JPH04284850A - Production of composite metal cyanide complex catalyst - Google Patents

Abstract

PURPOSE:To prepare a composite metal cyanide complex catalyst wherein a hardly water-soluble org. ligand is coordinated with the composite metal cyanide. CONSTITUTION:The reactional product obtained by reacting an aqueous metal cyanide solution with an aqueous acrylic metal cyanomethylate is aged in a water-soluble org. ligand and, after drying, a hardly water-soluble ligand is coordinated with the reactional product. After drying, a composite metal cyanide complex catalyst wherein a characteristic ligand is coordinated is obtained.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a multimetal cyanide complex catalyst.

0002

BACKGROUND OF THE INVENTION Conventionally, multimetal cyanide complexes have been known as catalysts for ring-opening reactions of monoepoxides such as alkylene oxides. (US 3278457, U.S.
S3278458, US 3278459) The method for producing the multimetal cyanide complex catalyst used at this time is US 3427256, US 3941849, US
No. 4,472,560, US Pat. No. 4,477,589.

0003

[Problems to be Solved by the Invention] In the method for producing a composite metal cyanide complex catalyst, a composite metal cyanide is synthesized by dropping an aqueous alkali metal cyanometalate solution into an aqueous solution of a metal halide salt, and then a water-soluble Although a multimetal cyanide complex catalyst is produced by dropping an organic ligand, only water-soluble organic ligands can be used as catalyst ligands in this method. For this reason, the usable ligands are limited and a characteristic multi-metal cyanide complex catalyst cannot be synthesized.

Although the mechanism of ring-opening polymerization of monoepoxide in a multimetal cyanide complex catalyst is not necessarily clear, the type and state of the organic ligand in the multimetal cyanide complex affect the activity of the catalyst and It is thought that this has a great influence on the lifespan and the molecular weight distribution of the polymerization reaction product, and there is a need for a method of coordinating substances other than water-soluble organic ligands.

[0005]

[Means for Solving the Problems] The present invention has been made to solve the above-mentioned problems, and in a method for producing a multimetal cyanide complex catalyst, a metal halide salt aqueous solution and an alkali metal cyanometalate aqueous solution are mixed together. A multi-metal cyanide complex characterized in that the reaction product obtained by the reaction is aged in a water-soluble organic ligand and then dried, then coordinated with a poorly water-soluble organic ligand and dried. A method for producing a catalyst is provided.

[0006] 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), Al(IV), V(V),
Sr(II), W(IV), W(VI), Mn(II
), Cr(III), Cu(II), Sn(II),
It is preferable to use at least one selected from Pb(II) and Pb(II). Especially Zn(II) or Fe
It is preferable to use (II).

[0007] As the alkali metal of the alkali metal cyanometalate, Fe(II), Fe(III), Co(
II), Co(III), Cr(II), Cr(III
), Mn(II), Mn(III), Ni(II), V
It is preferable to use at least one selected from (IV) and V(V). In particular, it is preferable to use Co(III) or Fe(II).

[0008] As the water-soluble organic ligand, it is preferable to use at least one type of ligand selected from ether, ester, alcohol, aldehyde, ketone, amide, nitrile, and sulfide. It is particularly preferable to select ether or alcohol, and it is particularly preferable to use at least one type of ligand selected from ethylene glycol dimethyl ether, dimethylene glycol diethyl ether, i-propyl alcohol, and t-butanol.

The poorly water-soluble organic ligand is selected from higher alkyl group-containing ethers, esters, alcohols, aldehydes, ketones, amides, nitriles, and sulfides, which have a solubility in 100 g of water at 20° C. of 20 g or less. It is preferable to use at least one selected type of ligand. In particular, it is preferable to use ether or alcohol, especially i-propyl ether, n-
It is preferable to use at least one type of ligand selected from butanol and n-pentanol.

[0010] The metal halide salt aqueous solution concentration is 0.1
g/cc or more, preferably 0.5 g/cc
The above is used at a saturated concentration aqueous solution or less. In the concentration range below the specified concentration, the catalyst will be synthesized without excessive metal halide salt being incorporated into the multimetal cyanide complex catalyst, which will be disadvantageous to its activity. Furthermore, if the concentration is higher than the saturation concentration, solution mixing becomes non-uniform, which is also a disadvantageous condition for catalyst activity.

The concentration of the alkali metal cyanometalate aqueous solution is 0.5 g/cc or less, preferably 0.02 to 0.5 g/cc.
Used at 2 g/cc. If the concentration is higher than the specified concentration, the area where it is dropped into the metal halide salt aqueous solution will partially become an excess area of alkali metal cyanometalate, resulting in the same effect as when the concentration of the metal halide salt is low, resulting in a decrease in activity. . In addition, if it is carried out under conditions of low concentration, the metal halide salt incorporated into the composite metal cyanide complex catalyst will dissolve in water, which will be disadvantageous to the activity.

The reaction temperature at which the metal halide salt aqueous solution and the alkali metal cyanometalate aqueous solution are added dropwise is 0°C or higher and lower than 40°C, preferably 30°C or higher and lower than 40°C. When the reaction is carried out in a high temperature range, a highly crystalline multi-metal cyanide complex catalyst containing no metal halide salt is synthesized, and furthermore, the organic solvent cannot coordinate and no catalytic activity occurs. Furthermore, in the low temperature range, the synthesis reaction of the multi-metal cyanide complex catalyst becomes insufficient, which again becomes a disadvantageous condition for the catalytic activity.

Adding an organic solvent dropwise into the above reaction solution and stirring;
The aging temperature is set to be higher than the reaction temperature and lower than 125°C, preferably higher than 60°C and lower than 80°C. The resulting slurry is filtered, washed with a water-soluble organic ligand, filtered again, and dried. Drying is done in a vacuum or under a nitrogen atmosphere.
Alternatively, it is preferable to carry out in air at a temperature of 0° C. or higher and 300° C. or lower. After drying, pulverize, add and coordinate a poorly water-soluble organic ligand, and dry in vacuum, under a nitrogen atmosphere, or in air at a temperature of 0°C or more and 300°C or less to form the desired poorly water-soluble organic ligand. A multi-metal cyanide complex catalyst having a coordinating group is produced.

[0014] The present invention will be specifically explained below with reference to Examples and Comparative Examples, but the present invention is not limited only to these Examples.

[0015]

[Example] [Example 1] 15 containing 10g of zinc chloride
75 cc of an aqueous solution containing 4 g of potassium cobalt cyanate was added dropwise over 30 minutes while keeping the temperature at 35°C. After dropping, add 100cc of 50% ethylene glycol dimethyl ether aqueous solution,
The temperature was raised to ℃. After stirring for 1 hour, the mixture was filtered to obtain a filter cake. This filter cake was washed with a 30% aqueous ethylene glycol dimethyl ether solution and further filtered to obtain a filter cake, which was then washed with diethylene glycol dimethyl ether and filtered. The filter cake was dried in vacuo at 200° C. for 1 hour and ground. Thereafter, n-butanol was added and dried in air at 80°C to obtain an n-butanol coordination composite metal cyanide complex catalyst.

[Example 2] 1 containing 10 g of zinc chloride
4 g of potassium cobalt cyanate in 5 cc of aqueous solution
75 cc of an aqueous solution containing was added dropwise over 30 minutes while keeping the temperature at 35°C. After the dropwise addition was completed, 100 cc of 50% i-propyl alcohol aqueous solution was added, stirred for 1 hour under the same temperature conditions as in Example 1, and then filtered to obtain a filter cake. This filter cake was washed with a 30% i-propyl alcohol aqueous solution and further filtered to obtain a filter cake, which was then washed with i-propyl alcohol and filtered. Filter cake in vacuum 160
It was dried at ℃ for 1 hour and pulverized. Thereafter, n-pentanol was added and dried in air at 140°C to obtain an n-pentanol coordination composite metal cyanide complex catalyst.

[Comparative Example 1] 1 containing 10 g of zinc chloride
Potassium cobalt cyanate in 0 cc aqueous solution 4.1
75 cc of an aqueous solution containing 7 g and 100 cc of a 50% diethylene glycol dimethyl ether aqueous solution were added and reacted at a reaction temperature of 35°C. Next, this solution was filtered to obtain a filter cake. This filter cake was washed with a 30% diethylene glycol dimethyl ether aqueous solution and further filtered to obtain a filter cake, which was then washed with a diethylene glycol dimethyl ether aqueous solution, filtered, dried and pulverized to obtain a composite metal cyanide complex catalyst.

[Comparative Example 2] An attempt was made to synthesize a multimetal cyanide complex catalyst using zinc chloride, an aqueous solution of potassium cobalt cyanate, and n-butanol, but the phase separation of the n-butanol and the aqueous solution prevented the synthesis of the catalyst. It was possible.

As a result of analyzing the multimetal cyanide complex catalysts of Example 1, Example 2, Comparative Example 1, and Example 2 by differential thermal analysis, it was found that in Example 1 and Example 2, n
It was confirmed that -butanol and n-pentanol were each coordinated with diethylene glycol dimethyl ether in Comparative Example 1. In addition. In Example 1, ethylene glycol dimethyl ether was used, and in Example 2, i
- Some amount of propyl alcohol was coordinated.

[0020]

Effects of the Invention The present invention is a method for producing a multimetal cyanide complex catalyst coordinated with a poorly water-soluble organic ligand, which has been difficult in the past. A metal cyanide complex catalyst is obtained.

Claims (6)

[Claims] Claim 1: A method for producing a multimetal cyanide complex catalyst, in which a reaction product obtained by reacting an aqueous solution of a metal halide salt and an aqueous alkali metal cyanometalate solution is aged in a water-soluble organic ligand. A method for producing a multimetal cyanide complex catalyst, which comprises post-drying, then coordinating a poorly water-soluble organic ligand, and drying. Claim 2: The water-soluble organic ligand is an ether, an ester,
alcohol, aldehyde, ketone, amide, nitrile,
and sulfide. Claim 3: The water-soluble organic ligand is at least one ligand selected from i-propyl alcohol, ethylene glycol dimethyl ether, dimethylene glycol diethyl ether, and t-butanol. Manufacturing method of item 2. 4. The poorly water-soluble organic ligand is a higher alkyl group-containing ether, ester, alcohol, aldehyde, ketone, amide, nitrile, and has a solubility in 100 g of water at 20°C of 20 g or less The manufacturing method according to claim 1, wherein the ligand is at least one kind selected from sulfides. 5. The poorly water-soluble organic ligand is n-butanol,
5. The manufacturing method according to claim 4, wherein the ligand is at least one kind selected from n-pentanol and i-propyl ether. 6. The production method according to claim 1, wherein in the step of coordinating the poorly water-soluble organic ligand, a mixture of the poorly water-soluble organic ligand and the water-soluble organic ligand is used.