WO1999044940A1 - Procede de production de catalyseurs de cyanure metallique double - Google Patents

Procede de production de catalyseurs de cyanure metallique double Download PDF

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Publication number
WO1999044940A1
WO1999044940A1 PCT/EP1999/001152 EP9901152W WO9944940A1 WO 1999044940 A1 WO1999044940 A1 WO 1999044940A1 EP 9901152 W EP9901152 W EP 9901152W WO 9944940 A1 WO9944940 A1 WO 9944940A1
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Prior art keywords
metal
double metal
metal cyanide
solid
group
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PCT/EP1999/001152
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German (de)
English (en)
Inventor
Georg Heinrich Grosch
Harald Larbig
Reinhard Lorenz
Dieter Junge
Eugen Gehrer
Ulrich Treuling
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Basf Aktiengesellschaft
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Priority to AU29280/99A priority Critical patent/AU2928099A/en
Publication of WO1999044940A1 publication Critical patent/WO1999044940A1/fr

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Classifications

    • 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
    • C08G65/04—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 only
    • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
    • C08G65/08—Saturated oxiranes
    • C08G65/10—Saturated oxiranes characterised by the catalysts used
    • 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
    • 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
    • C08G65/2693—Supported catalysts

Definitions

  • the invention relates to a process for the preparation of double metal cyanide catalysts and their use as catalysts for the production of polyether alcohols with a low content of unsaturated components.
  • Polyether alcohols are used in large quantities for the production of polyurethanes. They are usually produced by base-catalyzed addition of lower alkylene oxides, mostly ethylene oxide and / or propylene oxides, to H-functional starting substances. Basic metal hydroxides or salts are mostly used as catalysts, with the potassium hydroxide having the greatest technical importance.
  • EP-A-268 922 proposes the use of cesium hydroxide as a catalyst for the production of polyether alcohol. This can reduce the unsaturated content, but cesium hydroxide is expensive and problematic to dispose of.
  • Zinc hexacyanoiridate is produced here by reacting zinc chloride with hexacyanoiridic acid, which was previously isolated as a solid and used in this form.
  • a disadvantage of using zinc hexacyanoiridate is its color.
  • the polyether alcohols produced using this catalyst are also colored yellow, which is perceived as a poor quality for many applications.
  • EP-A-283 148 describes a process for the preparation of double metal cyanide complex catalysts in which the alkali metal chloride formed is bound to filter aids. Inorganic substances, in particular aluminosilicates, are used as filter aids. However, the step of removing the alkali chloride is an additional process step and is therefore complex. The catalyst produced by this process shows properties comparable to those which are produced without the addition of filter aids.
  • the object of the invention was to provide multimetal cyanide complex catalysts which are simple to produce and have high catalytic activity.
  • the object of the invention was surprisingly achieved by a process for the preparation of multimetal cyanide catalysts in which a metal salt is reacted with a cyanometalic acid in the presence of solids which are inert to the reaction participants.
  • the invention accordingly relates to a process for the preparation of multimetal catalysts, characterized in that a) reacting a solution of a metal salt of the general formula M 1 m (X) n / where 3
  • M 1 is a metal ion selected from the group containing Zn 2+ , Fe 2+ , Co 3+ , NL 2+ , Mn + , Co 2+ , Sn 2 ⁇ , Pb 2+ , Fe 3+ , Mo 4+ , Mo ⁇ + , AI 3 -, v 5+ , Sr 2+ , W 4+ , W ⁇ + , Cu 2+ , Cr 2+ , Cr 3+ , Cd 2 ",
  • X is an anion selected from the group consisting of halide, hydroxide, sulfate, carbonate, cyanide, thiocyanate, isocyanate, carboxylate, oxalate, nitrate, m and n are integers, corresponding to the valencies of M 1 and X a solution of a cyanometalate compound of the general formula
  • M 2 is a metal ion selected from the group comprising Fe 2+ , Fe 3+ , Co 3 ⁇ , Cr 3+ , Mn 2+ , Mn 3+ , Rh 3 -, Ru 3+ , V 4+ , V 5+ , Ir 3+ , Co 2 "and Cr 2+ , where M 2 may be the same or different M 1 , H is hydrogen,
  • A is an anion selected from the group consisting of halide, hydroxide, sulfate, carbonate, cyanate, thiocyanate, isocyanate, carboxylate, nitrate or cya id
  • At least one of the two solutions comprising at least one water-miscible, heteroatom-containing organic ligand selected from the group comprising alcohols, aldehydes, Can contain ketones, ethers, polyethers, esters, urea, amides, nitriles and sulfides and at least one of the two solutions contains at least one inert, inorganic or organic solid which is insoluble in the starting materials and end products,
  • step b) associations of the aqueous suspension formed in step a) with at least one water-miscible ligand, selected from the group described in step a), which may be the same or different from the ligands in step a)
  • M 1 is preferably selected from the group containing Zn 2+ , Fe 2+ , Co 2+ and Ni 2+ , in particular Zn 2+
  • X is preferably selected from the group containing carboxylate, halide, oxalate and nitrate, in particular carboxylate
  • M 2 is preferably selected from the group comprising Co 2+ , Co 3+ , Fe + , Fe 3+ , Cr 3+ , Rh 3+ and Ir 3+ , in particular Co 3+ .
  • the preparation of the preferably used cyanometallic acid H a M 2 (CN) - D (A) C can be carried out, for example, as described in W. Klemm, W. Brandt, R. Hoppe, Z. Anorg. Ailg. Chem. 308, 179 (1961) 4 wrote, starting from alkali metal cyanometalate via the silicon cyanometalate to cyanometalate hydrogen acid.
  • a further possibility is to convert an alkali metal or alkaline earth metal cyanometalate into a cyanometalate hydrogen acid using an acidic ion exchanger, as described, for example, in F. Hein, H. Lilie, Z. Anorg. All. Chem. 270, 45 (1952) or A.
  • the acids are stable in aqueous solution and keep well. They can be processed immediately after synthesis, but it is also possible to store them for a longer period. Storage should take place in the dark.
  • Keteroatoms are understood to mean non-carbon atoms, in particular oxygen, nitrogen and sulfur.
  • Ligands which are preferably used are alcohols, aldehydes, ketones, ethers, polyethers, esters, polyesters, ureas, amides, nitriles and sulfides, particularly preferably alcohols, ketones, ethers, polyethers or mixtures thereof, in particular alcohols, ethers, polyethers and mixtures thereof.
  • the solids which are added according to the invention and which are inert towards the reaction participants in the catalyst synthesis can be both inorganic and organic.
  • Oxides, nitrides, carbides, inert metals or metal alloys are preferably used as inorganic substances.
  • Oxides of metals from groups IIB to VIIIB and oxides of metals from groups IIIA and IVA and mixtures thereof can be used as oxides.
  • Oxides of group III A, IV A, Illb, IVb to VIb, manganese oxides, iron oxides, cobalt oxides, nickel oxides and zinc oxide and mixtures thereof are particularly preferably used.
  • Silicon nitride, boron nitride, vanadium nitride, chromium nitride or tungsten nitride can be used as nitrides.
  • the covalent or metallic carbides are preferably used as carbides, for example silicon carbide, boron carbide, titanium, zirconium, hafnium, vanadium, niobium, tantalum, molybdenum or woifram carbide. 5
  • the inorganic solids are added either in the form of fine powder or as grit, fibers, fiber fabrics or moldings, such as balls, strands or stars. Powder, grit and fibers and fiber fabrics are preferred.
  • the BET surface areas of the solids are preferably between 0.1 and 1000 m 2 / g, particularly preferably between 1 and 900 m 2 / g and in particular between 10 and 800 m 2 / g.
  • Organic inert solids can be natural or synthetic polymers, but also graphite, carbon black, activated carbons and oxidatively treated activated carbons.
  • Natural polymers include cellulose, keratins and water-insoluble pectins.
  • Synthetic polymers are, for example, polyethylene, polypropylene, polystyrene, polyurethane, polycarbonate, polyacrylate, polymethacrylate, polyamide as well as polyether or polyester. Cellulose, polyurethanes and polyalkylenes are preferred. They are added in the form of powder, fibers, fiber fabrics, moldings, granules.
  • the inert solids are mostly used in 0.05 to 20 times the amount of the double metal cyanide to be precipitated. 0.1 to 10 times the amount is preferred, particularly preferably 0.2 to 5 times the amount.
  • an inorganic or in particular organic solid which is inert under the production conditions of the double metal cyanide salt, but which dissolves under the reaction conditions during the preparation of the polyetherol and remains in the polyetherol after the preparation, for example polyester.
  • an aqueous solution of a cyanometalate hydrogen acid is combined with the aqueous solution of a metal salt of the general formula M 1 m (x) n , where the symbols have the meaning explained above. This is done in particular with a stoichiometric excess of the metal salt.
  • 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 submit the solution of the cyanometalate hydrogen acid and to add the metal salt, 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 hydrogen acid in the solution is 0.1 to 30% by weight, preferably 1 to 20% by weight, and in particular 2 to 10% by weight, based on the reaction mixture.
  • the content of the metal salt component in the solution is 1 to 50% by weight, preferably 2 to 40% by weight and in particular 5 to 30% by weight.
  • the inert solid is preferably added to the solution which is initially introduced and / or has the larger volume.
  • the ligands containing heteroatoms are added to the resulting suspension, in particular after the two starting material solutions have been combined, and here too thorough mixing must be ensured. However, it is also possible to add all or part of the ligand to one or both of the starting material solutions. It is advantageous to add the ligands preferably to the cyanometalate-hydrogen acid solution due to the change in the salt solubilities.
  • the content of the ligands in the solution is preferably 1 to 60% by weight, particularly preferably 5 to 40% by weight and in particular 10 to 30% by weight.
  • the double metal cyanide complexes formed are separated from the aqueous phase. This can be done by the usual and known separation methods, for example by filtration or centrifugation.
  • the starting materials are preferably mixed at temperatures between 10 and 80 ° C., particularly preferably between 15 and 60 ° C. and in particular between 20 and 50 ° C.
  • the double metal cyanide complexes are then dried. Drying can take place at room temperature and normal pressure. Drying is preferably carried out at temperatures from 20 to 90 ° C. and pressures from 0.01 to 1 bar, in particular at temperatures from 20 to 70 ° C. and pressures from 0.05 to 0.7 bar.
  • the double metal cyanide complexes can be treated again with the aqueous solution of the ligands or the pure ligands themselves, separated and dried.
  • the double metal cyanide complexes according to the invention are used in particular as catalysts in the production of polyetherols by polymerizing lower alkylene oxides, in particular ethylene oxide and / or propylene oxide with a low content of unsaturated constituents. 7
  • the catalysts prepared by the process according to the invention have a significantly increased activity with extremely short light-off times of 1 to 20 minutes. It is therefore possible to work with catalyst concentrations of less than 250 ppm, preferably less than 150 ppm and particularly preferably less than 75 ppm, based on the weight of the polyether alcohol.
  • Washed ethylene glycol dimethyl ether The solid thus treated was dried at room temperature.
  • the polyetherol obtained was filtered once. It had a hydroxyl number of 55.7 mg KOH / g, a content of unsaturated Be ⁇ was share of 0.0099 meq / g, a zinc content of 6 ppm and a cobalt content of 3ppm.
  • the polyetherol obtained was filtered once. It had a hydroxyl number of 54.4 mg KOE / g, an unsaturated content of 0.0101 meq / g, a zinc content of ⁇ 1 ppm and a cobalt content of ⁇ 1 ppm.
  • the polyetherol obtained was filtered once. It had a hydroxyl number of 56.3 mg KOH / g, an unsaturated component content of 0.0065 meq / g, a zinc content of 12 ppm and a cobalt content of 6 ppm.
  • Gel permeation chromatography (GPC) was used to determine a number average molecular weight of 1800 g / mol, a weight average molecular weight of 1828 g / mol and a polydispersity of 1.016, the GPC being calibrated using commercial polypropylene glycol standards.
  • the polyetherol obtained was filtered once. It had a 5 hydroxyl number of 56.4 mg KOH / g, an unsaturated component content of 0.0089 meq / g, a zinc content of 3 ppm and a cobalt content of 1 ppm.
  • Gel permeation chromatography (GPC) was used to determine a number average molecular weight of 1802 g / mol, a weight average molecular weight of 2031 g / mol and a polydispersity of 1.127, the GPC being calibrated using commercial polypropylene glycol standards.
  • the polyetherol obtained was filtered once. It had a hydroxyl number of 56.8 mg KOH / g, an unsaturated component content of 0.0104 meq / g, a zinc content of 6 ppm and a cobalt content of 2 ppm.
  • Gel permeation chromatography (GPC) was used to determine a number average molecular weight of 1807 g / mol, a weight average molecular weight of 1880 g / mol and a polydispersity of 1.040, the GPC being calibrated using commercial polypropylene glycol standards.
  • the polyetherol obtained was filtered once. It had a hydroxyl number of 56.7 mg KOH / g, an unsaturated component content of 0.0085 meq / g, a zinc content of 5 ppm and a cobalt content of 2 ppm.
  • Gel permeation chromatography (GPC) was used to determine a number average molecular weight of 1806 g / mol, a weight average molecular weight of 1857 g / mol and a polydispersity of 1.028, the GPC being calibrated using commercial polypropylene glycol standards.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Toxicology (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Health & Medical Sciences (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

L'invention concerne un procédé de production de composés de cyanure métallique double. Ce procédé consiste a) à faire réagir une solution d'un sel métallique de la formule générale M1m(X)n avec une solution d'un composé cyanométallate de la formule générale HaM2(CN)b(A)c, M1 et M2 représentant des cations métalliques, X et A représentant respectivement un anion. a, b, c, m et n sont des nombres entiers choisis de telle façon que l'électroneutralité du sel considéré soit garantie. En outre, au moins une des solutions contient au moins un ligand organique qui est soluble dans l'eau et qui contient des hétéroatomes. Ce procédé consiste ensuite b) à combiner la suspension ainsi obtenue à un ligand miscible à l'eau, ce ligand et le ligand utilisé en a) pouvant être identiques ou différents. Ce procédé consiste enfin c) à séparer le composé de cyanure métallique double de la suspension. Au moins une des solutions de base utilisées en a) contient au moins un solide organique ou inorganique insoluble dans les solutions de base et les produits finaux.
PCT/EP1999/001152 1998-03-05 1999-02-23 Procede de production de catalyseurs de cyanure metallique double WO1999044940A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU29280/99A AU2928099A (en) 1998-03-05 1999-02-23 Method for producing double metal cyanide catalysts

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19809538.4 1998-03-05
DE19809538A DE19809538A1 (de) 1998-03-05 1998-03-05 Verfahren zur Herstellung von Doppelmetallcyanidkatalysatoren

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WO1999044940A1 true WO1999044940A1 (fr) 1999-09-10

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AR (1) AR018316A1 (fr)
AU (1) AU2928099A (fr)
DE (1) DE19809538A1 (fr)
WO (1) WO1999044940A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6429166B1 (en) 2000-05-19 2002-08-06 Dow Global Technologies Inc. Method for preparing metal cyanide catalyst/polyol initiator slurries
DE102008042715A1 (de) 2007-10-12 2009-04-16 Basf Se Polyetherpolyole

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2479878A1 (fr) * 2002-03-21 2003-10-02 Dow Global Technologies Inc. Procede pour preparer des catalyseurs a base de cyanure metallique au moyen de metaux de valence nulle
HUE044164T2 (hu) 2009-10-19 2019-10-28 Basf Se Kettõs fém-cianid katalizátorok kondicionálása
WO2011160296A1 (fr) 2010-06-23 2011-12-29 Basf Se Catalyseur de type cyanure métallique double modifié

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4843054A (en) * 1987-02-26 1989-06-27 Arco Chemical Technology, Inc. Preparation of filterable double metal cyanide complex catalyst for propylene oxide polymerization
US5158922A (en) * 1992-02-04 1992-10-27 Arco Chemical Technology, L.P. Process for preparing metal cyanide complex catalyst
US5525565A (en) * 1993-12-23 1996-06-11 Arco Chemical Technology, L.P Foam-supported double metal cyanide catalysts for polyol synthesis
EP0755716A1 (fr) * 1995-07-24 1997-01-29 ARCO Chemical Technology, L.P. Catalyseurs à base de complexe de cyanure de deux métaux hautement actifs

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4843054A (en) * 1987-02-26 1989-06-27 Arco Chemical Technology, Inc. Preparation of filterable double metal cyanide complex catalyst for propylene oxide polymerization
US5158922A (en) * 1992-02-04 1992-10-27 Arco Chemical Technology, L.P. Process for preparing metal cyanide complex catalyst
US5525565A (en) * 1993-12-23 1996-06-11 Arco Chemical Technology, L.P Foam-supported double metal cyanide catalysts for polyol synthesis
EP0755716A1 (fr) * 1995-07-24 1997-01-29 ARCO Chemical Technology, L.P. Catalyseurs à base de complexe de cyanure de deux métaux hautement actifs

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
FR. HEIN, H. LILIE: "Zur Darstellung von Komplexsäuren nach der Austauscher-Methode", Z. ALLG. ANORG. CHEM., vol. 270, 1952, S02B02, pages 45 - 48, XP002107072 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6429166B1 (en) 2000-05-19 2002-08-06 Dow Global Technologies Inc. Method for preparing metal cyanide catalyst/polyol initiator slurries
DE102008042715A1 (de) 2007-10-12 2009-04-16 Basf Se Polyetherpolyole

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Publication number Publication date
DE19809538A1 (de) 1999-09-09
AR018316A1 (es) 2001-11-14
AU2928099A (en) 1999-09-20

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