MXPA98005379A - New complex compositions of zinc / metal hexacianocobaltato, a process for its preparation and its use in the processes for the manufacture of polyeterpolio - Google Patents

Abstract

The invention relates to novel zinc / metal hexacyanocobaltate complex compounds of the formula Zn3 ~ vMv [Co (CN) 6] 2. w (H2O). x (L) and [Zn (X) n]. z [M (Y) m)], These complex compounds with convenient catalysts. This invention also relates to a process for the production of the compounds, and to the use of the compounds in a process for the production of polyester polyols. These new zinc / metal hexacyanocobaltate complex compounds when used as catalysts in a process for the production of polyether polyols substantially reduce the induction period of the polyaddition reaction of alkylene oxides to initiator compounds containing hydrogen atoms. In addition, polyether polyols with a more stable molecular weight dispersion are obtained.

Description

New complex compositions of zinc / metal hexacyanocobaltate, a process for its preparation and its use in processes for the manufacture of polyether polyols FIELD OF THE INVENTION The present invention relates to new zinc / metal hexacyanocobaltate complex compounds, which can be used as catalysts, to a process for their production, and to the production of polyether polyols from these new zinc / metal hexacyanocobaltate complex compounds.

The complex compounds of bimetallic cyanide (DMC) are known as suitable catalysts for the polyaddition of alkylene oxides to initiator compounds having active hydrogen atoms. Such catalysts and processes for the production of polyether polyols from these catalysts are described in, for example, US Pat. Nos. 3,404,109; 3,829,505; 3,941,849 and 5,158,922. The use of these complex bi-metal cyanide compounds as catalysts for the manufacture of REP: 27743 polyether polyols give rise in particular to a reduction in the proportion of monofunctional polyethers with terminal double bonds, the so-called monooles, in comparison with the conventional manufacture of polyether polyols using alkali metal catalysts, such as alkali metal hydroxides.

US Pat. No. 4,470,813 and JP 4 145 123 disclose improved bimetal cyanide complex compounds which make it possible to further reduce the proportion of monofunctional polyethers with terminal double bonds in the production of polyether polyols. In addition, by using the improved bimetallic cyanide complex compounds, the induction time in the polyaddition reaction of alkylene oxides to the corresponding initiator compounds is reduced and the activity of the catalyst is also increased.

It is therefore an object of the present invention to provide even more improved bimetallic cyanide complexes (DMC) as catalysts for the polyaddition of alkylene oxides to the corresponding initiator compounds, which have a remarkably reduced induction period compared to the types of known catalysts. until now. A reduction of the induction period leads, by shortening the times of the manufacturing cycles of polyether polyols, to an improved process efficiency. In addition to this, it has been the object of the present invention to achieve a dispersion of the molar masses in the polyether polyols to be as narrow as possible. A dispersion of the molar masses which is as narrow as possible of the polyols is very advantageous for the processing to very valuable polyurethanes, such as for example elastomers.

DESCRIPTION OF THE INVENTION The present invention provides novel zinc / metal hexacyanocobaltate complex compounds, which are suitable catalysts corresponding to the formula Zn3-vMv [C? (CN) 6] 2. w (H20). x (L) and [Zn (X) J z [M (Y) m)] I) wherein M means a divalent metal selected from the group of cadmium (II), mercury (II), palladium (II), platinum (II) , vanadium (II), magnesium (II), calcium (II), barium (II), iron (II), nickel (II), manganese (II), cobalt (II), tin (II), lead (II) , Strontium (II) and Copper (II), X and Y are the same or different and each represents a halogenide or a hydroxy group, sulfate, carbonate, cyanate, thiocyanate, isocyanate, isothiocyanate, carboxylate, oxalate or nitrate, L represents an organic complex ligand selected from the group of alcohols, aldehydes, ketones, ethers, esters, amides, ureas, nitriles or sulfides, v means a number from 0.005 to 2.995 w represents a number from 0.1 to 10, x means a number from 0.01 to 10, and a number from 0.001 to 3.0 and a number from 0.001 to 3.0 and m and n are the same or different and each represent the numbers 1 or 2.

Especially preferred are zinc / metal hexacyanocobaltates corresponding to the above formula in which: M represents a divalent metal atom selected from the group consisting of cadmium (II), mercury (II), palladium (II), platinum (II), vanadium (II), magnesium (II), calcium (II) and barium (II), X and Y are the same or different, and each represent halides, especially chlorine or bromine, L represents an organic complex ligand selected from the group consisting of alcohols, ketones and ethers and v means a number of 0.01 to 2.99, with w, x, y, z, and m, defined as the formula (I) above.

As ligand L with ether bonds, especially those compounds which are capable of forming chelates with metals are taken into consideration. For example, the following are considered as ligands: methanol, ethanol, propanol, isopropanol, butanol, hexanol, octanol, terbutanol, formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, i-butyraldehyde, glyoxal, benzaldehyde, tolualdehyde, acetone, methyl ethyl ketone, 3- pentanone, 2-pentanone, 2-hexanone, 2,4-pentanedione, 2,5-hexanedione, 2,4-hexanedione, m-dioxane, p-dioxane, trioxymethylene, paraldehyde, diethyl ether, 1-ethoxypentane, bis (β-) chloroethyl) ether, bis (β-ethoxyethyl) ether, dibutyl ether, ethylpropyl ether, bis (β-methoxyethyl) ether, dimethoxyethane (glime), diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether, dimethoxymethane, methylpropyl ether, poly (alkylene oxide) polyols, formamide, acetamide, propionamide, butyramide, valeramide, N, N'-dimethylacetamide, amyl formate, ethyl formate, n-hexyl formate, n-propyl phomate, ethyl ethanoate, methyl acetate, methyl propionate , triethylene glycol diacetate, acetonitrile, propioni trile, butyronitrile, dimethyl sulfide, diethyl sulfide, dibutyl sulfide, dipropyl sulfide, diamyl sulfide, 1,1,3,3-tetramethylurea and 1, 1,3,3-tetraethylurea.

The zinc / metal hexacyanocobaltate complex compounds (which are preferably catalysts) are preferred those corresponding to the formula: Zn3-vMv [Co (CN) 6] 2 • w (H20). x (L) and (ZnCl2). z (MCl2) (II) where v represents a number from 0.005 to 2.995 w represents a number from 0.1 to 10, x represents a number from 0.01 to 10, and y and z are the same or different, and each represents a number from 0.001 to 3.0. with M and L are defined as in formula (I) above.

Of these preferred complex compounds, it is more preferred that M, X and Y, L, and m and n, are selected so that the compositions correspond to the general formula: Zn3-vCdv [Co (CN) 6] 2. w (H20). x (tere, utanol) and (ZnCl2). z (CdCl2) (III) where v represents a number from 0.005 to 2.995 w represents a number from 0.1 to 10, x represents a number from 0.01 to 10, and y and z are the same or different, and each represents a number from 0.001 to 3.0.

The present invention also provides a process for the preparation of the zinc / metal hexacyanocobaltate catalysts described above.

These zinc / metal hexacyanocobaltate complex compounds, which are suitable for use as catalysts, are prepared by A) reacting (1) an aqueous solution of 1 to 90% by weight of (a) a zinc salt of formula Zn ( X) n and (b) a metal salt of formula M (Y) m wherein: M represents a divalent metal atom selected from the group consisting of cadmium (II); mercury (II); palladium (II), platinum (II), vanadium (II), magnesium (II), calcium (II), barium (II), iron (II), nickel (II), manganese (II), cobalt (II), tin (II), lead (II), strontium (II), and copper (II), X and Y are the same or different and each represents a halide group, a hydroxy, a sulfate, a carbonate, a cyanate, a thiocyanate, an isocyanate, an isothiocyanate, a carboxylate, an oxalate or a nitrate group. and m and n are the same or different, and each represents the number 1 or 2; with (2) an aqueous solution of 0.5 to 50% by weight of a cobalt (III) cyanide salt corresponding to the formula M'3 [Co (CN) 6] r (IV) wherein r represents 1 or 2, and M 'represents an alkali metal atom or an alkaline earth metal atom, in the presence of complexes of organic ligands of formula L. wherein: L represents an organic complex ligand selected from the group consisting of alcohols, aldehydes, ketones, ethers, esters, amides, ureas, nitriles and sulfur ^ and where the salts Zn (X) n, M (Y) m and the salt of cobalt cyanide (III) and the ligand Complexes L are present in amounts such that: (i) the molar ratio of zinc and metal M to cobalt is from 2: 1 to 10: 1. (ii) the molar ratio of zinc and metal M to ligand L is from 1: 100 to 100: 1. and (iii) the molar ratio of zinc salt Zn (X) n to metal M (Y) a is from 500: 1 to 1: 500.

Particularly convenient cobalt (III) cyanide salts correspond to the above formula (IV) being those salts where M 'represents sodium, potassium, lithium or calcium, and more preferably potassium.

In the processes for the preparation of these new zinc / metal hexacyanocobaltate complex compounds, a solution of 5 to 70% by weight of the zinc (Zn (X) n) and metal (M (Y)) salts is preferably used in the reaction. m). The aqueous solution of the cobalt (III) cyanide salt is preferably used at a concentration of 1 to 30% by weight.

It is preferred in the processes of preparation of these zinc / metal hexacyanocobaltate complex compounds that the salts Zn (X) n, M (Y) m, the salt of cobalt cyanide (III) and the ligand complex L are present in amounts such that: (i) the molar ratio of zinc and metal M to cobalt (III) is 2. 25: 1 to 8: 1 (ii) the molar ratio of zinc and metal M to ligand L is 1:50 to 50: 1, and (iii) the molar ratio of zinc salt Zn (X) to metal salt M (Y) m is in the range of 300: 1 to 1: 300.

In the process of preparing the zinc / metal hexacyanocobaltate complex compounds of the present invention zinc compounds Zn (X) n are used as the zinc salt, for example, zinc chloride, zinc bromide, zinc iodide, zinc, zinc acetylacetonate, zinc carbonate hydroxide, zinc fluoride, zinc nitrate, zinc sulfate, zinc benzoate, zinc carbonate, zinc citrate, zinc form, zinc thiocyanate, mixtures of various zinc salts, etc. Particular preference is given to zinc chloride and zinc bromide.

As the metal salt M (Y) m is preferably used: calcium chloride, mercury chloride, palladium chloride, platinum chloride, vanadium chloride, calcium chloride, barium chloride, barium nitrate, calcium bromide, formate calcium, calcium iodide, calcium oxalate, calcium propionate, cadmium acetate, cadmium bromide, cadmium iodide, calcium sulfate, palladium acetate, palladium nitrate, mercury acetate, mercury nitrate, magnesium chloride, manganese chloride, iron sulfate, iron acetate, iron bromide, iron chloride, iron iodide, iron nitrate, iron thiocyanate, cobalt chloride, cobalt bromide, cobalt acetate, cobalt nitrate, sulphate cobalt, nickel chloride, nickel bromide, nickel iodide, nickel nitrate, nickel sulfate, strontium chloride, copper chloride or lead chloride. Especially preferred are metal halides, especially chlorides and bromides. Mixtures of different metal salts can also be used. As salts of cobalt cyanide (III.) Of formula M * 3 [Co (CN) 6] r are preferably used: lithium hexacyanocobaltate (III), hexacyanocobaltate (III) sodium, hexacyano-cobaltate (III) potassium or hexacyanocobaltate (III) of calcium, hexacyano-cobaltate (III) of potassium is especially preferred.

Mixtures of different salts of cobalt (III) cyanide can also be used.

The abovementioned alcohols, ketones and ethers are particularly preferably used as the complex ligands L in the reaction according to the invention. The ligands can be used alone or in combination.

The preparation of the catalysts according to the invention is carried out by mixing both aqueous solutions of the aforementioned metal salts between 10 and 80 ° C, preferably between 20 and 60 ° C. In this respect, the aqueous solution of the zinc salts Zn (X) n and the metal salts M (Y) 'can be added to the aqueous solution of the cobalt (III) cyanide salts. In principle, it is also possible to add the aqueous solution of the cobalt (III) cyanide salt to the aqueous solution of the zinc and metal salts.

In the process according to the invention, it has proved particularly advantageous to mix the two aqueous solutions mentioned intensively with each other. In addition, it may be advantageous if the aqueous solution of cobalt (III) cyanide salt is passed through an ion exchange column with an acidic ion exchanger before mixing with the combined aqueous zinc / metal salt solution ( form H).

After the mixture of both aqueous solutions, the zinc / metal hexacyanocobaltate mixed catalyst precipitates. The precipitated catalyst is then treated with one or more of the ligands L of said complex.

Of course, it is also possible to add the organic ligands L to the aqueous solutions of the aforementioned metal salts or to add the organic ligands to the suspension obtained after mixing the aqueous solutions of the metal salts.

The process according to the invention for the preparation of the new zinc / metal hexacyanocobaltate catalysts is in principle known and is described, for example, in the state of the art described above.

In order to increase the activity of the catalysts according to the invention, it is advantageous to treat the obtained catalyst, for example by filtration or centrifugation, again with water or with the aforementioned organic ligands, optionally in the presence of water. Thus, for example, water-soluble by-products, such as potassium chloride, can be separated from the catalyst according to the invention, which adversely affect the polyaddition reaction.

The catalyst treated with water and / or the corresponding organic ligands are then dried, optionally after spraying, at temperatures of 20 to 100 ° C and at pressures of 0.1 mbar at normal pressure (1013 mbar).

Another object of the invention is the use of the hexacyanocobaltate catalyst according to the invention for the production of polyether polyols by polyaddition 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. Synthesis of the polyether chains by alkoxylation can be carried out, for example, with only one monomeric epoxide or else, nevertheless, statically or blockwise with 2 or 3 monomeric epoxides. The most recent can be taken from the "Ullmann's Encyclopedia of Industrial Chemistry", English edition, 1992, volume A21, pages 670-671.

As starter compounds having active hydrogen atoms, compounds with molecular weights of 18 to 2,000 and 1 to 8 hydroxyl groups are used. For example, mention may be made of ethylene glycol, diethylene glycol 1,2-propylene glycol, 1,4-butanediol, hexamethylene glycol, bisphenol A, trimethylolpropane, glycerin, pentaerythrin, sorbitol, sucrose, starch hydrolysates and water.

It is advantageous to use those initiator compounds which have active hydrogen atoms obtained, for example, by conventional alkaline catalysis from the aforementioned low molecular weight initiators and which represent oligomeric alkoxylation products with molecular weights of 200 to 2,000.

The polyaddition of alkylene oxides to initiator compounds having active hydrogen atoms catalyzed by catalysts according to the invention 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 normal pressure or at pressures from 0 to 20 bar (absolute). The polyaddition can be carried out without solvents or in an inert organic solvent, such as, for example, toluene and / or tetrahydrofuran. The amount of solvent usually reaches 10 to 30% by weight, based on the final amount of the polyetherpolyol.

The amount of catalyst is selected so that under the given reaction conditions a good control of the polyaddition reaction is possible, under the given conditions. This amount of catalyst 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, based on the final amount of the polyetherpolyol.

The reaction times for the polyaddition of the alkylene oxides to suitable initiator compounds are in the range of a few minutes to several days, preferably a few hours.

The molecular weights (average number, determined by final group analysis) of the polyether polyols produced according to the process 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.

The polyaddition can be carried out continuously, in loading or semicarga procedure.

The novel catalysts according to the invention generally need an induction period in the range of a few minutes to several hours.

With the aid of the novel catalysts according to the invention, the induction period is reduced by approximately 30% compared to the DMC catalysts known hitherto.

The dispersion of molecular weights M "/ Mn (determined by MALDITOF-MS, see U. Bahr, A. Deppe, M. Karas, F. Hillenkamp, U. Giessmann, Analytical Chemistry 64, (1992), S. 2866-2869 and B. Trathingg, B. Maier, G. Schulz, RP Krüger, U. Just, Macromol, Symp. 110, (1996), S. 231-240) of the polyether polyols produced using the new zinc / metal hexacyanocobaltate catalyst of the present invention is from about 1.01 to about 1.07. Accordingly, this is considerably narrower than the molecular weight distribution of the polyethers produced using the previously known DMC catalysts as described in the prior art. This is demonstrated in the following examples.

The following examples further illustrate details for the process of this invention. The invention which is set forth in the following described points is not limited either in spirit or scope by these examples. Those skilled in the art will quickly understand that variations of the conditions of the following procedures can be used. Unless otherwise noted, all temperatures are in degrees Celsius and all percentages are percentages by weight.

Examples Preparation of the catalyst Comparative example 1 Preparation of the DMC catalyst Hexacyanocobaltate (III) zinc with tert-butanol as the organic ligand of the complex. (This catalyst is referred to as a Catalyst A, through the examples; the synthesis of the synthesis process according to JP 4 145 123).

A solution of 10 g (73.3 mmol) of zinc chloride in 15 ml of distilled water is added with vigorous stirring to a solution of 4 g (12 mmol) of potassium hexacyanocobaltate in 75 ml of distilled water. Immediately afterwards a mixture of 50 ml of tert-butanol and 50 ml of distilled water is slowly added to the suspension formed and then stirred for 10 min. The solid matter is isolated by filtration, then it is stirred for 10 minutes with 125 ml of a mixture of tert-butanol and distilled water (70/30; v / v) and filtered again. Finally wash again for 10 min. with 125 ml of tert-butanol. After filtration the catalyst is dried at 50 ° C and normal pressure to constant weight.

Dry pulverulent catalyst yield: 3.08 g Elemental analysis: Cobalt = 13.6%; zinc = 27.35% Example 2 Preparation of zinc / cadmium hexacyanocobaltate (III) catalyst with tert-butanol as organic ligand of the complex and 0.9% cadmium. (This catalyst is referred to as Catalyst B through the examples).

A solution of 9 g (66 mmol) of zinc chloride and 1.34 g (7.3 mmol) of cadmium chloride in 15 ml of distilled water is added to 4 g (12 mmol) of potassium hexacyanocobaltate in 75 ml of water with vigorous stirring. distilled Immediately afterwards a mixture of 50 ml of tert-butanol and 50 ml of distilled water is slowly added to the formed suspension and then stirred for 10 min.

The solid matter is isolated by filtration, then it is stirred for 10 min with 125 ml of a mixture of tert-butanol and distilled water (70/30, v / v.) And filtered again. 10 min with 125 ml of tert-butanol After filtration the catalyst is dried at 50 ° C and normal pressure to constant weight.

Dry pulverulent catalyst yield: 2.83 g Elemental analysis: Cobalt = 11.8%; zinc = 22.9%; Cadmium = 0.9% Example 3 Preparation of hexacyanocobaltate (III) zinc / cadmium catalyst with tert-butanol as organic ligand of the complex and 7.1% cadmium. (This is referred to as a Catalyst C through the examples).

This catalyst was prepared using the same procedure set forth above in Example 2, but with the following exceptions / changes: A solution of 7 g (51.3 mmol) of zinc chloride and 4.0 g (22 mmol) of cadmium chloride in 15 ml of distilled water were added while stirring vigorously to a solution of 4 g (12 mmol) of potassium hexacyanocobaltate. in 75 ml of distilled water as described above. Dry pulverulent catalyst yield: 3.32 g Elemental analysis: Cobalt = 16.5%; zinc = 25.2%; Cadmium = 7.1% Manufacture of polyether polyols General realization In a pressure reactor of 500 ml capacity, 50 g of indicator polypropylene glycol (molecular weight = 1,000 g / mol) and 20 mg of catalyst (100 ppm, based on the amount of polyol to be produced) are placed under protective gas (argon). ) and heated with stirring at 105 ° C. Next, propylene oxide (approximately 5 g) is dosed at a time until the pressure rises to 2.5 bar (absolute). No more propylene oxide is dosed until an accelerated pressure drop is observed indicating that the catalyst is activated. The rest of the propylene oxide (145 g) is then metered in continuously at a constant pressure of 2.5 bar (absolute). After completion of the propylene oxide dosing and 5 hours of subsequent reaction time at 105 ° C, the volatile fractions are distilled off at 90 ° C (1 mbar) and then cooled to room temperature.

The polyether polyols obtained were characterized by determination of the OH values, the content of double bonds as well as the means of molecular weights and the dispersions of molecular masses M "/ Mn (MALDI-TOF-MS).

The induction periods were determined from the time-transformation curves (consumption of propylene oxide [g] versus reaction time [min]) by the tangent cut-off point at the steepest point of the time-curve. transformation with the prolongation of the base line of the curve.

Comparative example 4 A polyetherpolyol was manufactured in accordance with the general procedure as described above using Catalyst A (100 ppm). The induction period for this catalyst and the resulting polyetherpolyol was characterized as follows: Induction period: 290 min Polyetherpolyol: OH number (mg KOH / g) 28.5 Content of double bonds (moles / kg) 6 Mn 3426 Mw / Mn: 1.12 Example 5 A polyetherpolyol was manufactured in accordance with the general procedure as described above using Catalyst B (100 ppm). The induction period for this catalyst and the resulting polyetherpolyol was characterized as follows: Induction period: 240 min Polyetherpolyol: OH number (mg KOH / g): 28.0 Content of double bonds (mmol / kg) 7 Mn: 3426 Mw / Mn: 1.03 Example 6 A polyetherpolyol was manufactured in accordance with the general procedure as described above using Catalyst C (100 ppm). The induction period for this catalyst and the polyether polyol was characterized as follows: Induction period: 195 min Polyetherpolyol: OH number (mg KOH / g): 29.3 Content of double bonds (mmol / kg) 8 Mn: 3324 Mw / Mn: 1.06 A comparison between Examples 5 and 6 and the Comparative Example 4 clearly shows that in the production of polyether polyols with the zinc / metal hexacyanocobaltate (III) catalysts according to the invention compared to catalysis with zinc hexacyanocobaltate (III) catalysts DMC clearly induce periods of induction and that The dispersion of molar masses of the polyether polyols produced according to the invention is substantially narrower than in the corresponding polyols produced by DMC catalysis of zinc hexacyanocobaltate (III).

Through the invention have been described in detail in the aforementioned points for purposes of illustration, it should be understood that such details for purposes and variations can be made here by those skilled in the art without departing from the spirit and scope of the invention except by the limitations of the claims.

It is noted that in relation to this date the best method known by the applicant to carry out the aforementioned invention, is that which is clear from the manufacture of the objects to which it refers.

Having described the invention as above, the content of the following is claimed as property.

Claims (12)

1. Zinc hexacyanocobaltate catalyst / metal formula Zn3-vMv [Co (CN) 6] 2. w (H20). x (L) and [Zn (X) n]. zfM j characterized in that M means a divalent metal selected from the group of cadmium (II), mercury (II), palladium (II), platinum (II), vanadium (II), magnesium (II), calcium (II), barium (II) ), iron (II), nickel (II), manganese (II), cobalt (II), tin (II), lead (II), strontium (II) and copper (II), X and Y are the same or different and represent a halogenide or a hydroxy group, sulfate, carbonate, cyanate, thiocyanate, isocyanate, isothiocyanate, carboxylate, oxalate or nitrate, L represents an organic ligand of complex selected from the group of alcohols, aldehydes, ketones, ethers, esters, amides, ureas, nitriles or sulfides, v represents a number from 0.005 to 2.995 w represents a number from 0.1 to 10, x represents a number from 0.01 to 10, and represents a number from 0.001 to 3.0 and z represents a number from 0.001 to 3.0 and m and n are same or different and represent the numbers 1 or 2.

2. The composition according to claim 1, characterized in that in the formula (I) M represents a divalent metal atom selected from the group consisting of cadmium (II), mercury (II), palladium (II), platinum (II) ), vanadium (II), magnesium (II), calcium (II) and barium (II), X and Y are the same or different, and each represent halides, especially chlorine or bromine, L represents an organic complex ligand selected from from the group consisting of alcohols, ketones and ethers and v means a number from 0.01 to 2.99.

3. The composition according to claim 2, characterized in that X and Y are the same or different and each represents chlorine or bromine.

4. The composition according to claim 1, characterized in that X and Y, m and n are selected so that the composition corresponds to the formula Zn3-vMv [C? (CN) 6] 2. (H20). x (L) and (ZnCl2). z (MCl2) (II) where v represents a number from 0.005 to 2.995 w represents a number from 0.1 to 10, x represents a number from 0.01 to 10, and y and z are the same or different, and each represents a number from 0.001 to 3.0.

5. The composition according to claim 1, characterized in that M, X and Y, L, and m and n are selected so that the compositions correspond to the general formula: Zn3-vCdv [Co (CN) 6] 2. (H20). x (tere, butanol). and (ZnCl2) z (CdCl2) (III) where v represents a number from 0.005 to 2.995 w represents a number from 0.1 to 10, x represents a number from 0.01 to 10, and y and z are the same or different, and each represents a number from 0.001 to 3.0.

6. A process for the production of the zinc / metal hexacyanocobaltate complex compounds according to claim 1, characterized in that it comprises A) reacting (1) an aqueous solution of 1 to 90% by weight of (a) a zinc salt of formula Zn (X) n and (b) a metal salt of formula M (Y) m wherein: X, And, myn are as defined in claim 1; with 2) an aqueous solution of 0.5 to 50% by weight of a salt of cobalt (III) cyanide corresponding to the formula M'3 [Co (CN) 6] r where r represents 1 6 2, and M * represents an alkali metal atom or an alkaline earth metal atom, in the presence of complex ligands of formula L, where L is as defined in claim 1, wherein the salts Zn (X) M (Y) m, the saal of cobalt cyanide (III) and n the ligand L of the complex are present in such quantities. dades that; (i) the mole ratio of zinc and metal M to cobalt (III) is 2: 1 to 10: 1 (ii) the molar ratio of zinc and metal M to L is 1: 100 to 100: 1 and (iii) the molar ratio of zinc salt Zn (X) to metal salt M (Y) m is 500: 1 to 1: 500.

7. The process according to claim 6, characterized in that M 'represents sodium, potassium, lithium or calcium.

8. The process in accordance with the claim 6, characterized in that the salts Zn (X) n and M (Y) m, the salt of cobalt cyanide (II), and the complex ligand L are present in such quantities that: (i) the molar ratio of zinc and metal M a cobalt is 2: 25: 1 to 8: 1 (ii) the molar ratio of zinc and metal M to L is 1:50 to 50: 1, and (iii) the molar ratio of the zinc salt Zn (X) A metal salt M (Y) m is 300: 1 to 1: 300.

9. The process according to claim 6, characterized in that the zinc salt Zn (X) n is selected from the group consisting of zinc chloride and zinc bromide.

10. The process according to claim 6, characterized in that the metal salt M (Y) m is selected from the group consisting of metal chlorides and metal bromides,

11. The process according to claim 6, characterized in that the cobalt (III) cyanide salt is sodium hexacyanocobaltate (III).

12. A process for the production of polyether polyols, characterized in that it comprises the alkoxylation of at least one initiator compound containing active hydrogen atoms in the presence of a catalyst, comprising the zinc / metal hexacyanocobaltate complex compounds according to claim 1.