JP2884614B2 - Method for producing double metal cyanide complex catalyst - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for continuously producing a double metal cyanide complex catalyst.

[Related Art] Conventionally, a double metal cyanide complex has been known as a catalyst for causing a ring-opening reaction of a monoepoxide such as an alkylene oxide. (US 3278457, US 3278458, US 3278459).
The production method of the double metal cyanide complex catalyst used at this time is described in US 3427256, US 3941849, US 4472560, US 4477589.
It is proposed in the specification and the like.

[Problems to be Solved by the Invention] In the method for producing a double metal cyanide complex catalyst, the double metal cyanide is synthesized by dropping an aqueous alkali metal cyanometalate solution into the aqueous metal halide solution to form an organic ligand. To produce a double metal cyanide complex catalyst, but has the disadvantage that a highly active catalyst cannot be continuously and stably synthesized.

Means for Solving the Problems The present invention has been made to solve the above-mentioned problems, and is a composite metal cyanide comprising an aqueous solution of a metal halide, an aqueous solution of an alkali metal cyanometalate, and an organic ligand. In the method for producing a complex catalyst, an aqueous solution of a metal halide and an aqueous solution of an alkali metal cyanometalate are continuously mixed at a reaction temperature of 0 ° C. or more and 40 ° C. or less at a constant ratio, and a residence time of 1 minute or more and 360 minutes or less is used. The present invention provides a method for producing a double metal cyanide complex catalyst, which comprises continuously mixing an organic ligand at a constant ratio after holding, and aging at an aging temperature not lower than the reaction temperature and lower than 125 ° C. It is.

As the metal of the metal halide salt used in the present invention,
Zn (II), Fe (II), Fe (III), Co (II), Ni (II), Mo
(IV), Mo (VI), Al (III), V (V), Sr (II), W (I
V), W (VI), Mn (II) and Cr (III) are selected from one type or two or more types, preferably Zn (II) and Fe (II).

Fe (II), Fe (III), Co (II), Co (III), Cr (III), as the alkali metal D of the alkali metal cyanometallate
One type or two or more types are selected from the group of Mn (II), Mn (III), V (IV) and V (V), and preferably Co (III) and Fe (II) are used.

Ethers, esters, alcohols as organic ligands,
One or more mixed ligands selected from aldehydes, ketones, amides, nitriles and sulfides are used, and preferably ethers and esters are used, and particularly ethylene glycol dimethyl ether and diethylene glycol dimethyl ether are used.

The concentration of the metal halide salt aqueous solution is 0.1 g / cc or more, preferably 1 g / cc or more, and the saturation concentration aqueous solution or less. In the concentration region below the specified concentration, the catalyst is synthesized without taking in an excessive amount of the metal halide into the double metal cyanide complex catalyst, and the activity is disadvantageous. On the other hand, if the concentration is higher than the saturation concentration, the mixing of the solution becomes non-uniform, which is also disadvantageous for the catalytic activity.

Alkali metal cyanometalate aqueous solution concentration is 0.5 g / c
c or less, preferably 0.02 to 0.2 g / cc. When the concentration is higher than the specified concentration, the place where the metal halide is mixed with the aqueous solution of the metal halide partially becomes an alkali metal cyanometallate excess region, and the same effect as when the concentration of the above metal halide is low is caused to lower the activity. . If the reaction is carried out at a low concentration, the metal halide incorporated in the double metal cyanide complex catalyst is dissolved in water, which is disadvantageous for the activity.

When the reaction is carried out in a high temperature range where the aqueous solution of the metal halide salt and the aqueous solution of the alkali metal cyanometalate are mixed, a highly crystalline double metal cyanide complex catalyst containing no metal halide is synthesized. The ligand cannot coordinate and no catalytic activity occurs. Further, in the low temperature region, the synthesis reaction of the double metal cyanide complex catalyst becomes insufficient, which is also disadvantageous to the catalytic activity.

If the residence time until the organic ligand is mixed in the reaction solution is shortened, the organic ligand comes into contact with unreacted raw materials, which is disadvantageous for the catalytic activity. Further, even if the reaction is performed for a long time, no further improvement in activity is desired. The ripening process for ripening has the purpose of sufficiently coordinating the organic ligand to the double metal cyanide complex catalyst, so that the coordination rate is disadvantageous below the specified temperature range, and in the high temperature range, the double metal cyanide complex catalyst The crystallinity of the compound increases, and the organic ligand cannot be coordinated, which is disadvantageous for the catalytic activity.

The obtained slurry is filtered, washed with an organic ligand, then dried and pulverized to produce a double metal cyanide complex catalyst.

In the present invention, the function of ring-opening polymerization of the monoepoxide of the double metal cyanide complex catalyst is not necessarily clear.However, the crystal structure of the double metal cyanide and the coordination state of the organic ligands accompanying the function of the double metal oxide are important for the catalytic activity. It is considered that this has had a major impact.

EXAMPLES Example 1 An aqueous solution of zinc chloride 1.5 g / cc and an aqueous solution of potassium hexacyanocobaltate 0.05 g / cc at 40 ° C. at a constant flow rate.
After having a residence time of 15 minutes, a 50% aqueous solution of diethylene glycol dimethyl ether at a constant flow rate was added dropwise, and the temperature was raised to 60 ° C. After stirring for 1 hour, the mixture was filtered to obtain a filter cake. The filter cake was washed with a 30% aqueous solution of diethylene glycol dimethyl ether and further filtered to obtain a filter cake, and then washed with diethylene glycol dimethyl ether, filtered, dried and pulverized to obtain a double metal cyanide complex catalyst.

Example 2 At a constant flow rate, an aqueous solution of zinc chloride 1.5 g / cc and an aqueous solution of potassium hexacyanocobaltate 0.05 g / cc were heated at 20 ° C.
After a reaction time of 5 minutes was given, a 50% aqueous solution of ethylene glycol dimethyl ether at a constant flow rate was added dropwise, and the temperature was raised to 40 ° C. After stirring for 1 hour, the mixture was filtered to obtain a filter cake. The filter cake was washed with a 30% aqueous solution of diethylene glycol dimethyl ether and further filtered to obtain a filter cake, and then washed with ethylene glycol dimethyl ether, filtered, dried and pulverized to obtain a double metal cyanide complex catalyst.

When the ring-opening polymerization of propylene oxide was performed using the above catalyst, the following results were obtained.

Comparative Example 1 A 10 cc aqueous solution containing 10 g of zinc chloride and a 75 cc aqueous solution containing 4.17 g of potassium hexacyanocobaltate and 50
% Diethylene glycol dimethyl ether aqueous solution 100cc
Were added and reacted at a reaction temperature of 35 ° C. This solution was filtered to obtain a filter cake. The filter cake was washed with a 30% aqueous solution of diethylene glycol dimethyl ether and further filtered to obtain a filter cake, and then washed with diethylene glycol dimethyl ether, filtered, dried and pulverized to obtain a double metal cyanide complex catalyst.

Comparative Example 2 A 75 cc aqueous solution containing 4.17 g of potassium hexacyanocobaltate was added to a 10 cc aqueous solution containing 10 g of zinc chloride.
The solution was added dropwise over 30 minutes while keeping the temperature at ° C. 50% after dropping
100cc of diethylene glycol dimethyl ether aqueous solution
The mixture was added, stirred at the same temperature for 1 hour, and then filtered to obtain a filter cake. The filter cake was washed with a 30% aqueous solution of diethylene glycol dimethyl ether and further filtered to obtain a filter cake, and then washed with diethylene glycol dimethyl ether, filtered, dried and pulverized to obtain a double metal cyanide complex catalyst.

The following results were obtained when ring-opening polymerization of propylene oxide was performed using the above catalyst [Comparative Example 1]. [Comparative Example 2] An attempt was made to add 0.5% of this catalyst per diol having a molecular weight of 700 to the ring-opening polymerization of propylene oxide, but no trace of the reaction was observed at a reaction temperature of 120 ° C.

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Claims (3)

(57) [Claims] 1. A process for producing a double metal cyanide complex catalyst comprising a metal halide aqueous solution, an alkali metal cyanometalate aqueous solution and an organic ligand, wherein the reaction temperature is 0 ° C. or higher.
Continuously mix the metal halide aqueous solution and the alkali metal cyanometalate aqueous solution at a constant ratio at 40 ° C or less,
After having a residence time of 1 minute or more and 360 minutes or less, the organic ligand is continuously mixed at a fixed ratio, and the reaction temperature is 125 ° C or more.
A method for producing a double metal cyanide complex catalyst, wherein the catalyst is aged at a ripening temperature of less than. 2. The method for producing a double metal cyanide complex catalyst according to claim 1, wherein the concentration of the aqueous metal halide salt solution is 0.1 g / cc or more. 3. The method for producing a double metal cyanide complex catalyst according to claim 1, wherein the concentration of the aqueous alkali metal cyanometalate solution is 0.5 g / cc or less.