Method for producing polyether compound having urethane bond

Abstract

To provide a method for producing a polyether compound having a urethane bond, capable of improving filterability in a purification process.SOLUTION: The method for producing a polyether compound having a urethane bond comprises polymerizing an initiator having an active hydrogen and an alkylene oxide in the presence of a double metal cyanide complex catalyst and reacting a composition containing the obtained polyether compound having a hydroxy group with a polyisocyanate. The double metal cyanide complex catalyst is in the form of particles, the double metal cyanide complex catalyst has a 50% cumulative volume particle size of from 0.01 to 4.0 μm as determined from a volume-based cumulative particle size distribution obtained by a laser diffraction scattering method, and the content of the particles having a particle size of at least 11 μm is at most 10 vol% based on the total volume of the double metal cyanide complex catalyst.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing a polyether compound having a urethane bond. [Background technology]

[0002] Polyether compounds having urethane bonds, such as urethane prepolymers, are used as raw materials for adhesives, paints, sealants, coatings, etc. Polyether compounds having urethane bonds are produced using polyether compounds having hydroxyl groups as raw materials. Polyether compounds having hydroxyl groups are produced by polymerizing alkylene oxide with an initiator having active hydrogen. Double metal cyanide complex catalysts are known as polymerization catalysts for obtaining polyether compounds with narrow molecular weight distribution.

[0003] Patent Document 1 discloses a urethane prepolymer composition (G) containing a hydroxyl-terminated urethane prepolymer (E) and a polyalkylene oxide (B). It also discloses that the urethane prepolymer (E) is a reaction product of a polyol and a polyisocyanate (C) and has at least one urethane group and at least one hydroxyl group per molecule. It also discloses that the polyol can be produced using a double metal cyanide complex catalyst. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2023-155601 Summary of the Invention [Problem to be solved by the invention]

[0005] When a polyether compound having a urethane bond is used in applications such as the above-mentioned adhesives, paints, sealants, and coatings, solid impurities in the polyether compound having a urethane bond may cause problems. Therefore, after producing a polyether compound having a urethane bond, purification by filtration may be performed to remove impurities. When a urethane prepolymer (a polyether compound having a urethane bond) is produced by the production method described in Patent Document 1 using a polyol produced using a composite metal cyanide complex catalyst and then purified by filtration, problems arise such as a slow filtration rate and clogging.

[0006] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for producing a polyether compound having a urethane bond, which can improve filterability in the purification step. [Means for solving the problem]

[0007] The present invention provides the following means. [1] A method for producing a polyether compound having a urethane bond, comprising reacting a composition containing a polyether compound having a hydroxyl group obtained by polymerizing an initiator having active hydrogen with an alkylene oxide in the presence of a double metal cyanide complex catalyst with a polyisocyanate, wherein the double metal cyanide complex catalyst is in the form of particles, and the double metal cyanide complex catalyst has a 50% cumulative volume particle size of 0.01 to 4.0 μm as determined from a volume-based cumulative particle size distribution obtained by a laser diffraction scattering method, and the content of particles having a particle size of 11 μm or more relative to the total volume of the double metal cyanide complex catalyst is 10% by volume or less. [2] The method for producing a polyether compound having a urethane bond according to [1], wherein the content of the particles having a particle diameter of 11 μm or more relative to the total volume of the composite metal cyanide complex catalyst is 5% by volume or less. [3] The method for producing a polyether compound having a urethane bond according to [1] or [2], wherein the polyether compound having a hydroxyl group has a number average molecular weight of 1,000 to 100,000. [4] The method for producing a polyether compound having a urethane bond according to any one of [1] to [3], wherein the polyether compound having a hydroxyl group has a molecular weight distribution of 1.00 to 1.15. [5] The method for producing a polyether compound having a urethane bond according to any one of [1] to [4], wherein the polyether compound having a hydroxyl group has a total degree of unsaturation of 0.001 to 0.040 meq / g. [6] The method for producing a polyether compound having a urethane bond according to any one of [1] to [5], wherein the amount of the double metal cyanide complex catalyst used is 1 to 200 ppm by mass relative to the total mass of the polyether compound having a hydroxyl group. [Effects of the Invention]

[0008] According to the present invention, a method for producing a polyether compound having a urethane bond, which can improve filterability in the purification step, can be provided. DETAILED DESCRIPTION OF THE INVENTION

[0009] The meanings and definitions of terms used in this specification are as follows: A numerical range expressed by "to" means that the numerical values ​​before and after "to" are the lower and upper limits of the numerical range.

[0010] The particle size distribution of the composite metal cyanide complex catalyst particles can be determined by laser diffraction scattering. Hereinafter, the X% cumulative volume particle diameter determined from the volume-based cumulative particle size distribution obtained by laser diffraction scattering is referred to as D X Also expressed as D X This refers to the particle size obtained by accumulating up to a specific X% of the total volume of the particle size distribution obtained by the laser diffraction scattering method, which is taken as 100%. The particle size distribution in the reaction liquid (composition) after the production of the polyether compound can also be determined by dynamic light scattering particle size distribution measurement. Hereinafter, the X% cumulative volume particle size determined from the volume-based cumulative particle size distribution obtained by dynamic light scattering particle size distribution measurement is referred to as d X Also expressed as d X represents the particle size obtained by accumulating up to a specific X% of the total volume of the particle size distribution obtained by dynamic light scattering particle size distribution measurement, where the volume is 100%. Also, the X% cumulative light intensity particle size calculated from the cumulative particle size distribution based on light intensity in the range of 0.1 to 6.5 μm obtained by dynamic light scattering particle size distribution measurement is called d X ' is also expressed as d X ' represents the particle size obtained by accumulating up to a specific X% of the light intensity of the entire particle size distribution in the range of 0.1 to 6.5 μm obtained by dynamic light scattering particle size distribution measurement, with the light intensity being 100%.

[0011] The "unit" constituting the polyether compound having a hydroxyl group means an atomic group formed directly by polymerization of a monomer. The term "main chain" refers to a polymer chain formed by polymerization of two or more monomers. In the case of a polyether compound having a hydroxyl group, which will be described later, the "main chain" refers to a residue obtained by removing active hydrogen from an initiator and a portion containing a repeating unit based on alkylene oxide (polyoxyalkylene chain). The polyether compound having a hydroxyl group is a polymer consisting of a main chain and terminal groups. The "end group" of a polyether compound having a hydroxyl group means an atomic group containing the oxygen atom closest to the molecular end among the oxygen atoms in the polyoxyalkylene chain. However, if the atomic group contains a residue of an initiator, it is not considered to be an end group but is considered to be part of the main chain. The "number of end groups" in a polyether compound having a hydroxyl group is the same as the number of active hydrogen atoms in the initiator, which will be described later. The "active hydrogen-containing group" refers to at least one group selected from the group consisting of a hydroxyl group bonded to a carbon atom, a carboxyl group, an amino group, a monovalent functional group obtained by removing one hydrogen atom from a primary amine, a hydrazide group, and a sulfanyl group. The term "active hydrogen" refers to a hydrogen atom derived from the active hydrogen-containing group and a hydrogen atom derived from the hydroxyl group of water. The content of isocyanate groups relative to the total mass of the polyether compound having a urethane bond is a value measured in accordance with JIS K 7301:1995.

[0012] In this specification, the number average molecular weight (Mn) and weight average molecular weight (Mw) are polystyrene-equivalent molecular weights measured using GPC with tetrahydrofuran as an eluent and a calibration curve prepared using polystyrene polymers of known molecular weights. The molecular weight distribution (Mw / Mn) is the ratio of Mw to Mn.

[0013] The "hydroxyl value" of a polyether compound having a hydroxyl group is a value measured in accordance with Method B (phthalation method) described in JIS K 1557-1:2007. The hydroxyl value-based molecular weight is a value calculated by multiplying the hydroxyl value of the hydroxyl-containing polyether compound by the number of hydroxyl groups in the hydroxyl-containing polyether compound (the number of active hydrogen atoms in the initiator). When the polyether compound contains two or more types of hydroxyl-containing polyether compounds with different numbers of hydroxyl groups, the number of hydroxyl groups in the hydroxyl-containing polyether compound is the average number of hydroxyl groups.

[0014] The total degree of unsaturation of the polyether compound having a hydroxyl group can be measured in accordance with JIS K 1557-3:2007. The viscosity of the polyether compound having a hydroxyl group and the polyether compound having a urethane bond can be measured using an E-type viscometer.

[0015] <Method for producing polyether compound having urethane bond> In the method for producing a polyether compound having a urethane bond according to this embodiment, in the presence of a double metal cyanide complex catalyst, an initiator having active hydrogen is polymerized with an alkylene oxide, and the resulting composition containing a polyether compound having a hydroxyl group is reacted with a polyisocyanate. The double metal cyanide complex catalyst is in particulate form. The 50% cumulative volume particle diameter determined from the volume-based cumulative particle size distribution obtained by the laser diffraction scattering method in the double metal cyanide complex catalyst is 0.01 to 4.0 μm, and the content of the particles having a particle diameter of 11 μm or more with respect to the total volume of the double metal cyanide complex catalyst is 10% by volume or less.

[0016] Hereinafter, the polyether compound having a hydroxyl group is also referred to as "polyether compound A", the polyether compound having a urethane bond is also referred to as "polyether compound B", the double metal cyanide complex catalyst after the polymerization reaction is also referred to as "DMC catalyst (U)", and the double metal cyanide complex catalyst before the polymerization reaction is also referred to as "DMC catalyst (F)".

[0017] <DMC catalyst (F)> The DMC catalyst (F) of this embodiment is in particulate form. It is particles having a 50% cumulative volume particle diameter of 0.01 to 4.0 μm determined from the volume-based cumulative particle size distribution obtained by the laser diffraction scattering method. The content of the particles having a particle diameter of 11 μm or more with respect to the total volume of the DMC catalyst (F) is 10% by volume or less.

[0018] The DMC catalyst (F) functions as a polymerization catalyst for alkylene oxide. The DMC catalyst (F) is a crystalline solid and contains a reaction product of a metal halide salt and a transition metal cyanide compound, an organic ligand, and crystal water (coordination water, etc.) encapsulated in the crystal. In addition, it may contain impurities inevitably contained in trace amounts in the above metal salts and metal compounds during production and moisture other than crystal water. Metal halide salts, transition metal cyanide compounds, and organic ligands known in the production of the DMC catalyst (F) can be used.

[0019] The DMC catalyst (F) is considered to be represented by the following formula 1. M 1a1 [M 2 (CN) b1 ] c1 d1(M 1 e1 X 1 f1 )·g1(Ligand)·h1(H2O) Equation 1 In the above formula 1, M 1 e1 X 1 f1 is a metal halide salt, and M 1 is the metal atom that becomes a cation, X 1 is a halogen atom that serves as a counter anion, and M 2 is a transition metal atom contained in the transition metal cyanide compound and serves as an active site, and Ligand is an organic ligand. a1, b1, c1, d1, e1, f1, g1, and h1 are integers, and a1, b1, c1, e1, and f1 are numbers that result in electrical neutrality.

[0020] The above M 1 Examples of such elements include Zn(II), Fe(II), Fe(III), Co(II), Ni(II), Al(III), Sr(II), Mn(II), Cr(III), Cu(II), Sn(II), Pb(II), Mo(IV), Mo(VI), W(IV), and W(VI). The above M 2 Examples of such elements include Co(III), Fe(II), Fe(III), Co(II), Co(III), Cr(II), Cr(III), Mn(II), Mn(III), V(IV), and V(V). Above X 1 Examples of the ions include Cl, Br, and I. M 1 e1 X 1 f1 The metal halide salt represented by the formula (I) is preferably one or more selected from zinc fluoride, zinc chloride, zinc bromide, zinc iodide, zinc sulfate, zinc nitrate, and zinc acetate. 2 and X 1 In view of the interatomic distance, it is more preferable that the zinc oxide layer contains at least one selected from zinc chloride and zinc bromide. Examples of the ligand (organic ligand) include alcohols, ethers, esters, aldehydes, ketones, amides, nitriles and sulfides, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and polyoxyalkylene poly(or mono)ols. One type of organic ligand may be used, or two or more types may be used. Examples of the alcohol include tert-butyl alcohol, n-butyl alcohol, sec-butyl alcohol, iso-butyl alcohol, tert-pentyl alcohol, iso-pentyl alcohol, and ethylene glycol mono-tert-butyl ether. Examples of the polyoxyalkylene poly(or mono)ol include polypropylene diol. Tert-butyl alcohol is preferred as the organic ligand.

[0021] A preferred example of the DMC catalyst (F) is zinc hexacyanocobaltate (Zn3[Co(CN)6]2) containing an organic ligand (Ligand), water, zinc chloride, or zinc bromide. Its chemical formula can be Zn3[Co(CN)6]2·d(ZnCl2)·g(Ligand)·h(H2O) or Zn3[Co(CN)6]2·d(ZnBr2)·g(Ligand)·h(H2O).

[0022] The DMC catalyst (F) is preferably a zinc hexacyanocobaltate (Zn3[Co(CN)6]2) complex with tert-butyl alcohol as the ligand. Water and zinc chloride may be coordinated to the complex.

[0023] D of DMC catalyst (F) particles 50 is 0.01 to 4.0 μm, preferably 0.05 to 3.5 μm, more preferably 0.1 to 3.0 μm, even more preferably 0.1 μm or more but less than 3.0 μm, and particularly preferably 0.5 to 2.5 μm. 50 When the value of D is equal to or greater than the lower limit, the catalyst has sufficient catalytic activity as a polymerization catalyst for alkylene oxide. 50 When is equal to or less than the upper limit, the filterability in the purification step of polyether compound A and polyether compound B is likely to be improved.

[0024] The content of particles having a particle size of 11 μm or more relative to the total volume of the DMC catalyst (F) is 10% by volume or less, preferably 5% by volume or less, more preferably 4% by volume or less, and even more preferably 3% by volume or less. When the content of particles having a particle size of 11 μm or more is the above upper limit or less, filterability in the purification step of polyether compound A and polyether compound B tends to be improved.

[0025] The content of particles having a particle size of 0.15 to 1 μm relative to the total volume of the DMC catalyst (F) is preferably 5% by volume or more, more preferably 7% by volume or more, and even more preferably 10% by volume or more. The upper limit is not particularly limited, but may be, for example, 50% by volume or less, or 30% by volume or less. When the content of particles having a particle size of 0.15 to 1 μm is equal to or more than the above lower limit, the filterability in the purification step of polyether compound A and polyether compound B is likely to be improved.

[0026] The content of particles having a particle size of 0.1 to 0.2 μm relative to the total volume of the DMC catalyst (F) is preferably 3% by volume or less, more preferably 1% by volume or less, and even more preferably 0% by volume. When the content of particles having a particle size of 0.1 to 0.2 μm is equal to or less than the above upper limit, the filterability in the purification step of polyether compound A and polyether compound B tends to be improved.

[0027] D of DMC catalyst (F) particles 10 is preferably 0.01 to 2.0 μm, more preferably 0.05 to 1.8 μm, and even more preferably 0.1 to 1.5 μm. 10 When the amount of the alkylene oxide in the polyether compound A is within the above range, the polyether compound A has sufficient catalytic activity as a polymerization catalyst for alkylene oxide, and a polyether compound A having a narrow molecular weight distribution can be obtained. In addition, the filterability of the polyether compound A and the polyether compound B in the purification step is likely to be improved.

[0028] D of DMC catalyst (F) particles 90 is preferably 1 to 15 μm, more preferably 1.5 to 10 μm, and even more preferably 2 to 8 μm. 90When the amount of the alkylene oxide in the polyether compound A is within the above range, the polyether compound A has sufficient catalytic activity as a polymerization catalyst for alkylene oxide, and a polyether compound A having a narrow molecular weight distribution can be obtained. In addition, the filterability of the polyether compound A and the polyether compound B in the purification step is likely to be improved.

[0029] The particle size distribution of the DMC catalyst (F) particles in the range of 0.1 to 10 μm is preferably unimodal, i.e., has only one peak. A unimodal distribution tends to improve filterability in the purification process of polyether compound A and polyether compound B. Being unimodal means having only one peak in the particle size distribution in the range of 0.1 to 10 μm.

[0030] DMC catalyst (F) (D 90 -D 10 ) / D 50 is preferably 0.1 to 3.0, more preferably 0.5 to 2.5, even more preferably 1.0 to 2.0, and most preferably 1.05 to 1.50. (D 90 -D 10 ) / D 50 indicates the height of the particle size distribution, and when the particle size distribution of the DMC catalyst (F) particles is unimodal, (D 90 -D 10 ) / D 50 is likely to be below the upper limit. (D 90 -D 10 ) / D 50 When the amount of the alkylene oxide in the polyether compound A falls within the above range, the polyether compound A has sufficient catalytic activity as a polymerization catalyst for alkylene oxide, a polyether compound having a narrow molecular weight distribution can be obtained, and the filterability of the polyether compound A and the polyether compound B in the purification step can be easily improved.

[0031] DMC catalyst D 90 / D 10 is preferably 1.5 to 8.0, more preferably 2.0 to 6.5, and even more preferably 2.5 to 4.5. 90 / D 10 indicates that the particle size distribution is narrow. When the particle size distribution of the DMC catalyst (F) particles is narrow, D 90 / D 10 is likely to be 4.5 or less. D90 / D 10 When the amount of the alkylene oxide in the polyether compound A falls within the above range, the polyether compound A has sufficient catalytic activity as a polymerization catalyst for alkylene oxide, a polyether compound having a narrow molecular weight distribution can be obtained, and the filterability of the polyether compound A and the polyether compound B in the purification step can be easily improved.

[0032] The DMC catalyst (F) may be used in the production of polyether compound A, for example, in the above-mentioned solid state, or in the state of a slurry in which particles of the DMC catalyst (F) are dispersed in a dispersion medium (hereinafter also referred to as a "slurry catalyst").

[0033] The slurry catalyst contains a DMC catalyst (F) and a dispersion medium. The slurry catalyst preferably contains the DMC catalyst (F) and a dispersion medium, and may also contain water and impurities that are unavoidable in the production process.

[0034] As the dispersion medium for the slurry catalyst, a known organic solvent for slurry catalysts can be used. For example, the hardly volatile hydroxy compound described in Japanese Patent No. 3194255 can be used. The hydroxy compound is a hydroxyl group-containing compound having 1 to 8 hydroxyl groups and a molecular weight of 100 to 8000, and a compound having an alcoholic hydroxyl group, such as a polyether compound, is preferred. As the dispersion medium for the slurry catalyst, a polyether compound is preferred in that it does not become an impurity for the product (polyether compound A) obtained by polymerization of alkylene oxide. The Mn of the polyether compound used as the dispersion medium is preferably 100 to 8000, more preferably 600 to 3000. When Mn is equal to or greater than the lower limit, the compound is less likely to act as a catalyst poison, and when Mn is equal to or less than the upper limit, the slurry catalyst is easy to handle. Furthermore, an initiator used in polymerizing alkylene oxide may be used as part of the dispersion medium.

[0035] The dispersion medium of the slurry catalyst preferably contains substantially no water. Specifically, the water content of the dispersion medium is preferably 500 mass ppm or less, more preferably 200 mass ppm or less, and may even be an undetectable amount. The water content of the dispersion medium is the content of water measured by the Karl Fischer method.

[0036] The content of the DMC catalyst (F) relative to the total mass of the slurry catalyst is preferably, for example, 0.001 to 60% by mass, more preferably 0.003 to 50% by mass, and even more preferably 0.006 to 30% by mass. In particular, when the dispersion medium is a polyether compound, the content of the DMC catalyst (F) relative to the total mass of the slurry catalyst is preferably 0.1 to 60% by mass, more preferably 0.5 to 40% by mass, and even more preferably 1 to 30% by mass. In particular, when the dispersion medium contains the above initiator, the content of the DMC catalyst (F) relative to the total mass of the slurry catalyst is preferably 0.003 to 0.02% by mass, more preferably 0.004 to 0.015% by mass, and even more preferably 0.006 to 0.01% by mass.

[0037] <Method for producing the DMC catalyst (F)> The DMC catalyst (F) of the present embodiment can be produced by coordinating an organic ligand to a reaction product obtained by reacting a metal halide salt and a transition metal cyanide compound. Further, after synthesizing the DMC catalyst (F), the water content of the DMC catalyst (F) may be adjusted.

[0038] In the presence of water, an organic ligand is coordinated to a reaction product obtained by reacting a metal halide salt and a transition metal cyanide compound in the presence of water to obtain a mixed solution containing the DMC catalyst (F) and water. Impurities and water may be removed from the obtained mixed solution, and the water content of the obtained solid may be reduced to a predetermined range to obtain the DMC catalyst (F).

[0039] As a preferred embodiment of the method for producing the DMC catalyst (F) of the present embodiment, for example, the following methods can be mentioned. First, an aqueous solution of a metal halide salt and an aqueous solution of a transition metal cyanide compound are reacted to produce a reaction product. An aqueous solution of an organic ligand is added to the reaction product and stirred to coordinate the organic ligand, thereby obtaining a mixed solution containing the DMC catalyst (F) and water. The resulting mixed solution is subjected to solid-liquid separation to obtain a solid. The resulting solid is washed with an aqueous solution containing the organic ligand, and this solid-liquid separation procedure is repeated at least once, preferably at least twice. The resulting solid may be dried so that the moisture content falls within the specified range, and then pulverized as necessary.

[0040] The concentration of the metal halide salt in the aqueous solution of the metal halide salt is preferably 10% by mass or more, more preferably 30% by mass or more, and even more preferably 50% by mass or more, and is preferably equal to or less than the saturated concentration. The concentration of the cyanide transition metal compound in the aqueous solution of the cyanide transition metal compound is preferably 2 to 50 mass %, more preferably 2 to 20 mass %, and even more preferably 3 to 10 mass %. The molar ratio of the metal contained in the metal halide salt to the transition metal contained in the transition metal cyanide compound is preferably 1.6 to 12, more preferably 1.8 to 8.

[0041] According to the investigations by the inventors of the present application, the D of the DMC catalyst (F) 50 It was found that the content of particles with a particle size of 11 μm or more relative to the total volume of the DMC catalyst (F) is highly dependent on the mixing conditions of the aqueous solution of metal halide salt and the aqueous solution of transition metal cyanide compound.

[0042] The mixing of the aqueous solution of the metal halide salt and the aqueous solution of the transition metal cyanide compound is preferably carried out by adding the aqueous solution of the transition metal cyanide compound dropwise to the aqueous zinc halide solution, rather than by adding the aqueous solution of the metal halide salt dropwise to the aqueous solution of the transition metal cyanide compound. Adding the aqueous solution of the transition metal cyanide compound dropwise to the aqueous zinc halide solution makes it easier to obtain a DMC catalyst (F) that satisfies the above-mentioned particle size and particle size distribution. The ratio of the dropwise addition rate (mol / hour) calculated as the transition metal in the transition metal cyanide compound to the total amount (mol) of metal derived from the metal halide salt contained in the metal halide salt aqueous solution is preferably 0.30 (mol / hour / mol) or less, more preferably 0.25 (mol / hour / mol) or less, and even more preferably 0.20 (mol / hour / mol) or less. The lower limit of this ratio is not particularly limited, but may be 0.01 (mol / hour / mol) or more, or may be 0.1 (mol / hour / mol) or more. When this ratio is equal to or less than the upper limit, the DMC catalyst (F) 50 and the content of particles having a particle size of 11 μm or more relative to the total volume of the DMC catalyst (F) can be easily controlled within the above-mentioned ranges. The dropwise addition time of the aqueous solution of the transition metal cyanide compound is preferably 40 minutes or more, more preferably 60 minutes or more, and even more preferably 80 minutes or more. The upper limit of the dropwise addition time may be, for example, 180 minutes or less, or 150 minutes or less. If the dropwise addition time is equal to or longer than the lower limit, the DMC catalyst D 50 The content of particles having a particle size of 11 μm or more relative to the total volume of the DMC catalyst can be easily controlled within the above-mentioned ranges. When the dropping rate is equal to or less than the above-mentioned upper limit, the DMC catalyst can be produced more efficiently.

[0043] When mixing the aqueous solution of the metal halide salt and the aqueous solution of the transition metal cyanide compound, it is preferable to stir the mixture thoroughly. The stirring blades used are preferably meniscus-shaped, full-zone-type, or anchor-type blades. When using meniscus-shaped blades in a 500 mL flask, the diameter is preferably 60 mm or more, and more preferably 70 mm or more.

[0044] The reaction temperature in the reaction between the aqueous solution of the metal halide salt and the aqueous solution of the transition metal cyanide compound is preferably 10 to 65°C, more preferably 20 to 60°C, and even more preferably 30 to 55°C.

[0045] The concentration of the organic ligand in the aqueous solution of the organic ligand is preferably 10 to 90% by mass, more preferably 25 to 75% by mass, and even more preferably 35 to 65% by mass.

[0046] The temperature at which the organic ligand is coordinated is preferably 10 to 90°C, more preferably 20 to 80°C, and even more preferably 30 to 70°C.

[0047] After the organic ligand is coordinated, it is preferable to carry out solid-liquid separation. For solid-liquid separation, methods known in the art, such as filtration and centrifugation, can be used. The obtained solid contains the DMC catalyst (F) as well as a salt (alkali metal halide) produced in the reaction. Therefore, it is preferable to remove the salt by washing the obtained solid. Specifically, an aqueous solution of the organic ligand is added to the obtained solid, the mixture is stirred, and then solid-liquid separation is carried out again. The washing time is preferably 10 to 90 minutes, more preferably 20 to 60 minutes. It is preferable to carry out washing multiple times.

[0048] When producing a slurry catalyst, a method can be used in which a mixed liquid containing the DMC catalyst (F) and water is obtained as described above, impurities and water are removed from the obtained mixed liquid, and then a dispersion medium is added to prepare a slurry containing the DMC catalyst (F) and the dispersion medium. Note that washing with an aqueous solution of an organic ligand may be performed before adding the dispersion medium.

[0049] <Method of producing polyether compound A> In the method for producing the polyether compound A of this embodiment, an alkylene oxide is polymerized with an initiator having active hydrogen in the presence of the DMC catalyst (F).

[0050] The number of active hydrogens in the initiator is preferably 2 or more, more preferably 2 to 10, even more preferably 2 to 8, and particularly preferably 2 to 6. The number of active hydrogens in the initiator is preferably selected depending on the number of hydroxyl groups per molecule of the polyether compound A to be obtained. The number of active hydrogens in the initiator and the number of terminal groups in the polyether compound A are the same. The initiator may be used alone or in combination of two or more kinds.

[0051] The initiator preferably has a hydroxyl group as the active hydrogen-containing group, and an initiator having two or more hydroxyl groups is preferred. Examples of initiators having two hydroxyl groups include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, neopentyl glycol, 1,4-butanediol, and 1,6-hexanediol. Water is also an example of an initiator having two hydroxyl groups. Examples of initiators having three hydroxyl groups include glycerin, trimethylolpropane, and trimethylolethane. Examples of initiators having four or more hydroxyl groups include pentaerythritol, diglycerin, meso-erythritol, methyl glucoside, sucrose, glucose, sorbitol, dipentaerythritol, trehalose, diglycerin, and polyglycerin. Alternatively, a low molecular weight polymer obtained by polymerizing an alkylene oxide with these initiators in the presence of an alkali metal hydroxide may be used as the initiator. The hydroxyl value of the initiator is, for example, preferably from 3 to 842 mgKOH / g, more preferably from 7 to 561 mgKOH / g.

[0052] The alkylene oxide is selected depending on the structural units of the polyoxyalkylene chain of the polyether compound A to be obtained. Examples of alkylene oxides include ethylene oxide, propylene oxide, 1,2-butylene oxide, and 2,3-butylene oxide, of which ethylene oxide and propylene oxide are preferred, and propylene oxide is more preferred.

[0053] When the DMC catalyst (F) is used as the polymerization catalyst, the Mw / Mn of the polyether compound A tends to be smaller and the total degree of unsaturation of the polyether compound A tends to be smaller than when a polymerization catalyst other than the DMC catalyst (F) is used.

[0054] When the polyoxyalkylene chain of the polyether compound A is a random copolymer chain composed of propylene oxide units and ethylene oxide units, a method of obtaining the polyether compound A by reacting a mixture of propylene oxide and ethylene oxide with an initiator in the presence of a DMC catalyst (F) is preferred.

[0055] When the polyoxyalkylene chain of the polyether compound A is a copolymer chain having a block composed of propylene oxide units and a block composed of ethylene oxide units, the polyether compound A may be obtained by reacting propylene oxide with an initiator in the presence of a DMC catalyst (F) to obtain a precursor, which is then reacted with ethylene oxide, or the polyether compound A may be obtained by reacting ethylene oxide with an initiator in the presence of a DMC catalyst (F) to obtain a precursor, which is then reacted with propylene oxide,

[0056] The amount of DMC catalyst (F) used relative to the total mass of the resulting polyether compound A is preferably 1 to 200 ppm by mass, more preferably 2 to 100 ppm by mass, and even more preferably 5 to 50 ppm by mass. When the amount of DMC catalyst (F) used is equal to or greater than the above lower limit, the polymerization reaction is likely to proceed. When the amount of DMC catalyst (F) used is equal to or less than the above upper limit, the amount of DMC catalyst (F) used is reduced, which is economical.

[0057] The polymerization may be carried out continuously or batchwise, but is preferably carried out batchwise. The polymerization temperature is preferably from 30 to 180°C, more preferably from 70 to 160°C, and even more preferably from 90 to 140°C. The polymerization pressure is preferably 1.0 MPa or less, more preferably 0.8 MPa or less, and even more preferably 0.3 MPa or less. The alkylene oxide is preferably fed to the reactor at a rate that allows the above reaction temperature to be maintained. The reaction atmosphere is preferably one that is less susceptible to moisture contamination, and more preferably an inert gas atmosphere such as nitrogen.

[0058] The reaction liquid (composition) after the polymerization contains polyether compound A and the DMC catalyst after the polymerization reaction (i.e., DMC catalyst (U)). It may also contain a stabilizer and trace amounts of impurities. The DMC catalyst (F) is pulverized during the reaction and contained as fine particles (DMC catalyst (U)). The 50% cumulative volume particle diameter determined from the volume-based cumulative particle size distribution obtained by dynamic light scattering particle size distribution measurement of the reaction liquid is preferably 0.1 to 100 nm, more preferably 0.5 to 50 nm, and even more preferably 1 to 30 nm. The 50% cumulative light intensity particle diameter determined from the light intensity-based cumulative particle size distribution in the range of 0.1 to 6.5 μm obtained by dynamic light scattering particle size distribution measurement of the reaction liquid is preferably 1.0 μm or less, more preferably 0.9 μm or less, and even more preferably 0.8 μm or less. The lower limit of the 50% cumulative light intensity particle diameter may be, for example, 0.01 μm or more, or 0.1 μm or more. The peak particle size determined from the cumulative particle size distribution based on light intensity in the range of 0.1 to 6.5 μm obtained by dynamic light scattering particle size distribution measurement of the reaction solution is preferably 1.0 μm or less, more preferably 0.9 μm or less, and even more preferably 0.8 μm or less. The lower limit of the peak particle size may be, for example, 0.01 μm or more, or 0.1 μm or more.

[0059] The content of the DMC catalyst (U) relative to the total mass of the reaction liquid (composition) is preferably 1 to 200 ppm by mass, more preferably 2 to 100 ppm by mass, and even more preferably 5 to 50 ppm by mass. The content of the DMC catalyst (U) is determined based on the amount of the DMC catalyst (F) used in producing the polyether compound A. The content of polyether compound A relative to the total mass of the composition is preferably 98.0 mass % or more, more preferably 99.0 mass % or more, and even more preferably 99.5 mass % or more. In this embodiment, it is preferable that the reaction liquid is used as it is for producing polyether compound B without purification (filtration) of the reaction liquid.

[0060] <Polyether compound A> The main chain of polyether compound A is a polymer chain consisting of a residue obtained by removing active hydrogen from an initiator and an oxyalkylene chain containing one or more repeating units based on alkylene oxide (hereinafter, a repeating unit based on a monomer will be simply referred to as a "monomer unit", for example, a repeating unit based on alkylene oxide will be referred to as an "alkylene oxide unit"). When the polymer chain has two or more types of alkylene oxide units, the alkylene oxide units may form a block polymer or a random polymer. Examples of the oxyalkylene chain include a polymer chain having an ethylene oxide unit, a polymer chain having a propylene oxide unit, a polymer chain having an ethylene oxide unit and a propylene oxide unit, a polymer chain consisting of an ethylene oxide unit, a polymer chain consisting of a propylene oxide unit, a polymer chain consisting of a butylene oxide unit, a polymer chain consisting of a tetramethylene oxide unit, a polymer chain consisting of an ethylene oxide unit and a propylene oxide unit, and a polymer chain consisting of a propylene oxide unit and a butylene oxide unit. A polymer chain having an ethylene oxide unit, a polymer chain having a propylene oxide unit, a polymer chain having an ethylene oxide unit and a propylene oxide unit, a polymer chain consisting of a propylene oxide unit, and a polymer chain consisting of an ethylene oxide unit and a propylene oxide unit are preferred, and a polymer chain consisting of a propylene oxide unit is particularly preferred. The terminal groups of the polyether compound A are hydroxyl groups. The number of terminal groups of the polyether compound A (i.e., the number of hydroxyl groups) is the same as the number of active hydrogens of the initiator.

[0061] The Mn of polyether compound A is preferably 1,000 to 100,000, more preferably 1,500 to 80,000, and even more preferably 2,000 to 60,000. When Mn is equal to or greater than the lower limit, sufficient flexibility is imparted when used as an adhesive or coating material, and good elongation properties are likely to be obtained. When Mn is equal to or less than the upper limit, the viscosity of polyether compound A and polyether compound B can be kept low, making them easy to handle.

[0062] The hydroxyl value of the polyether compound A is preferably 0.5 to 350 mgKOH / g, more preferably 1 to 200 mgKOH / g, and even more preferably 5 to 100 mgKOH / g. When the hydroxyl value is equal to or greater than the lower limit, sufficient curing is likely to be achieved when resinified. When the hydroxyl value is equal to or less than the upper limit, sufficient flexibility is imparted to the resin, and good elongation properties are likely to be achieved.

[0063] The hydroxyl value-based molecular weight of polyether compound A is preferably 1,000 to 100,000, more preferably 1,500 to 80,000, and even more preferably 2,000 to 60,000. When the hydroxyl value-based molecular weight is equal to or greater than the lower limit, sufficient flexibility is imparted when used as an adhesive or coating material, and good elongation properties are likely to be obtained. When the hydroxyl value-based molecular weight is equal to or less than the upper limit, the viscosity of polyether compound A and polyether compound B can be kept low, making them easy to handle.

[0064] The Mw of polyether compound A is preferably 1,200 to 120,000, more preferably 2,000 to 90,000, and even more preferably 3,000 to 70,000. When the Mw is equal to or greater than the lower limit, sufficient flexibility is imparted when used as an adhesive or coating material, and good elongation properties are likely to be obtained. When the Mw is equal to or less than the upper limit, the viscosity of polyether compound A and polyether compound B can be kept low, making them easy to handle.

[0065] The Mw / Mn of the polyether compound A is preferably 1.00 to 1.15, more preferably 1.00 to 1.12, and even more preferably 1.00 to 1.10. When the Mw / Mn is equal to or less than the upper limit, the viscosity of the polyether compound A and the polyether compound B can be kept low, making them easy to handle.

[0066] The total degree of unsaturation of the polyether compound A is preferably from 0.001 to 0.040 meq / g, more preferably from 0.002 to 0.030 meq / g, and even more preferably from 0.003 to 0.010 meq / g.

[0067] The viscosity of the polyether compound A at a measurement temperature of 25°C is preferably from 100 to 30,000 mPa·s, more preferably from 200 to 20,000 mPa·s, and even more preferably from 400 to 10,000 mPa·s.

[0068] <Polyether compound B> Polyether compound B is a reaction product of polyether compound A and polyisocyanate. A urethane bond is formed between polyether compound A and polyisocyanate through a urethane reaction between the hydroxyl groups of polyether compound A and the isocyanate groups of the polyisocyanate. Of the isocyanate groups in the polyisocyanate units introduced into polyether compound B, those that remain unreacted with the hydroxyl groups of polyether compound A become the isocyanate groups at the molecular terminals of polyether compound B. Furthermore, of the hydroxyl groups in the polyether compound A units, those that remain unreacted with the isocyanate groups of the polyisocyanate become the hydroxyl groups at the molecular terminals of polyether compound B. In other words, the molecular terminal groups of polyether compound B contain either or both of a hydroxyl group and an isocyanate group.

[0069] The Mn of polyether compound B is preferably 1,000 to 1,000,000, more preferably 1,500 to 500,000, and even more preferably 2,000 to 100,000. When Mn is equal to or greater than the lower limit, sufficient flexibility is imparted and good elongation properties are obtained when used as an adhesive or coating material. When Mn is equal to or less than the upper limit, the viscosity of polyether compound B can be kept low, making it easy to handle.

[0070] The Mw / Mn of the polyether compound B is preferably 1.00 to 1.50, more preferably 1.00 to 1.45, and even more preferably 1.00 to 1.40. When the Mw / Mn is equal to or less than the upper limit, good elongation properties are easily obtained, and the viscosity is reduced, resulting in good workability.

[0071] When the molecular terminal of polyether compound B is an isocyanate group, the content of the isocyanate group relative to the total mass of polyether compound B is preferably 0.1 to 25 mass%, more preferably 0.5 to 18 mass%, and even more preferably 1 to 15 mass%. When the content of isocyanate groups is equal to or greater than the above lower limit, the tensile strength of the cured product is likely to be improved.When the content of isocyanate groups is equal to or less than the above upper limit, gelation is unlikely to occur during the reaction.

[0072] The content of urethane bonds relative to the total mass of polyether compound B is preferably from 0.01 to 40 mass %, more preferably from 0.1 to 30 mass %, and even more preferably from 1 to 15 mass %.

[0073] The viscosity of polyether compound B at a measurement temperature of 25° C. is preferably 100 to 100,000 mPa·s, more preferably 200 to 50,000 mPa·s, and even more preferably 500 to 30,000 mPa / s. When the viscosity is equal to or less than the above upper limit, handling is excellent.

[0074] <Method of producing polyether compound B> In the method for producing the polyether compound B, the polyether compound A is reacted with a polyisocyanate. If necessary, a urethane catalyst may be used. The polyether compound A may be used alone or in combination of two or more kinds.

[0075] Examples of polyisocyanates include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and araliphatic polyisocyanates. The number of isocyanate groups in the polyisocyanate is preferably 2 to 3, and more preferably 2.

[0076] Examples of the aliphatic polyisocyanate include linear aliphatic polyisocyanates such as tetramethylene diisocyanate, dodecamethylene diisocyanate, and hexamethylene diisocyanate, and branched aliphatic polyisocyanates such as 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane-1,5-diisocyanate, and 3-methylpentane-1,5-diisocyanate.

[0077] Examples of alicyclic polyisocyanates include isophorone diisocyanate (3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, IPDI), hydrogenated xylylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, and 1,3-bis(isocyanatomethyl)cyclohexane.

[0078] Examples of aromatic polyisocyanates include tolylene diisocyanate (TDI), 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate (diphenylmethane 4,4'-diisocyanate, MDI), 4,4'-dibenzyl diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate, 1,3-phenylene diisocyanate, and 1,4-phenylene diisocyanate.

[0079] Examples of the araliphatic polyisocyanate include dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, and α,α,α,α-tetramethylxylylene diisocyanate.

[0080] As the polyisocyanate, alicyclic polyisocyanates and aromatic polyisocyanates are preferred, and IPDI, MDI and TDI are more preferred. One type of polyisocyanate may be used alone, or two or more types may be used in combination.

[0081] The functional groups at the molecular terminals of polyether compound B can be controlled by adjusting the molar ratio of the total number of isocyanate groups in the polyisocyanate to the total number of hydroxyl groups in polyether compound A (hereinafter also referred to as the "NCO / OH ratio"). For example, when producing a polyether compound B having isocyanate groups at its molecular terminals, the NCO / OH ratio is preferably 2 to 10, more preferably 2 to 8, even more preferably 2 to 7, and particularly preferably 2 to 5. When producing a polyether compound B having hydroxyl groups at its molecular terminals, the NCO / OH ratio is preferably 0.1 to 0.8, more preferably 0.2 to 0.7, and even more preferably 0.3 to 0.6.

[0082] The urethanization catalyst is preferably one or more selected from tertiary amine compounds and organometallic compounds. When a highly reactive polyisocyanate is used, the urethanization catalyst may not be used.

[0083] Examples of tertiary amine compounds include triethylamine, triethylenediamine, and 1,8-diazabicyclo(5,4,0)-undecene-7.

[0084] The organometallic compound is preferably one or more selected from tin-based compounds and non-tin-based compounds. Examples of tin compounds include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, and tin 2-ethylhexanoate. Examples of non-tin compounds include titanium compounds such as dibutyltitanium dichloride, tetrabutyltitanium, and butoxytitanium trichloride; lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate; iron compounds such as iron 2-ethylhexanoate and iron acetylacetonate; cobalt compounds such as cobalt benzoate and cobalt 2-ethylhexanoate; zinc compounds such as zinc naphthenate and zinc 2-ethylhexanoate; and zirconium compounds such as zirconium naphthenate.

[0085] The urethanization catalyst may be used alone or in combination of two or more kinds. When a urethanization catalyst is used, the amount of the urethanization catalyst used is preferably 0.001 to 1.0 parts by mass per 100 parts by mass of the polyether compound A, for example.

[0086] In producing the polyether compound B, a solvent can be used as needed. The solvent is preferably one or more selected from ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, and aromatic hydrocarbons such as toluene and xylene. The solvent may be used alone or in combination of two or more kinds. When a solvent is used, the amount of the solvent used is not particularly limited, but is preferably 100 to 1000 parts by mass per 100 parts by mass of the polyether compound A.

[0087] Examples of methods for producing the polyether compound B include a method of mixing the polyether compound A, a polyisocyanate, and, if necessary, a urethanization catalyst and a solvent. Alternatively, a method may be used in which the polyisocyanate is added dropwise to a mixed liquid obtained by mixing the polyether compound A, and, if necessary, a urethanization catalyst and a solvent.

[0088] The reaction temperature is preferably 50 to 120° C., more preferably 50 to 100° C. When the reaction temperature is equal to or higher than the lower limit, the urethane reaction is likely to be accelerated. When the reaction temperature is equal to or lower than the upper limit, side reactions other than the urethane reaction are likely to be suppressed.

[0089] When a urethanization catalyst is used, it is preferable to inactivate the urethanization catalyst after the reaction by adding a reaction terminator such as acetylacetone. The reaction terminator may be used alone or in combination of two or more.

[0090] If unreacted polyisocyanate remains after the reaction, it is preferable to purify polyether compound B by removing the polyisocyanate by distillation.

[0091] The reaction solution after producing polyether compound B contains polyether compound B and a DMC catalyst. It may also contain a stabilizer and trace amounts of impurities. Therefore, it is preferable to purify the reaction solution by filtration. The pore size of the filter paper is, for example, preferably 0.1 to 10 μm, more preferably 0.3 to 6 μm. Since the DMC catalyst does not contribute to the urethanization reaction, it is considered that the particle size is almost unchanged from that of the DMC catalyst (U). The 50% cumulative volume particle size determined from the volume-based cumulative particle size distribution obtained by dynamic light scattering particle size distribution measurement of the reaction solution is preferably 0.1 to 100 nm, more preferably 0.5 to 50 nm, and even more preferably 1 to 30 nm. The 50% cumulative light intensity particle size determined from the light intensity-based cumulative particle size distribution in the range of 0.1 to 6.5 μm obtained by dynamic light scattering particle size distribution measurement of the reaction solution is preferably 1.0 μm or less, more preferably 0.9 μm or less, and even more preferably 0.8 μm or less. The lower limit of the 50% cumulative light intensity particle size may be, for example, 0.01 μm or more, or 0.1 μm or more. The peak particle size determined from the cumulative particle size distribution based on light intensity in the range of 0.1 to 6.5 μm obtained by dynamic light scattering particle size distribution measurement of the reaction solution is preferably 1.0 μm or less, more preferably 0.9 μm or less, and even more preferably 0.8 μm or less. The lower limit of the peak particle size may be, for example, 0.01 μm or more, or 0.1 μm or more. The content of the DMC catalyst relative to the total mass of the reaction liquid is preferably from 1 to 200 ppm by mass, more preferably from 2 to 100 ppm by mass, and even more preferably from 5 to 50 ppm by mass.

[0092] (Polyurethane composition containing polyether compound B) The polyether compound B is used in a polyurethane composition. The polyurethane composition is obtained by mixing the polyether compound B with other optional components as required. As the polyether compound B, only one type may be used, or two or more types may be used in combination. The content of polyether compound B relative to the total mass of the polyurethane composition is 15% by mass or more and 100% by mass or less, and preferably 30 to 100% by mass. The polyurethane composition may further contain optional components other than polyether compound B.

[0093] Examples of optional components contained in the polyurethane composition include catalysts, fillers, plasticizers, stabilizers, pigments, fibers, dyes, drying agents, adhesion improvers, rheology modifiers, solvents, natural resins, non-reactive polymers, and other additives. Each optional component may be used alone, or two or more may be used in combination. When the polyurethane composition contains optional components, the content of the optional components relative to the total mass of the polyurethane composition is preferably more than 0% by mass and 50% by mass or less.

[0094] A cured product can be produced by reacting a polyurethane composition with a curing agent. When the molecular terminal of polyether compound B is an isocyanate group, a curing agent having active hydrogen is used. The active hydrogen-containing group of the curing agent is preferably a hydroxyl group. When the molecular terminal of polyether compound B is a hydroxyl group, a curing agent having an isocyanate group is used. When the molecular terminal of polyether compound B is an isocyanate group, the isocyanate group of polyether compound B contained in the polyurethane composition undergoes a urethane reaction with an active hydrogen-containing group (e.g., a hydroxyl group) of the curing agent, thereby crosslinking polyether compound B with a urethane bond, and a cured product is obtained. When the molecular terminal of polyether compound B is a hydroxyl group, the hydroxyl group of polyether compound B contained in the polyurethane composition undergoes a urethane reaction with an isocyanate group of the curing agent, thereby crosslinking polyether compound B with a urethane bond, and a cured product is obtained. In the case of a curing agent having hydroxyl groups, the number of hydroxyl groups in the curing agent is preferably 2 or more, more preferably 2 to 4, and even more preferably 2 to 3. Water is a curing agent having two hydroxyl groups. In the case of a curing agent having an isocyanate group, the number of isocyanate groups in the curing agent is preferably 2 or more, more preferably 2 to 4, and even more preferably 2 to 3.

[0095] Examples of the curing agent having a hydroxyl group include the initiators and water described in the method for producing the polyether compound. Examples of the curing agent having an isocyanate group include the above-mentioned polyisocyanates.

[0096] When the molecular terminal of polyether compound B is an isocyanate group, the molar ratio of the total amount of isocyanate groups of polyether compound B to the total amount of hydroxyl groups of the curing agent is preferably more than 1, more preferably 1.0 to 1.2. When the molecular terminal of polyether compound B is a hydroxyl group, the molar ratio of the total amount of hydroxyl groups in polyether compound B to the total amount of isocyanate groups in the curing agent is preferably more than 0.8, more preferably 0.8 to 1.2.

[0097] The polyurethane composition and curing agent can be mixed in a single-component system, in which all components except the curing agent are premixed to produce a single-component polyurethane composition, which is then sealed and stored, and cured by atmospheric moisture after application. Alternatively, the polyurethane composition, which is the base composition, and the curing agent composition containing at least a curing agent are stored separately, and the curing agent composition and base composition are mixed before use. In the case of a single-component system, atmospheric moisture (water) functions as the curing agent. In other words, when the molecular terminal of polyether compound B is an isocyanate group, a single-component system is preferred. The one-liquid composition preferably does not contain water. It is preferable that the ingredients containing water are dehydrated and dried in advance, or that they are dehydrated under reduced pressure during the preparation of the one-liquid composition. In the case of a two-component type, the curing agent composition may contain water. The main composition is unlikely to gel even if it contains a small amount of water, but from the viewpoint of storage stability, it is preferable to dehydrate and dry the blended components beforehand. In the case of a two-component type, the above-mentioned optional components may be contained in the curing agent composition. In order to improve storage stability, a dehydrating agent may be added to the one-component composition or the two-component base composition. The reaction temperature is preferably 20 to 40° C. In the case of a one-component type, the relative humidity at the above reaction temperature is preferably 40 to 60%.

[0098] (Use of polyurethane composition containing polyether compound B) Suitable applications of the polyurethane composition containing polyether compound B include adhesives, sealants (for example, elastic sealants for construction, sealants for double glazing, anti-rust and waterproof sealants for glass edges, sealants for the backside of solar cells, sealants for buildings, sealants for ships, sealants for automobiles, and sealants for roads), coating materials (for paint applications), and electrical insulating materials (insulating coating materials for electric wires and cables). As an adhesive, it is suitable as an elastic adhesive for joining plastics together, metals together, and plastics and metals, and is also suitable as an elastic sealing material and elastic coating material. [Example]

[0099] The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following descriptions.

[0100] [Particle size distribution (laser diffraction scattering method)] The particle size distribution of the DMC catalyst (F) particles was measured by a laser diffraction scattering method. Specifically, the DMC catalyst (F) was dispersed in methanol, and the particle size distribution of the resulting dispersion was measured using a particle size distribution analyzer (SALD-2300 manufactured by Shimadzu Corporation), and the cumulative particle size distribution on a volume basis was obtained. From the obtained cumulative particle size distribution, D X The content of particles with a particle diameter of 11 μm or more relative to the total volume of the DMC catalyst (F) and the content of particles with a particle diameter of 0.15 to 1 μm relative to the total volume of the DMC catalyst (F) were determined.

[0101] [Particle size distribution (dynamic light scattering particle size distribution measurement)] In Examples 1 to 6 described below, the particle size distribution of a composition containing polyether compound A and DMC catalyst (U) was measured by dynamic light scattering particle size distribution measurement. Specifically, a dynamic light scattering measurement device (Microtrac-Bell Corporation particle size distribution measurement device: NANOTRAC WAVE II-UT151) was used to measure the particle size distribution of a composition containing polyether compound A and DMC catalyst (U) using methanol as the dispersion solvent, and the volume-based cumulative particle size distribution and the light intensity-based cumulative particle size distribution in the range of 0.1 to 6.5 μm were obtained. From the obtained volume-based cumulative particle size distribution, d 50 , the peak particle diameter and d from the cumulative particle size distribution based on light intensity in the range of 0.1 to 6.5 μm 50 ' was asked.

[0102] [Hydroxyl value and hydroxyl value-equivalent molecular weight] The hydroxyl value was calculated in accordance with Method B of JIS K 1557-1: 2007. The hydroxyl value-based molecular weight was calculated based on the formula "56,100 / hydroxyl value of polyether compound A × number of hydroxyl groups in polyether compound A."

[0103] [Mn, Mw, Mw / Mn] Several monodisperse polystyrenes with different degrees of polymerization were measured as standard samples for molecular weight measurement using a gel permeation chromatograph analyzer (HLC-8420GPC, Tosoh Corporation). A calibration curve was created based on the relationship between the molecular weight of the polystyrene and its retention time. Polyether compound A or polyether compound B was diluted to 0.5% by mass with tetrahydrofuran and passed through a 0.5 μm pore size filter to obtain a measurement sample. Using the resulting measurement sample, Mn, Mw, and Mw / Mn of polyether compound A and polyether compound B were determined by analyzing the peaks appearing between 6 and 11 minutes of collection time using tetrahydrofuran as the solvent, the sample pump at a flow rate of 0.350 mL / min, the reference pump at a flow rate of 0.350 mL / min, the detector temperature at 40 °C, and the collection time from 6 to 15 minutes.

[0104] [Total unsaturation] The total degree of unsaturation of polyether compound A was measured in accordance with JIS K 1557-3:2007.

[0105] [viscosity] The viscosities of polyether compound A and polyether compound B were measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., product name: RE85U) at a measurement temperature of 25° C. with rotor No. 1.

[0106] [Isocyanate group content] The content of isocyanate groups relative to the total mass of polyether compound B was measured in accordance with JIS K 7301:1995.

[0107] [Filterability] A glass filter container was attached to the weighed container, and a 5.0 μm filter paper (PTFE filter, diameter 25 mm) was further attached. 10 g of the reaction solution containing the polyether compound having a urethane bond and the DMC catalyst obtained in Examples 1 to 6 described below was added to 10 g of methyl ethyl ketone as a dilution solvent, and the resulting sample was poured into the filter paper from above and filtered. The natural filtration was allowed for 30 minutes, and the amount of filtered sample was weighed. The larger the amount of filtered sample, the better the filterability. If the amount of filtered sample was 2 g or more, the filterability was judged to be good, and if the amount of filtered sample was less than 2 g, the filterability was judged to be poor.

[0108] [Manufacturing Example 1] Propylene glycol was polymerized with propylene oxide (hereinafter also referred to as "PO") in the presence of a KOH catalyst, and the resulting polymer was dealkalized and purified to obtain polyoxypropylene diol (hereinafter also referred to as "polyol P1"). The average number of hydroxyl groups per molecule of polyol P1 was 2, and Mn was 1,000. A 500 mL flask was used to prepare an aqueous zinc chloride solution consisting of 10.2 g of zinc chloride and 10 g of water. While stirring the aqueous zinc chloride solution at 300 rpm using an 80 mm diameter half-moon stirring blade, an aqueous potassium hexacyanocobaltate solution consisting of 4.2 g of potassium hexacyanocobaltate and 75 g of water was added dropwise to the aqueous zinc chloride solution at a constant rate over 90 minutes. During this time, the mixture in the flask was maintained at 40°C. After the addition of the aqueous potassium hexacyanocobaltate solution was completed, the mixture in the flask was stirred for an additional 30 minutes, after which a mixture consisting of 80 g of tert-butyl alcohol (hereinafter also referred to as "TBA"), 80 g of water, and 0.6 g of polyol P1 was added, followed by stirring at 40°C for 30 minutes and then at 60°C for an additional 60 minutes. The resulting mixture was filtered under pressure (0.25 MPa) using a circular filter plate with a diameter of 125 mm and quantitative filter paper for fine particles (product name: No. 5C, manufactured by ADVANTEC) to obtain a solid containing a composite metal cyanide complex (hereinafter referred to as the "filter cake"). The filter cake was transferred to a flask, and a mixture of 36 g of TBA and 84 g of water was added. After stirring for 30 minutes, the mixture was filtered under pressure under the same conditions as above. The resulting filter cake was transferred to a flask, and a mixture of 108 g of TBA and 12 g of water was added and stirred for 30 minutes, yielding a dispersion of the composite metal cyanide complex catalyst in the TBA-water mixture. 120 g of polyol P1 was added to the dispersion, and the volatile components were distilled off under reduced pressure at 80°C for 3 hours, and then at 115°C for another 3 hours to obtain TBA-DMC catalyst slurry A. The concentration of TBA-DMC catalyst contained in TBA-DMC catalyst slurry A was 5.33% by mass. The particle size distribution of the resulting TBA-DMC catalyst was measured. X , the content of particles with a particle diameter of 11 μm or more relative to the total volume of the TBA-DMC catalyst, and the content of particles with a particle diameter of 0.15 to 1 μm relative to the total volume of the TBA-DMC catalyst, (D 90 -D 10 ) / D 50 , D 90 / D 10are shown in Table 1 (the same applies to Production Examples 2 to 4 below). Note that no particles with a particle size of 0.1 to 0.2 μm were observed. Furthermore, the particle size distribution of the TBA-DMC catalyst particles in the range of 0.1 to 10 μm measured by laser diffraction scattering was monomodal, with only one peak.

[0109] [Manufacturing Example 2] A 67% by mass aqueous zinc chloride solution was introduced into one branch conduit connected to a 600 mL first reactor, and a 5.5% by mass aqueous potassium hexacyanocobaltate solution was introduced into the other. The two solutions were combined at a branch just before the first reactor, and the combined solution was introduced into the first reactor. The zinc chloride solution was continuously fed at a rate of 12.3 g / min (6.83 mL / min assuming a specific gravity of 1.80 g / mL), and the potassium hexacyanocobaltate solution was continuously fed at a rate of 31.5 g / min (31.5 mL / min assuming a specific gravity of 1.0 g / mL) (Zn / Co atomic ratio = 11.5). The combined solution in the first reactor, maintained at 40 °C, was stirred at 300 rpm with a stirring blade, and then the reaction solution from the first reactor was introduced into the second reactor, maintained at 60 °C, via a conduit. The average residence time in the first reactor was 15.7 minutes, which was calculated by dividing the volume of the portion of the first reactor where mixing and stirring was sufficient (600 mL) by the rate of the liquid supply (38.2 mL / min). Simultaneously with the supply of the reaction liquid, a 50% by mass aqueous TBA solution was supplied to the second reactor (2300 mL in internal volume) at 63.2 g / min (71.0 mL / min assuming a specific gravity of 0.89 g / mL). The liquid in the second reactor was stirred at 300 rpm with a stirring blade, and the dispersion produced in the second reactor was sent from the second reactor through a conduit to a storage tank and stored there. The average residence time of the liquid in the second reactor was 21.5 minutes. This average residence time was calculated by dividing the volume of the second reactor's sufficient mixing and stirring capacity (2300 mL) by the liquid supply rate (109.3 mL / min). The proportion of TBA in the steady state was 29.5 mass% of the liquid volume in the second reactor. The amount of TBA introduced was approximately 9.7 times the mass of zinc hexacyanocobaltate (Zn3[Co(CN)6]2), calculated from the amount of potassium hexacyanocobaltate used as the raw material. Next, 1100 g of the dispersion stored in the storage tank was filtered, and a solid containing a composite metal cyanide complex (hereinafter referred to as a "filter cake") was obtained in about 25 minutes. 112 g of the filter cake was mixed with 500 g of a 30% by weight TBA aqueous solution at room temperature, stirred at 300 rpm for 1 hour, and then filtered. After about 20 minutes, a filter cake containing a composite metal cyanide complex was separated. The TBA-DMC catalyst content in the filter cake was 28.0% by weight. 30 g of the filter cake was mixed with 90 g of polyol P1 and stirred at room temperature for 3 hours, and then volatile components were distilled off at 80°C under a reduced pressure of 0.005 MPa for 5 hours to obtain TBA-DMC catalyst slurry B. The concentration of the TBA-DMC catalyst contained in TBA-DMC catalyst slurry B was 8.53 mass%.

[0110] [Manufacturing Example 3] A TBA-DMC catalyst slurry C was obtained in the same manner as in Production Example, except that the stirring blades used in stirring the zinc chloride aqueous solution were changed to half-moon blades with a diameter of 40 mm. The concentration of the TBA-DMC catalyst in TBA-DMC catalyst slurry C was 5.50 mass%.

[0111] [Manufacturing Example 4] A TBA-DMC catalyst slurry D was obtained in the same manner as in Production Example 1, except that the dropwise addition time of the potassium hexacyanocobaltate aqueous solution was changed from 90 minutes to 10 minutes. The concentration of the TBA-DMC catalyst in TBA-DMC catalyst slurry D was 5.40 mass%.

[0112] [Table 1]

[0113] Below, Examples 1 and 2 are working examples, and Examples 3 to 6 are comparative examples.

[0114] [Example 1] In the presence of a KOH catalyst, propylene glycol was polymerized with PO, followed by dealkalization and purification to obtain a polyoxypropylene diol (hereinafter also referred to as "polyol P2"). The average number of hydroxyl groups per molecule of polyol P2 was 2, and the Mn was 700. Using polyol P2 as an initiator, 3,300 g of PO was polymerized in the presence of TBA-DMC catalyst slurry A to obtain a hydroxyl-containing polyether compound A-1. The polymerization was carried out with the addition of 0.1 mass% of Irganox 1010 (manufactured by BASF) as a stabilizer. The amount of TBA-DMC catalyst slurry A used was such that the TBA-DMC catalyst concentration was 44 mass ppm relative to the total mass of hydroxyl-containing polyether compound A-1. The hydroxyl value, hydroxyl value-based molecular weight, Mn, Mw, Mw / Mn, total unsaturation, and viscosity of hydroxyl-containing polyether compound A-1 are shown in Table 2 (the same applies to Examples 2 to 6 below). After the reaction, the TBA-DMC catalyst in the composition containing the hydroxyl-containing polyether compound A-1, the TBA-DMC catalyst, and the stabilizer was measured by dynamic light scattering particle size distribution measurement. 50 , peak particle size in the range of 0.1 to 6.5 μm, d in the range of 0.1 to 6.5 μm 50 The results are shown in Table 2 (the same applies to Examples 2 to 6 below).

[0115] To 150 g of hydroxyl-containing polyether compound A-1 in a composition containing hydroxyl-containing polyether compound A-1, a TBA-DMC catalyst, and a stabilizer, 0.015 g of dibutyltin dilaurate and 16.6 g of isophorone diisocyanate (NCO content: 37.8% by mass) were added and reacted at 80°C for 2 hours. The molar ratio of the isocyanate content of isophorone diisocyanate to the hydroxyl content of hydroxyl-containing polyether compound A-1 (NCO / OH) was 2.0. The reaction was terminated when the NCO content of the resulting urethane-containing polyether compound B-1 reached the theoretical value of approximately 1.9% by mass. The isocyanate content and viscosity of the resulting urethane-containing polyether compound B-1 are shown in Table 2 (the same applies to Examples 2 to 6 below). A filterability test was conducted using the resulting urethane-containing polyether compound B-1. The results are shown in Table 2 (the same applies to Examples 2 to 6 below).

[0116] [Example 2] In the production of polyether compound A having hydroxyl groups, polyether compound A-2 having hydroxyl groups and polyether compound B-2 having urethane bonds were obtained in the same manner as in Example 1, except that the amount of TBA-DMC catalyst slurry A used was changed so that the concentration of the TBA-DMC catalyst was 30 ppm by mass.

[0117] [Example 3] Polyether compound A-3 and polyether compound B-3 having a urethane bond were obtained in the same manner as in Example 1, except that in the production of polyether compound A having a hydroxyl group, TBA-DMC catalyst slurry B was used instead of TBA-DMC catalyst slurry A.

[0118] [Example 4] Polyether compound A-4 and polyether compound B-4 having a urethane bond were obtained in the same manner as in Example 3, except that in the production of polyether compound A having a hydroxyl group, the amount of TBA-DMC catalyst slurry B used was changed so that the concentration of the TBA-DMC catalyst was 30 ppm by mass.

[0119] [Example 5] Polyether compound A-5 and polyether compound B-5 having a urethane bond were obtained in the same manner as in Example 1, except that in the production of polyether compound A having a hydroxyl group, TBA-DMC catalyst slurry C was used instead of TBA-DMC catalyst slurry A.

[0120] [Example 6] Polyether compound A-6 and polyether compound B-6 having a urethane bond were obtained in the same manner as in Example 1, except that in the production of polyether compound A having a hydroxyl group, TBA-DMC catalyst slurry D was used instead of TBA-DMC catalyst slurry A.

[0121] [Table 2]

[0122] As shown in Table 2, it was found that Examples 1 and 2 had improved filterability compared to Examples 3 to 6. In Examples 1 to 6, the d 50 are similar (rather, d in Examples 4 to 6) 50 The d in Examples 1 and 2 is 50 It was found that the majority of particles were extremely small. Furthermore, since the TBA-DMC catalyst does not contribute to the urethane reaction, the particle size in the reaction solution during the production of polyether compound B having urethane bonds is thought to be of a similar order of magnitude. 50 is extremely small compared to the pore size of the filter paper, which is 5.0 μm. 50 The difference in filterability is due to the peak particle size in the range of 0.1 to 6.5 μm and d due to trace components in the reaction solution. 50 On the other hand, the peak particle size and d in the range of 0.1 to 6.5 μm in Examples 1 and 2 and Examples 3 to 6 are 50 The difference in the peak particle size and d 50In order to control the ', the D of the TBA-DMC catalyst before the polymerization reaction is 50 It was also found that adjusting the content of particles with a particle size of 11 μm or more relative to the total volume of the TBA-DMC catalyst before the polymerization reaction is effective. Furthermore, the Mw / Mn of polyether compounds A-1 and A-2 having hydroxyl groups is smaller than the Mw / Mn of polyether compounds A-3 to A-6 having hydroxyl groups. Therefore, it is possible that the Mw / Mn of polyether compounds B-1 and B-2 having urethane bonds is also smaller than the Mw / Mn of polyether compounds B-3 to B-6 having urethane bonds. It is thought that this small Mw / Mn also contributes to improved filterability.

Claims

1. A method for producing a polyether compound having a urethane bond, comprising polymerizing an initiator having active hydrogen and an alkylene oxide in the presence of a composite metal cyanide complex catalyst, and reacting a composition containing the resulting polyether compound having a hydroxyl group with a polyisocyanate, the composite metal cyanide complex catalyst is in particulate form; a 50% cumulative volume particle diameter of the composite metal cyanide complex catalyst calculated from a volume-based cumulative particle size distribution obtained by a laser diffraction scattering method is 0.01 to 4.0 μm, and the content of particles having a particle diameter of 11 μm or more relative to the total volume of the composite metal cyanide complex catalyst is 10% by volume or less.

2. 2. The method for producing a polyether compound having a urethane bond according to claim 1, wherein the content of the particles having a particle diameter of 11 μm or more relative to the total volume of the composite metal cyanide complex catalyst is 5% by volume or less.

3. 3. The method for producing a polyether compound having a urethane bond according to claim 1, wherein the polyether compound having a hydroxyl group has a number average molecular weight of 1,000 to 100,000.

4. 3. The method for producing a polyether compound having a urethane bond according to claim 1, wherein the molecular weight distribution of the polyether compound having a hydroxyl group is 1.00 to 1.

15.

5. 3. The method for producing a polyether compound having a urethane bond according to claim 1, wherein the polyether compound having a hydroxyl group has a total degree of unsaturation of 0.001 to 0.040 meq / g.

6. 3. The method for producing a polyether compound having a urethane bond according to claim 1, wherein the amount of the double metal cyanide complex catalyst used is 1 to 200 ppm by mass relative to the total mass of the polyether compound having a hydroxyl group.

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