Composite metal cyanide complex catalyst powder, method for producing polyether compound, method for producing polyether compound having reactive silicon group, method for producing polyether compound having urethane bond, and method for producing polyether compound having polymerizable unsaturated group

Abstract

The present invention relates a particulate composite metal cyanide complex catalyst powder in which the value of A1 / A2 is 0.5 or less as measured by simultaneous thermogravimetry and differential thermal analysis, where A1 is the ratio of the mass decreasing at 30-150°C to the total mass of the composite metal cyanide complex catalyst powder and A2 is the ratio of the mass decreasing at 150-220°C to the total mass of the composite metal cyanide complex catalyst powder.

Description

Composite metal cyanide complex catalyst powder, method for producing polyether compound, method for producing polyether compound having reactive silicon group, method for producing polyether compound having urethane bond, and method for producing polyether compound having polymerizable unsaturated group

[0001] The present invention relates to a composite metal cyanide complex catalyst powder, a method for producing a polyether compound, a method for producing a polyether compound having a reactive silicon group, a method for producing a polyether compound having a urethane bond, and a method for producing a polyether compound having a polymerizable unsaturated group. This application claims priority based on Japanese Patent Application Nos. 2024-200741, 2024-200776, 2024-200734, and 2024-200742 filed in Japan on November 18, 2024, and incorporates the contents thereof herein by reference.

[0002] Polyether compounds are used as raw materials for adhesives, paints, sealants, coating agents, and the like. Polyether compounds are produced by polymerizing alkylene oxide with an initiator having active hydrogen. Composite metal cyanide complex catalysts are known as polymerization catalysts for obtaining polyether compounds with a narrow molecular weight distribution.

[0003] Patent Document 1 discloses a method for producing a DMC catalyst in which an aqueous solution of a metal salt is reacted with an aqueous solution of a metal cyanide salt in the presence of an organic complex ligand to form a DMC catalyst dispersion, the formed dispersion is filtered, the obtained filter cake is washed with a solution of the organic complex ligand by filter cake washing, and the washed filter cake is dried. The above washing is performed with a mixed solution of tert-butanol, which is an organic complex ligand, and distilled water.

[0004] 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 reactive silicon groups have already been industrially produced and are widely used in applications such as sealing materials and adhesives.

[0005] Polyether compounds containing reactive silicon groups are manufactured using polyether compounds containing hydroxyl groups as raw materials. Polyether compounds containing hydroxyl groups are manufactured by polymerizing alkylene oxides onto an initiator containing active hydrogen. Complex metal cyanide catalysts are known as polymerization catalysts for obtaining polyether compounds with a small molecular weight distribution and low viscosity.

[0006] Patent Document 2 discloses a method for producing a hydrolyzable silyl group-containing polyoxyalkylene (B), comprising the steps of obtaining a hydroxyl group-containing polyoxyalkylene (A) by ring-opening polymerization of a monoepoxide with a water content of 5 ppm or more and less than 50 ppm, and introducing a hydrolyzable silyl group into the hydroxyl group-containing polyoxyalkylene (A). It also describes carrying out the step of obtaining the hydroxyl group-containing polyoxyalkylene (A) in the presence of a complex metal cyanide catalyst.

[0007] Polyether compounds containing urethane bonds, such as urethane prepolymers, are used as raw materials for adhesives, paints, sealants, and coatings. Polyether compounds containing urethane bonds are manufactured using polyether compounds containing hydroxyl groups as raw materials. Polyether compounds containing hydroxyl groups are manufactured by polymerizing alkylene oxides with an initiator containing active hydrogen. Complex metal cyanide catalysts are known as polymerization catalysts for obtaining polyether compounds with a small molecular weight distribution.

[0008] Patent Document 3 discloses a urethane prepolymer composition (G) comprising a hydroxyl-terminated urethane prepolymer (E) and a polyalkylene oxide (B). It also discloses that the urethane prepolymer (E) is a reaction product of a polyol and a polyisocyanate (C), and has at least one urethane group and at least one hydroxyl group in one molecule. Furthermore, it is disclosed that the polyol can be produced by a complex metal cyanide catalyst.

[0009] Polyether compounds having polymerizable unsaturated groups are used as raw materials for adhesives, sealants, paints, and coatings in fields such as optical components and liquid crystal panels. These polymerizable polyether compounds are manufactured using polyether compounds having hydroxyl groups as raw materials. Polyether compounds having hydroxyl groups are manufactured by polymerizing alkylene oxides onto an initiator containing active hydrogen. Complex metal cyanide catalysts are known as polymerization catalysts for obtaining polyether compounds with a small molecular weight distribution.

[0010] Patent Document 4 discloses a method for producing an oligomer having a polyoxypropylenediol by polymerizing propylene oxide as an initiator in the presence of a complex metal cyanide catalyst, an isocyanate-terminated urethane prepolymer by reacting the obtained polyoxypropylenediol with isophorone diisocyanate, and an acryloyloxy group by reacting the obtained isocyanate-terminated urethane prepolymer with 2-hydroxyethyl acrylate.

[0011] Japanese Patent Publication No. 2003-531251, International Publication No. 2023 / 095636, Japanese Patent Publication No. 2023-155601, Japanese Patent No. 7255604

[0012] However, according to the inventors' research, even when using a composite metal cyanide complex catalyst produced by the method described in Patent Document 1, the molecular weight distribution of the polyether compound may not be sufficiently narrowed. In this case, the viscosity of the polyether compound increases, which may worsen workability.

[0013] Furthermore, 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 2 is not sufficiently low, which may lead to poor workability.

[0014] Furthermore, according to the inventors' research, the viscosity of the polyether compound having a urethane bond produced by the method described in Patent Document 3 is not sufficiently low, which may lead to poor workability.

[0015] Furthermore, according to the inventors' research, the viscosity of the polyether compound having polymerizable unsaturated groups produced by the method described in Patent Document 4 is not sufficiently low, which may lead to poor workability.

[0016] The present invention has been made in view of the above circumstances, and aims to provide a composite metal cyanide complex catalyst powder capable of producing a polyether compound with lower viscosity, and a method for producing a polyether compound using the composite metal cyanide complex catalyst powder. The present invention also aims to provide a method for producing a polyether compound having reactive silicon groups capable of producing a polyether compound having reactive silicon groups with lower viscosity. The present invention also aims to provide a method for producing a polyether compound having urethane bonds capable of producing a polyether compound having urethane bonds with lower viscosity. The present invention also aims to provide a method for producing a polyether compound having polymerizable unsaturated groups capable of producing a polyether compound having polymerizable unsaturated groups with lower viscosity.

[0017] The present invention provides the following means: [1] A composite metal cyanide complex catalyst powder wherein, when A1 is the ratio of the mass of the composite metal cyanide complex catalyst powder to the total mass 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 at 150 to 220°C, as measured by simultaneous thermogravimetric-differential thermal measurement, A1 / A2 is 0.5 or less. [2] The composite metal cyanide complex catalyst powder 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] The composite metal cyanide complex catalyst powder according to [1] or [2], wherein, as measured by simultaneous thermogravimetric-differential thermal measurement, the ratio of the mass of the composite metal cyanide complex catalyst powder to the total mass at 30 to 100°C is 1.50% by mass or less. [4] A method for producing a polyether compound, comprising polymerizing an alkylene oxide having 2 to 12 carbon atoms onto an initiator having active hydrogen in the presence of a complex metal cyanide catalyst powder according to any one of [1] to [3]. [5] The method for producing a polyether compound according to [4], wherein the number of hydroxyl groups per molecule of the polyether compound is 1 to 8.

[0018] [1A] A method for producing a polyether compound having reactive silicon groups, comprising polymerizing an alkylene oxide having 2 to 12 carbon atoms on 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 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. ａ X ３－ａFormula 1 In Formula 1, R is a monovalent organic group having 1 to 20 carbon atoms, other than a hydrolyzable group, and X is a hydroxyl group, a halogen atom, 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. [2A] The method for producing a polyether compound having a reactive silicon group according to [1A], wherein the organic ligand of the composite metal cyanide complex catalyst powder is either ethylene glycol dimethyl ether or tert-butyl alcohol or both. [3A] The method for producing a polyether compound having a reactive silicon group according to [1A] or [2A], wherein the ratio of the mass decrease of the composite metal cyanide complex catalyst powder at 30 to 100°C relative to the total mass, as measured by simultaneous thermogravimetric-differential thermal analysis, is 1.5% by mass or less. [4A] The method for producing a polyether compound having a reactive silicon group according to any one of [1A] to [3A], wherein the number of hydroxyl groups per molecule of the polyether compound having a hydroxyl group is 1 to 8.

[0019] [1B] A method for producing a polyether compound having a urethane bond, 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 a hydroxyl group, and reacting the polyether compound having a hydroxyl group with a polyisocyanate, wherein A1 / A2 is 0.5 or less, 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. [2B] The method for producing a polyether compound having a urethane bond according to [1B], wherein the organic ligand of the complex metal cyanide catalyst powder is either ethylene glycol dimethyl ether or tert-butyl alcohol or both. [3B] A method for producing a polyether compound having a urethane bond according to [1B] or [2B], wherein the ratio of the mass decrease of the composite metal cyanide complex catalyst powder at 30 to 100°C relative to the total mass, as measured by simultaneous thermogravimetric-differential thermal measurement, is 1.50% by mass or less. [4B] A method for producing a polyether compound having a urethane bond according to any one of [1B] to [3B], wherein the number of hydroxyl groups per molecule of the polyether compound having hydroxyl groups is 1 to 8.

[0020] [1C] A method for producing a polyether compound having polymerizable unsaturated groups, comprising polymerizing an alkylene oxide having 2 to 12 carbon atoms on 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 polymerizable unsaturated 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. [2C] The method for producing a polyether compound having polymerizable unsaturated groups according to [1C], wherein the organic ligand of the complex metal cyanide catalyst powder is either ethylene glycol dimethyl ether or tert-butyl alcohol or both. [3C] A method for producing a polyether compound having polymerizable unsaturated groups according to [1C] or [2C], wherein the ratio of the decrease in mass of the composite metal cyanide complex catalyst powder at 30 to 100°C, as measured by simultaneous thermogravimetric-differential thermal analysis, is 1.50% by mass or less. [4C] A method for producing a polyether compound having polymerizable unsaturated groups according to any one of [1C] to [3C], wherein the number of hydroxyl groups per molecule of the polyether compound having hydroxyl groups is 1 to 8.

[0021] The present invention provides a composite metal cyanide complex catalyst powder capable of producing polyether compounds with lower viscosity, and a method for producing polyether compounds using the composite metal cyanide complex catalyst powder. The present invention also provides a method for producing polyether compounds having reactive silicon groups capable of producing polyether compounds having reactive silicon groups with lower viscosity. The present invention also provides a method for producing polyether compounds having urethane bonds capable of producing polyether compounds having urethane bonds with lower viscosity. The present invention also provides a method for producing polyether compounds having polymerizable unsaturated groups capable of producing polyether compounds having polymerizable unsaturated groups with lower viscosity.

[0022] The meanings and definitions of terms used in this specification are as follows: A numerical range represented by "~" means a numerical range whose lower and upper limits are the numbers before and after "~".

[0023] Simultaneous 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 ranges specified in the cumulative range of each volatile component. Temperature range: 30°C to 450°C; Heating rate: 10°C / min; Atmosphere gas: Nitrogen (50 mL / min); Sample volume: 10 mg; Cumulative range of volatile component amounts: 30°C to 100°C, 30°C to 150°C, 150°C to 220°C, 100°C to 200°C, 150°C to 200°C, 30°C to 220°C.

[0024] "Polyether compound" means a polyether compound having a hydroxyl group. "Polyether compound" does not have a reactive silicon group, a urethane bond, or a polymerizable unsaturated group. "Polyether compound having a reactive silicon group" has a reactive silicon group. "Polyether compound having a reactive silicon group" may have one or more of a hydroxyl group, a urethane bond, and a polymerizable unsaturated group. "Polyether compound having a urethane bond" has a urethane bond. "Polyether compound having a urethane bond" may have a hydroxyl group. "Polyether compound having a urethane bond" does not have a reactive silicon group or a polymerizable unsaturated group. "Polyether compound having a urethane bond" is also referred to as "prepolymer" below. "Polyether compound having a polymerizable unsaturated group" has a polymerizable unsaturated group. "Polyether compound having a polymerizable unsaturated group" may have one or more of a hydroxyl group and a urethane bond. "Polyether compound having a polymerizable unsaturated group" does not have a reactive silicon group. Hereinafter, "polyether compounds," "polyether compounds having reactive silicon groups," "polyether compounds having urethane bonds," and "polyether compounds having polymerizable unsaturated groups" will be collectively referred to as "polyether compounds, etc." The "units" constituting polyether compounds, etc. refer to atomic groups directly formed by the polymerization of monomers. The "main chain" refers to a polymer chain formed by the polymerization of two or more monomers. In the polyether compounds, polyether compounds having reactive silicon groups, and polyether compounds having polymerizable unsaturated groups described later, the "main chain" refers to the portion (polyoxyalkylene chain) that includes residues obtained by removing active hydrogen from the initiator and repeating units based on alkylene oxide. Polyether compounds, polyether compounds having reactive silicon groups, and polyether compounds having polymerizable unsaturated groups are polymers consisting of a main chain and terminal groups. The "terminal groups" of polyether compounds, polyether compounds having reactive silicon groups, and polyether compounds having polymerizable unsaturated groups refer to atomic groups containing the oxygen atom closest to the molecular end among the oxygen atoms in the polyoxyalkylene chain described above.However, if an atomic group contains a residue of the initiator, it is not considered a terminal group but rather part of the main chain. The "number of terminal groups" in polyether compounds, polyether compounds having a reactive silicon group, and polyether compounds having a polymerizable unsaturated group is the same as the number of active hydrogens of the initiator, as described below. 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 bonded to a carbon atom. "Active hydrogen" refers to hydrogen atoms based on the above-mentioned active hydrogen-containing group and hydrogen atoms based on the hydroxyl group of water.

[0025] The "silylation rate" in a polyether compound having 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 having reactive silicon groups. 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 value of 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 silylating agent to the number of terminal groups when introducing the above-mentioned reactive silicon groups to the terminal groups of a polyether compound using the silylating 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. The isocyanate group content relative to the total mass of the prepolymer described below is a value measured in accordance with JIS K 7301:1995.

[0026] 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.

[0027] The "hydroxyl value" of a polyether compound is measured according to Method B (phthalation method) described in JIS K 1557-1:2007. The molecular weight converted to hydroxyl value is calculated as 56,100 / hydroxyl value of the polyether compound × number of hydroxyl groups in the polyether compound (number of active hydrogens of the initiator). If two or more polyether compounds with different numbers of hydroxyl groups are included, the number of hydroxyl groups of the polyether compound is the average number of hydroxyl groups.

[0028] The total degree of unsaturation of polyether compounds can be measured in accordance with JIS K 1557-3:2007. The viscosity of polyether compounds, polyether compounds having reactive silicon groups, prepolymers, and polyether compounds having polymerizable unsaturated 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.

[0029] ≪Composite Metal Cyanide Complex Catalyst≫ 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 the total mass 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 at 150 to 220°C, and A1 / A2 is 0.5 or less.

[0030] The composite metal cyanide complex 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 the reaction product 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. Known metal halide salts, cyanide transition metal compounds, and organic ligands can be used in the production of the DMC catalyst.

[0031] The DMC catalyst is thought to be represented by the following equation 2. １ ａ１ [M ２ (CN) ｂ１ ] ｃ１・d1(M １ ｅ１ X １ ｆ１ ).g1(Ligand).h1(H ２ O) 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.

[0032] 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. The metal halide salt that is M １ ｅ１ X １ ｆ１ is preferably one or more selected from zinc fluoride, zinc chloride, zinc bromide, zinc iodide, zinc sulfate, zinc nitrate, and zinc acetate. M ２ and X １It 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 organic ligand or two or more. 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, and tert-butyl alcohol is more preferred.

[0033] A preferred example of a DMC catalyst is zinc hexacyanocobaltate (Zn), which contains an organic ligand, water, zinc chloride, or zinc bromide. ３ [Co(CN) ６ ] ２ ) Its chemical formula is Zn ３ [Co(CN) ６ ] ２ d1(ZnCl ２ )・g1(Ligand)・h1(H ２ O) or Zn ３ [Co(CN) ６ ] ２ d1(ZnBr ２ )・g1(Ligand)・h(H ２ It is thought to be O).

[0034] As a DMC catalyst, zinc hexacyanocobaltate (Zn) has ethylene glycol dimethyl ether or tert-butyl alcohol as a ligand. ３ [Co(CN) ６ ] ２ A complex is preferred. Water and zinc chloride may be coordinated to the above complex.

[0035] 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 by mass%, and the ratio of the mass of the DMC catalyst to the total mass, measured at 30 to 150°C, is denoted as A2 by 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. A1 / A2 is preferably 0.1 to 0.5, more preferably 0.2 to 0.45, and even more preferably 0.3 to 0.43. When A1 / A2 is below the above upper limit, it is easier to obtain polyether compounds with a narrow molecular weight distribution and low viscosity. Also, when A1 / A2 is above the above lower limit, it is easier to obtain polyether compounds with a narrow molecular weight distribution and low viscosity.

[0036] 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, and the molecular weight distribution and viscosity of the resulting polyether compounds, etc., decrease.

[0037] 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. When A1 is within the above range, polyether compounds with a narrow molecular weight distribution and low viscosity are easily obtained.

[0038] 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. When A2 is within the above range, polyether compounds with a narrow molecular weight distribution and low viscosity are easily obtained.

[0039] The ratio of the mass of the DMC catalyst to the total mass that decreases at 30 to 100°C (hereinafter also referred to as "A3"), as measured by simultaneous thermogravimetric-differential thermal analysis, is preferably 1.50% by mass or less, more preferably 1.49% by mass or less, and even more preferably 1.48% by mass or less. The lower limit of A3 is, for example, preferably 0.40% by mass or more, more preferably 0.50% by mass or more, and even more preferably 0.60% by mass or more. A3 is preferably 0.40 to 1.50% by mass, more preferably 0.50 to 1.49% by mass, and even more preferably 0.60 to 1.48% by mass. When A3 is within the above range, it is easier to obtain polyether compounds with a narrow molecular weight distribution and low viscosity.

[0040] The percentage of the total mass of the DMC catalyst that decreases at 100 to 200°C, as measured by simultaneous thermogravimetric-differential thermal analysis (hereinafter also referred to as "A4"), is preferably 5.0 to 11.0% by mass, more preferably 5.2 to 10.0% by mass, and even more preferably 5.4 to 9.9% by mass. When A4 is within the above range, polyether compounds with a narrow molecular weight distribution and low viscosity are easily obtained.

[0041] The percentage of the total mass of the DMC catalyst that decreases at 150 to 200°C, as measured by simultaneous thermogravimetric-differential thermal analysis (hereinafter also referred to as "A5"), is preferably 4.0 to 8.0% by mass, more preferably 4.1 to 7.5% by mass, and even more preferably 4.2 to 7.0% by mass. When A5 is within the above range, polyether compounds with a narrow molecular weight distribution and low viscosity are easily obtained.

[0042] The ratio of the mass of the DMC catalyst to the total mass that decreases between 30 and 220°C (hereinafter also referred to as "A6"), as measured by simultaneous thermogravimetric-differential thermal analysis, is preferably 8.0 to 14.0% by mass, more preferably 8.5 to 13.5% by mass, and even more preferably 9.0 to 13.2% by mass. When A6 is within the above range, polyether compounds with a narrow molecular weight distribution and low viscosity are easily obtained.

[0043] The ratio of 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 compounds with a narrow molecular weight distribution and low viscosity are easily obtained.

[0044] The ratio of 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, it is easier to obtain polyether compounds with a narrow molecular weight distribution and low viscosity.

[0045] The ratio of 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, it is easier to obtain polyether compounds with a narrow molecular weight distribution and low viscosity.

[0046] 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.

[0047] 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.

[0048] 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 the dispersion medium for the slurry catalyst, polyether compounds are preferred because they do not become impurities in the products (polyether compounds) produced by the polymerization of alkylene oxides. The Mn of the polyether compound used as the dispersion medium is preferably 100 to 8,000, and more preferably 600 to 3,000. If the Mn is above the lower limit, it is less likely to become a catalyst poison, and if it is below the upper limit, the handling of the slurry catalyst is excellent. In addition, the initiator used when polymerizing alkylene oxides may be used as part of the dispersion medium.

[0049] The dispersion medium of the slurry catalyst is preferably substantially water-free. Specifically, the water content 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 preferably 0 to 500 ppm by mass, more preferably 0 to 200 ppm by mass. The water content of the dispersion medium and the water content relative to the total mass of the slurry catalyst described later are the water content measured by the Karl Fischer assay.

[0050] 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 relative 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.

[0051] <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 with a cyanide transition metal compound. Furthermore, it is preferable to wash the DMC catalyst after synthesis.

[0052] In the presence of water, a metal halide salt and a cyanide transition metal compound are reacted to obtain a reaction product to which an organic ligand is coordinated in the presence of water to obtain a mixture containing the DMC catalyst and water. Impurities and water are removed from the obtained mixture, and the water content of the resulting solid is reduced to a predetermined range to obtain the DMC catalyst.

[0053] A preferred embodiment of the method for producing the DMC catalyst of this embodiment is as follows: First, an aqueous solution of a metal halide salt is reacted with an aqueous solution of a cyanide transition metal compound to produce a reaction product. An aqueous solution of an organic ligand is added to this and stirred to coordinate the organic ligand to obtain a mixture containing the DMC catalyst and water. The obtained mixture is subjected to solid-liquid separation to obtain a solid. The obtained solid is washed with a solution containing the organic ligand, and the solid-liquid separation operation is performed one or more times, preferably two or more times. Alternatively, the obtained solid may be dried so that its moisture content is within the specified range and pulverized as necessary.

[0054] 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 preferable that it be below the saturation concentration. The concentration of the metal halide salt in the aqueous solution of the metal halide salt is preferably 10% or more and below the saturation concentration, more preferably 30% by mass or more and below the saturation concentration, and even more preferably 50% by mass or more and below the saturation concentration. The concentration of the cyanide transition metal compound in the aqueous solution of the cyanide transition metal 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 contained in the metal halide salt to the transition metal contained in the cyanide transition metal compound is preferably 1.6 to 12.0, and more preferably 1.8 to 8.0.

[0055] Mixing an aqueous solution of a metal halide salt and an aqueous solution of a cyanide transition metal compound is preferably done by adding the other aqueous solution dropwise to one. Furthermore, 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 A1 / A2, etc., within the above-mentioned range. Other mixing methods that can be considered include adding the aqueous solution of the metal halide salt dropwise to an aqueous solution of the cyanide transition metal compound, or mixing the aqueous solutions of the cyanide transition metal compound and the aqueous solution of the metal halide salt directly without dropwise mixing. In this regard, the inventors have found that the surface state of the DMC catalyst structure changes when these methods are used compared to when the aqueous solution of the cyanide transition metal compound is added dropwise to an aqueous solution of metal halide. Specifically, when an aqueous solution of a cyanide transition metal compound is added dropwise to an aqueous solution of a metal halide salt, the presence of a large excess of the metal halide salt in the mixed system makes it easier for metal (e.g., zinc) to be distributed on the surface of the structure of the produced DMC catalyst, making it easier to control the A1 / A2 ratio to 0.5 or less. The ratio of the dropping rate (mol / hour) in terms of 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. The above 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 above ratio is below the above upper limit, it becomes easier to control A1 / A2 etc. within the above range. The dropping time of 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.If the dripping time is within the above range, it becomes easier to control A1 / A2, etc., within the aforementioned range.

[0056] When mixing an aqueous solution of a metal halide salt with an aqueous solution of a cyanide transition metal 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.

[0057] 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.

[0058] 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.

[0059] 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.

[0060] 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.

[0061] 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.

[0062] The terminal group of polyether compound a is a hydroxyl group. The number of hydroxyl groups in polyether compound a is preferably 1 to 8, more preferably 1 to 6, and even more preferably 1 to 4. In one embodiment, 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.

[0063] The Mn of polyether compound a is preferably 400 to 3000, more preferably 500 to 2500, and even more preferably 600 to 1500.

[0064] 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.

[0065] 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 relative to 100 parts by mass of the total of the 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 inclusion of polyether compound a in the aqueous solution of the organic ligand improves the filterability when filtration is used in solid-liquid separation. It also makes it easier to control the A1 / A2 ratio within the above range.

[0066] 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 not only the DMC catalyst but also 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. The inventors have found that the first washing after coordinating the organic ligand, performed by solid-liquid separation, and then washing the resulting solid containing the DMC catalyst with a washing solution that has a high organic ligand content (relative amount of organic ligand to water), affects the structure of the DMC catalyst. The preferred content of the organic ligand will be described later. Specifically, by performing solid-liquid separation after coordinating the organic ligand, excess alkali metal halides can be removed. Furthermore, if the initial washing is performed with a washing solution that has a high content of organic ligands (relative amount of organic ligands to water) after removing excess alkali metal halides, the efficient coordination of organic ligands is more easily promoted, A2 tends to increase, and as a result, it becomes easier to control A1 / A2 to 0.5 or less. Conversely, if the initial washing is performed without solid-liquid separation, or if the initial washing is performed with a washing solution that has a low content of organic ligands (relative amount of organic ligands to water), A2 tends to decrease, and as a result, A1 / A2 tends to increase.

[0067] In this embodiment, it is preferable to use in combination a cleaning solution containing an organic ligand, water, and the polyether compound a (hereinafter also referred to as "cleaning solution 1") and a cleaning solution containing an organic ligand and the polyether compound a, but without water (hereinafter also referred to as "cleaning solution 2").

[0068] 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.

[0069] 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.

[0070] 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.

[0071] In the case of cleaning 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.

[0072] In the case of washing solution 1, the content of polyether compound a relative to the total mass of the washing 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 relative to 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 makes it easier to improve the filterability when filtration is used in solid-liquid separation. It also makes it easier to control A1 / A2 within the above range.

[0073] 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.

[0074] 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.

[0075] 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.

[0076] In the case of washing solution 2, the content of polyether compound a relative to the total mass of the washing 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 relative to 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 makes it easier to improve the filterability when filtration is used in solid-liquid separation. It also makes it easier to control A1 / A2 within the above range.

[0077] 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.

[0078] 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.

[0079] 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.

[0080] ≪Method for Producing Polyether Compounds≫ The method for producing polyether compounds in this embodiment involves polymerizing alkylene oxide on an initiator having active hydrogen in the presence of the above-mentioned DMC catalyst.

[0081] 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 to be obtained. The number of active hydrogen atoms in the initiator and the number of terminal groups in the polyether compound are the same. One type of initiator may be used alone, or two or more types may be used in combination.

[0082] The initiator is preferably one that has a hydroxyl group as an active hydrogen-containing group. As an initiator having one hydroxyl group, a monohydric alcohol having a linear or branched hydrocarbon group is 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, oleyl alcohol, etc. As an initiator having two hydroxyl groups, examples include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, etc. Water is also an example of an initiator having two hydroxyl groups. As an initiator having three hydroxyl groups, examples include glycerin, trimethylolpropane, trimethylolethane, etc. 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.

[0083] The alkylene oxide is selected according to the constituent units of the polyoxyalkylene chain of the resulting polyether compound. The number of carbon atoms in the alkylene oxide is preferably 2 to 12, more preferably 2 to 8, and even 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.

[0084] When a DMC catalyst is used as a polymerization catalyst, the Mw / Mn ratio of the polyether compound tends to be lower, and the total degree of unsaturation of the polyether compound tends to be lower, compared to when a polymerization catalyst other than a DMC catalyst is used.

[0085] When the polyoxyalkylene chain of a polyether compound is a random copolymer chain consisting of propylene oxide units and ethylene oxide units, a method of obtaining the polyether compound by reacting an initiator with a mixture of propylene oxide and ethylene oxide in the presence of a DMC catalyst is preferred.

[0086] When the polyoxyalkylene chain of the polyether compound is a copolymer chain having a block consisting of propylene oxide units and a block consisting of ethylene oxide units, the polyether compound 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 the polyether compound.

[0087] The amount of DMC catalyst used relative to the total mass of the resulting polyether compound 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.

[0088] Polymerization may be carried out in a continuous or batch manner, but batch polymerization is preferred. 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. The lower limit is not particularly limited, but for example, it is atmospheric pressure. The polymerization pressure is preferably atmospheric pressure or higher and 1.0 MPa or less, more preferably atmospheric pressure or higher and 0.8 MPa or less, and even more preferably atmospheric pressure or higher and 0.3 MPa or less. The alkylene oxide is preferably supplied to the reactor at a rate that maintains the above reaction temperature. The reaction atmosphere is preferably one that is less susceptible to moisture contamination, and more preferably an inert gas atmosphere such as nitrogen.

[0089] 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 when producing the polyether compound. The content of the polyether compound 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.

[0090] <Polyether Compounds> The main chain of a polyether compound 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"). In the case of a polymer chain having two or more types of alkylene oxide units, these alkylene oxide units may form block polymers or random polymers. Examples of oxyalkylene chains include polymer chains having ethylene oxide units, polymer chains having propylene oxide units, polymer chains having ethylene oxide units and propylene oxide units, polymer chains consisting of ethylene oxide units, polymer chains consisting of propylene oxide units, polymer chains consisting of butylene oxide units, polymer chains consisting of tetramethylene oxide units, polymer chains consisting of ethylene oxide units and propylene oxide units, and polymer chains consisting of propylene oxide units and butylene oxide units. Polymer chains having ethylene oxide units, polymer chains having propylene oxide units, polymer chains having ethylene oxide units and propylene oxide units, polymer chains consisting of propylene oxide units, and polymer chains consisting of ethylene oxide units and propylene oxide units are preferred, with polymer chains consisting of propylene oxide units being particularly preferred. The terminal groups of the polyether compound are hydroxyl groups. The number of terminal groups of the polyether compound (i.e., the number of hydroxyl groups) is the same as the number of active hydrogens of the initiator.

[0091] The manganese (Mn) of the polyether compound 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 the polyether compound can be kept low, making it easy to handle.

[0092] The hydroxyl value of the polyether compound 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 resin formation occurs. If the hydroxyl value is below the upper limit, sufficient flexibility is imparted to the resin, and good elongation properties are easily obtained.

[0093] The hydroxyl value-based molecular weight of the polyether compound 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 provides 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 the polyether compound can be kept low, making it easy to handle.

[0094] The viscosity (Mw) of the polyether compound 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 the polyether compound can be kept low, making it easy to handle.

[0095] The Mw / Mn of the polyether compound 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 the polyether compound can be kept low, making it easier to handle.

[0096] The total degree of unsaturation of the polyether compound 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.

[0097] The viscosity of the polyether compound 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.

[0098] For polyether compounds with a hydroxyl value-based molecular weight of 16,000 to 19,000, the viscosity 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.

[0099] <Uses of Polyether Compounds> Polyether compounds can be used as lubricants, raw materials for polyurethane foams, adhesives, sealants, coatings, etc. Furthermore, by reacting them with compounds that can react with the hydroxyl groups of polyether compounds, they may be used to produce polyether compounds having reactive silicon groups, prepolymers, and polyether compounds having polymerizable unsaturated groups.

[0100] <Polyether compounds having reactive silicon groups> Polyether compounds having reactive silicon groups (hereinafter also referred to as "polyether compound A") have reactive silicon groups represented by formula 1 described below.

[0101] (Reactive Silicon Group) A reactive silicon group has a hydroxyl group, halogen atom, or 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 A is represented by formula 1 below. -SiR ａ X ３－ａ Formula 1

[0102] 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. Preferably, R is at least one group selected from the group consisting of hydrocarbon groups and triorganosiloxy groups having 1 to 20 carbon atoms.

[0103] 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 from the viewpoint of good curability of polyether compound A and stability of the curable composition. An α-chloromethyl group is preferred from the viewpoint of a fast curing rate of the cured product. A methyl group is particularly preferred from the viewpoint of being readily available.

[0104] In Formula 1 above, X represents a hydroxyl group, a halogen atom, 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. Methoxy groups, ethoxy groups, or isopropoxy groups are preferred, 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 easier to form a crosslinked structure in the cured product, and the physical properties of the cured product tend to be good.

[0105] 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 decrease the modulus of the cured product, a is preferably 2 or less, and a is more preferably 1 or less.

[0106] Examples of reactive silicon groups represented by Formula 1 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.

[0107] Polyether compound A 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.

[0108] Polyether compound A 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 A is the same as the number of terminal groups in the above-mentioned polyether compound. The terminal groups of polyether compound A have one of the following: a reactive silicon group, an unsaturated group, an isocyanate group, or a hydroxyl group, represented by formula 1 above. These terminal groups may be the same or different from each other.

[0109] The average number of reactive silicon groups represented by formula 1 per terminal group of polyether compound A 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.

[0110] The average number of reactive silicon groups represented by the above formula 1 per molecule of polyether compound A 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.

[0111] 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, 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.

[0112] The Mw / Mn of polyether compound A 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.

[0113] The viscosity of polyether compound A 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.

[0114] When the hydroxyl value-based molecular weight of the raw material polyether compound (polyether compound having hydroxyl groups) is 16,000 to 19,000, the viscosity of polyether compound A 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.

[0115] When the hydroxyl value-based molecular weight of the raw material polyether compound (polyether compound having hydroxyl groups) is 16,000 to 19,000, the viscosity of polyether compound A 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.

[0116] <Method for producing polyether compounds having reactive silicon groups> In the method for producing polyether compound A, the hydroxyl group of the polyether compound is converted into a group having a reactive silicon group represented by the above formula 1. Examples of methods for producing polyether compound A include the following methods (a1), (b1), or (c1). Method (a1): A method in which the hydroxyl group of the polyether compound is converted into an alkenyloxy group having a carbon-carbon double bond at the molecular end or an alkynyloxy group having a carbon-carbon triple bond, and then a silylating agent capable of introducing a reactive silicon group represented by the above formula 1 is reacted with the carbon-carbon double bond at the molecular end 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 the above formula 1. Method (b1): A method in which the hydroxyl group of the polyether compound is reacted with a silylating agent having a functional group that can react 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 of converting the hydroxyl group of a polyether compound 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.

[0117] In method (a1), a polyether compound 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 the polyether compound into an alkenyloxy group having a carbon-carbon double bond or an alkynyloxy group having a carbon-carbon triple bond at the molecular terminus.

[0118] 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 viewpoint 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 viewpoint of availability. The alkali metal salt may be used in a dissolved state in a solvent.

[0119] Examples of halogenated hydrocarbon compounds containing a carbon-carbon double bond at the molecular terminus 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-octin, 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, and 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. Halogenated hydrocarbon compounds having carbon-carbon double bonds and halogenated hydrocarbon compounds having triple bonds at the molecular terminus may be used in combination. One halogenated hydrocarbon compound having carbon-carbon double bonds at the molecular terminus may be used, or two or more may be used in combination. One halogenated hydrocarbon compound having carbon-carbon triple bonds may be used, or two or more may be used in combination. Furthermore, as halogenated hydrocarbon compounds having a carbon-carbon triple bond, halogenated hydrocarbon compounds having a carbon-carbon triple bond at the molecular terminus are preferred.

[0120] 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－ａExamples 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.

[0121] In method (b1), a polyether compound is reacted with a silylating agent. It is preferable to use an isocyanate silane compound represented by formula 3 below as the silylating agent: OCN-(CH ２ ) ｎ -SiR ａ X ３－ａ Equation 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 reaction between the hydroxyl group of the polyether compound and the isocyanate silane compound results in the hydroxyl group of the polyether compound being -O-C(=O)NH-(CH ２ ) ｎ -SiR ａ X ３－ａ Represented by a urethane bond (-O-C(=O)NH-) and -SiR ａ X ３－ａIt is converted to a terminal group having the following characteristics. 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. Among the isocyanate silane compounds, 3-isocyanate propyltrimethoxysilane, 3-isocyanate propyltriethoxysilane, 3-isocyanate propyltriethoxysilane, 3-isocyanate propylmethyldimethoxysilane, isocyanate methylmethyldimethoxysilane, and isocyanate methyltrimethoxysilane are preferred due to their reactivity with polyether compounds and ease of handling.

[0122] The active hydrogen of the polyether compound reacts with the isocyanate group of the isocyanate silane compound represented by formula 3 above, thereby introducing a reactive silicon group into the polyether compound. When the active hydrogen-containing group of the polyether compound 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. A polyether compound A is obtained in which a reactive silicon group is bonded to ) via a urethane bond and an organic group. That is, -(R ５ O) ｍ -C(=O)NH-(CH ２ ) ｎ -SiR ａ X ３－ａ A connected structure represented by is formed.

[0123] 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.

[0124] 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 the polyether compound is preferably set according to the number of reactive silicon groups per molecule of the polyether compound A to be obtained. It is preferable to react the isocyanate-silane compound represented by formula 3 such that at least 0.7 reactive silicon groups are obtained per molecule of the polyether compound A. For example, if the active hydrogen-containing group of the polyether compound is a hydroxyl group, the molar ratio NCO / OH, which represents the total number of isocyanate groups (NCO) in the isocyanate-silane compound represented by formula 3 to the total number of active hydrogens (total number of hydroxyl groups) in the polyether compound, 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.

[0125] In method (c1), a polyisocyanate compound is reacted with the hydroxyl group of a polyether compound to convert the hydroxyl group into a monovalent organic group containing an isocyanate group having a urethane bond (-O-C(=O)NH-) at the terminal end bonded to the polyether compound (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 (-O-C(=O)NH-) and a silylation agent residue that has reacted with an isocyanate group (hereinafter also referred to as the "urethane bond 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.

[0126] OCN-R ３ -NCO Equation 4 R in Equation 4 above ３ This indicates a divalent organic group.

[0127] W-R 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 This is a divalent organic group, -SiR ａ X ３－ａ This is the same as equation 1 above.

[0128] When a diisocyanate compound represented by formula 4 is reacted with the hydroxyl group of a polyether compound, the isocyanate-containing group becomes -O-C(=O)NH-R ３ -NCO is the group that is formed. 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 are -O-C(=O)NH-R ３ -NHC(=O)-W'-R ４ -SiR ａ X ３－ａ(However, W' is a divalent group obtained by removing one active hydrogen from W.) It becomes a group represented by. For example, when W is a hydroxyl group, the urethane bond and the reactive silicon group-containing group are -O-C(=O)NH-R ３ -NHC(=O)-O-R ４ -SiR ａ X ３－ａ It is a group represented by. In this case, the urethane bond and the reactive silicon group-containing group have two urethane bonds. Further, for example, when W is an amino group (-NH ２ ), the urethane bond and the reactive silicon group-containing group are -O-C(=O)NH-R ３ -NHC(=O)-NH-R ４ -SiR ａ X ３－ａ It is a group represented by.

[0129] R ３ is preferably a divalent organic group having 2 to 20 carbon atoms, 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 bonded through an alkylene group as a substituent, a divalent group obtained by removing two hydrogen atoms from two or more aromatic hydrocarbons which may have an alkyl group bonded through an alkylene group as a substituent, etc. are mentioned.

[0130] Examples of the diisocyanate compound represented by the above formula 4 and other polyisocyanate compounds include aromatic polyisocyanate, non-yellowing aromatic polyisocyanate (a compound having no isocyanate group directly bonded to a carbon atom constituting an aromatic ring), aliphatic polyisocyanate, and alicyclic polyisocyanate, and urethane-modified products, burette-modified products, allophanate-modified products, carbodiimide-modified products, and isocyanurate-modified products obtained from the above polyisocyanates.

[0131] 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.

[0132] 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 R ４Preferably, 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.

[0133] In methods (b1) and (c1), the resulting polyether compound A has reactive silicon groups formed via one or more organic groups represented by the following formula (i). That is, the polyether compound A 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 A obtained by method (b1) contains only one organic group represented by the following formula (i) per terminal group, while the polyether compound A obtained by method (c1) contains two or more organic groups represented by the following formula (i) per terminal group. -C(=O)NH- Formula (i)

[0134] 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) per terminal group.

[0135] It is preferable that the organic group (i) forms a urethane bond (-O-C(=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 A. When polyether compound A is produced by the above method (b1), the number of organic groups represented by the above formula (i) per terminal group in polyether compound A is one. When polyether compound A is produced by method (b1), it is easy to obtain polyether compound A with a high silylation rate. When produced by method (b1), it is easy to obtain polyether compound A with a narrow molecular weight distribution. The viscosity of polyether compound A 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 A and the number of groups (i) per molecule are the same.

[0136] The silylation rate of polyether compound A 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 A, it is sufficient if the average silylation rate of all polyether compounds A is within the above range.

[0137] (Curable composition containing a polyether compound having a reactive silicon group) A polyether compound having a reactive silicon group is used in a curable composition. The curable composition is obtained by mixing polyether compound A with other necessary components. One type of polyether compound A may be used, or two or more types may be used in combination. The content of polyether compound A 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 better and the elongation properties will be better.

[0138] Other components included in the curable composition include curable compounds other than polyether compound A, 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-imparting 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, and others. Two or more of each ingredient may be used in combination.

[0139] The curable composition may be a one-component type in which polyether compound A 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 A 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. A one-component curable composition is preferably free of water. It is preferable to pre-dehydrate and dry any water-containing components, 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, but from the viewpoint of storage stability, it is preferable to pre-dehydrate and dry the components. To improve storage stability, a dehydrating agent may be added to the one-component curable composition or the two-component main component composition.

[0140] (Uses of curable compositions containing polyether compounds having reactive silicon groups) Suitable uses for curable compositions containing polyether compound A include adhesives, sealants (e.g., elastic sealants for buildings, sealants for double-glazed windows, sealants for rust prevention and waterproofing of glass edges, back-surface sealants for solar cells, sealants for buildings, sealants for ships, sealants for automobiles, sealants for roads), and electrical insulating materials (insulating coatings for electric wires and cables).

[0141] <Prepolymer> The prepolymer (hereinafter also referred to as "polyether compound B") is a reaction product of a polyether compound and a polyisocyanate. A urethane bond is formed between the polyether compound and the polyisocyanate through a urethane reaction between the hydroxyl groups of the polyether compound and the isocyanate groups of the polyisocyanate. Of the isocyanate groups in the polyisocyanate units introduced into polyether compound B, the isocyanate groups that remain unreacted with the hydroxyl groups of the polyether compound become the isocyanate groups at the molecular end of polyether compound B. In addition, of the hydroxyl groups in the polyether compound units, the hydroxyl groups that remain unreacted with the isocyanate groups of the polyisocyanate become the hydroxyl groups at the molecular end of polyether compound B. In other words, the molecular end groups of polyether compound B include either a hydroxyl group or an isocyanate group, or both.

[0142] The manganese (Mn) of polyether compound B is preferably 1,000 to 1,000,000, more preferably 1,500 to 500,000, and even more preferably 2,000 to 100,000. When Mn is above the lower limit, it provides sufficient flexibility when used as an adhesive or coating material, and good elongation properties are obtained. When Mn is below the upper limit, the viscosity of polyether compound B can be kept low, making it easy to handle.

[0143] The Mw / Mn of polyether compound B is preferably 1.00 to 1.50, more preferably 1.00 to 1.45, and even more preferably 1.00 to 1.40. When the Mw / Mn is below the above upper limit, good elongation properties are easily obtained, and the viscosity decreases, resulting in good workability.

[0144] When the molecular terminus of polyether compound B is an isocyanate group, the content of isocyanate groups relative to the total mass of polyether compound B is preferably 0.1 to 25% by mass, more preferably 0.5 to 18% by mass, and even more preferably 1 to 15% by mass. If the content of isocyanate groups is above the lower limit, the tensile strength of the cured product tends to improve. If the content of isocyanate groups is below the upper limit, gelation during the reaction is less likely to occur.

[0145] The content of urethane bonds relative to the total mass of polyether compound B is preferably 0.01 to 40% by mass, more preferably 0.1 to 30% by mass, and even more preferably 1 to 15% by mass.

[0146] The viscosity of polyether compound B at a measurement temperature of 25°C is preferably 100 to 100,000 mPa·s, more preferably 200 to 50,000 mPa·s, and even more preferably 500 to 30,000 mPa·s. When the viscosity is below the above upper limit, it is easy to handle.

[0147] When the hydroxyl value-based molecular weight of the raw material polyether compound (polyether compound having hydroxyl groups) is 16,000 to 19,000, the viscosity of polyether compound B at a measurement temperature of 25°C is preferably 20 to 50 Pa·s, more preferably 25 to 48 Pa·s, and even more preferably 30 to 45 Pa·s.

[0148] <Method for producing prepolymer> In the method for producing polyether compound B, a polyether compound is reacted with a polyisocyanate. A urethane catalyst may be used as needed. One type of polyether compound may be used, or two or more types may be used in combination.

[0149] Examples of polyisocyanates include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and aromatic aliphatic polyisocyanates. The number of isocyanate groups in the polyisocyanate is preferably 2 to 3, and more preferably 2.

[0150] Examples of aliphatic polyisocyanates include linear aliphatic polyisocyanates such as tetramethylene diisocyanate, dodecamethylene diisocyanate, and hexamethylene diisocyanate, as well as branched aliphatic polyisocyanates such as 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane-1,5-diisocyanate, and 3-methylpentane-1,5-diisocyanate.

[0151] Examples of alicyclic polyisocyanates include isophorone diisocyanate (3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, IPDI), hydrogenated xylylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, and 1,3-bis(isocyanate methyl)cyclohexane.

[0152] Examples of aromatic polyisocyanates include tolylene diisocyanate (TDI), 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate (diphenylmethane 4,4'-diisocyanate, MDI), 4,4'-dibenzyl diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate, 1,3-phenylene diisocyanate, and 1,4-phenylene diisocyanate.

[0153] Examples of aromatic aliphatic polyisocyanates include dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, and α,α,α,α-tetramethylxylylene diisocyanate.

[0154] Preferred polyisocyanates include alicyclic polyisocyanates and aromatic polyisocyanates, with IPDI, MDI, and TDI being more preferred. One type of polyisocyanate may be used alone, or two or more types may be used in combination.

[0155] The functional groups at the molecular ends of polyether compound B can be controlled by adjusting the molar ratio of the total amount of isocyanate groups of the polyisocyanate to the total amount of hydroxyl groups of the polyether compound (hereinafter also referred to as the "NCO / OH ratio"). For example, when producing polyether compound B with isocyanate groups at the molecular ends, the NCO / OH ratio is preferably 2 to 10, more preferably 2 to 8, even more preferably 2 to 7, and particularly preferably 2 to 5. When producing polyether compound B with hydroxyl groups at the molecular ends, the NCO / OH ratio is preferably 0.1 to 0.8, more preferably 0.2 to 0.7, and even more preferably 0.3 to 0.6.

[0156] As the urethane catalyst, one or more selected from tertiary amine compounds and organometallic compounds are preferred. However, when using highly reactive polyisocyanates, the urethane catalyst may not be necessary.

[0157] Examples of tertiary amine compounds include triethylamine, triethylenediamine, and 1,8-diazabicyclo(5,4,0)-undecene-7.

[0158] As the organometallic compound, one or more selected from tin compounds and non-tin compounds are preferred. Examples of tin compounds include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, and tin 2-ethylhexanoate. Examples of non-tin compounds include titanium compounds such as dibutyltitanium dichloride, tetrabutyltitanate, and butoxytitanium trichloride; lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate; iron compounds such as iron 2-ethylhexanoate and iron acetylacetonate; cobalt compounds such as cobalt benzoate and cobalt 2-ethylhexanoate; zinc compounds such as zinc naphthenate and zinc 2-ethylhexanoate; and zirconium compounds such as zirconium naphthenate.

[0159] The urethane catalyst may be used alone or in combination of two or more types. When using a urethane catalyst, the amount of urethane catalyst used is preferably 0.001 to 1.0 parts by mass per 100 parts by mass of the polyether compound.

[0160] A solvent may be used as needed in the production of polyether compound B. Preferably, one or more solvents are selected from ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, and aromatic hydrocarbons such as toluene and xylene. The solvent may be used alone or in combination of two or more. The amount of solvent used is not particularly limited, but 100 to 1000 parts by mass per 100 parts by mass of the polyether compound is preferred.

[0161] One method for producing polyether compound B is to mix a polyether compound, a polyisocyanate, and optionally a urethane catalyst and a solvent. Alternatively, the polyisocyanate may be added dropwise to a mixture obtained by mixing the polyether compound, and optionally a urethane catalyst and a solvent.

[0162] The reaction temperature is preferably 50 to 120°C, and more preferably 50 to 100°C. If the reaction temperature is above the lower limit, the urethane reaction is more easily accelerated. If the reaction temperature is below the upper limit, side reactions other than the urethane reaction are more easily suppressed.

[0163] When using a urethane catalyst, it is preferable to add a reaction stopper after the reaction is complete to deactivate the urethane catalyst. Examples of reaction stoppers include acetylacetone. One reaction stopper may be used alone, or two or more may be used in combination.

[0164] If unreacted polyisocyanate remains after the reaction, it is preferable to remove the polyisocyanate by distillation and purify polyether compound B.

[0165] (Polyurethane composition containing prepolymer) Polyether compound B is used in the polyurethane composition. The polyurethane composition is obtained by mixing polyether compound B with other optional components as needed. Only one type of polyether compound B may be used, or two or more types may be used in combination. The content of polyether compound B relative to the total mass of the polyurethane composition is 15 to 100% by mass, and preferably 30 to 100% by mass. The polyurethane composition may further contain optional components other than polyether compound B.

[0166] Examples of optional components included in a polyurethane composition include catalysts, fillers, plasticizers, stabilizers, pigments, fibers, dyes, desiccants, adhesion improvers, rheological modifiers, solvents, natural resins, non-reactive polymers, and other additives. Each optional component may be used individually or in combination of two or more. When a polyurethane composition contains optional components, the content of the optional components relative to the total mass of the polyurethane composition is preferably more than 0% by mass and 50% by mass or less.

[0167] A cured product can be produced by reacting a polyurethane composition with a curing agent. When the molecular ends of polyether compound B are isocyanate groups, a curing agent having active hydrogen is used. The active hydrogen-containing group of the curing agent is preferably a hydroxyl group. When the molecular ends of polyether compound B are hydroxyl groups, a curing agent having isocyanate groups is used. When the molecular ends of polyether compound B are isocyanate groups, the isocyanate groups of polyether compound B contained in the polyurethane composition and the active hydrogen-containing group (e.g., a hydroxyl group) of the curing agent undergo a urethane reaction, crosslinking the polyether compound B by urethane bonds and obtaining a cured product. When the molecular ends of polyether compound B are hydroxyl groups, the hydroxyl groups of polyether compound B contained in the polyurethane composition and the isocyanate groups of the curing agent undergo a urethane reaction, crosslinking the polyether compound B by urethane bonds and obtaining a cured product. In the case of a curing agent having hydroxyl groups, the number of hydroxyl groups in the curing agent is preferably two or more, more preferably two to four, and even more preferably two to three. Furthermore, the water used as a curing agent has two hydroxyl groups. In the case of a curing agent having isocyanate groups, the number of isocyanate groups in the curing agent is preferably two or more, more preferably two to four, and even more preferably two to three.

[0168] Examples of curing agents having a hydroxyl group include the initiator described in the method for producing polyether compounds and water. Examples of curing agents having an isocyanate group include the polyisocyanate mentioned above.

[0169] When the molecular ends of polyether compound B are isocyanate groups, the molar ratio of the total amount of isocyanate groups of polyether compound B to the total amount of hydroxyl groups of the curing agent is preferably greater than 1, and more preferably between 1.0 and 1.2. When the molecular ends of polyether compound B are hydroxyl groups, the molar ratio of the total amount of hydroxyl groups of polyether compound B to the total amount of isocyanate groups of the curing agent is preferably greater than 0.8, and more preferably between 0.8 and 1.2.

[0170] As for the method of mixing the polyurethane composition and the curing agent, it may be a one-component type in which the polyurethane composition, which is a one-component type composition obtained by pre-mixing all components except the curing agent, is sealed and stored, and cured by moisture in the air after application. Alternatively, it may be a two-component type in which the polyurethane composition, which is the main component, and the curing agent composition, which contains at least the curing agent, are stored separately, and the curing agent composition and the main component composition are mixed before use. In the case of the one-component type, moisture (water) in the air functions as the curing agent. That is, when the molecular end of polyether compound B is an isocyanate group, the one-component type is preferred. It is preferable that the one-component composition does not contain water. It is preferable to pre-dehydrate and dry the components containing water, or to dehydrate them by reducing the pressure during the preparation of the one-component composition. In the case of the two-component type, 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, but from the viewpoint of storage stability, it is preferable to pre-dehydrate and dry the components. In the case of the two-component type, the above optional components may be included in the curing agent composition. To improve storage stability, a dehydrating agent may be added to the one-component composition or the two-component main component composition. The reaction temperature is preferably 20 to 40°C. In the case of a one-component type, the relative humidity at the above reaction temperature is preferably 40 to 60%.

[0171] (Uses of Polyurethane Compositions Containing Prepolymers) Suitable uses for polyurethane 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, sealants for roads), coatings (for paint applications), and electrical insulating materials (insulating coatings for electric wires and cables). As an adhesive, it is suitable as an elastic adhesive for joining plastics together, joining metals together, and joining plastics and metals together. It is also suitable as an elastic sealant and an elastic coating.

[0172] <Polyether Compounds Having Polymerizable Unsaturated Groups> Polyether compounds having polymerizable unsaturated groups (hereinafter also referred to as "polyether compound C") are reaction products of a polyether compound and a compound having polymerizable unsaturated groups. Examples of polymerizable unsaturated groups include carbon-carbon double bonds at the molecular terminals. Preferred polymerizable unsaturated groups are (meth)acryloyl groups and (meth)acryloyloxy groups. "(meth)acryloyl group" is a general term for acryloyl groups and methacryloyl groups. "(meth)acryloyloxy group" is a general term for acryloyloxy groups and methacryloyloxy groups.

[0173] Polyether compound C 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, as this improves the crosslinking reaction and curability when resinified. The number of terminal groups in polyether compound C is the same as the number of terminal groups in the above-mentioned polyether compound.

[0174] The average number of polymerizable unsaturated groups per terminal group of polyether compound C is preferably 0.5 to 2.0, and more preferably 0.8 to 1.2. When the average number of polymerizable unsaturated groups is above the lower limit, the crosslinking reaction and curing properties when resin is formed tend to be good. When the average number of polymerizable unsaturated groups is below the upper limit, sufficient flexibility is imparted to the resin, and good elongation properties tend to be obtained.

[0175] The average number of polymerizable unsaturated groups per molecule of polyether compound C is preferably 1.0 to 8.0, more preferably 1.5 to 6.0, and even more preferably 2.0 to 4.0. When the average number of polymerizable unsaturated groups is above the lower limit, the crosslinking reaction and curing properties when resin is formed tend to be good. When the average number of polymerizable unsaturated groups is below the upper limit, sufficient flexibility is imparted to the resin, and good elongation properties tend to be obtained.

[0176] The manganese (Mn) of polyether compound C is preferably 1,000 to 1,000,000, more preferably 1,500 to 500,000, and even more preferably 2,000 to 100,000. When Mn is 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 C can be kept low, making it easy to handle.

[0177] The Mw / Mn of polyether compound C is preferably 1.00 to 1.50, more preferably 1.00 to 1.45, and even more preferably 1.00 to 1.40. When the Mw / Mn is below the above upper limit, good elongation properties are easily obtained, and the viscosity decreases, resulting in good workability.

[0178] When polyether compound C has urethane bonds, the content of urethane bonds relative to the total mass of polyether compound C is preferably 0.01 to 40% by mass, more preferably 0.1 to 30% by mass, and even more preferably 1 to 15% by mass.

[0179] The viscosity of polyether compound C at a measurement temperature of 25°C is preferably 100 to 100,000 mPa·s, more preferably 200 to 50,000 mPa·s, and even more preferably 500 to 30,000 mPa·s. When the viscosity is below the above upper limit, it is easy to handle.

[0180] <Method for Producing Polyether Compounds Having Polymerizable Unsaturated Groups> In the method for producing polyether compound C, the hydroxyl groups of the polyether compound are converted into groups having polymerizable unsaturated groups. Examples of methods for producing polyether compound C include the following methods (a2), (b2), or (c2). Method (a2): A method in which the hydroxyl groups of a polyether compound are reacted with a compound having a functional group that can react with the hydroxyl groups and a polymerizable unsaturated group (hereinafter also referred to as "compound 1") to convert the hydroxyl groups into groups having polymerizable unsaturated groups. Method (b2): A method in which the hydroxyl groups of a polyether compound are reacted with a polyisocyanate to obtain a prepolymer whose molecular termini are isocyanate groups, and then the hydroxyl groups are reacted with a compound having a functional group that can react with isocyanate groups and a polymerizable unsaturated group (hereinafter also referred to as "compound 2") to convert the hydroxyl groups into groups having polymerizable unsaturated groups. Method (c2): A method in which a hydroxyl group of a polyether compound is reacted with a polyisocyanate to obtain a prepolymer in which the molecular ends are hydroxyl groups, and then the hydroxyl group is reacted with compound 1 to convert the hydroxyl group into a group having a polymerizable unsaturated group.

[0181] As the prepolymer having isocyanate groups at the molecular ends in method (b2), the polyether compound B having isocyanate groups at the molecular ends as described above can be used. As the prepolymer having hydroxyl groups at the molecular ends in method (c2), the polyether compound B having hydroxyl groups at the molecular ends as described above can be used.

[0182] Compound 1 is preferably a compound having one isocyanate group and a polymerizable unsaturated group, more preferably a (meth)acrylate having one isocyanate group, even more preferably an isocyanate alkyl (meth)acrylate, particularly preferably an isocyanate alkyl (meth)acrylate with 8 or fewer carbon atoms excluding the carbon in the isocyanate group of the isocyanate alkyl group, and most preferably an isocyanate alkyl (meth)acrylate with 4 or fewer carbon atoms excluding the carbon in the isocyanate group of the isocyanate alkyl group. "(meth)acrylate" is a general term for acrylate and methacrylate. Examples of Compound 1 include 2-isocyanate ethyl (meth)acrylate and isocyanate methyl (meth)acrylate. Commercial products include Karenz-AOI and Karenz-MOI (both product names of Showa Denko Co., Ltd.).

[0183] As compound 2, compounds having an active hydrogen-containing group such as a hydroxyl group or an amino group and a polymerizable unsaturated group are preferred, (meth)acrylates having an active hydrogen-containing group such as a hydroxyl group or an amino group are preferred, hydroxyalkyl (meth)acrylates or hydroxycycloalkyl (meth)acrylates having one hydroxyl group are more preferred, and hydroxyalkyl (meth)acrylates with 8 or fewer carbon atoms in the alkyl group are particularly preferred. Examples of compound 2 include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 6-hydroxyhexyl (meth)acrylate. Commercially available products include Light Ester HO-250 (N), Light Ester HOP (N), Light Ester HOA (N), Light Ester HOP-A (N), Light Ester HOB (N) (all are product names of Kyoei Chemical Co., Ltd.), and 4-HBA (product name of Osaka Organic Chemical Industry Co., Ltd.).

[0184] When a composition containing polyether compound C is a photocurable composition, it is preferable that all polymerizable unsaturated groups in polyether compound C are acryloyloxy groups. Such polyether compound C can be obtained by using compounds in which the polymerizable unsaturated groups in compounds 1 and 2 are acryloyloxy groups.

[0185] In methods (a2) and (c2), the molar ratio of the amount of compound 1 used to the amount of hydroxyl groups in the polyether compound or the amount of hydroxyl groups in the prepolymer whose molecular ends are hydroxyl groups is preferably 0.8 to 1.2, more preferably 0.9 to 1.1, and even more preferably 0.95 to 1.05. In method (b2), the molar ratio of the amount of compound 2 used to the amount of isocyanate groups in the prepolymer whose molecular ends are isocyanate groups may be greater than 1. Excess compound 2 remains unreacted but may be contained in the composition containing polyether compound C. The above molar ratio is preferably 0.8 to 1.5, more preferably 0.9 to 1.3, and even more preferably 0.95 to 1.1.

[0186] In methods (a2), (b2), and (c2), the reaction between a hydroxyl group and a functional group that can react with the hydroxyl group, and the reaction between an isocyanate group and a functional group that can react with the isocyanate group, can be carried out using methods known in the art. When the above reaction is between a hydroxyl group and an isocyanate group, the above-mentioned urethane catalyst may be used as necessary.

[0187] (Composition containing a polyether compound having polymerizable unsaturated groups) Polyether compound C is used in the curable composition. The curable composition is obtained by mixing polyether compound C with other optional components. Only one type of polyether compound C may be used, or two or more types may be used in combination. The content of polyether compound C relative to the total mass of the curable product is preferably 65% ​​by mass or more, and more preferably 75% by mass or more.

[0188] The curable composition may contain, in addition to polyether compound C, compounds having polymerizable unsaturated groups other than polyether compound C (hereinafter also referred to as "other compounds"), photopolymerization initiators, and other components.

[0189] Other compounds include the following examples of other compounds 1 and 2. Other compound 1 is a compound other than polyether compound C, and preferably has one (meth)acryloyloxy group and one or more hydroxyl groups, and preferably has one or two hydroxyl groups. Other compound 1 may be a compound having a polyoxyalkylene chain, in which case a compound without urethane and urea bonds (a compound produced by methods other than (a2) to (c2) above) is preferred. Other compound 1 may also be a compound having an aliphatic polyester chain obtained by ring-opening addition polymerization of a lactone.

[0190] Other examples of compound 1 include hydroxyalkyl (meth)acrylates, dihydroxyalkyl (meth)acrylates, lactone-modified hydroxyalkyl (meth)acrylates, polyoxyalkylenediol mono(meth)acrylates, and (meth)acrylic acid monoepoxide adducts.

[0191] The number of carbon atoms in the hydroxyalkyl (meth)acrylate is preferably 2 to 8, and more preferably 2 to 6. The number of carbon atoms in the dihydroxyalkyl (meth)acrylate is preferably 2 to 8, and more preferably 2 to 6. Specific examples of hydroxyalkyl (meth)acrylate include the hydroxyalkyl (meth)acrylate exemplified as compound 2 above. Among these, 4-hydroxybutyl acrylate and 6-hydroxyhexyl acrylate are preferred in terms of flexibility and low volatility.

[0192] Examples of lactone-modified hydroxyalkyl (meth)acrylates include compounds obtained by ring-opening addition of a lactone to the hydroxyalkyl (meth)acrylate exemplified as compound 2 above. The number of added lactones is preferably 1 to 3. Examples of lactones include ε-caprolactone, γ-butyrolactone, and γ-valerolactone.

[0193] The (meth)acrylic acid-monoepoxide adduct is preferably a reaction product of (meth)acrylic acid with glycidyl ether or glycidyl ester, such as (meth)acrylic acid with phenylglycidyl ether.

[0194] Of these, hydroxyalkyl (meth)acrylates and (meth)acrylic acid monoepoxide adducts are preferred because they are readily available industrially and contain few impurities.

[0195] Other compound 1 may be used alone or in combination of two or more. When the curable composition contains other compound 1, the content of other compound 1 relative to the total mass of the curable composition is preferably 1 to 20% by mass, and more preferably 1 to 15% by mass. If the content of other compound 1 is above the lower limit, the effect of improving adhesion by adding other compound 1 is easily obtained. If the content of other compound 1 is below the upper limit, good physical properties in terms of low curing shrinkage rate are easily obtained.

[0196] Other compound 2 is a compound other than polyether compound C and other compound 1, and preferably has one (meth)acryloyloxy group and does not contain a urethane bond. Preferred other compound 2s are (meth)acrylates having a long-chain alkyl group with 8 or more carbon atoms, and (meth)acrylates having an amide group. Examples of other other compound 2s include alkyl (meth)acrylates having 7 or fewer carbon atoms, alkoxyalkyl (meth)acrylates, and (meth)acrylates having an aliphatic cyclic hydrocarbon group.

[0197] When a curable composition contains a long-chain alkyl (meth)acrylate with 8 or more carbon atoms, when forming a cured product by a method in which the curable composition is sealed under reduced pressure and cured in a higher-pressure atmosphere (reduced pressure sealing-pressure curing method), air bubbles in the cured product tend to disappear more easily. The number of carbon atoms in the long-chain alkyl group is preferably 8 to 22, and more preferably 8 to 18. Examples of long-chain alkyl (meth)acrylates include lauryl (meth)acrylate, isostearyl (meth)acrylate, and isodecyl (meth)acrylate. Among these, lauryl acrylate and isostearyl acrylate are preferred in terms of flexibility, low viscosity, and low crystallinity.

[0198] As for (meth)acrylates having an amide group, compounds in which the hydrogen atom bonded to the nitrogen atom of (meth)acrylamide is substituted with a hydrocarbon group such as an alkyl group or a divalent organic group are preferred because they easily suppress whitening of the cured product of the curable composition under humid heat conditions. Examples of (meth)acrylamide derivatives include 4-(meth)acryloylmorpholine, N,N-dimethyl(meth)acrylamide, and N,N-diethyl(meth)acrylamide.

[0199] Other compound 2 may be used alone or in combination of two or more. When the curable composition contains other compound 2, the content of other compound 2 relative to the total mass of the curable composition is preferably 1 to 30% by mass, and more preferably 1 to 25% by mass. If the content of other compound 2 is above the lower limit, the effects of adding other compound 2 are easily obtained. If the content of other compound 2 is below the upper limit, good physical properties in terms of low curing shrinkage rate are easily obtained.

[0200] The curable composition may be a photocurable composition or a thermosetting composition. A photocurable composition is preferred because it can be cured at low temperatures and has a fast curing rate. If the curable composition is a photocurable composition, it is preferable that it contains a photopolymerization initiator. In the case of a photocurable composition, for example, when used in the manufacture of a display device, high temperatures are not required, thus reducing the risk of damage to the display device due to high temperatures.

[0201] Examples of photopolymerization initiators include acetophenone-based, ketal-based, benzoin or benzoin ether-based, phosphine oxide-based, benzophenone-based, thioxanthone-based, and quinone-based photopolymerization initiators. Of these, phosphine oxide-based and thioxanthone-based photopolymerization initiators are preferred, and phosphine oxide-based ones are preferred because they tend to suppress discoloration after the photopolymerization reaction. One type of photopolymerization initiator may be used alone, or two or more types may be used in combination.

[0202] The photopolymerization initiator is not particularly limited, and commercially available products can also be used. Examples of commercially available products include BASF's IRGACURE 819, IRGACURE TPO, IRGACURE 184, IRGACURE 2959, IRGACURE 1173, IRGACURE 127, IRGACURE 907, IRGACURE OXE01, and IRGACURE OXE02. When the curable composition contains a photopolymerization initiator, the content of the photopolymerization initiator is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the total curable components.

[0203] Other components include tackifiers such as rosin esters, terpene phenols, and hydrogenated terpene phenols; plasticizers such as adipic acid esters and phthalate esters; polyether compounds without polymerizable unsaturated groups; and polyether polyols with alkoxylated molecular ends. When a curable composition contains plasticizers, its flexibility and adhesion tend to improve. The content of these compounds relative to the total mass of the curable composition is preferably 48% by mass or less, and more preferably 28% by mass or less.

[0204] Other components include polymerization inhibitors, photocuring accelerators, chain transfer agents, light stabilizers (UV absorbers, radical scavengers, etc.), antioxidants, flame retardants, adhesion enhancers (silane coupling agents, etc.), pigments, dyes, and the like. Among these, the inclusion of polymerization inhibitors and light stabilizers is preferable. In particular, including a smaller amount of polymerization inhibitor than polymerization initiators improves the storage stability of the curable composition and makes it easier to adjust the molecular weight after curing.

[0205] Examples of polymerization inhibitors include hydroquinone-based (e.g., 2,5-di-tert-butylhydroquinone), catechol-based (e.g., p-tert-butylcatechol), anthraquinone-based, phenothiazine-based, and hydroxytoluene-based polymerization inhibitors.

[0206] UV absorbers are used to prevent photodegradation of curable compositions and improve their weather resistance. Examples of UV absorbers include benzotriazole-based, triazine-based, benzophenone-based, and benzoate-based UV absorbers. For example, a benzotriazole-based UV absorber described in paragraph

[0076] of International Publication No. 2014 / 017328 can be used.

[0207] Light stabilizers are used to prevent photodegradation of curable compositions and improve their weather resistance. Examples of light stabilizers include hindered amine-based light stabilizers. Examples of hindered amine-based light stabilizers can be used that are described in paragraph

[0077] of International Publication No. 2014 / 017328.

[0208] Antioxidants are used to prevent oxidation of curable compositions and improve their weather resistance and heat resistance. Examples of antioxidants include phenolic and phosphorus-based antioxidants. For example, phenolic antioxidants described in paragraph

[0078] of International Publication No. 2014 / 017328 can be used. For example, phosphorus-based antioxidants described in paragraph

[0078] of International Publication No. 2014 / 017328 can be used.

[0209] Products containing a mixture of multiple antioxidants, light stabilizers, etc., can also be used. Examples include BASF's IRGASTAB PUR68 and TINUVIN B75.

[0210] If the curable composition contains other components, the total content of the other components is preferably 100 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably 35 parts by mass or less, per 100 parts by mass of the curable component.

[0211] In a curable composition, the content of the chain transfer agent is preferably low, preferably 3 parts by mass or less, more preferably 2 parts by mass or less, per 100 parts by mass of the curable component, and it is particularly preferable that there is no chain transfer agent at all.

[0212] (Uses of curable compositions containing polyether compounds having polymerizable unsaturated groups) Suitable uses for curable compositions containing polyether compound C include adhesives in various fields such as building materials, packaging materials, printing materials, display materials, electrical and electronic component materials, optical component materials, and liquid crystal panels.

[0213] The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following description.

[0214] [Simultaneous Thermogravimetric-Differential Thermal Analysis] Simultaneous thermogravimetric-differential thermal analysis and analysis of the DMC catalysts produced in Production Examples 1 to 4 were performed under the following conditions: Apparatus: STA 2500 Regulus (manufactured by NETZSCH) Temperature range: 30°C to 450°C Heating rate: 10°C / min Atmospheric gas: Nitrogen (50 mL / min) Sample volume: 10 mg Cumulative range of volatile component amount: 30°C to 100°C, 30°C to 150°C, 150°C to 220°C, 100°C to 200°C, 150°C to 200°C, 30°C to 220°C

[0215] [Hydroxyl Value and Hydroxyl-Equivalent Molecular Weight] The hydroxyl value was measured in accordance with Method B of JIS K 1557-1:2007. The hydroxyl-equivalent molecular weight was calculated as 56,100 / hydroxyl value of the polyether compound × number of hydroxyl groups in the polyether compound (number of active hydrogens of the initiator).

[0216] [Mn, Mw, Mw / Mn] Several types of monodisperse polystyrene with different degrees of polymerization were measured using a gel permeation chromatograph analyzer HLC-8420GPC (manufactured by 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 the retention time. Polyether compounds, polyether compounds having reactive silicon groups, or polyether compounds having polymerizable unsaturated groups were diluted to 0.5% by mass with tetrahydrofuran and passed through a filter with a pore size of 0.5 μm to obtain a sample for measurement. Using the obtained sample for measurement, 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 (manufactured by Tosoh Corporation) were used, and the column temperature was set to 40°C. The injection volume of the sample for measurement was 20 μL.

[0217] [Total unsaturation] The total unsaturation of the polyether compound was measured in accordance with JIS K 1557-3:2007.

[0218] [Viscosity] The viscosity of polyether compounds was measured using an E-type viscometer in accordance with JIS K 1557-5:2007, except that the measurement temperature was 40°C. The viscosity of polyether compounds having reactive silicon groups, polyether compounds having urethane bonds, and polyether compounds having polymerizable unsaturated groups was measured using an E-type viscometer at a measurement temperature of 25°C in accordance with JIS K 1557-5:2007.

[0219] [Number of reactive silicon groups] The number of reactive silicon groups (silylation rate) in a polyether compound containing reactive silicon groups is: １ Measurements were taken using the internal standard method of H-NMR.

[0220] [Production Example 1] Polypropylene glycol was polymerized with propylene oxide (hereinafter also referred to as "PO") in the presence of a KOH catalyst, 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 of 1,500, and a hydroxyl value of 75 mg KOH / g. 15 mL of an aqueous zinc chloride solution consisting of 10 g of zinc chloride and water was prepared in a flask. While stirring the aqueous zinc chloride solution, 80 mL of an aqueous potassium hexacyanocobaltate solution consisting of 4 g of potassium hexacyanocobaltate and water was added dropwise to the aqueous zinc chloride solution at a constant rate over 30 minutes. During this time, the reaction solution in the flask was kept at 40°C. After the addition of potassium hexacyanocobaltate aqueous 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 mixture containing the obtained 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 filter cake was transferred to a flask, a mixture consisting of 40 g of TBA, 70 g of water, and 1 g of polyol P1 was added, and the mixture was stirred at 40°C for 30 minutes. Then, under the same conditions as above, the filter cake after the first wash was obtained by filtering under pressure. The first washed filtration cake 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 second washed filtration cake. The obtained second washed filtration cake 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 loss and are expressed as absolute values.

[0221] [Production Example 2] DMC catalyst B was obtained in the same manner as in Production Example 1, except that the filtered cake after the second washing was dried under reduced pressure until there was no change in mass.

[0222] [Production 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.

[0223] [Production 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 80 g 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.

[0224]

[0225] <Polyether Compounds> Examples 1 and 2 below are examples, and Examples 3 and 4 are comparative examples.

[0226] [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 the mixture. The average number of hydroxyl groups per molecule of polyol P2 was 2, and the molecular weight in terms of 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 200 rpm, while maintaining the temperature inside the reactor at 130°C and reducing the pressure inside the reactor 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 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 polyether compound 1. The hydroxyl value, viscosity, Mw / Mn, and total unsaturation of polyether compound 1 are shown in Table 2 (the same applies to Examples 2-4 below).

[0227] [Example 2] Polyether compound 2 was obtained in the same manner as in Example 1, except that TBA-DMC catalyst B was used instead of TBA-DMC catalyst A.

[0228] [Example 3] Polyether compound 3 was obtained in the same manner as in Example 1, except that TBA-DMC catalyst C was used instead of TBA-DMC catalyst A.

[0229] [Example 4] Polyether compound 4 was obtained in the same manner as in Example 1, except that TBA-DMC catalyst D was used instead of TBA-DMC catalyst A.

[0230]

[0231] As shown in Table 2, the hydroxyl value-based molecular weights of polyether compounds 1 to 4 in Examples 1 to 4 are almost equivalent. On the other hand, the viscosity at 40°C was found to be lower for polyether compounds 1 and 2 in Examples 1 and 2 than for polyether compounds 3 and 4 in Examples 3 and 4.

[0232] <Polyether compounds having reactive silicon groups> Examples 1A and 2A below are examples, and Examples 3A and 4A are comparative examples.

[0233] [Example 1A] In a reaction vessel equipped with a stirrer and a nitrogen inlet tube, 900 g of polyether compound 1 obtained in Example 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 polyether compound 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 polyether compounds used as raw materials, the silylation rate of the obtained polyether compound A-1 having reactive silicon groups, and the viscosity are shown in Table 3 (the same applies to Examples 2A to 4A below).

[0234] [Example 2A] Polyether compound A-2 having a reactive silicon group was obtained in the same manner as in Example 1A, except that polyether compound 2 obtained in Example 2 was used instead of polyether compound 1.

[0235] [Example 3A] Polyether compound A-3 having a reactive silicon group was obtained in the same manner as in Example 1A, except that polyether compound 3 obtained in Example 3 was used instead of polyether compound 1.

[0236] [Example 4A] Polyether compound A-4 having a reactive silicon group was obtained in the same manner as in Example 1A, except that polyether compound 4 obtained in Example 4 was used instead of polyether compound 1.

[0237]

[0238] As shown in Table 2, the hydroxyl value-based molecular weights of the raw materials polyether compounds 1 to 4, which are the reactive silicon group-containing polyether compounds A-1 to A-4 in Examples 1A to 4A, are almost the same. Furthermore, the conditions for converting the hydroxyl groups of polyether compounds 1 to 4 to the reactive silicon group-containing groups represented by Formula 1 above are the same for Examples 1A to 4A. On the other hand, as shown in Table 3, it was found that the viscosity at 25°C is lower for the reactive silicon group-containing polyether compounds A-1 and A-2 in Examples 1A and 2A than for the reactive silicon group-containing polyether compounds A-3 and A-4 in Examples 3A and 4A.

[0239] <Polyether compounds having urethane bonds> Examples 1B and 2B below are examples, and Examples 3B and 4B are comparative examples.

[0240] [Example 1B] In a reaction vessel equipped with a stirrer and a nitrogen inlet tube, 900 g of polyether compound 1 obtained in Example 1 and 43.5 g of isophorone diisocyanate (Sumika Covestro Urethane Co., Ltd. product name "Desmodule I", NCO content: 37.8% by mass) were added and the reaction was carried out by stirring at 80°C for 6 hours in the presence of 0.09 g of dibutyltin dilaurate. The molar ratio of isocyanate in isophorone diisocyanate to hydroxyl groups in polyether compound 1, NCO / OH, was set to 2.0. The reaction was terminated after confirming that the NCO content of the obtained urethane-bonded polyether compound B-1 was approximately 1.31% by mass, which is the theoretical value. The types of polyether compounds used as raw materials and the viscosity of the obtained urethane-bonded polyether compound B-1 are shown in Table 4 (the same applies to Examples 2B to 4B below).

[0241] [Example 2B] Polyether compound B-2 having a urethane bond was obtained in the same manner as in Example 1B, except that polyether compound 2 obtained in Example 2 was used instead of polyether compound 1.

[0242] [Example 3B] Polyether compound B-3 having a urethane bond was obtained in the same manner as in Example 1B, except that polyether compound 3 obtained in Example 3 was used instead of polyether compound 1.

[0243] [Example 4B] Polyether compound B-4 having a urethane bond was obtained in the same manner as in Example 1B, except that polyether compound 4 obtained in Example 4 was used instead of polyether compound 1.

[0244]

[0245] As shown in Table 2, the hydroxyl value-based molecular weights of the raw materials polyether compounds 1 to 4, which are the urethane-bonded polyether compounds B-1 to B-4 in Examples 1B to 4B, are almost the same. Furthermore, the conditions for reacting polyether compounds 1 to 4 with polyisocyanates are the same in Examples 1B to 4B. On the other hand, as shown in Table 4, it was found that the viscosity at 25°C is lower for polyether compounds B-1 and B-2, which are urethane-bonded polyether compounds B-3 and B-4, which are urethane-bonded polyether compounds B-3 and B-4, in Examples 3B and 4B.

[0246] <Polyether compounds having polymerizable unsaturated groups> Examples 1C and 2C below are examples, and Examples 3C and 4C are comparative examples.

[0247] [Example 1C] In a reaction vessel equipped with a stirrer and a nitrogen inlet tube, 900 g of polyether compound 1 obtained in Example 1 and 13.8 g of 2-acryloyloxyethyl isocyanate (Showa Denko Corporation, "Karenz-AOI") were added and reacted at 80°C for 5 hours in the presence of 0.2 g of bismuth 2-ethylhexanoate. The molar ratio of the isocyanate amount of 2-acryloyloxyethyl isocyanate to the amount of hydroxyl groups of polyether compound 1, NCO / OH, was set to 1, and the reaction was terminated after confirming that there was no absorption from NCO by IR. The types of polyether compounds used as raw materials and the viscosity of the obtained polymerizable unsaturated polyether compound C-1 are shown in Table 5 (the same applies to Examples 2C to 4C below).

[0248] [Example 2C] Polyether compound C-2 having polymerizable unsaturated groups was obtained in the same manner as in Example 1C, except that polyether compound 2 obtained in Example 2 was used instead of polyether compound 1.

[0249] [Example 3C] Polyether compound C-3 having polymerizable unsaturated groups was obtained in the same manner as in Example 1C, except that polyether compound 3 obtained in Example 3 was used instead of polyether compound 1.

[0250] [Example 4C] Polyether compound C-4 having polymerizable unsaturated groups was obtained in the same manner as in Example 1C, except that polyether compound 4 obtained in Example 4 was used instead of polyether compound 1.

[0251]

[0252] As shown in Table 2, the hydroxyl value-based molecular weights of the raw materials for polyether compounds C-1 to C-4 having polymerizable unsaturated groups in Examples 1C to 4C are almost the same. Furthermore, the conditions for converting the hydroxyl groups of polyether compounds 1 to 4 to groups having polymerizable unsaturated groups are the same for Examples 1C to 4C. On the other hand, as shown in Table 5, it was found that the viscosity at 25°C is lower for polyether compounds C-1 and C-2 having polymerizable unsaturated groups in Examples 1C and 2C than for polyether compounds C-3 and C-4 having polymerizable unsaturated groups in Examples 3C and 4C.

Claims

1. A composite metal cyanide complex catalyst powder, wherein when A1 is the ratio of the mass of the composite metal cyanide complex catalyst powder to the total mass of the composite metal cyanide complex catalyst powder 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 of the composite metal cyanide complex catalyst powder that decreases at 150 to 220°C, as measured by simultaneous thermogravimetric-differential thermal analysis, A1 / A2 is 0.5 or less.

2. The composite metal cyanide complex catalyst powder 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. The composite metal cyanide complex catalyst powder according to claim 1 or 2, wherein the ratio of the mass decrease of the composite metal cyanide complex catalyst powder at 30 to 100°C relative to the total mass, as measured by simultaneous thermogravimetric-differential thermal measurement, is 1.50% by mass or less.

4. A method for producing a polyether compound, comprising polymerizing an alkylene oxide having 2 to 12 carbon atoms onto an initiator having active hydrogen in the presence of a complex metal cyanide catalyst powder according to any one of claims 1 to 3.

5. The method for producing a polyether compound according to claim 4, wherein the number of hydroxyl groups per molecule of the polyether compound is 1 to 8.

6. A method for producing a polyether compound having a reactive silicon group, comprising obtaining a polyether compound by the method for producing a polyether compound described in claim 4 or 5, and converting the hydroxyl group of the polyether compound to a group having a reactive silicon group represented by the following formula 1. -SiR ａ X ３－ａ Formula 1 In 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 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.

7. A method for producing a polyether compound having a urethane bond, comprising obtaining a polyether compound by the method for producing a polyether compound described in claim 4 or 5, and reacting the polyether compound with a polyisocyanate.

8. A method for producing a polyether compound having polymerizable unsaturated groups, comprising obtaining a polyether compound by the method for producing a polyether compound described in claim 4 or 5, and converting the hydroxyl groups of the polyether compound to groups having polymerizable unsaturated groups.

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