Method for producing polyether compounds having reactive silicon groups

Abstract

To provide a method for producing polyether compounds having reactive silicon groups that have lower viscosity. [Solution] A method for producing a polyether compound having reactive silicon groups, comprising polymerizing an alkylene oxide having 2 to 12 carbon atoms in an initiator having active hydrogen in the presence of a complex metal cyanide catalyst powder to obtain a polyether compound having hydroxyl groups, and converting the hydroxyl groups of the polyether compound having hydroxyl groups into groups having reactive silicon groups, wherein when A1 is the ratio of the mass decrease of the complex metal cyanide catalyst powder relative to the total mass at 30 to 150°C and A2 is the ratio of the mass decrease of the complex metal cyanide catalyst powder relative to the total mass at 150 to 220°C, as measured by simultaneous thermogravimetric-differential thermal analysis, A1 / A2 is 0.5 or less.

Description

Technical Field

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

Background Art

[0002] It is known that a polyether compound having a reactive silicon group has the property that even at room temperature, it crosslinks by forming a siloxane bond accompanied by a hydrolysis reaction of the reactive silicon group due to moisture or the like, and a rubbery cured product can be obtained. Therefore, polyether compounds having a reactive silicon group have already been industrially produced and are widely used in applications such as sealing materials and adhesives.

[0003] Polyether compounds having a reactive silicon group are produced using polyether compounds having a hydroxyl group as a raw material. Polyether compounds having a hydroxyl group are produced by polymerizing an alkylene oxide with an initiator having an active hydrogen. A double metal cyanide complex catalyst is known as a polymerization catalyst for obtaining a polyether compound having a narrow molecular weight distribution and low viscosity.

[0004] Patent Document 1 discloses a method for producing a hydrolyzable silyl group-containing polyoxyalkylene (B) including a step of subjecting a monoepoxide having a water content of 5 ppm or more and less than 50 ppm to ring-opening polymerization to obtain a hydroxyl group-containing polyoxyalkylene (A), and a step of introducing a hydrolyzable silyl group into the hydroxyl group-containing polyoxyalkylene (A). It is also described that the step of obtaining the hydroxyl group-containing polyoxyalkylene (A) is carried out in the presence of a double metal cyanide complex catalyst.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

[0006] However, according to the inventors' research, the viscosity of the polyether compound having a reactive silicon group (polyoxyalkylene containing a hydrolyzable silyl group) produced by the method described in Patent Document 1 is not sufficiently low, which may lead to poor workability.

[0007] The present invention has been made in view of the above circumstances, and aims to provide a method for producing a polyether compound having reactive silicon groups that can produce a polyether compound having reactive silicon groups with lower viscosity. [Means for solving the problem]

[0008] The present invention provides the following means. [1] A method for producing a polyether compound having reactive silicon groups, comprising polymerizing an alkylene oxide having 2 to 12 carbon atoms in an initiator having active hydrogen in the presence of a complex metal cyanide catalyst powder to obtain a polyether compound having hydroxyl groups, and converting the hydroxyl groups of the polyether compound having hydroxyl groups to groups having reactive silicon groups represented by the following formula 1, wherein A1 is the ratio of the mass decrease of the complex metal cyanide catalyst powder at 30 to 150°C as measured by simultaneous thermogravimetric-differential thermal analysis, and A2 is the ratio of the mass decrease of the complex metal cyanide catalyst powder at 150 to 220°C as measured by simultaneous thermogravimetric-differential thermal analysis, and A1 / A2 is 0.5 or less. -SiR a X 3-a formula 1 In Formula 1 above, R represents a monovalent organic group having 1 to 20 carbon atoms, excluding hydrolyzable groups, and X represents a hydroxyl group or a hydrolyzable group. a is an integer from 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 organic ligand of the composite metal cyanide complex catalyst powder is either ethylene glycol dimethyl ether or tert-butyl alcohol or both. [3] A method for producing a polyether compound having a reactive silicon group according to [1] or [2], wherein the percentage of the mass of the composite metal cyanide complex catalyst powder that decreases at 30 to 100°C, as measured by simultaneous thermogravimetric-differential thermal analysis, is 1.5% by mass or less. [4] The method for producing a polyether compound having a reactive silicon group according to any one of [1] to [3], wherein the number of hydroxyl groups per molecule of the polyether compound having a hydroxyl group is 1 to 8. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a method for producing polyether compounds having reactive silicon groups that have even lower viscosity. [Modes for carrying out the invention]

[0010] The meanings and definitions of terms used in this specification are as follows: A numerical range represented by "~" means a range of numbers whose lower and upper limits are the numbers before and after the "~".

[0011] The thermogravimetric and differential thermal analysis of complex metal cyanide catalyst powders can be performed using a thermogravimetric and differential thermal analysis apparatus. Examples of measurement and analysis conditions include the following: Specifically, the mass loss of the complex metal cyanide catalyst powder is calculated within the temperature range specified in the cumulative range of each volatile component. Temperature range: 30℃~450℃ Heating rate: 10℃ / min Atmospheric gas: Nitrogen (50 mL / min) Sample amount: 10 mg Cumulative range of volatile components: 30℃~100℃, 30℃~150℃, 150℃~220℃, 100℃~200℃, 150℃~200℃, 30℃~220℃

[0012] The "units" that make up polyether compounds containing hydroxyl groups refer to atomic groups directly formed by the polymerization of monomers. The term "main chain" refers to a polymer chain formed by the polymerization of two or more monomers. In the case of polyether compounds having hydroxyl groups and polyether compounds having reactive silicon groups, as described later, the "main chain" refers to the portion containing the residues obtained by removing the active hydrogen from the initiator and repeating units based on alkylene oxide (polyoxyalkylene chain). Polyether compounds having hydroxyl groups and polyether compounds having reactive silicon groups are polymers consisting of a main chain and terminal groups. In polyether compounds having hydroxyl groups and polyether compounds having reactive silicon groups, the "end group" refers to the group of atoms containing the oxygen atom closest to the end of the molecule among the oxygen atoms in the polyoxyalkylene chain described above. However, if the group of atoms contains a residue of the initiator, it is not considered an end group but rather part of the main chain. The "number of end groups" in polyether compounds having hydroxyl groups and polyether compounds having reactive silicon groups is the same as the number of active hydrogen atoms of the initiator, as described later. An "active hydrogen-containing group" is at least one group selected from the group consisting of a hydroxyl group, carboxyl group, amino group, monovalent functional group obtained by removing one hydrogen atom from a primary amine, hydrazide group, and sulfanyl group, all of which are bonded to a carbon atom. "Active hydrogen" refers to hydrogen atoms based on the active hydrogen-containing group described above, and hydrogen atoms based on the hydroxyl group of water.

[0013] The "silylation rate" in a polyether compound containing reactive silicon groups 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 containing reactive silicon groups. Specifically, the silylation rate is calculated using 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 of the added silylation agent to the number of terminal groups when introducing the reactive silicon groups to the terminal groups of a polyether compound having hydroxyl groups using the silylation agent described later. However, in this case, a diisocyanate compound is used as the polyisocyanate compound in method (c1) described later. A "silylation agent" refers to a compound having a functional group that reacts with an active hydrogen-containing group, an unsaturated group, or an isocyanate group, and a reactive silicon 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 the eluent, with a calibration curve created using polystyrene polymers of known molecular weight. The molecular weight distribution (Mw / Mn) is the ratio of Mw to Mn.

[0015] The "hydroxyl value" of polyether compounds containing hydroxyl groups is a value measured in accordance with Method B (phthalation method) described in JIS K 1557-1:2007. The molecular weight on a hydroxyl value basis is calculated as 56,100 / hydroxyl value of the polyether compound having hydroxyl groups × number of hydroxyl groups in the polyether compound having hydroxyl groups (number of active hydrogens of the initiator). Note that if the compound contains two or more polyether compounds having hydroxyl groups with different numbers of hydroxyl groups, the number of hydroxyl groups in the polyether compound having hydroxyl groups is the average number of hydroxyl groups.

[0016] The total degree of unsaturation of polyether compounds containing hydroxyl groups can be measured in accordance with JIS K 1557-3:2007. The viscosity of polyether compounds containing hydroxyl groups and polyether compounds containing reactive silicon groups can be measured using an E-type viscometer in accordance with JIS K 1557-5:2007. Suitable measurement temperatures include 25°C and 40°C.

[0017] Method for producing polyether compounds containing reactive silicon groups In the method for producing a polyether compound having a reactive silicon group according to this embodiment, an alkylene oxide having 2 to 12 carbon atoms is polymerized in an initiator having active hydrogen in the presence of a complex metal cyanide catalyst powder to obtain a polyether compound having a hydroxyl group, and the hydroxyl group of the polyether compound having a hydroxyl group is converted into a group having a reactive silicon group represented by Formula 1 described later. When A1 is the ratio of the mass of the composite metal cyanide complex catalyst powder to its total mass, measured by simultaneous thermogravimetric-differential thermal analysis, and A2 is the ratio of the mass of the composite metal cyanide complex catalyst powder to its total mass, measured at 30-150°C, then A1 / A2 is 0.5 or less.

[0018] Hereinafter, polyether compounds having hydroxyl groups will also be referred to as "polyether compound A," and polyether compounds having reactive silicon groups will also be referred to as "polyether compound B."

[0019] ≪Composite Metal Cyanide Complex Catalyst Powder≫ In this embodiment, the composite metal cyanide complex catalyst powder is measured by simultaneous thermogravimetric-differential thermal analysis, where A1 is the ratio of the mass of the composite metal cyanide complex catalyst powder to its total mass that decreases between 30 and 150°C, and A2 is the ratio of the mass of the composite metal cyanide complex catalyst powder to its total mass that decreases between 150 and 220°C, and A1 / A2 is 0.5 or less.

[0020] The complex metal cyanide catalyst powder (hereinafter also referred to as "DMC catalyst") functions as a polymerization catalyst for alkylene oxides. The DMC catalyst is an amorphous solid and contains reaction products of a metal halide salt and a cyanide transition metal compound, an organic ligand, and water (coordinating water, etc.) encapsulated within the solid. In addition, it may contain trace amounts of impurities unavoidable during manufacturing, which are present in the above-mentioned metal salt and metal compound, as well as water other than coordinating water. Metal halide salts, transition metal cyanide compounds, and organic ligands known in the production of DMC catalysts can be used.

[0021] The DMC catalyst is considered 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) Formula 2 In the above formula 2, M 1 e1 X 1 f1 is a metal halide salt, M 1 is a metal atom that becomes a cation, X 1 is a halogen atom that becomes a counter anion, M 2 is a transition metal contained in the transition metal cyanide compound and is a metal atom that becomes an active site, and Ligand is an organic ligand. a1, b1, c1, d1, e1, f1, g1, h1 are integers, and a1, b1, c1 and e1, f1 are electrically neutral numbers.

[0022] As the above M 1 , examples 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). As the above M 2 , examples include Co(III), Fe(II), Fe(III), Co(II), Co(III), Cr(II), Cr(III), Mn(II), Mn(III), V(IV), and V(V). As the above X 1 , examples include Cl, Br, and I. M 1 e1 X 1 f1The metal halide salt 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 It is more preferable to include one or more selected from zinc chloride and zinc bromide in terms of interatomic distance. Examples of ligands (organic ligands) include alcohols, ethers, esters, aldehydes, ketones, amides, nitriles, sulfides, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and polyoxyalkylene poly(or mono)ols. There may be one or more organic ligands. Examples of alcohols 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. An example of polyoxyalkylene poly(or mono)ol is polypropylene diol. As organic ligands, ethylene glycol dimethyl ether and tert-butyl alcohol are preferred, with tert-butyl alcohol being more preferred.

[0023] A preferred example of a DMC catalyst is zinc hexacyanocobaltate (Zn3[Co(CN)6]2) containing an organic ligand, water, and zinc chloride or zinc bromide. Its chemical formula is thought to be Zn3[Co(CN)6]2·d1(ZnCl2)·g1(Ligand)·h1(H2O) or Zn3[Co(CN)6]2·d1(ZnBr2)·g1(Ligand)·h(H2O).

[0024] As the DMC catalyst, a zinc hexacyanocobaltate (Zn3[Co(CN)6]2) complex with ethylene glycol dimethyl ether or tert-butyl alcohol as a ligand is preferred. Water and zinc chloride may also be coordinated to the above complex.

[0025] When the ratio of the mass of the DMC catalyst to the total mass, measured by simultaneous thermogravimetric-differential thermal analysis, is denoted as A1 mass%, and the ratio of the mass of the DMC catalyst to the total mass, measured at 30-150°C, is denoted as A2 mass%, then A1 / A2 is 0.5 or less, more preferably 0.45 or less, and even more preferably 0.43 or less. As a lower limit for A1 / A2, for example, 0.1 or more is preferred, 0.2 or more is more preferred, and 0.3 or more is even more preferred. When A1 / A2 is within the above range, polyether compound A with a narrow molecular weight distribution and low viscosity is easily obtained. As a result, polyether compound B with a narrow molecular weight distribution and low viscosity is easily obtained.

[0026] A1 is a mass loss originating from components that desorb or decompose at relatively low temperatures. These components have weak interactions with the DMC catalyst and are thought to be mainly adsorbed water and coordinated water. On the other hand, A2 is a mass loss originating from components that desorb or decompose at relatively high temperatures. These components have strong interactions with the DMC catalyst and are thought to be mainly organic ligands. In other words, A1 / A2 can be considered to substantially represent the ratio of the content of adsorbed water and coordinated water to the content of organic ligands in the DMC catalyst. The inventors of this application have found that when the ratio of the content of adsorbed water and coordinated water to the content of organic ligands (A1 / A2) is below a certain value, the activity of the DMC catalyst increases, the molecular weight distribution and viscosity of the resulting polyether compound A decrease, and as a result, the molecular weight distribution and viscosity of polyether compound B also decrease.

[0027] A1 is preferably 2.0 to 4.0% by mass, more preferably 2.2 to 3.9% by mass, and even more preferably 2.4 to 3.9% by mass. If A1 is within the above range, a polyether compound A with a narrow molecular weight distribution and low viscosity is easily obtained. As a result, a polyether compound B with a narrow molecular weight distribution and low viscosity is easily obtained.

[0028] A2 is preferably 6.0 to 10.0% by mass, more preferably 6.5 to 9.5% by mass, and even more preferably 6.6 to 9.4% by mass. If A2 is within the above range, a polyether compound A with a narrow molecular weight distribution and low viscosity is easily obtained. As a result, a polyether compound B with a narrow molecular weight distribution and low viscosity is easily obtained.

[0029] The ratio of the mass of the DMC catalyst to the total mass lost at 30 to 100°C (hereinafter also referred to as "A3"), as measured by simultaneous thermogravimetric-differential thermal analysis, is preferably 1.50 mass% or less, more preferably 1.49 mass% or less, and even more preferably 1.48 mass% or less. The lower limit of A3 is preferably, for example, 0.40 mass% or more, more preferably 0.50 mass% or more, and even more preferably 0.60 mass% or more. If A3 is within the above range, polyether compound A with a narrow molecular weight distribution and low viscosity is easily obtained. As a result, polyether compound B with a narrow molecular weight distribution and low viscosity is easily obtained.

[0030] The percentage of the total mass of the DMC catalyst that decreases at 100-200°C, as measured by simultaneous thermogravimetric-differential thermal analysis (hereinafter also referred to as "A4"), is preferably 5.0-11.0% by mass, more preferably 5.2-10.0% by mass, and even more preferably 5.4-9.9% by mass. If A4 falls within the above range, polyether compound A with a narrow molecular weight distribution and low viscosity is easily obtained. As a result, polyether compound B with a narrow molecular weight distribution and low viscosity is easily obtained.

[0031] The ratio of the mass of the DMC catalyst to the total mass lost at 150-200°C, as measured by simultaneous thermogravimetric-differential thermal analysis (hereinafter also referred to as "A5"), is preferably 4.0-8.0 mass%, more preferably 4.1-7.5 mass%, and even more preferably 4.2-7.0 mass%. If A5 is within the above range, polyether compound A with a narrow molecular weight distribution and low viscosity is easily obtained. As a result, polyether compound B with a narrow molecular weight distribution and low viscosity is easily obtained.

[0032] The ratio of the mass of the DMC catalyst to the total mass that decreases at 30 to 220°C (hereinafter also referred to as "A6"), as measured by simultaneous thermogravimetric-differential thermal analysis, is preferably 8.0 to 14.0 mass%, more preferably 8.5 to 13.5 mass%, and even more preferably 9.0 to 13.2 mass%. When A6 is within the above range, polyether compound A with a narrow molecular weight distribution and low viscosity is easily obtained. As a result, polyether compound B with a narrow molecular weight distribution and low viscosity is easily obtained.

[0033] A1 / A4 is preferably 0.20 to 0.50, more preferably 0.30 to 0.50, and even more preferably 0.35 to 0.50. When A1 / A4 is within the above range, polyether compound A with a narrow molecular weight distribution and low viscosity is easily obtained. As a result, polyether compound B with a narrow molecular weight distribution and low viscosity is easily obtained.

[0034] A1 / A5 is preferably 0.40 to 0.70, more preferably 0.50 to 0.70, and even more preferably 0.55 to 0.70. When A1 / A5 is within the above range, polyether compound A with a narrow molecular weight distribution and low viscosity is easily obtained. As a result, polyether compound B with a narrow molecular weight distribution and low viscosity is easily obtained.

[0035] A1 / A6 is preferably 0.10 to 0.30, more preferably 0.20 to 0.30, and even more preferably 0.22 to 0.30. When A1 / A6 is within the above range, polyether compound A with a narrow molecular weight distribution and low viscosity is easily obtained. As a result, polyether compound B with a narrow molecular weight distribution and low viscosity is easily obtained.

[0036] The DMC catalyst may be used, for example, in the production of polyether compounds in the solid state described above, or in the production of polyether compounds in the form of a slurry (hereinafter also referred to as "slurry catalyst") in which DMC catalyst particles are dispersed in a dispersion medium.

[0037] The slurry catalyst comprises a DMC catalyst and a dispersion medium. The slurry catalyst preferably comprises a DMC catalyst and a dispersion medium, and may also contain impurities and water that are unavoidable during production.

[0038] As the dispersion medium for the slurry catalyst, organic solvents known for slurry catalysts can be used. For example, a non-volatile hydroxyl compound described in Japanese Patent Publication No. 3194255 can be used. The above hydroxyl compound is a hydroxyl group-containing compound having 1 to 8 hydroxyl groups and a molecular weight of 100 to 8000, and compounds having alcoholic hydroxyl groups, such as polyether compounds, are preferred. As a dispersion medium for the slurry catalyst, polyether compounds are preferred because they do not impurity the products of polymerization of alkylene oxides (polyether compound A). The Mn value of the polyether compound used as a dispersion medium is preferably 100 to 8,000, and more preferably 600 to 3,000. If the Mn value is above the lower limit, it is less likely to act as a catalyst poison, and if it is below the upper limit, the slurry catalyst has excellent handling properties. Furthermore, an initiator used in the polymerization of alkylene oxide may be used as part of the dispersion medium.

[0039] The dispersion medium of the slurry catalyst is preferably substantially water-free. Specifically, the amount of water relative to the total mass of the dispersion medium is preferably 500 ppm by mass or less, more preferably 200 ppm by mass or less, and may even be undetectable. The water content of the dispersion medium is the water content measured by the Karl Fischer assay.

[0040] The content of the DMC catalyst relative to the total mass of the slurry catalyst is preferably, for example, 0.001 to 60% by mass, more preferably 0.003 to 50% by mass, and even more preferably 0.006 to 30% by mass. In particular, when the dispersion medium is a polyether compound, the content of the DMC catalyst relative to the total mass of the slurry catalyst is preferably 0.1 to 60% by mass, more preferably 0.5 to 40% by mass, and even more preferably 1 to 30% by mass. In particular, when the dispersion medium contains the above initiator, the content of the DMC catalyst with respect to the total mass of the slurry catalyst is preferably 0.003 to 0.020% by mass, more preferably 0.004 to 0.015% by mass, and even more preferably 0.006 to 0.010% by mass.

[0041] <Method for Producing DMC Catalyst> The DMC catalyst of this 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, it is preferable to perform washing after synthesizing the DMC catalyst.

[0042] 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 liquid containing a DMC catalyst and water. Impurities and water may be removed from the obtained mixed liquid, and the moisture content of the obtained solid may be reduced to a predetermined range to obtain a DMC catalyst.

[0043] Preferable embodiments of the method for producing the DMC catalyst of this embodiment include, for example, the following methods. First, an aqueous solution of a metal halide salt and an aqueous solution of a transition metal cyanide compound are reacted to form a reaction product. An aqueous solution of an organic ligand is added thereto and stirred to coordinate the organic ligand to obtain a mixed liquid containing a DMC catalyst and water. The obtained mixed liquid is subjected to solid-liquid separation to obtain a solid. The obtained solid is washed with a 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 moisture content is within the above specific range and pulverized as necessary.

[0044] 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. Also, it is preferably below the saturation concentration. The concentration of the transition metal cyanide compound in the aqueous solution of the transition metal cyanide compound is preferably 2 to 50% by mass, more preferably 2 to 20% by mass, and even more preferably 3 to 10% by mass. The molar ratio of the metal in the metal halide salt to the transition metal in the cyanide transition metal compound is preferably 1.6 to 12.0, and more preferably 1.8 to 8.0.

[0045] When mixing an aqueous solution of a metal halide salt and an aqueous solution of a cyanide transition metal compound, it is preferable to add the aqueous solution of the cyanide transition metal compound dropwise to an aqueous solution of zinc halide rather than adding the aqueous solution of the metal halide salt dropwise to an aqueous solution of the cyanide transition metal compound. Adding the aqueous solution of the cyanide transition metal compound dropwise to an aqueous solution of zinc halide makes it easier to control the A1 / A2 ratio, etc., within the aforementioned range. The ratio of the dropping rate (mol / hour) of the transition metal in the cyanide transition metal compound to the total amount (mol) of metal derived from the metal halide salt in the aqueous solution of the metal halide salt 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 the above ratio is not particularly limited, but may be 0.01 (mol / hour / mol) or more, or 0.1 (mol / hour / mol) or more. When the above ratio is below the upper limit, it becomes easier to control A1 / A2, etc., within the above range. The dropping time for the aqueous solution of the cyanide transition metal compound is preferably 20 to 180 minutes, more preferably 25 to 150 minutes, and even more preferably 30 to 130 minutes. When the dropping time is within the above range, it becomes easier to control the A1 / A2 ratio, etc., within the aforementioned range.

[0046] When mixing an aqueous solution of a metal halide salt with an aqueous solution of a transition metal cyanide compound, it is preferable to stir thoroughly. Preferred stirring blades include crescent-shaped blades, full-zone blades, and anchor-shaped blades. When using a crescent-shaped blade in a 500 mL flask, the diameter is preferably 60 mm or larger, and more preferably 70 mm or larger.

[0047] The reaction temperature in the reaction between an aqueous solution of a metal halide salt and an aqueous solution of a cyanide transition metal compound is preferably 10 to 65°C, more preferably 20 to 60°C, and even more preferably 30 to 55°C.

[0048] The content of the organic ligand relative to the total mass of 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.

[0049] The temperature for coordinating the organic ligand is preferably 10 to 90°C, more preferably 20 to 80°C, and even more preferably 30 to 70°C.

[0050] The aqueous solution of the organic ligand preferably contains a low molecular weight polyether compound (hereinafter also referred to as "polyether compound a") in addition to the organic ligand and water.

[0051] Polyether compound a is a compound obtained by polymerizing an alkylene oxide with an initiator having active hydrogen. Examples of initiators include those exemplified in the method for producing polyether compounds described later. Examples of polymerization catalysts include alkali metal catalysts. Examples of alkali metal catalysts include alkali metals such as sodium and potassium; alkali metal alkoxides such as sodium methoxide, sodium ethoxide, sodium propoxide, potassium methoxide, potassium ethoxide, and potassium propoxide; hydroxides such as sodium hydroxide, potassium hydroxide, and cesium hydroxide; and carbonates such as sodium carbonate and potassium carbonate.

[0052] The terminal group of polyether compound a is a hydroxyl group. The number of hydroxyl groups in polyether compound a is preferably 2 to 8, more preferably 2 to 6, and even more preferably 2 to 4.

[0053] The Mn of polyether compound a is preferably 400 to 3000, more preferably 500 to 2500, and even more preferably 600 to 1500.

[0054] The hydroxyl value of polyether compound a is preferably 30 to 1200 mg KOH / g, more preferably 40 to 700 mg KOH / g, and even more preferably 70 to 380 mg KOH / g.

[0055] The content of polyether compound a relative to the total mass of the aqueous solution of the organic ligand is preferably 0.3 to 1.5% by mass, more preferably 0.4 to 1.0% by mass, and even more preferably 0.5 to 0.8% by mass. The content of polyether compound a per 100 parts by mass of the total amount of organic ligand and water is preferably 0.4 to 1.2 parts by mass, more preferably 0.5 to 1.1 parts by mass, and even more preferably 0.6 to 1.0 parts by mass. The presence of polyether compound a in the aqueous solution of the organic ligand improves the filterability when filtration is used in solid-liquid separation. Furthermore, it becomes easier to control the A1 / A2 ratio within the aforementioned range.

[0056] After coordinating the organic ligand, it is preferable to perform solid-liquid separation. Solid-liquid separation can be carried out using methods known in this field, such as filtration or centrifugation. The resulting solid contains the DMC catalyst as well as salts (alkali metal halides) produced in the reaction. Therefore, it is preferable to remove the salts by washing the resulting solid. Specifically, a solution of the organic ligand (washing solution) is added to the resulting solid, stirred, and then solid-liquid separation is performed again. The washing time is preferably 10 to 90 minutes, and more preferably 20 to 60 minutes. It is preferable to perform multiple washes.

[0057] In this embodiment, it is preferable to use in combination a cleaning solution containing an organic ligand, water, and the above-mentioned polyether compound a (hereinafter also referred to as "cleaning solution 1") and a cleaning solution containing an organic ligand and the above-mentioned polyether compound a, but without water (hereinafter also referred to as "cleaning solution 2").

[0058] The amount of cleaning solution 1 used per 100 parts by mass of solid to be cleaned is preferably 300 to 1400 parts by mass, more preferably 400 to 1300 parts by mass, and even more preferably 500 to 1200 parts by mass.

[0059] The temperature when washing with cleaning solution 1 is preferably 10 to 50°C, more preferably 20 to 45°C, and even more preferably 20 to 40°C.

[0060] In the case of cleaning solution 1, the content of organic ligands relative to the total mass of the cleaning solution is preferably 10 to 100% by mass, more preferably 20 to 90% by mass, and even more preferably 30 to 80% by mass.

[0061] In the case of washing solution 1, the ratio of ligand content to water content is preferably 0.3 to 1.3, more preferably 0.4 to 1.2, and even more preferably 0.5 to 1.1.

[0062] In the case of cleaning solution 1, the content of polyether compound a relative to the total mass of the cleaning solution is preferably 0.4 to 1.5% by mass, more preferably 0.5 to 1.2% by mass, and even more preferably 0.6 to 1.0% by mass. In the case of washing solution 1, the content of polyether compound a per 100 parts by mass of the total of organic ligand and water is preferably 0.4 to 1.5 parts by mass, more preferably 0.5 to 1.2 parts by mass, and even more preferably 0.6 to 1.0 parts by mass. The inclusion of polyether compound a in washing solution 1 improves filterability when filtration is used in solid-liquid separation. Furthermore, it becomes easier to control the A1 / A2 ratio within the aforementioned range.

[0063] The amount of cleaning solution 2 used per 100 parts by mass of solid to be cleaned is preferably 300 to 800 parts by mass, more preferably 400 to 700 parts by mass, and even more preferably 500 to 600 parts by mass.

[0064] The temperature when washing with cleaning solution 2 is preferably 10 to 50°C, more preferably 15 to 45°C, and even more preferably 20 to 40°C.

[0065] In the case of cleaning solution 2, the content of organic ligands relative to the total mass of the cleaning solution is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, and even more preferably 90 to 100% by mass.

[0066] In the case of cleaning solution 2, the content of polyether compound a relative to the total mass of the cleaning solution is preferably 1.0 to 1.5% by mass, more preferably 1.1 to 1.4% by mass, and even more preferably 1.2 to 1.3% by mass. In the case of washing solution 2, the content of polyether compound a per 100 parts by mass of organic ligand is preferably 1.0 to 1.5 parts by mass, more preferably 1.1 to 1.4 parts by mass, and even more preferably 1.2 to 1.3 parts by mass. The inclusion of polyether compound a in washing solution 2 improves the filterability when filtration is used in solid-liquid separation. Furthermore, it becomes easier to control the A1 / A2 ratio within the aforementioned range.

[0067] In this embodiment, it is preferable to perform washing multiple times. One washing cycle is defined as adding a solution of organic ligands (washing solution) to the obtained solid, stirring, and then performing solid-liquid separation again. It is preferable to use washing solution 2 in the final washing cycle. It is also preferable to use washing solution 1 in washing cycles other than the final one. The inventors of this application have found that by using washing solution 2 in the final washing cycle, it becomes easier to control A1 / A2 within the above-mentioned range. That is, the inventors of this application have found that by washing with washing solution 2, which contains organic ligands and polyether compound a, and does not contain water, and then drying, it becomes easier to control A1 / A2 within the above-mentioned range.

[0068] After the above washing, drying is preferable. The drying temperature is preferably 50 to 100°C, more preferably 55 to 95°C, and even more preferably 60 to 90°C. The drying atmosphere may be an inert gas atmosphere or air. The drying pressure may be atmospheric pressure or reduced pressure. Drying should be carried out at the above drying temperature until no change in mass is detected. No change in mass is detected means that the rate of mass loss relative to the total mass of the dried solid over a period of one hour is 0.1% or less.

[0069] To produce a slurry catalyst, obtain the DMC catalyst as described above, and then add the above-mentioned dispersion medium to the obtained DMC catalyst.

[0070] Method for producing polyether compound A The method for producing polyether compound A in this embodiment involves polymerizing an alkylene oxide having 2 to 12 carbon atoms onto an initiator having active hydrogen in the presence of the above-mentioned DMC catalyst.

[0071] The number of active hydrogen atoms in the initiator is preferably 1 to 8, more preferably 1 to 6, and even more preferably 2 to 6. The number of active hydrogen atoms in the initiator is preferably selected according to the number of hydroxyl groups per molecule of the polyether compound A to be obtained. The number of active hydrogen atoms in the initiator and the number of terminal groups in the polyether compound A are the same. Initiating agents may be used individually or in combination of two or more.

[0072] The initiator preferably has a hydroxyl group as an active hydrogen-containing group. As initiators having one hydroxyl group, monohydric alcohols having a linear or branched hydrocarbon group are preferred. Specifically, examples include 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, and oleyl alcohol. Examples of initiators having two hydroxyl groups include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, triethylene glycol, tripylene glycol, neopentyl glycol, 1,4-butanediol, and 1,6-hexanediol. Water is also cited as 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, low molecular weight polymers obtained by polymerizing alkylene oxides onto these initiators in the presence of alkali metal hydroxides may also be used as initiators. The hydroxyl value of the initiator is preferably, for example, 3 to 850 mg KOH / g, and more preferably 7 to 570 mg KOH / g.

[0073] The alkylene oxide is selected according to the constituent units of the polyoxyalkylene chain of the resulting polyether compound A. The number of carbon atoms in the alkylene oxide is 2 to 12, preferably 2 to 8, and more preferably 2 to 6. Examples of alkylene oxides include ethylene oxide, propylene oxide, 1,2-butylene oxide, and 2,3-butylene oxide. Among these, ethylene oxide and propylene oxide are preferred, and propylene oxide is more preferred.

[0074] When a DMC catalyst is used as a polymerization catalyst, the Mw / Mn ratio of polyether compound A tends to be lower, and the total degree of unsaturation of polyether compound A tends to be lower, compared to when a polymerization catalyst other than a DMC catalyst is used.

[0075] When the polyoxyalkylene chain of polyether compound A is a random copolymer chain consisting of propylene oxide units and ethylene oxide units, a method of obtaining polyether compound A by reacting an initiator with a mixture of propylene oxide and ethylene oxide in the presence of a DMC catalyst is preferred.

[0076] If the polyoxyalkylene chain of polyether compound A is a copolymer chain having a block consisting of propylene oxide units and a block consisting of ethylene oxide units, polyether compound A may be obtained by reacting an initiator with propylene oxide in the presence of a DMC catalyst to obtain a precursor, and then reacting it with ethylene oxide, or by reacting an initiator with ethylene oxide in the presence of a DMC catalyst to obtain a precursor, and then reacting it with propylene oxide, to obtain polyether compound A.

[0077] The amount of DMC catalyst 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. If the amount of DMC catalyst used is above the lower limit, the polymerization reaction proceeds easily. If the amount of DMC catalyst used is below the upper limit, the amount of DMC catalyst used is reduced, making it more economical.

[0078] Polymerization can be carried out in a continuous or batch manner, but it is preferable to carry it out in a batch manner. The polymerization temperature is preferably 30 to 180°C, more preferably 70 to 160°C, and even more preferably 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. It is preferable to supply the alkylene oxide to the reactor at a rate that maintains the above reaction temperature. The reaction atmosphere should preferably be one that is less susceptible to moisture contamination, and an inert gas atmosphere such as nitrogen is more preferable.

[0079] The content of the DMC catalyst relative to the total mass of the reaction solution 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 is determined based on the amount of DMC catalyst used in producing polyether compound A. The content of polyether compound A relative to the total mass of the reaction solution is preferably 98.0% by mass or more, more preferably 99.0% by mass or more, and even more preferably 99.5% by mass or more.

[0080] <Polyether compound A> The main chain of polyether compound A is a polymer chain consisting of residues obtained by removing active hydrogen from an initiator and an oxyalkylene chain containing one or more repeating units based on alkylene oxides (hereinafter, repeating units based on monomers will simply be referred to as "monomer units," for example, repeating units based on alkylene oxides will be referred to as "alkylene oxide units"). If the polymer chain has two or more types of alkylene oxide units, these alkylene oxide units may form block polymers or random polymers. Examples of oxyalkylene chains include polymerization chains having ethylene oxide units, polymerization chains having propylene oxide units, polymerization chains having ethylene oxide units and propylene oxide units, polymerization chains consisting of ethylene oxide units, polymerization chains consisting of propylene oxide units, polymerization chains consisting of butylene oxide units, polymerization chains consisting of tetramethylene oxide units, polymerization chains consisting of ethylene oxide units and propylene oxide units, and polymerization chains consisting of propylene oxide units and butylene oxide units. Polymerization chains having ethylene oxide units, polymerization chains having propylene oxide units, polymerization chains having ethylene oxide units and propylene oxide units, polymerization chains consisting of propylene oxide units, and polymerization chains consisting of ethylene oxide units and propylene oxide units are preferred, and polymerization chains consisting of propylene oxide units are particularly preferred. The terminal group of polyether compound A is a hydroxyl group. The number of terminal groups in polyether compound A (i.e., the number of hydroxyl groups) is the same as the number of active hydrogen atoms in the initiator.

[0081] The manganese (Mn) of polyether compound A is preferably 1,000 to 100,000, more preferably 1,500 to 80,000, and even more preferably 2,000 to 60,000. When Mn is above the lower limit, it provides sufficient flexibility when used as an adhesive or coating material, and good elongation properties are easily obtained. When Mn is below the upper limit, the viscosity of polyether compound A can be kept low, making it easy to handle.

[0082] The hydroxyl value of polyether compound A is preferably 0.5 to 350 mg KOH / g, more preferably 1 to 200 mg KOH / g, and even more preferably 3 to 100 mg KOH / g. If the hydroxyl value is above the lower limit, sufficient curability is easily obtained when forming the resin. If the hydroxyl value is below the upper limit, sufficient flexibility is imparted to the resin, and good elongation properties are easily obtained.

[0083] The hydroxyl value-based molecular weight of polyether compound A is preferably 1,000 to 100,000, more preferably 1,500 to 80,000, and even more preferably 2,000 to 70,000. When the hydroxyl value-based molecular weight is above the lower limit, it imparts sufficient flexibility when used as an adhesive or coating material, and good elongation properties are easily obtained. When the hydroxyl value-based molecular weight is below the upper limit, the viscosity of polyether compound A can be kept low, making it easy to handle.

[0084] The Mw of polyether compound A is preferably 1,200 to 120,000, more preferably 2,000 to 90,000, and even more preferably 3,000 to 80,000. When Mw is above the lower limit, it provides sufficient flexibility when used as an adhesive or coating material, and good elongation properties are easily obtained. When Mw is below the upper limit, the viscosity of polyether compound A can be kept low, making it easy to handle.

[0085] The Mw / Mn of 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 below the above upper limit, the viscosity of polyether compound A can be kept low, making it easier to handle.

[0086] The total degree of unsaturation of polyether compound A is preferably 0.001 to 0.040 meq / g, more preferably 0.002 to 0.030 meq / g, and even more preferably 0.003 to 0.010 meq / g.

[0087] The viscosity of polyether compound A at a measurement temperature of 25°C is preferably 100 to 30,000 mPa·s, more preferably 200 to 20,000 mPa·s, and even more preferably 400 to 10,000 mPa·s.

[0088] The viscosity of polyether compound A, having a molecular weight based on hydroxyl value of 16,000 to 19,000, at a measurement temperature of 40°C is preferably 6.0 to 8.8 Pa·s, more preferably 6.1 to 8.6 Pa·s, and even more preferably 6.2 to 8.5 Pa·s.

[0089] <Polyether compound B> Polyether compound B has a reactive silicon group represented by formula 1, which will be described later.

[0090] (Reactive silicon group) The reactive silicon group has a hydroxyl group or a hydrolyzable group bonded to a silicon atom and can crosslink by forming a siloxane bond. The reaction that forms the siloxane bond is promoted by a curing catalyst. The reactive silicon group in polyether compound B is represented by formula 1 below. -SiR a X 3-a formula 1

[0091] In Formula 1 above, R is a monovalent organic group having 1 to 20 carbon atoms, and represents an organic group 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.

[0092] R is preferably at least one group selected from the group consisting of alkyl groups, cycloalkyl groups, aryl groups, α-chloroalkyl groups, and triorganosiloxy groups. More preferably, R is at least one group selected from the group consisting of linear or branched alkyl groups having 1 to 4 carbon atoms, cyclohexyl groups, phenyl groups, benzyl groups, α-chloromethyl groups, trimethylsiloxy groups, triethylsiloxy groups, and triphenylsiloxy groups. A methyl group or an ethyl group is preferred in terms of good curability of the polyether compound B and stability of the curable composition. An α-chloromethyl group is preferred in terms of the fast curing rate of the cured product. A methyl group is particularly preferred in terms of its easy availability.

[0093] In Formula 1 above, X represents a hydroxyl group or a hydrolyzable group. Examples of hydrolyzable groups include alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, acid amide groups, aminooxy groups, sulfanyl groups, and alkenyloxy groups. Alkoxy groups are preferred because they are mildly hydrolyzable and easy to handle. The alkoxy group is preferably a methoxy group, ethoxy group, or isopropoxy group, with methoxy or ethoxy groups being more preferred. When the alkoxy group is a methoxy or ethoxy group, siloxane bonds are quickly formed, making it easy to form a crosslinked structure in the cured product, which tends to result in good physical properties of the cured product.

[0094] In the above formula 1, a is an integer between 0 and 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 lower crosslinking density due to siloxane bonds tends to lower the modulus of the cured product, a is preferably 2 or less, and a is more preferably 1 or less.

[0095] Examples of reactive silicon groups represented by Formula 1 above include trimethoxysilyl group, triethoxysilyl group, triisopropoxysilyl group, tris(2-propenyloxy)silyl group, triacetoxysilyl group, dimethoxymethylsilyl group, diethoxymethylsilyl group, dimethoxyethylsilyl group, methyldiisopropoxysilyl group, (α-chloromethyl)dimethoxysilyl group, and (α-chloromethyl)diethoxysilyl group. From the viewpoint of high activity and good curability, trimethoxysilyl group, triethoxysilyl group, dimethoxymethylsilyl group, and diethoxymethylsilyl group are preferred, and trimethoxysilyl group and dimethoxymethylsilyl group are more preferred.

[0096] Polyether compound B has an average of 1.0 or more terminal groups per molecule and contains a reactive silicon group represented by the above formula 1, wherein the terminal group is a polyether compound having the above reactive silicon group, an unsaturated group, an isocyanate group, or a hydroxyl group.

[0097] Polyether compound B has an average of 1.0 or more terminal groups per molecule. Since the cured product has higher tensile strength, better modulus, and better elongation, 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. The number of terminal groups in polyether compound B is the same as the number of terminal groups in the above-mentioned polyether compound. The terminal groups of polyether compound B have one of the reactive silicon group, unsaturated group, isocyanate group, or hydroxyl group represented by formula 1 above. Each terminal group may be the same or different from the others.

[0098] The average number of reactive silicon groups represented by formula 1 per terminal group of polyether compound B is preferably 0.5 to 2.0, and more preferably 0.60 to 1.94. When the average number of reactive silicon groups is above the lower limit, the crosslinking density due to siloxane bonds increases, and a good cured product with high modulus can be obtained.

[0099] 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 above the above lower limit, the crosslinking density due to siloxane bonds increases, and a good cured product with high modulus can be obtained.

[0100] The manganese (Mn) of polyether compound B is preferably 1,000 to 100,000, more preferably 1,500 to 80,000, and even more preferably 2,000 to 60,000. When Mn is above the lower limit, the elongation properties of the cured product are better. When Mn is below the upper limit, the viscosity is low and the workability is good.

[0101] The Mw / Mn of 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 below the above upper limit, good elongation properties are easily obtained, and the viscosity decreases, resulting in good workability.

[0102] 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 below the above upper limit, it is easy to handle.

[0103] When the molecular weight of the raw material polyether compound A, calculated based on hydroxyl value, is 16,000 to 19,000, the viscosity of polyether compound B at a measurement temperature of 25°C is preferably 15 to 30 Pa·s, more preferably 16 to 28 Pa·s, and even more preferably 17 to 25 Pa·s.

[0104] When the molecular weight of the raw material polyether compound A, calculated on a hydroxyl value basis, is 16,000 to 19,000, the viscosity of polyether compound B at a measurement temperature of 40°C is preferably 6.0 to 8.8 Pa·s, more preferably 6.1 to 8.6 Pa·s, and even more preferably 6.2 to 8.5 Pa·s.

[0105] <Method for producing polyether compound B> In the method for producing polyether compound B, the hydroxyl group of polyether compound A is converted into a group having a reactive silicon group represented by the above formula 1. Methods for producing polyether compound B include the following methods (a1), (b1), or (c1). Method (a1): A method of converting the hydroxyl group of polyether compound A into an alkenyloxy group having a carbon-carbon double bond at its molecular terminus or an alkynyloxy group having a carbon-carbon triple bond, and then reacting the carbon-carbon double bond at the molecular terminus of the alkenyloxy group or the carbon-carbon triple bond of the alkynyloxy group with a silylating agent capable of introducing a reactive silicon group represented by formula 1 above, thereby converting the alkenyloxy group or alkynyloxy group into a group having a reactive silicon group represented by formula 1 above. Method (b1): A method for converting a hydroxyl group of polyether compound A into a group having a reactive silicon group represented by formula 1 by reacting the hydroxyl group with a silylating agent having a functional group that can react with the hydroxyl group and a reactive silicon group represented by formula 1. Method (c1): A method of converting the hydroxyl group of polyether compound A into a group having an isocyanate group, and then reacting it with a silylating agent having a functional group that can react with an isocyanate group and a reactive silicon group represented by the above formula 1, thereby converting the hydroxyl group into a group having a reactive silicon group represented by the above formula 1.

[0106] In method (a1), polyether compound A is reacted with an alkali metal salt to alkoxideize it, and then reacted with a halogenated hydrocarbon compound having a carbon-carbon double bond or a carbon-carbon triple bond at the molecular terminus to convert the hydroxyl group of polyether compound A into an alkenyloxy group having a carbon-carbon double bond or an alkynyloxy group having a carbon-carbon triple bond at the molecular terminus.

[0107] Examples of alkali metal salts include sodium hydroxide, sodium alkoxide, potassium hydroxide, potassium alkoxide, lithium hydroxide, lithium alkoxide, cesium hydroxide, and cesium alkoxide. From the standpoint of ease of handling and solubility, sodium hydroxide, sodium methoxide, sodium ethoxide, potassium hydroxide, potassium methoxide, and potassium ethoxide are preferred, with sodium methoxide and potassium ethoxide being more preferred. Sodium methoxide is particularly preferred from the standpoint of availability. Alkali metal salts may also be used in a dissolved state in a solvent.

[0108] Examples of halogenated hydrocarbon compounds containing carbon-carbon double bonds at the molecular termini 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. Examples of 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-pentine, 1,4-dichloro-2-butyne, 5-chloro-1-pentine, 6-chloro-1-hexine, propargyl bromide, 1-bromo-2-butyne, 4-bromo-1-butyne, 1-bromo- Examples include 2-octyne, 1-bromo-2-pentine, 1,4-dibromo-2-butine, 5-bromo-1-pentine, 6-bromo-1-hexine, propargyl iodide, 1-iodo-2-butine, 4-iodo-1-butine, 1-iodo-2-octyne, 1-iodo-2-pentine, 1,4-diiodo-2-butine, 5-iodo-1-pentine, and 6-iodo-1-hexine. Propargyl chloride, propargyl bromide, and propargyl iodide are preferred. A halogenated hydrocarbon compound having a carbon-carbon double bond at the molecular end and a halogenated hydrocarbon compound having a carbon-carbon triple bond may be used in combination. The halogenated hydrocarbon compound having a carbon-carbon double bond at the molecular end may be used individually or in combination of two or more. The halogenated hydrocarbon compound having a carbon-carbon triple bond may be used individually or in combination of two or more. Of the halogenated hydrocarbon compounds having a carbon-carbon triple bond, a halogenated hydrocarbon compound having a carbon-carbon triple bond at the molecular end is preferred.

[0109] Next, a silylation agent capable of introducing a reactive silicon group represented by formula 1 is reacted with the carbon-carbon double bond at the molecular terminus of the alkenyloxy group or the carbon-carbon triple bond of the alkynyloxy group to convert the alkenyloxy group or alkynyloxy group into a group having a reactive silicon group represented by formula 1. The silylation agent may be a compound having both a group that can react with an unsaturated group to form a bond (e.g., a sulfanyl group) and a reactive silicon group represented by formula 1, or a hydrosilane compound (e.g., HSiR a X 3-a Examples include (where R, X, and a are the same as in Formula 1 above). Specifically, examples include dimethoxymethylsilane, diethoxymethylsilane, dimethoxyethylsilane, methyldiisopropoxysilane, (α-chloromethyl)dimethoxysilane, (α-chloromethyl)diethoxysilane, trimethoxysilane, triethoxysilane, triisopropoxysilane, tris(2-propenyloxy)silane, triacetoxysilane, and 3-mercaptopropyltrimethoxysilane. Trimethoxysilane, dimethoxymethylsilane, and diethoxymethylsilane are preferred, and dimethoxymethylsilane is more preferred, due to their high activity and good curability.

[0110] In method (b1), a silylating agent is reacted with polyether compound A. It is preferable to use an isocyanate silane compound represented by formula 3 below as the silylating agent. OCN-(CH2) n -SiR a X 3-a formula 3 -SiR in equation 3 above a X 3-a This is the same as formula 1 above. n is an integer from 1 to 8, preferably from 1 to 3. The hydroxyl group of polyether compound A reacts with the above isocyanate silane compound, resulting in the hydroxyl group of polyether compound A being converted to -OC(=O)NH-(CH2) n -SiR a X 3-a Represented by a urethane bond (-OC(=O)NH-) and -SiR a X 3-a It is converted to a terminal group having a . Examples of isocyanate silane compounds include 3-isocyanate propyltrimethoxysilane, 3-isocyanate propyltriethoxysilane, isocyanate methyltrimethoxysilane, isocyanate methyltriethoxysilane, 3-isocyanate propylmethyldimethoxysilane, 3-isocyanate propylmethyldiethoxysilane, isocyanate methylmethyldimethoxysilane, and isocyanate methylmethyldiethoxysilane. As isocyanate silane compounds, 3-isocyanate propyltrimethoxysilane, 3-isocyanate propyltriethoxysilane, 3-isocyanate propylmethyldimethoxysilane, isocyanate methylmethyldimethoxysilane, and isocyanate methyltrimethoxysilane are preferred due to their reactivity with polyether compound A and ease of handling.

[0111] The active hydrogen of polyether compound A reacts with the isocyanate group of the isocyanate silane compound represented by formula 3 above, thereby introducing a reactive silicon group to polyether compound A. If the active hydrogen-containing group of polyether compound A is a hydroxyl group, then the polyoxyalkylene chain (-(R 5 O) m -, R 5 -(R 5 O)m -C(=O)NH-(CH2) n -SiR a X 3-a A connected structure represented by is formed.

[0112] This reaction may be carried out in the presence of a urethane catalyst. The urethane catalyst is not particularly limited, and any known urethane catalyst 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, and more preferably 50 to 150°C. Furthermore, the urethane reaction is preferably carried out under an inert gas atmosphere. Nitrogen is preferred as the inert gas.

[0113] The molar ratio of the total number of isocyanate groups in the isocyanate-silane compound represented by 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 formula 3 such that the number of reactive silicon groups per molecule of the obtained polyether compound B is at least 0.7. For example, if the active hydrogen-containing group of polyether compound A is a hydroxyl group, the molar ratio NCO / OH, which represents the total number of isocyanate groups (NCO) of the isocyanate silane compound represented by formula 3 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. If NCO / OH is above the lower limit, the strength of the cured product is excellent, and if it is below the upper limit, the elongation of the cured product is excellent.

[0114] In method (c1), a polyisocyanate compound is reacted with the hydroxyl group of polyether compound A to convert the hydroxyl group into a monovalent organic group containing an isocyanate group having a urethane bond (-OC(=O)NH-) at the terminal end that is bonded to polyether compound A (hereinafter also referred to as the "isocyanate-containing group"). Then, the isocyanate-containing group is reacted with a silylation agent having a functional group that can react with an isocyanate group and a reactive silicon group represented by the above formula 1 to obtain a terminal group that is a monovalent organic group having one or more urethane bonds (-OC(=O)NH-) and a silylation agent residue that has reacted with the isocyanate group (hereinafter also referred to as the "urethane-bonded and reactive silicon group-containing group"). Hereinafter, the polyisocyanate compound described above will be a diisocyanate compound represented by formula 4 below, and the silylation agent having a functional group that can react with an isocyanate group and a reactive silicon group represented by formula 1 above will be a compound represented by formula 5 below, and method (c1) will be described below, but will not be limited thereto.

[0115] OCN-R 3 -NCO formula 4 R in formula 4 above 3 This indicates a divalent organic group.

[0116] WR 4 -SiR a X 3-a formula 5 In formula 5 above, W is a functional group that can react with a monovalent isocyanate group (a group having one or more active hydrogen atoms), R 4 -SiR is a divalent organic group. a X 3-a This is the same as equation 1 above.

[0117] When the hydroxyl group of polyether compound A is reacted with the diisocyanate compound represented by formula 4 above, the isocyanate-containing group becomes -OC(=O)NH-R 3 The group is represented by -NCO. When the above isocyanate-containing group is reacted with the silylating agent represented by formula 5, the above urethane bond and reactive silicon group-containing group become -OC(=O)NH-R 3 -NHC(=O)-W'-R4 -SiR a X 3-a (However, W' is a divalent group obtained by removing one active hydrogen atom from W.) This results in a group represented by -OC(=O)NH-R 3 -NHC(=O)-OR 4 -SiR a X 3-a This is a group represented by . In this case, the above urethane bond and reactive silicon group-containing group have two urethane bonds. Also, for example, when W is an amino group (-NH2), the above urethane bond and reactive silicon group-containing group are -OC(=O)NH-R 3 -NHC(=O)-NH-R 4 -SiR a X 3-a It is a base represented by .

[0118] R 3 Preferably, the group is a divalent organic group having 2 to 20 carbon atoms, and examples include alkylene groups, cycloalkylene groups, bicycloalkylene groups, monocyclic or polycyclic divalent aromatic hydrocarbon groups, divalent groups obtained by removing two hydrogen atoms from a cycloalkane having an alkyl group as a substituent, divalent groups obtained by removing two hydrogen atoms from an aromatic hydrocarbon having an alkyl group as a substituent, divalent groups obtained by removing two hydrogen atoms from two or more cycloalkanes that may have an alkyl group as a substituent and are bonded via an alkylene group, and divalent groups obtained by removing two hydrogen atoms from two or more aromatic hydrocarbons that may have an alkyl group as a substituent and are bonded via an alkylene group.

[0119] Examples of diisocyanate compounds represented by the above formula 4 and other polyisocyanate compounds include aromatic polyisocyanates, non-yellowing modified aromatic polyisocyanates (compounds that do not have isocyanate groups directly bonded to carbon atoms constituting the 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.

[0120] Examples of aromatic polyisocyanates include naphthalene-1,5-diisocyanate, polyphenylene-polymethylene-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 aliphatic polyisocyanates 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, with hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, and 2,6-tolylene diisocyanate being more preferred, and tolylene diisocyanate being even more preferred because it is easier to obtain the tensile strength of the cured product. One polyisocyanate compound may be used, or two or more may be used in combination.

[0121] Functional groups that can react with the isocyanate group represented by the above formula 5 and -SiR a X 3-a In silylating agents having R4 Preferably, the group is 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; more preferably, a group obtained by removing two hydrogen atoms from an aromatic hydrocarbon having 6 to 10 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms; more preferably, a group obtained by removing two hydrogen atoms from a cyclic hydrocarbon having 3 to 10 carbon atoms; more preferably, a group obtained by removing two hydrogen atoms from a linear hydrocarbon having 1 to 12 carbon atoms; even more preferably, a group obtained by removing two hydrogen atoms from a linear hydrocarbon having 1 to 8 carbon atoms; and particularly preferably, a group obtained by removing two hydrogen atoms from a linear hydrocarbon having 1 to 6 carbon atoms. The W is preferably a group having one or two active hydrogens 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. Hydroxyl groups, sulfanyl groups, amino groups, methylamino groups, ethylamino groups, and butylamino groups are preferred, and hydroxyl groups, amino groups, methylamino groups, ethylamino groups, and butylamino groups are more preferred.

[0122] In methods (b1) and (c1), the resulting polyether compound B has reactive silicon groups 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). Note that the polyether compound B obtained by method (b1) contains only one organic group represented by the following formula (i), while the polyether compound B obtained by method (c1) contains two or more organic groups represented by the following formula (i). -C(=O)NH- Equation (i)

[0123] The organic group (i) is a divalent group derived from a urethane bond or a urea bond. When the isocyanate silane compound represented by formula 3 above is used as a silylating agent, there is one organic group (i).

[0124] The organic group (i) preferably forms a urethane bond (-OC(=O)NH-, where -O- represents the terminal oxygen atom of the polyoxyalkylene chain) with the polyoxyalkylene chain. That is, it is preferable that one organic group (i) exists between the polyoxyalkylene chain and the reactive silicon group in polyether compound B. When polyether compound B is produced by the above method (b1), the number of organic groups represented by the above formula (i) contained in polyether compound B becomes one. When polyether compound B is produced by method (b1), it is easy to obtain polyether compound B with a high silylation rate. When produced by method (b1), it is easy to obtain polyether compound B with a narrow molecular weight distribution. The viscosity of polyether compound B is suppressed, resulting in good workability. If the isocyanate silane compound represented by formula 3 contains one isocyanate group and one reactive silicon group, the number of reactive silicon groups per molecule of polyether compound B will be the same as the number of groups (i) per molecule.

[0125] The silylation rate of polyether compound B is preferably 50 to 100 mol%, and more preferably 60 to 98 mol%. When the silylation rate is above the lower limit of the above range, the cured product exhibits excellent tensile strength and high modulus. If the curable composition contains two or more types of polyether compound B, it is sufficient that the average silylation rate of the polyether compound B as a whole is within the above range.

[0126] (Curable composition containing polyether compound B) Polyether compound B is used in curable compositions. The curable composition is obtained by mixing polyether compound B with other necessary components. Polyether compound B may be used alone or in combination of two or more types. The content of polyether compound B relative to the total mass of the curable composition is preferably 1 to 90% by mass, more preferably 10 to 80% by mass, and even more preferably 20 to 70% by mass. If the content is below the upper limit of the above range, the tensile strength of the cured product will be superior and the elongation properties will be better.

[0127] Other components included 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, thixotropic agents, stabilizers, adhesion modifiers, property modifiers, dehydrating agents, adhesion-improving resins, reinforcing materials such as fillers, surface modifiers, flame retardants, foaming agents, solvents, and silicates. Other components can be used in any combination without limitation from those conventionally known as described in International Publication No. 2013 / 180203, International Publication No. 2014 / 192842, International Publication No. 2016 / 002907, Japanese Patent Publication No. 2014-88481, Japanese Patent Publication No. 2015-10162, Japanese Patent Publication No. 2015-105293, Japanese Patent Publication No. 2017-039728, Japanese Patent Publication No. 2017-214541, etc. Two or more of each component may be used in combination.

[0128] The curable composition may be a one-component type in which polyether compound B and all other components are pre-mixed and sealed for storage, and cured by moisture in the air after application. Alternatively, it may be a two-component type in which a main component 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 main component composition are mixed before use. It is preferable that the one-component curable composition does not contain water. It is preferable to dehydrate and dry any water-containing components beforehand, or to dehydrate them by reducing the pressure during mixing. In a two-component curable composition, the curing agent composition may contain water, and the main component composition is less likely to gel even if it contains a small amount of water. However, from the viewpoint of storage stability, it is preferable to dehydrate and dry the components beforehand. To improve storage stability, a dehydrating agent may be added to the one-component curable composition or the two-component main component composition.

[0129] (Uses of curable compositions containing polyether compound B) Suitable applications for curable compositions containing polyether compound B include adhesives, sealants (e.g., elastic sealants for buildings, sealants for double-glazed windows, sealants for rust prevention and waterproofing of glass edges, sealants for the back surface of solar cells, sealants for buildings, sealants for ships, sealants for automobiles, and sealants for roads), and electrical insulating materials (insulating coatings for electric wires and cables). [Examples]

[0130] The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following description.

[0131] [Simultaneous thermogravimetric and differential thermal measurement] The thermogravimetric and differential thermal measurements and analysis of the DMC catalysts produced in Production Examples 1-4 were performed under the following conditions. Equipment: STA 2500 Regulus (manufactured by NETZSCH) Temperature range: 30℃~450℃ Heating rate: 10℃ / min Atmospheric gas: Nitrogen (50 mL / min) Sample amount: 10 mg Cumulative range of volatile components: 30℃~100℃, 30℃~150℃, 150℃~220℃, 100℃~200℃, 150℃~200℃, 30℃~220℃

[0132] [Hydroxyl value and molecular weight equivalent to hydroxyl value] The hydroxyl value was measured in accordance with Method B of JIS K 1557-1:2007. The molecular weight converted to hydroxyl value was calculated as 56,100 / hydroxyl value of polyether compound A having hydroxyl groups × number of hydroxyl groups in polyether compound A having hydroxyl groups (number of active hydrogens of the initiator).

[0133] [Mn, Mw, Mw / Mn] Several types of monodisperse polystyrene with different degrees of polymerization were measured using a gel permeation chromatograph analyzer HLC-8420GPC (Tosoh Corporation) as standard samples for molecular weight measurement, and a calibration curve was created based on the relationship between the molecular weight of polystyrene and its retention time. A polyether compound was diluted to 0.5% by mass with tetrahydrofuran and passed through a 0.5 μm pore filter to obtain a sample for measurement. Using the obtained sample, tetrahydrofuran was used as the solvent, the sample pump was set to a flow rate of 0.350 mL / min, the reference pump was set to a flow rate of 0.350 mL / min, the detector (RI) temperature was set to 40°C, and the collection time was set to 6 to 15 minutes. Mw / Mn was determined by analyzing the peaks that appeared between 6 and 11 minutes of collection. Two TSG gel SuperHZ 4000 and two TSG gel SuperHZ 2500 columns (Tosoh Corporation) were used, and the column temperature was set to 40°C. The injection volume of the sample for measurement was 20 μL.

[0134] [Total unsaturation] The total degree of unsaturation of polyether compound A, which contains hydroxyl groups, was measured in accordance with JIS K 1557-3:2007.

[0135] [viscosity] The viscosities of polyether compound A, which has hydroxyl groups, and polyether compound B, which has reactive silicon groups, were measured using an E-type viscometer in accordance with JIS K 1557-5:2007. The viscosity of polyether compound A, which has hydroxyl groups, was measured at 40°C, and the viscosity of polyether compound B, which has reactive silicon groups, was measured at 25°C as described in JIS K 1557-5:2007.

[0136] [Number of reactive silicon groups] The number of reactive silicon groups (silylation rate) in polyether compound B, which contains reactive silicon groups, is: 1 Measurement was performed using the internal standard method of H-NMR.

[0137] [Manufacturing Example 1] In the presence of a KOH catalyst, propylene glycol was polymerized with propylene oxide (hereinafter also referred to as "PO"), and the mixture was dealkalized and purified to obtain polyoxypropylene diol (hereinafter also referred to as "polyol P1"). Polyol P1 had 2 hydroxyl groups per molecule, a manganese content of 1,500, and a hydroxyl value of 75 mgKOH / g. A 15 mL aqueous solution of zinc chloride was prepared in a flask, consisting of 10 g of zinc chloride and water. While stirring the zinc chloride solution, 80 mL of an aqueous solution of potassium hexacyanocobaltate, consisting of 4 g of potassium hexacyanocobaltate and water, was added dropwise to the zinc chloride solution at a constant rate over 30 minutes. During this time, the reaction solution in the flask was maintained at 40°C. After the addition of the potassium hexacyanocobaltate solution was complete, a mixture consisting of 80 g of tert-butyl alcohol (hereinafter also referred to as "TBA"), 80 g of water, and 1 g of polyol P1 was added, the temperature was raised to 60°C, and the mixture was stirred at 60°C for 1 hour to coordinate the TBA. Subsequently, the resulting mixture containing the DMC catalyst 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 (ADVANTEC product name, No. 5C) to obtain a solid containing the DMC catalyst (hereinafter referred to as "filter cake"). The filtration cake was transferred to a flask, and a mixture of 40 g of TBA, 70 g of water, and 1 g of polyol P1 was added. The mixture was stirred at 40°C for 30 minutes, and then filtered under pressure under the same conditions as above to obtain the filtration cake after the first wash. The obtained filtration cake after the first wash was transferred to a flask, and a mixture of 80 g of TBA and 1 g of polyol P1 was added. The mixture was stirred at 40°C for 30 minutes, and then filtered under pressure under the same conditions as above to obtain the filtration cake after the second wash. The obtained filtration cake after the second wash was dried at 80°C in an air atmosphere at atmospheric pressure until there was no change in mass, and then pulverized to obtain powdered DMC catalyst A. Thermogravimetric-differential thermal analysis was performed on the obtained DMC catalyst A to obtain A1 to A6 and A1 / A2 as described above. The results are shown in Table 1 (the same applies to production examples 2 to 4 below). Note that A1 to A6 are the amount of decrease and are expressed as absolute values.

[0138] [Manufacturing Example 2] DMC catalyst B was obtained in the same manner as in Production Example 1, except that the filtered cake after the second wash was dried under reduced pressure until there was no change in mass.

[0139] [Manufacturing Example 3] A filtration cake after the first wash was obtained in the same manner as in Production Example 1. The obtained filtration cake after the first wash was transferred to a flask, and a mixture consisting of 80 g of TBA, 10 g of water, and 1 g of polyol P1 was added and stirred at 40°C for 30 minutes. Then, under the same conditions as above, the filtration cake after the second wash was obtained by filtration under pressure. The obtained filtration cake after the second wash was dried and pulverized in the same manner as in Production Example 1 to obtain DMC catalyst C.

[0140] [Manufacturing Example 4] A filtration cake after the first wash was obtained in the same manner as in Production Example 1. The obtained filtration cake after the first wash was transferred to a flask, and 80g of TBA was added and stirred at 40°C for 30 minutes. Then, under the same conditions as above, the filtration cake after the second wash was obtained by filtration under pressure. The obtained filtration cake after the second wash was dried and pulverized in the same manner as in Production Example 1 to obtain DMC catalyst D.

[0141] [Table 1]

[0142] Examples 1 and 2 below are examples of actual cases, and Examples 3 and 4 are comparative examples.

[0143] [Example 1] Polyoxypropylene diol (hereinafter also referred to as "polyol P2") was obtained by polymerizing PO onto propylene glycol in the presence of a KOH catalyst and then dealkalizing and purifying it. The average number of hydroxyl groups per molecule of polyol P2 was 2, and the molecular weight based on hydroxyl value was 2000. 447 g of polyol P2 and 0.225 g of DMC catalyst A were added to a 5 L reactor equipped with a stirrer, impeller, heating jacket, cooling coil, nitrogen introduction piping, and vacuum piping. After purging with nitrogen gas, the temperature was raised to 130°C, and the mixture was stirred for 1 hour under reduced pressure of -0.1 MPaG at a stirring speed of 200 rpm, while maintaining the internal temperature at 130°C and reducing the internal pressure to 0.01 MPaG. After the above pretreatment was completed, 40 g of PO was supplied at 130°C for initial activation. After confirming that initial activation had occurred due to a decrease in internal pressure, 3,048 g of primary PO was supplied at 130°C over 6.5 hours, followed by 1,016 g of secondary PO over 2.5 hours. After a maturation period of 0.5 hours at 130°C, the reactor pressure was reduced to -0.1 MPaG to confirm that there was no unreacted PO in the reactor. Subsequently, 4.5 g of Irganox 1076 was added to the reactor as an antioxidant to obtain hydroxyl-containing polyether compound A-1. The type of DMC catalyst used, the hydroxyl value of hydroxyl-containing polyether compound A-1, hydroxyl value-based molecular weight, Mw / Mn, total unsaturation, and viscosity are shown in Table 2 (the same applies to Examples 2-4 below).

[0144] In a reaction vessel equipped with a stirrer and a nitrogen inlet tube, 900 g of hydroxyl-containing polyether compound A-1, 0.045 g of Neostan U-860 manufactured by Nitto Kasei Co., Ltd., and 19.5 g of 3-isocyanatopropyltriethoxysilane (NCO content: 20.5% by mass) were added and the reaction was carried out at 80°C for 5 hours. The molar ratio of the amount of isocyanate in 3-isocyanatopropyltriethoxysilane to the amount of hydroxyl groups in hydroxyl-containing polyether compound A-1, NCO / OH, was set to 0.97, and the reaction was terminated after confirming that there was no absorption from NCO by IR. The types of hydroxyl-containing polyether compound A used as raw materials, the silylation rate of the obtained reactive silicon-containing polyether compound B-1, and the viscosity are shown in Table 3 (the same applies to Examples 2-4 below).

[0145] [Example 2] Polyether compound A-2 having a hydroxyl group and polyether compound B-2 having a reactive silicon group were obtained in the same manner as in Example 1, except that TBA-DMC catalyst B was used instead of TBA-DMC catalyst A in the production of polyether compound A having a hydroxyl group.

[0146] [Example 3] Polyether compound A-3 having a hydroxyl group and polyether compound B-3 having a reactive silicon group were obtained in the same manner as in Example 1, except that TBA-DMC catalyst C was used instead of TBA-DMC catalyst A in the production of polyether compound A having a hydroxyl group.

[0147] [Example 4] Polyether compound A-4 having a hydroxyl group and polyether compound B-4 having a reactive silicon group were obtained in the same manner as in Example 1, except that TBA-DMC catalyst D was used instead of TBA-DMC catalyst A in the production of polyether compound A having a hydroxyl group.

[0148] [Table 2]

[0149] [Table 3]

[0150] As shown in Table 2, the hydroxyl value-based molecular weights of the hydroxyl-containing polyether compounds A-1 to A-4, which are the starting materials for reactive silicon-containing polyether compounds B-1 to B-4 in Examples 1 to 4, are almost equivalent. Furthermore, the conditions for converting the hydroxyl groups of hydroxyl-containing polyether compounds A-1 to A-4 to the reactive silicon-containing groups represented by Formula 1 above are the same for Examples 1 to 4. On the other hand, as shown in Table 3, it was found that the viscosity at 25°C is lower for reactive silicon-containing polyether compounds B-1 and B-2 in Examples 1 and 2 than for reactive silicon-containing polyether compounds B-3 and B-4 in Examples 3 and 4.

Claims

1. A method for producing a polyether compound having reactive silicon groups, comprising polymerizing an alkylene oxide having 2 to 12 carbon atoms in an initiator having active hydrogen in the presence of a complex metal cyanide catalyst powder to obtain a polyether compound having hydroxyl groups, and converting the hydroxyl groups of the polyether compound having hydroxyl groups to a group having reactive silicon groups represented by the following formula 1, A method for producing a polyether compound having reactive silicon groups, wherein A1 is the ratio of the mass of the composite metal cyanide complex catalyst powder to the total mass, measured by simultaneous thermogravimetric-differential thermal analysis, that decreases at 30 to 150°C, and A2 is the ratio of the mass of the composite metal cyanide complex catalyst powder to the total mass, that decreases at 150 to 220°C, and A1 / A2 is 0.5 or less. -SiR ａ X ３－ａ Formula 1 In Formula 1 above, R represents a monovalent organic group having 1 to 20 carbon atoms, other than a hydrolyzable group, and X represents a hydroxyl group or a hydrolyzable group. a is an integer from 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 claim 1, wherein the organic ligand of the composite metal cyanide complex catalyst powder is either ethylene glycol dimethyl ether or tert-butyl alcohol, or both.

3. A method for producing a polyether compound having a reactive silicon group according to claim 1, wherein the percentage of the mass of the composite metal cyanide complex catalyst powder that decreases at 30 to 100°C, as measured by simultaneous thermogravimetric-differential thermal analysis, is 1.50% by mass or less.

4. A method for producing a polyether compound having a reactive silicon group according to any one of claims 1 to 3, wherein the number of hydroxyl groups per molecule of the polyether compound having a hydroxyl group is 1 to 8.

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