MXPA01008136A - Double metal cyanide catalysts for producing polyether polyols - Google Patents

Abstract

The invention relates to novel double metal cyanide (DMC) catalyts for producing polyether polyols by polyaddition of alkylene oxides to starter compounds with active hydrogen atoms. The catalyst contains a) double metal cyanide compounds, b) bile acids or their salts, esters or amides and c) organic complex ligands. The inventive catalysts show increased activity in the production of polyether polyols.

Description

Catalysts of cyanur-p > The invention relates to novel bimetallic cyanide (DMC) catalysts for the production of polyether polyols from alkylene oxides to initiator compounds having active hydrogen atoms. The bimetallic cyanide (DMC) catalysts for the polyaddition of alkylene oxides to initiator compounds having active hydrogen atoms are known (see, for example, 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 causes, in particular, a reduction of the part of monofunctional polyethers with terminal double bonds, called monooles, in comparison with the conventional production of polyether polyols by means of alkaline catalysts, such as alkali hydroxides. The polyether polyols thus obtained can be processed into valuable polyurethanes (eg elastomers, foams, coatings). DMC catalysts are usually obtained by reacting 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. In a typical catalyst preparation by way of example, aqueous solutions of REF: 132004 zinc chloride (in excess) and potassium hexacyanocobaltate and then dimethoxyethane (glime) is added to the suspension formed. After filtration and washing of the catalyst with aqueous glime solution, an active catalyst of the general formula is obtained (see, for example, EP-A 700 949).

Zn3 [Co (CN) 6] 2 • x ZnCl2 • and H20 • z Glime From JP-A 4145123, US Pat. No. 5,470,813, EP-A 700 949, EP-A 743 093, EP-A 761 708 and WO 97/40086 DMC catalysts are known that when using tert-butanol as a ligand of organic complex (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 production of polyether polyols. In addition to this, when using these DMC catalysts the induction time in the polyaddition reaction of the alkylene oxides with corresponding initiator compounds is reduced and the activity of the catalyst is raised. It has been the object of the present invention to provide improved DMC catalysts for the polyaddition of alkylene oxides to corresponding initiator compounds which have a higher catalytic activity compared to the types of catalysts known hitherto. This leads to shortened alkoxylation times to improved profitability of the polyol ether production process.

Ideally, upon increasing activity the catalyst can then be used in such low concentrations (25 ppm or less) that the very expensive separation of the catalyst from the product is no longer necessary and the product can be used directly for the manufacture of the polyurethane. Surprisingly it has now been found that DMC catalysts containing a bile acid or its salt, ester or amide as a complex ligand possess a very high activity in the production of polyether polyols. The object of the present invention is therefore a bimetallic cyanide catalyst (DMC) containing a) one or more bimetallic cyanide compounds, preferably one, b) one or more, preferably one, bile acids or their salts, esters or amides, and c) one or more, preferably one, organic complex ligands other than b). The catalyst according to the invention can optionally contain d) water, preferably 1 to 10% by weight and / or e) one or more water-soluble metal salts, preferably from 5 to 25% by weight, of formula (I) M (X) n of the preparation of the bimetal cyanide compounds a). In the formula (I) 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), AKIII), 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 especially preferred.

The anions X are the same or different, preferably identical, preferably selected from the group of halides, hydroxides, sulfates, carbonates, cyanates, thiocyanates, isocyanates, isothiocyanates, carboxylates, oxalates or nitrates. The value of n is 1, 2 or 3. The bimetallic 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. For the preparation of bimetallic cyanide compounds a) suitable water-soluble metal salts preferably have the general formula (I) M (X) n wherein 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), Al (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 especially 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 of n is 1, 2 or 3. Examples of suitable water-soluble metal salts are zinc chloride, zinc bromide, zinc acetate, zinc acetylacetonate, zinc benzoate, zinc nitrate, iron (II) sulfate, iron (II) bromide, iron (II) chloride, cobalt (II) chloride, cobalt (II) thiocyanate, nickel (II) chloride and nickel (II) nitrate. It is also possible to use mixtures of different water-soluble metal salts. For the preparation of bimetallic cyanide compounds a) suitable water-soluble metal cyanide salts preferably have the general formula (II) (Y) aM '(CN) b (A) c, wherein M' is selected from the Fe metals (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 may contain one or more of these metals. The Y cations are the same or different, preferably the same, and are selected from the group comprising the alkali metal ions and the alkaline earth metal ions. The anions A 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. Both a and b and c are integers, the values of a, b and c being chosen so as to result in the electroneutrality of the metal cyanide salt; a is preferably 1, 2, 3 or 4; b is preferably 4, 5 or 6; c preferably has the value 0. Examples of suitable water-soluble metal cyanide salts are potassium hexanocyanocobaltate (III), potassium hexacyanoferrate (II), potassium hexacyanoferrate (III), calcium hexanocyanocobaltate (III) and hexanocyanocobaltate (III) of lithium. Preferred bimetallic cyanide compounds a) contained in the catalysts according to the invention are the compounds of general formula (III) MX [M \, (CN) y] z, wherein M is defined as in formula (I) and M 'as in formula (II), and x, x', y and z are integers and are chosen so as to result in the electroneutrality of the bimetallic cyanide compound. Preferably they are x = 3, x '= 1, y = 6 and z = 2, M = Zn (II), Fe (II), Co (II) or Ni (II) and M' = Co (III), Fe ( III), Cr (III) or Ir (III). Examples of suitable bimetal cyanide compounds are a) zinc hexanocyanocobaltate (III), zinc hexacyanidate (III), zinc hexacyanoferrate (III) and cobalt (II) hexanocyanocobaltate (III). Other examples of suitable bimetal cyanide compounds are ld, for example, in US Pat. No. 5,158,922. Zinc hexanocyanocobaltate (III) is particularly preferred. The organic complex ligands c) contained in the DMC catalysts according to the invention are in principle known and described in detail in the state of the art (see, for example, US-A 5 158 922, US-A 3 404 109, US-A 3 829 505, US-A 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 5 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 bimetallic cyanide compound a). Suitable organic complex ligands are, for example, alcohols, aldehydes, ketones, ethers, esters, amides, ureas, nitriles, sulfides and their mixtures. Preferred organic complex ligands are water-soluble aliphatic alcohols such as ethanol, isopropanol, n-butanol, iso-butanol, sec-butanol and tert-butanol. Especially preferred is tert-butanol. The organic complex ligand is added either during the preparation of the catalyst or immediately after precipitation of the bimetal cyanide compound a). Usually, the organic complex ligand is used in excess. The DMC catalysts according to the invention contain the bimetallic cyanide compounds a) in amounts of 25 to 90% by weight, preferably 30 to 85% by weight, based on the amount of the catalyst prepared, and the organic complex ligands c) in quantities of 0.5 to 30, Preferably from 1 to 25% by weight, based on the amount of the catalyst prepared. DMC catalysts conform The invention usually contains from 1 to 80% by weight, preferably from 1 to 40% by weight, based on the amount of the catalyst prepared, of a bile acid or its salt, ester or amide. . Suitable bile acids for the preparation of the catalysts according to the invention are steroid-C24-carboxylic acids which are decomposition products of cholesterol, and which are generally derived from 5-β-colan-24-oic acid by introduction of hydroxy groups in position a in C-3, C-6, C-7 and C-12. Preferred bile acids have the general formula wherein R1 R2, R3 and R4 independently denote H or OH and R5 OH, NH-CH2-COOH, NH-CH2-CH2-S03H, NH- (CH2) 3-N + (CH3) 2-CH2- CHOH-CH2-S03"or NH- (CH2) 3-N + (CH3) 2- (CH2) 3-S03 ~ Free acids or their salts, preferably alkali or alkaline earth metal salts, and esters thereof are suitable, preferably with alkyl radicals having 2 to 30 C atoms, and their amides, preferably with alkyl radicals or sulfoalkyl, sulfoalkylaminoalkyl, sulfohydroxyalkylaminoalkyl and carboxyalkyl radicals in the form of acid or salt Examples of suitable bile acids or their salts, esters or amides, cholic acid (3a, 7a, 12a-trihydroxy-5β-colan-24-oic acid, Rx = R3 = R4 = R5 = OH, R2 = OH), sodium salt of cholic acid (sodium cholate), cholate lithium, potassium cholate, glycocholic acid (N- [carboxymethyl] amide of 3a, 7a, 12a-trihydroxy-5β-colan-24-oic acid; Rx = R3 = R4 = OH, R2 = H, R5 = NH-CH2- COOH), sodium glycocholate, acid t aurocholic (N- [2-sulfoethyl] amide of 3a, 7a, 12a-trihydroxy-5β-colan-24-oic acid; Rx = R3 = R4 = OH, R2 = H, R5 = NH-CH2-CH2-S03H), sodium taurocholate, deoxycholic acid (3a, 12a-dihydroxy-5β-colan-24-oic acid, R: = R4 = R5 = OH, R2 = R3 = H), sodium deoxycholate, potassium deoxycholate, lithium deoxycholate, glycodeoxycholic acid (N- [carboxymethyl] amide of 3a, 12a-dihydroxy-5β-colan-24-oico, Rx = R4 = OH , R2 = R3 = H, R5 = NH-CH2-COOH), sodium glycodeoxycholate, taurodeoxycholic acid (N- [2-sulfoethyl] amide of 3a, 12a-dihydroxy-5β-colan-24-oico, Rx = R4 = OH, R2 = R3 = H, R5 = NH-CH2-CH2-S03H), sodium taurodeoxycholate, chenodeoxycholic acid (3a, 7a-dihydroxy-5β-colan-24-oic acid, Rx = R3 = R5 = OH, R2 = R4 = H), sodium chenodeoxylate, glycokenedeoxycholic acid (N- [carboxymethyl] amide of 3a, 7a, -dihydroxy-5β-colan-24-oic acid; Rx = R3 = OH, R2 = R4 = H, R5 = NH- CH2-COOH), sodium glycokenedeoxycholate, taurokenedeoxycholic acid (N- [2-sulfoethyl] amide of 3a, 7a-dihydroxy-5β-colan-24 acid -oic; Rx = R3 = OH, R2 = R4 = H, R5 = NH-CH2-CH2-S03H), sodium taurokenedeoxycholate, lithocholic acid (3a-hydroxy-5β-colan-24-oic acid; Rx = R5 = OH, R2 = R3 = R, = H), sodium lithocholate, potassium lithocholate, hiocholic acid (3a, 6a, 7a-trihydroxy-5β-colan-24-oic acid; Rx = R2 = R3 = R5 = OH, R4 = H), sodium hiocolate, lithium hiocolate, potassium hiocolate, hiodeoxycholic acid (3a, 6a-dihydroxy-5β-colan-24-oic acid); Rx = R2 = R5 = OH, R3 = R4 = H), sodium hyodeoxycholate, lithium hyodeoxycholate, potassium hyodeoxycholate, methyl cholate, ethyl cholate, ethyl deoxycholate and methyl hyocolate. The bile acids or their salts, esters or amides can be used alone or in the form of mixtures. Particular preference is given to using sodium, lithium or potassium salts or the methyl or ethyl esters of cholic acid, glycocholic acid, taurocholic acid, deoxycholic acid, glycodeoxycholic acid, taurodeoxycholic acid, chenodeoxycholic acid, glycokenedeoxycholic acid, taurokenedeoxycholic acid, lithocholic acid, hiocólico acid, hiodeoxycholic acid or their mixtures. Furthermore, bile acids such as ursodeoxycholic acid (3a-7β-dihydroxy-5β-colan-24-oic acid), 7-oxo-lithocholic acid (3a-hydroxy-7-oxo-5β-colan-24-oic acid) are suitable. , lithocholic acid-3-sulfate (3a-hydroxy-5β-colan-24-oico-3-sulfate acid), nor-colic acid and bisnor-colic acid, or their salts, esters or amides. Bile acids and their salts, esters or amides are generally well known and, for example, are described in detail in Nachr. Chem. Tech. Lab. 43. (1995) 1047 and "Rdmpp-Lexikon Naturstoffe", Stuttgart, New York 1997, p. 248 and next. It is also possible to use discrete mixtures of the aforementioned bile acids or their salts, esters or amides. The analysis of the catalyst composition is usually carried out by elemental analysis, thermogravimetry and extractive separation of the bile acid part or its salt, ester or amide and subsequent gravimetric determination. The catalysts according to the invention can be crystalline, partially crystalline or amorphous. The analysis of the crystallinity is usually carried out by powder X-ray diffractometry. Catalysts according to the invention are preferred which contain a) tin hexacyanocobaltate (III), b) a bile acid or its salt, ester or amide and c) tert-butanol The preparation of the DMC catalysts according to the invention is usually carried out in aqueous solution by reaction of) metal salts, in particular of formula (I), with metal cyanide salts, in particular of formula (II) ß) of organic complex ligands c), which are different from bile acid or its salt, ester or amide and y) of the bile acid or its salt, ester or amide. In this connection, the aqueous solutions of the metal salt (eg zinc chloride, used in stoichiometric excess (at least 50 mol% based on the metal cyanide salt)) and the metal cyanide salt (eg potassium hexacyanocobaltate) in the presence of the organic complex ligand c) (eg tertbutanol), forming a suspension containing the bimetallic cyanide compound a) (eg zinc hexacyanocobaltate) , water d), metal salt e) in excess, and the organic complex ligand c). The organic complex ligand c) may in this case be present in the aqueous solution of the metal salt and / or the metal cyanide salt, or may be added directly to the suspension obtained after the precipitation of the bimetal cyanide compound a). It has turned out to be advantageous to mix the aqueous solutions and the organic complex ligands c) under strong agitation. The suspension formed is then usually treated with bile acid or its salt, ester or amide b). The bile acid or its salt, ester or amide b) is preferably used in this connection in a mixture with water and organic complex ligand c). The isolation of the catalyst from the suspension is then carried out by known techniques, such as centrifugation or filtration. In a preferred embodiment, the isolated catalyst is then washed with an aqueous solution of the organic complex ligand c) (eg by resuspension and subsequent re-isolation by filtration or centrifugation). In this way, for example, water-soluble by-products can be eliminated., as potassium chloride, of the catalyst according to the invention. Preferably the amount of organic complex ligand c) in the aqueous wash solution is between 40 and 80% by weight, based on the total solution. Furthermore, it is advantageous to add a little of the bile acid or its salt, ester or amide to the aqueous washing solution, preferably from 0.5 to 5% by weight, based on the total solution. In addition, it is advantageous to wash the catalyst more than once. For this, the first washing process can be repeated, for example.

However, it is preferable to use non-aqueous solutions for the other washing processes, for example a mixture of the organic complex ligand and the bile acid or its salt, ester or amide.

Thereafter, the washed catalyst, if appropriate after spraying, is dried at temperatures of generally 20-100 ° C and at pressures of generally 0.1 bar at normal pressure (1013 nabar). Another object of the present invention is the use of the DMC catalysts according to the invention in a process for the production of polyether polyol ethers of alkylene oxides to initiator compounds having active hydrogen atoms. As the alkylene oxides, ethylene oxide, propylene oxide, butylene oxide and mixtures thereof are preferably used. The synthesis of the polyether chains by alkoxylation can, for example, be carried out with only one monomeric epoxide or else statistically or in block with 2 or 3 different monomeric epoxides. More details can be found in "Ullmanns Encyclopadie der industriellen Chemie", vol. A21, 1992, p. 670 and next As starter compounds having active hydrogen atoms, molecular weight compounds (number media) of 18 to 2,000 and 1 to 8 hydroxyl groups are preferably used. By way of example, mention may be made of: ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,4-butanediol, hexamethylene glycol, bisphenol A, trimethylolpropane, glycerin, pentaerythritol, sorbitol, cane sugar, digested starch or water. It is advantageous to use those initiator compounds having active hydrogen atoms obtained, for example, by conventional alkaline catalysis of the abovementioned low molecular weight initiators and to synthesize oligomeric alkoxylation products of molecular weights (number means) of 200 to 2,000. The polyaddition catalyzed by catalysts according to the invention of alkylene oxides to initiator compounds having active hydrogen atoms is generally carried out at temperatures of 20 to 200 ° C, preferably in the range of 40 to 180 ° C, with special preference at temperatures of 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 a substance or in an inert organic solvent, such as toluene and / or THF. The amount of solvent is usually between 10 and % by weight, based on the amount of the polyether polyol to be produced.

The catalyst concentration is chosen so that under the given reaction conditions a good control of the polyaddition is possible. The catalyst concentration is generally in the range of 0.0005% by weight to 1% by weight, preferably in the range of 0.001% by weight to 0.1% by weight, with particular preference in the range of 0.001 to 0.0025% by weight, based on the amount of the polyether polyol to be produced. The number average molecular weights of the polyether polyols produced according to the invention are in the range of 500 to 100,000 g / mol, preferably in the range of 1,000 to 50,000 g / mol, particularly preferably in the range of 2,000 to 20,000 g / mol. mol. The polyaddition can be carried out continuously or batchwise, for example in a discontinuous or semi-batch process. The catalysts according to the invention can be used, due to their clear greater activity, in very low concentrations (25 ppm and less, referred to the amount of the polyether polyol to be produced). If the polyether polyols produced in the presence of catalysts according to the invention are used for the production of polyurethanes (Kunststoffhandbuch, Vol 7, Polyurethane, 3rd edition, 1993, pp. 25-32 and 57-67), the removal of the catalyst can be suppressed. of the polyether without inconveniently affecting the product quality of the obtained polyurethane.

Preparation of the catalyst jotn i > A Preparation of a DMC catalyst using sodium salt of cholic acid (Catalyst A) To a solution of 2 g (6 mmol) of potassium hexacyanocobaltate in 35 ml of distilled water was added with vigorous stirring (24,000 rpm) a solution of 6.2 g (45.75 mmol) of zinc chloride in 10 ml of distilled water. Immediately afterwards a mixture of 25 g of tert-butanol and 25 g of distilled water was added to the formed suspension and then stirred vigorously (24,000 rpm) for 10 min. Then a mixture of 0.5 g of colic acid sodium salt was added (Fluka Chemie AG, CH-9471 Buchs), 0.5 g of tert-butanol and 50 g of distilled water and stirred for 3 min (1,000 rpm). The solid matter was isolated by filtration, then stirred (10,000 rpm) for 10 min with a mixture of 35 g of tert-butanol, 15 g of distilled water and 0.5 g of sodium salt of cholic acid and filtered again. Finally, it was stirred (10,000 rpm) again for 10 min with a mixture of 50 g of tert-butanol and 0.25 g of sodium salt of cholic acid. After filtering, the catalyst was dried at 50 ° C and under normal pressure to constant weight. Dry pulverulent catalyst yield: 2.1 g Elemental analysis, thermogravimetric analysis and extraction: Cobalt = 12.6% by weight, Zinc = 27.3% by weight, tert-Butanol = 10.9% by weight, Cholic acid sodium salt = 4.3% by weight. p oTn ifi B Preparation of a DMC catalyst using the sodium salt of hiodeoxycholic acid (Catalyst B) The procedure was as in Example A, but the sodium salt of hiodeoxycholic acid (Sigma-Aldrich Chemie GmbH, D-82041 Deisenhofen) was used. place of the colic acid sodium salt of Example A. Dry pulverulent catalyst yield: 2.0 g Elemental analysis, thermogravimetric analysis and extraction: Cobalt = 13.8% by weight, Zinc = 28.3% by weight, ter- Butanol = 7.3% by weight, Sodium salt of hiodeoxycholic acid = 6.2% by weight. Example C (comparative example) Preparation of a DMC catalyst using tert-butanol without bile acid or its salt, ester or amide (Catalyst C, synthesis according to JP-A 4145123) To a solution of 4 g (12 mmol) of Potassium hexacyanocobaltate in 75 ml of distilled water was added with vigorous stirring (24,000 rpm) a solution of 10 g (73.3 mmol) of zinc chloride in 15 ml of distilled water. Immediately afterwards a mixture of 50 g of tert-butanol and 50 g of distilled water was added to the formed suspension and then stirred vigorously (24,000 rpm) for 10 min. The solid matter was isolated by filtration, then stirred (10,000 rpm) for 10 min with 125 g of a mixture of tert-butanol and distilled water (70/30 w / w) and filtered again. Finally it was stirred again (10,000 rpm) for 10 min with 125 g of tert-butanol. After filtering, the catalyst was dried at 50 ° C and under normal pressure to constant weight. Dry pulverulent catalyst yield: 3.08 g Elemental analysis: Cobalt = 13.6% by weight, Zinc = 27.4% by weight, tert-butanol = 14.2% by weight. Polyol ether production General implementation In a 500 ml pressure reactor, 50 g of polypropylene glycol as starter (molecular weight = 1000 g / mol) and 3-5 mg of catalyst (15-25 ppm, referred to as the initiator) were placed under protective gas (argon). to the amount of the polyether polyol to be produced) and stirring was heated to 105 ° C. Thereafter, propylene oxide (approximately 5 g) was dosed at a time until the total pressure rose to 2.5 bar. Only more propylene oxide is dosed again when an accelerated pressure flow is observed in the reactor. This accelerated pressure flow indicates that the catalyst is activated. The rest of the propylene oxide (145 g) is then metered in continuously at a constant total pressure of 2.5 bar.

After the complete dosing of the propylene oxide and a further 2 hours of reaction time at 105 ° C, the volatile fractions were distilled off at 90 ° C (1 mbar) and then cooled to room temperature. The polyether polyols obtained were characterized by determining the OH indices, the content of double bonds and the viscosities. The development of the reaction was followed by transformation-time curves (consumption of propylene oxide [g] versus reaction time [min]). The induction time was determined by the tangent cut-off point at the steepest point of the transformation-time curve with the prolongation of the baseline curve. The propoxylation times determining the activity of the catalyst correspond to the time interval between the activation of the catalyst (end of the induction period) and the end of the dosage of the propylene oxide. The total reaction time is the sum of the induction time and the propoxylation time. Example 1 Polyol ether production with catalyst A (25 ppm) Induction time: 217 min Propoxylation time: 33 min Total reaction time: 250 min Polyol ether: OH number (mg KOH / g): 29, 6 Content of double bonds (mmol / kg): 6 Viscosity at 25 ° C (mPas): 855 p.jom go >; 9 Polyol ether production with catalyst A (15 ppm) Induction time: 387 min Propoxylation time: 168 min. Total reaction time: 555 min.

Polyol ether: OH number (mg KOH / g): 30.1 Content of double bonds (mmol / kg): 6 Viscosity at 25 ° C (mPas): 993 Without the separation of the catalyst the metal content in the polyol amounted to : Zn = 4 ppm, Co = 2 ppm. Example 3 Polyol ether production with catalyst B (25 ppm) Induction time: 371 min Propoxylation time: 40 min. Total reaction time: 411 min.

Polyol ether: OH number (mg KOH / g): 30.2 Content of double bonds (mmol / kg): 6 Viscosity at 25 ° C (mPas): 902 Example 4 (Comparative) Catalyst C (15 ppm) did not show any activity under the conditions described above or even after 14 h of induction time. Using 50 ppm of catalyst C the induction time amounted to approx. 9 h. The propoxylation time amounted to more than 12 hours, with deactivation of the catalyst taking place during the course of the reaction.

Examples 1-3 indicate that the novel DMC catalysts according to the invention can be used, due to their clearly high activity in the production of polyether polyols, in such low concentrations that the separation of the catalyst from the polyol can be suppressed. It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Claims (11)

CLAIMS Having described the invention as above, property is claimed as contained in the following claims

1. Birettallic cyanide catalyst (E)) characterized in that it contains a) one or more bimetallic cyanide compounds, b) one or more bile acids or their salts, esters or amides, and c) one or more organic complex ligands other than b) .

2 . DM3 catalyst according to claim 1, characterized in that it also contains d) water and / or e) water-soluble metal salt.

3 . DMC catalyst according to claim 1 or 2, characterized in that the biphalic riapide carbonate a) is zinc hexacyanocobaltate (I II).

Four . DMC catalyst according to one of the 1 to 3 characterized in that the cc organic ligand c) is tert-butanol.

5. DMC catalyst according to one of the claims 1 to 4, characterized in that it contains from 1 to 80 by weight of a bile acid or its salt, ester or amide.

6 DMC catalyst according to one of Claims 1 to 5, characterized in that the bile acid possesses the general formula. wherein Rx, R2, R3 and R4 independently denote H or OH and R5 OH, NH-CH2-CH2-S03H, NH- (CH2) 3-N + (CH3) 2- (CH2) 3-S03", NH- (CH2) 3-N + (CH3) 2-CH2-CHOH -CH2-S03"or NH-CH2-COOH.

7 DMC catalyst according to one of the claims 1 to 6, characterized in that the taster has COTO salt of bile acid the sodium, lithium or potassium salts of cholic acid, glycocholic acid, taurocholic acid, deoxycholic acid, glycodeoxycholic acid, taurodeoxycholic acid , chenodeoxycholic acid, glycokenedeoxycholic acid, taurokenedeoxycholic acid, lithocholic acid, hiocholic acid, hiodeoxycholic acid or mixtures thereof.

8 PROCESS FOR THE PREPARATION OF A DMC CATALYST ACCORDING TO NONE OF REVIVIECCIDES 1 TO 7, CHARACTERIZED IN THAT IT COMPRISES THE STEPS OF i) REACTION IN AQUEOUS SOLUTION OF METALLIC SALTS WITH METAL CYANIDE SALTS, B) ORGANIC COMPLEX LIGANDS WHICH ARE DIFFERENT of bile acids or their salts, esters or amides, and?) bile acids or their salts, esters or amides, ii) isolation, washing and drying of the catalyst obtained in step i).

9. Process for the production of polyether polyol ether by alkylene oxides to initiator compounds having active hydrogen atoms in the presence of one or more catalysts of DMC according to one of claims 1 to 7.

10. Polyol ether producible according to the process according to claim 9.

11. Use of one or more DMC catalysts according to one of claims 1 to 7 for the production of polyether polyol ether by alkylene oxides to initiator compounds having active hydrogen atoms.