a vacuum pump, to an internal pressure of less than 20 mbar abs. evacuated.
  • the autoclave was kept at these conditions.
  • the vacuum was then broken with nitrogen and the internal pressure in the autoclave to 1.2 bar abs. set.
  • the stirred autoclave was then heated to 150 ° C. 100 g of propylene oxide were metered in at a temperature of 150 ° C. and the reaction started. After 4 minutes, the start of the reaction was detected by the drop in pressure in the reactor. 12096 g of propylene oxide were then added at a temperature of 150 ° C. in the course of 4 hours. The propylene oxide reacted completely within 10 minutes after the end of the metering.
  • the product produced had a viscosity of 52 mm 2 / s at a temperature of 40 ° C.

Abstract

The invention relates to DMC catalysts consisting of at least 10 wt. %, (in relation to the weight of the DMC catalyst), of a crystalline multi-metal cyanide compound, whose X-ray diffractogram exhibits intense reflections at least at the d-values 11.4 Å ± 0.5 Å; 8.9 Å ± 0.5 Å; 6.3 Å ± 0.5 Å; 5.8 Å ± 0.5 Å; 5.5 Å ± 0.5 Å; 4.5 Å ± 0.5 Å; 4.4 Å ± 0.5 Å; 3.9 Å ± 0.4 Å; 3.7 Å ± 0.4 Å; 3.4 Å ± 0.4 Å.

Description

Multimetallcyanidverbindungenmultimetal
Beschreibungdescription
Die Erfindung betrifft Multimetallcyanidverbindungen, die insbesondere als Katalysatoren zur ringöffnenden Polymerisation von Alkylenoxiden eingesetzt werden können, ein Verfahren zu ihrer Herstellung sowie deren Verwendung als Katalysatoren für die Polymerisation von Alkylenoxiden.The invention relates to multimetal cyanide compounds which can be used in particular as catalysts for the ring-opening polymerization of alkylene oxides, a process for their preparation and their use as catalysts for the polymerization of alkylene oxides.
Multimetallcyanid-Katalysatoren, auch als DMC-Katalysatoren bezeichnet, sind effektive Katalysatoren zur Herstellung von Polyetherolen durch ring-öffnende Polymerisation von Alkylen- oxiden. Derartige Produkte finden in der Technik beispielsweise als Einsatzstoffe für die Herstellung von Polyurethanen durch Umsetzung mit Polyisocyanaten, als oberflächenaktive Verbindungen oder als Trägeröle Anwendung.Multimetal cyanide catalysts, also known as DMC catalysts, are effective catalysts for the production of polyetherols by ring-opening polymerization of alkylene oxides. Products of this type are used in industry, for example, as starting materials for the production of polyurethanes by reaction with polyisocyanates, as surface-active compounds or as carrier oils.
Durch die Verwendung von Multimetallcyanidverbindungen als Katalysatoren können Polyetheralkohole mit einem reduzierten Gehalt an ungesättigten Nebenprodukten hergestellt werden. Weiterhin ist die Reaktionsgeschwindigkeit bei der Anlagerung der Alkylenoxide gegenüber den gebräuchlichen basischen Katalysatoren und damit die Auslastung der Anlagen deutlich höher .By using multimetal cyanide compounds as catalysts, polyether alcohols with a reduced content of unsaturated by-products can be produced. Furthermore, the rate of reaction in the addition of the alkylene oxides to the common basic catalysts and thus the utilization of the plants is significantly higher.
Die DMC-Katalysatoren weisen jedoch auch Nachteile auf. So kann es beim Reaktionsstart zu einem verzögerten Anspringen der Reaktion kommen. Diese Verzögerung wird häufig auch als Induktionsperiode bezeichnet. Ein weiterer Nachteil ist die Bildung sehr hochmolekularer Anteile im Polyetheralkohol . Diese hochmolekularen Anteile können sich bei der Weiterverarbeitung zu Polyurethanen sehr nachteilig auswirken.However, the DMC catalysts also have disadvantages. This can delay the start of the reaction when the reaction starts. This delay is often referred to as the induction period. Another disadvantage is the formation of very high molecular weight fractions in the polyether alcohol. These high molecular weight components can have a very disadvantageous effect on further processing into polyurethanes.
Eine Möglichkeit, diese Nachteile zu überwinden, besteht in der Verbesserung der DMC-Katalysatoren. Im Stand der Technik wird eine große Zahl von Strukturen von DMC-Katalysatoren beschrieben.One way to overcome these disadvantages is to improve the DMC catalysts. A large number of structures of DMC catalysts are described in the prior art.
In WO 99/16775 werden kristalline monokline DMC-Katalysatoren beschrieben, die eine höhere katalytische Aktivität aufweisen als die bis dahin bevorzugten amorphen DMC-Katalysatoren. Es hat sich jedoch gezeigt, dass auch diese Katalysatoren eine noch zu lange Induktionsperiode aufweisen. Aufgabe der vorliegenden Erfindung war es, kristalline DMC- Katalysatoren bereitzustellen, die sich durch eine erhöhte katalytische Aktivität auszeichnen und bei deren Einsatz zur Polymerisation von Alkylenoxiden die Induktionsperiode deutlich unterdrückt wirdWO 99/16775 describes crystalline monoclinic DMC catalysts which have a higher catalytic activity than the previously preferred amorphous DMC catalysts. However, it has been shown that these catalysts also have an induction period that is still too long. The object of the present invention was to provide crystalline DMC catalysts which are distinguished by an increased catalytic activity and, when used for the polymerization of alkylene oxides, the induction period is clearly suppressed
Überraschenderweise wurde gefunden, dass DMC-Katalysatoren, die zu mindestens 10 Gew.-% aus einer kristallinen monoklinen Multi- metallcyanidverbindung bestehen, deren Röntgendiffraktogramm scharfe Reflexe bei mindestens den d-WertenSurprisingly, it was found that DMC catalysts, which consist of at least 10% by weight of a crystalline monoclinic multimetal cyanide compound, have an X-ray diffractogram with sharp reflections at at least the d values
11,4 Ä + 0,5 Ä 8,9 Ä + 0,5 Ä11.4 Ä + 0.5 Ä 8.9 Ä + 0.5 Ä
6.3 Ä + 0,5 Ä 5,8 Ä + 0,5 Ä6.3 Ä + 0.5 Ä 5.8 Ä + 0.5 Ä
5,5 Ä ± 0,5 Ä 4,5 Ä + 0,5 Ä5.5 Ä ± 0.5 Ä 4.5 Ä + 0.5 Ä
4.4 Ä + 0,5 Ä 3,9 Ä + 0,5 Ä 3,7 Ä + 0,5 Ä4.4 Ä + 0.5 Ä 3.9 Ä + 0.5 Ä 3.7 Ä + 0.5 Ä
3.4 Ä ± 0,5 Ä3.4 Ä ± 0.5 Ä
aufweist, eine besonders hohe katalytische Aktivität besitzen und die Anlagerung der Alkylenoxide unter Verwendung derartiger Katalysatoren nur eine kurze Induktionsperiode zeigt.has a particularly high catalytic activity and shows the addition of the alkylene oxides using such catalysts only a short induction period.
Gegenstand der Erfindung sind demzufolge DMC-Katalysatoren, die zu mindestens 10 Gew.-%, bezogen auf das Gewicht der DMC-Katalysatoren, aus einer kristallinen Multimetallcyanid- Verbindung bestehen, deren Röntgendiffraktogramm scharfe Reflexe bei mindestens den d-WertenThe invention accordingly relates to DMC catalysts which consist of at least 10% by weight, based on the weight of the DMC catalysts, of a crystalline multimetal cyanide compound whose X-ray diffractogram shows sharp reflections at at least the d values
11,4 Ä ± 0,5 Ä 8,9 Ä + 0,5 Ä 6,3 Ä + 0,5 Ä 5,8 Ä + 0,5 Ä11.4 Ä ± 0.5 Ä 8.9 Ä + 0.5 Ä 6.3 Ä + 0.5 Ä 5.8 Ä + 0.5 Ä
5.5 Ä + 0,5 Ä 4,5 A + 0,5 Ä 4,4 Ä + 0,5 Ä 3,9 Ä + 0,4 Ä 3,7 Ä + 0,4 Ä 3,4 Ä + 0,4 Ä5.5 Ä + 0.5 Ä 4.5 A + 0.5 Ä 4.4 Ä + 0.5 Ä 3.9 Ä + 0.4 Ä 3.7 Ä + 0.4 Ä 3.4 Ä + 0, 4 Ä
aufweist . Gegenstand der Erfindung sind weiterhin ein Verfahren zur Herstellung der erfindungsgemäßen DMC-Katalysatoren sowie deren Verwendung als Katalysatoren für die Polymerisation von Alkylenoxiden.having . The invention further relates to a process for the preparation of the DMC catalysts according to the invention and their use as catalysts for the polymerization of alkylene oxides.
Die Bestimmung der Röntgendiffraktogramme erfolgte bei einer Wellenlänge non 1,5406 A bei Raumtemperatur.The X-ray diffractograms were determined at a wavelength non 1.5406 A at room temperature.
Die übrigen Multimetallcyanidverbindungen der erfindungsgemäßen DMC-Katalysatoren können kristallin oder amorph, vorzugsweise kristallin sein. Insbesondere handelt es sich um Multimetallcyanidverbindungen mit der gleichen Summenformel wie die Multimetallcyanidverbindungen mit der oben beschriebenen Struktur. In einer besonderen Ausführungsform der Erfindung sind die übrigen Multimetallcyanidverbindungen kristallin und monoklin.The other multimetal cyanide compounds of the DMC catalysts according to the invention can be crystalline or amorphous, preferably crystalline. In particular, they are multimetal cyanide compounds with the same empirical formula as the multimetal cyanide compounds with the structure described above. In a special embodiment of the invention, the other multimetal cyanide compounds are crystalline and monoclinic.
Der DMC-Katalysator kann auch vollständig aus der oben näher beschriebenen Multimetallcyanidverbindung bestehen. Bei einem Gehalt unter 10 Gew.-% der oben näher charakterisierten Multi- metallcyanidverbindung ist der positive Effekt der Verbindung auf die katalytischen Eigenschaften der DMC-Katalysatoren nur noch in sehr geringem Maße nachweisbar.The DMC catalyst can also consist entirely of the multimetal cyanide compound described in more detail above. With a content of less than 10% by weight of the multimetal cyanide compound characterized in more detail above, the positive effect of the compound on the catalytic properties of the DMC catalysts can only be demonstrated to a very small extent.
In einer vorteilhaften Ausführungsform der erfindungsgemäßen DMC-Katalysatoren weist die oben näher charakterisierte Multimetallcyanidverbindung ein monoklines Kristallsystem auf. Die Elementarzelle dieses monoklinen Kristallsystems besitzt vorzugsweise folgende Gitterparameter:In an advantageous embodiment of the DMC catalysts according to the invention, the multimetal cyanide compound characterized in more detail above has a monoclinic crystal system. The unit cell of this monoclinic crystal system preferably has the following lattice parameters:
a= 12,4 Ä + 0,5 Ä b= 7,6 Ä ± 0,5 Ä c= 9,6 Ä + 0,5 Ä ß = 106,1° ±1°a = 12.4 Ä + 0.5 Ä b = 7.6 Ä ± 0.5 Ä c = 9.6 Ä + 0.5 Ä ß = 106.1 ° ± 1 °
In einer besonders bevorzugten Ausführungsform der erfindungsgemäßen DMC-Katalysatoren zeigen die monoklinen Multimetallcyanidverbindung folgende Reflexe:In a particularly preferred embodiment of the DMC catalysts according to the invention, the monoclinic multimetal cyanide compound shows the following reflections:
11,4 Ä + 0,5 Ä 8,9 Ä + 0,5 Ä 6,3 A + 0,5 Ä11.4 Ä + 0.5 Ä 8.9 Ä + 0.5 Ä 6.3 A + 0.5 Ä
5.8 Ä + 0,5 Ä 5,5 Ä + 0,5 A 4,5 Ä + 0,5 Ä 4,4 Ä + 0,5 Ä5.8 Ä + 0.5 Ä 5.5 Ä + 0.5 A 4.5 Ä + 0.5 Ä 4.4 Ä + 0.5 Ä
3.9 A + 0,4 Ä 3,7 A + 0,4 Ä 3,5 Ä + 0,5 Ä 3,4 A + 0,4 Ä 3,1 Ä ± 0,4 Ä 2,9 Ä + 0,3 A 2,41 Ä + 0,09 Ä 2,37 Ä + 0,09 Ä 2,31 Ä + 0,09 Ä 2,25 Ä + 0,09 Ä.3.9 A + 0.4 Ä 3.7 A + 0.4 Ä 3.5 Ä + 0.5 Ä 3.4 A + 0.4 Ä 3.1 Ä ± 0.4 Ä 2.9 Ä + 0.3 A 2.41 Ä + 0.09 Ä 2.37 Ä + 0.09 Ä 2.31 Ä + 0.09 Ä 2.25 Ä + 0.09 Ä.
Die erfindungsgemäßen Multimetallcyanidverbindungen haben vorzugsweise die allgemeine Formel (I)The multimetal cyanide compounds according to the invention preferably have the general formula (I)
Ml a[M2(CN)b(A)c]d-fM1 gXn-h(H20)-e -kP (I) ,M l a [M 2 (CN) b (A) c ] d -fM 1 g X n -h (H 2 0) -e -kP (I),
wobeiin which
M1 ein Metallion, ausgewählt aus der Gruppe, enthaltend Zn2+,M 1 is a metal ion selected from the group containing Zn 2+ ,
Fe +, Co3+, Ni2+, Mn2+, Co2+, Sn2+, Sn+, Pb2+, Mo +, Mo6+, Al3+, V4+, V5+, Sr2+, W4+, W6+, Cr2+, Cr3+, Cd2+, Cu2+, a3+,Fe + , Co 3+ , Ni 2+ , Mn 2+ , Co 2+ , Sn 2+ , Sn + , Pb 2+ , Mo + , Mo 6+ , Al 3+ , V 4+ , V 5+ , Sr 2+ , W 4+ , W 6+ , Cr 2+ , Cr 3+ , Cd 2+ , Cu 2+ , a 3+ ,
M2 ein Metallion, ausgewählt aus der Gruppe, enthaltend Fe2+, Fe3+, Co2+, Co3+, Mn2+, Mn3+ , Ni2+ V4+, V5+, Cr2+, Cr3+, Rh3+, Ru2+, Ir3+,M 2 is a metal ion selected from the group containing Fe 2+ , Fe 3+ , Co 2+ , Co 3+ , Mn 2+ , Mn 3+ , Ni 2+ V 4+ , V 5+ , Cr 2+ , Cr 3+ , Rh 3+ , Ru 2+ , Ir 3+ ,
bedeuten und M1 und M2 verschieden sind,mean and M 1 and M 2 are different,
A ein Anion, ausgewählt aus der Gruppe, enthaltend Halogenid, Hydroxyd, Sulfat, Carbonat, Cyanid, Thiocyanat, Isocyanat, Cyanat, Carboxylat, Oxalat oder Nitrat,A is an anion selected from the group consisting of halide, hydroxide, sulfate, carbonate, cyanide, thiocyanate, isocyanate, cyanate, carboxylate, oxalate or nitrate,
X ein Anion, ausgewählt aus der Gruppe, enthaltend Halogenid, Hydroxyd, Sulfat, Carbonat, Cyanid, Thiocyanat, Isocyanat, Cyanat, Carboxylat, Oxalat, Nitrat oder Nitrit (N02 ~) , sowie die ungeladene Spezies CO, H0 und NO,X is an anion selected from the group consisting of halide, hydroxide, sulfate, carbonate, cyanide, thiocyanate, isocyanate, cyanate, carboxylate, oxalate, nitrate or nitrite (N0 2 ~ ), and the uncharged species CO, H0 and NO,
ein mit Wasser mischbarer Ligand, ausgewählt aus der Gruppe, enthaltend Alkohole Aldehyde, Ketone, Ether, Polyether, Ester, Polyester, Polycarbonat, Harnstoffe, Amide, Nitrile, und Sulfide oder deren Mischungen,a water-miscible ligand selected from the group comprising alcohols aldehydes, ketones, ethers, polyethers, esters, polyesters, polycarbonate, ureas, amides, nitriles and sulfides or mixtures thereof,
P ein organischer Zusatzstoff, ausgewählt aus der Gruppe, enthaltend Polyether, Polyester, Polycarbonate , Polyalkylen- glykolsorbitanester, Polyalkylenglykolglycidylether , Poly- acrylamid, Poly (acrylamid-co-acrylsäure) , Polyacrylsäure, Poly (acrylamid-co-maleinsäure) , Polyacrylnitril , Polyalkyl- acrylate, Polyalkylmethacrylate, Polyvinylmethylether, Poly- vinylethylether, Polyvinylacetat, Polyvinylalkohol , Poly-N- vinylpyrrolidon, Poly (N-vinylpyrrolidon-co-acrylsäure) , Poly- vinylmethylketon, Poly (4-vinylphenol) , Poly (acrylsäure-co- styrol) , Oxazolinpolymere, Polyalkylenimine, Maleinsäure und Maleinsäureanhydridcopolymer, Hydroxyethylcellulose, Polyacetate, ionische Oberflächen und grenzflächenaktive Verbindungen, Gallensäure oder deren Salze, Ester oder Amide, Carbonsäureester mehrwertiger Alkohole und Glycoside bedeutet,P is an organic additive selected from the group consisting of polyethers, polyesters, polycarbonates, polyalkylene glycol sorbitan esters, polyalkylene glycol glycidyl ethers, polyacrylamide, poly (acrylamide-co-acrylic acid), polyacrylic acid, poly (acrylamide-co-maleic acid), polyacrylonitrile, polyalkyl - acrylates, polyalkyl methacrylates, polyvinyl methyl ether, poly vinyl ethyl ether, polyvinyl acetate, polyvinyl alcohol, poly-N- vinyl pyrrolidone, poly (N-vinyl pyrrolidone-co-acrylic acid), poly-vinyl methyl ketone, poly (4-vinyl phenol), poly (acrylic acid-co-styrene), oxazoline polymers, polyalkyleneimines, maleic acid and maleic anhydride copolymer, hydroxyethyl cellulose, polyacetates, ionic surfaces and surface-active compounds , Bile acid or its salts, esters or amides, carboxylic acid esters of polyhydric alcohols and glycosides,
sowiesuch as
a, b, d, g und n ganze oder gebrochene Zahlen größer null, c, f , e, h und k ganze oder gebrochene Zahlen größer gleich null sind,a, b, d, g and n are integer or fractional numbers greater than zero, c, f, e, h and k are integer or fractional numbers greater than zero,
wobeiin which
a, b, c,und d, sowie q und n so ausgewählt sind, dass die Elektroneutralität gewährleistet ist,a, b, c, and d, and q and n are selected so that electroneutrality is guaranteed,
Vorzugsweise dürfen f und k nur null sein, wenn c ungleich null ist und A ausschließlich Carboxylat, Oxalat oder Nitrat ist.Preferably, f and k may only be zero if c is non-zero and A is exclusively carboxylate, oxalate or nitrate.
Zur Herstellung der erfindungsgemäßen Multimetallcyanid- Verbindungen wird eine wässrige Lösung einer Cyanometallat- verbindung, insbesondere einer Cyanometallat-Wasserstoffsäure oder eines Cyanometallat-Salzes, mit der wässrigen Lösung eines Metallsalzes der allgemeinen Formel M^fXJn, wobei die Symbole die oben erläuterte Bedeutung haben, vereinigt. Hierbei wird mit einem stöchiometrischen Überschuss des Metallsalzes gearbeitet. Vorzugsweise wird mit einem molaren Verhältnis des Metallions zur Cyanometallat-Komponente von 1,1 bis 7,0, bevorzugt 1,2 bis 5,0 und besonders bevorzugt von 1,3 bis 3,0 gearbeitet. Es ist vorteilhaft, die Metallsalzlösung vorzulegen und die Cyanometallat- Verbindung zuzusetzen, es kann jedoch auch umgekehrt verfahren werden. Während und nach der Vereinigung der Eduktlösungen ist eine gute Durchmischung, beispielsweise durch Rühren, erforderlich.To produce the multimetal cyanide compounds according to the invention, an aqueous solution of a cyanometalate compound, in particular a cyanometalate hydrogen acid or a cyanometalate salt, is mixed with the aqueous solution of a metal salt of the general formula M ^ fXJ n , the symbols having the meaning explained above, united. Here, a stoichiometric excess of the metal salt is used. The molar ratio of the metal ion to the cyanometalate component is preferably from 1.1 to 7.0, preferably from 1.2 to 5.0 and particularly preferably from 1.3 to 3.0. It is advantageous to present the metal salt solution and add the cyanometalate compound, but the procedure can also be reversed. Thorough mixing, for example by stirring, is required during and after the starting material solutions have been combined.
Der Gehalt der Cyanometallat-Verbindung in der wässrigen Lösung, bezogen auf die Masse an wässriger Lösung, beträgt 0,1 bis 30 Gew.-%, bevorzugt 0,1 bis 20 Gew.-%, insbesondere 0,2 bis 10 Gew.-%. Der Gehalt der Metallsalzkomponente in der Metallsalzlösung, bezogen auf die Masse an Metallsalzlösung, beträgt 0,1 bis 50 Gew.-%, bevorzugt 0,2 bis 40 Gew.-%, insbesondere 0,5 bis 30 Gew.-%. Bevorzugt enthält mindestens eine der wässrigen Lösungen der Ausgangsstoffe einen Heteroatome enthaltenden Liganden, wie er in der allgemeinen Formel (I) als L bezeichnet und erläutert ist. Die Heteroatome enthaltenden Liganden können auch erst nach der Vereinigung der beiden Eduktlösungen zu der entstehenden Suspension gegeben werden, wobei auch hier auf eine gute Durchmischung zu achten ist .The content of the cyanometalate compound in the aqueous solution, based on the mass of aqueous solution, is 0.1 to 30% by weight, preferably 0.1 to 20% by weight, in particular 0.2 to 10% by weight. %. The content of the metal salt component in the metal salt solution, based on the mass of metal salt solution, is 0.1 to 50% by weight, preferably 0.2 to 40% by weight, in particular 0.5 to 30% by weight. At least one of the aqueous solutions of the starting materials preferably contains a ligand containing heteroatoms, as it is designated and explained as L in the general formula (I). The ligands containing heteroatoms can also be added to the resulting suspension only after the two starting material solutions have been combined, and here too thorough mixing must be ensured.
Der Gehalt der Heteroatome enthaltenden Liganden, sofern der- artige Verbindungen eingesetzt werden, in der nach der Fällung entstandenen Suspension sollte 1 bis 60 Gew.-%, vorzugsweise 5 bis 40 Gew.-%, insbesondere 10 bis 30 Gew.-% betragen.The content of the ligands containing heteroatoms, if such compounds are used, in the suspension formed after the precipitation should be 1 to 60% by weight, preferably 5 to 40% by weight, in particular 10 to 30% by weight.
Zur Einstellung der Morphologie der Multimetallcyanidverbindungen hat es sich bewährt, die Herstellung dieser Verbindungen in Gegenwart von oberflächenaktiven Substanzen durchzuführen. Die oberflächenaktiven Substanzen werden in der Regel bereits in mindestens einer der beiden Lösungen vorgelegt . Bevorzugt werden die oberflächenaktiven Substanzen in die Lösung gegeben, die bei der Fällung vorgelegt wird. Der Gehalt an oberflächenaktiven Substanzen in der Fälllösung bezogen auf die Gesamtmasse der Fällsuspension liegt vorzugsweise zwischen 0,01 und 40 Gew.-%, insbesondere zwischen 0,05 bis 30 Gew.-%. Eine weitere bevorzugte Ausführungsform sieht vor, die oberflächenaktiven Substanzen anteilig auf beide Eduktlösungen verteilt werden.To adjust the morphology of the multimetal cyanide compounds, it has proven useful to carry out the preparation of these compounds in the presence of surface-active substances. As a rule, the surface-active substances are already introduced in at least one of the two solutions. The surface-active substances are preferably added to the solution which is initially introduced during the precipitation. The content of surface-active substances in the precipitation solution, based on the total mass of the precipitation suspension, is preferably between 0.01 and 40% by weight, in particular between 0.05 and 30% by weight. Another preferred embodiment provides that the surface-active substances are distributed proportionally to both educt solutions.
Bei einer weiteren bevorzugten Ausführungsform der Herstellung der Multimetallcyanidverbindungen erfolgt die Umsetzung des Metallsalzes mit der Cyanometallatverbindung in zwei Stufen. Dabei wird zunächst eine katalytisch inaktive Phase der Multi- metallcyanidverbindung hergestellt und diese anschließend durch Umkristallisation in eine katalytisch aktive Phase der Multi- metallcyanidverbindung überführt. Die Umkristallisation kann durch verschiedene Maßnahmen erfolgen. So ist es möglich, der nach der Umsetzung entstehenden Suspension weitere Eduktlösungen, insbesondere die Lösung des Metallsalzes, zuzusetzen. Eine weitere Möglichkeit besteht darin, die Temperatur der Fällsuspension nach beendeter Fällung zu ändern, insbesondere die Suspension zu erwärmen. Eine weitere Möglichkeit besteht darin, der Fällsuspension nach beendeter Fällung weitere Heteroatome enthaltende Liganden und/oder oberflächenaktive Substanzen zuzusetzen. Eine weitere Möglichkeit besteht darin, den pH-Wert der Fällsuspension zu verändern.In a further preferred embodiment of the preparation of the multimetal cyanide compounds, the metal salt is reacted with the cyanometalate compound in two stages. In this case, a catalytically inactive phase of the multimetal cyanide compound is first produced and this is subsequently converted into a catalytically active phase of the multimetal cyanide compound by recrystallization. The recrystallization can be carried out by various measures. It is thus possible to add further reactant solutions, in particular the solution of the metal salt, to the suspension formed after the reaction. Another possibility is to change the temperature of the precipitation suspension after the precipitation has ended, in particular to heat the suspension. Another possibility is to add further heteroatoms containing ligands and / or surface-active substances to the precipitation suspension after the precipitation has ended. Another possibility is to change the pH of the precipitation suspension.
In einer besonders bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens wird zunächst eine insbesondere kristalline Multimetallcyanidverbindung hergestellt, wie beispielsweise in WO 99/16775 beschrieben. Diese kann dann in einem weiteren Schritt, beispielsweise durch eine Temperaturbehandlung, vorzugsweise in Anwesenheit eines Inertgases, in die erfindungsgemäße Multimetallcyanidverbindung umgewandelt werden.In a particularly preferred embodiment of the process according to the invention, an in particular crystalline multimetal cyanide compound is first prepared, for example described in WO 99/16775. This can then be converted into the multimetal cyanide compound according to the invention in a further step, for example by thermal treatment, preferably in the presence of an inert gas.
Zur Durchführung der Temperaturbehandlung kann die Multimetallcyanidverbindung aus der Fällsuspension abgetrennt und getrocknet werden. In einer Ausführungsform des Verfahrens kann die Multimetallcyanidverbindung auch in der Fällsuspension der Temperatur- behandlung unterzogen werden. In einer weiteren Ausführungsform des Verfahrens kann die nach herkömmlichen Verfahren hergestellte Multimetallcyanidverbindung zu der für die Herstellung der Poly- etheralkohole eingesetzten Startsubstanz zugegeben und diese Mischung, gegebenenfalls unter Vakuum und/oder unter Durchleiten eines Inertgases, der Temperaturbehandlung unterzogen werden.To carry out the temperature treatment, the multimetal cyanide compound can be separated off from the precipitation suspension and dried. In one embodiment of the method, the multimetal cyanide compound can also be subjected to the temperature treatment in the precipitation suspension. In a further embodiment of the process, the multimetal cyanide compound prepared by conventional processes can be added to the starter substance used for the production of the polyether alcohols and this mixture can be subjected to the temperature treatment, if appropriate under vacuum and / or by passing an inert gas through it.
Die Temperaturbehandlung wird vorzugsweise bei einer Temperatur im Bereich zwischen 90 und 200°C, insbesondere zwischen 100 und 160°C vorgenommen.The temperature treatment is preferably carried out at a temperature in the range between 90 and 200 ° C., in particular between 100 and 160 ° C.
Die erfindungsgemäße Herstellung von Polyetheralkoholen erfolgt, wie ausgeführt, indem man Alkylenoxide unter Verwendung der beschriebenen Katalysatoren an H-funktionelle Startsubstanzen anlagert .The production of polyether alcohols according to the invention takes place, as stated, by adding alkylene oxides to H-functional starter substances using the catalysts described.
Als Alkylenoxide können alle bekannten Alkylenoxide verwendet werden, beispielsweise Ethylenoxid, Propylenoxid, Butylenoxid, Styroloxid. Insbesondere werden als Alkylenoxide Ethylenoxid, Propylenoxid und Mischungen aus den genannten Verbindungen ein- gesetzt.All known alkylene oxides can be used as alkylene oxides, for example ethylene oxide, propylene oxide, butylene oxide, styrene oxide. In particular, ethylene oxide, propylene oxide and mixtures of the compounds mentioned are used as alkylene oxides.
Als Startsubstanzen kommen H-funktionelle Verbindungen zum Einsatz. Insbesondere werden Alkohole mit einer Funktionalität von 1 bis 8, vorzugsweise 2 bis 8, eingesetzt. Zur Herstellung von Polyetheralkoholen, die für Polyurethan-Weichschaumstoffe eingesetzt werden, kommen als Startsubstanzen insbesondere Alkohole mit einer Funktionalität von 2 bis 4, insbesondere von 2 und 3, zum Einsatz. Beispiele sind Ethylenglykol, Propylenglykol, Glyzerin, Trimethylolpropan, Pentaerythrit . Bei der Anlagerung der Alkylenoxide mittels DMC-Katalysatoren ist es vorteilhaft, zusammen mit oder an Stelle von den genannten Alkoholen deren Umsetzungsprodukte mit Alkylenoxiden, insbesondere Propylenoxid, einzusetzen. Derartige Verbindungen haben vorzugsweise eine Molmasse bis 500 g/mol. Die Anlagerung der Alkylenoxide bei der Herstellung dieser Umsetzungsprodukte kann mit beliebigen Katalysatoren erfolgen, beispielsweise mit basischen Katalysatoren. Die Polyetheralkohole für die Herstellung von Poly- urethan-Weichschaumstoffen haben zumeist eine Hydroxylzahl im Bereich zwischen 20 und 100 mgKOH/g.H-functional compounds are used as starting substances. In particular, alcohols with a functionality of 1 to 8, preferably 2 to 8, are used. For the production of polyether alcohols which are used for flexible polyurethane foams, the starting substances used are, in particular, alcohols with a functionality of 2 to 4, in particular 2 and 3. Examples are ethylene glycol, propylene glycol, glycerin, trimethylolpropane, pentaerythritol. When the alkylene oxides are added by means of DMC catalysts, it is advantageous to use their reaction products with alkylene oxides, in particular propylene oxide, together with or instead of the alcohols mentioned. Such compounds preferably have a molecular weight of up to 500 g / mol. The addition of the alkylene oxides in the production of these reaction products can take place with any catalysts, for example with basic catalysts. The polyether alcohols for the production of poly Flexible urethane foams mostly have a hydroxyl number in the range between 20 and 100 mgKOH / g.
Im allgemeinen wird die gesamte Startsubstanz vorgelegt und nach der Aktivierung das Alkylenoxid zudosiert .In general, the entire starter substance is introduced and the alkylene oxide is metered in after activation.
In einer besonderen Ausführungsform der Herstellung von Polyetheralkoholen wird nur ein Teil der Startsubstanz am Anfang vorgelegt und die Reaktion durch Zugabe von Alkylenoxid gestartet . Danach wird zumindest während eines Teils der Umsetzung weitere Startsubstanz sowie Alkylenoxid zudosiert. Diese Verfahrensweise ist beispielsweise in EP 879 259 beschrieben. Durch diese Ausgestaltung des Verfahrens kann die Bildung sehr hochmolekularer Anteile im Polyetheralkohol unterdrückt werden.In a special embodiment of the production of polyether alcohols, only a part of the starting substance is initially introduced and the reaction is started by adding alkylene oxide. Thereafter, further starting substance and alkylene oxide are metered in at least during part of the reaction. This procedure is described for example in EP 879 259. This configuration of the method can suppress the formation of very high molecular weight fractions in the polyether alcohol.
Zur Herstellung von oberflächenaktiven Verbindungen werden als Startsubstanzen insbesondere difunktionelle Alkohole eingesetzt. Zur Herstellung von Trägerölen werden als Startsubstanzen insbesondere monofunktioneile Alkohole mit 5 bis 20 Kohlenstoffatome in der Hauptkette eingesetzt .In order to produce surface-active compounds, difunctional alcohols in particular are used as starter substances. To produce carrier oils, the starting substances used are, in particular, monofunctional alcohols having 5 to 20 carbon atoms in the main chain.
Die Anlagerung der Alkylenoxide bei der Herstellung der Poly- etheralkohole kann nach den bekannten Verfahren erfolgen. So ist es möglich, dass die Polyetheralkohole nur ein Alkylenoxid enthalten. Bei Verwendung von mehreren Alkylenoxiden ist eine sogenannte blockweise Anlagerung, bei der die Alkylenoxide einzeln nacheinander angelagert werden, oder eine sogenannte statistische Anlagerung, bei der die Alkylenoxide gemeinsam zudosiert werden, möglich. Es ist auch möglich, bei der Herstellung der Polyether- alkohole sowohl blockweise als auch statistische Abschnitte in die Polyetherkette einzubauen. Zur Herstellung von oberflächenaktiven Verbindungen und Trägerölen erfolgt die Anlagerung der Alkylenoxide zumeist blockweise.The addition of the alkylene oxides in the preparation of the polyether alcohols can be carried out by the known processes. It is possible that the polyether alcohols contain only one alkylene oxide. When using several alkylene oxides, a so-called blockwise addition, in which the alkylene oxides are added individually one after the other, or a so-called statistical addition, in which the alkylene oxides are metered in together, is possible. It is also possible to incorporate both block-by-block and statistical sections into the polyether chain in the production of the polyether alcohols. To produce surface-active compounds and carrier oils, the alkylene oxides are usually added in blocks.
Vorzugsweise werden zur Herstellung von Polyurethan-Blockweichschaumstoffen Polyetheralkohole mit einem hohen Gehalt an sekundären Hydroxylgruppen und einem Gehalt an Ethylenoxid- einheiten in der Polyetherkette von maximal 30 Gew.-%, bezogen auf das Gewicht des Polyetheralkohols, verwendet. Vorzugsweise haben diese Polyetheralkohole am Kettenende einen Propylenoxid- block. Für die Herstellung von Polyurethan-Formweichschaumstoffen werden insbesondere Polyetheralkohole mit einem hohen Gehalt an primären Hydroxylgruppen und einem Ethylenoxid-Endblock in einer Menge von < 20 Gew.-%, bezogen auf das Gewicht des Polyether- alkohols, verwendet. Die Anlagerung der Alkylenoxide erfolgt bei den üblichen Bedingungen, bei Temperaturen im Bereich von 60 bis 180°C, bevorzugt zwischen 90 bis 140°C, insbesondere zwischen 100 bis 130°C und Drücken im Bereich von 0 bis 20 bar, bevorzugt im Bereich von 0 bis 10 bar und insbesondere im Bereich von 0 bis 5 bar. Die Mischung aus Startsubstanz und DMC-Katalysator kann vor Beginn der Alkoxylierung gemäß der Lehre von WO 98/52689 durch Strippen vorbehandelt werden.Polyether alcohols with a high content of secondary hydroxyl groups and a content of ethylene oxide units in the polyether chain of at most 30% by weight, based on the weight of the polyether alcohol, are preferably used for the production of flexible polyurethane foams. These polyether alcohols preferably have a propylene oxide block at the chain end. In particular, polyether alcohols with a high content of primary hydroxyl groups and an ethylene oxide end block in an amount of <20% by weight, based on the weight of the polyether alcohol, are used for the production of flexible molded polyurethane foams. The alkylene oxides are added under the usual conditions, at temperatures in the range from 60 to 180 ° C., preferably between 90 to 140 ° C., in particular between 100 to 130 ° C. and pressures in the range from 0 to 20 bar, preferably in the range from 0 to 10 bar and especially in the range of 0 to 5 bar. The mixture of starter substance and DMC catalyst can be pretreated by stripping before the start of the alkoxylation according to the teaching of WO 98/52689.
Nach Beendigung der Anlagerung der Alkylenoxide wird der Poly- etheralkohol nach üblichen Verfahren aufgearbeitet, indem die nicht umgesetzten Alkylenoxide sowie leicht flüchtige Bestandteile entfernt werden, üblicherweise durch Destillation, Wasserdampf- oder Gasstrippen und oder anderen Methoden der Desodorierung. Falls erforderlich, kann auch eine Filtration erfolgen.After the addition of the alkylene oxides has ended, the polyether alcohol is worked up by customary processes in that the unreacted alkylene oxides and volatile constituents are removed, usually by distillation, steam or gas stripping and or other methods of deodorization. If necessary, filtration can also be carried out.
Die so hergestellten Polyetheralkohole können beispielsweise zur Herstellung von Polyurethanen, als Tenside oder als Trägeröle verwendet werden.The polyether alcohols thus produced can be used, for example, for the production of polyurethanes, as surfactants or as carrier oils.
Durch die Verwendung der erfindungsgemäßen DMC-Katalysatoren können überraschenderweise Polyetheralkohole hergestellt werden, die sehr gute Eigenschaften aufweisen. Insbesondere wird die Induktionszeit am Reaktionsstart deutlich verringert.By using the DMC catalysts according to the invention, it is surprisingly possible to produce polyether alcohols which have very good properties. In particular, the induction time at the start of the reaction is significantly reduced.
Die Erfindung soll an den nachstehenden Beispielen näher erläutert werden.The invention is illustrated by the examples below.
Katalysatorherstellungcatalyst Preparation
Beispiel 1 (Vergleich)Example 1 (comparison)
Herstellung des DMC-Katalysators gemäß WO 99/16775Production of the DMC catalyst according to WO 99/16775
In einem 2-1-Reaktor, ausgestattet mit einer Schrägblattturbine, Tauchrohr für die Dosierung, pH-Elektrode, Leitfähigkeitmesszelle und Streulicht-Sonde, wurden 1000 g wässrige Hexacyanocobaltsäure (Cobalt-Gehalt : 9 g/1 Cobalt) vorgelegt und unter Rühren auf 50°C erwärmt. Anschließend wurden unter Rühren (Rührleistung 1 W/1) 588 g wässrige Zinkacetat-Dihydrat-Lösung (Zinkgehalt:1000 g of aqueous hexacyanocobaltoic acid (cobalt content: 9 g / 1 cobalt) were placed in a 2-1 reactor equipped with an inclined-blade turbine, dip tube for metering, pH electrode, conductivity measuring cell and scattered light probe and the mixture was brought to 50 with stirring ° C warmed. Then 588 g of aqueous zinc acetate dihydrate solution (zinc content:
2,6 Gew.-%), welche ebenfalls auf 50°C temperiert war, innerhalb von 45 min zugefahren.2.6% by weight), which was also heated to 50 ° C., within 45 minutes.
Nach der Zugabe wurden 20 g einer oberflächenaktiven Verbindung (Pluronic® PE 6200 der BASF Aktiengesellschaft) zugegeben. Der Ansatz wurde auf 55°C erhitzt und für zwanzig Minuten bei dieser Temperatur weiter gerührt. Dann wurden 189 g wässrige Zinkacetat- Dihydrat-Lösung (Zinkgehalt: 2,6 Gew.-%) unter Rühren 55°C innerhalb 20 min zudosiert. Nach wenigen Minuten begann die Leitfähigkeit zu fallen. Die Suspension wurde bei dieser Temperatur solange nachgerührt, bis der pH-Wert der Suspension von 4,03 auf 3,41 gefallen war und konstant blieb. Die so erhaltene Fällsuspension wurde abfiltriert und mit ca. 600 ml Wasser gewaschen. Der erhaltene Katalysator wurde dann über Nacht bei 50°C getrocknet.After the addition, 20 g of a surface-active compound (Pluronic® PE 6200 from BASF Aktiengesellschaft) were added. The mixture was heated to 55 ° C. and further stirred at this temperature for twenty minutes. Then 189 g of aqueous zinc acetate Dihydrate solution (zinc content: 2.6% by weight) is metered in with stirring at 55 ° C. within 20 min. After a few minutes, the conductivity started to drop. The suspension was stirred at this temperature until the pH of the suspension had dropped from 4.03 to 3.41 and remained constant. The precipitate suspension thus obtained was filtered off and washed with about 600 ml of water. The catalyst obtained was then dried at 50 ° C. overnight.
Zusammensetzung:Composition:
Co: 12,8 Gew.%; Zn: 28,7 Gew.%Co: 12.8% by weight; Zn: 28.7% by weight
Eine röntgenographische Untersuchung dieses Katalysators zeigt die in WO 99/16775 angegeben Röntgendiffraktogramm ReflexeAn X-ray examination of this catalyst shows the X-ray diffractogram reflections specified in WO 99/16775
Beispiel 2 (Erfindungsgemäß)Example 2
10 g des oben hergestellten Feststoffs wurden in einem Schlenk- gefäß vorgelegt. Der Feststoff wurde dann unter einem Strom trockenem Stickstoff (Stickstoffström: 20 1/h) folgender Temperaturbehandlung unterzogen:10 g of the solid prepared above were placed in a Schlenk vessel. The solid was then subjected to the following temperature treatment under a stream of dry nitrogen (nitrogen flow: 20 l / h):
Innerhalb von 2 h wurde der Feststoff von Raumtemperatur auf 100°C hochgeheizt und dort lh bei 100°C tempert. Anschließend wurde die Temperatur innerhalb einer weiteren Stunde auf 150°C angehoben und der Feststoff bei 150°C 3 h lang getempert. Nach Abschluss der Temperung wurde der Feststoff mit einer Rate von 2°C/min abgekühlt .The solid was heated from room temperature to 100 ° C. in the course of 2 hours, where it was heated at 100 ° C. for 1 hour. The temperature was then raised to 150 ° C. over a further hour and the solid was annealed at 150 ° C. for 3 hours. After the tempering was completed, the solid was cooled at a rate of 2 ° C./min.
Der so erzeugte Feststoff wurde unter Argonatmosphäre aufbewahrt. Das unter Stickstoffatmosphäre aufgenommenen XRD-Spektrum dieses Katalysators zeigt die Bildung der erfindungsgemäßen neuen Phase wie oben beschrieben.The solid produced in this way was stored under an argon atmosphere. The XRD spectrum of this catalyst recorded under a nitrogen atmosphere shows the formation of the new phase according to the invention as described above.
Herstellung von Trägerölen mittels DMCManufacture of carrier oils using DMC
Beispiel 3 (Vergleich)Example 3 (comparison)
Herstellung von Trägeröl mittels DMCProduction of carrier oil using DMC
In einen trockenen, mit Stickstoff beatmeten 20-1-Autoklaven wurden mittels Schlenktechnik 0,225 g getrockneter DMC-Kataly- sator aus Beispiel 1 eingefüllt . Ferner wurden in den Reaktor über eine Dosierleitung 2796 g getrocknetes und unter trockenem Stickstoff gelagertes Tridekanol N dosiert. Der gerührte Autoklav wurde anschließend unter Rühren auf 120°C hochgeheizt und mittels einer Vakuumpumpe auf einen Innendruck kleiner 20 mbar abs. evakuiert. Der Autoklav wurde 1 h bei diesen Bedingungen gehalten. Anschließend wurde das Vakuum mit Stick- stoff gebrochen und der Innendruck im Autoklav auf 1,2 bar abs. eingestellt.0.225 g of dried DMC catalyst from Example 1 were introduced into a dry, 20-1 autoclave ventilated with nitrogen using Schlenk technology. Furthermore, 2796 g of dried tridekanol N stored in dry nitrogen were metered into the reactor via a metering line. The stirred autoclave was then heated to 120 ° C. with stirring and, using a vacuum pump, to an internal pressure of less than 20 mbar abs. evacuated. The autoclave was kept at these conditions for 1 h. The vacuum was then broken with nitrogen and the internal pressure in the autoclave to 1.2 bar abs. set.
Der gerührte Autoklav wurde anschließend auf 150°C hochgeheizt. Bei einer Temperatur von 150°C wurden 100 g Propylenoxid dosiert und das Anspringen der Reaktion abgewartet. Nach 30 min wurde durch den Abfall des Druckes im Reaktor das Anspringen der Reaktion detektiert. Daraufhin wurden innerhalb 7 h 10586 g an Propylenoxid bei einer Temperatur von 150°C zugefahren. Der Katalysator schlief gegen Ende der Reaktion ein. Das nicht reagierte Propylenoxid wurde mittels Vakuum aus dem Autoklaven entfernt.The stirred autoclave was then heated to 150 ° C. 100 g of propylene oxide were metered in at a temperature of 150 ° C. and the reaction started. After 30 minutes, the start of the reaction was detected by the drop in pressure in the reactor. 10586 g of propylene oxide were then added at a temperature of 150 ° C. in the course of 7 hours. The catalyst fell asleep towards the end of the reaction. The unreacted propylene oxide was removed from the autoclave by means of vacuum.
Es wurden 13281 g an Produkt gewonnen. Das hergestellte Produkt hatte eine Viskosität von 40 mm2/s bei einer Temperatur von 40°C.13281 g of product were obtained. The product produced had a viscosity of 40 mm 2 / s at a temperature of 40 ° C.
Beispiel 4 (Erfindungsgemäß) Herstellung von Trägeröl mittels DMCExample 4 (According to the Invention) Production of Carrier Oil Using DMC
In einen trockenen, mit Stickstoff beatmeten 20-1-Autoklaven wurden mittels Schlenktechnik 0,225 g getrockneter DMC-Kataly- sator aus Beispiel 2 eingefüllt. Ferner wurden in den Reaktor über eine Dosierleitung 2796 g getrocknetes und unter trockenem Stickstoff gelagertes Tridekanol N dosiert.0.225 g of dried DMC catalyst from Example 2 were introduced into a dry, 20-1 autoclave ventilated with nitrogen using Schlenk technology. Furthermore, 2796 g of dried tridekanol N stored in dry nitrogen were metered into the reactor via a metering line.
Der gerührte Autoklav wurde anschließend unter Rühren auf 120°C hochgeheizt und mittels einer Vakuumpumpe auf einen Innendruck kleiner 20 mbar abs. evakuiert. Der Autoklav wurde lh bei diesen Bedingungen gehalten. Anschließend wurde das Vakuum mit Stickstoff gebrochen und der Innendruck im Autoklav auf 1,2 bar abs. eingestellt.The stirred autoclave was then heated to 120 ° C. with stirring and, using a vacuum pump, to an internal pressure of less than 20 mbar abs. evacuated. The autoclave was kept at these conditions. The vacuum was then broken with nitrogen and the internal pressure in the autoclave to 1.2 bar abs. set.
Der gerührte Autoklav wurde anschließend auf 150°C hochgeheizt. Bei einer Temperatur von 150°C wurden 100 g Propylenoxid dosiert und das Anspringen der Reaktion abgewartet . Nach 4 min wurde durch den Abfall des Druckes im Reaktor das Anspringen der Reaktion detektiert. Daraufhin wurden innerhalb 4 h 12096 g an Propylenoxid bei einer Temperatur von 150°C zugefahren. Das Propylenoxid reagierte nach Ende der Dosierung innerhalb von 10 min vollständig ab.The stirred autoclave was then heated to 150 ° C. 100 g of propylene oxide were metered in at a temperature of 150 ° C. and the reaction started. After 4 minutes, the start of the reaction was detected by the drop in pressure in the reactor. 12096 g of propylene oxide were then added at a temperature of 150 ° C. in the course of 4 hours. The propylene oxide reacted completely within 10 minutes after the end of the metering.
Es wurden 14985 g an Produkt gewonnen. Das hergestellte Produkt hatte eine Viskosität von 52 mm2/s bei einer Temperatur von 40°C. 14985 g of product were obtained. The product produced had a viscosity of 52 mm 2 / s at a temperature of 40 ° C.

Claims

Patentansprüche claims
1. DMC-Katalysatoren, die zu mindestens 10 Gew.-%, bezogen auf das Gewicht der DMC-Katalysatoren, einer kristallinen Multimetallcyanidverbindung bestehen, deren Röntgendiffraktogramm scharfe Reflexe bei mindestens den d-Werten1. DMC catalysts which consist of at least 10% by weight, based on the weight of the DMC catalysts, of a crystalline multimetal cyanide compound whose X-ray diffractogram has sharp reflections at at least the d values
11,4 A ± 0,5 Ä 8,9 Ä ± 0,5 A11.4 A ± 0.5 Ä 8.9 Ä ± 0.5 A
6.3 A + 0,5 Ä6.3 A + 0.5 Ä
5.8 Ä + 0,5 A 5,5 A + 0,5 Ä 4,5 Ä + 0,5 A 4,4 Ä ± 0,5 A5.8 Ä + 0.5 A 5.5 A + 0.5 Ä 4.5 Ä + 0.5 A 4.4 Ä ± 0.5 A
3.9 A ± 0,4 Ä 3,7 A + 0,4 A3.9 A ± 0.4 Ä 3.7 A + 0.4 A
3.4 Ä + 0,4 Ä3.4 Ä + 0.4 Ä
aufweist.having.
2. DMC-Katalysatoren nach Anspruch 1, dadurch gekennzeichnet, daß die kristalline Multimetallcyanidverbindung ein mono- klines Kristallsystem aufweist.2. DMC catalysts according to claim 1, characterized in that the crystalline multimetal cyanide compound has a monocline crystal system.
3. DMC-Katalysatoren nach Anspruch 1, dadurch gekennzeichnet, daß die kristalline Multimetallcyanidverbindung ein mono- klines Kristallsystem mit den Gitterparametern3. DMC catalysts according to claim 1, characterized in that the crystalline multimetal cyanide compound is a monoclinic crystal system with the lattice parameters
a= 12,a = 12,
4 A + 0,5 Ä b= 7,6 Ä ± 0,5 A c= 9,6 A + 0,5 Ä aufweist. 4 A + 0.5 Ä b = 7.6 Ä ± 0.5 A c = 9.6 A + 0.5 Ä having.
Multimetallcyanidverbindungen nach Anspruch 1, dadurch gekennzeichnet, daß sie die allgemeine Formel (I)Multimetal cyanide compounds according to Claim 1, characterized in that they have the general formula (I)
Ml a[M2(CN)b(A)c]d-fMi gXn-h(H20) eL-kP (I),M l a [M 2 (CN) b (A) c ] d -fM i g X n -h (H 2 0) eL-kP (I),
wobeiin which
M1 ein Metallion, ausgewählt aus der Gruppe, enthaltendM 1 contains a metal ion selected from the group
Zn2+, Fe2+, Co3+, Ni2+, Mn2+, Co2+, Sn2+, Sn4+, Pb2+, Mo4+, Mo6+, Al3+, V4+, V5+, Sr2+, W4+, W6+, Cr2+, Cr3+ , Cd2+, Cu2+,Zn 2+ , Fe 2+ , Co 3+ , Ni 2+ , Mn 2+ , Co 2+ , Sn 2+ , Sn 4+ , Pb 2+ , Mo 4+ , Mo 6+ , Al 3+ , V 4 + , V 5+ , Sr 2+ , W 4+ , W 6+ , Cr 2+ , Cr 3+ , Cd 2+ , Cu 2+ ,
La3+,La 3+ ,
M2 ein Metallion, ausgewählt aus der Gruppe, enthaltend Fe2+, Fe3+, Co2+, Co3+, Mn2+, Mn3+, Ni2+ V+, V5+, Cr2+, Cr3+, Rh+, Ru +, Ir3+,M 2 is a metal ion selected from the group containing Fe 2+ , Fe 3+ , Co 2+ , Co 3+ , Mn 2+ , Mn 3+ , Ni 2+ V + , V 5+ , Cr 2+ , Cr 3+ , Rh + , Ru + , Ir 3+ ,
bedeuten und M1 und M2 verschieden sind,mean and M 1 and M 2 are different,
A ein Anion, ausgewählt aus der Gruppe, enthaltend Halo- genid, Hydroxyd, Sulfat, Carbonat, Cyanid, Thiocyanat,A is an anion selected from the group containing halide, hydroxide, sulfate, carbonate, cyanide, thiocyanate,
Isocyanat, Cyanat, Carboxylat, Oxalat oder Nitrat,Isocyanate, cyanate, carboxylate, oxalate or nitrate,
X ein Anion, ausgewählt aus der Gruppe, enthaltend Halogenid, Hydroxyd, Sulfat, Carbonat, Cyanid, Thiocyanat, Isocyanat, Cyanat, Carboxylat, Oxalat, Nitrat oder NitritX is an anion selected from the group containing halide, hydroxide, sulfate, carbonate, cyanide, thiocyanate, isocyanate, cyanate, carboxylate, oxalate, nitrate or nitrite
(N02 ~) , sowie die ungeladene Spezies CO, H0 und NO,(N0 2 ~ ), as well as the uncharged species CO, H0 and NO,
L ein mit Wasser mischbarer Ligand, ausgewählt aus der Gruppe, enthaltend Alkohole Aldehyde, Ketone, Ether, Polyether, Ester, Polyester, Polycarbonat , Harnstoffe,L is a water-miscible ligand selected from the group comprising alcohols aldehydes, ketones, ethers, polyethers, esters, polyesters, polycarbonates, ureas,
Amide, Nitrile, und Sulfide oder deren Mischungen,Amides, nitriles, and sulfides or mixtures thereof,
P ein organischer Zusatzstoff, ausgewählt aus der Gruppe, enthaltend Polyether, Polyester, Polycarbonate, Poly- alkylenglykolsorbitanester, Polyalkylenglykolglycidyl- ether, Polyacrylamid, Poly (acrylamid-co-acrylsäure) , Polyacrylsäure, Poly (acrylamid-co-maleinsäure) , Poly- acrylnitril, Polyalkylacrylate, Polyalkylmethacrylate, Polyvinylmethylether, Polyvinylethylether , Polyvinyl- acetat, Polyvinylalkohol , Poly-N-vinylpyrrolidon, Poly(N- vinylpyrrolidon-co-acrylsäure) , Polyvinylmethylketon, Poly (4-vinylphenol) , Poly (acrylsäure-co-styrol) , Oxa- zolinpolymere, Polyalkylenimine, Maleinsäure und Malein- säureanhydridcopolymer, Hydroxyethylcellulose, Poly- acetate, ionische Oberflächen und grenzflächenaktiveP is an organic additive selected from the group consisting of polyethers, polyesters, polycarbonates, polyalkylene glycol sorbitan esters, polyalkylene glycol glycidyl ethers, polyacrylamide, poly (acrylamide-co-acrylic acid), polyacrylic acid, poly (acrylamide-co-maleic acid), polyacrylonitrile , Polyalkyl acrylates, polyalkyl methacrylates, polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl acetate, polyvinyl alcohol, poly-N-vinylpyrrolidone, poly (N-vinylpyrrolidone-co-acrylic acid), polyvinyl methyl ketone, poly (4-vinylphenol), poly (acrylic acid-co-styrene), Oxazoline polymers, polyalkyleneimines, maleic acid and maleic anhydride copolymer, hydroxyethyl cellulose, polyacetate, ionic surfaces and surface-active
Verbindungen, Gallensäure oder deren Salze, Ester oder Amide, Carbonsäureester mehrwertiger Alkohole und Glycoside bedutet,Compounds, bile acid or its salts, esters or Amides, carboxylic acid esters of polyhydric alcohols and glycosides mean
sowiesuch as
a, b, d, q und n ganze oder gebrochene Zahlen größer null, c, f, e, h und k ganze oder gebrochene Zahlen größer gleich null sind,a, b, d, q and n are integer or fractional numbers greater than zero, c, f, e, h and k are integer or fractional numbers greater than zero,
wobeiin which
a, b, c,und d, sowie q und n so ausgewählt sind, daß die Elektroneutralität gewährleistet ist,a, b, c, and d, as well as q and n are selected so that electroneutrality is ensured,
haben.to have.
5. Verfahren zur Herstellung von Multimetallcyanidverbindungen nach einem der Ansprüche 1 bis 4, umfassend die Schritte5. A method for producing multimetal cyanide compounds according to any one of claims 1 to 4, comprising the steps
a) Herstellung einer kristallinen Multimetallcyanidverbindung,a) preparation of a crystalline multimetal cyanide compound,
b) Temperaturbehandlung der Multimetallcyanidverbindung.b) heat treatment of the multimetal cyanide compound.
6. Verwendung der Multimetallcyanidverbindungen nach Anspruch 5 als Katalysatoren zur Polymerisation von Alkylenoxiden.6. Use of the multimetal cyanide compounds according to claim 5 as catalysts for the polymerization of alkylene oxides.
7. Verfahren zur Herstellung Polyetheralkoholen durch katalytische Polymerisation von Alkylenoxiden, dadurch gekenn- zeichnet, daß als Katalysatoren Multimetallcyanidverbindungen nach Anspruch 5 eingesetzt werden. 7. Process for the preparation of polyether alcohols by catalytic polymerization of alkylene oxides, characterized in that multimetal cyanide compounds according to claim 5 are used as catalysts.
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