JP2003093888A - Composite metal cyanide complex catalyst and manufacturing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composite metal cyanide complex catalyst that shortens an induction period until the initiation of a reaction without increasing the loading of the catalyst in ring opening polymerizing an alkylene oxide using the composite metal cyanide complex catalyst. SOLUTION: The composite metal cyanide complex catalyst, of which the number of cyanoferrate (III) ion is from 0.02 to 0.95 when the total number of cyanocobaltate ion and cyanoferrate (III) ion is 1, is manufactured by reacting a transition metal cyanide compound wherein the transition metal is cobalt, a transition metal cyanide compound wherein the transition metal is tervalent iron and a metal halide salt with an organic ligand in an aqueous medium.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a double metal cyanide complex catalyst for alkylene oxide ring-opening polymerization and a method for producing the same.

[0002]

2. Description of the Related Art Polyether polyols, which are raw materials for polyurethane elastomers, adhesives, paints, blowing agents, etc., have hitherto been treated with ethylene oxide and propylene oxide by using an initiator having active hydrogen. It has been produced by polymerizing such alkylene oxides. Alkali metal (anionic polymerization), BF ₃ etherate (cationic polymerization), and double metal cyanide complex catalyst (coordination polymerization) are well known as typical alkylene oxide polymerization catalysts. Among these catalysts, the double metal cyanide complex catalyst has higher polymerization activity than the other two catalysts, and the alkylene oxide compound is not produced as a by-product.
In addition, a high-molecular-weight polyol can be produced because there is little reaction by-producting monool having an unsaturated bond. The complex metal cyanide complex catalyst is a water-insoluble catalyst containing a complex metal cyanide complex, an organic ligand, water, and a metal salt, and is a typical complex metal cyanide complex catalyst having excellent polymerization performance. Examples include zinc hexacyanocobaltate (Zn ₃ [Co (CN) ₆ ]] containing organic ligands, water and zinc chloride.
₂ )

The use of a double metal cyanide complex catalyst as a catalyst for ring-opening polymerization reaction of alkylene oxide has been known for a long time (US3278457 etc.), and a method for producing a double metal cyanide complex catalyst is US3.
427256, US3941849, US447256.
0, US Pat. No. 4,477,589, etc., a method for producing a polyether polyol using a double metal cyanide complex catalyst is described in US Pat. No. 4,055,188, US Pat.

In order to produce a polyether polyol using a double metal cyanide complex catalyst, for example, a double metal cyanide complex catalyst is added to a hydroxy compound which is an initiator, and this is kept at a high temperature of, for example, about 120.degree. While gradually adding the alkylene oxide, the ring-opening of the alkylene oxide is carried out to add it to the hydroxy compound. By the way, in the initial stage of the ring-opening polymerization reaction using such a complex metal cyanide complex catalyst,
The reaction does not start immediately when alkylene oxide is added, but the reaction proceeds rapidly after an induction period of, for example, several tens of minutes. Therefore, the waiting time (induction period) until the start of the reaction is long, which is one of the factors that hinder the improvement of productivity. The length of this induction period varies depending on the catalyst concentration, and the induction period can be shortened by increasing the amount of catalyst added. However, since the complex metal cyanide complex catalyst is a relatively expensive catalyst, there is a problem that the production cost increases significantly if the addition amount is increased.

The present invention has been made in view of the above circumstances, and when the ring-opening polymerization of alkylene oxide is carried out using the double metal cyanide complex catalyst, the amount of the double metal cyanide complex catalyst added is not increased. An object of the present invention is to provide a complex metal cyanide complex catalyst capable of shortening the induction period until the start of the reaction and a method for producing the same.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have made a reaction between a metal halide salt, a transition metal cyanide compound and an organic ligand in an aqueous medium. When cobalt and trivalent iron (described as iron (III) in the present specification) are used together as the transition metal constituting the transition metal cyanide compound in the production of the double metal cyanide complex catalyst, The present invention has been completed by finding that the activity of the double metal cyanide complex catalyst is dramatically improved.

That is, in the method for producing a composite metal cyanide complex catalyst of the present invention, a composite metal cyanide complex catalyst is produced by reacting a metal halide salt, a transition metal cyanide compound and an organic ligand in an aqueous medium. And a transition metal cyanide compound in which the transition metal composing the transition metal cyanide compound is cobalt, and a transition metal cyanide compound in which the transition metal is trivalent iron are used in combination. When the total number of cyanocobaltate ions and cyanoferrate (III) ions in the metal cyanide complex catalyst is 1, the number of cyanoferrate (III) ions is 0.02 to 0.
A double metal cyanide complex catalyst of 95 is produced. The present invention also provides a double metal cyanide complex catalyst obtained by such a method.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below. In the present invention, in order to produce a composite metal cyanide complex catalyst, first, a metal halide and a transition metal cyanide compound are reacted in an aqueous medium. This reaction is preferably carried out by mixing an aqueous solution of a metal halide salt with an aqueous solution of a transition metal cyanide compound, and the aqueous solution of the transition metal cyanide compound is dropped into the aqueous solution of a metal halide salt, or vice versa. It is particularly preferable to add the metal halide salt aqueous solution dropwise to the compound aqueous solution.

The metal of the metal halide salt is Zn
(II), Fe (II), Fe (III), Co (II), Ni
(II), Mo (IV), Mo (VI), Al (III), V
(V), Sr (II), W (IV), W (VI), Mn (I
I), Cr (III), Cu (II), Sn (II), and P
It is preferable to use one or more selected from b (II), and Zn (II) is particularly preferable. The halide that constitutes the metal halide salt is particularly preferably chloride. A particularly preferred metal halide salt is zinc chloride (ZnCl ₂ ).

The metal halide salt is preferably used in the form of an aqueous metal halide salt solution. The concentration of this metal halide salt aqueous solution is preferably 0.1 g / ml or more,
0.2 g / ml or more is more preferable. Further, it is preferable that the concentration is not more than the saturation concentration. When the concentration of the aqueous metal halide salt solution is lower than the above range, the metal halide salt is not sufficiently taken up in the double metal cyanide complex catalyst, and the crystallinity of the double metal cyanide complex catalyst becomes high. The activity decreases. When the concentration of the metal halide salt aqueous solution exceeds the saturation concentration, the mixed state of the solution becomes non-uniform, and the obtained composite metal cyanide complex catalyst has low catalytic activity.

The transition metal cyanide compound is water-soluble
Used in alkali metal cyanometalates, alkaline earth
Metal cyanometallates, ammonium cyanometalates
And cyanometallate acid. In the present invention
The transition metal forming the cyanometallate is cobalt
The thing and iron (III) are used together. cobalt
Is Co (II) or Co (III), especially Co (II
I) is preferred. As a specific example, K₃Co (CN)₆,
K₃Fe (CN)₆, Na₃Co (CN)₆, Na₃Fe
(CN)₆, Mg₃(Co (CN)₆)₂, Mg₃(Fe
(CN)₆)₂, (NH_Four)₃Co (CN)₆, (NH_Four)₃
Fe (CN)₆, H₃Co (CN)₆, H₃Fe (C
N)₆, And so on. Among these, cyanation
As the transition metal compound, an alkali metal cyanometallate is used.
And particularly preferred transition metal cyanide compounds
Is potassium hexacyanocobaltate (cyanocobalt
Potassium tote: K₃Co (CN)₆), And potassium
Xacyanoferrate (potassium cyanoferrate (III):
K₃Fe (CN) ₆).

The transition metal cyanide compound is preferably used in the form of an aqueous solution of transition metal cyanide compound. The concentration of the transition metal cyanide compound aqueous solution is such that the total concentration of the transition metal cyanide compound in which the transition metal is cobalt and the transition metal cyanide in which the transition metal is iron (III) is 1.0 g / ml or less. It is preferably 0.5 g / ml or less. Further, it is preferably 0.01 g / ml or more. When the concentration of the transition metal cyanide compound exceeds the above range, the metal halide is not sufficiently taken up by the double metal cyanide complex catalyst and the catalytic activity is lowered. When the concentration of the transition metal cyanide compound is lower than the above range, the metal halide salt incorporated in the double metal cyanide complex catalyst is dissolved in water, so that the catalytic activity is lowered.

The ratio of the content of the transition metal cyanide compound whose transition metal is cobalt and the content of the transition metal cyanide compound whose transition metal is iron (III) in the transition metal cyanide compound aqueous solution is: It is set according to the ratio between the number of cyanocobaltate ions and the number of cyanoferrate (III) ions in the composite metal cyanide complex catalyst to be obtained. Specifically, the number of cyanocobaltate ions and cyanoiron (III) in the transition metal cyanide compound aqueous solution.
When the total number of acid ions is 1, cyanoiron (III)
The number of acid ions is set within the range of 0.02 to 0.95.

The reaction temperature in the step of mixing the metal halide salt aqueous solution and the transition metal cyanide compound aqueous solution is 0.
C. or higher is preferable, and 20.degree. C. or higher is particularly preferable. Also,
It is preferably lower than 80 ° C, particularly preferably 70 ° C or lower. When the reaction is carried out in a high temperature range, a highly crystalline double metal cyanide complex catalyst containing no metal halide is synthesized, and the organic ligand cannot be coordinated, so that catalytic activity does not occur. Further, in the low temperature region, the reaction between the metal halide salt and the transition metal cyanide compound becomes insufficient and the catalytic activity decreases.

By such a reaction, as a reaction product
For example, M_a [Co (CN)₆ ]_b[Fe (CN)₆ ]_c 
・ D (MX_f) ・ G (H₂O) is generated. M is halogen
Metal of the metal halide salt, X is the halogen of the metal halide salt
It The subscripts a, b, and c are metal (M) ions and cyanocco.
Bartoate and cyanoferrate (III) ions are charged.
Determined to maintain a neutrality, the value of c / (b + c) is
It is 0.02-0.95. D and g are the reactions
Shows the amount of metal halide salt and water incorporated in the product.
You d is 0.1 to 10 and g is 0.1 to 20, respectively.
preferable. Especially Zn _a [Co (CN)₆ ]_b[Fe (C
N)₆ ]_c・ D (ZnCl₂) ・ G (H₂O) is preferred
Yes.

Next, an organic ligand is coordinated to the above reaction product. In this step, the reaction product obtained by reacting a metal halide salt with a transition metal cyanide compound is preferably aged in an aqueous medium containing an organic ligand. For example, it can be performed by a method of adding an organic ligand to a solution containing the above reaction product and stirring. Further, the organic ligand may be added in advance to one or more liquids of the metal halide salt aqueous solution and the transition metal cyanide compound aqueous solution.

As the organic ligand, all electron donors which are well known in the synthesis of complex metal cyanide complex catalysts such as alcohols, ethers, ketones, esters, amines and amides can be used. Preferred organic ligands are water-soluble, and specific examples thereof include tert-butyl alcohol, n-butyl alcohol, iso-butyl alcohol, tert-pentyl alcohol, and iso-.
Pentyl alcohol, N, N-dimethylacetamide,
Ethylene glycol dimethyl ether (glyme), diethylene glycol dimethyl ether (diglyme),
Examples include one or more compounds selected from triethylene glycol dimethyl ether (triglyme), ethylene glycol mono-tert-butyl ether, iso-propyl alcohol, and dioxane. As dioxane, 1,4-dioxane is 1,
It may be 3-dioxane, preferably 1,4-dioxane. A particularly preferred organic ligand is tert-butyl alcohol.

The lower limit of the aging temperature for coordinating the organic ligand is preferably the reaction temperature or higher, more preferably 20 ° C. or higher. The upper limit of the aging temperature is preferably lower than 125 ° C, more preferably 80 ° C or lower. The aging time is preferably 10 minutes or more. There is no particular upper limit for the aging time, but it is preferable to industrially set the upper limit to about 2 to 3 hours.

The slurry obtained by the above aging is filtered or centrifuged and then decanted to obtain a cake containing the organic phase of the complex metal cyanide complex catalyst. If necessary, the cake is washed by adding a compound selected from the group consisting of water, an organic ligand used in the synthesis and an organic ligand different from the organic ligand used in the synthesis. Further, it is preferable to perform decantation after further filtration or centrifugation (washing operation). The washing operation may be repeated multiple times. Unless the organic ligand used for washing has a particularly strong coordinating force compared to the organic ligand already coordinated to the catalyst, the organic ligand used for washing is already coordinated. The organic ligand is rarely partially or wholly replaced. The obtained composite metal cyanide complex catalyst is dried to obtain a composite metal cyanide complex catalyst by drying the cake containing the organic phase. Examples of the drying method include a heating drying method, a vacuum drying method, and a method of removing volatile water and organic ligands after mixing with a hardly volatile liquid. The drying temperature is preferably 0 ° C to 150 ° C, particularly preferably 90 ° C or lower. This is because all the coordinated organic solvent and water are not volatilized.

Further, as the hardly volatile liquid, it can be dispersed in an alkylene oxide ring-opening polymer to remove excess amount of water and organic ligands and used as a catalyst slurry for the polymerization reaction. As the alkylene oxide ring-opening polymer, polyether polyol can be preferably used, and the molecular weight is usually
300-12000, preferably 500-10000,
It is particularly preferably 700 to 5,000, and the amount used is usually 10 to 9 relative to the double metal cyanide complex catalyst.
It is 5% by mass.

[0021] Through these steps, the reaction product _{(e.g., M a [Co (CN)} 6] b [Fe (CN)
₆ ] _c ), an organic ligand (Ligand), water, and a residual metal halide salt, and a water-insoluble complex metal cyanide complex catalyst is obtained. In this complex metal cyanide complex catalyst, when the total number of cyanocobaltate ions and cyanoferrate (III) ions is 1, cyanoiron (I
II) The number of acid ions is within the range of 0.02 to 0.95, preferably within the range of 0.02 to 0.7, and more preferably within the range of 0.02 to 0.5. Cyano iron (II
I) Whether the number of acid ions is too large or too small, the use of both cobalt and iron (III) as the transition metal constituting the transition metal cyanide compound results in a complex metal cyanide complex catalyst. The activity improving effect cannot be sufficiently obtained. The thus obtained double metal cyanide complex catalyst of the present invention is considered to have high activity for the ring-opening polymerization of alkylene oxide due to the distortion of the crystal structure.

The composite metal cyanide complex catalyst of the present invention comprises
This can be used to ring-opening polymerize alkylene oxide to produce a polyether polyol. That is,
In the presence of the complex metal cyanide complex catalyst produced by the above production method, a hydroxy compound as an initiator is subjected to ring-opening polymerization of an alkylene oxide containing an alkylene oxide having 3 or more carbon atoms to produce a polyether polyol. The alkylene oxide preferably contains an alkylene oxide having 3 or more carbon atoms. As the alkylene oxide having 3 or more carbon atoms, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, epichlorohydrin and the like are preferable. These can be used in combination of two or more, and in that case, they can be mixed and reacted, or can be reacted sequentially.

When the double metal cyanide complex catalyst of the present invention is used, it is difficult to react ethylene oxide, which is an alkylene oxide having 2 carbon atoms, by itself, but it is mixed with an alkylene oxide having 3 or more carbon atoms. It can be reacted by adding it to the reaction system. A particularly preferred alkylene oxide is propylene oxide alone or a combination of propylene oxide and ethylene oxide. When producing an elastic polyurethane foam, it is preferable that the polyether polyol has an oxyethylene group at the terminal, and it is particularly preferable that the content of the terminal oxyethylene group is 5 to 30% by mass. The polyether polyol having an oxyethylene group at the terminal is obtained by ring-opening polymerization of an alkylene oxide containing an alkylene oxide having 3 or more carbon atoms as an initiator using the above-mentioned complex metal cyanide complex catalyst, and then using an alkali catalyst to obtain ethylene oxide. Can be produced by reacting As the alkali catalyst here, alkali metals such as sodium and potassium, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and alkali metal alkoxides such as sodium alkoxide and potassium alkoxide are suitable.

Specific examples of the hydroxy compound that can be used as the initiator include, but are not limited to, the following compounds. Methyl alcohol, isopropyl alcohol, n-butyl alcohol, 2-ethylhexanol,
Stearyl alcohol, allyl alcohol, oleyl alcohol, monoethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, trimethylolpropane, pentaerythritol, ciglycerin, sorbitol, dextrose, methyl glucoside, sucrose, bisphenol A, etc. Further, alkylene oxide adducts of these initiators can also be used as the initiator. Further, when the molecular weight of the initiator is small, the ring-opening polymerization reaction of the alkylene oxide may not occur, so the initiator has a molecular weight of 500.
It is preferable to use the above.

The polyether polyol can be produced by adding the complex metal cyanide complex catalyst of the present invention to a hydroxy compound as an initiator and carrying out the reaction while gradually adding alkylene oxide. Although the amount of the double metal cyanide complex catalyst used is not particularly limited, it is preferably about 1 to 5000 ppm, more preferably 10 to 1000 ppm, based on the hydroxy compound used.
0 to 300 ppm is more preferable. Reaction temperature is 30 ~
180 degreeC is preferable and 90-130 degreeC is more preferable.
Regarding the introduction of the double metal cyanide complex catalyst into the reaction system, it may be introduced all at once at the beginning, or may be introduced sequentially dividedly. The polyether polyol after the reaction may be used as it is, or may be purified by removing the catalyst or the like depending on the use. It is preferable to carry out purification. The molecular weight of the obtained polyether polyol is not particularly limited, but a hydroxyl value of 5 to 70 mgKOH / g is preferable.

According to the present invention, by using both cobalt and iron (III) as the transition metal constituting the transition metal cyanide compound, which is a raw material for the production of the double metal cyanide complex catalyst, the catalytic activity is significantly improved. An improved composite metal cyanide complex catalyst is obtained. Therefore, when ring-opening polymerization of alkylene oxide is carried out using the double metal cyanide complex catalyst of the present invention, even when the amount of catalyst added is similar to the conventional amount,
The induction period until the start of the reaction is greatly shortened. Alternatively, even if the amount of catalyst added is reduced compared to the conventional case, the induction period becomes equal to or shorter than that of the conventional case. Therefore, when a polyether polyol is produced by ring-opening polymerization of alkylene oxide, it is possible to shorten the waiting time until the start of the reaction to improve productivity, and reduce the amount of catalyst added to reduce the production cost. be able to.

When the complex metal cyanide complex catalyst of the present invention is used in the alkylene oxide ring-opening polymerization reaction, side reactions are suppressed and a relatively high molecular weight polyether monool or polyether polyol having a low degree of unsaturation is obtained. Can be manufactured. The hydroxyl value of the polyether polyol that can be produced using the double metal cyanide complex catalyst of the present invention is not particularly limited, but is usually 2 to 70 mgKOH / g, and the degree of unsaturation thereof is 0.003 to 0.01 meq / g. Is. When an elastic polyurethane foam is produced using this low unsaturation polyether polyol, the hardness decreases.
Problems such as a decrease in impact resilience, deterioration of compression set, and a decrease in cure property during foam molding can be improved. The unsaturation degree of the polyether polyol used for the polyurethane elastomer is preferably 0.010 meq / g or less. When the degree of unsaturation is 0.010 meq / g or less, the curing speed is high and the polyurethane elastomer can be provided with excellent physical properties such as elongation and strength.
It is considered that this is because the amount of unsaturated monool contained in the polyether polyol is small and thus the number of functional groups is substantially large.

The polyether monools and polyether polyols obtained by the above method can be used not only as raw materials for polyurethane but also as surfactants, lubricating oils and the like. It can also be used as a polymer-dispersed polyether polyol containing polymer particles.

[0029]

[Examples] The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In addition, Example 1 is an example, Example 2 is a comparative example, Examples 3 and 4
Is an example of evaluation of a catalyst. <Production of Complex Metal Cyanide Complex Catalyst> (Example 1) 10.2 g of zinc chloride in a 500 ml flask.
In an aqueous solution containing 10 ml of potassium hexacyanocobaltate K ₃ Co (CN) ₆ of 2.94 g and potassium hexacyanoferrate K ₃ Fe (CN) ₆ of 1.26 g, a 75 ml aqueous solution was kept at 50 ° C. While being stirred, it was added dropwise over 30 minutes while stirring with a polytetrafluoroethylene stirrer. After the dropping was completed, a mixture of 80 g of tert-butyl alcohol and 80 g of water was added, and the temperature was raised to 70 ° C. After stirring for 1 hour, 196 kPa
A pressure filtration operation was performed under pressure to obtain a cake containing the organic phase of the complex metal cyanide complex catalyst. Then, the cake containing the mixed metal cyanide complex catalyst organic phase was tert
-A mixture of 40 g of butyl alcohol and 70 g of water was added, stirred for 30 minutes, and then filtered in the same manner. To the resulting cake containing the composite metal cyanide complex catalyst organic phase, 100 g of tert-butyl alcohol was further added and stirred, and then the same filtering operation was performed. The cake obtained is dried at 50 ° C. under reduced pressure for 3 hours, pulverized,
A composite metal cyanide complex catalyst A was obtained. As a result of elemental analysis of the obtained metal cyanide complex catalyst A, zinc was found to be 3
The content was 1.0% by mass, cobalt was 8.5% by mass, and iron was 3.6% by mass. In this complex metal cyanide complex catalyst A, when the total number of cyanocobaltate ions and cyanoferrate (III) ions was 1, it was confirmed that the number of cyanoferrate (III) ions was 0.31. .

(Example 2) In Example 1, zinc chloride 10.2
In the same manner, except that the aqueous solution added dropwise to 10 ml of an aqueous solution containing g was replaced with a 75 ml aqueous solution containing 4.2 g of potassium hexacyanocobaltate K ₃ Co (CN) ₆ , the iron-free composite metal cyanide was prepared. A compound complex catalyst B was obtained. As a result of elemental analysis of the obtained metal cyanide complex catalyst B, zinc was 30.4% by mass and cobalt was 12.
It was 2% by mass.

<Evaluation of Catalytic Activity in Polyether Polyol Production> (Example 3) Propylene oxide (hereinafter referred to as PO) was added to glycerin as an initiator in a pressure-resistant reaction tank of stainless steel 5 liter equipped with a stirrer. Obtained molecular weight 10
1470 g of polyoxypropylene triol of 0.
14 g was added. After purging with nitrogen, raise the temperature to 120 ° C and
147 g of the above was added for spot reaction, and changes in pressure and temperature in the reaction tank with time were measured. About 5 minutes after the PO was charged, the pressure in the reaction vessel started to decrease and the temperature started to rise. This is because the PO, which was present as a gas in the reaction tank at 120 ° C., was ring-opened and added to the initiator. It was confirmed that the induction period until the start of the reaction was about 5 minutes because the pressure inside the reaction tank decreased and the temperature inside the reaction tank increased due to the heat of reaction. While maintaining the inside of the reaction tank at 120 ° C, gradually PO
Was added, and a total amount of PO of 3140 g was added. The hydroxyl value of the polyether polyol thus obtained is 56 m.
gKOH / g, and the polystyrene-equivalent molecular weight distribution (M _w / M _n ) measured by gel permeation chromatography is 1.
It was 07.

(Example 4) In Example 3, instead of the composite metal cyanide complex catalyst A, the composite metal cyanide complex catalyst B was used.
The same was done except that 0.14 g of was used. As a result, the induction period until the start of the reaction was about 90 minutes. The hydroxyl value of the obtained polyether polyol is 56 mgKOH.
/ G and the molecular weight distribution was 1.13.

[0033]

As described above, according to the present invention, a double metal cyanide complex catalyst having high catalytic activity can be obtained, and the induction period in the ring-opening polymerization reaction of alkylene oxide can be significantly shortened. Therefore, the productivity at the time of producing a polyether polyol can be improved. Further, since the catalytic activity of the complex metal cyanide complex catalyst is high, the amount of the catalyst added can be reduced to reduce the manufacturing cost.

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Claims (4)

[Claims] 1. A method for producing a composite metal cyanide complex catalyst by reacting a metal halide salt, a transition metal cyanide compound and an organic ligand in an aqueous medium, wherein the transition metal cyanide compound is A transition metal cyanide compound whose transition metal is cobalt and a transition metal cyanide compound whose transition metal is trivalent iron are used in combination to produce a cyanocobaltate ion and a cyanocobaltate ion in the complex metal cyanide complex catalyst. When the total number of iron (III) ion is 1, the number of cyanoferrate (III) ion is 0.02.
A method for producing a composite metal cyanide complex catalyst, which comprises producing a composite metal cyanide complex catalyst having a concentration of about 0.95. 2. The method for producing a composite metal cyanide complex catalyst according to claim 1, wherein the metal halide salt is a zinc compound. 3. The method for producing a double metal cyanide complex catalyst according to claim 1, wherein the organic ligand contains tert-butyl alcohol. 4. A composite metal cyanide complex catalyst obtained by the production method according to claim 1.