JP2619138B2 - Preservation method of double metal cyanide complex - Google Patents

Description

The present invention relates to a method for preserving a double metal cyanide complex.

[Prior Art] Conventionally, double metal cyanide complexes have been known as catalysts for ring-opening reactions of monoepoxides such as alkylene oxides (US 3278457, US 3278458, US 3278459). The production method of the double metal cyanide complex catalyst used at this time is proposed in US Pat. No. 3,427,256, US Pat. No. 3,418,491, US Pat. No. 4,472,560, US Pat.

[Problems to be Solved by the Invention] In the method for producing a composite metal cyanide complex catalyst, the composite metal cyanide complex catalyst is produced from an aqueous solution of a metal halide, an aqueous solution of an alkali metal cyanometalate and an aqueous solution of an organic ligand. However, the resulting double metal cyanide complex catalyst is a powder and difficult to handle,
It has the disadvantage that the storage of the milled double metal cyanide complex catalyst is unstable.

[Means for Solving the Problems] The present invention is the following invention which has been made to solve the above problems.

In a method of storing a complex metal cyanide complex obtained by using an aqueous solution of a metal halide salt, an aqueous solution of an alkali metal cyanometalate, and an organic ligand, the complex that has been reacted, aged, and washed is replaced with an organic compound using an organic ligand. In a ligand, or in a different kind of organic ligand, heat-treated at a temperature of not less than 40 ° C and not more than 160 ° C, and then stored in an excess of an organic ligand. A method for storing a complex metal cyanide complex.

The metal of the metal halide salt used in the present invention includes 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), Cr (III), one or more types are selected, preferably Zn (II) or Fe
(II) is used.

Examples of the metal constituting the cyanometalate anion of the alkali metal cyanometalate include Fe (II), Fe (III), C
o (II), Co (III), Cr (III), Mn (II), Mn (III), V
One type or two or more types are selected from the group of (IV) and V (V), and Co (III) or Fe (II) is preferably used.

Ethers, esters, alcohols as organic ligands,
Using one kind of ligand selected from aldehydes, ketones, amides, nitriles, sulfides, or two or more kinds of mixed ligands, preferably ethers, esters, particularly ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, Use tert-butanol. These organic ligands are usually in a liquid state, and are used in excess with respect to the coordination amount when coordinated to the complex. In the present invention, a heat treatment is performed in an excess of the organic ligand used for or after the production of the complex, and then the complex is stored in the organic ligand. The heat treatment is preferably performed by heating at a temperature of 40 to 160 ° C., preferably 60 to 160 ° C. for several minutes or more.

The weight of the double metal cyanide complex in the organic ligand is 10 ppm to 75%, preferably the storage volume and slurry viscosity of the double metal cyanide complex-containing organic ligand, and the amount of the organic metal to the reaction by the double metal cyanide complex. The content is 10 to 50% by weight in consideration of the influence of the ligand.

The organic metal ligand containing the composite metal cyanide complex is stored in a container made of one or more materials selected from glass, stainless steel, polypropylene, polyethylene, and polyvinyl chloride in a container made of air. , Nitrogen, helium,
A closed system in one or two or more gases selected from oxygen, hydrogen and carbon dioxide, preferably closed in a nitrogen atmosphere, and the volume ratio of the double metal cyanide complex catalyst to the storage container volume is 1 / 5 to 1/1.

ADVANTAGE OF THE INVENTION By this invention, drying of the double metal cyanide complex immediately before use conventionally and the necessity of grinding | pulverization of the solid substance obtained by drying were eliminated, the manufacturing process was greatly simplified, and the performance with reduction of a process is further reduced. And the improvement of the yield was recognized.

In addition, since the double metal cyanide complex was stored in the organic ligand, the double metal cyanide complex was protected by the organic ligand, and there was little deterioration of the double metal cyanide complex catalyst and high storage stability was observed. .

Further, since the obtained composite metal cyanide complex catalyst is not a powder but a slurry, the handling of the composite metal cyanide complex catalyst becomes easy.

[Example] Example 1 A slurry solution was obtained by reacting and ripening an aqueous solution of zinc chloride, an aqueous solution of potassium cyanocobaltate and an aqueous solution of diethylene glycol dimethyl ether. Thereafter, filtration was performed to obtain a filter cake. The filter cake was washed with an aqueous solution of diethylene glycol dimethyl ether and further filtered to obtain a filter cake, which was then washed with diethylene glycol dimethyl ether and filtered. Diethylene glycol dimethyl ether was added to the filter cake so that the content of the dried double metal cyanide complex catalyst became 10% by weight, and heat treatment was performed at 80 ° C. for 1 hour to obtain a slurry double metal cyanide complex catalyst. The container was filled with nitrogen and stored.

Example 2 An aqueous solution of zinc chloride, an aqueous solution of potassium cyanocobaltate and an aqueous solution of diethylene glycol dimethyl ether were reacted and aged to obtain a slurry solution. Thereafter, filtration was performed to obtain a filter cake. The filter cake was washed with an aqueous solution of ethylene glycol dimethyl ether and further filtered to obtain a filter cake, which was then washed with ethylene glycol dimethyl ether and filtered. Diethylene glycol dimethyl ether was added to the filter cake so that the content of the dried double metal cyanide complex catalyst was 30% by weight, and the mixture was heat-treated at 40 ° C. for 5 hours to obtain a slurry double metal cyanide complex catalyst. Stored in glass containers in air.

Example 3 An aqueous solution of zinc chloride, an aqueous solution of potassium cyanocobaltate and an aqueous solution of ethylene glycol dimethyl ether were reacted and aged to obtain a slurry solution. Then filtered,
A filter cake was obtained. The filter cake was washed with an aqueous solution of ethylene glycol dimethyl ether and then filtered to obtain a filter cake.
Ethylene glycol dimethyl ether is added to the filter cake so that the content of the dried double metal cyanide complex catalyst becomes 20% by weight, and the mixture is heat-treated at 120 ° C. for 5 hours under reflux to obtain a slurry of double metal cyanide complex. The halide complex catalyst was obtained and stored in a closed glass container in air.

Comparative Example 1 An aqueous solution of zinc chloride, an aqueous solution of potassium cyanocobaltate, and an aqueous solution of diethylene glycol dimethyl ether were reacted and aged to obtain a slurry solution. Thereafter, filtration was performed to obtain a filter cake. The filter cake was washed with an aqueous solution of diethylene glycol dimethyl ether and further filtered to obtain a filter cake, which was then washed with diethylene glycol dimethyl ether and filtered. The filter cake was dried under reduced pressure to obtain a catalyst mass,
Thereafter, the mixture was crushed with a hammer and crushed with a ball mill. A catalyst having a size of 72 mesh or less was separated by a sieve, and stored in a glass container sealed in the air.

Comparative Example 2 An aqueous solution of zinc chloride, an aqueous solution of potassium cyanocobaltate and an aqueous solution of ethylene glycol dimethyl ether were reacted and aged to obtain a slurry solution. Then filtered,
A filter cake was obtained. The filter cake was washed with an aqueous solution of ethylene glycol dimethyl ether and further filtered to obtain a filter cake, which was then washed with ethylene glycol dimethyl ether and filtered. The filter cake is dried at 80 ° C. to obtain a catalyst cake, which is then crushed with a hammer, crushed with a ball mill, and sieved.
The catalyst of 72 mesh or less was separated and stored in a glass container open to the air.

Comparative Example 3 An aqueous solution of zinc chloride, an aqueous solution of potassium cyanocobaltate and an aqueous solution of ethylene glycol dimethyl ether were reacted and aged to obtain a slurry solution. Then filtered,
A filter cake was obtained. The filter cake was washed with an aqueous solution of ethylene glycol dimethyl ether and further filtered to obtain a filter cake, which was then washed with ethylene glycol dimethyl ether and filtered. The filter cake was dried at 140 ° C. to obtain a catalyst mass, which was then crushed with a hammer, crushed with a ball mill, separated with a sieve to a catalyst of 72 mesh or less, and stored in a nitrogen-filled polypropylene container.

Double metal cyanide complex catalyst 7 synthesized by the above method
For the sample, the reaction rate ratio of the ring-opening polymerization of propylene oxide when using a trifunctional polyether polyol having a number average molecular weight of 1000 as the initiator, and the ratio of the polymerizable amount were measured immediately after synthesis and after storage for one month, The results are shown below.

It can be seen that the performance after storage for one month is not deteriorated as compared with the performance immediately after the synthesis in each of Examples 1, 2, and 3. This is different from the comparative example in which the composite metal cyanide complex is preserved only by using the composite metal cyanide complex containing the organic ligand as in the example. It is considered that the performance was improved because of further processing.

Further, Examples 1, 2, and 3 were all slurry-like substances, and were easier to handle than the fine powder substances of Comparative Examples 1, 2, and 3.

[Effects of the Invention] According to the present invention, long-term storage of a double metal cyanide complex is made possible. That is, there is little decrease in activity even after long-term storage,
In some cases, an increase in activity is also observed. In addition, there are effects such that the complex can be handled in a slurry state, and a drying treatment before use is not required.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical indication location C07F 9/00 9450-4H C07F 9/00 A 11/00 9450-4H 11/00 A 13/00 9450-4H 13/00 A 15/00 9450-4H 15/00 Z

Claims (3)

(57) [Claims] 1. A method for preserving a complex metal cyanide complex obtained by using an aqueous solution of a metal halide salt, an aqueous solution of an alkali metal cyanometalate and an organic ligand, the complex having undergone the reaction, aging and washing is obtained. In the organic ligand used, or in a different kind of organic ligand, at 40 ° C
A method for storing a double metal cyanide complex, comprising performing heat treatment at a temperature of not less than 160 ° C. and storing in an excess amount of an organic ligand. 2. As the organic ligand, one kind of ligand selected from ether, ester, alcohol, aldehyde, ketone, amide, nitrile, and sulfide, or two or more kinds of mixed ligands is used. The storage method according to claim 1. 3. The method according to claim 1, wherein the weight of the double metal cyanide complex in the organic ligand is from 10 ppm to 75%.