Method for producing polyether compound having reactive silicon group

Abstract

To provide a method for producing a polyether compound having a reactive silicon group, capable of improving filterability in a purification process.SOLUTION: A process for producing a reactive silicon group-containing polyether compound, which comprises converting a hydroxy group of a hydroxy group-containing polyether compound in a composition containing the hydroxy group-containing polyether compound and a double metal cyanide complex catalyst to a reactive silicon group-containing group represented by the following formula 1, wherein the double metal cyanide complex catalyst is in the form of particles, and the 50% cumulative light intensity particle size determined from a cumulative particle size distribution on a light intensity basis in a range of from 0.1 to 6.5 μm obtained by dynamic light scattering particle size distribution measurement of the composition, is at most 1.0 μ m: SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing a polyether compound having a reactive silicon group. [Background technology]

[0002] Polyether compounds having reactive silicon groups are known to have the property of crosslinking even at room temperature through the formation of siloxane bonds accompanied by hydrolysis of the reactive silicon groups due to moisture, etc., to give rubber-like cured products. Therefore, polyether compounds having reactive silicon groups are already produced industrially and are widely used in applications such as sealants and adhesives.

[0003] Polyether compounds having reactive silicon groups are produced from 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.

[0004] Patent Document 1 discloses an oxyalkylene polymer having a urethane bond and an alkoxysilyl group, which is obtained by subjecting a polymer having a polyoxyalkylene chain and a hydroxy group to a urethanization reaction with a compound having an alkoxysilyl group and an isocyanate group. It also discloses that the polymer having a polyoxyalkylene chain and a hydroxy group can be obtained by ring-opening polymerization of an alkylene oxide with a compound having an active hydrogen atom in the presence of a double metal cyanide complex catalyst. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent No. 5521326 Summary of the Invention [Problem to be solved by the invention]

[0006] When a polyether compound having a reactive silicon group is used in applications such as the above-mentioned sealants, adhesives, and paints, solid impurities in a composition containing the polyether compound having a reactive silicon group can cause problems. Therefore, after producing the polyether compound having a reactive silicon group, purification by filtration may be performed to remove impurities. When a polyether compound having a reactive silicon group (an oxyalkylene polymer having a urethane bond and an alkoxysilyl group) is produced by the production method described in Patent Document 1 using a polyol (a polymer having a polyoxyalkylene chain and a hydroxyl group) produced using a composite metal cyanide complex catalyst and then purified by filtration, the filtration rate is slow and clogging occurs.

[0007] 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 reactive silicon group, which can improve filterability in the purification step. [Means for solving the problem]

[0008] The present invention provides the following means. [1] A method for producing a polyether compound having a reactive silicon group, comprising converting a hydroxyl group of a polyether compound having a hydroxyl group in a composition containing the polyether compound and a double metal cyanide complex catalyst into a group having a reactive silicon group represented by the following formula 1, wherein the double metal cyanide complex catalyst is in a particulate form, and the 50% cumulative light intensity particle size of the composition calculated from a 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 1.0 μm or less. -SiR a X 3-a formula 1 In the formula 1, R represents a monovalent organic group having 1 to 20 carbon atoms other than a hydrolyzable group, and X represents a hydroxyl group, a halogen atom, or a hydrolyzable group. a is an integer of 0 to 2. When a is 2, R may be the same or different from each other, and when a is 0 or 1, X may be the same or different from each other. [2] The method for producing a polyether compound having a reactive silicon group according to [1], wherein the peak particle size of the composition determined from a 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 1.0 μm or less. [3] The method for producing a polyether compound having a reactive silicon group according to [1] or [2], wherein the composition has a 50% cumulative volume particle size of 0.1 to 100 nm as determined from a volume-based cumulative particle size distribution obtained by dynamic light scattering particle size distribution measurement. [4] The method for producing a polyether compound having a reactive silicon group according to any one of [1] to [3], wherein the polyether compound having a hydroxyl group has a number average molecular weight of 500 to 100,000. [5] The method for producing a polyether compound having a reactive silicon group according to any one of [1] to [4], wherein the polyether compound having a hydroxyl group has a molecular weight distribution of 1.00 to 1.15. [6] The method for producing a polyether compound having a reactive silicon group according to any one of [1] to [5], wherein the content of the double metal cyanide complex catalyst relative to the total mass of the polyether compound having a hydroxyl group is 1 to 200 ppm by mass. [Effects of the Invention]

[0009] According to the present invention, a method for producing a polyether compound having a reactive silicon group, which can improve filterability in the purification step, can be provided. DETAILED DESCRIPTION OF THE INVENTION

[0010] 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.

[0011] 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 of the composite metal cyanide complex catalyst particles 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%.

[0012] 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 polyether compounds having a hydroxyl group and the polyether compounds having a reactive silicon 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 and the polyether compound having a reactive silicon group are polymers consisting of a main chain and terminal groups. The polyether compound having a hydroxyl group and a reactive silicon group is a polyether compound having a reactive silicon group. The polyether compound having a reactive silicon group may have one or more of a hydroxyl group, a urethane bond, a polymerizable unsaturated group, and an isocyanate group. The "end group" of a polyether compound having a hydroxyl group and a polyether compound having a reactive silicon 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 and a polyether compound having a reactive silicon group is the same number as the number of active hydrogen atoms in the initiator, as described below. 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.

[0013] The "silylation rate" of a polyether compound having a reactive silicon group is the ratio of the number of reactive silicon groups to the total number of reactive silicon groups, hydroxyl groups, unsaturated groups, and isocyanate groups in the terminal groups of the polyether compound having a reactive silicon group. Specifically, the silylation rate is calculated by the following formula: Silylation rate (%) = 100 × number of reactive silicon groups / [number of reactive silicon groups + number of hydroxyl groups + number of isocyanate groups + (number of carbon-carbon double bonds) + (number of carbon-carbon triple bonds) × 2] The silylation rate can be measured by NMR analysis. Alternatively, it may be the ratio (mol %) of the number of silyl groups in the silylating agent added to the number of terminal groups of a polyether compound having a hydroxyl group when the reactive silicon group is introduced into the terminal group of the hydroxyl group-containing polyether compound using the silylating agent described below. In this case, however, a diisocyanate compound is used as the polyisocyanate compound in the method (c1) described below. The term "silylating agent" refers to a compound having a reactive silicon group and a functional group that reacts with an active hydrogen-containing group, an unsaturated group, or an isocyanate group.

[0014] 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.

[0015] 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.

[0016] 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 reactive silicon group can be measured using an E-type viscometer.

[0017] <Method for producing polyether compound having reactive silicon group> In the method for producing a polyether compound having a reactive silicon group according to this embodiment, the hydroxyl group of the polyether compound having a hydroxyl group in the composition containing the polyether compound having a hydroxyl group and the double metal cyanide complex catalyst is converted into a group having a reactive silicon group represented by the following formula 1 described later. The 50% cumulative light intensity particle diameter determined from the cumulative particle size distribution based on the light intensity in the range of 0.1 to 6.5 μm obtained by dynamic light scattering particle size distribution measurement in the composition is 1.0 μm or less. By controlling the particle size in the composition in this way, it is considered that the filtration property is improved in the purification step of the polyether compound having a reactive silicon group. Hereinafter, the polyether compound having a hydroxyl group is also referred to as "polyether compound A", and the polyether compound having a reactive silicon group is also referred to as "polyether compound B".

[0018] <Composition containing polyether compound A and double metal cyanide complex catalyst> In the method for producing a composition containing the polyether compound A and the double metal cyanide complex catalyst according to this embodiment, an initiator having active hydrogen and an alkylene oxide are polymerized in the presence of the double metal cyanide complex catalyst. Hereinafter, 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)".

[0019] <DMC catalyst (F)> The DMC catalyst (F) of this embodiment is in a particulate form. The 50% cumulative volume particle diameter determined from the particle size distribution of the particles of the DMC catalyst (F) is preferably 0.01 to 4.0 μm. The content of particles having a particle diameter of 11 μm or more with respect to the total volume of the double metal cyanide complex catalyst of the DMC catalyst (F) is preferably not more than 10% by volume.

[0020] 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 water of crystallization (e.g., coordinated water) encapsulated in the crystal. In addition, the catalyst may contain trace amounts of impurities unavoidable during production and moisture other than water of crystallization contained in the metal salts and metal compounds. As the metal halide salt, transition metal cyanide compound, and organic ligand, those known in the production of the DMC catalyst (F) can be used.

[0021] The DMC catalyst (F) is believed to be represented by the following formula 2. M 1 a1 [M 2 (CN) b1 ] c1 d1(M 1 e1 X 1 f1 )·g1(Ligand)·h1(H2O) Equation 2 In the above formula 2, 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.

[0022] 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 2Examples 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.

[0023] 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).

[0024] 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.

[0025] D of DMC catalyst (F) particles 50 is preferably 0.01 to 4.0 μm, more preferably 0.05 to 3.5 μm, even more preferably 0.1 to 3.0 μm, particularly preferably 0.1 μm or more and less than 3.0 μm, and most 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.

[0026] The content of particles having a particle size of 11 μm or more relative to the total volume of the DMC catalyst (F) is preferably 10% by volume or less, more preferably 5% by volume or less, even more preferably 4% by volume or less, and particularly preferably 3% by volume or less. When the content of particles having a particle size of 11 μm or more is the above-mentioned upper limit or less, filterability in the purification process of polyether compound A and polyether compound B is likely to be improved. The content of particles having a particle size of 11 μm or more relative to the total volume of the DMC catalyst is preferably 0 to 10% by volume, more preferably 0 to 5% by volume, even more preferably 0 to 4% by volume, and particularly preferably 0 to 3% by volume.

[0027] The content of particles having a particle diameter 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. The content of particles having a particle diameter of 0.15 to 1 μm relative to the total volume of the DMC catalyst is preferably 5 to 50% by volume, more preferably 7 to 50% by volume, and even more preferably 7 to 30% by volume. When the content of particles having a particle diameter of 0.15 to 1 μm is equal to or greater than the above lower limit, filterability in the purification step of polyether compound A and polyether compound B is likely to be improved.

[0028] 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.

[0029] 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 molecular weight of the polyether compound A falls 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.

[0030] 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. 90 When the molecular weight of the polyether compound A falls 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.

[0031] 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 the 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. More specifically, when the particle size with the highest frequency in the particle size distribution in the range of 0.1 to 10 μm is defined as the peak particle size, the frequency of plots monotonically decreases (i.e., does not increase) from the peak particle size toward the minimum particle size and the maximum particle size.

[0032] DMC catalyst (F) (D90 -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.

[0033] 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. D 90 / 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.

[0034] 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").

[0035] 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.

[0036] 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.

[0037] It is preferable that the dispersion medium of the slurry catalyst does not substantially contain 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 be an undetectable amount. The water content of the dispersion medium is preferably 0 to 500 mass ppm, more preferably 0 to 200 mass ppm. The water content of the dispersion medium and the water content relative to the total mass of the slurry catalyst described below are the water contents measured by Karl Fischer measurement method.

[0038] The content of the DMC catalyst (F) relative to the total mass of the slurry catalyst is, for example, preferably from 0.001 to 60 mass%, more preferably from 0.003 to 50 mass%, and even more preferably from 0.006 to 30 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. The water content relative to the total mass of the slurry catalyst is preferably, for example, 0 to 10,000 ppm by mass, more preferably 10 to 6,000 ppm by mass, and even more preferably 100 to 4,000 ppm by mass.

[0039] <Method for Producing 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.

[0040] 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).

[0041] As a preferred embodiment of the method for producing the DMC catalyst (F) of the present embodiment, for example, the following method 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 thereto and stirred to coordinate the organic ligand to obtain a mixed solution containing the DMC catalyst (F) and water. 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 the operation of solid-liquid separation is performed one or more times, preferably two or more times. Further, the obtained solid may be dried so that the water content is within the above specific range, and may be pulverized as necessary.

[0042] 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. It is also preferably below the saturated concentration. The concentration of the metal halide salt in the aqueous solution of the metal halide salt is preferably 10% by mass or more but below the saturated concentration, more preferably 30% by mass or more but below the saturated concentration, and even more preferably 50% by mass or more but below 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.

[0043] 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.

[0044] 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 one aqueous solution dropwise to the other aqueous solution. It is more preferable to add the aqueous solution of the transition metal cyanide compound dropwise to an aqueous zinc halide solution than to add the aqueous solution of the metal halide salt dropwise to an aqueous solution of the transition metal cyanide compound. Adding the aqueous solution of the transition metal cyanide compound dropwise to an 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. The ratio is preferably 0.01 to 0.30 (mol / hour / mol), more preferably 0.01 to 0.25 (mol / hour / mol), and even more preferably 0.1 to 0.20 (mol / hour / mol). When the 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. The dropwise addition time is preferably 40 to 180 minutes, more preferably 60 to 180 minutes, and even more preferably 60 to 150 minutes. If the dropwise addition time is equal to or longer than the lower limit, the DMC catalyst 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.

[0045] 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.

[0046] 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.

[0047] 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.

[0048] 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.

[0049] 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) generated 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.

[0050] 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.

[0051] <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).

[0052] The number of active hydrogens in the initiator is preferably 1 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.

[0053] The initiator preferably has a hydroxyl group as the active hydrogen-containing group. The initiator having one hydroxyl group is preferably a monohydric alcohol having a linear or branched hydrocarbon group, such as methyl alcohol, ethyl alcohol, 1-propyl alcohol, 2-propyl alcohol, n-butyl alcohol, isobutyl alcohol, 2-butyl alcohol, tert-butyl alcohol, 2-ethylhexanol, decyl alcohol, lauryl alcohol, tridecanol, cetyl alcohol, stearyl alcohol, or oleyl alcohol. 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.

[0054] 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.

[0055] 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.

[0056] 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.

[0057] 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,

[0058] 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.

[0059] 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 lower limit is not particularly limited, but is, for example, atmospheric pressure. The polymerization pressure is preferably atmospheric pressure or more and 1.0 MPa or less, more preferably atmospheric pressure or more and 0.8 MPa or less, and even more preferably atmospheric pressure or more and 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.

[0060] 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 1.0 μm or less, preferably 0.9 μm or less, and 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 50% cumulative light intensity particle diameter is preferably 0.01 to 1.0 μm, more preferably 0.01 to 0.9 μm, and even more preferably 0.1 to 0.8 μm. The peak particle diameter 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 diameter may be, for example, 0.01 μm or more, or 0.1 μm or more. The peak particle diameter is preferably 0.01 to 1.0 μm, more preferably 0.01 to 0.9 μm, and even more preferably 0.1 to 0.8 μm.

[0061] 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.

[0062] <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.

[0063] The Mn of polyether compound A is preferably 500 to 100,000, more preferably 1,000 to 100,000, even more preferably 1,500 to 80,000, and particularly 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.

[0064] 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.

[0065] The hydroxyl value-based molecular weight of polyether compound A is preferably 500 to 100,000, more preferably 1,000 to 100,000, even more preferably 1,500 to 80,000, and particularly 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.

[0066] The Mw of polyether compound A is preferably 600 to 120,000, more preferably 1,200 to 120,000, even more preferably 2,000 to 90,000, and particularly 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.

[0067] 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.

[0068] 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.

[0069] 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.

[0070] <Method of producing polyether compound B> In the method for producing polyether compound B, the hydroxyl group of the polyether compound having a hydroxyl group in a composition containing polyether compound A and DMC catalyst (U) is converted into a group having a reactive silicon group represented by the following formula 1.

[0071] (reactive silicon group) The reactive silicon group has a hydroxyl group, a halogen atom, or a hydrolyzable group bonded to a silicon atom, and can form a siloxane bond to crosslink. The reaction to form the siloxane bond is accelerated by a curing catalyst. The reactive silicon group in polyether compound B is represented by the following formula 1: -SiR a X 3-a formula 1

[0072] In the above formula 1, R represents a monovalent organic group having 1 to 20 carbon atoms other than a hydrolyzable group. R is preferably at least one group selected from the group consisting of hydrocarbon groups having 1 to 20 carbon atoms and triorganosiloxy groups.

[0073] R is preferably at least one group selected from the group consisting of an alkyl group, a cycloalkyl group, an aryl group, an α-chloroalkyl group, and a triorganosiloxy group. It is more preferably at least one group selected from the group consisting of a linear or branched alkyl group having 1 to 4 carbon atoms, a cyclohexyl group, a phenyl group, a benzyl group, an α-chloromethyl group, a trimethylsiloxy group, a triethylsiloxy group, and a triphenylsiloxy group. A methyl group or an ethyl group is preferred in view of the good curability of the polyether compound B and the stability of the curable composition. An α-chloromethyl group is preferred in view of the fast curing rate of the cured product. A methyl group is particularly preferred in view of its easy availability.

[0074] In the above formula 1, X represents a hydroxyl group, a halogen atom, or a hydrolyzable group. Examples of the hydrolyzable group include an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a sulfanyl group, and an alkenyloxy group. An alkoxy group is preferred because it is mildly hydrolyzable and easy to handle. The alkoxy group is preferably a methoxy group, an ethoxy group, or an isopropoxy group, and more preferably a methoxy group or an ethoxy group. When the alkoxy group is a methoxy group or an ethoxy group, it is easy to quickly form a siloxane bond and form a crosslinked structure in the cured product, and the physical properties of the cured product tend to be good.

[0075] In the above formula 1, a is an integer of 0 to 2. When a is 2, R may be the same or different from each other. When a is 1 or less, X may be the same or different from each other. Since a low crosslink density due to siloxane bonds tends to reduce the modulus of the cured product, a is preferably 2 or less, and more preferably 1 or less.

[0076] Examples of the reactive silicon group represented by the above formula 1 include a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a tris(2-propenyloxy)silyl group, a triacetoxysilyl group, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, a dimethoxyethylsilyl group, a methyldiisopropoxysilyl group, an (α-chloromethyl)dimethoxysilyl group, and an (α-chloromethyl)diethoxysilyl group. In terms of high activity and good curability, a trimethoxysilyl group, a triethoxysilyl group, a dimethoxymethylsilyl group, and a diethoxymethylsilyl group are preferred, and a trimethoxysilyl group and a dimethoxymethylsilyl group are more preferred.

[0077] Examples of the method for producing the polyether compound B include the following production methods (a1), (b1), and (c1). Method (a1): Converting the hydroxyl groups of polyether compound A into alkenyloxy groups having a carbon-carbon double bond or alkynyloxy groups having a carbon-carbon triple bond at the molecular terminal, and then converting the carbon-carbon double bond at the molecular terminal of the alkenyloxy group or the carbon-carbon triple bond of the alkynyloxy group into a reactive silicon group -SiR represented by the above formula 1. a X 3-a A method of converting an alkenyloxy group or an alkynyloxy group into a group having a reactive silicon group represented by the above formula 1 by reacting the alkenyloxy group or the alkynyloxy group with a silylating agent capable of introducing the following formula: Method (b1): A method in which a hydroxyl group of a polyether compound A is reacted with a silylating agent having a functional group reactive with the hydroxyl group and a reactive silicon group represented by the above formula 1 to convert the hydroxyl group into a group having a reactive silicon group represented by the above formula 1. Method (c1): A method in which the hydroxyl groups of polyether compound A are converted into groups having an isocyanate group, and then the hydroxyl groups are converted into groups having a reactive silicon group represented by formula 1 by reacting the polyether compound A with a silylating agent having a functional group reactive with an isocyanate group and a reactive silicon group represented by formula 1 above.

[0078] In method (a1), polyether compound A is subjected to the action of an alkali metal salt to form an alcoholate, and then reacted with a halogenated hydrocarbon compound having a carbon-carbon double bond or a halogenated hydrocarbon compound having a carbon-carbon triple bond at the molecular terminal to convert the hydroxyl groups of polyether compound A into alkenyloxy groups having a carbon-carbon double bond or alkynyloxy groups having a carbon-carbon triple bond at the molecular terminal.

[0079] Examples of alkali metal salts include sodium hydroxide, sodium alkoxide, potassium hydroxide, potassium alkoxide, lithium hydroxide, lithium alkoxide, cesium hydroxide, and cesium alkoxide. In terms of ease of handling and solubility, sodium hydroxide, sodium methoxide, sodium ethoxide, potassium hydroxide, potassium methoxide, and potassium ethoxide are preferred, and sodium methoxide and potassium ethoxide are more preferred, with sodium methoxide being particularly preferred in terms of availability. The alkali metal salt may be used in a state of being dissolved in a solvent.

[0080] Examples of halogenated hydrocarbon compounds containing a carbon-carbon double bond at the molecular terminal include vinyl chloride, allyl chloride, methallyl chloride, vinyl bromide, allyl bromide, methallyl bromide, vinyl iodide, allyl iodide, and methallyl iodide. Allyl chloride and methallyl chloride are preferred. Halogenated hydrocarbon compounds containing a carbon-carbon triple bond include propargyl chloride, 1-chloro-2-butyne, 4-chloro-1-butyne, 1-chloro-2-octyne, 1-chloro-2-pentyne, 1,4-dichloro-2-butyne, 5-chloro-1-pentyne, 6-chloro-1-hexyne, propargyl bromide, 1-bromo-2-butyne, 4-bromo-1-butyne, 1-bromo- Examples include 2-octyne, 1-bromo-2-pentyne, 1,4-dibromo-2-butyne, 5-bromo-1-pentyne, 6-bromo-1-hexyne, propargyl iodide, 1-iodo-2-butyne, 4-iodo-1-butyne, 1-iodo-2-octyne, 1-iodo-2-pentyne, 1,4-diiodo-2-butyne, 5-iodo-1-pentyne, and 6-iodo-1-hexyne. Propargyl chloride, propargyl bromide, and propargyl iodide are preferred. A halogenated hydrocarbon compound having a carbon-carbon double bond at the molecular terminal and a halogenated hydrocarbon compound having a carbon-carbon triple bond may be used in combination. One halogenated hydrocarbon compound having a carbon-carbon double bond at the molecular terminal may be used, or two or more halogenated hydrocarbon compounds may be used in combination. One halogenated hydrocarbon compound having a carbon-carbon triple bond may be used, or two or more halogenated hydrocarbon compounds may be used in combination.

[0081] Next, a reactive silicon group -SiR represented by the above formula 1 is bonded to the carbon-carbon double bond at the molecular terminal of the alkenyloxy group or the carbon-carbon triple bond of the alkynyloxy group. a X 3-a The alkenyloxy group or alkynyloxy group is converted into a group having a reactive silicon group represented by the above formula 1 by reacting with a silylating agent capable of introducing the following:

[0033] Examples of the silylating agent include compounds having both a group capable of reacting with an unsaturated group to form a bond (e.g., a sulfanyl group) and a reactive silicon group represented by the above formula 1, hydrosilane compounds (e.g., HSiR a X 3-a, R, X, and a are the same as in formula 1 above). Specific examples include dimethoxymethylsilane, diethoxymethylsilane, dimethoxyethylsilane, methyldiisopropoxysilane, (α-chloromethyl)dimethoxysilane, (α-chloromethyl)diethoxysilane, trimethoxysilane, triethoxysilane, triisopropoxysilane, tris(2-propenyloxy)silane, triacetoxysilane, and 3-mercaptopropyltrimethoxysilane. In view of high activity and good curability, trimethoxysilane, dimethoxymethylsilane, and diethoxymethylsilane are preferred, and dimethoxymethylsilane is more preferred.

[0082] In the method (b1), a silylating agent is reacted with the polyether compound A. It is preferable to use an isocyanate silane compound represented by the following formula 3 as the silylating agent. OCN-(CH2) n -SiR a X 3-a formula 3 -SiR in the above formula 3 a X 3-a is the same as in the above formula 1. n is an integer of 1 to 8, and preferably 1 to 3. The reaction between the hydroxyl group of polyether compound A and the isocyanate silane compound converts the hydroxyl group of polyether compound A to -OC(=O)NH-(CH2) n -SiR a X 3-a The urethane bond (-OC(=O)NH-) and -SiR a X 3-a is converted to an end group having the formula: Examples of the isocyanate silane compound include 3-isocyanate propyl trimethoxy silane, 3-isocyanate propyl triethoxy silane, isocyanate methyl trimethoxy silane, isocyanate methyl triethoxy silane, 3-isocyanate propyl methyl dimethoxy silane, 3-isocyanate propyl methyl diethoxy silane, isocyanate methyl methyl dimethoxy silane, and isocyanate methyl methyl diethoxy silane. As the isocyanate silane compound, 3-isocyanate propyl trimethoxy silane, 3-isocyanate propyl triethoxy silane, 3-isocyanate propyl methyl dimethoxy silane, isocyanate methyl methyl dimethoxy silane, and isocyanate methyl trimethoxy silane are preferred in view of their reactivity with polyether compound A and ease of handling.

[0083] The active hydrogen of the polyether compound A reacts with the isocyanate group of the isocyanate silane compound represented by the above formula 3, thereby introducing a reactive silicon group into the polyether compound A. When the active hydrogen-containing group of the polyether compound A is a hydroxyl group, the polyoxyalkylene chain (-(R 5 O) m -, R 5 represents an alkylene group, and m represents the number of moles of oxyalkylene groups.) to which a reactive silicon group is bonded via a urethane bond and an organic group is obtained. 5 O) m -C(=O)NH-(CH2) n -SiR a X 3-a A linking structure represented by the following formula is formed.

[0084] This reaction may be carried out in the presence of a urethanization catalyst. The urethanization catalyst is not particularly limited, and known urethanization catalysts can be used as appropriate. Examples include organotin compounds such as dibutyltin dilaurate and dioctyltin dilaurate, metal catalysts such as bismuth compounds, and base catalysts such as organic amines. The reaction temperature is preferably 20 to 200°C, more preferably 50 to 150°C. The urethanization reaction is preferably carried out under an inert gas atmosphere. Nitrogen is preferred as the inert gas.

[0085] The molar ratio of the total number of isocyanate groups in the isocyanate silane compound represented by the above formula 3 to the total number of active hydrogens in polyether compound A is preferably set according to the number of reactive silicon groups per molecule of the polyether compound B to be obtained. It is preferable to react the isocyanate silane compound represented by the above formula 3 so that the number of reactive silicon groups per molecule of the resulting polyether compound B is at least 0.7. For example, when the active hydrogen-containing group of polyether compound A is a hydroxyl group, NCO / OH, which represents the molar ratio of the total number of isocyanate groups (NCO) of the isocyanate silane compound represented by formula 3 above to the total number of active hydrogens (total number of hydroxyl groups) of polyether compound A, is preferably 0.7 to 1.0, more preferably 0.8 to 1.0, and even more preferably 0.9 to 1.0. When NCO / OH is at least the lower limit, the strength of the cured product is excellent, and when it is at most the upper limit, the elongation of the cured product is excellent.

[0086] In method (c1), a polyisocyanate compound is reacted with the hydroxyl groups of polyether compound A to convert the hydroxyl groups into monovalent organic groups containing an isocyanate group (hereinafter also referred to as "isocyanate-containing groups") that have a urethane bond (-O-C(=O)NH-) at the bond terminal with polyether compound A. Next, a silylating agent having a functional group reactive with an isocyanate group and a reactive silicon group represented by formula 1 above is reacted with the isocyanate-containing group to form a terminal group that is a monovalent organic group (hereinafter also referred to as "urethane bond- and reactive silicon-group-containing group") that has one or more urethane bonds (-O-C(=O)NH-) and a silylating agent residue that has reacted with an isocyanate group. Hereinafter, method (c1) will be described assuming that the polyisocyanate compound is a diisocyanate compound represented by the following formula 4, and that the silylating agent having a functional group reactive with an isocyanate group and a reactive silicon group represented by the above formula 1 is a compound represented by the following formula 5, but the present invention is not limited thereto.

[0087] OCN-R 3 -NCO formula 4 R in the above formula 4 3represents a divalent organic group.

[0088] WR 4 -SiR a X 3-a formula 5 In the above formula 5, W is a functional group (a group having one or more active hydrogen atoms) capable of reacting with a monovalent isocyanate group, R 4 is a divalent organic group, -SiR a X 3-a is the same as Equation 1 above.

[0089] When the hydroxyl group of the polyether compound A is reacted with the diisocyanate compound represented by the above formula 4, the isocyanate-containing group is -OC(=O)NH-R 3 When the isocyanate-containing group is reacted with the silylating agent represented by formula 5, the urethane bond and the reactive silicon-containing group are converted to a group represented by -OC(=O)NH-R 3 -NHC(=O)-W'-R 4 -SiR a X 3-a (wherein W' is a divalent group obtained by removing one active hydrogen from W). For example, when W is a hydroxyl group, the urethane bond and reactive silicon group-containing group are represented by the formula: -OC(=O)NH-R 3 -NHC(=O)-OR 4 -SiR a X 3-a In this case, the urethane bond and reactive silicon group-containing group have two urethane bonds. For example, when W is an amino group (-NH), the urethane bond and reactive silicon group-containing group are represented by the formula -OC(=O)NH-R 3 -NHC(=O)-NH-R 4 -SiR a X 3-a It is a group represented by the formula:

[0090] R 3is preferably a divalent organic group having 2 to 20 carbon atoms, and examples thereof include an alkylene group, a cycloalkylene group, a bicycloalkylene group, a monocyclic or polycyclic divalent aromatic hydrocarbon group, a divalent group obtained by removing two hydrogen atoms from a cycloalkane having an alkyl group as a substituent, a divalent group obtained by removing two hydrogen atoms from an aromatic hydrocarbon having an alkyl group as a substituent, a divalent group obtained by removing two hydrogen atoms from two or more cycloalkanes which may have an alkyl group as a substituent and are bonded via an alkylene group, and a divalent group obtained by removing two hydrogen atoms from two or more aromatic hydrocarbons which may have an alkyl group as a substituent and are bonded via an alkylene group.

[0091] Examples of the diisocyanate compound represented by the above formula 4 and other polyisocyanate compounds include aromatic polyisocyanates, non-yellowing aromatic polyisocyanates (which refer to compounds that do not have an isocyanate group directly bonded to a carbon atom that constitutes an aromatic ring), aliphatic polyisocyanates, and alicyclic polyisocyanates, as well as urethane-modified products, biuret-modified products, allophanate-modified products, carbodiimide-modified products, and isocyanurate-modified products obtained from the above polyisocyanates.

[0092] Examples of aromatic polyisocyanates include naphthalene-1,5-diisocyanate, polyphenylenepolymethylene polyisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, and 2,6-tolylene diisocyanate. Examples of non-yellowing aromatic polyisocyanates include xylylene diisocyanate and tetramethylxylylene diisocyanate. Examples of the aliphatic polyisocyanate include hexamethylene diisocyanate, 2,2,4-trimethyl-hexamethylene diisocyanate, and 2,4,4-trimethyl-hexamethylene diisocyanate. Examples of alicyclic polyisocyanates include isophorone diisocyanate and 4,4'-methylenebis(cyclohexyl isocyanate). The polyisocyanate compound is preferably one having two isocyanate groups, more preferably hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, or 2,6-tolylene diisocyanate, and even more preferably tolylene diisocyanate because it is easy to obtain tensile strength in the cured product. One type of polyisocyanate compound may be used, or two or more types may be used in combination.

[0093] The functional group capable of reacting with an isocyanate group represented by the above formula 5 and -SiR a X 3-a R in the silylating agent having 4 is preferably a divalent organic group having 1 to 20 carbon atoms, more preferably a group obtained by removing two hydrogen atoms from an aromatic hydrocarbon having 6 to 10 carbon atoms, a group obtained by removing two hydrogen atoms from an aromatic hydrocarbon having 6 to 10 carbon atoms and substituted with an alkyl group having 1 to 4 carbon atoms, a group obtained by removing two hydrogen atoms from a cyclic hydrocarbon having 3 to 10 carbon atoms, or a group obtained by removing two hydrogen atoms from a straight-chain hydrocarbon having 1 to 12 carbon atoms, still more preferably a group obtained by removing two hydrogen atoms from a straight-chain hydrocarbon having 1 to 8 carbon atoms, and particularly preferably a group obtained by removing two hydrogen atoms from a straight-chain hydrocarbon having 1 to 6 carbon atoms. W is preferably a group having one or two active hydrogen atoms selected from the group consisting of a hydroxyl group, a carboxyl group, a sulfanyl group, an amino group, and an amino group in which one hydrogen atom is substituted with an alkyl group having 1 to 6 carbon atoms, and is preferably a hydroxyl group, a sulfanyl group, an amino group, a methylamino group, an ethylamino group, or a butylamino group, and more preferably a hydroxyl group, an amino group, a methylamino group, an ethylamino group, or a butylamino group.

[0094] In the methods (b1) and (c1), the reactive silicon group in the resulting polyether compound B is formed via one or more organic groups represented by the following formula (i): That is, the polyether compound B obtained by methods (b1) and (c1) contains one or more organic groups represented by the following formula (i) per terminal group. Note that the polyether compound B obtained by method (b1) contains only one organic group represented by the following formula (i) per terminal group, while the polyether compound B obtained by method (c1) contains two or more organic groups represented by the following formula (i) per terminal group. -C(=O)NH- Formula (i)

[0095] The organic group (i) is a divalent group derived from a urethane bond or a urea bond. When the isocyanate silane compound represented by the above formula 3 is used as a silylating agent, there is one organic group (i) per terminal group.

[0096] The organic group (i) preferably forms a urethane bond (-OC(=O)NH-, where -O- represents the oxygen atom at the terminal of the polyoxyalkylene chain) with the polyoxyalkylene chain. That is, it is preferable that one organic group (i) is present between the polyoxyalkylene chain and the reactive silicon group in the polyether compound B. When the polyether compound B is produced by the above-mentioned method (b1), the number of organic groups represented by the above formula (i) per terminal group contained in the polyether compound B is one. When the polyether compound B is produced by the method (b1), a polyether compound B with a high silylation rate is easily obtained. When the polyether compound B is produced by the method (b1), a polyether compound B with a narrow molecular weight distribution is easily obtained. The viscosity of the polyether compound B is suppressed, resulting in good workability. When the isocyanate silane compound represented by the above formula 3 contains one isocyanate group and one reactive silicon group, the number of reactive silicon groups per molecule of polyether compound B is the same as the number of groups (i) per molecule.

[0097] The silylation rate of polyether compound B is preferably 50 to 100 mol %, more preferably 60 to 98 mol %. When the silylation rate is at least the lower limit of the above range, the cured product has excellent tensile strength and a high modulus. When the curable composition contains two or more types of polyether compounds B, it is sufficient that the average silylation rate of all the polyether compounds B is within the above range.

[0098] 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 silylation 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 diameter may be, for example, 0.01 μm or more, or 0.1 μm or more. The 50% cumulative light intensity particle diameter is preferably 0.01 to 1.0 μm, more preferably 0.01 to 0.9 μm, and even more preferably 0.1 to 0.8 μm. The peak particle diameter 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 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 diameter may be, for example, 0.01 μm or more, or 0.1 μm or more. The peak particle diameter is preferably 0.01 to 1.0 μm, more preferably 0.01 to 0.9 μm, and even more preferably 0.1 to 0.8 μm. 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.

[0099] <Polyether compound B> The polyether compound B has a reactive silicon group represented by the above formula 1. Polyether compound B is a polyether compound having an average of 1.0 or more terminal groups per molecule and having a reactive silicon group represented by the above formula 1, wherein the terminal group is the above reactive silicon group, an unsaturated group, an isocyanate group, or a hydroxyl group.

[0100] Polyether compound B has an average of 1.0 or more terminal groups per molecule. The average number of terminal groups is preferably 1.0 to 8.0, more preferably 2.0 to 6.0, and even more preferably 2.0 to 4.0, since this results in a cured product with higher tensile strength and better modulus and elongation. The number of terminal groups of polyether compound B is the same as the number of terminal groups of polyether compound A. The terminal groups of polyether compound B have any of the reactive silicon group, unsaturated group, isocyanate group, or hydroxyl group represented by formula 1 above. The respective terminal groups may be the same or different.

[0101] The average number of reactive silicon groups represented by the above formula 1 per terminal group of polyether compound B is preferably 0.5 to 2.0, more preferably 0.60 to 1.94. When the average number of reactive silicon groups is at least the above lower limit, the crosslinking density due to siloxane bonds increases, making it possible to obtain a good cured product with a high modulus.

[0102] The average number of reactive silicon groups represented by the above formula 1 per molecule of polyether compound B is preferably 0.6 to 8.0, more preferably 0.8 to 6.0, and even more preferably 1.2 to 4.0. When the average number of reactive silicon groups is equal to or greater than the above lower limit, the crosslinking density due to siloxane bonds increases, making it possible to obtain a good cured product with a high modulus.

[0103] The Mn of the polyether compound B is preferably 500 to 100,000, more preferably 1,000 to 100,000, even more preferably 1,500 to 80,000, and particularly preferably 2,000 to 60,000. When Mn is equal to or greater than the lower limit, the elongation properties of the cured product are improved. When Mn is equal to or less than the upper limit, the viscosity is low and workability is improved.

[0104] The Mw / Mn of the polyether compound B is preferably 1.00 to 1.50, more preferably 1.00 to 1.45, even more preferably 1.00 to 1.40, and most preferably 1.00 to 1.20. 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.

[0105] 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 70,000 mPa·s, and even more preferably 400 to 30,000 mPa / s. When the viscosity is equal to or less than the above upper limit, handling is excellent.

[0106] (Curable composition containing polyether compound B) The polyether compound B is used in a curable composition. The curable composition is obtained by mixing the polyether compound B with other necessary components. 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 curable composition is preferably 1 to 90 mass%, more preferably 10 to 80 mass%, and even more preferably 20 to 70 mass%. When it is equal to or less than the upper limit of the above range, the cured product has better tensile strength and elongation properties.

[0107] Examples of other components contained in the curable composition include curable compounds other than polyether compound B, such as epoxy resins, epoxy resin curing agents, curing catalysts (silanol condensation catalysts), fillers, plasticizers, thixotropy-imparting agents, stabilizers, adhesion-imparting agents, physical property adjusters, dehydrating agents, adhesion-imparting resins, reinforcing materials such as fillers, surface modifiers, flame retardants, foaming agents, solvents, and silicates. Other components can be used in combination without limitation with conventionally known components described in International Publication No. 2013 / 180203, International Publication No. 2014 / 192842, International Publication No. 2016 / 002907, JP 2014-88481 A, JP 2015-10162 A, JP 2015-105293 A, JP 2017-039728 A, JP 2017-214541 A, etc. Two or more types of each component may be used in combination.

[0108] The curable composition may be a one-component type in which polyether compound B and all other components are mixed in advance, sealed, and stored, and then cured by moisture in the air after application, or a two-component type in which a base composition containing at least polyether compound B and a curing agent composition containing at least a curing catalyst are stored separately, and the curing agent composition and the base composition are mixed before use. The one-component curable composition preferably does not contain water. It is preferable that the components containing water are dehydrated and dried in advance, or that the components are dehydrated under reduced pressure during mixing and kneading. In the two-component curable composition, the curing agent composition may contain water. The base 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 in advance. In order to improve storage stability, a dehydrating agent may be added to the one-component curable composition or the two-component base composition.

[0109] (Use of curable composition containing polyether compound B) Suitable applications of the curable 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), and electrical insulating materials (insulating coating materials for electric wires and cables).

[0110] The method for producing a polyether compound having a reactive silicon group of the present invention converts the hydroxyl group of the hydroxyl-containing polyether compound in a composition containing a polyether compound having a hydroxyl group and a composite metal cyanide complex catalyst into a group having the reactive silicon group. The 50% cumulative light intensity particle size of the composition, 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, is 1.0 μm or less, thereby improving filterability. Furthermore, the filterability of a composition containing a polyether compound having a reactive silicon group produced using the composition is also improved. The 50% cumulative light intensity particle size is thought to be affected by the physical properties of the composite metal cyanide complex catalyst used in producing a polyether compound having a hydroxyl group. Specifically, when the composite 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 composite metal cyanide complex catalyst is 10% by volume or less, the 50% cumulative light intensity particle size of the resulting composition is likely to be 1.0 μm or less. In addition, the (D 90 -D 10 ) / D 50 , D 90 / D 10 By controlling the above parameters, it becomes easier to further reduce the 50% cumulative light intensity particle size of the resulting composition.

[0111] The present inventors produced polyether compounds having hydroxyl groups and polyether compounds having reactive silicon groups using conventionally known DMC catalysts and purified them by filtration, but found problems such as slow filtration rates and clogging. Therefore, it can be concluded that compositions containing polyether compounds having hydroxyl groups produced by conventionally known methods do not have a 50% cumulative light intensity particle size of 1.0 μm or less, as determined from a light intensity-based cumulative particle size distribution in the 0.1 to 6.5 μm range obtained by dynamic light scattering particle size distribution measurement. Furthermore, conventionally known DMC catalysts have 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 laser diffraction scattering, and the content of particles having a particle size of 11 μm or more relative to the total volume of the DMC catalyst is thought to be greater than 10% by volume. In particular, conventionally known DMC catalysts do not have a content of particles having a particle size of 11 μm or more relative to the total volume of the DMC catalyst of 10% by volume or less. The characteristic that the content of particles having a particle diameter of 11 μm or more relative to the total volume of the DMC catalyst is 10% by volume or less can be determined by a laser diffraction scattering method, as will be described below, but it is extremely difficult (impossible to determine) to determine this by observation with an electron microscope such as a scanning electron microscope.

[0112] For example, consider a spherical particle with a diameter of 1 μm (hereinafter also referred to as "Particle A") and a spherical particle with a diameter of 11.1 μm (hereinafter also referred to as "Particle B"). In this case, the volume of Particle A is 0.52 μm. 3 ((4π / 3)×0.5 3 ) and the volume of particle B is 716 μm 3 ((4π / 3)×5.55 3 ), and the volumes are significantly different. Suppose particle A is 89% by volume and particle B is 11% by volume. If the number of particle A is X and the number of particle B is Y, then (0.52 μm 3 ×X pieces) / (716μm 3Since the equation (X / Y) = 89 / 11 holds, X / Y = 11141. In other words, even if there are 11141 particles A and 1 particle B, the requirement that "the content of particles having a particle diameter of 11 μm or more is 10% by volume or less" is not met. On the other hand, when there are 11141 particles A and 1 particle B, observation with an electron microscope such as a scanning electron microscope is sufficient to determine that the particles are "uniform particles having a particle diameter of 1 μm." From this perspective, even if the level is such that "the particle size uniformity is high" when observed with an electron microscope such as a scanning electron microscope, it is unclear whether the characteristic that "the content of particles having a particle diameter of 11 μm or more is 10% by volume or less" is met. If the particle diameter of particle A is assumed to be 2.5 μm, the X / Y ratio calculated above is 706. In this case, there are 706 particles A and 1 particle B, which is also a sufficient level for determining that the particles are "uniform particles with a particle diameter of 2.5 μm." Furthermore, when observing with an electron microscope such as a scanning electron microscope, the size of particles outside the selected field of view is not taken into account. In the above, the particle diameter of particle B was set to 11.1 μm, which is near the lower limit, but if this particle diameter were increased, X / Y would become even larger. [Example]

[0113] The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following descriptions.

[0114] [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.

[0115] [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.

[0116] [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."

[0117] [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.

[0118] [Total unsaturation] The total degree of unsaturation of polyether compound A was measured in accordance with JIS K 1557-3:2007.

[0119] [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.

[0120] [Number of reactive silicon groups] The number of reactive silicon groups (silylation rate) contained in polyether compound B was measured by the internal standard method of 1H-NMR.

[0121] [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 reactive silicon group-containing polyether compound and 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 mixture was allowed to naturally filter 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 3.00 g or more, the filterability was judged to be good, and if the amount of filtered sample was less than 3.00 g, the filterability was judged to be poor.

[0122] [Stretching durability] The test was conducted in accordance with the fatigue resistance classification CR90 of the fatigue resistance test described in 5.22 of JIS A 1439:2016. The adherend used was anodized aluminum whose surface had been treated with a primer (MP-2000, a product name of Cemedine Co., Ltd.). The modulus, which is the stress at 50% elongation (shown as "M50" in Table 6, unit: N / mm 2 ), and the tensile strength, which is the maximum cohesive strength (referred to as "Tmax" in Table 6. Unit: N / mm 2The elongation at maximum point (represented as "Emax" in Table 6, unit: %) was measured. Cracks in the cured product near the adhesive interface between the adherend and the cured product were observed every 500 stretches, and the number of stretches (represented as "durability" in Table 6, unit: times) at which the cracks reached 2.5 mm or more was recorded. The higher the number of stretches, the better the stretch durability.

[0123] [Tensile properties] One part by mass of dibutyltin dilaurate was added to 100 parts by mass of the polyether compounds obtained in Examples 1 to 6, and after thorough mixing and vacuum degassing, the mixture was applied to a film with a thickness of 100 μm using an applicator. The mixture was then cured at 23°C and a relative humidity of 50% for 5 days and at 50°C for 3 days to obtain dumbbell-shaped test pieces of size 3 as the cured product. In accordance with JIS K 6251:2017, a tensile test was conducted using the above test specimens at a tensile speed of 100 mm / min, in accordance with the tensile test method for vulcanized rubber, and the stress at 50% elongation (shown as "M50" in Table 2, unit: MPa), maximum tensile strength (shown as "tensile strength" in Table 2, unit: MPa), and maximum elongation (shown as "elongation" in Table 2, unit: %) were measured. The higher the M50 and tensile strength values, the higher the tensile strength. The higher the elongation value, the better the elongation properties.

[0124] [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.

[0125] [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%.

[0126] [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%.

[0127] [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%.

[0128] [Table 1]

[0129] [Manufacturing Example 5] Polyoxypropylene diol (hereinafter also referred to as "polyol P2") was obtained by polymerizing propylene glycol with PO in the presence of a KOH catalyst and then dealkalizing and refining the mixture to obtain a polyoxypropylene diol. Polyol P2 had an average hydroxyl group number of 2 per molecule and an Mn of 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 Production Examples 6 to 12 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 Production Examples 6 to 10 below).

[0130] [Manufacturing Example 6] A composition containing a hydroxyl group-containing polyether compound A-2, a TBA-DMC catalyst, and a stabilizer was obtained in the same manner as in Production Example 5, 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.

[0131] [Manufacturing Example 7] A composition containing a hydroxyl group-containing polyether compound A-3, a TBA-DMC catalyst, and a stabilizer was obtained in the same manner as in Production Example 5, except that TBA-DMC catalyst slurry B was used instead of TBA-DMC catalyst slurry A.

[0132] [Manufacturing Example 8] A composition containing polyether compound A-4 having a hydroxyl group, a TBA-DMC catalyst, and a stabilizer was obtained in the same manner as in Production Example 7, except that 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.

[0133] [Manufacturing Example 9] A composition containing a hydroxyl group-containing polyether compound A-5, a TBA-DMC catalyst, and a stabilizer was obtained in the same manner as in Production Example 5, except that TBA-DMC catalyst slurry C was used instead of TBA-DMC catalyst slurry A.

[0134] [Manufacturing Example 10] A composition containing a hydroxyl group-containing polyether compound A-6, a TBA-DMC catalyst, and a stabilizer was obtained in the same manner as in Production Example 5, except that TBA-DMC catalyst slurry D was used instead of TBA-DMC catalyst slurry A.

[0135] [Manufacturing Example 11] Using polyol P2 as an initiator, 14,300 g of PO was polymerized in the presence of TBA-DMC catalyst slurry A to obtain a composition containing hydroxyl-containing polyether compound A-7, a TBA-DMC catalyst, and a stabilizer. The polymerization was carried out with the addition of 0.1% by mass of Irganox 1076 (manufactured by BASF) as a stabilizer. The amount of TBA-DMC catalyst slurry A used was such that the concentration of the TBA-DMC catalyst was 50 ppm by mass relative to the total mass of hydroxyl-containing polyether compound A-7.

[0136] [Manufacturing Example 12] A composition containing polyether compound A-8 having hydroxyl groups, a TBA-DMC catalyst, and a stabilizer was obtained in the same manner as in Production Example 11, except that in the production of polyether compound A having hydroxyl groups, TBA-DMC catalyst slurry B was used instead of TBA-DMC catalyst slurry A.

[0137] [Table 2]

[0138] Below, Examples 1 and 2 are working examples, Examples 3 to 6 are comparative examples, and Examples 7 and 8 are reference examples.

[0139] [Example 1] To 150 g of the hydroxyl-containing polyether compound A-1 obtained in Production Example 5 in a composition containing the hydroxyl-containing polyether compound A-1, a TBA-DMC catalyst, and a stabilizer, 0.0075 g of Neostan U-860 manufactured by Nitto Kasei Co., Ltd. and 14.5 g of 3-isocyanatopropyltriethoxysilane (NCO content: 20.5% by mass) were added and reacted at 80°C for 3 hours. The molar ratio of the amount of isocyanate in 3-isocyanatopropyltriethoxysilane to the amount of hydroxyl groups in the hydroxyl-containing polyether compound A-1, NCO / OH, was 0.97. The reaction was terminated when the absence of absorption due to NCO was confirmed by IR. The Mn, Mw, Mw / Mn, viscosity, and silylation rate of the resulting reactive silicon-containing polyether compound B-1 are shown in Table 3 (the same applies to Examples 2 to 6 below). The resulting reactive silicon group-containing polyether compound B-1 was subjected to a filterability test and an evaluation of tensile properties, and the results are shown in Table 3 (the same applies to Examples 2 to 6 below).

[0140] [Example 2] Polyether compound B-2 having a reactive silicon group was obtained in the same manner as in Example 1, except that the composition containing polyether compound A-2 having a hydroxyl group, a TBA-DMC catalyst, and a stabilizer obtained in Production Example 6 was used instead of the composition containing polyether compound A-1 having a hydroxyl group, a TBA-DMC catalyst, and a stabilizer.

[0141] [Example 3] Polyether compound B-3 having a reactive silicon group was obtained in the same manner as in Example 1, except that the composition containing polyether compound A-3 having a hydroxyl group, TBA-DMC catalyst, and stabilizer obtained in Production Example 7 was used instead of the composition containing polyether compound A-1 having a hydroxyl group, TBA-DMC catalyst, and stabilizer.

[0142] [Example 4] Polyether compound B-4 having a reactive silicon group was obtained in the same manner as in Example 1, except that the composition containing polyether compound A-4 having a hydroxyl group, TBA-DMC catalyst, and stabilizer obtained in Production Example 8 was used instead of the composition containing polyether compound A-1 having a hydroxyl group, TBA-DMC catalyst, and stabilizer.

[0143] [Example 5] Polyether compound B-5 having a reactive silicon group was obtained in the same manner as in Example 1, except that the composition containing polyether compound A-5 having a hydroxyl group, TBA-DMC catalyst, and stabilizer obtained in Production Example 9 was used instead of the composition containing polyether compound A-1 having a hydroxyl group, TBA-DMC catalyst, and stabilizer.

[0144] [Example 6] Polyether compound B-6 having a reactive silicon group was obtained in the same manner as in Example 1, except that the composition containing polyether compound A-6 having a hydroxyl group, a TBA-DMC catalyst, and a stabilizer obtained in Production Example 10 was used instead of the composition containing polyether compound A-1 having a hydroxyl group, a TBA-DMC catalyst, and a stabilizer.

[0145] [Table 3]

[0146] [Example 7] A composition containing the hydroxyl-containing polyether compound A-7 obtained in Production Example 11, a TBA-DMC catalyst, and a stabilizer was prepared. To the hydroxyl groups of the hydroxyl-containing polyether compound A-7, 1.05 molar equivalents of sodium methoxide in methanol was added to alcoholate the hydroxyl-containing polyether compound A-7. The methanol was then distilled off under reduced pressure, and an excess amount of allyl chloride relative to the amount of hydroxyl groups in the hydroxyl-containing polyether compound A-7 was added to convert the terminal groups to allyloxy groups. Next, in the presence of hexachloroplatinic acid (IV) hexahydrate, 0.77 molar equivalents of dimethoxymethylsilane were added relative to the converted allyloxy groups of the hydroxyl-containing polyether compound A-7, and the mixture was allowed to react at 70°C for 5 hours to obtain reactive silicon-containing polyether compound B-7. The Mn, Mw, Mw / Mn, and silylation rate of the resulting reactive silicon-containing polyether compound B-7 are shown in Table 6 (the same applies to Example 8 below).

[0147] [Example 8] Polyether compound B-8 having a reactive silicon group was obtained in the same manner as in Example 7, except that the composition containing polyether compound A-8 having a hydroxyl group, a TBA-DMC catalyst, and a stabilizer obtained in Production Example 12 was used instead of the composition containing polyether compound A-7 having a hydroxyl group, a TBA-DMC catalyst, and a stabilizer.

[0148] (Other ingredients) The additives listed in Tables 4 and 5 are as follows: White Glazing CCR: Colloidal calcium carbonate, product name of Shiraishi Kogyo Co., Ltd. Whiten SB: Heavy calcium carbonate, product name of Shiraishi Kogyo Co., Ltd. R820: Titanium oxide, Ishihara Sangyo Kaisha product name. PREMINOL S 4012: AGC product name for a high molecular weight polyol with two hydroxyl groups per molecule and an Mn of 13,000. Sanso Cizer EPS: 4,5-epoxycyclohexane-1,2-dicarboxylic acid-di-2-ethylhexyl, product name of New Japan Chemical Co., Ltd. Disparlon 305: Hydrogenated castor oil-based thixotropic agent, product name of Kusumoto Chemicals. Balloon 80GCA: Organic balloon, product name of Matsumoto Oil Co., Ltd. M309: Aronix M-309: Photocurable resin, product name of Toagosei Co., Ltd. KBM-403: 2-glycidyloxypropyltrimethoxysilane, product name of Shin-Etsu Chemical Co., Ltd. IRGANOX1135: Hindered phenolic antioxidant, BASF product name. TINUVIN326: Benzotriazole-based UV absorber, product name of BASF. Tung oil: Air oxidation curing compound, manufactured by Kimura Company. Stannoct: Stannous octylate, Yoshitomi Pharmaceutical's product name. Laurylamine: Reagent, manufactured by Junsei Chemical Co., Ltd. DINP: Sanso Cizer DINP, diisononyl phthalate, product name of New Japan Chemical Co., Ltd. Glomax LL: Calcined kaolin, product name of Takehara Chemical Industry Co., Ltd.

[0149] [Table 4]

[0150] [Table 5]

[0151] <Preparation of Curable Composition> A base composition was prepared by mixing 100 parts by mass of the reactive silicon group-containing polyether compounds B-7 and B-8 obtained in Examples 7 and 8 with the additives in the amounts (parts by mass) shown in Table 4. This base composition was mixed with the curing agent composition in the amounts shown in Table 5, and the stretch durability was evaluated. The results are shown in Table 6.

[0152] [Table 6]

[0153] As shown in Table 3, 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 silylation reaction, the particle size in the reaction solution during the production of polyether compound B having reactive silicon groups 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 50 In 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 was effective. Furthermore, it was found that Examples 1 and 2 provided cured products with superior strength and elongation compared to Examples 3 to 6. Furthermore, as shown in Table 6, it was found that Example 7 provided cured products with improved stretch durability compared to Example 8.

Claims

1. A method for producing a polyether compound having a reactive silicon group, comprising converting a hydroxyl group of the polyether compound having a hydroxyl group in a composition containing the polyether compound having a hydroxyl group and a double metal cyanide complex catalyst into a group having a reactive silicon group represented by the following formula 1: the composite metal cyanide complex catalyst is in particulate form; the composition has a 50% cumulative light intensity particle size of 1.0 μm or less, as determined from a 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. -SiR ａ X ３－ａ Formula 1 In the formula 1, R represents a monovalent organic group having 1 to 20 carbon atoms other than a hydrolyzable group, and X represents a hydroxyl group, a halogen atom, or a hydrolyzable group. a is an integer of 0 to 2. When a is 2, R may be the same or different from each other, and when a is 0 or 1, X may be the same or different from each other.

2. 2. The method for producing a polyether compound having a reactive silicon group according to claim 1, wherein the composition has a peak particle size of 1.0 μm or less, as determined from a 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.

3. 3. The method for producing a polyether compound having a reactive silicon group according to claim 1, wherein the composition has a 50% cumulative volume particle size of 0.1 to 100 nm as determined from a volume-based cumulative particle size distribution obtained by dynamic light scattering particle size distribution measurement.

4. 3. The method for producing a polyether compound having a reactive silicon group according to claim 1, wherein the polyether compound having a hydroxyl group has a number average molecular weight of 500 to 100,000.

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

15.

6. 3. The method for producing a polyether compound having a reactive silicon group according to claim 1, wherein the content of the composite metal cyanide complex catalyst relative to the total mass of the polyether compound having a hydroxyl group is 1 to 200 ppm by mass.

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