MXPA01001115A - Bimetallic-cyanide catalysts used for preparing polyether polyols - Google Patents

Abstract

The present invention relates to new bimetallic-cyanide catalysts which are used for producing polyether polyols by the poly-addition of alkylene oxides to starter compounds comprising hydrogen atoms. This catalyst contains a) compounds of the bimetallic-cyanide type, b) organic complex ligands different from c), and c) complex ligands obtained by the introduction of a glycidyle ether in the catalyst. These catalysts exhibit a substantially increased activity during the preparation of polyether polyol.

Description

Bimetallic cyanide catalysts for the preparation of ppljoléteyes DESCRIPTION OF THE INVENTION The invention relates to novel bimetallic cyanide (D C) catalysts for the preparation of polyether polyols by 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 3 404 109, US 3 829 505, US 3 941 849 and US Pat. 5 158 922). The use of these DMC catalysts for the preparation 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 preparation of polyether polyols by 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. Aqueous solutions of sodium chloride are mixed in a typical catalyst preparation by way of example.

Ref: 1126266 zinc (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 700 949).

Zn3 [Co (CN) 6] 2 • x ZnCl2 • and H20 • z Glime From JP 4 145 123, US 5 470 813, EP 700 949, EP 743 093, EP 761 708 and WO 97/40086 DMC catalysts are known that when using tert-butanol as an organic complex ligand (alone or in combination) with a polyether (EP 700 949, EP 761 708, WO 97/40086)) further reduce the proportion of monofunctional polyethers with terminal double bonds in the preparation 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. In this connection, combinations of tert-butanol ligands and polyalkylene glycols (for example polypropylene glycol) are preferably used. 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 an improved catalyst activity compared to the types of catalysts known hitherto. This leads to shortened alkoxylation times to improved profitability of the polyether preparation 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 complex ligand, formed by incorporation of a glycidyl ether in the catalyst, possess in the polyol ether preparation a strongly increased activity. The object of the present invention is therefore a bimetallic cyanide catalyst (DMC) containing a) one or more, preferably one, bimetal cyanide compounds, b) one or more, preferably one, organic complex ligands other than c), and c) one or more, preferably one, complex ligands formed by incorporation of a glycidyl ether into the catalyst. 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), 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 X's are the same or different, preferably the same, and anions, 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 a water-soluble metal salt and a water-soluble metal cyanide salt. For the preparation of bimetal cyanide compounds a) suitable water-soluble metal salts preferably have the general formula (I) M (X) n in which M is selected from the metals Zn (II), Fe (II), Ni ( II), Mn (II), C (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 X's are the same or different, preferably the same, and anions, 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 chloride ( II), cobalt (II) chloride, cobalt thiocyanate (II), nickel (II) chloride and nickel (II) nitrate. Mixtures of different water-soluble metal salts can also be used. 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's are the same or different, preferably the same, and are an alkali metal ion or an alkaline earth metal ion. The A's are the same or different, preferably the same, and anions, 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 lithium hexanocyanocobaltate (III). Preferred bimetallic cyanide compounds a) contained in the catalysts according to the invention are the compounds of general formula (III) MX [M'X, (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 bimetallic cyanide compounds are listed, for example, in US 5 158 922 (column 8, lines 29-66). Particular preference is given to zinc hexanocyanocobaltate (III). The organic complex ligands b) 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 5 158 922, especially column 6, lines 9-65, US 3 404 109, US 3 829 505, US 3 941 849, EP 700 949, EP 761 708, JP 4 145 123, US 5 470 813, EP 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 bimetal cyanide compound a) _. Suitable organic complex ligands are, for example, alcohols, aldehydes, ketones, ethers, esters, amides, ureas, nitriles, sulfides and mixtures thereof. 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 the 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 20 to 90% by weight, preferably from 25 to 80% by weight, based on the amount of the catalyst prepared, and the organic complex ligands b) in quantities of 0.5 to 30, preferably 1 to 25% by weight, based on the amount of the catalyst prepared. The DMC catalysts according to the invention usually contain from 5 to 80% by weight, preferably from 10 to 60% by weight, based on the amount of the catalyst prepared, of complex ligands c) formed by incorporation of a glycidyl ether into the catalyst.

For the preparation of the catalysts according to the invention, for example, glycidyl ethers of monomeric or aromatic or araliphatic mono-, di-, tri-, tetra- or polyfunctional monomers or polymers (with at least two monomer units) are suitable. Preferably they are glycidyl ethers of mono, di, tri, tetra or polyfunctional aliphatic alcohols such as butanol, hexanol, octanol, decanol, dodecanol, tetradecanol, ethanediol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2, 2-dimethyl-1,3-propanediol, 1,2,3-propanetriol, 1,6-hexanediol, 1,1-tris (hydroxymethyl) ethane, 1,1,1-tris (hydroxymethyl) propane, tetrakis (hydroxymethyl) methane, sorbitol, polyethylene glycol and polypropylene glycol, both mono, di, tri, tetra and polyethers can be considered. Particular preference is given to mono- or diglycidyl ethers of butanol, hexanol, octanol, decanol, dodecanol, tetradecanol, ethanediol or 1,4-butanediol as well as polypropylene glycol or polyethylene glycol, in particular with polymerization degrees of 2 to 1000 monomer units. It is also possible to use discrete mixtures of the above-mentioned glycidyl ethers. The glycidyl ethers are generally obtained by reacting mono, di, tri, tetra or polyfunctional alcohols with epichlorohydrin in the presence of a Lewis acid such as, for example, tin tetrachloride or boron trifluoride, which gives the corresponding chlorohydrins and subsequent dehydrohalogenation with a base (eg sodium hydroxide).

Methods for the preparation of glycidyl ethers are generally well known and are described in detail, for example, in "Kir -Othmer, Encyclopedia of Chemical Technology", volume 9, 4th edition, 1994, p. 739 and next. and "Ullmann-Encyclopedia of Industrial Chemistry", volume A9, 5th edition, Weinheim / New York, 1987, p. 552. The glycidyl ether used for the preparation of the catalyst according to the invention can be present in the catalyst prepared in the originally used form or also in a modified chemical form, eg hydrolyzed. The analysis of the catalyst composition is usually carried out by elemental analysis and gravimetry or separation by extraction of the complex ligand formed by incorporation of an ether, glycidyl in the catalyst, with 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 X-ray powder diffractometry. Preferred catalysts according to the invention are a) zinc hexacyanocobaltate (III), b) tert-butanol and c) mono or diglycidyl ether of butanol, hexanol, octanol, decanol, dodecanol, tetradecanol, ethanediol, 1,4-butanediol, polypropylene glycol or polyethylene glycol. The preparation of the DMC catalysts according to the invention is usually carried out in aqueous solution by reacting metal salts, in particular of formula (I), with metal cyanide salts, in particular of formula (II), β). organic complex b), other than the glycidyl ether and y) glycidyl ether. 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 b) (eg tert-butanol), forming a suspension containing the bimetal cyanide compound a) (eg hexacyanocobaltate zinc), water d), metal salt in excess e), and the organic complex ligand b). • The organic complex ligand b) may in this case be present in the aqueous solution of the metal salt and / or the metal cyanide salt, or it 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 b) under strong stirring. The suspension formed is then usually treated with the glycyl ether. The glycidyl ether is used in this connection preferably in a mixture with water and organic complex ligand b). The suspension catalyst is then isolated by known techniques, as centrifugation or filtration. In a preferred embodiment, the isolated catalyst is then washed with an aqueous solution of the organic complex ligand b) (eg by resuspension and subsequent re-isolation by filtration or centrifugation). In this way, for example, water-soluble by-products, such as potassium chloride, can be removed from the catalyst according to the invention. Preferably the amount of organic complex ligand b) in the aqueous wash solution is between 40 and 80% by weight, based on the total solution. In addition, it is advantageous to add some glycidyl ether, preferably 0.5 to 5% by weight, based on the total solution to the aqueous washing 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 glycidyl ether. Subsequently, the washed catalyst, if appropriate after spraying, is dried at temperatures of generally 20-100 ° C and at pressures of generally 0.1 mbar at normal pressure (1013 mbar). Another object of the present invention is the use of the DMC catalysts according to the invention for the preparation 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 Encyclopaedia der industriellen Cheie", English edition, 1992, vol. A21, pgs. 670-671. As starter compounds having active hydrogen atoms, compounds of molecular weights of 18 to 2000 and 1 to 8 hydroxyl groups are 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, sugar cane, 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 above-mentioned low molecular weight initiators and to synthesize oligomeric alkoxylation products of molecular weights of 200 to 2000. The polyaddition catalyzed by The catalysts according to the invention of alkylene oxides to initiator compounds having active hydrogen atoms are generally carried out at temperatures of 20 to 200 ° C, preferably in the range of 40 to 180 ° C, particularly preferably at temperatures of 50 to 50 ° C. 150 ° C. The reaction can be carried out at total pressures from 0 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 30% 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, particularly preferably in the range of 0.001% by weight. 0.0025% by weight, based on the amount of the polyether polyol to be produced. The molecular weights of the polyether polyols produced according to the invention are in the range of 500 to 100000 g / mol, preferably in the range of 1000 to 50000 g / mol, particularly preferably in the range of 2000 to 20 000 g / mol. The polyaddition can be carried out continuously or batchwise, for example in a discontinuous or semi-batch process. When using the DMC catalysts according to the invention, the alkoxylation times in the preparation of polyether polyols are typically reduced by 70-75% compared to the previously known DMC catalysts with tert-butanol and polyalkylene glycols as ligands. The shortening of the alkoxylation times leads to improved process efficiency. 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 manufacture of polyurethanes (Kunststoffhandbuch, vol. 7, Polyurethane, 3rd edition, 1993, p. 25-32 and 57-67), the elimination of the catalyst from the polyether polyol can be suppressed without inconveniently affecting the product quality of the obtained polyurethane. The following Examples illustrate the invention but by no means have a limiting character. Examples Preparation of the catalyst Example 1 Preparation of a DMC catalyst using a polypropylene glycol diglycidyl ether with a number average molecular weight of 640 (Catalyst A) To a solution of 4 g (12 mmol) of potassium hexacyanocobaltate in 70 ml of distilled water was added with vigorous stirring (24000 rpm) a solution of 12.5 g (91.5 mmol) of zinc chloride in 20 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 (24000 rpm) for 10 min. Then a mixture of 1 g of a polypropylene glycol bis (2,3-epoxypropyl ether) with an average number-average molecular weight of 640 (Aldrich), 1 g of tert-butanol and 100 g of distilled water was added and stirred for 3 min (1000 rpm). The solid matter was isolated by filtration, then stirred (10000 rpm) for 10 min with a mixture of 70 g of tert-butanol, 30 g of distilled water and 1 g of polypropylene glycol bis (2,3-epoxypropyl ether) previous and it was filtered again. Finally it was stirred (10000 rpm) again for 10 min with a mixture of 100 g of tert-butanol and 0.5 g of the above polypropylene glycol bis (2,3-epoxypropyl ether). After filtering, the catalyst was dried at 50 ° C and under normal pressure to constant weight. Dry pulverulent catalyst yield: 8.70 g Elemental analysis, thermogravimetric analysis and extraction: Cobalt = 8.7%, Zinc = 20.2%, tert-Butanol = 4.2%, Ligand polypropylene glycol diglycidyl ether = 30.5%. Example 2 Preparation of a DMC catalyst using a polypropylene glycol diglycidyl ether with a number average molecular weight of 380 (Catalyst B) The procedure was as in Example 1, but a polypropylene glycol bis (2,3-epoxypropyl ether) was used as the glycidyl ether. ) with an average numerical molecular weight of 380 (Aldrich signature) in place of the polypropylene glycol bis (2,3-epoxypropyl ether) of Example 1. Dry pulverulent catalyst yield: 6.40 g Elemental analysis, thermogravimetric analysis and extraction: Cobalt = 9.1%, Zinc = 22 , 1%, tert-Butanol = 2.2%, Ligand polypropylene glycol diglycidyl ether = 37.8%. Example 3 Preparation of a DMC catalyst using a polyethylene glycol diglycidyl ether with a number average molecular weight of 3350 (Catalyst C) The procedure was as in Example 1, but a poly (oxyethylene) bis (glycidyl ether) with a weight was used as the glycidyl ether. number average molecular weight of 3350 (Sigma signature) in place of the polypropylene glycol bis (2,3-epoxypropyl ether) of Example 1. Dry pulverulent catalyst yield: 5.60 g Elemental analysis, thermogravimetric analysis and extraction: Cobalt = 7.7%, Zinc = 17.6%, tert-Butanol = 10.0%, Ligand polyethylene glycol diglycidyl ether = 35.6%. Example 4 (Comparative Example) Preparation of a DMC catalyst using a polypropylene glycol with a number average molecular weight of 420 (Catalyst D, synthesis according to WO 97/40086) _ To a solution of 4 g (12 mmol) of potassium hexacyanocobaltate in 70 ml of distilled water, a solution of 12.5 was added with vigorous stirring (24000 rpm). g (91.5 mmol) of zinc chloride in 20 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 (24000 rpm) for 10 min. Then a mixture of 1 g of a polypropylene glycol with an average number molecular weight of 420, 1 g of tert-butanol and 100 g of distilled water was added and stirred for 3 min (1000 rpm). The solid matter was isolated by filtration, then stirred (10000 rpm) for 10 min with a mixture of 70 g of tert-butanol, 30 g of distilled water and 1 g of the above polypropylene glycol and filtered again. Finally, it was stirred (10000 rpm) again for 10 min with a mixture of 100 g of tert-butanol and 0.5 g of the above polypropylene glycol. After filtering, the catalyst was dried at 50 ° C and under normal pressure to constant weight. Dry pulverulent catalyst yield: 5.7 g Elemental analysis, thermogravimetric analysis and extraction: Cobalt = 10.1%, Zinc = 23.0%, tert-Butanol = 6.3%, Polypropylene glycol = 33.3%. Preparation of polyether polyols General implementation In a 500 ml pressure reactor, 50 g of polypropylene glycol were introduced under protective gas (argon) as initiator (molecular weight = 1000 g / mol) and 3 mg of catalyst (15 ppm, referring to the amount of the polyoliteate 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 drop is observed in the reactor. This accelerated pressure drop indicates that the catalyst is activated (end of the induction time). 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 cutoff point of the tangent at the steepest point of the transformation-time curve with the extension of the baseline. The propoxylation times which determine the activity of the catalyst correspond to the time interval between the activation of the catalyst (end of the induction time) and the end of the dosage of the propylene oxide. Example 5 Polyol ether preparation with catalyst A (15 ppm) Propoxylation time: 160 min Polyol ether: OH number (mg KOH / g): 30.0 Content of double bonds (mmol / kg): 7 Viscosity at 25 ° C ( mPas): 897 Example 6 Polyol ether preparation with catalyst B (15 ppm) Propoxylation time: 190 min Polyol ether: OH number (mg KOH / g): 29.6 Content of double bonds (mmol / kg): 9 Viscosity at 25 ° C (mPas): 954 Example 7 Polyol ether preparation with catalyst C (15 ppm) Propoxylation time: 185 min Polyol ether: OH number (mg KOH / g): 29.0 Content of double bonds (mmol / kg): 8 Viscosity at 25 ° C ( mPas): 839 Example 8 (Comparative example) Polyol ether preparation with catalyst D (15 ppm) Propoxylation time: 650 min Polyol ether: OH number (mg KOH / g): 29.0 Content of double bonds (mmol / kg) : 8 _ Viscosity at 25 ° C (mPas): 967 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. invention.

Claims (10)

1. CLAIMS Having described the invention as above, the content of the following claims is declared as property 1 . Catalyst of Fauideal Closure (EMTJ) characterized by acptieriB a) one or more bimetallic cyanide compounds, b) one or more organic complex ligands other than c), and c) one or more complex ligands formed by incorporation of a glycidyl ether in the catalyst.
2. 2 . Catalyst 1X acnfcaprie cxn la reivirr3icarticn 1, characterized perqué also contains d) water and / or e) water-soluble metal salt. 3 _ Grsliza ± ar of EMC amfcoiB acn the vindicated 1 or 2 characterized patrjje e? compound of bimetallic cyanide is zinc hexacyanocobaltate (III).
3. Four .
4. Catalyst of UC acpfcapre ccri would go from claims 1 to 3 because the organic linker ligand is tert-butanol.
5. 5 . Catalyst efe WC O? EC? TB COI tria of claims 1 to 4 characterized by having from 5 to 8C% by weight, preferably from 10 to 60% by weight of a complex ligand formed by incorporation of a glycidyl ether in the catalyst.
6. 6. WC acnficoie coi see of the reivirriieacioens 1 to 5, caractecizacb parque the glycidyl ether d = riva of an aliphatic alcohol.
7. 7 The preparation for the CNS catalyst acpfaie scn of the claims 1 to 6 described by the steps of: i) reaction in aqueous solution of OI) metal salts with metal cyanide salts, ß) ligands of organic complexes other than glycidyl ether, and Y) glycidyl ether, ii) isolation, washing and drying of the catalyst obtained in step i).
8. 8 The preparation for the preparation of polyethereals characterized by polyaddition of alkylene oxides to initiator compounds having active hydrogen atoms in the presence of one or more DMC catalysts according to claim 1 to 6.
9. 9. The characterization of the percussion can be prepared by the pharmacist according to claim 8. rc "
10. 10. Use of one or more DMC catalysts according to one of claims 1 to 6 for the preparation of polyether polyols by alkylene oxides to initiator compounds having active hydrogen atoms.