WO2001038421A1 - Procede de traitement de polyetheralcools - Google Patents

Procede de traitement de polyetheralcools Download PDF

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Publication number
WO2001038421A1
WO2001038421A1 PCT/EP2000/011342 EP0011342W WO0138421A1 WO 2001038421 A1 WO2001038421 A1 WO 2001038421A1 EP 0011342 W EP0011342 W EP 0011342W WO 0138421 A1 WO0138421 A1 WO 0138421A1
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WO
WIPO (PCT)
Prior art keywords
catalyst
polyether
polyether alcohols
molecular weight
dmc
Prior art date
Application number
PCT/EP2000/011342
Other languages
German (de)
English (en)
Inventor
Kathrin Harre
Gerd Hoeppner
Georg Heinrich Grosch
Wolfgang Heider
Eva Baum
Thomas Ostrowski
Original Assignee
Basf Aktiengesellschaft
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 Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to EP00979572A priority Critical patent/EP1237985A1/fr
Priority to AU17012/01A priority patent/AU1701201A/en
Publication of WO2001038421A1 publication Critical patent/WO2001038421A1/fr

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    • 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
    • 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
    • C08G65/30—Post-polymerisation treatment, e.g. recovery, purification, drying

Definitions

  • the invention relates to a process for working up polyether alcohols which have been prepared by addition of alkylene oxides onto H-functional starter substances by means of multimetal cyanide catalysts.
  • Polyurethanes are manufactured in large quantities.
  • An essential starting product for their production are polyether alcohols. They are usually produced by catalytic addition of lower alkylene oxides, in particular ethylene oxide and propylene oxide, to H-functional starters.
  • lower alkylene oxides in particular ethylene oxide and propylene oxide
  • H-functional starters mainly basic metal hydroxides or salts are used as catalysts, the potassium hydroxide being of the greatest practical importance.
  • One way of producing polyether alcohols with a low content of unsaturated constituents is the use of multimetal cyanide catalysts, also known as DMC catalysts, mostly zinc hexacyanometalates, as alkoxylation catalysts.
  • DMC catalysts also known as zinc hexacyanometalates
  • alkoxylation catalysts There are a large number of documents in which ___ the production of polyether alcohols using such catalysts is described.
  • the production of polyether polyols using zinc hexacyanocobaltate is described in DD-A-203 735 and DD-A-203 734.
  • multimetal cyanide catalysts the content of unsaturated constituents in the polyether polyol can be reduced to approx. 0.003 to 0.009 meq / g - in conventional catalysis with potassium hydroxide, about 10 times the amount (approx. 0.03 to 0.08 meq / g) ,
  • the production of the multimetal cyanide catalysts is also known. These compounds are usually prepared by reacting solutions of metal salts, such as zinc chloride, with solutions of alkali metal or alkaline earth metal cyanometalates, such as potassium hexacyanocobaltate.
  • metal salts such as zinc chloride
  • alkali metal or alkaline earth metal cyanometalates such as potassium hexacyanocobaltate.
  • a water-miscible component containing heteroatoms is generally added to the precipitate suspension formed immediately after the precipitation process. This component can also already be present in one or in both educt solutions.
  • This water-miscible component containing heteroatoms can be, for example, an ether, polyether,
  • the multimetal cyanide catalyst is mostly separated off from the polyether alcohol. Since the multimetal cyanide catalyst is usually present in a very finely divided form in the polyether alcohol, the separation is very difficult.
  • No. 5,416,241 describes a process for the preparation of polyether alcohols by means of DMC catalysts, in which after the alkylene oxides have been added on, the catalyst is made insoluble by adding alkali compounds and then filtered. In this process, however, the DMC catalyst is destroyed and can therefore no longer be reused.
  • No. 4,877,906 describes a process for the purification of DMC-catalyzed polyether alcohols by treatment with alkali metal compounds, filtration, treatment with phosphorus compounds, renewed filtering and recovery of the so cleaned polyol described.
  • the DMC catalyst cannot be reused.
  • the DMC catalyst is rendered poorly soluble by means of alkali metal hydrides and is separated off in this form.
  • DMC catalysts are very expensive to manufacture, it is desirable to use them several times without reducing their catalytic activity and without other substances which impair the activity of the catalysts or the handling of the catalysts or the reaction mixture eg difficult to change due to viscosity change, can be recycled together with the DMC catalysts.
  • the invention accordingly relates to a process for working up polyether alcohols which have been prepared by means of DMC catalysts, characterized in that, after the reaction, the catalyst is separated from the polyether alcohol by sedimentation, without being chemically changed after the addition of the alkylene oxides has ended becomes.
  • the preferred embodiment of sedimentation is centrifugation. Surprisingly, it is possible to bring the DMC catalyst content to values below 2 ppm by centrifugation. The catalytic activity of the DMC catalysts is completely retained.
  • the sedimentation according to the invention is preferably carried out at temperatures in the range between 10 to 200 ° C. It is particularly advantageous to use the process according to the invention to remove those DMC catalysts which are prepared using a hexacyanometalate acid, preferably in the presence of a surfactant.
  • DMC catalysts are mostly crystalline and have a monoclinic crystal system. Such catalysts have been described, for example, in EP-A-862 947 and WO 99/16775.
  • the method can be used particularly advantageously for those polyether alcohols whose molecular weight distribution has a pronounced high-molecular flank with molecular weights above 80,000 daltons. Surprisingly, this very high molecular weight fraction of the polyether alcohol is separated from the polyether alcohol together with the DMC catalyst.
  • this mixture of DMC catalyst and very high molecular weight polyether alcohol can also be used for the production of polyether alcohols whose molecular weight distribution does not have a very high molecular weight flank. It turns out that this mixture of DMC catalyst and very high molecular weight polyether alcohol remains stable and can be separated from the polyether alcohol in this form after the reaction. There is no contamination of the polyether alcohol with the high molecular weight polyether alcohols which have entered the reaction mixture with the DMC catalyst.
  • “Very high molecular weight” here means a molecular weight of more than 80,000 Da, in particular in the range between 80,000 and 1,000,000 Da, preferably between 80,000 and 300,000.
  • the DMC catalyst can be freed from adhering polyetherol after separation from the polyether alcohol. This can be done by washing, for example with water or organic solvents. Then it can be converted into a form in which it can be used again as a catalyst for the production of polyether alcohols. This can be done, for example, by emulsification in solvents.
  • the catalyst is worked up in particular when the catalyst is to be used after the separation to produce another polyether alcohol in order to avoid impurities in the product.
  • This process variant is used in particular if the catalyst is to be used after the workup to produce the same polyether alcohol. As explained above, this process variant can also be carried out if the DMC catalyst has been separated from a polyether alcohol, the molar weight distribution of which has a high molecular weight flank.
  • a so-called post-reaction phase is initially connected after the alkylene oxides have been metered in, in which the alkylene oxide still present in the reaction mixture is to react completely. This is usually followed by distillation, in which unreacted monomers and other volatile constituents are to be removed from the reaction mixture.
  • the catalyst can then be separated off according to the invention. The separated catalyst can then, as described, be used for the next batch with or without working up.
  • filtration of the polyether alcohol can be carried out to remove coarse mechanical impurities or also larger ones Agglomerates of the DMC catalyst used are carried out.
  • the end product is separated off continuously or in batches.
  • the stripped-off polyether alcohol is then usually worked up as described above.
  • the separated catalyst can then be added to one of the starting products, preferably the starter substance, which is continuously metered into the reaction mixture. With this procedure, it is usually possible to dispense with working up the separated catalyst.
  • the work-up process according to the invention surprisingly makes it possible to remove the DMC catalyst from the polyether alcohol almost completely by a simple process which can be easily integrated into existing plants for the production of polyether alcohols, that is to say except for residual zinc and cobalt contents below 10 ppm to remove and then use it again with practically no losses for the production of polyether alcohols.
  • the regenerated ion exchanger was now used to produce a substantially alkali-free hexacyanocobaltic acid.
  • a 0.24 molar solution of potassium hexacyanocobaltate in water was passed over the exchanger at a rate of one bed volume per hour. After 2.5 bed volume, the potassium hexacyanocobaltate solution was changed to water.
  • the 2.5 bed volumes obtained had on average a hexacyanocobaltic acid content of 4.5% by weight and alkali contents of less than 1 ppm.
  • hexacyanocobaltic acid solutions used for the further examples were diluted accordingly with water.
  • the moist filter cake was processed with water to form a suspension which had a multimetal cyanide content of 5% by weight.
  • the synthesis was carried out in a cleaned and dried 1 l stirred autoclave. 400 g of polypropylene glycol with a molecular weight of 400 g / mol were added to the stirred tank and intimately mixed with 8.4 g of the catalyst according to Example 2. The boiler Contents were rendered inert with nitrogen and treated in vacuo at 140 ° C. for 1 h.
  • the synthesis was carried out in a cleaned and dried 1 l stirred autoclave. 400 g of polypropylene glycol with a molecular weight of 400 g / mol were added to the stirred tank and intimately mixed with the catalyst according to Example 1. The contents of the kettle were rendered inert with nitrogen and treated in vacuo at 105 ° C. for 1 h.
  • Viscosity at 25 ° C 146 mPas; (determined with a capillary viscometer according to Ubbelohde)
  • the synthesis was carried out in a cleaned and dried 1 l stirred autoclave. 200 g of polypropylene glycol with a molecular weight of 400 g / mol were added to the stirred tank and intimately mixed with the catalyst residue from Example 4. The kettle contents were rendered inert with nitrogen and treated in vacuo at 135 ° C. for 1 h.
  • Hydroxyl number 53 mg KOH / g viscosity at 25 ° C: 655 mPa (determined with a capillary viscometer according to Ubbelohde) Zn / Co content: 9.5 / 5 ppm.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Toxicology (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polyethers (AREA)

Abstract

La présente invention concerne un procédé permettant de traiter des polyétheralcools pouvant être obtenus par addition catalytique d'oxydes d'alkylène à des composés de départ à fonction H. L'invention se caractérise en ce qu'au moins un composé de cyanure multimétal est utilisé comme catalyseur et en ce que le catalyseur, après l'addition de l'oxyde d'alkylène, est éliminé du polyétheralcool par sédimentation.
PCT/EP2000/011342 1999-11-26 2000-11-16 Procede de traitement de polyetheralcools WO2001038421A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP00979572A EP1237985A1 (fr) 1999-11-26 2000-11-16 Procede de traitement de polyetheralcools
AU17012/01A AU1701201A (en) 1999-11-26 2000-11-16 Method for working up polyether alcohols

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19957105A DE19957105A1 (de) 1999-11-26 1999-11-26 Verfahren zur Aufarbeitung von Polyetheralkoholen
DE19957105.8 1999-11-26

Publications (1)

Publication Number Publication Date
WO2001038421A1 true WO2001038421A1 (fr) 2001-05-31

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PCT/EP2000/011342 WO2001038421A1 (fr) 1999-11-26 2000-11-16 Procede de traitement de polyetheralcools

Country Status (4)

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EP (1) EP1237985A1 (fr)
AU (1) AU1701201A (fr)
DE (1) DE19957105A1 (fr)
WO (1) WO2001038421A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7101823B2 (en) 2002-03-21 2006-09-05 United States Of America Method for preparing metal cyanide catalyst complexes using partially miscible complexing agents
EP2065424A1 (fr) 2007-11-28 2009-06-03 Evonik Goldschmidt GmbH Procédé de fabrication d'alcools de polyéther avec des catalyseurs DMC en utilisant des liaisons porteuses de groupes SiH en tant qu'additifs
EP2065425A1 (fr) 2007-11-28 2009-06-03 Evonik Goldschmidt GmbH Procédé de fabrication d'alcools de polyéther avec des catalyseurs DMC en utilisant des additifs spécifiques dotés d'une fonctionnalisation d'hydroxy aromatique
EP2241352A2 (fr) 2009-04-15 2010-10-20 Evonik Goldschmidt GmbH Procédé de fabrication d'alcools de polyéther inodores à l'aide de catalyseurs DMC et leur utilisation dans des préparations cosmétiques et/ou dermatologiques

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3900518A (en) * 1967-10-20 1975-08-19 Gen Tire & Rubber Co Hydroxyl or thiol terminated telomeric ethers
EP0776922A1 (fr) * 1995-11-30 1997-06-04 ARCO Chemical Technology, L.P. Procédé de préparation de dispersions de polyols polymères
US5731407A (en) * 1993-11-23 1998-03-24 Arco Chemical Technology, L.P. Double metal cyanide complex catalysts
DE19742978A1 (de) * 1997-09-29 1999-04-01 Basf Ag Multimetallcyanidkomplexe als Katalysatoren
DE19840585A1 (de) * 1998-09-05 2000-03-09 Basf Ag Verfahren zur Herstellung von Polyetherolen durch ringöffnende Polymerisation von Alkylenoxiden

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3900518A (en) * 1967-10-20 1975-08-19 Gen Tire & Rubber Co Hydroxyl or thiol terminated telomeric ethers
US5731407A (en) * 1993-11-23 1998-03-24 Arco Chemical Technology, L.P. Double metal cyanide complex catalysts
EP0776922A1 (fr) * 1995-11-30 1997-06-04 ARCO Chemical Technology, L.P. Procédé de préparation de dispersions de polyols polymères
DE19742978A1 (de) * 1997-09-29 1999-04-01 Basf Ag Multimetallcyanidkomplexe als Katalysatoren
DE19840585A1 (de) * 1998-09-05 2000-03-09 Basf Ag Verfahren zur Herstellung von Polyetherolen durch ringöffnende Polymerisation von Alkylenoxiden

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7101823B2 (en) 2002-03-21 2006-09-05 United States Of America Method for preparing metal cyanide catalyst complexes using partially miscible complexing agents
US7396963B2 (en) 2002-03-21 2008-07-08 Dow Global Technologies, Inc. Method for preparing metal cyanide catalyst complexes using partially miscible complexing agents
EP2065424A1 (fr) 2007-11-28 2009-06-03 Evonik Goldschmidt GmbH Procédé de fabrication d'alcools de polyéther avec des catalyseurs DMC en utilisant des liaisons porteuses de groupes SiH en tant qu'additifs
EP2065425A1 (fr) 2007-11-28 2009-06-03 Evonik Goldschmidt GmbH Procédé de fabrication d'alcools de polyéther avec des catalyseurs DMC en utilisant des additifs spécifiques dotés d'une fonctionnalisation d'hydroxy aromatique
DE102007057146A1 (de) 2007-11-28 2009-06-04 Evonik Goldschmidt Gmbh Verfahren zur Herstellung von Polyetheralkoholen mit DMC-Katalysatoren unter Verwendung von speziellen Additiven mit aromatischer Hydroxy-Funktionalisierung
DE102007057145A1 (de) 2007-11-28 2009-06-04 Evonik Goldschmidt Gmbh Verfahren zur Herstellung von Polyetheralkoholen mit DMC-Katalysatoren unter Verwendung von SiH-Gruppen tragenden Verbindungen als Additive
EP2241352A2 (fr) 2009-04-15 2010-10-20 Evonik Goldschmidt GmbH Procédé de fabrication d'alcools de polyéther inodores à l'aide de catalyseurs DMC et leur utilisation dans des préparations cosmétiques et/ou dermatologiques
DE102009002371A1 (de) 2009-04-15 2010-10-21 Evonik Goldschmidt Gmbh Verfahren zur Herstellung von geruchlosen Polyetheralkoholen mittels DMC-Katalysatoren und deren Verwendung in kosmetischen und/oder dermatologischen Zubereitungen

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Publication number Publication date
EP1237985A1 (fr) 2002-09-11
DE19957105A1 (de) 2001-05-31
AU1701201A (en) 2001-06-04

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