Composite metal cyanide complex catalyst and method for producing same, composite metal cyanide complex slurry catalyst and method for producing same, and method for producing polymer

Abstract

The present invention relates to a composite metal cyanide complex catalyst having a water content of 8,000-140,000 ppm as determined by the Karl Fischer method, having diffraction peaks at 2 [theta] = 36 DEG and 2 [theta] = 47 DEG in an X-ray diffraction pattern, and having no diffraction peak at 2 [theta] = 34 DEG.

Description

TECHNICAL FIELD

[0001] The present application relates to a composite metal cyanide complex catalyst, a method for producing a composite metal cyanide complex catalyst, a composite metal cyanide complex slurry catalyst, a method for producing a composite metal cyanide complex slurry catalyst, and a method for producing a polymer using a composite metal cyanide complex catalyst.

[0002] This application claims priority based on Japanese Patent Application No. 2023-090792 filed on June 1, 2023, the contents of which are incorporated herein. BACKGROUND

[0003] A composite metal cyanide complex catalyst (hereinafter also referred to as a DMC catalyst) is known as a polymerization catalyst for an epoxide. The composite metal cyanide complex catalyst has high activity compared to an alkali catalyst such as KOH, and has an advantage that a by-product having an unsaturated bond is less likely to be generated.

[0004] Various studies have been made on the DMC catalyst.

[0005] Patent Document 1 describes a method in which a DMC catalyst is substantially formed into an amorphous state by applying a strong shear force at the time of production, thereby increasing the polymerization rate of an epoxide without increasing the amount of the catalyst used.

[0006] Patent Document 2 describes an example in which a DMC catalyst obtained by producing a composite metal cyanide in the presence of an organic complexing agent (e.g., t-butanol) and a polyol having a number average molecular weight of less than 500 shows high activity for the polymerization of an epoxide, and a polyether polyol having extremely low unsaturation is obtained. In contrast, a comparative example in which the organic complexing agent is not used is inactive, and a comparative example in which the aforementioned polyol is not used has low activity. In addition, regarding the difference in crystal structure, it is described that in an X-ray diffraction pattern, the aforementioned example shows a signal that cannot be seen in the aforementioned two comparative examples.

[0007] In Patent Document 3, it is considered that in a DMC catalyst, moisture is a catalyst poison that hinders catalytic activity, and a method for producing a DMC catalyst using an organic solvent substantially free of moisture is proposed.

[0008] PRIOR ART DOCUMENTS

[0009] PATENT DOCUMENTS

[0010] Patent Document 1: Japanese Patent Application Laid-Open No. H7-196778

[0011] Patent Document 2: International Publication No. 1997 / 040086

[0012] Patent Document 3: Japanese Patent Application Laid-Open No. 2003-103177 SUMMARY

[0013] PROBLEMS TO BE SOLVED BY THE INVENTION

[0014] In the polymerization reaction of an epoxide, if a DMC catalyst is used, the molecular weight distribution (Mw / Mn) of the polymer easily becomes small, and on the other hand, an ultrahigh molecular weight component which becomes an impurity is easily generated.

[0015] According to the insight of the present inventors, if the catalytic activity is high, there is a tendency that a large amount of an ultrahigh molecular weight component is generated.

[0016] The object of the present application is to provide a composite metal cyanide complex catalyst which is excellent in catalytic activity and can suppress the generation of a high molecular weight impurity.

[0017] SOLUTION TO THE PROBLEM

[0018] The present inventors have made intensive studies in order to solve the aforementioned problem, and have found that by controlling the water content and the crystal structure of a DMC catalyst, a DMC catalyst which is long in catalyst life (high in catalytic activity) and can suppress the generation of a high molecular weight impurity can be obtained, and thus the present application has been accomplished.

[0019] The present application has the following modes.

[0020] [1] A composite metal cyanide complex catalyst having a water content of 8,000 to 140,000 ppm based on the Karl Fischer method of JIS K0068:2001, having a diffraction peak at 2θ = 36° and 2θ = 47° and not having a diffraction peak at 2θ = 34° in an X-ray diffraction pattern.

[0021] [2] A method of producing a composite metal cyanide complex catalyst, which is a method of producing a composite metal cyanide complex catalyst by allowing an organic ligand to coordinate to a reaction product obtained by reacting a halogenated metal salt with a cyanide transition metal compound,

[0022] wherein after the aforementioned organic ligand is allowed to coordinate, the water content of the aforementioned composite metal cyanide complex catalyst is adjusted so that the water content of the aforementioned composite metal cyanide complex catalyst based on the Karl Fischer method of JIS K0068:2001 is 8,000 to 140,000 ppm, and in the X-ray diffraction pattern of the aforementioned composite metal cyanide complex catalyst, a diffraction peak is present at 2θ = 36° and 2θ = 47° and a diffraction peak is not present at 2θ = 34°.

[0023] [3] The method of producing a composite metal cyanide complex catalyst according to [2], wherein the halogenated metal salt contains one or more selected from the group consisting of zinc chloride and zinc bromide.

[0024] [4] The production method of the complex metal cyanide complex catalyst according to [2] or [3], wherein the organic ligand contains tert-butyl alcohol.

[0025] [5] A complex metal cyanide complex slurry catalyst, comprising: the complex metal cyanide complex catalyst according to the aforementioned [1], and a dispersion medium having a water content of 500 ppm or less based on the Karl-Fischer method of JIS K0068:2001.

[0026] [6] The complex metal cyanide complex slurry catalyst according to [5], wherein the content of the complex metal cyanide complex catalyst is 0.001 to 60 mass% with respect to the total mass of the complex metal cyanide complex slurry catalyst.

[0027] [7] A production method of a complex metal cyanide complex slurry catalyst, having:

[0028] a slurry preparation step of preparing a slurry containing a complex metal cyanide complex catalyst and a dispersion medium; and a water content adjustment step of adjusting the water content of the slurry so that the water content of the aforementioned complex metal cyanide complex catalyst based on the Karl-Fischer method of JIS K0068:2001 is 8,000 to 140,000 ppm, the water content of the aforementioned dispersion medium based on the Karl-Fischer method of JIS K0068:2001 is 500 ppm or less, and diffraction peaks exist at 2θ = 36° and 2θ = 47° and a diffraction peak does not exist at 2θ = 34° in an X-ray diffraction pattern of the aforementioned complex metal cyanide complex catalyst.

[0029] [8] The production method of the complex metal cyanide complex slurry catalyst according to [7], wherein the slurry preparation step has the following steps: for a reaction product obtained by reacting a halogenated metal salt with a cyanated transition metal compound in the presence of water, an organic ligand is coordinated with the reaction product in the presence of water to obtain a mixed solution containing a complex metal cyanide complex catalyst and water, impurities and water are removed from the mixed solution, a dispersion medium is added, and a slurry containing a complex metal cyanide complex catalyst and a dispersion medium is prepared.

[0030] [9] A production method of a polymer, which polymerizes an epoxide in the presence of the complex metal cyanide complex catalyst according to the aforementioned [1].

[0031] Effects of the Invention

[0032] According to the present invention, a complex metal cyanide complex catalyst having excellent catalytic activity and capable of suppressing the generation of high-molecular-weight impurities can be obtained. DETAILED DESCRIPTION

[0033] In the present specification and claims, a numerical range indicated by "~" means a numerical range having a lower limit value and an upper limit value of the numerical values before and after the "~".

[0034] In the present specification and claims, "ppm" as a unit of content is mass-based, unless otherwise specified.

[0035] In the present specification, the water content of the complex metal cyanide complex catalyst is the water content determined by the 6.4 coulometric titration method based on the Karl Fischer titration method in the water content determination method described in JIS K0068:2001, using a Karl Fischer moisture meter (for example, manufactured by Mitsubishi Analytech Co., Ltd., product name: CA-07 or CA-200). The water content is the total content (unit: ppm) of the crystal water (bound water, coordinated water) enclosed in the crystal of the complex metal cyanide complex catalyst and the water (free water) not enclosed, with respect to the mass of the complex metal cyanide complex catalyst as a solid.

[0036] In the case of a complex metal cyanide complex slurry catalyst (hereinafter, also referred to as "slurry catalyst") containing a complex metal cyanide complex catalyst and a dispersion medium, the slurry catalyst is taken as the measurement object, and the value determined by the 6.4 coulometric titration method based on the Karl Fischer titration method in the water content determination method described in JIS K0068:2001, using a Karl Fischer moisture meter (for example, manufactured by Mitsubishi Analytech Co., Ltd., product name: CA-07 or CA-200), is used as the water content in the slurry catalyst (hereinafter, also referred to as "slurry water content").

[0037] The slurry water content is the total amount of the water content in the complex metal cyanide complex catalyst and the water content in the dispersion medium.

[0038] The content of the water remaining after removing the water in the dispersion medium from the slurry water content is converted into a value of the water content with respect to the solid content in the slurry, and is used as the water content of the complex metal cyanide complex catalyst.

[0039] The solid content in the slurry can be obtained by the following heating and drying method. That is, the slurry catalyst is washed with a solvent (for example, hexane) that does not coordinate with the complex metal cyanide complex, and the operation of centrifugal separation is performed several times to remove the dispersion medium. Next, the recovered complex metal cyanide complex is heated and dried at 100°C for 12 hours, and the mass of the obtained dried substance is used as the mass of the solid content in the slurry catalyst, and the solid content is obtained.

[0040] Note that the solid content in the slurry catalyst can also be found in the middle of the process of manufacturing the slurry catalyst. Specifically, in a method of manufacturing a target slurry catalyst by adding a prescribed amount of a dispersing medium to a filter cake obtained by washing a reaction product containing a synthesized complex metal cyanide complex and a by-product salt and performing solid-liquid separation, removing volatile components such as water, and the like, a prescribed amount of the filter cake is taken out for measurement, and the mass after drying at 100°C for 12 hours is taken as the mass of the solid content. From the amount of the dispersing medium added to the filter cake and the mass of the solid content, the solid content in the slurry catalyst can be found.

[0041] The X-ray diffraction pattern in the present specification is a one-dimensional pattern obtained using CuKα rays (wavelength: 1.5418 A) as X-rays, with the horizontal axis being the diffraction angle (2θ, unit: °) and the vertical axis being the intensity (arbitrary unit). In the X-ray diffraction pattern, a waveform reaching a maximum value after simply increasing from a minimum value and reaching a minimum value after simply decreasing from the maximum value is taken as a diffraction peak. The height from a straight line connecting the two minimum values to the maximum value is taken as the peak intensity.

[0042] In the present specification, having a diffraction peak at 2θ = x° means that there is a maximum value of a diffraction peak in a range of 2θ being (x - 0.5)° or more and less than (x + 0.5)°, and the peak intensity thereof is 1% or more relative to the peak intensity of a diffraction peak at 2θ = 24° (reference peak intensity).

[0043] Note that the aforementioned diffraction peak at 2θ = 24° means a diffraction peak having a maximum value in a range of 2θ being (24 - 0.5)° or more and less than (24 + 0.5)°.

[0044] In the present specification, not having a diffraction peak at 2θ = x° means that there is no maximum value in a range of 2θ being (x - 0.5)° or more and less than (x + 0.5)°, or even if there is a maximum value, the peak intensity thereof is less than 1% relative to the aforementioned reference peak intensity.

[0045] In the present specification, measurement of the X-ray diffraction pattern is performed under the following conditions. The measurement sample is a solid. In the case of a slurry catalyst, the dried material obtained by the aforementioned heat drying method is used as the measurement sample.

[0046] X-ray: CuKα rays (λ = 1.54180 A)

[0047] Tube voltage: 45 kV

[0048] Tube current: 200 mA

[0049] Light source: monochromatized light source

[0050] Measurement angle range: 2θ = 10 to 80°

[0051] Step: Stepwise scanning with Δ2θ = 0.010°

[0052] Scanning speed: 20° / min

[0053] By analyzing the obtained X-ray diffraction pattern using analysis software (such as the analysis software attached to the device such as SmartLab Studio II), analysis of each peak can be performed.

[0054] <Composite metal cyanide complex catalyst>

[0055] The composite metal cyanide complex catalyst of the present embodiment (hereinafter also referred to as DMC catalyst (A)) is a crystalline solid, and contains a reaction product of a halogenated metal salt and a transition metal cyanide compound, an organic ligand, and crystal water (coordination water or the like) enclosed in the crystal. In addition to these, manufacturing-inevitable impurities and moisture other than the crystal water, which are contained in trace amounts in the aforementioned metal salt and metal compound or the like, can be contained.

[0056] The aforementioned halogenated metal salt, transition metal cyanide compound, and organic ligand can use substances known in the production of DMC catalysts.

[0057] It is considered that the DMC catalyst (A) is represented by the following formula (1).

[0058] M 1 a [M 2 (CN) b ] c · d (M 1 e X f ) · g (Ligand) · h (H2O) … (1)

[0059] In formula (1), M 1 e X f is a halogenated metal salt, M 1 is a metal atom that becomes a cation, X is a halogen atom that becomes a counter anion, M 2 is a transition metal contained in the transition metal cyanide compound and is a metal atom that becomes an active site, Ligand is an organic ligand. a, b, c, d, e, f, g, and h are integers, and a, b, c, and e, f are numbers that become electrically neutral.

[0060] As the aforementioned M 1Examples of M include Zn (II), Fe (II), Fe (III), Co (II), Co (III), Cr (II), Cr (III), Mn (II), Mn (III), V (IV), V (V), Al (III), Sr (II), Ni (II), Sn (II), Pb (II), Mo (IV), Mo (VI), W (IV), and W (VI).

[0061] Examples of M include Zn (II), Fe (II), Fe (III), Co (II), Co (III), Cr (II), Cr (III), Mn (II), Mn (III), V (IV), V (V), Al (III), Sr (II), Ni (II), Sn (II), Pb (II), Mo (IV), Mo (VI), W (IV), and W (VI). 2 Examples of M include Zn (II), Fe (II), Fe (III), Co (II), Co (III), Cr (II), Cr (III), Mn (II), Mn (III), V (IV), V (V), Al (III), Sr (II), Ni (II), Sn (II), Pb (II), Mo (IV), Mo (VI), W (IV), and W (VI).

[0062] Examples of X include Cl, Br, and I.

[0063] Examples of M include Zn (II), Fe (II), Fe (III), Co (II), Co (III), Cr (II), Cr (III), Mn (II), Mn (III), V (IV), V (V), Al (III), Sr (II), Ni (II), Sn (II), Pb (II), Mo (IV), Mo (VI), W (IV), and W (VI). 1 e Examples of X include Cl, Br, and I. f The halogenated metal salt of M 2 From the viewpoint of the interatomic distance of M

[0064] Examples of the organic ligand include alcohols, ethers, esters, aldehydes, ketones, amides, nitriles, and thioethers, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and polyoxyalkylene polyhydric (or monohydric) alcohol. The organic ligand can be one or two or more. Examples of the alcohol include t-butyl alcohol, n-butyl alcohol, sec-butyl alcohol, isobutyl alcohol, t-amyl alcohol, isoamyl alcohol, and ethylene glycol mono-t-butyl ether. Examples of the polyoxyalkylene polyhydric (or monohydric) alcohol include polypropylene glycol. The organic ligand is preferably t-butyl alcohol.

[0065] A preferred example of the DMC catalyst (A) is zinc hexacyanocobaltate (Zn3[Co(CN)6]2) containing an organic ligand (Ligand), water, zinc chloride, or zinc bromide. The chemical formula thereof can be considered to be Zn3[Co(CN)6]2·d(ZnCl2)·g(Ligand)·h(H2O) or Zn3[Co(CN)6]2·d(ZnBr2)·g(Ligand)·h(H2O).

[0066] The DMC catalyst (A) has a water content of 8,000 to 140,000 ppm as measured by the Karl Fischer method, and has diffraction peaks at 2θ = 36° and 2θ = 47° and no diffraction peak at 2θ = 34° in an X-ray diffraction pattern.

[0067] The DMC catalyst (A) having such a water content and crystal structure can achieve both good catalytic activity and suppression of high-molecular-weight impurities. Furthermore, even when stored in an environment with a high water content, the catalytic activity is unlikely to decrease, and such a DMC catalyst (A) has excellent water resistance.

[0068] Either too much or too little water content can decrease the catalytic activity. In the case of too much, it is considered that hydrolysis of active sites caused by water other than crystal water (water not incorporated in the crystal) is likely to occur. In the case of too little, it is considered that the crystal structure changes due to a decrease in crystal water, and a structure that contributes to achieving both good catalytic activity and suppression of high-molecular-weight impurities is likely to be lost.

[0069] The aforementioned water content is preferably 9,000 to 120,000 ppm, and more preferably 10,000 to 100,000 ppm.

[0070] The DMC catalyst (A) has diffraction peaks at 2θ = 14° and 2θ = 16° in an X-ray diffraction pattern, and the ratio of the peak intensity at 2θ = 16° (P16) to the peak intensity at 2θ = 14° (P14) (P16 / P14) is less than 3, which is preferable from the viewpoint of obtaining good catalytic activity.

[0071] It is considered that P16 / P14 varies depending on the number of water molecules incorporated in the crystal of the DMC catalyst, and there is a tendency that the value of P16 / P14 increases if the number of incorporated water molecules decreases.

[0072] The spectrum of the DMC catalyst (A) measured by the XAFS (X-ray Absorption Fine Structure) method, which is analyzed by EXAFS (Extend X-ray Absorption Fine Structure), is preferably a spectrum in which the interatomic distance between the transition metal atom (M 2 ) that becomes an active site and the halogen atom (X) from the metal salt is 2.20 to 2.40 angstrom (Å).

[0073] When the aforementioned halogen atom (X) having an interatomic distance of 2.20 to 2.40 Å is used, good catalytic activity is easily obtained.

[0074] The interatomic distance based on EXAFS analysis in the DMC catalyst is also described in a literature ("X-RAY SPECTROMETRY", 2015, volume 44, Issue 5, p. 330-338, title "Structual properties and chemical bondes in double metal cyanide catalysts").

[0075] <Composite metal cyanide complex slurry catalyst>

[0076] The slurry catalyst of the present embodiment contains the DMC catalyst (A) and a dispersion medium.

[0077] The content of the DMC catalyst (A) with respect to the total mass of the slurry catalyst is, for example, preferably 0.001 to 60 mass%, more preferably 0.003 to 50 mass%, and further preferably 0.006 to 30 mass%.

[0078] The slurry catalyst is preferably a slurry in which the DMC catalyst (A) is dispersed in a dispersion medium, that is, a slurry containing the DMC catalyst (A) and the dispersion medium, and can contain impurities and moisture that are unavoidable in production.

[0079] The dispersion medium of the slurry catalyst preferably contains substantially no water. Specifically, the moisture content of the dispersion medium is preferably 500 ppm or less, and more preferably 200 ppm or less, and can be an undetectable amount.

[0080] The moisture content of the dispersion medium is the same as the moisture content of the DMC catalyst (A), which is the water content (unit: mass ppm) measured by the Karl Fischer method.

[0081] As the dispersion medium of the slurry catalyst, an organic solvent known in the slurry catalyst can be used. For example, a non-volatile hydroxyl compound described in Japanese Patent No. 3194255 can be used. The hydroxyl compound is a hydroxyl-containing compound having a hydroxyl number of 1 to 8 and a molecular weight of 100 to 8000, and is preferably a compound having an alcoholic hydroxyl group such as a polyether polyol.

[0082] In the case where the DMC catalyst (A) is used as a catalyst for producing a polyether polyol by ring-opening polymerization of an epoxide, the dispersion medium of the slurry catalyst is preferably the polyether polyol from the viewpoint that it does not become an impurity for the product (polyether polyol).

[0083] In addition, an initiator (polyether polyol) for ring-opening polymerization of an epoxide can also be used as part of the dispersion medium.

[0084] The number average molecular weight of the polyether polyol used as the dispersion medium is preferably 100 to 8000, and more preferably 600 to 3000. When the number average molecular weight of the polyether polyol is equal to or greater than the lower limit of the above range, it does not become a catalyst poison, and when it is equal to or less than the upper limit, the handling properties of the slurry catalyst are excellent.

[0085] The hydroxyl value of the polyether polyol as the initiator is, for example, preferably 3 to 842 mgKOH / g, and more preferably 7 to 561 mgKOH / g.

[0086] The content of the DMC catalyst (A) is preferably 1 to 60% by mass, more preferably 3 to 40% by mass, and further preferably 5 to 30% by mass, relative to the total mass of the slurry catalyst, particularly when the dispersion medium is the aforementioned product (polyether polyol).

[0087] The content of the DMC catalyst (A) is preferably 0.003 to 0.02% by mass, more preferably 0.004 to 0.015% by mass, and further preferably 0.006 to 0.01% by mass, relative to the total mass of the slurry catalyst, particularly when the dispersion medium contains the aforementioned initiator (polyether polyol).

[0088] <Method for producing composite metal cyanide complex catalyst>

[0089] In the method for producing the composite metal cyanide complex catalyst of the present embodiment, an organic ligand is coordinated to a reaction product obtained by reacting a halogenated metal salt with a cyanide transition metal compound to synthesize a composite metal cyanide complex catalyst, and then the amount of moisture of the composite metal cyanide complex catalyst is adjusted to become a composite metal cyanide complex catalyst satisfying a specific moisture amount and a specific X-ray diffraction pattern.

[0090] The method for synthesizing the composite metal cyanide complex catalyst is not particularly limited, and a publicly known method can be used.

[0091] Preferably, first, an organic ligand is coordinated to a reaction product obtained by reacting a halogenated metal salt with a cyanide transition metal compound in the presence of water to obtain a mixed solution containing the DMC catalyst (A) and water. Impurities and water are removed from the obtained mixed solution, and the amount of moisture of the obtained solid is reduced to a prescribed range to obtain the DMC catalyst (A).

[0092] As shown in the examples described later, in the DMC catalyst having an amount of moisture exceeding 140,000 ppm, there is a tendency to observe a diffraction peak at 2θ = 34° and it is not possible to achieve both good catalytic activity and suppression of high molecular weight impurities. In addition, even in the DMC catalyst having an amount of moisture temporarily reduced to a range of 8,000 to 140,000 ppm, the DMC catalyst contacted with water not containing an organic ligand exhibits a diffraction peak at 2θ = 34° and the catalytic activity is greatly reduced or not exhibited. In addition, if the amount of moisture is excessively reduced, the peak at 2θ = 47° disappears and the catalytic activity is not exhibited.

[0093] Therefore, in the process of removing water from the aforementioned mixed solution, by gradually reducing the water content of the DMC catalyst to a prescribed range while avoiding contact with water that does not contain an organic ligand, a DMC catalyst (A) having a prescribed crystal structure that can balance good catalytic activity and suppression of high-molecular-weight impurities can be produced.

[0094] The method of obtaining the aforementioned mixed solution and the method of removing impurities and water from the aforementioned mixed solution can be selected from publicly known methods that do not allow the DMC catalyst to come into contact with water that does not contain an organic ligand.

[0095] The method of removing water from the aforementioned mixed solution can use, for example, a drying method for obtaining a solid DMC catalyst.

[0096] However, in the conventional drying method, the water content of the DMC catalyst cannot be controlled to be within the range of 8,000 to 140,000 ppm, and therefore a water content adjustment process for controlling the water content to a water content at which the DMC catalyst can maintain an optimal structure is provided. In the water content adjustment process, it is preferable to strictly manage so that the DMC catalyst does not come into contact with water from outside the DMC catalyst. The water content adjustment process can also be performed continuously with the process preceding it.

[0097] The water content adjustment process when producing a solid DMC catalyst is performed by heating and drying at a temperature of 160°C or lower, preferably 140°C or lower, for example. The heating time is determined in such a way that the water content in the solid after drying becomes within the range of 8,000 to 140,000 ppm. If necessary, the time-dependent change in the water content in the solid in the heating and drying process is monitored, and the heating time is determined. The drying conditions are more preferably 80°C to 140°C for 5 hours to 24 hours. When the drying temperature exceeds the upper limit of the above range, it can be difficult to maintain the crystal structure of the DMC catalyst. That is, when the drying temperature is equal to or lower than the upper limit of the above range, the crystal structure of the DMC catalyst is easily maintained.

[0098] The heat drying can be performed in an atmospheric atmosphere or in a reduced pressure atmosphere, but is preferably performed in an atmospheric atmosphere. In order to avoid contact with moisture as much as possible after the heat drying, it is preferable to provide a step of recovering to normal temperature in a dry gas (dry nitrogen or the like) after the heat drying. In addition, in the case where the heat drying is performed in a reduced pressure atmosphere, in order to avoid contact with moisture as much as possible, it is preferable to provide a step of recovering to normal pressure by introducing a dry gas (dry nitrogen or the like) which does not react with the DMC catalyst. In the case where the heat drying is performed in either of an atmospheric atmosphere and a reduced pressure atmosphere, it is also preferable to avoid contact of the DMC catalyst with moisture as much as possible during the temperature decrease from the heat stop to normal temperature. It is particularly preferable to avoid contact of the DMC catalyst with moisture at a temperature close to normal temperature due to the temperature decrease process as much as possible. The dry gas refers to a gas in which the content of water vapor with respect to the total volume of the gas is 12 volume ppm or less at 25°C.

[0099] In the case where the recovery to normal temperature and normal pressure is performed using a dry gas, the time of the heat drying can be shortened, and this is advantageous in that the moisture amount adjustment step can be efficiently performed. On the other hand, by adjusting the temperature and the time of the heat drying, the moisture amount in the dried solid can also be controlled to be 8,000 to 140,000 ppm. As to the temperature of the heat drying, there is an upper limit value as described above, and thus the moisture amount in the dried solid is practically controlled by the drying time. The longer the drying time, the more easily the moisture amount in the dried solid can be controlled to be 140,000 ppm or less. In addition, in this case, even if the recovery to normal temperature and normal pressure is not performed in a dry gas but in an atmosphere, the moisture amount in the dried solid sometimes becomes 8,000 to 140,000 ppm. However, since the drying time becomes longer, the efficiency of the moisture amount adjustment step decreases.

[0100] As a preferred mode of the production method of the complex metal cyanide complex catalyst of the present embodiment, for example, the following method can be cited.

[0101] First, a reaction product is produced by reacting an aqueous solution of a halogenated metal salt with an aqueous solution of a transition metal cyanide compound. An aqueous solution of an organic ligand is added thereto and stirred to coordinate the organic ligand, and a mixed solution containing the complex metal cyanide complex catalyst and water is obtained. The obtained mixed solution is subjected to solid-liquid separation to obtain a solid. The solid-liquid separation can be performed by a method known in the art, and for example, filtration, centrifugal separation, or the like can be exemplified. The obtained solid is washed with an aqueous solution containing an organic ligand and subjected to solid-liquid separation one or more times, preferably two or more times.

[0102] The obtained solid is dried so that the moisture amount becomes within the above-described specific range, and is pulverized as necessary.

[0103] <Production method of complex metal cyanide complex slurry catalyst>

[0104] The slurry catalyst manufacturing method of the present embodiment has a slurry preparation step of preparing a slurry containing a complex metal cyanide complex catalyst and a dispersion medium, and a water content adjustment step of adjusting the water content of the slurry so that the water content of the complex metal cyanide complex catalyst in the slurry catalyst is in a specific range, the water content of the dispersion medium is in a specific range, and the complex metal cyanide complex catalyst satisfies a specific X-ray diffraction pattern. The preferable range of the water content of the complex metal cyanide complex catalyst in the slurry catalyst, the preferable range of the water content of the dispersion medium, and the preferable range of the X-ray diffraction pattern of the complex metal cyanide complex catalyst are the same as those described above. In addition, the preferable range of the X-ray diffraction pattern of the complex metal cyanide complex catalyst is also the same as that described above.

[0105] The slurry preparation step is not particularly limited, and a publicly known method can be used.

[0106] Preferably, first, an organic ligand is allowed to coordinate with a reaction product obtained by allowing a halogenated metal salt to react with a transition metal cyanide compound in the presence of water, to obtain a mixed solution containing a DMC catalyst and water. A method of removing impurities and water from the obtained mixed solution, adding a dispersion medium, and preparing a slurry containing a DMC catalyst and a dispersion medium can be used.

[0107] The method of obtaining the aforementioned mixed solution and the method of removing impurities and water from the aforementioned mixed solution can be selected from publicly known methods, using a method in which the DMC catalyst is not brought into contact with water not containing an organic ligand.

[0108] The method of removing water from the aforementioned mixed solution is preferably a method of gradually reducing the water content of the slurry to a prescribed range while avoiding contact with water not containing an organic ligand. For example, it can be a solvent replacement method for replacing water in the aforementioned mixed solution with a dispersion medium to obtain a slurry catalyst.

[0109] However, in the conventional solvent replacement method, the water content of the DMC catalyst cannot be controlled to be in the range of 8,000 to 140,000 ppm, and therefore a water content adjustment step for controlling the water content to be a water content at which the DMC catalyst can maintain an optimal structure is provided. In the water content adjustment step, it is preferable to strictly manage so that the slurry is not brought into contact with water other than the slurry. The water content adjustment step can also be performed continuously with the preceding step.

[0110] The moisture amount adjustment step at the time of manufacturing the slurry catalyst is, for example, preferably a step in which the slurry catalyst is subjected to reduced-pressure drying at 0°C to 160°C for 1 hour to 24 hours until the moisture amount of the DMC catalyst in the slurry catalyst reaches 8,000 to 140,000 ppm, and then, in order to avoid contact with moisture as much as possible, a dry gas (dry nitrogen or the like) that does not react with the DMC catalyst is introduced to restore the pressure to the normal pressure. The reduced-pressure drying conditions are more preferably 25°C to 140°C for 2 to 10 hours. When the drying temperature exceeds the upper limit of the above range, it can be impossible to maintain the crystal structure of the DMC catalyst. That is, when the drying temperature is below the upper limit of the above range, it is easy to maintain the crystal structure of the DMC catalyst.

[0111] In the case where the pressure is restored to the normal pressure using a dry gas, it is possible to shorten the time of the heating drying, and this is advantageous in that the moisture amount adjustment step can be efficiently performed. On the other hand, by adjusting the temperature and the time of the heating drying, it is also possible to control the moisture amount of the DMC catalyst in the dried slurry catalyst to 8,000 to 140,000 ppm. As for the temperature of the heating drying, there is an upper limit as described above, and thus the moisture amount of the DMC catalyst in the dried slurry catalyst is substantially controlled by the drying time. The longer the drying time, the easier it is to control the moisture amount of the DMC catalyst in the dried slurry catalyst to 140,000 ppm or less. In addition, in this case, even if the pressure is not restored to the normal pressure in the atmosphere but is restored to the normal temperature and the normal pressure in the atmosphere, the moisture amount of the DMC catalyst in the dried slurry catalyst is sometimes 8,000 to 140,000 ppm. However, since the drying time becomes longer, the efficiency of the moisture amount adjustment step decreases.

[0112] In addition, it is preferable to use a dispersing medium that has been previously dehydrated so that the moisture amount of the dispersing medium in the slurry catalyst after the moisture amount adjustment step is 500 ppm or less.

[0113] As a preferred mode of the method for manufacturing the complex metal cyanide complex catalyst of the present embodiment, for example, the following mode can be cited.

[0114] First, a reaction product is produced by reacting an aqueous solution of a halogenated metal salt with an aqueous solution of a transition metal cyanide compound. An aqueous solution of an organic ligand is added thereto and stirred to coordinate the organic ligand, and a mixed solution containing the complex metal cyanide complex catalyst and water is obtained. The obtained mixed solution is subjected to solid-liquid separation to obtain a solid. The obtained solid is washed with an aqueous solution containing an organic ligand and subjected to solid-liquid separation one or more times, preferably two or more times. After the dispersing medium is added to the obtained solid and mixed, uncoordinated organic ligand and water are volatilized and removed.

[0115] Thus, a slurry in which the DMC catalyst is dispersed in the dispersion medium is obtained. The obtained slurry is subjected to the aforementioned water content adjustment process, and a slurry catalyst containing the target DMC catalyst is produced.

[0116] <Method for producing polymer>

[0117] The DMC catalyst of the present embodiment is suitable as a catalyst for producing a polymer such as a polyether polyol, a polyester polyol, or the like, by polymerizing a cyclic ether such as an epoxide.

[0118] The method for producing a polymer using the DMC catalyst can employ a publicly known method.

[0119] As the epoxide, propylene oxide (hereinafter also referred to as "PO"), a combination of PO and ethylene oxide, or the like can be exemplified.

[0120] The polyol such as a polyether polyol, a polyester polyol, or the like can be used, for example, as a raw material for various polyurethane paints, elastomers, sealants, foams, and adhesives.

[0121] According to the present embodiment, a DMC catalyst capable of balancing good catalytic activity and suppression of high-molecular-weight impurities can be obtained.

[0122] For example, a DMC catalyst having a catalytic activity lifespan [kg-PO / g-cat] of 140 kg / g or more as determined by the method described in the catalytic activity lifespan evaluation of the examples, and a content of ultra-high-molecular-weight components of 1,000 ppm or less as determined by the [method for determining content of ultra-high-molecular-weight components] of the examples can be obtained.

[0123] The content of the aforementioned ultra-high-molecular-weight components is more preferably 950 ppm or less, and further preferably 900 ppm or less. By reducing the content of the ultra-high-molecular-weight components, the physical properties (for example, stability, strength, and the like) of the polyol produced using the DMC catalyst and the article produced using the aforementioned polyol can be improved.

[0124] In addition, the conventional DMC catalyst lacks water resistance, and the catalytic activity easily decreases when stored in an atmosphere with a high moisture content, but according to the present embodiment, a DMC catalyst having excellent water resistance can be obtained.

[0125] For example, a DMC catalyst having a decrease rate of catalytic activity lifespan of less than 25% as determined by the method described in the water resistance evaluation of the examples can be obtained.

[0126] <Method for evaluating DMC catalyst>

[0127] The water content and X-ray diffraction pattern of the DMC catalyst were measured, and in the case where the water content was 8,000 to 140,000, diffraction peaks were present at 2θ = 36° and 2θ = 47°, and no diffraction peak was present at 2θ = 34°, the DMC catalyst was evaluated as being excellent in catalytic activity and less likely to generate a high molecular weight impurity when used as a polymerization catalyst for an epoxide.

[0128] In addition, the water content and X-ray diffraction pattern of the DMC catalyst were measured, and in the case where the water content was 8,000 to 140,000, diffraction peaks were present at 2θ = 36° and 2θ = 47°, and no diffraction peak was present at 2θ = 34°, the DMC catalyst was evaluated as being excellent in water resistance.

[0129] Examples

[0130] Hereinafter, the present application will be described in detail by way of examples. However, the present application is not limited to the following examples.

[0131] <Evaluation method>

[0132] [X-ray diffraction measurement]

[0133] The X-ray diffraction (XRD) measurement was performed using an X-ray diffractometer (manufactured by Rigaku Corporation, device name: SmartLab).

[0134] The X-ray was set to CuKα ray (λ = 1.54180 A), and the tube voltage and tube current were set to 45 kV and 200 mA, respectively. A light source that was monochromatized using a concentrating optical system Johansson monochromator was used.

[0135] A high-speed detector (manufactured by Rigaku Corporation, device name: D / teX) was used as the detector, and the measurement angle range was set to 2θ = 10 to 80°, the stepwise scanning was set to a step (Δ2θ) = 0.010°, and the scanning speed was set to 20° / min.

[0136] The obtained X-ray diffraction pattern was analyzed by analysis software, and the presence or absence of diffraction peaks at 2θ = 34°, 36°, and 47° was recorded.

[0137] In addition, the ratio (P16 / P14) of the peak intensity at 2θ = 16° (P16) to the peak intensity at 2θ = 14° (P14) was calculated. When P16 / P14 was less than 3, it was determined as "O", and when it was 3 or more, it was determined as "X".

[0138] [Water content measurement]

[0139] The moisture content of each sample was measured using a Karl Fischer moisture meter (manufactured by Mitsubishi Analytech Co., Ltd.) according to the moisture measurement method described in JIS K0068:2001, based on the 6.4 Coulometric Titration method of Karl Fischer titration.

[0140] The moisture content of the slurry was measured using the slurry as the sample.

[0141] The moisture content of the solid (powder) was measured using the powder as the sample.

[0142] The moisture content of the dispersion medium was measured using a substance obtained by increasing or decreasing the moisture content of the dispersion medium under the same conditions as the operation for increasing or decreasing the moisture content of the slurry catalyst after the addition of the dispersion medium. The moisture content (unit: ppm) of the DMC catalyst (solid content) was calculated by the following equations (i) and (ii).

[0143] Moisture content of DMC catalyst = (Sw - Pw x B / 100) / (A / 100)... (i)

[0144] B = 100 - A... (ii)

[0145] Sw: Moisture content of slurry (unit: ppm)

[0146] Pw: Moisture content of dispersion medium (unit: ppm)

[0147] A: Solid content content of slurry (unit: mass%)

[0148] B: Proportion of dispersion medium in slurry (unit: mass%)

[0149] [XAFS measurement]

[0150] For the EXAFS spectrum obtained by Fourier transformation of the spectrum measured by the XAFS method, the shift of the phase was corrected, and the interatomic distance (coordination distance) between the transition metal atom (M 2 ) as the active site and the halogen atom (X) from the metal salt was calculated.

[0151] The aforementioned interatomic distance was determined to be "O" when it was in the range of 2.20 to 2.40 A, and "X" when it was outside the range.

[0152] [Catalytic activity life evaluation]

[0153] Into a 200 mL autoclave, 25 g of polyoxypropylene triol having Mn of 1,500 and a hydroxyl value of 168 mgKOH / g as an initiator and the DMC catalyst obtained in each example (in a slurry state or in a solid state) were charged, and PO was added sequentially at a temperature of 120°C.

[0154] The amount of the DMC catalyst to be fed was set so that the metal concentration of the DMC catalyst relative to 1000 g of the initiator was the catalyst concentration (unit: ppm) described in Table 3.

[0155] The point at which no decrease in the pressure after the PO was charged was observed was judged to be the deactivation of the catalyst. Based on the amount of the PO (substrate) charged until the deactivation and the amount of the DMC catalyst charged, in order to evaluate "how much function the catalyst exerts in terms of mass ratio relative to the substrate", the value (unit: kg / g) of the catalytic activity lifetime [kg-PO / g-cat] (the ratio of the mass (kg) of the polypropylene oxide polymerized relative to 1 g of the catalyst) was calculated. In the case where no decrease in the pressure after the PO was charged was observed at all, it was judged to be "no activity".

[0156] [Water resistance evaluation]

[0157] The DMC catalyst obtained in each example (in a slurry state or in a solid state) was stored in a high-humidity atmosphere at a temperature of 40°C and a relative humidity of 80% for 1 day. Before the start of the storage and immediately after the end of the storage, the catalytic activity lifetime [kg-PO / g-cat] was measured by the above method.

[0158] The decrease rate (%) of the catalytic activity lifetime immediately after the end of the storage (A2) relative to the catalytic activity lifetime before the start of the storage (A1) was calculated by the following equation. Based on the obtained decrease rate, the water resistance was judged according to the following criteria.

[0159] Decrease rate of catalytic activity lifetime = (A1-A2) / A1 x 100

[0160] (Criteria for judgment)

[0161] O: The decrease rate is less than 25%.

[0162] X: The decrease rate is 25% or more.

[0163] [Number average molecular weight (Mn) measurement]

[0164] The molecular weight of the polyether polyol was analyzed using a GPC system (product name HLC-8320, manufactured by Tosoh Corporation) using an RI detector.

[0165] For the column, two of TSK-GEL Super HZ4000 (4.6 mm x 150 mm) and two of Super HZ2500 (4.6 mm x 150 mm) were connected in series in that order. Tetrahydrofuran (THF) was used as the eluent at a flow rate of 0.35 ml / min, and the column temperature was set to 40°C. The number average molecular weight Mn was calculated by using a standard curve prepared using a polystyrene standard sample (product name Easical PS-2, molecular weight range 580 to 400,000, manufactured by Agilent Technologies).

[0166] [Method for measuring the content ratio of the ultra-high molecular weight component (CAD-HPLC method)]

[0167] The DMC catalyst obtained in each example was used to synthesize the polyether polyol by the method of Production Example 1 below.

[0168] When the number average molecular weight of the polyether polyol to be measured is W, the component from 12 times the molecular weight thereof (12W) to 46 times the molecular weight thereof (46W) is regarded as the ultra-high molecular weight component.

[0169] The content ratio of the ultra-high molecular weight component with respect to the total mass of the polyether polyol was calculated by the measurement method described in Japanese Patent Application Publication No. 2019-137810.

[0170] Specifically, the content ratio of the ultra-high molecular weight component was measured under the following conditions.

[0171] Apparatus and detector: high-performance liquid chromatograph (product name U3000 HPLC system, manufactured by Themo Fisher SCIENTIFIC), degasser (SRD-3600), pump (DGP3600SD), automatic sampler (WPS-3000TSL), column compartment (TCC-3000SD), UV-Vis detector (VWD-3400RS), charged particle detector (Corona Veo)

[0172] Eluent: THF for HPLC

[0173] Flow rate of eluent: 0.2 mL / min

[0174] Injection amount of sample: 20 μL

[0175] Column: One upstream column described below and one downstream column described below were connected in series in that order. The exclusion limit molecular weight of each column is the exclusion limit molecular weight when the molecular weight of polystyrene is measured using THF for HPLC as the eluent.

[0176] Column on the upstream side: Shodex KF-404HQ (styrene-divinylbenzene copolymer with an average particle diameter of 3 μm, inner diameter of 4.6 mm, length of 250 mm, theoretical plate number of 25,000 or more TP / column, exclusion limit molecular weight of 1,000,000, organic solvent system liquid chromatography column) manufactured by Showa Denko K.K.

[0177] Column on the downstream side: Shodex KF-403HQ (styrene-divinylbenzene copolymer with an average particle diameter of 3 μm, inner diameter of 4.6 mm, length of 250 mm, theoretical plate number of 25,000 or more TP / column, exclusion limit molecular weight of 70,000, organic solvent system liquid chromatography column) manufactured by Showa Denko K.K.

[0178] (1) The polyether polyol to be tested was dissolved in HPLC THF at a concentration of 0.6 mass% and filtered through a 0.45-μm injection filter to prepare a sample, and the sample was analyzed under the above HPLC conditions to obtain a chromatogram in which the retention time was set as the X axis and the signal intensity was set as the Y axis.

[0179] (2) A polystyrene standard sample (Easical PS-2 manufactured by Agilent Technologies, Inc., molecular weight range 580 to 400,000) was used to prepare a calibration curve showing the relationship between the molecular weight and the retention time.

[0180] (3) The calibration curve prepared in (2) was used to find the retention time X1 corresponding to 12W and the retention time X2 corresponding to 46W.

[0181] (4) The area of the portion enclosed by the above chromatogram, the baseline, the straight line of X = X1, and the straight line of X = X2 was electronically integrated to find the value.

[0182] (5) A polystyrene standard sample with a molecular weight of 92,600 (PSS-05 No. 500-16 manufactured by Gasukuro Kogyo Inc., Ltd.) was dissolved in HPLC THF at a concentration of 1, 6, 20, and 60 mass ppm, and the resulting standard solution was used as a sample to obtain a chromatogram under the above HPLC conditions. The area of the portion enclosed by the obtained chromatogram and the baseline was taken as the area. The area at each concentration was calculated to prepare a standard curve showing the relationship between the concentration of polystyrene with a molecular weight of 92,600 and the area, with an intercept of zero.

[0183] (6) Using the standard curve prepared in (5), the area calculated in (4) is converted to the concentration of polystyrene having a molecular weight of 92,600, and this is taken as the concentration of the ultra-high molecular weight component in the sample prepared in (1).

[0184] (7) From the value of the concentration of the ultra-high molecular weight component obtained in (6), the mass of the ultra-high molecular weight component in the sample prepared in (1) is calculated, and further, the content ratio of the ultra-high molecular weight component with respect to the mass of the test substance (polyether polyol) used in the preparation of the sample is calculated.

[0185] [Production Example 1: Production of polyether polyol]

[0186] PO was subjected to ring-opening addition polymerization with respect to glycerin using a KOH catalyst, and further, Kyoward 600S (product name of Kyowa Chemical Industry Co., Ltd., synthetic adsorbent) was used for purification, to produce a polyoxypropylene triol (Initiator 1) having an Mn of 1,500 and a hydroxyl value of 112 mgKOH / g.

[0187] A reaction vessel was charged with 1,000 g of the Initiator 1 and the DMC catalyst obtained in each example, to prepare a reaction liquid.

[0188] The amount of the DMC catalyst to be fed was set so that the metal concentration of the DMC catalyst with respect to 1,000 g of the Initiator was the catalyst concentration (unit: ppm) described in Table 3.

[0189] Next, after nitrogen replacement was performed in the reaction vessel, the above reaction liquid was heated while being stirred, and after the temperature reached 135°C, heating was stopped, and 120 g of PO was supplied to the reaction vessel while continuing the stirring, to allow the reaction to proceed.

[0190] When the PO was supplied to the reaction vessel, the internal pressure of the reaction vessel was confirmed to temporarily increase, and thereafter, gradually decrease to the same as the internal pressure of the reaction vessel immediately before the PO was supplied. During this period, when the decrease in the internal pressure started, the temperature of the reaction liquid temporarily increased, and thereafter, gradually decreased. After the temperature increase of the reaction liquid stopped, the temperature was cooled to 135°C.

[0191] Next, while the reaction liquid was stirred, 4,728 g of PO was supplied to the reaction vessel while maintaining the temperature at 135°C. The disappearance of the change in the internal pressure was confirmed, and the reaction was completed. Thereby, a polyether polyol was obtained.

[0192] [Examples 1 to 11, 16]

[0193] A slurry catalyst was prepared. Examples 2 to 4 and Example 8 are examples, and Examples 1, Examples 5 to 7, and Examples 9 to 11, 16 are comparative examples.

[0194] [Example 1]

[0195] An alkylene oxide ring-opening polymer was prepared in advance.

[0196] That is, PO is subjected to ring-opening polyaddition polymerization in the presence of a KOH catalyst, and is subjected to dealkali purification to produce a polyoxypropylene glycol having an average number of hydroxyl groups of 2 per molecule and an Mn of 2,000 (hereinafter referred to as "polyol P1").

[0197] In this example, a zinc hexacyanocobaltate complex coordinated with t-butanol (hereinafter also referred to as "TBA" ) (hereinafter also referred to as "TBA-DMC catalyst") was produced by the following method.

[0198] First, a zinc chloride aqueous solution containing 10.2 g of zinc chloride and 10 g of water was added to a 500 mL flask. While stirring the zinc chloride aqueous solution at 300 rpm per minute, an aqueous potassium hexacyanocobaltate solution containing 4.2 g of potassium hexacyanocobaltate and 75 g of water was added dropwise to the zinc chloride aqueous solution over 30 minutes. During this period, the liquid in the flask was maintained at 40°C. After the dropwise addition of the aqueous potassium hexacyanocobaltate solution was completed, the liquid in the flask was further stirred for 30 minutes, and then a mixture containing 80 g of TBA, 80 g of water, and 0.6 g of polyol P1 was added, stirred at 40°C for 30 minutes, and further stirred at 60°C for 60 minutes to obtain a mixed solution containing the TBA-DMC catalyst and water. This mixed solution contained a salt (i.e., KCl) produced in the reaction.

[0199] The obtained mixed solution was filtered under pressure (0.25 MPa) using a circular filter plate having a diameter of 125 mm and a quantitative filter paper for fine particles (product name: No. 5C, manufactured by ADVANTEC), and a solid containing the TBA-DMC catalyst (hereinafter referred to as "filter cake") was separated.

[0200] Next, the filter cake was washed with a mixture of TBA and water to remove the salt (i.e., KCl). Specifically, the filter cake was moved to a flask, a mixture containing 36 g of TBA and 84 g of water was added and stirred for 30 minutes, and then filtration was performed under pressure under the same conditions as described above. The obtained filter cake was moved to a flask, a mixture containing 108 g of TBA and 12 g of water was further added and stirred for 30 minutes to obtain a dispersion (1) in which the TBA-DMC catalyst was dispersed in a mixture of TBA and water.

[0201] The dispersion medium of the obtained dispersion (1) was replaced with polyol P1 to produce a slurry catalyst (catalyst 1).

[0202] Specifically, the dispersion liquid (1) was filtered under pressure under the same conditions as described above. In the obtained filter cake, after adding the polyol P1 so that the solid content became 5 mass%, the volatile components were distilled off under reduced pressure at 80°C for 3 hours, and the atmosphere (air) was introduced to return to normal pressure, to obtain a slurry catalyst (catalyst 1) in which the TBA-DMC catalyst was dispersed in the polyol P1. Note that it is considered that a part of the polyol P1 contained in the slurry coordinates with the TBA-DMC catalyst.

[0203] The water content in the slurry catalyst (catalyst 1) was measured by the above-described method. In addition, an equivalent amount of the polyol P1 to the polyol P1 added as the dispersion medium was prepared, and the material obtained by distilling off the volatile components under reduced pressure at 80°C for 3 hours was used as a sample to measure the water content, as the water content of the dispersion medium. The water content in the DMC catalyst was calculated by the above-described method. The results are shown in Table 1 (hereinafter, the same applies in the absence of a specific description).

[0204] The uncoordinated polyol P1 was removed from the obtained slurry catalyst using hexane, and XRD and XAFS measurements were performed on the obtained solid sample by the above-described method. The measurement results are shown in Table 1 (hereinafter, the same applies in the absence of a specific description).

[0205] The obtained slurry catalyst was evaluated for catalytic activity life and water resistance by the above-described method. In addition, using the obtained slurry catalyst, a polyether polyol was manufactured by the method of Production Example 1, and the content of the ultrahigh molecular weight component was measured.

[0206] These results are shown in Table 3 (hereinafter, the same applies in the absence of a specific description).

[0207] [Example 2]

[0208] In this example, a water content adjustment step was provided, and the water content was adjusted to be lower than that of Example 1.

[0209] That is, a slurry catalyst (catalyst 1) was prepared in the same manner as in Example 1, and further, as a water content adjustment step, after drying under reduced pressure at 115°C for 6 hours to distill off the volatile components, dry nitrogen gas was introduced to return to normal pressure, to obtain a slurry catalyst (catalyst 2).

[0210] The obtained slurry catalyst was measured in the same manner as in Example 1.

[0211] [Example 3]

[0212] In this example, a water content adjustment step was provided, and the water content was adjusted to be lower than that of Example 1.

[0213] Specifically, the drying time in the moisture amount adjustment step of Example 2 was changed from 6 hours to 4 hours. Other than this, the same operation as Example 2 was performed to obtain a slurry catalyst (Catalyst 3).

[0214] For the obtained slurry catalyst, the same measurement as Example 1 was performed.

[0215] [Example 4]

[0216] In this example, a target slurry catalyst was produced by further adding a dispersion medium to a slurry catalyst (Catalyst 2) produced in the same manner as Example 2.

[0217] That is, after adding polyoxypropylene triol as Initiator 1 in Production Example 1 to a slurry catalyst (Catalyst 2) produced in the same manner as Example 2 so that the solid content amount was 0.0292 mass%, further, as a moisture amount adjustment step, it was dried under reduced pressure at 130°C for 3 hours, and after distilling off the volatile components, dry nitrogen was introduced and returned to normal pressure, to obtain a slurry catalyst (Catalyst 4).

[0218] For the obtained slurry catalyst, the same measurement as Example 1 was performed.

[0219] [Example 5]

[0220] In this example, the moisture amount was adjusted to be lower than in Example 2.

[0221] That is, the same operation as Example 1 was performed to prepare a dispersion liquid (1) in which a TBA-DMC catalyst was dispersed in a mixed solution of TBA and water, and it was filtered. In Example 1, polyol PI was added to the obtained filter cake, and in this example, the filter cake was freeze-dried before the addition of polyol PI. The obtained freeze-dried product was dispersed in polyol PI so that the solid content amount was 5 mass% to obtain a slurry catalyst (Catalyst 5).

[0222] For the obtained slurry catalyst, the same measurement as Example 1 was performed.

[0223] Note that in the measurement of the catalytic activity life, no catalytic activity was shown, and therefore the water resistance and the content of the ultra-high molecular weight component were not evaluated.

[0224] [Example 6]

[0225] In this example, a slurry catalyst (Catalyst 6) was produced by increasing the moisture amount of the slurry catalyst (Catalyst 2) of Example 2.

[0226] That is, the slurry catalyst (Catalyst 2) obtained in Example 2 was left in a high humidity atmosphere at an atmosphere temperature of 40°C and a relative humidity of 80% for 7 days to obtain a slurry catalyst (Catalyst 6).

[0227] The obtained slurry catalyst was measured in the same manner as in Example 1.

[0228] [Example 7]

[0229] In this example, after water was brought into contact with the slurry catalyst of Example 2 (Catalyst 2), the amount of water was reduced to the same extent as in Example 2.

[0230] That is, the slurry catalyst (Catalyst 2) obtained in Example 2 was added to distilled water 500 g, and after stirring for 1 hour, water was distilled off under reduced pressure at 80°C to obtain a slurry catalyst (Catalyst 7).

[0231] The obtained slurry catalyst was measured in the same manner as in Example 1.

[0232] In the measurement of the catalytic activity life, no catalytic activity was shown, and thus the water resistance and the content of the ultra-high molecular weight component were not evaluated.

[0233] [Example 8]

[0234] In Example 2, zinc chloride 10.2 g was changed to zinc bromide 16.9 g, and otherwise, a slurry catalyst (Catalyst 8) was obtained in the same manner.

[0235] The obtained slurry catalyst was measured in the same manner as in Example 1.

[0236] [Example 9]

[0237] In Example 6, zinc chloride 10.2 g was changed to zinc iodide 23.9 g, and otherwise, a slurry catalyst (Catalyst 9) was obtained in the same manner.

[0238] The obtained slurry catalyst was measured in the same manner as in Example 1.

[0239] [Example 10]

[0240] In Example 2, zinc chloride 10.2 g was changed to zinc fluoride 7.7 g. Since the solubility of zinc fluoride in water is small, the synthesis of the DMC catalyst was attempted by solid-phase synthesis, but the obtained product did not show catalytic activity in the polymerization of the epoxide.

[0241] [Example 11]

[0242] In Example 2, zinc chloride 10.2 g was changed to zinc nitrate 14.2 g, and otherwise, a slurry catalyst (Catalyst 11) was obtained in the same manner.

[0243] The obtained slurry catalyst was measured in the same manner as in Example 1.

[0244] [Example 16]

[0245] A dispersion liquid (1) in which a TBA-DMC catalyst was dispersed in a mixture of TBA and water was prepared in the same manner as in Example 1. The dispersion liquid (1) was filtered under pressure (0.25 MPa) using a circular filter plate with a diameter of 125 mm and a quantitative filter paper for fine particles (product name: No. 5C, manufactured by ADVANTEC). The obtained filter cake was dried under reduced pressure at 80°C for 3 hours, and further dried under reduced pressure at 115°C for 4 hours, whereby volatile components were distilled off, and the atmosphere (air) was introduced to return to normal pressure, to obtain a slurry catalyst in which the TBA-DMC catalyst was dispersed in polyol PI (catalyst 16).

[0246] The obtained slurry catalyst was measured in the same manner as in Example 1.

[0247] <Examples 12 to 15, 17 to 19>

[0248] A DMC catalyst in powder form was produced. Examples 13, 14, and 19 are examples, and Examples 12, 15, 17, and 18 are comparative examples.

[0249] [Example 12]

[0250] The dispersion liquid (1) produced in the same manner as in Example 1 was filtered under pressure (0.25 MPa) using a circular filter plate with a diameter of 125 mm and a quantitative filter paper for fine particles (product name: No. 5C, manufactured by ADVANTEC), and the filter cake was separated. In the obtained filter cake, polyol PI was not added, and the filter cake was dried under reduced pressure at 60°C for 2 hours. After the reduced pressure drying, the atmosphere (air) was introduced to return to normal pressure, to obtain a DMC catalyst in powder form (catalyst 12).

[0251] The obtained DMC catalyst in powder form was measured in the same manner as in Example 1. The results are shown in Tables 2 and 3 (hereinafter, the same applies in the absence of a specific description).

[0252] [Example 13]

[0253] The filter cake was obtained in the same manner as in Example 12. In the obtained filter cake, polyol PI was not added, and the filter cake was subjected to atmospheric drying at 100°C for 7 hours. After the atmospheric drying, the filter cake was returned to normal temperature under dry nitrogen gas, to obtain a DMC catalyst in powder form (catalyst 13). The amount of moisture in the DMC catalyst in powder form (catalyst 13) was in the range of 8,000 to 140,000 ppm.

[0254] The obtained DMC catalyst in powder form was measured in the same manner as in Example 1.

[0255] [Example 14]

[0256] A filter cake was obtained in the same manner as in Example 12. The obtained filter cake was subjected to atmospheric drying under the conditions of 100°C for 5 hours without adding the polyol PI, and after the atmospheric drying, was returned to normal temperature under dry nitrogen to obtain a powder-like DMC catalyst (Catalyst 14). The moisture content in the powder-like DMC catalyst (Catalyst 14) was in the range of 8,000 to 140,000 ppm.

[0257] For the obtained powder-like catalyst, the same measurement as in Example 1 was performed.

[0258] [Example 15]

[0259] A filter cake was obtained in the same manner as in Example 12. The obtained filter cake was subjected to freeze-drying treatment without adding the polyol PI to obtain a powder-like DMC catalyst (Catalyst 15).

[0260] For the obtained powder-like catalyst, the same measurement as in Example 1 was performed.

[0261] [Example 17]

[0262] First, in a 5L flask, an aqueous solution containing zinc chloride 81.25 g was prepared, and was stirred at 450 rpm per minute while being kept at 45°C in order to improve dispersibility / mixability and shear force. An aqueous solution containing potassium hexacyanocobaltate 26 g (water: 200 g) was added dropwise to the above aqueous solution of zinc chloride over 30 minutes. After the dropwise addition was completed, a mixture of TBA 325 g and water 325 g was metered and supplied, and was stirred at 45°C for 80 minutes. Next, a mixture of sodium cholate salt 6.5 g, TBA 6.5 g, and water 650 g was metered and supplied, and was stirred for 20 minutes to obtain a dispersion. The dispersion 350 g was filtered using a pressure suction filter under pressurization of 2.0 bar. Next, the wet filter cake in the pressure suction filter was washed by filter cake washing using a mixture of sodium cholate salt 2 g, TBA 70 g, and water 30 g under pressurization of 3.0 bar. The washed wet filter cake was dried at 100°C for 5 hours under high vacuum, was returned to normal pressure by introducing air (air), and a powder-like DMC catalyst (Catalyst 17) was obtained.

[0263] For the obtained powder-like catalyst, the same measurement as in Example 1 was performed.

[0264] [Example 18]

[0265] First, an aqueous zinc chloride solution containing 10.2 g of zinc chloride and 10 g of water was prepared in a 500 mL flask, and was kept at 40°C while stirring at 450 rpm per minute for improving dispersibility / mixability and shear force. To the above aqueous zinc chloride solution, an aqueous solution containing 4.2 g of potassium hexacyanocobaltate and 75 g of water was added dropwise over 30 minutes. After the end of the dropwise addition, further stirring was carried out for 30 minutes, and then a mixture containing 80 g of TBA, 80 g of water, and 0.6 g of polyol P1 was added, and stirring was carried out at 40°C for 30 minutes, and further stirring was carried out at 60°C for 60 minutes, to obtain a mixed solution containing a TBA-DMC catalyst and water. The obtained mixed solution was filtered under pressure (0.25 MPa) using a circular filter plate of 125 mm in diameter and a quantitative filter paper for fine particles (No. 5C made by ADVANTEC) to separate a solid containing a TBA-DMC catalyst (hereinafter referred to as "filter cake"). Subsequently, the obtained filter cake was transferred to a flask, and a mixture containing 36 g of TBA and 84 g of water was added and stirred for 30 minutes, and then pressure filtration was carried out under the same conditions as described above for 15 minutes. The obtained filter cake was transferred to a flask, and a mixture containing 108 g of TBA and 12 g of water was further added and stirred for 30 minutes to obtain a dispersion liquid (18) in which a TBA-DMC catalyst was dispersed in a mixture of TBA and water. The dispersion liquid (18) was filtered under pressure (0.25 MPa) using a circular filter plate of 125 mm in diameter and a quantitative filter paper for fine particles (product name by ADVANTEC, No. 5C), and a filter cake was separated. The washed wet filter cake was dried at 100°C under high vacuum for 5 hours, was introduced into the atmosphere (air) to return to normal pressure, and a powder-like DMC catalyst (catalyst 18) was obtained.

[0266] For the obtained powder-like catalyst, the same measurement as in Example 1 was carried out.

[0267] [Example 19]

[0268] A mixture liquid containing the TBA-DMC catalyst and water was prepared in the same manner as in Example 1. The resulting mixture liquid was subjected to solid-liquid separation with a centrifugal separator, and a solid containing the TBA-DMC catalyst (hereinafter referred to as "filter cake") was separated. Next, the filter cake was transferred to a flask, and a mixture liquid containing 36 g of TBA and 84 g of water was added and stirred for 30 minutes, and then the resulting mixture liquid was subjected to solid-liquid separation with a centrifugal separator, and the resulting filter cake was transferred to a flask, and a mixture liquid containing 108 g of TBA and 12 g of water was further added and stirred for 30 minutes, to obtain a dispersion liquid (19) in which the TBA-DMC catalyst was dispersed in a mixture liquid of TBA and water. For the dispersion liquid (19), the resulting mixture liquid was subjected to solid-liquid separation with a centrifugal separator, and a filter cake was separated. In the resulting filter cake, no polyol P1 was added, and after drying at 100°C under high vacuum for 8 hours to distill off volatile components, dry nitrogen was introduced, and the pressure was returned to normal pressure, to obtain a DMC catalyst (Catalyst 19) in powder form.

[0269] For the resulting catalyst in powder form, the same measurements as in Example 1 were performed.

[0270] [Table 1]

[0271]

[0272] [Table 2]

[0273]

[0274] [Table 3]

[0275]

[0276] As shown in the results of Tables 1 to 3, the DMC catalysts of Example 1 and Example 12 had high catalytic activity in the polymerization of an epoxide, but a large amount of ultrahigh molecular weight components were generated. The DMC catalysts of Example 5, Example 7, Example 10, and Example 15 had no activity. The catalysts of Example 6, Example 9, and Example 11 had low activity. The DMC catalysts of Example 16 to Example 18 had high catalytic activity in the polymerization of an epoxide, but a large amount of ultrahigh molecular weight components were generated.

[0277] In contrast, the DMC catalysts of Example 2 to Example 4, Example 8, Example 13, Example 14, and Example 19, in which the water content adjustment step was provided and adjustment was performed so that the water content of the DMC catalyst was 8,000 to 140,000 ppm, had a diffraction peak at 2θ = 36° and 47° and had no diffraction peak at 2θ = 34°, had high catalytic activity and were able to reduce the content of ultrahigh molecular weight components. In addition, even when stored in an environment with a high water content, the catalytic activity was difficult to decrease, and such water resistance was excellent.

Claims

1. A composite metal cyanide complex catalyst, used for the polymerization reaction of epoxides, wherein the composite metal cyanide complex catalyst contains zinc and cobalt. The composite metal cyanide complex catalyst has a water content of 8,000~140,000 ppm based on the Karl Fischer process. In the X-ray diffraction pattern, it has diffraction peaks at 2θ=36° and 2θ=47°, but no diffraction peak at 2θ=34°.

2. A method for manufacturing a composite metal cyanide complex catalyst, comprising coordinating an organic ligand with a reaction product obtained by reacting a halide metal salt with a cyanide transition metal compound to manufacture a composite metal cyanide complex catalyst for the polymerization reaction of epoxides. in, The metal halide salt is zinc, and the transition metal of the cyanide transition metal compound is cobalt. After coordinating the organic ligand, the water content of the composite metal cyanide complex catalyst is adjusted so that the water content of the composite metal cyanide complex catalyst based on Karl Fischer is 8,000~140,000 ppm, and in the X-ray diffraction pattern of the composite metal cyanide complex catalyst, diffraction peaks exist at 2θ=36° and 2θ=47°, and no diffraction peak exists at 2θ=34°.

3. The method for manufacturing the composite metal cyanide complex catalyst according to claim 2, wherein, The halide metal salt comprises one or more selected from zinc chloride and zinc bromide.

4. The method for manufacturing the composite metal cyanide complex catalyst according to claim 2 or 3, wherein, The organic ligand comprises tert-butanol.

5. A composite metal cyanide complex slurry catalyst, comprising: The composite metal cyanide complex catalyst according to claim 1, and Dispersion media with a water content of less than 500 ppm based on the Karl Fischer process.

6. The composite metal cyanide complex slurry catalyst according to claim 5, wherein, The content of the composite metal cyanide complex catalyst is 0.001~60% by mass relative to the total mass of the composite metal cyanide complex slurry catalyst.

7. A method for manufacturing a composite metal cyanide complex slurry catalyst, comprising a method for manufacturing a composite metal cyanide complex slurry catalyst for polymerization reactions containing epoxides. in, The composite metal cyanide complex catalyst contains zinc and cobalt. The manufacturing method includes: a slurry preparation step, which prepares a slurry containing the composite metal cyanide complex catalyst and a dispersion medium; The process includes a moisture adjustment step to adjust the moisture content of the slurry so that the Karl Fischer-based moisture content of the composite metal cyanide complex catalyst is 8,000~140,000 ppm, the Karl Fischer-based moisture content of the dispersion medium is below 500 ppm, and in the X-ray diffraction pattern of the composite metal cyanide complex catalyst, diffraction peaks exist at 2θ=36° and 2θ=47°, but no diffraction peak exists at 2θ=34°.

8. The method for manufacturing the composite metal cyanide complex slurry catalyst according to claim 7, wherein, The slurry preparation process includes the following steps: for the reaction product obtained by reacting a zinc halide metal salt with a cobalt cyanide transition metal compound in the presence of water, an organic ligand is coordinated with the reaction product in the presence of water to obtain a mixture containing a composite metal cyanide complex catalyst and water; impurities and water are removed from the mixture; a dispersion medium is added to prepare a slurry containing a composite metal cyanide complex catalyst and a dispersion medium.

9. A method for manufacturing a polymer, wherein an epoxide is polymerized in the presence of the composite metal cyanide complex catalyst of claim 1.

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