JP2003073469A - Composite metal cyanide complex catalyst for ring- opening polymerization of alkylene oxide and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composite metal cyanide complex catalyst for ring- opening polymerization of an alkylene oxide capable of producing a polyetherpolyol with low unsaturation degree at a high catalyst activity, and a method for producing the catalyst. SOLUTION: This method for producing the composite metal cyanide complex catalyst for ring-opening polymerization of an alkylene oxide comprises the steps of mixing an organic ligand, a metal salt and a transition metal cyanide compound, separating a solid product deposited from the obtained mixed solution, washing the solid product with water, bringing the washed solid product into contact under heating with an aqueous solution containing the organic ligand and the metal salt, and separating a solid from the slurry. The composite metal cyanide complex catalyst for ring-opening polymerization of an alkylene oxide obtained by such method is provided.

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 the raw materials for polyurethane elastomers, adhesives, paints, foaming agents, etc., have hitherto been treated with an initiator having active hydrogen, such as ethylene oxide or propylene oxide. Have been produced by polymerizing alkylene oxides such as Alkali metal (anionic polymerization), BF3 etherate (cationic polymerization), and double metal cyanide complex catalyst (hereinafter referred to as DMC catalyst) (coordination polymerization) are well known as typical alkylene oxide polymerization catalysts. Among these catalysts, the DMC catalyst has a higher polymerization activity than the former two catalysts, a cyclic ether compound such as a dioxane derivative does not form as a by-product, and a reaction that produces a monool having an unsaturated bond as a by-product is small. It is possible to produce a high molecular weight polyol.

DMC catalysts have been found long ago (U
S3278457). In recent years, among the organic ligands for DMC catalysts, it has been proposed by the applicant that tert-butyl alcohol is particularly excellent (JP-A-4-145).
No. 123, No. 8-311171), and many improved methods for DMC catalysts have been continuously proposed thereafter. When using tert-butyl alcohol,
The life of the catalyst is remarkably extended, and the catalyst residue in the product polyol is reduced to a level of several tens of ppm or less even if it is unrefined.

The DMC catalyst is a water-insoluble catalyst containing an organic ligand, water and a metal salt. DMC with excellent polymerization performance
Typical examples of the catalyst are zinc hexacyanocobaltate (Zn3 [Co (C
N) 6] 2). A typical method for producing such a DMC catalyst is shown by taking zinc hexacyanocobaltate as an example.
As represented by the general formula (1), in the presence of an organic ligand, a solid of a cyanide double metal compound is precipitated by mixing an aqueous solution of excess zinc chloride and an aqueous solution of alkali metal hexacyanocobaltate, The solid is washed with a mixed solution of water and an organic ligand and dried to obtain a powdery solid catalyst.

[Chemical Formula 1] ZnCl 2 ＋ K3Co (CN) 6 (H2O / Ligand) Zn3 [Co (CN) 6] 2X (ZnCl2) Y (H2O) Z (Ligand) ＋ KCl (1)

Further, the solid of the double metal cyanide compound is precipitated by mixing an aqueous solution of excess zinc chloride containing no organic ligand and an aqueous solution of alkali metal hexacyanocobaltate, and then the solid is filtered, or Before separation by a method such as centrifugation, an organic ligand or an organic ligand-containing aqueous solution is added to the mixed solution. When no organic ligand is used, the activity as a polymerization catalyst is very low or does not show any activity (US547013).

The type of organic ligand, the ratio of each of the organic ligand to zinc hexacyanocobaltate, water, and zinc chloride are important factors affecting the catalytic performance. In the formula (1), as is clear from the chemical structural formula of the product double metal cyanide compound, zinc chloride has a stoichiometric ratio (Zn / Co) to alkali metal hexacyanocobaltate.
It is used much more than the atomic ratio of 1.5), and the water-soluble alkali metal salt, which is a by-product of ligand exchange, dissolves in the mixed solution. It has been proposed that zinc chloride be mixed with alkali metal hexacyanocobaltate in a stoichiometric ratio or lower to produce an active DMC catalyst. It is a special condition of coexistence of compounds of the family (US59
52261).

The water-insoluble solid deposited by mixing the aqueous solution of zinc chloride and the aqueous solution of alkali metal hexacyanocobaltate is separated from the solution by a method such as filtration or centrifugation. Alkali metal salts partially remain in the solid, but this acts as a catalyst poison and causes the deterioration of polymerization activity (US3278457, US4472).
560). This unwanted alkali metal salt is removed by washing the solid with an aqueous solution containing the organic ligand.
Since the alkali metal salt reduces the catalytic activity, it is desirable to wash the precipitated solid with water to remove it as much as possible. However, washing with water also removes the zinc chloride necessary for manifesting the catalytic activity (US5158922). . Therefore, in many cases, the washing is performed plural times with an aqueous solution containing organic ligands having different compositions so that a certain amount of zinc chloride remains. In addition, when precipitating a solid by mixing an aqueous solution of zinc chloride and an aqueous solution of alkali metal hexacyanocobaltate, by reducing the amount of organic ligand used, it is possible to remove the by-produced alkali metal salt only by filtration separation. However, the required amount of zinc chloride is also removed, and only a catalyst with extremely low activity is obtained.

Furthermore, when an aqueous solution containing an organic ligand is used for washing in order to produce a DMC catalyst having high activity, a slurry of a double metal cyanide compound containing zinc chloride, an organic ligand and water is used. Both the solution and the slurry solution of the double metal cyanide compound when washed with an organic ligand-containing aqueous solution are pasty, and it is difficult to separate the solid from the solution, and the number of washings increases the manufacturing time. There is also a problem that (US4843054, same 5158922, same 5952)
261).

The conventionally proposed DMC catalyst has a high activity, and when a polyether polyol is produced using the catalyst, it is possible to suppress the by-product of polyether monool having an unsaturated bond. As described above, there is a problem in that the catalyst manufacturing method is complicated and time-consuming, and as a result, the catalyst cost is increased. Therefore, there has been a demand for a method for easily producing a DMC catalyst capable of producing a highly active polyether polyol having a low degree of unsaturation in a short time.

[0011]

Means for Solving the Problems As a result of intensive studies aimed at achieving the above object, the present inventors found that an excess metal salt to be coordinated with a double metal cyanide compound for the purpose of manifesting catalytic activity is caused by water. In order to prevent removal by washing, the conventional idea of washing the precipitated solid with an aqueous solution containing an organic ligand is changed, and the precipitated solid is washed with water to form an active DMC catalyst. It was decided to add the required amount of metal salt, organic ligand and water. That is, the solid product obtained by reacting the metal salt and the transition metal cyanide compound,
It is considered that the metal salt, the organic ligand and water are added. In addition, a metal salt (usually an alkali metal salt or the like) produced as a by-product of the solid production reaction is added, and the by-product metal salt has a property as a catalyst poison. Therefore, conventionally, the solid product was washed with an organic ligand-containing aqueous solution so as to remove only the by-product metal salt without removing the metal salt and the organic ligand. Was not fully removed.

Therefore, in the first aspect of the present invention, the precipitated solid is washed with water to remove the added metal salt, organic ligand and water, and the above-mentioned by-product metal salt, and then the metal salt,
It was decided to add the required amount of organic ligand and water. Since the washing is performed with water containing no organic ligand, the cost for treating the waste water for washing is low, and the by-product metal salt which is difficult to remove with the aqueous solution containing the organic ligand can be easily removed. In addition, since it is washed with water, the metal salt added together with the by-product metal salt and the organic ligand are also removed, but since the metal salt, the organic ligand and water are added in the required amounts thereafter, the catalytic activity is increased. can do.

That is, the first invention of the present invention is to mix an organic ligand, a metal salt and a transition metal cyanide compound, separate a solid product precipitated from the resulting mixed solution, and produce the solid product. A method for producing a DMC catalyst for alkylene oxide ring-opening polymerization, which comprises: washing a product with water and then subjecting it to a heat contact treatment with an aqueous solution containing an organic ligand and a metal salt to separate a solid from a slurry. It is a thing. The second invention of the present invention provides a DMC catalyst for alkylene oxide ring-opening polymerization obtained by such a production method.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION A first aspect of the present invention is to mix an organic ligand, a metal salt and a transition metal cyanide compound, and separate a precipitated solid product from the resulting mixed solution. A method for producing a DMC catalyst for ring-opening polymerization of alkylene oxide, which comprises washing a solid product with water, and then subjecting it to a heat contact treatment with an aqueous solution containing an organic ligand and a metal salt to separate the solid from the slurry. is there. The metal of the metal 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 (IV), W (VI), Mn (II), C
r (III), Cu (II), Sn (II), Cd (II), and Pb
It is preferable to use one or more divalent or higher valent transition metals selected from (II). Especially Zn (II) or Fe (I
I) is preferred. Examples of the anion ligand of the metal salt include halides, sulfates, carbonates, nitrates, thiocyanates, isothiocyanates, and carboxylates, but halides are preferable, and chlorides are particularly preferable. A more preferred metal salt is zinc halide, and a particularly preferred metal salt is zinc chloride.

In the present invention, examples of the transition metal cyanide compound include alkali metal cyanometallates, alkaline earth metal cyanometallates, ammonium cyanometallates and cyanometallate acids. As the metal constituting the cyanometallate, Fe (II), Fe (III)
, Co (II), Co (III), Cr (II), Cr (III), M
n (II), Mn (III), Ni (II), Ir (III), Rh (I
I), Ru (II), V (IV), and V (V), and it is preferable to use one or more divalent or more transition metal selected from Co (III) or Fe (III). Is preferred. A preferred transition metal cyanide compound is an alkali metal cyanometallate, more preferably an alkali metal hexacyanometallate, and particularly preferably an alkali metal hexacyanocobaltate. Preferred specific examples of the transition metal cyanide compound in the present invention include H
3Fe (CN) 6, H3Co (CN) 6, K3Fe (C
N) 6, K3Co (CN) 6, Na3Fe (CN) 6,
Na3Co (CN) 6, Mg3 (Fe (CN) 6) 2,
Mg3 (Co (CN) 6) 2, (NH4) 3Fe (C
N) 6, (NH4) 3Co (CN) 6 and the like, but potassium hexacyanocobaltate (K3Co (C
N) 6) is particularly preferred.

Organic ligands such as alcohols, ethers, ketones, esters, amines, amides, etc.
All well known electron donors for the synthesis of MC catalysts can be used. The preferred organic ligand is water-soluble, and specific examples thereof include tert-butyl alcohol, n-butyl alcohol, iso-butyl alcohol, tert-pentyl alcohol, 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, i
Examples include one or more compounds selected from so-propyl alcohol and dioxane. The dioxane may be 1,4-dioxane or 1,3-dioxane, and 1,4-dioxane is preferable. Particularly preferred organic ligands are tert-butyl alcohol, t
ert-pentyl alcohol and ethylene glycol mono-tert-butyl ether.

In the first aspect of the present invention, first, an organic ligand, a metal salt and a transition metal cyanide compound are mixed. The metal salt and the transition metal cyanide compound can be mixed in the form of an organic ligand-containing aqueous solution as is usually done. Alternatively, the metal salt and the transition metal cyanide compound may be mixed in the form of an aqueous solution containing no organic ligand, and the organic ligand or the organic ligand-containing aqueous solution may be added to the mixed aqueous solution containing the precipitated solid. The concentration of the aqueous solution of the metal salt and the transition metal cyanide compound is preferably below the saturation concentration. When the concentration is lower than the saturation concentration, the mixed state of the solution becomes uniform, and a double metal cyanide complex catalyst having high catalytic activity can be obtained. The reaction between the aqueous solution of the metal salt and the aqueous solution of the transition metal cyanide compound can be carried out by adding the latter to the former or vice versa. It is preferable that the both are mixed with sufficient stirring. Since an aqueous solution is used, the reaction temperature is preferably 5 to 95 ° C, more preferably 30 to 90 ° C, and particularly preferably 50 to 80 ° C. If it is 5 to 95 ° C., the transition metal cyanide compound is effectively used, and the solid precipitation reaction of the double metal cyanide compound is sufficiently carried out.

In the present invention, the molar relative ratio of the metal salt and the transition metal cyanide compound used (metal salt / transition metal cyanide compound) is preferably 12/1 to 1.6 / 1, and 6
/ 1 to 1.8 / 1 is more preferable, and 5/1 to 2.0 / 1
Is particularly 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. Further, the concentration of the organic ligand with respect to the total amount of the organic ligand and water in the mixed aqueous solution of the metal salt and the transition metal cyanide compound is preferably 3 to 60% by weight, and 5 to 30%.
Is particularly preferable. Conventionally, in the manufacture of DMC catalyst,
The concentration of the organic ligand with respect to the total amount of the organic ligand and water is
It was necessary to be 20 to 30% or more. In the present invention, the concentration of the organic ligand during solid separation can be lowered,
The filtration separability is improved.

Next, after separating the precipitated solid from the organic ligand-containing mixed solution obtained by mixing the metal salt and the transition metal cyanide compound, the solid product is washed with water to obtain the organic ligand and the metal. A composite metal cyanide complex catalyst is produced by heat contact treatment with an aqueous solution containing a salt. Conventionally, by washing with an organic ligand-containing aqueous solution instead of water, metal salts that are poorly soluble in organic ligands were not removed, and only by-product metal salts that were easily soluble were removed. However, it was necessary to change the kind and the blending amount of the organic ligand in the aqueous solution and wash the solution a plurality of times. In the first invention of the present invention, by washing only with water, the metal salts and organic ligands added to the solid product are almost completely removed, and the metal by-product which is a catalyst poison is produced. The salt is also almost completely removed. Then, the solid product after washing is subjected to a heat contact treatment with an aqueous solution containing an organic ligand and a metal salt, so that the metal salt, the organic ligand and water in an amount necessary for manifesting the catalytic activity are solid products. To give a highly active complex metal cyanide complex catalyst for alkylene oxide ring-opening polymerization. Solids can be separated from the aqueous solution after washing with water by a method such as ordinary filtration or centrifugation. Washing with water has better filterability than washing with water containing an organic ligand. Usually, when the double metal cyanide compound, which is a precipitated solid, is washed only with water, considering the past experience that the polymerization activity is lost or the activity is extremely suppressed, while performing the water washing operation,
Further, the production method of the present invention, which can obtain a complex metal cyanide complex catalyst for alkylene oxide ring-opening polymerization, which has high catalytic activity is surprising.

The metal salts and organic ligands used in the heat contact treatment may be the same as those described above. Zn (II) or Fe (II) are particularly preferred metal salts. tert-butyl alcohol, tert-pentyl alcohol, glyme, ethylene glycol mono-te
rt-Butyl ether is a particularly preferred organic ligand.

In the present invention, the concentration of the organic ligand with respect to the total amount of the organic ligand and water in the heat contact treatment is important, preferably 10 to 85% by mass, particularly preferably 15%.
˜78% by mass. When it is 10 to 85% by mass, a double metal cyanide complex catalyst for alkylene oxide ring-opening polymerization having a high catalytic activity can be obtained. The amount of the metal salt used in the aqueous solution containing the organic ligand and the metal salt is 1.5 to 12 in terms of molar ratio (metal salt / transition metal cyanide compound) to the transition metal cyanide compound used for solid precipitation.
Is preferable and 1.7-6 is more preferable. The heating contact treatment may be performed by stirring and mixing the solid product and an aqueous solution of a metal salt containing an organic ligand. The contact temperature is preferably 20 to 150 ° C, more preferably 30 to 125 ° C, and 40 to 100 ° C.
C is especially preferred. The contact time is preferably 15 to 300 minutes, more preferably 30 to 120 minutes.

A cake containing a DMC catalyst can be obtained by separating the slurry obtained by the above heating contact treatment by a method such as ordinary filtration or centrifugation. Further, although not particularly necessary, the cake is washed by adding an aqueous solution of a compound selected from the group consisting of an organic ligand used in the synthesis and an organic ligand different from the organic ligand used in the synthesis. It can be performed. The washing operation may be repeated multiple times. When washing with an aqueous solution containing an organic ligand, the concentration of the organic ligand is preferably 30 to 99% by mass, more preferably 50 to 95% by mass.

From the cake containing the DMC catalyst obtained,
For example, under the following conditions, except for excess water and organic ligand,
The DMC catalyst of the present invention is obtained. Examples of methods for removing excess water and organic ligands include a drying method by heating, a drying method in a vacuum state, and a method of removing water and volatile organic ligands after mixing with a hardly volatile liquid. To be 20-150 degreeC is preferable and, as for the temperature of dry removal, it is 30-90.
C. is more preferable, and 40-60.degree. C. is particularly preferable. This is to prevent all the organic ligands and water contained in the catalyst from volatilizing.

A cake containing a DMC catalyst is dispersed in the above-mentioned alkylene oxide ring-opening polymer as a hardly volatile liquid, and excess water and organic ligands are removed to be used as a catalyst slurry for the polymerization reaction. be able to. As the alkylene oxide ring-opening polymer, polyether polyol can be preferably used, and the molecular weight is preferably 300 to 12000, more preferably 500 to 10000, and 700 to 50.
00 is particularly preferred. The amount used is 1 for solids
0 to 95 mass% is preferable.

The second invention of the present invention is an alkylene oxide ring-opening polymerization catalyst comprising the composite metal cyanide complex catalyst produced by the above method, which is the alkylene oxide ring-opening polymerization composite metal of the present invention. It can be produced using the method for producing a cyanide complex catalyst. Polyether polyol can be produced by ring-opening polymerization of alkylene oxide using the DMC catalyst for ring-opening polymerization of alkylene oxide.

The alkylene oxide ring-opening polymerization is carried out in the presence of the alkylene oxide ring-opening polymerization catalyst of the present invention. For example, polyether monool is produced by ring-opening polymerization of an alkylene oxide containing an alkylene oxide having 3 or more carbon atoms with a monohydroxy compound as an initiator.
Alternatively, a polyether polyol is produced by ring-opening polymerization of an alkylene oxide containing an alkylene oxide having 3 or more carbon atoms with a polyhydroxy compound having 2 or more hydroxyl groups as an initiator. 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 can be mentioned. These are 2
One or more species may be used in combination, in which case they may be mixed and reacted, or they may be reacted sequentially.

When the alkylene oxide ring-opening polymerization 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, the polyether polyol preferably has an oxyethylene group at the terminal, and the content of the terminal oxyethylene group is particularly preferably 5 to 30% by mass. The polyether polyol having an oxyethylene group at the terminal is an alkali catalyst after ring-opening polymerization of an alkylene oxide containing an alkylene oxide having 3 or more carbon atoms as an initiator using the above-mentioned catalyst for ring-opening polymerization of alkylene oxide in the present invention. Can be produced by reacting ethylene oxide with. As the alkali catalyst, alkali metals such as sodium and potassium, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal alkoxides such as sodium alkoxide and potassium alkoxide are suitable.

Specific examples of the monohydroxy compound or the polyhydroxy compound having two or more hydroxyl groups which can be used as the initiator include the followings, but are not limited thereto. Methanol, isopropyl alcohol, n-butyl alcohol, 2-ethylhexanol, 1-octadecanol, allyl alcohol, oleyl alcohol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, trimethylolpropane, pentaerythritol, diglycerin , Sorbitol, dextrose, methyl glucoside, sucrose, bisphenol A, etc. Further, alkylene oxide adducts of these initiators can also be used as the initiator.

The polyether monool or polyether polyol is prepared by adding the DMC catalyst for alkylene oxide ring-opening polymerization of the present invention to a hydroxy compound as an initiator,
It can be produced by carrying out the reaction while gradually adding alkylene oxide. The amount of the catalyst used is not particularly limited, but is preferably 1 based on the hydroxy compound used.
~ 5000 ppm, more preferably 10-1000 pp
m, particularly preferably 20 to 300 ppm. The reaction temperature is preferably 30 to 180 ° C, more preferably 90 to 130 ° C. Regarding the introduction of the catalyst into the reaction system, it may be introduced all at once at the beginning, or may be introduced sequentially in portions. The DMC catalyst for alkylene oxide ring-opening polymerization of the present invention is active,
Since the catalyst has a long life, only a small amount of the catalyst finally remains in the polyether polyol, and the polyether polyol after the reaction may be used as it is. of course,
Depending on the purpose, the catalyst can be removed by various commonly known methods.

The alkylene oxide ring-opening polymerization D of the present invention
By using the MC catalyst, side reactions are 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 DMC catalyst for alkylene oxide ring-opening polymerization 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. When an elastic polyurethane foam is produced using this low unsaturation polyether polyol, it is possible to improve problems such as a decrease in hardness, a decrease in impact resilience, deterioration of compression set, and a decrease in cure property during foam molding. The crushing property of the seat cushion can be dramatically improved. Therefore, even when manufacturing a seat cushion having a large and complicated shape, crushing becomes easy. 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-mentioned 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.

[0032]

[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, Examples 2 and 3 are comparative examples, and Examples 4 to 6 are evaluation examples.

Production Example 1 of Complex Metal Cyanide Complex Catalyst for Ring-Opening Polymerization of Alkylene Oxide In a 200 ml flask, potassium hexacyanocobaltate K3Co (CN) 6 kept at 40 ° C. was used in an amount of 2.1.
15 g of an aqueous solution containing 5.1 g of zinc chloride (Zn / Co atomic ratio of 6) was added dropwise to the aqueous solution containing g of 8 g of tert-butyl alcohol and 78 g of water over 30 minutes. In the meantime, the reaction solution was mixed with a Teflon (registered trademark) stirring blade to 3
Stir at 00 rpm, and after the addition is complete, add 60 at 60 ° C.
Minute stirring was continued. After that, filtration was performed under reduced pressure using a filter paper for quantifying fine particles (No. 5C manufactured by ADVANTEC, abbreviated as 5C hereinafter) with a circular filter plate having a diameter of 4 cm, and solids were separated in about 50 minutes. Next, this solid was redispersed with 40 g of water and stirred at room temperature for 30 minutes, and the solid washed by filtration in the same manner as above was separated in about 30 minutes. Thereafter, the washed solid was treated with 1.43 g of zinc chloride (Zn / Co atomic ratio of 1.7),
The solution was dispersed in an aqueous solution containing 20 g of tert-butyl alcohol and 20 g of water, and the slurry was subjected to heat contact treatment with stirring while stirring at 60 ° C. for 60 minutes. The contact-treated solid was separated by filtration (about 120 minutes) as described above. The wet solid cake was dried at 50 ° C. for 4 hours, crushed,
A composite metal cyanide complex catalyst A was obtained. Compared to the catalyst preparation of Example 2, the total filtration time was shorter.

Example 2 2.1 g of potassium hexacyanocobaltate K3Co (CN) 6 kept at 40 ° C. was heated in a 200 ml flask.
g, tert-butyl alcohol 40 g, and water 78 g in an aqueous solution, zinc chloride 5.1 g (Zn / Co molar ratio 6)
15 g of an aqueous solution containing P was added dropwise over 30 minutes. In the meantime, the reaction solution was mixed with a Teflon (registered trademark) stirring blade to 3
Stir at 00 rpm, and after the addition is complete, add 60 at 60 ° C.
Minute stirring was continued. After that, 5 with a circular filter plate with a diameter of 4 cm
The filter paper of C was used for filtration under reduced pressure, and the solid was separated in about 90 minutes. Next, this solid was redispersed with 15 g of tert-butyl alcohol and 25 g of water, stirred at room temperature for 30 minutes, and the solid washed by filtration in the same manner as above was separated in about 120 minutes. After that, the washed solid was redispersed with 36 g of tert-butyl alcohol and 4 g of water and stirred at room temperature for 30 minutes, and the solid washed by filtration in the same manner as above was separated in about 150 minutes. The wet solid cake was dried at 50 ° C. for 4 hours and pulverized to obtain a composite metal cyanide complex catalyst B.

Example 3 A DMC catalyst C was obtained in the same manner as in Example 2 except that 8 g was used instead of 40 g of tert-butyl alcohol in the solid precipitation reaction. However, the initial filtration separation time of the precipitated solid was about 50 minutes.

Production Example 4 of Polyether Polyol 30 g of polyoxypropylene triol having a molecular weight of 1000 obtained by reacting glycerin with propylene oxide (hereinafter referred to as PO) in a 500 ml pressure-resistant reactor made of stainless steel equipped with a stirrer and a catalyst As DMC catalyst A
5.1 mg of was added. After purging with nitrogen, the temperature was raised to 120 ° C., 8 g of PO was spot-reacted, and when the pressure in the system dropped, 230 g of PO was continuously introduced and reacted at a stirring speed of 700 rpm. The molecular weight of the obtained polyether polyol was about 11,300 in terms of polystyrene as a result of analysis by GPC. The total unsaturation is 0.005
It was 0 meq / g. Catalytic activity is 45 kg PO / g
Catalyst (PO reaction amount per 1 g of catalyst) (Catalyst remaining 20 pp
m), which was sufficiently high, and the catalyst life was long at the same time.

Example 5 Glycerin was reacted with PO in a 500 ml pressure resistant reactor made of stainless steel equipped with a stirrer to obtain a molecular weight of 10
30 g of polyoxypropylene triol No. 00 and 5.5 mg of the composite metal cyanide complex catalyst B as a catalyst were added. After purging with nitrogen, the temperature was raised to 120 ° C., 8 g of PO was spot-reacted, and when the pressure in the system dropped, the stirring speed was 70
230 g of PO was continuously introduced and reacted at 0 rpm. The molecular weight of the obtained polyether polyol is GPC
As a result of analysis by the above, it was about 11,200 in terms of polystyrene. The total degree of unsaturation was 0.0052 meq / g. The catalyst activity is 42 kg PO / g catalyst (catalyst remaining 21 pp
m), and the catalyst life was still continuing.

Example 6 C was added as a DMC catalyst, and 8 g of PO was fed to the reactor for spot reaction in the same manner as in Example 5, but 12
After 0 minutes, no decrease in pressure was observed and there was no catalytic activity. It is considered that, since the concentration of tert-butyl alcohol at the time of solid precipitation was low, catalyst C removed zinc chloride, and unlike the method of the present invention, required zinc chloride was not replenished and activity could not be obtained.

[0039]

INDUSTRIAL APPLICABILITY The composite metal cyanide complex catalyst for alkylene oxide ring-opening polymerization obtained by the production method of the present invention has high catalyst productivity, high activity, and long life. Further, by using this, an alkylene oxide is reacted with a polyhydroxy compound having 2 or more hydroxyl groups as an initiator to produce a polyether polyol having a low degree of unsaturation.

Claims (6)

[Claims] 1. An organic ligand, a metal salt, and a transition metal cyanide compound are mixed, a solid product precipitated from the mixed solution is separated, and the solid product is washed with water, Heat contact treatment with an aqueous solution containing a ligand and a metal salt,
A method for producing a composite metal cyanide complex catalyst for alkylene oxide ring-opening polymerization, which comprises separating a solid from a slurry. 2. The method for producing a composite metal cyanide complex catalyst for alkylene oxide ring-opening polymerization according to claim 1, wherein the metal salt is zinc halide. 3. The method for producing a composite metal cyanide complex catalyst for alkylene oxide ring-opening polymerization according to claim 1, wherein the transition metal cyanide compound is an alkali metal hexacyanometallate. 4. The organic ligand is tert-butyl alcohol, n-butyl alcohol, iso-butyl alcohol, tert-pentyl alcohol, iso-pentyl alcohol, N, N-dimethylacetamide, ethylene glycol dimethyl ether, ethylene glycol mono. The alkylene oxide ring-opening polymerization according to any one of claims 1 to 3, which is one or more compounds selected from -tert-butyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, iso-propyl alcohol and dioxane. Method for producing complex metal cyanide complex catalyst. 5. An aqueous solution containing an organic ligand and a metal salt contains 10 organic ligands based on the total amount of the organic ligands and water.
To 85% by mass, the method for producing a composite metal cyanide complex catalyst for alkylene oxide ring-opening polymerization according to any one of claims 1 to 4. 6. A composite metal cyanide complex catalyst for alkylene oxide ring-opening polymerization, which is obtained by the production method according to claim 1.