Classifications

• • 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
• • 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
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
  • C07F15/06—Cobalt compounds
  • C07F15/065—Cobalt compounds without a metal-carbon linkage
• • 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

• Double metal cyanide catalysts for the production of polyether polyols Double metal cyanide catalysts for the production of polyether polyols
• the invention relates to new double metal cyanide (DMC) catalysts for the production of polyether polyols by polyaddition of alkylene oxides to active ones
• Double metal cyanide (DMC) catalysts for the polyaddition of alkylene oxides to starter compounds having active hydrogen atoms are known (e.g. from US-A 3 404 109, US-A 3 829 505, US-A 3 941 849 and US-A 5 158 922).
• the use of these DMC catalysts for the production of polyether polyols leads in particular to a reduction in the proportion of monofunctional polyethers with terminal double bonds, so-called monools, compared to the conventional production of polyether polyols using alkali catalysts, such as alkali metal hydroxides.
• the polyether polyols thus obtained can be processed into high-quality polyurethanes (e.g. elastomers, foams, coatings).
• DMC catalysts are usually obtained by combining an aqueous solution of a metal salt with the aqueous solution of a metal cyanide salt in the presence of an organic complex ligand, e.g. of an ether.
• an organic complex ligand e.g. of an ether.
• aqueous solutions of zinc chloride in a typical catalyst preparation, for example, aqueous solutions of zinc chloride (in
• DMC catalysts which are organic by the use of tert-butanol Complex ligands (alone or in combination with a polyether (EP-A 700 949, EP-A 761 708, WO 97/40086)) further reduce the proportion of monofunctional polyethers with terminal double bonds in the preparation of polyether polyols.
• the use of these DMC catalysts reduces the induction time in the polyaddition reaction of the alkylene oxides with corresponding starter compounds and increases the catalyst activity.
• DMC catalysts which contain a bile acid or its salt, ester or amide as complex ligands have greatly increased activity in the production of polyether polyol.
• the present invention therefore relates to a double metal cyanide (DMC) catalyst comprising
• d) water, preferably 1 to 10% by weight and / or e) one or more water-soluble metal salts, preferably 5 to 25% by weight, of the formula (I) M (X) ⁇ can optionally be used from the preparation of the double metal cyanide compounds a).
• M is selected from the metals Zn (II), Fe (II), Ni (II), Mn (II), Co (II), Sn (II), Pb (II), Fe (III) , Mo (IV), Mo (VI), AI (III), V (V), V (IV), Sr (II), W (IV), W (VI), Cu (II) and Cr (III) .
• the anions X are the same or different, preferably the same, and are preferably selected from the group of halides, hydroxides, sulfates, carbonates, cyanates, thiocyanates, isocyanates, isothiocyanates, carboxylates, oxalates or nitrates.
• the value for n is 1, 2, or 3.
• the double metal cyanide compounds a) contained in the catalysts according to the invention are the reaction products of water-soluble metal salts and water-soluble metal cyanide salts.
• Metal salts preferably have the general formula (I) M (X) n , where M is selected from the metals Zn (II), Fe (II), Ni (II), Mn (II), Co (II), Sn (II ), Pb (II), Fe (III), Mo (IV), Mo (VI), AI (III), V (V), V (IV), Sr (II), W (IV), W (VI ), Cu (II) and Cr (III). Zn (II), Fe (II), Co (II) and Ni (II) are particularly preferred.
• the anions X are the same or different, preferably the same, and are preferably selected from the group of halides, hydroxides, sulfates, carbonates, cyanates, thiocyanates, isocyanates, isothiocyanates, carboxylates, oxalates or nitrates.
• the value for n is 1, 2, or 3.
• water-soluble metal salts examples include zinc chloride, zinc bromide,
• Metal cyanide salts preferably have the general formula (II) (Y) a M '(CN) b (A) c , where M' is selected from the metals Fe (II), Fe (III), Co (II), Co (III ), Cr (II), Cr (III), Mn (II), Mn (III), Ir (III), Ni (II), Rh (III), Ru (II), V (IV) and V (V ). M 'is particularly preferably selected from the metals Co (II), Co (III), Fe (II), Fe (III), Cr (III), Ir (III) and Ni (II).
• the water-soluble metal cyanide salt can contain one or more of these metals.
• the cations Y are the same or different, preferably the same, and are selected from the group containing alkali metal ions and alkaline earth metal ions.
• the anions A are the same or different, preferably the same, and are selected from the group of halides, hydroxides, sulfates, carbonates, cyanates, thiocyanates, isocyanates, isothiocyanates,
• Carboxylates, oxalates or nitrates Both a, and b and c are integers, the values for a, b and c being chosen such that the electroneutrality of the metal cyanide salt is given; a is preferably 1, 2, 3 or 4; b is preferably 4, 5 or 6; c preferably has the value 0.
• suitable water-soluble metal cyanide salts are potassium hexacyanocobaltate (III), potassium hexacyanoferrate (II), potassium hexacyanoferrate (III), calcium hexacyanocobaltate (III) and lithium hexacyano cobaltate (III).
• Preferred double metal cyanide compounds a) which are contained in the catalysts according to the invention are compounds of the general formula (III)
• M is as defined in formula (I) and M 'as defined in formula (II), and x, x ', y and z are integers and are selected so that the electron neutrality of the double metal cyanide compound is given.
• Suitable double metal cyanide compounds a) are zinc hexacyanocobalate (III), zinc hexacyanoiridate (III), zinc hexacyanoferrate (III) and cobalt (II) hexacyano cobaltate (III). Further examples of suitable double metal cyanide compounds are e.g. See US-A 5 158 922. Zinc hexacyanocobaltate (III) is particularly preferably used.
• organic complex ligands c) contained in the DMC catalysts according to the invention are known in principle and are described in detail in the prior art (see, for example, US Pat. No. 5,158,922, US Pat. No. 3,404,109, US Pat. No. 3,829,505, US Pat 3 941 849, EP-A 700 949, EP-A 761 708, JP-A 4145123, US-A 5 470 813, EP-A 743 093 and WO 97/40086).
• Preferred organic complex ligands are water-soluble, organic compounds with heteroatoms, such as oxygen, nitrogen, phosphorus or sulfur, which can form complexes with the double metal cyanide compound a).
• Suitable organic complex ligands are e.g.
• organic complex ligands are water-soluble aliphatic alcohols, such as ethanol, isopropanol, n-butanol, iso-butanol, sec-butanol and tert.-
• Butanol Tert-butanol is particularly preferred.
• the organic complex ligand is either added during the catalyst preparation or immediately after the precipitation of the double metal cyanide compound a).
• the organic complex ligand is usually used in excess.
• the DMC catalysts according to the invention contain the double metal cyanide compounds a) in amounts of 25 to 90% by weight, preferably 30 to 85% by weight, based on the amount of the finished catalyst, and the organic complex ligands c) in amounts of 0 , 5 to 30 wt .-%, preferably 1 to 25 wt .-%, based on the amount of the finished catalyst.
• the DMC catalysts according to the invention usually contain 1 to 80% by weight, preferably 1 to 40% by weight, based on the amount of the finished catalyst, a bile acid or its salt, ester or amide.
• Bile acids suitable for the preparation of the catalysts according to the invention are C 24 steroid carboxylic acids, which are breakdown products of cholesterol, and which are generally derived from 5 ⁇ -cholan-24-acid by introducing ⁇ -hydroxyl groups at C-3, C Derive -6, C-7 and C-12.
• Preferred bile acids have the general formula
• R "R 2 , R 3 and R 4 independently of one another are H or OH and R 5 OH, NH-CH 2 - COOH, NH-CH 2 -CH 2 -SO 3 H, NH- (CH 2 ) 3 -N + (CH 3 ) 2 -CH 2 -CHOH-CH 2 -SO 3 " or NH- (CH 2 ) 3 -N + (CH 3 ) 2 - (CH 2 ) 3 -SO 3 ' .
• Suitable are the free acids or their salts, preferably alkali or alkaline earth metal salts, and their esters, preferably with alkyl radicals having 2 to 30 carbon atoms, and their amides, preferably with alkyl radicals or sulfoalkyl, sulfoalkylaminoalkyl, sulfohydroxyalkylaminoalkyl and carboxyalkyl radicals in Acid or salt form.
• sodium chenodeoxycholate, glycochenodeoxycholic acid (3 ⁇ , 7 ⁇ -dihydroxy-5ß-cholan-24-acid-N- [carboxymethyl] amide
• R 5 NH-CH 2 -COOH
• sodium glycochnodeoxycholate, taurochenodeoxycholic acid (3 ⁇ , 7 ⁇ -dihydroxy-5ß-cholan-24-acid-N- [2-sulfoethyl] amide
• R 5 NH-CH 2 -CH 2 -SO 3 H
• sodium taurochenodeoxycholate, lithocholic acid (3 ⁇ -hydroxy-5ß-cholan-24-acid
• sodium lithocholate, potassium lithocholate, hyocholic acid (3 ⁇ , 6 ⁇ , 7
• the bile acids or their salts, esters or amides can be used individually or in the form of mixtures.
• the sodium, lithium or potassium salts or the methyl or ethyl esters of cholic acid, glycocholic acid, taurocholic acid are particularly preferably used.
• Hyocholic acid hyodeoxycholic acid or mixtures thereof.
• Bile acids such as ursodeoxycholic acid (3 ⁇ , 7ß-dihydroxy-5ß-cholan-24-acid), 7-oxo-lithocholic acid (3 ⁇ -hydroxy-7-oxo-5ß-cholan-24-acid), lithocholic acid-3-sulfate are also suitable (3 ⁇ -Hydroxy-5 ⁇ -cholan-24-acid-3-sulfate), nor-cholic acid and bisnor-cholic acid, or their salts, esters or amides.
• bile acids and their salts, esters or amides are generally well known and e.g. described in detail in Nachr. Chem. Tech. Lab. 43 (1995) 1047 and "Römpp-Lexikon Naturtechnik", Stuttgart, New York 1997, pp. 248ff.
• the analysis of the catalyst composition is usually carried out by means of elemental analysis, thermogravimetry and extractive removal of the proportion of bile acid or its salt, ester or amide with subsequent gravimetric determination.
• the catalysts of the invention can be crystalline, semi-crystalline or amorphous.
• the crystallinity is usually analyzed by powder X-ray diffractometry.
• the DMC catalysts according to the invention are usually prepared in aqueous solution by reacting ⁇ ) metal salts, in particular of the formula (I) with metal cyanide salts, in particular of the formula (II) ⁇ ), of organic complex ligands c) which are derived from bile acid or its salt, ester or amide are different and ⁇ ) bile acid or its salt, ester or amide.
• aqueous solutions of the metal salt for example zinc chloride, used in a stoichiometric excess (at least 50 mol% based on the metal cyanide salt)
• the metal cyanide salt for example potassium hexacyanocobaltate
• the organic complex ligand c) for example tert.-) Butanol
• the organic complex ligand c) can be present in the aqueous solution of the metal salt and / or the metal cyanide salt, or it is added directly to the suspension obtained after precipitation of the double metal cyanide compound a). It has proven advantageous to mix the aqueous solutions and the organic complex ligand c) with vigorous stirring. The suspension formed is then usually mixed with the bile acid or its salt,
• the bile acid or its salt, ester or amide b) is preferably used in a mixture with water and organic complex ligand c).
• the catalyst is then isolated from the suspension by known techniques, such as centrifugation or filtration.
• the isolated catalyst is then washed with an aqueous solution of the organic complex ligand c) (for example by resuspending and then isolating again by filtration or centrifugation).
• an aqueous solution of the organic complex ligand c) for example by resuspending and then isolating again by filtration or centrifugation.
• water-soluble by-products such as potassium chloride
• the amount of the organic complex ligand c) in the aqueous washing solution is preferably between 40 and 80% by weight, based on the total solution. It is also advantageous to add some bile acid or its salt, ester or amide to the aqueous washing solution, preferably in the range between 0.5 and 5% by weight, based on the
• the washed catalyst is then dried, if appropriate after pulverization, at temperatures of generally 20-100 ° C. and at pressures generally from 0.1 mbar to normal pressure (1013 mbar).
• the present invention furthermore relates to the use of the DMC catalysts according to the invention in a process for the preparation of polyether polyols by polyaddition of alkylene oxides onto starter compounds having active hydrogen atoms.
• Preferred alkylene oxides are ethylene oxide, propylene oxide, butylene oxide and mixtures thereof.
• the construction of the polyether chains by alkoxylation can, for example, only be carried out with one monomeric epoxide or also statistically or in blocks with 2 or 3 different monomeric epoxides respectively. More details are "Ulimann's Encyclopedia of Industrial Chemistry", Volume A21, 1992, pp. 670f. refer to.
• starter compounds are preferably compounds with (number average) molecular weights from 18 to 2,000 and 1 to
• hydroxyl groups used.
• examples include: ethylene glycol, ethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,4-butanediol, hexamethylene glycol, bisphenol A, trimethylolpropane, glycerol, pentaerythritol, sorbitol, cane sugar, degraded starch or water.
• starter compounds containing active hydrogen atoms are used which e.g. were prepared by conventional alkali catalysis from the abovementioned low molecular weight starters and are oligomeric alkoxylation products with (number average) molecular weights of 200 to 2,000.
• the polyaddition of alkylene oxides to starter compounds having active hydrogen atoms, which is catalyzed by the catalysts according to the invention, generally takes place at temperatures from 20 to 200 ° C., preferably in the range from 40 to 180 ° C., particularly preferably at temperatures from 50 to 150 ° C.
• the reaction can be carried out at total pressures of 0.001 to 20 bar.
• the polyaddition can be carried out in bulk or in an inert, organic solvent, such as toluene and / or THF.
• the amount of solvent is usually 10 to 30% by weight, based on the amount of the polyether polyol to be prepared.
• the catalyst concentration is selected so that the polyaddition reaction can be well mastered under the given reaction conditions.
• the catalyst concentration is generally in the range from 0.0005% by weight to 1% by weight, preferably in the range from 0.001% by weight to 0.1% by weight, particularly preferably preferably in the range from 0.001 to 0.0025% by weight, based on the amount of the polyether polyol to be prepared.
• the number average molecular weights of the polyether polyols produced by the process according to the invention are in the range from 500 to 100,000 g / mol, preferably in the range from 1,000 to 50,000 g / mol, particularly preferably in the range from 2,000 to 20,000 g / mol.
• the polyaddition can be continuous or discontinuous, e.g. be carried out in a batch or semi-batch process.
• the catalysts according to the invention can be used in very low concentrations (25 ppm and less, based on the amount of the polyether polyol to be prepared). If the polyether polyols produced in the presence of the catalysts according to the invention are used for the production of polyurethanes (Kunststoff Handbuch, Vol. 7, Polyurethane, 3rd edition, 1993, pp. 25-32 and 57-67), the catalyst can be removed the polyether polyol can be dispensed with without adversely affecting the product qualities of the polyurethane obtained.
• a solution of 6.2 g (45.75 mmol) of zinc chloride in 10 ml of distilled water is added to a solution of 2 g (6 mmol) of potassium hexacyanocobaltate in 35 ml of distilled water with vigorous stirring (24,000 rpm).
• a mixture of 25 g of tert-butanol and 25 g of distilled water is added to the suspension formed and then stirred vigorously for 10 minutes (24,000 rpm).
• a mixture of 0.5 g of cholic acid sodium salt (Fluka Chemie AG, CH-9471 Buchs)
• 0.5 g of tert-butanol and 50 g of distilled water is added and the mixture is stirred for 3 minutes (1,000 rpm).
• the solid is isolated by filtration, then stirred for 10 minutes with a mixture of 35 g of tert-butanol, 15 g of distilled water and 0.5 g of sodium cholic acid salt (10,000 rpm) and filtered again. Finally, the mixture is stirred again for 10 minutes with a mixture of 50 g of tert-butanol and 0.25 g of sodium cholic acid salt (10,000 rpm). After filtration, the catalyst is dried to constant weight at 50 ° C. and normal pressure.
• Example A The procedure was as in Example A, but hyodeoxycholic acid sodium salt (Sigma-Aldrich Chemie GmbH, D-82041 Deisenhofen) was used instead of cholic acid sodium salt from Example A.
• hyodeoxycholic acid sodium salt Sigma-Aldrich Chemie GmbH, D-82041 Deisenhofen
• Example C (comparative example) Preparation of a DMC catalyst using tert-butanol without bile acid or its salt, ester or amide
• the polyether polyols obtained were characterized by determining the OH numbers, the double bond contents and the viscosities.
• Polyether polyol OH number (mg KOH / g): 29.6
• catalyst C (15 ppm) shows no activity even after an induction time of 14 h.
• the induction time was approx. 9 h.
• the propoxylation time was more than 12 hours, with catalyst deactivation occurring in the course of the reaction.
• Examples 1-3 show that the new DMC catalysts according to the invention, owing to their significantly increased activity in the production of polyether polyol, can be used in such low concentrations that it is not necessary to separate the catalyst from the polyol.

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