JP2003165837A - Metal cyanide complex catalyst and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a metal cyanide complex catalyst which has high catalyst activity, can produce a polyetherpolyol at a large polymerization rate even in a small catalyst amount, and can inhibit high mol.wt. side reaction products. <P>SOLUTION: This metal cyanide complex catalyst obtained by reacting a metal halide, a transition metal cyanide, and an organic ligand, has the rate of weight loss ≥30 wt.% from 110 to 170° C among total weight losses from 20 to 450°C is by differential thermogravimetric analysis. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a double metal cyanide complex catalyst suitable as a catalyst for an alkylene oxide ring-opening polymerization reaction.

[0002]

2. Description of the Related Art The use of a complex metal cyanide complex as a catalyst for ring-opening polymerization reaction of alkylene oxide has been known for a long time (US 3278457-9, etc.), and a method for producing a complex metal cyanide complex is US 342.
7256, US3941849, US4472560,
It is described in US Pat. No. 4,477,589. Further, a method for producing a polyether polyol using a complex metal cyanide compound complex as a catalyst is described in US40555188 and US4.
721818 and the like. Many of the polyether polyols obtained by these methods are used to react with isocyanates to produce polyurethane compounds such as polyurethane elastomers, polyurethane foams and polyurethane adhesives.

The complex metal cyanide complex catalyst is a catalyst which is composed of a double metal cyanide compound containing an organic ligand, water, and a metal salt and is insoluble in water. A typical example of the _double metal cyanide complex catalyst having excellent polymerization performance is zinc hexacyanocobaltate (Zn ₃ [Co (CN) ₆ ] ₂ ) containing an organic ligand, water, and zinc chloride. In recent years, as an organic ligand of a complex metal cyanide complex catalyst, te
It has been proposed by the present applicant that rt-butyl alcohol is particularly excellent (JP-A-4-145123).
Gazette, gazette of the same 8-311171, etc.). When tert-butyl alcohol is used, the life of the catalyst is remarkably extended, so that the amount of the catalyst used can be reduced, and the catalyst residue in the product polyol can be lowered to a level of several tens ppm or less even if it is unpurified.

By the way, as a method for producing a complex metal cyanide complex catalyst, an organic ligand is contacted with a solid product obtained by reacting an aqueous solution of a metal halide salt with an aqueous solution of a transition metal cyanide compound and aged. It is well known how to do this. Generally, the organic ligand is added after the solid product is precipitated. For example, JP-A-8-3111.
No. 71 discloses a method in which an organic ligand is added to one or both of an aqueous metal halide salt solution and an aqueous transition metal cyanide compound solution, and then both aqueous solutions are mixed to precipitate a solid product. There is. In this publication, as an effect of previously containing an organic ligand in two aqueous solutions to be reacted, when these two aqueous solutions are mixed and reacted, intimate mixing using a homogenizer or the like is performed. Is described as unnecessary.

However, the above-mentioned Japanese Patent Laid-Open No. 8-31117 is used.
The method described in, for example, Examples 8 to 11 of Japanese Unexamined Patent Publication 1 No. 1-96, describes potassium hexacyanocobaltate as a transition metal cyanide compound, and tert- as an organic ligand.
Heating an aqueous solution containing butyl alcohol to 30 ° C.,
After adding an aqueous solution of zinc chloride as a metal halide to this aqueous solution, the method has a step of stirring at 30 ° C. for 30 minutes, and the concentration of tert-butanol in the step of performing the heating stirring is 9.4% by mass or less. Is. When a polyether polyol was produced using the catalyst obtained here, the polymerization time was long and the molecular weight distribution tended to be broadened, which was problematic in terms of catalytic activity.

[0006]

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 as an initiator, and this is added to, for example, 120 By gradually adding alkylene oxide while maintaining it at a high temperature of about 0 ° C., a reaction of ring-opening the alkylene oxide and adding it to the hydroxy compound is carried out. As described above, when the polyether polyol is produced using the complex metal cyanide complex catalyst, it is preferable to reduce the amount of the complex metal cyanide complex catalyst used, particularly from the viewpoint of production cost. However, when the amount of the catalyst used is reduced, the time required for the polymerization tends to be long and the molecular weight distribution of the polyol tends to be broadened due to the generation of a high molecular weight by-reactant, so that the catalyst having a higher catalytic activity can be used. It has been desired to develop a metal cyanide complex catalyst.

Therefore, the present invention has a high catalytic activity,
When producing a polyether polyol, even if the amount of catalyst added is small, the polymerization rate is high, and a double metal cyanide complex catalyst capable of suppressing the formation of high molecular weight by-products,
And a method for manufacturing the same.

[0008]

In order to solve the above-mentioned problems, the complex metal cyanide complex catalyst of the present invention is a complex obtained by reacting a metal halide salt, a transition metal cyanide compound and an organic ligand. A metal cyanide complex catalyst,
Among the mass reductions at 20 to 450 ° C. by differential thermogravimetric analysis, the ratio of mass reduction at 110 to 170 ° C. is 30 mass% or more.

Further, the method for producing a composite metal cyanide complex catalyst of the present invention comprises reacting a metal halide, a transition metal cyanide compound and an organic ligand in an aqueous medium to form a composite metal cyanide complex catalyst. A method for producing, wherein, when a first aqueous solution containing a metal halide salt and a second aqueous solution containing a transition metal cyanide compound are mixed to obtain a mixed solution, the first aqueous solution and the An organic ligand is contained in one or both of the second aqueous solutions, and an organic ligand is present in the obtained mixed solution so that the content is 10% by mass or more, and 40 ° C or more and 125 ° C or less It is characterized in that it is aged at the temperature of. Tert as the organic ligand
-Preference is given to using butyl alcohol.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The complex metal cyanide complex catalyst of the present invention is obtained by reacting a metal halide salt, a transition metal cyanide compound and an organic ligand, and is measured by differential thermogravimetric analysis. Of the mass loss at ~ 450 ° C,
The ratio of the mass reduction at 110 to 170 ° C. is 30 mass% or more. Here, the differential thermogravimetric analysis (T
G-DTA) is a method of analyzing a mass change when a sample is heated, and in the present invention, a measurement for analyzing a mass change at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere. Adopt conditions.

Generally, the complex metal cyanide complex catalyst exhibits several desorption peaks in the temperature range of 20 to 450 ° C. (there are a plurality of ligands which selectively desorb in a certain temperature range). However, the present inventors have found that a very high catalytic activity can be obtained when the desorption in a specific temperature range occurs at a certain ratio or higher, and have completed the present invention. It is presumed that this is because the catalytic activity is high because the coordinating force of a certain organic ligand is in a predetermined condition. That is, in the double metal cyanide complex catalyst of the present invention, the fact that the mass reduction (elimination of organic ligand) at 110 to 170 ° C. in the differential thermogravimetric analysis is not less than a predetermined ratio means that a predetermined coordination force is required. It is shown that the ligand is present in a certain ratio or more, and thus the catalytic activity is high. Therefore, according to the double metal cyanide complex catalyst of the present invention, the catalytic activity is high, and when it is used for the production of polyether polyol, the polymerization rate is high even if the amount of the catalyst added is small, and the high molecular weight by-reactant is also present. Can be suppressed. In the present invention, 110 to 170 ° C. of the mass reduction at 20 to 450 ° C. by differential thermogravimetric analysis
The upper limit of the rate of decrease in mass is 100% by mass, and the more preferred range of the ratio is 34 to 100% by mass.

The composite metal cyanide complex catalyst of the present invention having the above characteristics can be obtained by the production method of the present invention. Hereinafter, an embodiment of the method for producing the double metal cyanide complex catalyst of the present invention will be described. First, a first aqueous solution containing a metal halide salt and a second aqueous solution containing a transition metal cyanide compound are mixed to obtain a mixed solution. At this time, one or both of the first aqueous solution and the second aqueous solution contain an organic ligand in advance.
The reaction between the first aqueous solution and the second aqueous solution is preferably performed by a method of dropping the other aqueous solution into one aqueous solution,
It is preferable that the two aqueous solutions are mixed with sufficient stirring.

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), Cd (I
It is preferable to use one or more divalent or higher valent fibrous metals selected from I) and Pb (II), especially Zn (II)
Alternatively, Fe (II) is 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 transition metal cyanide compound is water-soluble
Used in alkali metal cyanometalates, alkaline earth
Metal cyanometallates, ammonium cyanometalates
And cyanometallate acid. Cyanometa
The transition metals constituting the rate are Fe (II), Fe (I
II), Co (II), Co (III), Cr (II), Cr (III),
Mn (II), Mn (III), Ni (II), Ir (III), Rh
(II), Ru (II), V (IV), and V (V)
Use of one or more divalent or higher valent transition metals
Preferred is Co (III) or Fe (III).
Preferred transition metal cyanide compounds are alkali metal cyano
Metallate, more preferably alkali metal hexa
Cyanometallate, particularly preferably alkali metal
Hexacyanocobaltate. Shear in the present invention
Specific examples of the transition metal halide compound include H₃Fe (C
N)₆, H₃Co (CN)₆, K₃Fe (CN)₆, K₃Co
(CN)₆, Na₃Fe (CN)₆, Na₃Co (C
N)₆, Mg₃(Fe (CN)₆)₂, Mg₃(Co (C
N)₆) ₂, (NH_Four)₃Fe (CN)₆, (NH_Four)₃Co
(CN)₆, And so on. Among these, especially
Potassium hexacyanocobaltate (cyanocobaltate
Potassium: K₃Co (CN)₆) Is preferred.

Organic ligands contained in the first aqueous solution and / or the second aqueous solution include alcohols, ethers, ketones, esters, amines, amides, etc., which are well known in the synthesis of complex metal cyanide complex catalysts. All of the electron donors given 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), triethylene glycol dimethyl ether (triglyme), ethylene glycol mono-tert-butyl ether, iso-propyl alcohol, and dioxane. One or more compounds may be mentioned. The dioxane may be 1,4-dioxane or 1,3-dioxane, and 1,4-dioxane is preferable. A particularly preferred organic ligand is tert-butyl alcohol. When both the first aqueous solution and the second aqueous solution contain organic ligands, the organic ligands added to both aqueous solutions may be the same or different.

The concentration of the metal halide in the first aqueous solution is preferably 0.1 g / ml or more, more preferably 0.2 g / ml or more. Further, it is preferable that the concentration is not more than the saturation concentration. When the concentration of the metal halide salt is lower than the above range, the incorporation of the metal halide salt into the double metal cyanide complex catalyst becomes insufficient, resulting in high crystallinity of the double metal cyanide complex catalyst. , The catalytic activity is reduced. Further, when the concentration of the metal halide salt exceeds the saturation concentration, the mixed state when the first aqueous solution and the second aqueous solution are mixed becomes non-uniform, and as a result, the resulting composite metal cyanide complex catalyst becomes a catalyst. It becomes less active.

The concentration of the transition metal cyanide compound in the second aqueous solution is preferably 1.0 g / ml or less, 0.5
It is more preferably g / ml or less. In addition, 0.01 g / ml
The above is preferable. 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 molar relative ratio of the metal halide salt to the transition metal cyanide compound used (metal halide salt / transition metal cyanide compound) is preferably 12/1 to 1.6 / 1, and 6/1 to 1 8/1 is more preferable. If it is less than 1.6 / 1, the transition metal cyanide compound is likely to remain in the water, and the wastewater treatment is costly.

The concentration of the organic ligand in the first aqueous solution and the concentration of the organic ligand in the second aqueous solution are both 0 to 80% by mass (provided that at least one of the aqueous solutions has an organic ligand concentration of 0). Is not preferable), and more preferably in the range of 2 to 70% by mass. Further, the concentration of the organic ligand in the mixed solution obtained by mixing the first aqueous solution and the second aqueous solution is preferably within the range of 1 to 80% by mass, more preferably 2 to 70% by mass. Here, in this specification, the concentration of the organic ligand in the first aqueous solution, the concentration of the organic ligand in the second aqueous solution, and the concentration of the organic ligand in the mixed solution thereof are
All of them are the ratio of the organic ligand to the total of water and the organic ligand, and metal halide salts, transition metal cyanide compounds, etc. are not considered. Before the mixing of the first aqueous solution and the second aqueous solution, if the concentration of the organic ligand is higher than the above range, the solubility of the raw material is significantly reduced. In addition, when the concentration of the organic ligand after mixing both aqueous solutions is lower or higher than the above range, the catalytic activity tends to be insufficient in both cases.

The reaction temperature at the time of mixing the first aqueous solution and the second aqueous solution is preferably in the range of 5 to 95 ° C., more preferably 20 to 90 ° C. or more, since the aqueous solution is used, 20
-80 degreeC is especially preferable. When the reaction is performed in a high temperature range, a highly crystalline double metal cyanide compound is synthesized, and the coordination of the metal halide salt and the organic ligand becomes less than the required amount, and the 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.

Next, a reaction solution obtained by adding an organic ligand and / or water to the mixed solution obtained by mixing the first aqueous solution and the second aqueous solution, if necessary, at a predetermined aging temperature. Let it mature. Aging is preferably performed with stirring. As the organic ligand to be added to the mixed solution, one or more kinds of those listed above as the organic ligand to be contained in the first aqueous solution and / or the second aqueous solution can be used. The concentration of all organic ligands present in the reaction solution to be aged is 10% by mass or more, preferably 20% by mass or more. When the organic ligand concentration during aging is less than 10% by mass, coordination of the metal halide salt and the organic ligand tends to be insufficient. Further, if the concentration of the organic ligand at the time of aging is too high, the catalytic activity becomes low, so the content is preferably 80% by mass or less. It is presumed that this is because poisonous substances are likely to precipitate and cannot be sufficiently removed by filtration or washing work. Here, the concentration of the organic ligand in the reaction solution used for aging is the ratio of the organic ligand to the total amount of water and the organic ligand.

Before the aging, it is preferable to add the organic ligand and water to the mixed solution obtained by mixing the first aqueous solution and the second aqueous solution. As a result, the double metal cyanide compound produced by the reaction between the first aqueous solution and the second aqueous solution is uniformly dispersed in the solution, and the aging and the cleaning of the poisoning substance are effectively performed, so that the catalytic activity It is possible to improve and reduce the variation between the production lots of the catalyst. In the mixed solution obtained by mixing the first aqueous solution and the second aqueous solution, the concentration of the organic ligand with respect to the total amount of water and the organic ligand is already 10% by mass or more. In this case, the organic ligand may not be added, and the amount of water added may be adjusted so that the concentration of the organic ligand in the reaction solution is 10% by mass or more for aging. Further, even if the concentration of the organic ligand in the mixed solution obtained in the previous step is 10% by mass or more based on the total amount of water and the organic ligand, the organic ligand is further added. Good.

The aging temperature for aging the reaction solution is in the range of 40 ° C to 125 ° C. It is preferably in the range of 40 to 100 ° C., more preferably 4
It shall be in the range of 0 to 90 ° C. In the present invention, when the aging temperature is lower than 40 ° C., the coordination of the metal halide salt and the organic ligand becomes insufficient, and when the aging temperature exceeds 125 ° C., the formed double metal cyanide compound is crystallized, and both of the catalysts The activity is greatly reduced. 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.

Then, the slurry obtained by aging the reaction solution is subjected to solid-liquid separation to obtain a double metal cyanide compound (for example, Zn ₃ [Co (CN) ₆ ] ₂ ), an organic ligand, water, A cake is obtained which contains a solid product containing and and a metal salt. Solid-liquid separation can be performed by well-known filtration, pressure filtration, centrifugation, or the like. Thereafter, if necessary, water and an organic ligand are added to the cake for washing, and solid-liquid separation is preferably performed (washing operation), whereby a washed cake is obtained. If this washing is performed only with water, the metal salt (for example, an alkali metal salt) produced as a by-product of the reaction between the metal halide salt and the transition metal cyanide compound can be removed, but at the same time, the catalytic action of the double metal cyanide complex catalyst is achieved. It also removes the metal halide salt required for the expression of. Therefore, it is preferable to use water and an organic ligand together for washing. The organic ligand used in this washing step is one of those listed above as the organic ligand to be contained in the first aqueous solution and / or the second aqueous solution.
More than one species can be used. Unless the organic ligand used for washing has a particularly strong coordinating force as compared with the organic ligand already coordinated to the double metal cyanide complex catalyst, the organic ligand used for washing is already It is rare that a part or the whole of the coordinated organic ligand is replaced. The washing operation may be repeated a plurality of times or may be performed a plurality of times using different organic ligands.

By drying the cake thus obtained, a double metal cyanide complex catalyst is obtained. 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 to 150 ° C, more preferably 0 to 90 ° C. This is to prevent all the organic ligands coordinated to the catalyst from volatilizing. A powdery composite metal cyanide complex catalyst is obtained by pulverizing after drying.

Further, an alkylene oxide ring-opening polymer is used as the hardly volatile liquid, and a cake containing a complex metal cyanide complex catalyst is dispersed in the alkylene oxide ring-opening polymer, and then the excess amount of water and the organic ligand are removed to remove the catalyst. It can also be used as a slurry for the polymerization reaction. In this case, a polyether polyol can be preferably used as the alkylene oxide ring-opening polymer, and the molecular weight thereof is usually 300 to 12000, preferably 500 to 10000, and particularly preferably 700 to 5
The amount used is preferably 10 to 95 mass% with respect to the double metal cyanide complex catalyst.

The double metal cyanide complex catalyst can be used for ring-opening polymerization of 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, the hydroxy compound as the initiator is subjected to ring-opening polymerization of alkylene oxide 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 a double metal cyanide complex catalyst is used for ring-opening polymerization of alkylene oxide, it is difficult to react ethylene oxide, which is an alkylene oxide having 2 carbon atoms, by itself, but alkylene oxide having 3 or more carbon atoms. It can be made to react by mixing with and adding to a reaction system. A particularly preferred alkylene oxide is propylene oxide alone or a combination of propylene oxide and ethylene oxide.

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 a double metal cyanide complex catalyst to a hydroxy compound which is an initiator, and carrying out the reaction while gradually adding alkylene oxide. The amount of the double metal cyanide complex catalyst to be used is not particularly limited, but is appropriately about 1 to 5000 ppm, more preferably 10 to 1000 ppm, more preferably 10 to 3 with respect to the hydroxy compound used.
00 ppm is more preferable. Reaction temperature is 30 to 180
C is preferable, and 90 to 130 C 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.

According to the production method of the present invention, an organic ligand is contained in the first aqueous solution containing a metal halide salt and / or the second aqueous solution containing a transition metal cyanide compound, After reacting the aqueous solution, the metal halide and the organic ligand are heated and aged at a temperature of 40 ° C. or higher and 125 ° C. or lower in a state where the organic ligand is present at a concentration of 10% by mass or higher. The coordination of is sufficient.
According to the production method of the present invention, 20 by differential thermogravimetric analysis.
The composite metal cyanide complex catalyst of the present invention is obtained, in which the ratio of the mass reduction at 110 to 170 ° C of the mass reduction at -450 ° C is 30% by mass or more.

The composite metal cyanide complex catalyst of the present invention has a high catalytic activity and can suppress the formation of a high molecular weight by-product even when the amount of the catalyst is small. That is, the molecular weight distribution can be narrowed. Moreover, by using this, a side reaction is suppressed and a relatively high molecular weight polyether monool or polyether polyol having a low degree of unsaturation can be produced. 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 0.03 meq / g or less. When an elastic polyurethane foam is produced using this low unsaturation polyether polyol, the hardness decreases, the impact resilience decreases,
It is possible to solve problems such as deterioration of compression set and deterioration of cure property during foam molding. 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 monool and polyether polyol obtained by the above method can be used not only as a raw material for polyurethane but also as a surfactant, a lubricating oil and the like. It can also be used as a polymer-dispersed polyether polyol containing polymer particles.

[0034]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples. In addition, Example 1 is an example, Examples 2 and 3 are comparative examples, and Examples 4 to
6 is an evaluation example. Further, the differential thermogravimetric analysis was performed by the following method. That is, as the measuring device, TG-DTA2000S manufactured by Mac Science Co. was used. The measurement conditions are as follows: nitrogen atmosphere, heating rate 10 ° C./min, sample weight 10 mg,
The measurement temperature range was 20 to 450 ° C., and the sampling interval was 1 second. Under these measurement conditions, the ratio of the mass reduction at 110 to 170 ° C. was calculated among the mass reductions at 20 to 450 ° C.

<Production of Complex Metal Cyanide Complex Catalyst> (Example 1) 4.2 g of potassium hexacyanocobaltate K ₃ Co (CN) _{6 in} a 500 ml flask, 70 g of distilled water, and 10 g of tert-butyl alcohol. The second aqueous solution of and was added dropwise to the first aqueous solution of 10.2 g of zinc chloride, 10 g of distilled water, and 10 g of tert-butyl alcohol and kept at 50 ° C. over 30 minutes. After completion of the dropping, a mixture of 80 g of tert-butyl alcohol and 80 g of distilled water was added to
A reaction solution containing t-butyl alcohol at a concentration of 38.5% by mass was obtained. The reaction solution is heated to 70 ° C.,
After stirring for 90 minutes for aging, pressure filtration operation was performed under a pressure of 196 kPa. To the cake obtained, tert
-Butyl alcohol (40 g) and distilled water (70 g) were added and redispersed, and the mixture was stirred at room temperature (20 ° C, the same below) for 30 minutes for washing, and then filtered in the same manner as above. Next, 100 g of tert-butyl alcohol was added to the obtained cake for redispersion, the mixture was stirred at room temperature for 30 minutes, and then filtered in the same manner as above. Then, the obtained cake was dried at 50 ° C. under reduced pressure for 3 hours and pulverized to obtain a composite metal cyanide complex catalyst A. As a result of performing a differential thermogravimetric analysis of this composite metal cyanide complex catalyst A, the ratio of the mass reduction at 110 to 170 ° C. of the mass reduction at 20 to 450 ° C. (hereinafter,
The mass reduction ratio) was 40.1% by mass.

(Example 2) In Example 1, 160 g of distilled water was added after the dropwise addition was completed, tert-butyl alcohol was not added, and otherwise the same as in Example 1, except that tert-butyl alcohol was added in an amount of 7.7% by mass. A reaction solution containing the above solution was obtained. The reaction solution was aged in the same manner as in Example 1, then washed, dried and pulverized to obtain a composite metal cyanide complex catalyst B. As a result of a differential thermogravimetric analysis of this composite metal cyanide complex catalyst B, the mass reduction ratio was 1
It was 9.9 mass%.

Example 3 In Example 1, tert-butyl alcohol was not contained in the first aqueous solution and the second aqueous solution, and tert-butyl alcohol 100 was added after the dropping was completed.
g and 80 g of distilled water are added to give tert-
A composite metal cyanide complex catalyst C was obtained in the same manner except that a reaction solution containing butyl alcohol at a concentration of 38.5% by mass was obtained. As a result of the differential thermogravimetric analysis of this complex metal cyanide complex catalyst C, the mass reduction ratio was 1
It was 2.0 mass%.

<Evaluation of Catalytic Activity in Polyether Polyol Production> (Example 4) Propylene oxide (hereinafter referred to as PO) was added to glycerin as an initiator in a stainless steel 5 liter pressure resistant reactor 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 20 minutes after the introduction of PO, the pressure in the reaction vessel started to decrease and the temperature started to rise. This is 120 ℃
This is because the reaction of PO, which was present as a gas in the reaction tank, was opened and added to the initiator. It was confirmed that the induction period until the start of the reaction was about 20 minutes due to the decrease in the pressure in the reaction tank and the temperature increase in the reaction tank due to the heat of reaction. Then, PO was gradually added while keeping the inside of the reaction vessel at 120 ° C., and a total amount of 3140 g of PO was added to obtain a polyether polyol having a molecular weight of 3000.
The polyether polyol thus obtained had a hydroxyl value of 56.1 mg KOH / g, and the polystyrene-equivalent molecular weight distribution (M _w / M _n ) was 1.0 as a result of GPC analysis.
It was 40.

(Example 5) The same procedure as in Example 4 was repeated except that 0.14 g of the composite metal cyanide complex catalyst B was used in place of the composite metal cyanide complex catalyst A. As a result, it was confirmed that the induction period until the start of the reaction was 100 minutes. Further, the obtained polyether polyol (molecular weight 30
The hydroxyl value of 00) was 56.0 mgKOH / g, and the molecular weight distribution was 1.162.

(Example 6) The same procedure as in Example 4 was carried out except that 0.14 g of the composite metal cyanide complex catalyst C was used in place of the composite metal cyanide complex catalyst A. As a result, it was confirmed that the induction period until the start of the reaction was 90 minutes.
The obtained polyether polyol (molecular weight 300
The hydroxyl value of 0) was 55.9 mgKOH / g, and the molecular weight distribution was 1.130.

[0041]

INDUSTRIAL APPLICABILITY The double metal cyanide complex catalyst of the present invention has high catalytic activity when producing a polyether polyol using the same, and can suppress the formation of a high molecular weight by-reactant to a small amount. . That is, the molecular weight distribution of the obtained polyether polyol can be narrowed. As a result, by using such a polyether polyol, it is possible to easily produce a polyurethane having excellent properties such as foamability and hardness. 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. According to the method for producing a composite metal cyanide complex catalyst of the present invention, the composite metal cyanide complex catalyst of the present invention having such excellent characteristics can be obtained.

Claims (3)

[Claims] 1. A composite metal cyanide complex catalyst obtained by reacting a metal halide salt, a transition metal cyanide compound and an organic ligand, which comprises 20 to 4 by differential thermogravimetric analysis.
A composite metal cyanide complex catalyst characterized in that, of the mass reduction at 50 ° C, the mass reduction ratio at 110 to 170 ° C is 30% by mass or more. 2. 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, which comprises a metal halide salt. When the first aqueous solution and the second aqueous solution containing a transition metal cyanide compound are mixed to obtain a mixed solution, an organic ligand is added to one or both of the first aqueous solution and the second aqueous solution. A mixed metal cyanide, characterized in that it is contained, and an organic ligand is present in the obtained mixed solution so that the content is 10% by mass or more and aged at a temperature of 40 ° C. or higher and 125 ° C. or lower. Method for producing complex catalyst. 3. The method for producing a double metal cyanide complex catalyst according to claim 2, wherein tert-butyl alcohol is used as the organic ligand.