EP1534426A1 - Composes de cyanure polymetallique - Google Patents

Composes de cyanure polymetallique

Info

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
Authority
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.)
Withdrawn
Application number
EP03790833A
Other languages
German (de)
English (en)
Inventor
Georg Heinrich Grosch
Edward Bohres
Raimund Ruppel
Kathrin Harre
Eva Baum
Michael Stösser
Jeffery T. Miller
Richard B. Prager
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1534426A1 publication Critical patent/EP1534426A1/fr
Withdrawn legal-status Critical Current

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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

L'invention concerne des catalyseurs DMC qui contiennent au moins 10 % en poids, par rapport au poids des catalyseurs DMC, d'un composé de cyanure polymétallique cristallin dont un diffractogramme de rayons X présente d'intenses reflets au moins aux valeurs d 11,4 ANGSTROM +/- 0,5 ANGSTROM ; 8,9 ANGSTROM +/- 0,5 ANGSTROM ; 6,3 ANGSTROM +/- 0,5 ANGSTROM ; 5,8 ANGSTROM +/- 0,5 ANGSTROM ; 5,5 ANGSTROM +/- 0,5 ANGSTROM ; 4,5 ANGSTROM +/- 0,5 ANGSTROM ; 4,4 ANGSTROM +/- 0,5 ANGSTROM ; 3,9 ANGSTROM +/- 0,4 ANGSTROM ; 3,7 ANGSTROM +/- 0,4 ANGSTROM ; 3,4 ANGSTROM +/- 0,4 ANGSTROM .
EP03790833A 2002-08-28 2003-07-30 Composes de cyanure polymetallique Withdrawn EP1534426A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US229979 1999-01-13
US10/229,979 US6764978B2 (en) 2002-08-28 2002-08-28 Multimetal cyanide compounds
PCT/EP2003/008404 WO2004020091A1 (fr) 2002-08-28 2003-07-30 Composes de cyanure polymetallique

Publications (1)

Publication Number Publication Date
EP1534426A1 true EP1534426A1 (fr) 2005-06-01

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP03790833A Withdrawn EP1534426A1 (fr) 2002-08-28 2003-07-30 Composes de cyanure polymetallique

Country Status (4)

Country Link
US (1) US6764978B2 (fr)
EP (1) EP1534426A1 (fr)
AU (1) AU2003260339A1 (fr)
WO (1) WO2004020091A1 (fr)

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DE19905611A1 (de) * 1999-02-11 2000-08-17 Bayer Ag Doppelmetallcyanid-Katalysatoren für die Herstellung von Polyetherpolyolen
US20050209438A1 (en) * 2004-03-19 2005-09-22 Browne Edward P Starter feed stream acidification in DMC-catalyzed process
US7842653B2 (en) * 2005-06-16 2010-11-30 Council Of Scientific & Industrial Research Process for the preparation of lubricants
US7754643B2 (en) * 2005-10-07 2010-07-13 Council Of Scientific & Industrial Research Transesterification catalyst and a process for the preparation thereof
DE102005057895A1 (de) 2005-12-02 2007-06-06 Basf Ag Verfahren zur Herstellung von Multimetallcyanidverbindungen
US20080132729A1 (en) 2006-12-01 2008-06-05 Mcdaniel Kenneth G Continuous process for the production of ethoxylates
US20080132728A1 (en) 2006-12-01 2008-06-05 Mcdaniel Kenneth G Continuous processes for the production of alkylphenol ethoxylates
US7473677B2 (en) 2007-04-16 2009-01-06 Bayer Materialscience Llc High productivity process for alkylphenol ethoxylates
US20080255378A1 (en) 2007-04-16 2008-10-16 Bayer Materialscience Llc High productivity process for non-phenolic ethoxylates
WO2009158379A2 (fr) * 2008-06-25 2009-12-30 Benefuel Inc. Procédé de fabrication d’alkylesters d’acides gras
US20100324340A1 (en) 2009-06-23 2010-12-23 Bayer Materialscience Llc Short chain polyether polyols prepared from ultra-low water-content starters via dmc catalysis
MY163273A (en) 2011-03-09 2017-08-30 Benefuel Inc Systems and methods for making bioproducts
ES2599073T3 (es) 2011-07-04 2017-01-31 Repsol, S.A. Método continuo para la síntesis de polioles
US9051412B2 (en) 2013-03-14 2015-06-09 Bayer Materialscience Llc Base-catalyzed, long chain, active polyethers from short chain DMC-catalyzed starters
US9994506B2 (en) 2016-04-20 2018-06-12 Covestro Llc Process for transitioning reactors from base-catalyzed polyol production to DMC-catalyzed polyol production

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DE19742978A1 (de) * 1997-09-29 1999-04-01 Basf Ag Multimetallcyanidkomplexe als Katalysatoren
US6800583B2 (en) * 1999-06-02 2004-10-05 Basf Aktiengesellschaft Suspension of multimetal cyanide compounds, their preparation and their use
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CA2401602A1 (fr) * 2000-02-29 2001-09-07 Basf Aktiengesellschaft Procede de production de composes du type des cyanures polymetalliques
AU2001255735A1 (en) * 2000-04-28 2001-11-12 Synuthane International, Inc. Double metal cyanide catalysts containing polyglycol ether complexing agents
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Also Published As

Publication number Publication date
US6764978B2 (en) 2004-07-20
WO2004020091A1 (fr) 2004-03-11
AU2003260339A1 (en) 2004-03-19
US20040044240A1 (en) 2004-03-04

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