Method for producing polyether compound

Abstract

To provide a method for producing a reactive silicon group-containing polyether compound, by which the hydroxyl group-containing polyether compound having a narrow molecular weight distribution and a low viscosity can more surely be obtained, and the reactive silicon group-containing polyether compound reduced in discoloration can be obtained.SOLUTION: Contacting an initiator having active hydrogen with an alkylene oxide-containing starting material to polymerize alkylene oxides in the alkylene oxide-containing starting material with the initiator, wherein the chloride content of the alkylene oxide-containing starting material is less than 20ppm based on the total mass of the alkylene oxide-containing starting material.SELECTED DRAWING: None

Description

[Technical Field]

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

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

[0003] Polyether compounds having reactive silicon groups are produced from polyether compounds having hydroxyl groups as raw materials. Polyether compounds having hydroxyl groups are produced by polymerizing alkylene oxide with an initiator having active hydrogen. Double metal cyanide complex catalysts are known as polymerization catalysts for obtaining polyether compounds with narrow molecular weight distribution.

[0004] Patent Document 1 discloses a method for producing a hydrolyzable silyl group-containing polyoxyalkylene, which includes a step of ring-opening polymerizing a monoepoxide having a water content of 5 ppm or more but less than 50 ppm to obtain a hydroxyl group-containing polyoxyalkylene, and a step of introducing a hydrolyzable silyl group into the hydroxyl group-containing polyoxyalkylene. It discloses that by using a monoepoxide with a low water content, the obtained hydrolyzable silyl group-containing polyoxyalkylene can exhibit a high modulus after curing. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2023 / 095636 Summary of the Invention [Problem to be solved by the invention]

[0006] However, according to the inventor's investigations, even when a composite metal cyanide complex catalyst is used, the molecular weight distribution of the polyether compound having hydroxyl groups may not be sufficiently narrow. If the molecular weight distribution is broad, the viscosity of the polyether compound increases, which may result in poor workability. In addition, in the conventional method, there is a risk of coloration of the polyether compound having reactive silicon groups obtained from the polyether compound having hydroxyl groups.

[0007] An object of the present invention is to provide a production method that can more reliably produce a polyether compound having a hydroxyl group with a narrow molecular weight distribution and low viscosity, and can also produce a polyether compound having a reactive silicon group with reduced coloration. [Means for solving the problem]

[0008] The present invention has the following aspects. [1] A method for producing a polyether compound, comprising: contacting an initiator having active hydrogen with an alkylene oxide-containing raw material in the presence of a composite metal cyanide complex catalyst, and polymerizing the alkylene oxide in the alkylene oxide-containing raw material with the initiator; The method of claim 1, wherein the alkylene oxide-containing feedstock has a chlorine content of less than 20 ppm based on the total mass of the alkylene oxide-containing feedstock. [2] The production method according to [1], wherein the total aldehyde content of the alkylene oxide-containing raw material is less than 15 ppm based on the total mass of the alkylene oxide-containing raw material. [3] The method according to [1] or [2], wherein the hydroxyl group of the polyether compound having a hydroxyl group obtained by polymerizing the alkylene oxide with the initiator is converted into a group having a reactive silicon group represented by the following formula 2: -SiR a X 3-a formula 2 In the formula 2, R represents a monovalent organic group having 1 to 20 carbon atoms other than a hydrolyzable group, and X represents a hydroxyl group, a halogen atom, or a hydrolyzable group. a is an integer of 0 to 2. When a is 2, R may be the same or different from each other, and when a is 0 or 1, X may be the same or different from each other. [Effects of the Invention]

[0009] According to the present invention, a production method can be provided that can more reliably produce a polyether compound having a hydroxyl group with a narrow molecular weight distribution and low viscosity, and can also produce a polyether compound having a reactive silicon group with reduced coloration. DETAILED DESCRIPTION OF THE INVENTION

[0010] The meanings and definitions of terms used in this specification are as follows: A numerical range expressed by "to" means that the numerical values ​​before and after "to" are the lower and upper limits of the numerical range.

[0011] The "unit" constituting a polyether compound or the like means an atomic group formed directly by polymerization of a monomer. The term "main chain" refers to a polymer chain formed by polymerization of two or more monomers. In the polyether compounds, polyether compounds having a reactive silicon group, and polyether compounds having a polymerizable unsaturated group described below, the "main chain" refers to a residue obtained by removing active hydrogen from an initiator and a portion containing a repeating unit based on alkylene oxide (polyoxyalkylene chain). The polyether compound, the polyether compound having a reactive silicon group, and the polyether compound having a polymerizable unsaturated group are polymers consisting of a main chain and terminal groups. The "end group" of a polyether compound, a polyether compound having a reactive silicon group, and a polyether compound having a polymerizable unsaturated group refers to an atomic group containing the oxygen atom closest to the molecular end among the oxygen atoms in the polyoxyalkylene chain. However, if the atomic group contains a residue of an initiator, it is not considered to be an end group but is considered to be part of the main chain. The "number of end groups" in a polyether compound, a polyether compound having a reactive silicon group, and a polyether compound having a polymerizable unsaturated group is the same number as the number of active hydrogen atoms in the initiator, as described below. The "active hydrogen-containing group" refers to at least one group selected from the group consisting of a hydroxyl group bonded to a carbon atom, a carboxyl group, an amino group, a monovalent functional group obtained by removing one hydrogen atom from a primary amine, a hydrazide group, and a sulfanyl group. The term "active hydrogen" refers to a hydrogen atom derived from the active hydrogen-containing group and a hydrogen atom derived from the hydroxyl group of water.

[0012] The "silylation rate" of a polyether compound having a reactive silicon group is the ratio of the number of reactive silicon groups to the total number of reactive silicon groups, hydroxyl groups, unsaturated groups, and isocyanate groups in the terminal groups of the polyether compound having a reactive silicon group. Specifically, the silylation rate is calculated by the following formula: Silylation rate (%) = 100 × number of reactive silicon groups / [number of reactive silicon groups + number of hydroxyl groups + number of isocyanate groups + (number of carbon-carbon double bonds) + (number of carbon-carbon triple bonds) × 2] The silylation rate can be measured by NMR analysis. Alternatively, it may be the ratio (mol %) of the number of silyl groups of the silylating agent added to the polyether compound when the reactive silicon groups are introduced into the terminal groups of the polyether compound using the silylating agent described below to the number of terminal groups. In this case, however, a diisocyanate compound is used as the polyisocyanate compound in the method (c1) described below. The term "silylating agent" refers to a compound having a reactive silicon group and a functional group that reacts with an active hydrogen-containing group, an unsaturated group, or an isocyanate group. The content of isocyanate groups relative to the total mass of the prepolymer described below is a value measured in accordance with JIS K 7301:1995.

[0013] In this specification, the number average molecular weight (Mn) and weight average molecular weight (Mw) are polystyrene-equivalent molecular weights measured using GPC (Gel Permeation Chromatography) with tetrahydrofuran as an eluent, with a calibration curve prepared using polystyrene polymers of known molecular weights. The molecular weight distribution (Mw / Mn) is the ratio of Mw to Mn.

[0014] The "hydroxyl value" of the polyether compound is a value measured in accordance with Method B (phthalation method) described in JIS K 1557-1:2007. The hydroxyl value-based molecular weight is calculated by multiplying the hydroxyl value of the polyether compound by the number of hydroxyl groups in the polyether compound (the number of active hydrogen atoms in the initiator). When two or more polyether compounds with different numbers of hydroxyl groups are contained, the number of hydroxyl groups in the polyether compound is the average number of hydroxyl groups.

[0015] The degree of unsaturation of the polyether compound is measured in accordance with JIS K 1557-3:2007. The viscosity of the polyether compound is measured using an E-type viscometer.

[0016] The chlorine content of the alkylene oxide-containing raw material is the content calculated as an atom (Cl) and is measured by titration, as described in detail in the Examples. The total aldehyde content of the alkylene oxide-containing raw material is the total amount of compounds having a formyl group, and is measured by titration, as described in detail in the Examples. "ppm" is by mass unless otherwise specified.

[0017] <Method for producing polyether compound> In the method for producing a polyether compound of the present embodiment, an initiator having active hydrogen is contacted with an alkylene oxide-containing raw material in the presence of a composite metal cyanide complex catalyst, and the alkylene oxide in the alkylene oxide-containing raw material is polymerized with the initiator.

[0018] <Alkylene oxide-containing raw materials> The alkylene oxide (hereinafter also referred to as "AO") is selected depending on the structural unit of the polyoxyalkylene chain of the polyether compound to be produced. Examples of AO include ethylene oxide (hereinafter also referred to as "EO"), propylene oxide (hereinafter also referred to as "PO"), 1,2-butylene oxide, and 2,3-butylene oxide. From the viewpoint of reactivity, the AO is preferably an AO having 3 or more carbon atoms. As the AO having 3 or more carbon atoms, an AO having 3 to 5 carbon atoms is preferred, and PO is more preferred. The AO-containing raw material may contain one type of AO or two or more types of AO.

[0019] The AO-containing raw material may contain, in addition to AO, components other than AO (hereinafter also referred to as "impurities"). The crude product obtained in the synthesis of AO contains impurities. Normally, the crude product is purified, but some impurities remain even after the purification process. Furthermore, the impurity content may vary depending on the lot, even for the same product. Although impurities vary depending on the AO synthesis method, examples of impurities include water, aldehydes, acids, methanol, methyl formate, and chlorine. Examples of aldehydes include formaldehyde, acetaldehyde, and propionaldehyde. The AO-containing raw material may contain one or more impurities.

[0020] The chlorine content of the AO-containing raw material is less than 20 ppm, preferably less than 18 ppm, more preferably less than 16 ppm, even more preferably less than 14 ppm, and particularly preferably less than the detection limit, based on the total mass of the AO-containing raw material. When the chlorine content is equal to or less than the upper limit, a polyether compound having a narrow molecular weight distribution and a low viscosity polyether compound having a reactive silicon group can be obtained more reliably. In addition, coloration and odor can be reduced. The detection limit for chlorine is typically 0.1 ppm.

[0021] The total aldehyde content of the AO-containing raw material is preferably less than 15 ppm, more preferably less than 14 ppm, and even more preferably less than 13 ppm, based on the total mass of the AO-containing raw material. When the total aldehyde content is equal to or less than the upper limit, the degree of unsaturation of the polyol compound can be reduced. The total aldehyde content of the AO-containing raw material is preferably 0 ppm or more, more preferably 0.5 ppm or more, based on the total mass of the AO-containing raw material. When the total aldehyde content is equal to or more than the above lower limit, the performance of the obtained polyol is superior. The above upper limit and lower limit of the total aldehyde content of the AO-containing raw material can be combined as appropriate.

[0022] The AO content (AO purity) of the AO-containing raw material is preferably 97 mass % or more, more preferably 98 mass % or more, and even more preferably 99 mass % or more, based on the total mass of the AO-containing raw material. The total content of AO and impurities does not exceed 100% by mass based on the total mass of the AO-containing raw material.

[0023] The AO-containing raw material may be selected from commercially available AO-containing raw materials having an impurity content within a desired range, or may be produced by a known production method. For example, the target AO-containing raw material may be obtained by synthesizing AO by a known method and adjusting the impurity content of the resulting crude product containing AO, or by adjusting the impurity content of a commercially available AO-containing raw material. Examples of methods for synthesizing AO include the chlorohydrin method, the organic peroxide method, and the hydrogen peroxide method (HPPO method). Examples of methods for adjusting the impurity content include a method of reducing the impurity content by a purification treatment and a method of adding impurities. Examples of purification treatment include washing with water and drying.

[0024] The type and content of impurities in the crude product or AO-containing raw material can be adjusted by the AO synthesis method and purification treatment conditions. For example, among the above-mentioned methods for synthesizing AO, the crude product obtained by the chlorohydrin method generally contains impurities such as aldehydes, acids, methanol, and chlorine, but does not contain methyl formate, whereas the crude product obtained by the hydrogen peroxide method generally contains impurities such as aldehydes, acids, methanol, and methyl formate, but does not contain chlorine.

[0025] <Initiator> The number of active hydrogens in the initiator is preferably 1 or more, more preferably 2 to 10, even more preferably 2 to 8, and particularly preferably 2 to 6. The number of active hydrogens in the initiator is preferably selected depending on the number of hydroxyl groups per molecule of the polyether compound to be obtained. The number of active hydrogens in the initiator and the number of terminal groups in the polyether compound are the same. The initiator may be used alone or in combination of two or more kinds.

[0026] The initiator preferably has a hydroxyl group as the active hydrogen-containing group. The initiator having one hydroxyl group is preferably a monohydric alcohol having a linear or branched hydrocarbon group, such as methyl alcohol, ethyl alcohol, 1-propyl alcohol, 2-propyl alcohol, n-butyl alcohol, isobutyl alcohol, 2-butyl alcohol, tert-butyl alcohol, 2-ethylhexanol, decyl alcohol, lauryl alcohol, tridecanol, cetyl alcohol, stearyl alcohol, or oleyl alcohol. Examples of initiators having two hydroxyl groups include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, neopentyl glycol, 1,4-butanediol, and 1,6-hexanediol. Water is also an example of an initiator having two hydroxyl groups. Examples of initiators having three hydroxyl groups include glycerin, trimethylolpropane, and trimethylolethane. Examples of initiators having four or more hydroxyl groups include pentaerythritol, diglycerin, meso-erythritol, methyl glucoside, sucrose, glucose, sorbitol, dipentaerythritol, trehalose, and diglycerin. Alternatively, a low molecular weight polymer obtained by polymerizing an alkylene oxide with these initiators in the presence of an alkali metal hydroxide may be used as the initiator. The hydroxyl value of the initiator is, for example, preferably from 3 to 842 mgKOH / g, more preferably from 7 to 561 mgKOH / g.

[0027] <Double metal cyanide complex catalyst> A composite metal cyanide complex catalyst (hereinafter also referred to as "DMC catalyst") functions as a polymerization catalyst for alkylene oxide. DMC catalysts are crystalline solids and contain a reaction product of a metal halide salt and a transition metal cyanide compound, organic ligands, and water of crystallization (such as coordinated water) encapsulated in the crystals. In addition, they may contain trace amounts of impurities unavoidable during production and moisture other than water of crystallization contained in the metal salts and metal compounds. The metal halide salt, transition metal cyanide compound, and organic ligand that can be used are those known in the production of DMC catalysts.

[0028] The DMC catalyst is believed to be represented by Formula 1 below. M 1 a [M 2 (CN) b ] c ·d(M 1 e X f)·g(Ligand)·h(H2O) Equation 1 In Equation 1, M 1 e X f is a metal halide salt, and M 1 is a metal atom that becomes a cation, X is a halogen atom that becomes a counter anion, and M 2 is the transition metal atom contained in the transition metal cyanide compound and serves as the active site, and Ligand is an organic ligand. a, b, c, d, e, f, g, and h are integers, and a, b, c, e, and f are electrically neutral numbers.

[0029] Said M 1 Examples of such elements include Zn(II), Fe(II), Fe(III), Co(II), Ni(II), Al(III), Sr(II), Mn(II), Cr(III), Cu(II), Sn(II), Pb(II), Mo(IV), Mo(VI), W(IV) and W(VI). Said M 2 Examples of such elements include Co(III), Fe(II), Fe(III), Co(II), Co(III), Cr(II), Cr(III), Mn(II), Mn(III), V(IV), and V(V). Examples of X include Cl, Br, and I. M 1 e X f The metal halide salt represented by the formula (I) is preferably one or more selected from zinc fluoride, zinc chloride, zinc bromide, zinc iodide, zinc sulfate, zinc nitrate, and zinc acetate. 2 In view of the interatomic distance between and X, it is more preferable that the compound contains at least one selected from zinc chloride and zinc bromide. Examples of the ligand (organic ligand) include alcohols, ethers, esters, aldehydes, ketones, amides, nitriles and sulfides, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and polyoxyalkylene poly(or mono)ols. One type of organic ligand may be used, or two or more types may be used. Examples of the alcohol include tert-butyl alcohol, n-butyl alcohol, sec-butyl alcohol, iso-butyl alcohol, tert-pentyl alcohol, iso-pentyl alcohol, and ethylene glycol mono-tert-butyl ether. Examples of the polyoxyalkylene poly(or mono)ol include polypropylene diol. Tert-butyl alcohol is preferred as the organic ligand.

[0030] A preferred example of a DMC catalyst is zinc hexacyanocobaltate (Zn3[Co(CN)6]2) containing an organic ligand (Ligand), water, and zinc chloride or zinc bromide. Its chemical formula can be Zn3[Co(CN)6]2·d(ZnCl2)·g(Ligand)·h(H2O) or Zn3[Co(CN)6]2·d(ZnBr2)·g(Ligand)·h(H2O).

[0031] The DMC catalyst is preferably a zinc hexacyanocobaltate (Zn3[Co(CN)6]2) complex with tert-butyl alcohol as the ligand. Water and zinc chloride may be coordinated to the complex.

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

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

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

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

[0036] The content of the DMC catalyst relative to the total mass of the slurry catalyst is, for example, preferably from 0.001 to 60 mass%, more preferably from 0.003 to 50 mass%, and even more preferably from 0.006 to 30 mass%. In particular, when the dispersion medium is a polyether compound, the content of the DMC catalyst relative to the total mass of the slurry catalyst is preferably 1 to 60 mass %, more preferably 3 to 40 mass %, and even more preferably 5 to 30 mass %. In particular, when the dispersion medium contains the initiator, the content of the DMC catalyst relative to the total mass of the slurry catalyst is preferably 0.003 to 0.02 mass%, more preferably 0.004 to 0.015 mass%, and even more preferably 0.006 to 0.01 mass%.

[0037] The DMC catalyst can be produced by a known method. For example, a DMC catalyst is synthesized by reacting a metal halide salt with a transition metal cyanide compound, and then coordinating an organic ligand with the resulting reaction product. After synthesizing the DMC catalyst, the water content of the DMC catalyst may be adjusted.

[0038] A metal halide salt and a transition metal cyanide compound are reacted in the presence of water to obtain a reaction product, and an organic ligand is then coordinated in the presence of water to obtain a mixture containing a DMC catalyst and water. Impurities and water may be removed from the mixture, and the water content of the resulting solid may be reduced to a predetermined range, thereby obtaining the DMC catalyst.

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

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

[0041] The reaction temperature in the reaction of an aqueous solution of a metal halide salt and an aqueous solution of a transition metal cyanide compound is preferably 10 to 65°C, more preferably 20 to 60°C, and even more preferably 30 to 55°C.

[0042] As the concentration of the organic ligand in the aqueous solution of the organic ligand, 10 to 90% by mass is preferable, 25 to 75% by mass is more preferable, and 35 to 65% by mass is even more preferable.

[0043] As the temperature for coordinating the organic ligand, 10 to 90°C is preferable, 20 to 80°C is more preferable, and 30 to 70°C is even more preferable.

[0044] After coordinating the organic ligand, it is preferable to perform solid-liquid separation. Solid-liquid separation can employ methods known in the art such as filtration and centrifugation. The obtained solid contains, in addition to the DMC catalyst, salts (alkali metal halides) generated in the reaction. Therefore, it is preferable to remove the salts by washing the obtained solid. Specifically, an aqueous solution of the organic ligand is added to the obtained solid, stirred, and then solid-liquid separation is performed again. The washing time is preferably 10 to 90 minutes, more preferably 20 to 60 minutes. It is preferable to perform washing a plurality of times.

[0045] When producing a slurry catalyst, a method can be used in which a mixed solution containing the DMC catalyst and water is obtained as described above, impurities and water are removed from the obtained mixed solution, and then a slurry containing the DMC catalyst and a dispersion medium is prepared by adding the dispersion medium. Note that washing may be performed with an aqueous solution of the organic ligand before adding the dispersion medium.

[0046] <Polymerization of AO> By contacting the initiator and the AO-containing raw material in the presence of the DMC catalyst, the AO in the AO-containing raw material is polymerized (ring-opening addition polymerization) to the initiator. When using a DMC catalyst as the polymerization catalyst for AO, compared with the case of using a polymerization catalyst other than the DMC catalyst, the Mw / Mn of the polyether compound tends to be smaller, and the unsaturation degree of the polyether compound tends to be smaller.

[0047] When the polyoxyalkylene chain of the polyether compound is a random copolymer chain consisting of PO units and EO units, a method of obtaining the polyether compound by contacting an initiator with an AO-containing raw material containing PO and EO in the presence of a DMC catalyst is preferred. The same applies to combinations of two or more AOs other than the combination of PO and EO.

[0048] When the polyoxyalkylene chain of the polyether compound is a block copolymer chain having a block of PO units and a block of EO units, the polyether compound may be obtained by reacting an initiator with an AO-containing raw material containing PO in the presence of a DMC catalyst to obtain a precursor, and then reacting the precursor with an AO-containing raw material containing EO, or by reacting an initiator with an AO-containing raw material containing EO in the presence of a DMC catalyst to obtain a precursor, and then reacting the precursor with an AO-containing raw material containing PO to obtain a polyether compound. The same applies to combinations of two or more AOs other than the combination of PO and EO.

[0049] The amount of the DMC catalyst used is preferably 1 to 200 ppm, more preferably 5 to 60 ppm, and particularly preferably 10 to 50 ppm, based on the total mass of the polyether compound finally obtained. When the amount of the DMC catalyst used is equal to or greater than the lower limit, the polymerization reaction is likely to proceed. When the amount of the DMC catalyst used is equal to or less than the upper limit, the amount of the DMC catalyst used can be reduced, which is economical.

[0050] The polymerization may be carried out continuously or batchwise, but is preferably carried out batchwise. The polymerization temperature is preferably from 30 to 180°C, more preferably from 70 to 160°C, and even more preferably from 90 to 140°C. The polymerization pressure is preferably 1.0 MPa or less, more preferably 0.8 MPa or less, and even more preferably 0.3 MPa or less. The AO-containing raw material is preferably supplied to the reactor at a rate that allows the above reaction temperature to be maintained. The reaction atmosphere is preferably one that is less susceptible to moisture contamination, and more preferably an inert gas atmosphere such as nitrogen.

[0051] The reaction solution after the polymerization contains a polyether compound and a DMC catalyst. It may also contain a stabilizer and trace amounts of impurities. Therefore, it is preferable to purify the reaction solution by filtration.

[0052] <Polyether compounds> The main chain of the polyether compound is a polymer chain consisting of a residue obtained by removing active hydrogen from an initiator and an oxyalkylene chain containing one or more repeating units based on alkylene oxide (hereinafter, repeating units based on a monomer will be simply referred to as "monomer units", for example, repeating units based on AO will be referred to as "AO units"). When the polymer chain has two or more types of AO units, the AO units may form a block polymer or a random polymer. Examples of the oxyalkylene chain include a polymer chain having an EO unit, a polymer chain having a PO unit, a polymer chain having an EO unit and a PO unit, a polymer chain consisting of an EO unit, a polymer chain consisting of a PO unit, a polymer chain consisting of a butylene oxide unit, a polymer chain consisting of a tetramethylene oxide unit, a polymer chain consisting of an EO unit and a PO unit, and a polymer chain consisting of a PO unit and a butylene oxide unit. As the oxyalkylene chain, a polymer chain consisting of an AO unit having 3 or more carbon atoms is preferred, and a polymer chain consisting of a PO unit is particularly preferred. The terminal groups of the polyether compound are hydroxyl groups, and the number of terminal groups (i.e., the number of hydroxyl groups) of the polyether compound is the same as the number of active hydrogens of the initiator.

[0053] The 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 the Mn is equal to or greater than the lower limit, sufficient flexibility is imparted when used as an adhesive or coating material, and good elongation properties are likely to be obtained. When the Mn is equal to or less than the upper limit, the viscosity of the polyether compound can be kept low, making it easy to handle.

[0054] The hydroxyl value of the polyether compound is preferably 0.5 to 350 mgKOH / g, more preferably 1 to 200 mgKOH / g, and even more preferably 5 to 100 mgKOH / g. When the hydroxyl value is equal to or greater than the lower limit, sufficient curing is likely to be achieved when resinified. When the hydroxyl value is equal to or less than the upper limit, sufficient flexibility is imparted to the resin, and good elongation properties are likely to be achieved.

[0055] The hydroxyl value-equivalent 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 60,000. When the hydroxyl value-equivalent molecular weight is equal to or greater than the lower limit, sufficient flexibility is imparted when used as an adhesive or coating material, and good elongation properties are likely to be obtained. When the hydroxyl value-equivalent molecular weight is equal to or less than the upper limit, the viscosity of the polyether compound can be kept low, making it easy to handle.

[0056] The 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 70,000. When the Mw is equal to or greater than the lower limit, sufficient flexibility is imparted when used as an adhesive or coating material, and good elongation properties are likely to be obtained. When the Mw is equal to or less than the upper limit, the viscosity of the polyether compound can be kept low, making it easy to handle.

[0057] 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 equal to or less than the above upper limit, the viscosity of the polyether compound can be kept low, making it easy to handle.

[0058] The degree of unsaturation of the polyether compound is preferably from 0.001 to 0.040 meq / g, more preferably from 0.002 to 0.030 meq / g, and even more preferably from 0.003 to 0.010 meq / g.

[0059] The viscosity of the polyether compound at a measurement temperature of 25°C is preferably from 100 to 100,000 mPa·s, more preferably from 200 to 80,000 mPa·s, and even more preferably from 400 to 60,000 mPa·s.

[0060] <Applications of polyether compounds> Polyether compounds can be used as lubricants, raw materials for polyurethane foams, adhesives, sealants, coating materials, etc. Furthermore, polyether compounds having reactive silicon groups, prepolymers, and polyether compounds having polymerizable unsaturated groups may be produced by reacting the polyether compounds with compounds that can react with the hydroxyl groups of the polyether compounds.

[0061] <Polyether compounds having reactive silicon groups> The polyether compound having a reactive silicon group (hereinafter also referred to as "polyether compound A") has a reactive silicon group represented by formula 2 described below.

[0062] (reactive silicon group) The reactive silicon group has a hydroxyl group, a halogen atom, or a hydrolyzable group bonded to a silicon atom, and can form a siloxane bond to crosslink. The reaction to form the siloxane bond is accelerated by a curing catalyst. The reactive silicon group in polyether compound A is represented by the following formula 2: -SiR a X 3-a formula 2

[0063] In the above formula 2, R represents a monovalent organic group having 1 to 20 carbon atoms other than a hydrolyzable group. R is preferably at least one group selected from the group consisting of hydrocarbon groups having 1 to 20 carbon atoms and triorganosiloxy groups.

[0064] R is preferably at least one group selected from the group consisting of an alkyl group, a cycloalkyl group, an aryl group, an α-chloroalkyl group, and a triorganosiloxy group. It is more preferably at least one group selected from the group consisting of a linear or branched alkyl group having 1 to 4 carbon atoms, a cyclohexyl group, a phenyl group, a benzyl group, an α-chloromethyl group, a trimethylsiloxy group, a triethylsiloxy group, and a triphenylsiloxy group. A methyl group or an ethyl group is preferred in view of the good curability of the polyether compound A and the stability of the curable composition. An α-chloromethyl group is preferred in view of the fast curing rate of the cured product. A methyl group is particularly preferred in view of its easy availability.

[0065] In the above formula 2, X represents a hydroxyl group, a halogen atom, or a hydrolyzable group. Examples of the hydrolyzable group include an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a sulfanyl group, and an alkenyloxy group. An alkoxy group is preferred because it is mildly hydrolyzable and easy to handle. The alkoxy group is preferably a methoxy group, an ethoxy group, or an isopropoxy group, and more preferably a methoxy group or an ethoxy group. When the alkoxy group is a methoxy group or an ethoxy group, it is easy to rapidly form a siloxane bond and form a crosslinked structure in the cured product, and the physical properties of the cured product tend to be good.

[0066] In the above formula 2, a is an integer of 0 to 2. When a is 2, R's may be the same or different. When a is 1 or less, X's may be the same or different. Since a low crosslink density due to siloxane bonds tends to reduce the modulus of the cured product, a is preferably 2 or less, and more preferably 1 or less.

[0067] Examples of the reactive silicon group represented by the above formula 2 include a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a tris(2-propenyloxy)silyl group, a triacetoxysilyl group, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, a dimethoxyethylsilyl group, a methyldiisopropoxysilyl group, an (α-chloromethyl)dimethoxysilyl group, and an (α-chloromethyl)diethoxysilyl group. In terms of high activity and good curability, a trimethoxysilyl group, a triethoxysilyl group, a dimethoxymethylsilyl group, and a diethoxymethylsilyl group are preferred, and a dimethoxymethylsilyl group is more preferred.

[0068] Polyether compound A is a polyether compound having an average of 1.0 or more terminal groups per molecule and having a reactive silicon group represented by formula 2 above, wherein the terminal group is the reactive silicon group, an unsaturated group, an isocyanate group, or a hydroxyl group.

[0069] Polyether compound A has an average of 1.0 or more terminal groups per molecule. The average number of terminal groups is preferably 1.0 to 8.0, more preferably 2.0 to 6.0, and even more preferably 2.0 to 4.0, since this results in a cured product with higher tensile strength and better modulus and elongation. The number of terminal groups of polyether compound A is the same as the number of terminal groups of the above polyether compound. The terminal groups of polyether compound A have any of a reactive silicon group, an unsaturated group, an isocyanate group, or a hydroxyl group represented by the above formula 2. The respective terminal groups may be the same or different.

[0070] The average number of reactive silicon groups represented by the above formula 2 per terminal group of polyether compound A is preferably 0.5 to 2.0, more preferably 0.60 to 1.94. When the average number of reactive silicon groups is at least the above lower limit, the crosslinking density due to siloxane bonds increases, making it possible to obtain a good cured product with a high modulus.

[0071] The average number of reactive silicon groups represented by the above formula 2 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 equal to or greater than the above lower limit, the crosslinking density due to siloxane bonds increases, making it possible to obtain a good cured product with a high modulus.

[0072] The Mn of the polyether compound A is preferably 1,000 to 100,000, more preferably 1,500 to 80,000, and particularly preferably 2,000 to 60,000. When Mn is equal to or greater than the lower limit, the elongation properties of the cured product are improved. When Mn is equal to or less than the upper limit, the viscosity is low and workability is improved.

[0073] The Mw / Mn of the 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 equal to or less than the upper limit, good elongation properties are easily obtained, and the viscosity is reduced, resulting in good workability.

[0074] The viscosity of the polyether compound A at a measurement temperature of 25° C. is preferably 100 to 120,000 mPa·s, more preferably 200 to 100,000 mPa·s, and even more preferably 400 to 80,000 mPa / s. When the viscosity is equal to or less than the above upper limit, handling is excellent.

[0075] <Method for producing polyether compound having reactive silicon group> In the method for producing polyether compound A, the hydroxyl groups of the polyether compound are converted into groups having a reactive silicon group. The method for producing the polyether compound A may be the following method (a1), (b1) or (c1). Method (a1): Converting the hydroxyl groups of a polyether compound into alkenyloxy groups having a carbon-carbon double bond at the molecular terminal or alkynyloxy groups having a carbon-carbon triple bond at the molecular terminal, and then converting the carbon-carbon double bond at the molecular terminal of the alkenyloxy group or the carbon-carbon triple bond at the molecular terminal of the alkynyloxy group into a reactive silicon group -SiR represented by the above formula 2. a X 3-a A method of converting an alkenyloxy group or an alkynyloxy group into a group having a reactive silicon group represented by the above formula 2 by reacting with a silylating agent capable of introducing the following formula: Method (b1): A method in which a hydroxyl group of a polyether compound is reacted with a silylating agent having a functional group reactive with the hydroxyl group and a reactive silicon group represented by the above formula 2, thereby converting the hydroxyl group into a group having the reactive silicon group represented by the above formula 2. Method (c1): A method in which a hydroxyl group of a polyether compound is converted into a group having an isocyanate group, and then a silylating agent having a functional group reactive with an isocyanate group and a reactive silicon group represented by the above formula 2 is reacted to convert the hydroxyl group into a group having a reactive silicon group represented by the above formula 2.

[0076] In method (a1), a polyether compound is subjected to the action of an alkali metal salt to form an alcoholate, and then reacted with a halogenated hydrocarbon compound having a carbon-carbon double bond at the molecular terminal or a halogenated hydrocarbon compound having a carbon-carbon triple bond at the molecular terminal to convert the hydroxyl groups of the polyether compound into alkenyloxy groups having a carbon-carbon double bond at the molecular terminal or alkynyloxy groups having a carbon-carbon triple bond at the molecular terminal.

[0077] Examples of alkali metal salts include sodium hydroxide, sodium alkoxide, potassium hydroxide, potassium alkoxide, lithium hydroxide, lithium alkoxide, cesium hydroxide, and cesium alkoxide. In terms of ease of handling and solubility, sodium hydroxide, sodium methoxide, sodium ethoxide, potassium hydroxide, potassium methoxide, and potassium ethoxide are preferred, and sodium methoxide and potassium ethoxide are more preferred, with sodium methoxide being particularly preferred in terms of availability. The alkali metal salt may be used in a state of being dissolved in a solvent.

[0078] Examples of halogenated hydrocarbon compounds containing a carbon-carbon double bond at the molecular terminal include vinyl chloride, allyl chloride, methallyl chloride, vinyl bromide, allyl bromide, methallyl bromide, vinyl iodide, allyl iodide, and methallyl iodide. Allyl chloride and methallyl chloride are preferred. Halogenated hydrocarbon compounds containing a carbon-carbon triple bond at the molecular end include propargyl chloride, 1-chloro-2-butyne, 4-chloro-1-butyne, 1-chloro-2-octyne, 1-chloro-2-pentyne, 1,4-dichloro-2-butyne, 5-chloro-1-pentyne, 6-chloro-1-hexyne, propargyl bromide, 1-bromo-2-butyne, 4-bromo-1-butyne, ... Examples include bromo-2-octyne, 1-bromo-2-pentyne, 1,4-dibromo-2-butyne, 5-bromo-1-pentyne, 6-bromo-1-hexyne, propargyl iodide, 1-iodo-2-butyne, 4-iodo-1-butyne, 1-iodo-2-octyne, 1-iodo-2-pentyne, 1,4-diiodo-2-butyne, 5-iodo-1-pentyne, and 6-iodo-1-hexyne. Propargyl chloride, propargyl bromide, and propargyl iodide are preferred. A halogenated hydrocarbon compound having a carbon-carbon double bond at the molecular terminal and a halogenated hydrocarbon compound having a triple bond at the molecular terminal may be used in combination. One halogenated hydrocarbon compound having a carbon-carbon double bond at the molecular terminal may be used, or two or more halogenated hydrocarbon compounds having a carbon-carbon triple bond at the molecular terminal may be used, or two or more halogenated hydrocarbon compounds having a carbon-carbon triple bond at the molecular terminal may be used, or two or more halogenated hydrocarbon compounds having a carbon-carbon triple bond at the molecular terminal may be used, or

[0079] Next, a reactive silicon group -SiR represented by the above formula 2 is bonded to the carbon-carbon double bond at the molecular terminal of the alkenyloxy group or the carbon-carbon triple bond at the molecular terminal of the alkynyloxy group. a X 3-a The alkenyloxy group or alkynyloxy group is converted into a group having a reactive silicon group represented by the above formula 2 by reacting with a silylating agent capable of introducing the following: a X 3-a , R, X, and a are the same as in formula 2 above). Specific examples include dimethoxymethylsilane, diethoxymethylsilane, dimethoxyethylsilane, methyldiisopropoxysilane, (α-chloromethyl)dimethoxysilane, (α-chloromethyl)diethoxysilane, trimethoxysilane, triethoxysilane, triisopropoxysilane, tris(2-propenyloxy)silane, triacetoxysilane, and 3-mercaptopropyltrimethoxysilane. In view of high activity and good curability, trimethoxysilane, dimethoxymethylsilane, and diethoxymethylsilane are preferred, and dimethoxymethylsilane is more preferred.

[0080] In the method (b1), a polyether compound is reacted with a silylating agent. As the silylating agent, an isocyanate silane compound represented by the following formula 3 is preferably used. OCN-(CH2) n -SiR a X 3-a ...Formula 3 -SiR in the above formula 3 a X 3-a is the same as in the above formula 2. n is an integer of 1 to 8, and preferably 1 to 3. The reaction between the hydroxyl group of the polyether compound and the isocyanate silane compound converts the hydroxyl group of the polyether compound to -OC(=O)NH-(CH2) n -SiR a X 3-a The urethane bond (-OC(=O)NH-) and -SiRa X 3-a is converted to an end group having the formula: Examples of the isocyanate silane compound include 3-isocyanate propyl trimethoxysilane, 3-isocyanate propyl triethoxysilane, isocyanate methyl trimethoxysilane, isocyanate methyl triethoxysilane, 3-isocyanate propyl methyl dimethoxysilane, 3-isocyanate propyl methyl diethoxysilane, isocyanate methyl methyl dimethoxysilane, and isocyanate methyl methyl diethoxysilane. As the isocyanate silane compound, 3-isocyanate propyl trimethoxy silane, 3-isocyanate propyl triethoxy silane, 3-isocyanate propyl methyl dimethoxy silane, isocyanate methyl methyl dimethoxy silane, and isocyanate methyl trimethoxy silane are preferred in view of their reactivity with polyether compounds and ease of handling.

[0081] The active hydrogen of the polyether compound reacts with the isocyanate group of the isocyanate silane compound represented by the above formula 3, thereby introducing a reactive silicon group into the polyether compound. 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.) to which a reactive silicon group is bonded via a urethane bond and an organic group is obtained. 5 O) m -C(=O)NH-(CH2) n -SiR a X 3-a A linking structure represented by the following formula is formed.

[0082] This reaction may be carried out in the presence of a urethanization catalyst. The urethanization catalyst is not particularly limited, and known urethanization catalysts can be used as appropriate. Examples include organotin compounds such as dibutyltin dilaurate and dioctyltin dilaurate, metal catalysts such as bismuth compounds, and base catalysts such as organic amines. The reaction temperature is preferably 20 to 200°C, more preferably 50 to 150°C. The urethanization reaction is preferably carried out under an inert gas atmosphere. Nitrogen is preferred as the inert gas.

[0083] 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 hydrogen atoms 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 so that the number of reactive silicon groups per molecule of the resulting polyether compound A is at least 0.7. For example, when the active hydrogen-containing group of the polyether compound is a hydroxyl group, NCO / OH, which represents the molar ratio of the total number of isocyanate groups (NCO) of the isocyanate silane compound represented by Formula 3 to the total number of active hydrogens (total number of hydroxyl groups) of 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. When NCO / OH is at least the lower limit, the strength of the cured product is excellent, and when it is at most the upper limit, the elongation of the cured product is excellent.

[0084] In method (c1), a polyisocyanate compound is reacted with the hydroxyl groups of a polyether compound to convert the hydroxyl groups into monovalent organic groups containing an isocyanate group (hereinafter also referred to as "isocyanate-containing groups") that have a urethane bond (-O-C(=O)NH-) at the bond terminal with the polyether compound. Next, a silylating agent having a functional group reactive with an isocyanate group and a reactive silicon group represented by the above formula 2 is reacted with the isocyanate-containing group to form a terminal group that is a monovalent organic group (hereinafter also referred to as "urethane bond- and reactive silicon-group-containing group") that has one or more urethane bonds (-O-C(=O)NH-) and a silylating agent residue that has reacted with an isocyanate group. Hereinafter, method (c1) will be described assuming that the polyisocyanate compound is a diisocyanate compound represented by the following formula 4, and that the silylating agent having a functional group reactive with an isocyanate group and a reactive silicon group represented by the above formula 2 is a compound represented by the following formula 5, but the present invention is not limited thereto.

[0085] OCN-R 3 -NCO...Formula 4 R in the above formula 4 3 represents a divalent organic group.

[0086] WR 4 -SiR a X 3-a ...Formula 5 In the above formula 5, W is a functional group (a group having one or more active hydrogen atoms) capable of reacting with a monovalent isocyanate group, R 4 is a divalent organic group, -SiR a X 3-a is the same as Equation 2 above.

[0087] When the diisocyanate compound represented by the above formula 4 is reacted with the hydroxyl group of the polyether compound, the isocyanate-containing group is -OC(=O)NH-R 3 When the isocyanate-containing group is reacted with the silylating agent represented by formula 5, the urethane bond and the reactive silicon-containing group are converted to a group represented by -OC(=O)NH-R 3 -NHC(=O)-W'-R4 -SiR a X 3-a (wherein W' is a divalent group obtained by removing one active hydrogen from W.) For example, when W is a hydroxyl group, the urethane bond and reactive silicon group-containing group are represented by the formula: -OC(=O)NH-R 3 -NHC(=O)-OR 4 -SiR a X 3-a In this case, the urethane bond and reactive silicon group-containing group have two urethane bonds. For example, when W is an amino group (-NH), the urethane bond and reactive silicon group-containing group are represented by the formula -OC(=O)NH-R 3 -NHC(=O)-NH-R 4 -SiR a X 3-a It is a group represented by the following formula:

[0088] R 3 is preferably a divalent organic group having 2 to 20 carbon atoms, and examples thereof include an alkylene group, a cycloalkylene group, a bicycloalkylene group, a monocyclic or polycyclic divalent aromatic hydrocarbon group, a divalent group obtained by removing two hydrogen atoms from a cycloalkane having an alkyl group as a substituent, a divalent group obtained by removing two hydrogen atoms from an aromatic hydrocarbon having an alkyl group as a substituent, a divalent group obtained by removing two hydrogen atoms from two or more cycloalkanes which are bonded via an alkylene group and which may have an alkyl group as a substituent, and a divalent group obtained by removing two hydrogen atoms from two or more aromatic hydrocarbons which are bonded via an alkylene group and which may have an alkyl group as a substituent.

[0089] Examples of the diisocyanate compound represented by the above formula 4 and other polyisocyanate compounds include aromatic polyisocyanates, non-yellowing aromatic polyisocyanates (which refer to compounds that do not have an isocyanate group directly bonded to a carbon atom that constitutes an aromatic ring), aliphatic polyisocyanates, and alicyclic polyisocyanates, as well as urethane-modified products, biuret-modified products, allophanate-modified products, carbodiimide-modified products, and isocyanurate-modified products obtained from the above polyisocyanates. Examples of aromatic polyisocyanates include naphthalene-1,5-diisocyanate, polyphenylenepolymethylene polyisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, and 2,6-tolylene diisocyanate. Examples of non-yellowing aromatic polyisocyanates include xylylene diisocyanate and tetramethylxylylene diisocyanate. Examples of the aliphatic polyisocyanate include hexamethylene diisocyanate, 2,2,4-trimethyl-hexamethylene diisocyanate, and 2,4,4-trimethyl-hexamethylene diisocyanate. Examples of alicyclic polyisocyanates include isophorone diisocyanate and 4,4'-methylenebis(cyclohexyl isocyanate). The polyisocyanate compound is preferably one having two isocyanate groups, more preferably hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, or 2,6-tolylene diisocyanate, and even more preferably tolylene diisocyanate because it is easy to obtain tensile strength in the cured product. One type of polyisocyanate compound may be used, or two or more types may be used in combination.

[0090] The functional group capable of reacting with an isocyanate group represented by formula 5 and -SiR a X 3-a R in the silylating agent having 4is preferably a divalent organic group having 1 to 20 carbon atoms, more preferably a group obtained by removing two hydrogen atoms from an aromatic hydrocarbon having 6 to 10 carbon atoms, a group obtained by removing two hydrogen atoms from an aromatic hydrocarbon having 6 to 10 carbon atoms and substituted with an alkyl group having 1 to 4 carbon atoms, a group obtained by removing two hydrogen atoms from a cyclic hydrocarbon having 3 to 10 carbon atoms, or a group obtained by removing two hydrogen atoms from a straight-chain hydrocarbon having 1 to 12 carbon atoms, still more preferably a group obtained by removing two hydrogen atoms from a straight-chain hydrocarbon having 1 to 8 carbon atoms, and particularly preferably a group obtained by removing two hydrogen atoms from a straight-chain hydrocarbon having 1 to 6 carbon atoms. W is preferably a group having one or two active hydrogen atoms selected from 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, more preferably a hydroxyl group, a sulfanyl group, an amino group, a methylamino group, an ethylamino group, or a butylamino group, and more preferably a hydroxyl group, an amino group, a methylamino group, an ethylamino group, or a butylamino group.

[0091] In the methods (b1) and (c1), the polyether compound A obtained has a reactive silicon group 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). Note that the polyether compound A obtained by method (b1) contains only one organic group represented by the following formula (i), and the polyether compound A obtained by method (c1) contains two or more organic groups represented by the following formula (i). -C(=O)NH- Formula (i)

[0092] The organic group (i) is a divalent group derived from a urethane bond or a urea bond. When the isocyanate silane compound represented by the above formula 3 is used as a silylating agent, the number of organic groups (i) becomes one.

[0093] The organic group (i) preferably forms a urethane bond (-OC(=O)NH-, where -O- represents the oxygen atom at the terminal of the polyoxyalkylene chain) with the polyoxyalkylene chain. That is, it is preferable that one organic group (i) is present between the polyoxyalkylene chain and the reactive silicon group in the polyether compound A. When the polyether compound A is produced by the above-mentioned method (b1), the number of organic groups represented by the above formula (i) contained in the polyether compound A is one. When the polyether compound A is produced by the method (b1), a polyether compound A with a high silylation rate is easily obtained. When the polyether compound A is produced by the method (b1), a polyether compound A with a narrow molecular weight distribution is easily obtained. The viscosity of the polyether compound 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 is the same as the number of groups (i) per molecule.

[0094] The silylation rate of polyether compound A is preferably 50 to 100 mol %, more preferably 60 to 98 mol %. When the silylation rate is at least the lower limit of the above range, the cured product has excellent tensile strength and a high modulus. When the curable composition contains two or more types of polyether compounds A, it is sufficient that the average silylation rate of all the polyether compounds A falls within the above range.

[0095] (Curable composition containing a polyether compound having a reactive silicon group) The polyether compound A is used in a curable composition. The curable composition is obtained by mixing the polyether compound A with other necessary components. As the polyether compound A, only one type 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 mass%, more preferably 10 to 80 mass%, and even more preferably 20 to 70 mass%. When it is equal to or less than the upper limit of the above range, the cured product has better tensile strength and elongation properties.

[0096] Examples of other components contained 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, thixotropy-imparting agents, stabilizers, adhesion-imparting agents, physical property adjusters, dehydrating agents, adhesion-imparting resins, reinforcing materials such as fillers, surface modifiers, flame retardants, foaming agents, solvents, and silicates. Other components can be used in combination without limitation with conventionally known components described in International Publication No. 2013 / 180203, International Publication No. 2014 / 192842, International Publication No. 2016 / 002907, JP 2014-88481 A, JP 2015-10162 A, JP 2015-105293 A, JP 2017-039728 A, JP 2017-214541 A, etc. Two or more types of each component may be used in combination.

[0097] The curable composition may be a one-component type in which the polyether compound A and all other components are mixed in advance, sealed, and stored, and then cured by moisture in the air after application, or a two-component type in which a base composition containing at least the polyether compound A and a curing agent composition containing at least a curing catalyst are stored separately, and the curing agent composition and the base composition are mixed before use. The one-component curable composition preferably does not contain water. It is preferable that the components containing water are dehydrated and dried in advance, or that the components are dehydrated under reduced pressure during mixing and kneading. In the two-component curable composition, the curing agent composition may contain water. The base composition is unlikely to gel even if it contains a small amount of water, but from the viewpoint of storage stability, it is preferable to dehydrate and dry the blended components in advance. In order to improve storage stability, a dehydrating agent may be added to the one-component curable composition or the two-component base composition.

[0098] (Use of curable composition containing polyether compound having reactive silicon group) Suitable applications of the curable composition containing polyether compound A include adhesives, sealants (for example, elastic sealants for construction, sealants for double glazing, anti-rust and waterproof sealants for glass edges, sealants for the backside of solar cells, sealants for buildings, sealants for ships, sealants for automobiles, and sealants for roads), and electrical insulating materials (insulating coating materials for electric wires and cables).

[0099] <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, those that remain unreacted with the hydroxyl groups of polyether compound B become the isocyanate groups at the molecular terminals of polyether compound B. Furthermore, of the hydroxyl groups in the polyether compound units, those that remain unreacted with the isocyanate groups of the polyisocyanate become the hydroxyl groups at the molecular terminals of polyether compound B. In other words, the molecular terminal groups of polyether compound B contain either or both of a hydroxyl group and an isocyanate group.

[0100] The Mn of polyether compound B is preferably 1,000 to 1,000,000, more preferably 1,500 to 500,000, and even more preferably 2,000 to 100,000. When Mn is equal to or greater than the lower limit, sufficient flexibility is imparted and good elongation properties are obtained when used as an adhesive or coating material. When Mn is equal to or less than the upper limit, the viscosity of polyether compound B can be kept low, making it easy to handle.

[0101] The Mw / Mn of the polyether compound B is preferably 1.00 to 1.50, more preferably 1.00 to 1.45, and even more preferably 1.00 to 1.40. When the Mw / Mn is equal to or less than the upper limit, good elongation properties are easily obtained, and the viscosity is reduced, resulting in good workability.

[0102] When the molecular terminal of polyether compound B is an isocyanate group, the content of the isocyanate group relative to the total mass of polyether compound B is preferably 0.1 to 20 mass%, more preferably 0.5 to 18 mass%, and even more preferably 1 to 15 mass%. When the content of isocyanate groups is equal to or greater than the above lower limit, the tensile strength of the cured product is likely to be improved.When the content of isocyanate groups is equal to or less than the above upper limit, gelation is unlikely to occur during the reaction.

[0103] The content of urethane bonds relative to the total mass of polyether compound B is preferably from 0.01 to 40 mass %, more preferably from 0.1 to 30 mass %, and even more preferably from 1 to 15 mass %.

[0104] The viscosity of polyether compound B at a measurement temperature of 25° C. is preferably 100 to 100,000 mPa·s, more preferably 200 to 50,000 mPa·s, and even more preferably 500 to 30,000 mPa / s. When the viscosity is equal to or less than the above upper limit, handling is excellent.

[0105] <Prepolymer manufacturing method> In the method for producing the polyether compound B, a polyether compound is reacted with a polyisocyanate. If necessary, a urethane catalyst may be used. One type of polyether compound may be used, or two or more types may be used in combination.

[0106] Examples of polyisocyanates include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and araliphatic polyisocyanates. The number of isocyanate groups in the polyisocyanate is preferably 2 to 3, and more preferably 2.

[0107] Examples of the aliphatic polyisocyanate include linear aliphatic polyisocyanates such as tetramethylene diisocyanate, dodecamethylene diisocyanate, and hexamethylene diisocyanate, and branched aliphatic polyisocyanates such as 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane-1,5-diisocyanate, and 3-methylpentane-1,5-diisocyanate.

[0108] Examples of alicyclic polyisocyanates include isophorone diisocyanate (3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, IPDI), hydrogenated xylylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, and 1,3-bis(isocyanatomethyl)cyclohexane.

[0109] Examples of aromatic polyisocyanates include tolylene diisocyanate, 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.

[0110] Examples of the araliphatic polyisocyanate include dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, and α,α,α,α-tetramethylxylylene diisocyanate.

[0111] As the polyisocyanate, alicyclic polyisocyanates and aromatic polyisocyanates are preferred, and IPDI, MDI and TDI are more preferred. One type of polyisocyanate may be used alone, or two or more types may be used in combination.

[0112] The functional groups at the molecular terminals of polyether compound B can be controlled by adjusting the molar ratio of the total number of isocyanate groups in the polyisocyanate to the total number of hydroxyl groups in the polyether compound (hereinafter also referred to as the "NCO / OH ratio"). For example, when producing a polyether compound B having isocyanate groups at its molecular terminals, the NCO / OH ratio is preferably 2 to 10, more preferably 2 to 8, even more preferably 2 to 7, and particularly preferably 2 to 5. When producing a polyether compound B having hydroxyl groups at its molecular terminals, the NCO / OH ratio is preferably 0.1 to 0.8, more preferably 0.2 to 0.7, and even more preferably 0.3 to 0.6.

[0113] The urethanization catalyst is preferably one or more selected from tertiary amine compounds and organometallic compounds. When a highly reactive polyisocyanate is used, the urethanization catalyst may not be used.

[0114] Examples of tertiary amine compounds include triethylamine, triethylenediamine, and 1,8-diazabicyclo(5,4,0)-undecene-7.

[0115] The organometallic compound is preferably one or more selected from tin-based compounds and non-tin-based compounds. Examples of tin compounds include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, and tin 2-ethylhexanoate. Examples of non-tin compounds include titanium compounds such as dibutyltitanium dichloride, tetrabutyltitanium trichloride, 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.

[0116] The urethanization catalyst may be used alone or in combination of two or more kinds. When a urethanization catalyst is used, the amount of the urethanization catalyst used is preferably, for example, 0.001 to 1.0 part by mass per 100 parts by mass of the polyether compound.

[0117] In producing the polyether compound B, a solvent can be used as needed. The solvent is preferably one or more selected from ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, and aromatic hydrocarbons such as toluene and xylene. The solvent may be used alone or in combination of two or more kinds. When a solvent is used, the amount of the solvent used is not particularly limited, but is preferably 100 to 1000 parts by mass per 100 parts by mass of the polyether compound.

[0118] Examples of methods for producing the polyether compound B include a method of mixing a polyether compound, a polyisocyanate, and, if necessary, a urethanization catalyst and a solvent. Alternatively, a method may be used in which a polyisocyanate is added dropwise to a mixed liquid obtained by mixing a polyether compound, and, if necessary, a urethanization catalyst and a solvent.

[0119] The reaction temperature is preferably 50 to 120° C., more preferably 50 to 100° C. When the reaction temperature is equal to or higher than the lower limit, the urethane reaction is likely to be accelerated. When the reaction temperature is equal to or lower than the upper limit, side reactions other than the urethane reaction are likely to be suppressed.

[0120] When a urethanization catalyst is used, it is preferable to inactivate the urethanization catalyst after the reaction by adding a reaction terminator such as acetylacetone. The reaction terminator may be used alone or in combination of two or more.

[0121] If unreacted polyisocyanate remains after the reaction, it is preferable to purify polyether compound B by removing the polyisocyanate by distillation.

[0122] (Polyurethane composition containing prepolymer) The polyether compound B is used in a polyurethane composition. The polyurethane composition is obtained by mixing the polyether compound B with other optional components as required. As the polyether compound B, only one type may be used, or two or more types may be used in combination. The content of polyether compound B relative to the total mass of the polyurethane composition is 15% by mass or more and 100% by mass or less, and preferably 30 to 100% by mass. The polyurethane composition may further contain optional components other than polyether compound B.

[0123] Examples of optional components contained in the polyurethane composition include catalysts, fillers, plasticizers, stabilizers, pigments, fibers, dyes, drying agents, adhesion improvers, rheology modifiers, solvents, natural resins, non-reactive polymers, and other additives. Each optional component may be used alone, or two or more may be used in combination. When the polyurethane composition contains optional components, the content of the optional components relative to the total mass of the polyurethane composition is preferably more than 0% by mass and 50% by mass or less.

[0124] A cured product can be produced by reacting a polyurethane composition with a curing agent. When the molecular terminal of polyether compound B is an isocyanate group, a curing agent having active hydrogen is used. The active hydrogen-containing group of the curing agent is preferably a hydroxyl group. When the molecular terminal of polyether compound B is a hydroxyl group, a curing agent having an isocyanate group is used. When the molecular terminal of polyether compound B is an isocyanate group, the isocyanate group of polyether compound B contained in the polyurethane composition undergoes a urethane reaction with an active hydrogen-containing group (e.g., a hydroxyl group) of the curing agent, thereby crosslinking polyether compound B with a urethane bond, and a cured product is obtained. When the molecular terminal of polyether compound B is a hydroxyl group, the hydroxyl group of polyether compound B contained in the polyurethane composition undergoes a urethane reaction with an isocyanate group of the curing agent, thereby crosslinking polyether compound B with a urethane bond, and a cured product is obtained. In the case of a curing agent having hydroxyl groups, the number of hydroxyl groups in the curing agent is preferably 2 or more, more preferably 2 to 4, and even more preferably 2 to 3. Water is a curing agent having two hydroxyl groups. In the case of a curing agent having an isocyanate group, the number of isocyanate groups in the curing agent is preferably 2 or more, more preferably 2 to 4, and even more preferably 2 to 3.

[0125] Examples of the curing agent having a hydroxyl group include the initiators and water described in the method for producing the polyether compound. Examples of the curing agent having an isocyanate group include the above-mentioned polyisocyanates.

[0126] When the molecular terminal of polyether compound B is an isocyanate group, the molar ratio of the total amount of isocyanate groups of polyether compound B to the total amount of hydroxyl groups of the curing agent is preferably more than 1, more preferably 1.0 to 1.2. When the molecular terminal of polyether compound B is a hydroxyl group, the molar ratio of the total amount of hydroxyl groups in polyether compound B to the total amount of isocyanate groups in the curing agent is preferably more than 0.8, more preferably 0.8 to 1.2.

[0127] The polyurethane composition and curing agent can be mixed in a single-component system, in which all components except the curing agent are premixed to produce a single-component polyurethane composition, which is then sealed and stored, and cured by atmospheric moisture after application. Alternatively, the polyurethane composition, which is the base composition, and the curing agent composition containing at least a curing agent are stored separately, and the curing agent composition and base composition are mixed before use. In the case of a single-component system, atmospheric moisture (water) functions as the curing agent. In other words, when the molecular terminal of polyether compound B is an isocyanate group, a single-component system is preferred. The one-liquid composition preferably does not contain water. It is preferable that the ingredients containing water are dehydrated and dried in advance, or that they are dehydrated under reduced pressure during the preparation of the one-liquid composition. In the case of a two-component type, the curing agent composition may contain water. The main composition is unlikely to gel even if it contains a small amount of water, but from the viewpoint of storage stability, it is preferable to dehydrate and dry the blended components beforehand. In the case of a two-component type, the above-mentioned optional components may be contained in the curing agent composition. In order to improve storage stability, a dehydrating agent may be added to the one-component composition or the two-component base composition. The reaction temperature is preferably 20 to 40° C. In the case of a one-component type, the relative humidity at the above reaction temperature is preferably 40 to 60%.

[0128] (Use of polyurethane composition containing prepolymer) Suitable applications of the polyurethane composition containing polyether compound B include adhesives, sealants (for example, elastic sealants for construction, sealants for double glazing, anti-rust and waterproof sealants for glass edges, sealants for the backside of solar cells, sealants for buildings, sealants for ships, sealants for automobiles, and sealants for roads), coating materials (for paint applications), and electrical insulating materials (insulating coating materials for electric wires and cables). As an adhesive, it is suitable as an elastic adhesive for joining plastics together, metals together, and plastics and metals, and is also suitable as an elastic sealing material and elastic coating material.

[0129] <Polyether Compound Having Polymerizable Unsaturated Group> A polyether compound having a polymerizable unsaturated group (hereinafter also referred to as "polyether compound C") is a reaction product of a polyether compound and a compound having a polymerizable unsaturated group. An example of the polymerizable unsaturated group is a carbon-carbon double bond at the molecular terminal. Preferred polymerizable unsaturated groups are a (meth)acryloyl group and a (meth)acryloyloxy group. "(meth)acryloyl group" is a general term for an acryloyl group and a methacryloyl group. "(meth)acryloyloxy group" is a general term for an acryloyloxy group and a methacryloyloxy group.

[0130] The polyether compound C has an average of 1.0 or more terminal groups per molecule. In order to improve the crosslinking reaction and curing properties when resinified, 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 of the polyether compound C is the same as the number of terminal groups of the above polyether compound.

[0131] The average number of polymerizable unsaturated groups per terminal group of the polyether compound C is preferably 0.5 to 2.0, more preferably 0.8 to 1.2. When the average number of polymerizable unsaturated groups is equal to or greater than the lower limit, crosslinking reaction and curing properties tend to be good when resinified. When the average number of polymerizable unsaturated groups is equal to or less than the upper limit, sufficient flexibility is imparted to the resin, and good elongation properties tend to be obtained.

[0132] 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 equal to or greater than the lower limit, crosslinking reaction and curing properties tend to be good when resinified. When the average number of polymerizable unsaturated groups is equal to or less than the upper limit, sufficient flexibility is imparted to the resin, and good elongation properties tend to be obtained.

[0133] The Mn of the 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 the Mn is equal to or greater than the lower limit, sufficient flexibility is imparted when the polyether compound C is used as an adhesive or a coating material, and good elongation properties are likely to be obtained. When the Mn is equal to or less than the upper limit, the viscosity of the polyether compound C can be kept low, making it easy to handle.

[0134] The Mw / Mn of the 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 equal to or less than the upper limit, good elongation properties are easily obtained, and the viscosity is reduced, resulting in good workability.

[0135] When the polyether compound C has a urethane bond, the content of the urethane bond relative to the total mass of the polyether compound C is preferably 0.01 to 40 mass %, more preferably 0.1 to 30 mass %, and even more preferably 1 to 15 mass %.

[0136] The viscosity of the 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 equal to or less than the above upper limit, handling is excellent.

[0137] <Method of producing polyether compound having polymerizable unsaturated group> In the method for producing the polyether compound C, the hydroxyl groups of the polyether compound are converted into groups having a polymerizable unsaturated group. The method for producing the polyether compound C may be the following method (a2), (b2) or (c2). Method (a2): A method in which a compound having a functional group reactive with the hydroxyl group of a polyether compound and a polymerizable unsaturated group (hereinafter also referred to as "compound 1") is reacted with the hydroxyl group to convert the hydroxyl group into a group having a polymerizable unsaturated group. Method (b2): A method in which the hydroxyl groups of a polyether compound are reacted with polyisocyanate to obtain a prepolymer having an isocyanate group at the molecular end, and then a compound having a functional group reactive with the isocyanate group and a polymerizable unsaturated group (hereinafter also referred to as "compound 2") is reacted to convert the hydroxyl groups into groups having a polymerizable unsaturated group. Method (c2): A method in which the hydroxyl groups of a polyether compound are reacted with polyisocyanate to obtain a prepolymer having hydroxyl groups at the molecular terminals, and then the prepolymer is reacted with the above-mentioned compound 1 to convert the hydroxyl groups into groups having polymerizable unsaturated groups.

[0138] In the method (b2), the prepolymer having an isocyanate group at the molecular terminal can be the polyether compound B having an isocyanate group at the molecular terminal.In the method (c2), the prepolymer having a hydroxyl group at the molecular terminal can be the polyether compound B having a hydroxyl group at the molecular terminal.

[0139] 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 having 8 or less carbon atoms excluding the carbon in the isocyanate group of the isocyanate alkyl group, and most preferably an isocyanate alkyl (meth)acrylate having 4 or less 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 2 include 2-isocyanatoethyl (meth)acrylate, isocyanatemethyl (meth)acrylate, etc. Commercially available products include Karenz-AOI and Karenz-MOI (both are product names of Showa Denko KK).

[0140] Compound 2 is preferably a compound having an active hydrogen-containing group such as a hydroxyl group or an amino group, and a polymerizable unsaturated group, more preferably a (meth)acrylate having an active hydrogen-containing group such as a hydroxyl group or an amino group, further preferably a hydroxyalkyl (meth)acrylate or hydroxycycloalkyl (meth)acrylate having one hydroxyl group, and particularly preferably a hydroxyalkyl (meth)acrylate in which the alkyl group has 8 or less carbon atoms. Examples of compound 2 include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, etc. 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 trade names of Kyoei Chemical Co., Ltd.), and 4-HBA (trade name of Osaka Organic Chemical Industry Co., Ltd.).

[0141] When the composition containing polyether compound C is a photocurable composition, it is preferable that all of the polymerizable unsaturated groups contained in polyether compound C are acryloyloxy groups. Such polyether compound C can be obtained by using compounds 1 and 2 in which the polymerizable unsaturated groups are acryloyloxy groups.

[0142] In the 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 having hydroxyl groups at the molecular terminals is preferably 0.8 to 1.2, more preferably 0.9 to 1.1, and even more preferably 0.95 to 1.05. In the method (b2), the molar ratio of the amount of compound 2 used relative to the amount of isocyanate groups in the prepolymer having isocyanate groups at the molecular terminals may be greater than 1. Excess compound 2 remains unreacted and may be contained in the composition containing polyether compound C. The 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.

[0143] In the methods (a2), (b2), and (c2), the reaction between a hydroxyl group and a functional group capable of reacting with the hydroxyl group, and the reaction between an isocyanate group and a functional group capable of reacting with the isocyanate group can be carried out by methods known in the art. When the reaction is between a hydroxyl group and an isocyanate group, the above-mentioned urethane catalyst may be used as necessary.

[0144] (Composition containing a polyether compound having a polymerizable unsaturated group) The polyether compound C is used in a curable composition. The curable composition is obtained by mixing the polyether compound C with other optional components. As the polyether compound C, only one type may be used, or two or more types may be used in combination. The content of the polyether compound C relative to the total mass of the curable composition is preferably 65 mass % or more, more preferably 75 mass % or more.

[0145] The curable composition may contain, in addition to the polyether compound C, a compound having a polymerizable unsaturated group other than the polyether compound C (hereinafter also referred to as "other compounds"), a photopolymerization initiator, and other components.

[0146] Examples of other compounds include the following other compounds 1 and 2. The other compound 1 is a compound other than the polyether compound C, and is preferably a compound having one (meth)acryloyloxy group and one or more hydroxyl groups, and more preferably one or two hydroxyl groups. The other compound 1 may be a compound having a polyoxyalkylene chain, and in this case, a compound having no urethane bond or urea bond (a compound produced by a method other than the above methods (a2) to (c2)) is preferred. The other compound may also be a compound having an aliphatic polyester chain obtained by ring-opening addition polymerization of lactone.

[0147] Examples of other compounds 1 include hydroxyalkyl (meth)acrylates, dihydroxyalkyl (meth)acrylates, lactone-modified hydroxyalkyl (meth)acrylates, polyoxyalkylene diol mono(meth)acrylates, and (meth)acrylic acid-monoepoxide adducts.

[0148] The number of carbon atoms in the hydroxyalkyl moiety of the hydroxyalkyl (meth)acrylate is preferably 2 to 8, more preferably 2 to 6. The number of carbon atoms in the dihydroxyalkyl moiety of the dihydroxyalkyl (meth)acrylate is preferably 2 to 8, more preferably 2 to 6. Specific examples of the hydroxyalkyl (meth)acrylate include the hydroxyalkyl (meth)acrylates exemplified above as Compound 2. Of these, 4-hydroxybutyl acrylate and 6-hydroxyhexyl acrylate are preferred in terms of flexibility and low volatility.

[0149] Examples of lactone-modified hydroxyalkyl (meth)acrylates include compounds obtained by ring-opening addition of lactone to the hydroxyalkyl (meth)acrylates exemplified above as Compound 2. The number of lactones added is preferably 1 to 3. Examples of lactones include ε-caprolactone, γ-butyrolactone, and γ-valerolactone.

[0150] The (meth)acrylic acid-monoepoxide adduct is preferably a reaction product of (meth)acrylic acid with a glycidyl ether or a glycidyl ester, such as (meth)acrylic acid with phenyl glycidyl ether.

[0151] Among these, hydroxyalkyl (meth)acrylate and (meth)acrylic acid-monoepoxide adduct are preferred because they are easily available industrially and contain few impurities.

[0152] The other compounds 1 may be used alone or in combination of two or more. When the curable composition contains the other compound 1, the content of the other compound 1 relative to the total mass of the curable composition is preferably 1 to 20 mass%, more preferably 1 to 15 mass%. When the content of the other compound 1 is equal to or greater than the above lower limit, the effect of improving adhesion by adding the other compound 1 is likely to be sufficiently obtained. When the content of the other compound 1 is equal to or less than the above upper limit, good physical properties in terms of low cure shrinkage are likely to be obtained.

[0153] The other compound 2 is a compound other than the polyether compound C and the other compound 1, and is preferably a compound having one (meth)acryloyloxy group and not containing a urethane bond. Preferred examples of the other compound 2 include a (meth)acrylate having a long-chain alkyl group with 8 or more carbon atoms and a (meth)acrylate having an amide group. Examples of other compounds 2 other than these include alkyl (meth)acrylates having 7 or less carbon atoms, alkoxyalkyl (meth)acrylates, and (meth)acrylates having an aliphatic cyclic hydrocarbon group.

[0154] When the curable composition contains a long-chain alkyl (meth)acrylate having 8 or more carbon atoms, bubbles in the cured product tend to disappear when the curable composition is sealed under reduced pressure and then cured in a higher-pressure atmosphere (vacuum sealing-pressure increase curing method). 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, isodecyl (meth)acrylate, etc. Among these, lauryl acrylate and isostearyl acrylate are preferred in terms of flexibility, low viscosity, and low crystallinity.

[0155] As the (meth)acrylate having an amide group, a compound 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 is preferred, as this easily prevents whitening of the cured product of the curable composition under humid and hot conditions. Examples of (meth)acrylamide derivatives include 4-(meth)acryloylmorpholine, N,N-dimethyl(meth)acrylamide, and N,N-diethyl(meth)acrylamide.

[0156] The other compounds 2 may be used alone or in combination of two or more. When the curable composition contains the other compound 2, the content of the other compound 2 relative to the total mass of the curable composition is preferably 1 to 30 mass%, more preferably 1 to 25 mass%. When the content of the other compound 2 is equal to or greater than the above lower limit, the effect of adding the other compound 2 is likely to be sufficiently obtained. When the content of the other compound 2 is equal to or less than the above upper limit, good physical properties in terms of low cure shrinkage are likely to be obtained.

[0157] The curable composition may be a photocurable composition or a thermosetting composition. Photocurable compositions are preferred because they can be cured at low temperatures and have a fast curing rate. When the curable composition is a photocurable composition, it preferably contains a photopolymerization initiator. When a photocurable composition is used in the manufacture of a display device, for example, high temperatures are not required, so there is little risk of damage to the display device due to high temperatures.

[0158] Examples of the photopolymerization initiator include acetophenone-based, ketal-based, benzoin or benzoin ether-based, phosphine oxide-based, benzophenone-based, thioxanthone-based, and quinone-based photopolymerization initiators. Among these, phosphine oxide-based and thioxanthone-based photopolymerization initiators are preferred, with phosphine oxide-based being preferred in that coloration after the photopolymerization reaction is easily suppressed. One type of photopolymerization initiator may be used alone, or two or more types may be used in combination.

[0159] The photopolymerization initiator is not particularly limited, and commercially available products can be used, such as IRGACURE 819, IRGACURE TPO, IRGACURE 184, IRGACURE 2959, IRGACURE 1173, IRGACURE 127, IRGACURE 907, IRGACURE OXE01, and IRGACURE OXE02, all manufactured by BASF. When the curable composition contains a photopolymerization initiator, the content of the photopolymerization initiator is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the total of the curable components.

[0160] Examples of other components include tackifiers such as rosin esters, terpene phenols, and hydrogenated terpene phenols; plasticizers such as adipates and phthalates; polyether compounds having no polymerizable unsaturated groups; and polyether polyols having alkoxylated molecular terminals. When the curable composition contains a plasticizer, flexibility and adhesion tend to be improved. 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.

[0161] Examples of other components include polymerization inhibitors, photocuring accelerators, chain transfer agents, light stabilizers (such as ultraviolet absorbers and radical scavengers), antioxidants, flame retardants, adhesion improvers (such as silane coupling agents), pigments, and dyes. Among these, it is preferable to include a polymerization inhibitor and a light stabilizer. In particular, by including a polymerization inhibitor in an amount smaller than that of the polymerization initiator, the storage stability of the curable composition can be improved and the molecular weight after curing can be easily adjusted.

[0162] Examples of the polymerization inhibitor include hydroquinone-based (2,5-di-tert-butylhydroquinone, etc.), catechol-based (p-tert-butylcatechol, etc.), anthraquinone-based, phenothiazine-based, and hydroxytoluene-based polymerization inhibitors.

[0163] The ultraviolet absorber is used to prevent photodegradation of the curable composition and improve weather resistance. Examples of the ultraviolet absorber include benzotriazole-based, triazine-based, benzophenone-based, and benzoate-based ultraviolet absorbers. As the benzotriazole-based ultraviolet absorber, for example, those described in paragraph

[0076] of WO 2014 / 017328 can be used.

[0164] The light stabilizer is used to prevent photodegradation of the curable composition and improve weather resistance. Examples of the light stabilizer include hindered amine light stabilizers. Examples of the hindered amine light stabilizer include those described in paragraph

[0077] of WO 2014 / 017328.

[0165] The antioxidant is used to prevent oxidation of the curable composition and improve weather resistance and heat resistance. Examples of the antioxidant include phenolic and phosphorus-based antioxidants. As the phenolic antioxidant, for example, those described in paragraph

[0078] of WO 2014 / 017328 can be used. As the phosphorus-based antioxidant, those described in paragraph

[0078] of WO 2014 / 017328 can be used.

[0166] Also, products containing a mixture of multiple antioxidants, light stabilizers, etc. can be used, such as IRGASTAB PUR68 and TINUVIN B75 manufactured by BASF.

[0167] When 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.

[0168] The content of the chain transfer agent in the curable composition is preferably small, 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 particularly preferably no chain transfer agent is contained.

[0169] (Use of curable composition containing polyether compound having polymerizable unsaturated group) Suitable applications of the curable composition containing polyether compound C include pressure-sensitive adhesives in the fields of various building materials, packaging materials, printing materials, display materials, electrical and electronic component materials, optical component materials, liquid crystal panels, and the like. [Example]

[0170] EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following descriptions. Examples 1 to 4 are working examples, and Examples 5 to 8 are comparative examples.

[0171] [Chlorine content of AO-containing raw materials] The chlorine content relative to the total mass of the AO-containing raw material was determined by titration. Specifically, the chlorine content was measured using the following reagents and by the following procedure. (1) Reagents Chloride standard solution (0.01 mg Cl - / mL): Standard stock solution for chemical analysis (1mgCl - / mL) into a 1 L volumetric flask and add water to make 1 L. Nitric acid: a mixture of nitric acid and pure water ·Silver nitrate solution (20 g / L): Dissolve 2 g of silver nitrate in 100 mL of water. 1 mol / L (1N) sodium hydroxide solution (2) Operation 1) Weigh 50 g of sample into a beaker (100 mL) using a balance. 2) Add two drops of 1 mol / L (1N) sodium hydroxide solution, cover with filter paper, and evaporate the sample in a water bath (70-80°C). 3) Once the sample has evaporated to dryness, rinse the inside of the beaker with pure water. 4) Transfer to a colorimetric tube and add pure water to make 20 mL. 5) Add 1 mL of nitric acid and shake gently, then add 1 mL of silver nitrate solution (20 g / L). 6) After leaving it in the dark for 15 minutes, compare it with the standard row with the naked eye. If the turbidity is higher than the standard column, use a measuring pipette to dispense an appropriate amount of the chloride standard solution into a colorimetric tube, add water to make 20 mL, and then quantify the amount in accordance with procedures 5) to 6).If the turbidity of the sample exceeds the standard column of 5 μg, perform procedures 2) to 6) to correct for chloride ions in the sample as a blank test. The standard column is prepared as follows: Place 0, 0.5, and 1.0 mL of chloride standard solution (0, 5, and 10 μg) in a colorimetric tube using a measuring pipette, add pure water to make 20 mL, and then perform steps 5) and 6). 7) Calculate the chlorine content using the following formula: A=(ab) / S where A is the chloride ion (Cl - ) concentration (ppm), and a is the chloride ion (Cl - ) (μg), and b is the amount of chloride ions (Cl) in the blank test tube determined from the standard column. - ) indicates the amount (μg) of sample taken, and S indicates the amount of sample taken (g).

[0172] [Total aldehyde content of AO-containing raw materials] The total aldehyde content relative to the total mass of the AO-containing raw material was determined by titration. Specifically, the total aldehyde content was measured using the following reagents and by the following procedure. (1) Reagents Sodium bisulfite Starch solution (5g / L): Dissolve 5g of water-soluble starch in approximately 100mL of water, pour into 1L of hot water while stirring, cool and store. 0.05mol / L (0.1N) iodine solution 0.005 mol / L (0.01 N) iodine solution: 0.05 mol / L (0.1 N) iodine solution diluted 10 times Sodium bicarbonate reagent (2) Operation 1) Using a measuring cylinder, measure 150 mL of distilled water that has been pre-cooled to 0-10°C into a 500 mL Erlenmeyer flask with a stopper. 2) Weigh out 0.05 g of sodium bisulfite reagent on a balance and add it. 3) Measure 36 mL of the sample using a measuring cylinder and transfer it to the flask. Then, re-stopper the flask, mix it, and keep the flask at 0 to 10°C for 15 minutes. 4) Measure 150 mL of distilled water that has been cooled to 0-10°C in advance into a measuring cylinder and add approximately 2 mL of the starch solution. 5) Titrate with 0.05 mol / L iodine solution until just before the end point, then continue titrating with 0.005 mol / L iodine solution until the blue color no longer disappears within 1 minute. 6) Add 1 g of sodium bicarbonate reagent and mix. 7) Titrate with 0.005 mol / L iodine solution until the pale blue color does not disappear within 1 minute, and read the titer. 8) Calculate the total aldehyde content using the following formula: A=(V×0.00029) / (36×0.83)×100 Here, A represents the total aldehyde content (%), and V represents the titer (mL) of 0.005 mol / L iodine solution.

[0173] [Hydroxyl value and hydroxyl value-equivalent molecular weight] The hydroxyl value (OHV) was calculated in accordance with Method B of JIS K 1557-1:2007. The OHV-equivalent molecular weight was calculated based on the formula "56,100 / hydroxyl value of polyether compound x number of hydroxyl groups of polyether compound." The number of hydroxyl groups of the polyether compound is the number of hydroxyl groups of the initiator. When two or more polyether compounds with different numbers of hydroxyl groups are contained, the number of hydroxyl groups of the polyether compound is the average number of hydroxyl groups.

[0174] [Mn, Mw, Mw / Mn] The molecular weight of the polyether compound was analyzed using a GPC system (Tosoh Corporation product name HLC-8320) and an RI detector. Two TSK-GEL Super HZ4000 (4.6 mm × 150 mm) columns and two Super HZ2500 (4.6 mm × 150 mm) columns were connected in series. Tetrahydrofuran (THF) was used as the eluent at a flow rate of 0.35 mL / min, and the column temperature was set at 40°C. Mn, Mw, and Mw / Mn were calculated using a calibration curve prepared using polystyrene standard samples (Agilent Technologies product name Easical PS-2, molecular weight range 580-400,000).

[0175] [viscosity] The viscosity of the polyether compound was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., product name: RE85U) under conditions of a measurement temperature of 25°C and rotor No. 1.

[0176] [Coloring] The coloration of the polyether compound A in each example was observed with the naked eye and evaluated according to the following criteria. A: No coloring. B: Slight discoloration is observed, but within the acceptable range. C: Discolored and unacceptable.

[0177] [Storage stability] Polyether compound A of each example was stored at 90°C for one week, and then the storage stability was evaluated according to the following criteria. A: The viscosity after storage at 90°C for one week is less than 2.5 times the viscosity before storage. B: The viscosity after storage at 90°C for one week is 2.5 times or more the viscosity before storage.

[0178] [AO-containing raw materials] Eight types of PO (PO(1) to (8)) from different sources and lots were used as AO-containing raw materials. The chlorine content and total aldehyde content of each of the eight types of PO are shown in Table 1 below. The PO content (PO purity) of each of the eight types of PO was 99% or more.

[0179] [Production Example 1: Preparation of Polyol P1 (Initiator)] In the presence of a KOH catalyst, PO(1) was polymerized with propylene glycol and then dealkalized to obtain polyoxypropylene diol (hereinafter also referred to as "polyol P1"). The average number of hydroxyl groups per molecule of polyol P1 was 2, and the molecular weight in terms of OHV was 1,000.

[0180] [Production Example 2: Preparation of Polyol P2 (Initiator)] In the presence of a KOH catalyst, PO(1) was polymerized with glycerin, followed by dealkalization and purification to obtain polyoxypropylene triol (hereinafter also referred to as "Polyol P2"). Polyol P2 had an average of 3 hydroxyl groups per molecule and an OHV-equivalent molecular weight of 1,000.

[0181] [Example 1] Using polyol P1 as an initiator, PO(1) was polymerized in the presence of a tert-butyl alcohol zinc hexacyanocobaltate complex catalyst (hereinafter referred to as "TBA-DMC catalyst") until the OHV-equivalent molecular weight reached 12,000, yielding polyether compound 1. The polymerization was carried out with the addition of 0.1% by mass of Irganox 1010 manufactured by BASF as a stabilizer. The amount of TBA-DMC catalyst used was such that the concentration of the TBA-DMC catalyst was 50 ppm relative to the total mass of polyether compound 1.

[0182] To 150 g of polyether compound 1, 0.0075 g of Neostan U-860 manufactured by Nitto Kasei Co., Ltd. and 4.97 g of 3-isocyanatopropyltriethoxysilane (NCO content: 20.5% by mass) were added, and the mixture was allowed to react at 80°C for 3 hours. The NCO / OH molar ratio of the isocyanate content of 3-isocyanatopropyltriethoxysilane to the hydroxyl group content of polyether compound 1 was set to 0.97. The reaction was terminated when it was confirmed by IR that there was no absorption due to NCO, yielding polyether compound A1 having a reactive silicon group.

[0183] [Example 2] Using polyol P1 as an initiator, PO (2) was polymerized in the presence of a TBA-DMC catalyst until the OHV-equivalent molecular weight reached 18,000, yielding polyether compound 2. The polymerization was carried out with the addition of 0.1% by mass of BASF's Irganox 1010 as a stabilizer. The amount of TBA-DMC catalyst used was such that the concentration of the TBA-DMC catalyst was 50 ppm relative to the total mass of polyether compound 2. Next, polyether compound A2 having a reactive silicon group was obtained in the same manner as in Example 1, except that polyether compound 2 was used instead of polyether compound 1 and the amount of 3-isocyanatopropyltriethoxysilane used was changed to 3.31 g.

[0184] [Example 3] Using polyol P2 as an initiator, PO (3) was polymerized in the presence of a TBA-DMC catalyst until the OHV-equivalent molecular weight reached 15,000, yielding polyether compound 3. The polymerization was carried out with the addition of 0.1% by mass of BASF's Irganox 1010 as a stabilizer. The amount of TBA-DMC catalyst used was such that the concentration of the TBA-DMC catalyst was 50 ppm relative to the total mass of polyether compound 3. Next, polyether compound A3 having a reactive silicon group was obtained in the same manner as in Example 1, except that polyether compound 3 was used instead of polyether compound 1 and the amount of 3-isocyanatopropyltriethoxysilane used was changed to 5.96 g.

[0185] [Example 4] Using polyol P1 as an initiator, PO (4) was polymerized in the presence of a TBA-DMC catalyst until the OHV-equivalent molecular weight reached 22,000, yielding polyether compound 4. The polymerization was carried out with the addition of 0.1% by mass of BASF's Irganox 1010 as a stabilizer. The amount of TBA-DMC catalyst used was such that the concentration of the TBA-DMC catalyst was 50 ppm relative to the total mass of polyether compound 4. Next, polyether compound A4 having a reactive silicon group was obtained in the same manner as in Example 1, except that polyether compound 4 was used instead of polyether compound 1 and the amount of 3-isocyanatopropyltriethoxysilane used was changed to 2.71 g.

[0186] [Example 5] Polyether compound 5 and polyether compound A5 were produced in the same manner as in Example 1, except that PO(5) was used instead of PO(1).

[0187] [Example 6] Polyether compound 6 and polyether compound A6 were produced in the same manner as in Example 2, except that PO(6) was used instead of PO(2).

[0188] [Example 7] Polyether compound 7 and polyether compound A7 were produced in the same manner as in Example 3, except that PO(7) was used instead of PO(3).

[0189] [Example 8] Polyether compound 8 and polyether compound A8 were produced in the same manner as in Example 4, except that PO(8) was used instead of PO(4).

[0190] Table 1 shows the evaluation results for the Mw / Mn, viscosity, and coloration of the polyether compound having a reactive silicon group for each example of the hydroxyl group-containing polyether compound.

[0191] [Table 1]

[0192] In Example 1, the Mw / Mn and viscosity of the polyether compound are lower than those of Example 5, which has the same initiator and OHV-equivalent molecular weight. Example 1 also has good storage stability. In Example 2, the Mw / Mn and viscosity of the polyether compound are lower than those of Example 6, which has the same initiator and OHV-equivalent molecular weight. Example 2 also has good storage stability. In Example 3, the Mw / Mn and viscosity of the polyether compound are lower than those of Example 7, which has the same initiator and OHV-equivalent molecular weight. Example 3 also has good storage stability. In Example 4, the polyether compound has a lower Mw / Mn and a lower viscosity than Example 8, which has the same initiator and OHV-equivalent molecular weight. Example 4 also has good storage stability. From the above results, it was confirmed that a polyether compound having a hydroxyl group and a narrow molecular weight distribution and low viscosity could be more reliably obtained. In addition, in Examples 1 to 4, the polyether compounds having reactive silicon groups were less colored. [Industrial Applicability]

[0193] According to the present invention, a production method can be provided that can more reliably produce a polyether compound having a hydroxyl group with a narrow molecular weight distribution and low viscosity, and can also produce a polyether compound having a reactive silicon group with reduced coloration.

Claims

1. A method for producing a polyether compound, comprising: contacting an initiator having active hydrogen with an alkylene oxide-containing raw material in the presence of a composite metal cyanide complex catalyst, and polymerizing the alkylene oxide in the alkylene oxide-containing raw material with the initiator; The alkylene oxide-containing feedstock has a chlorine content of less than 20 ppm based on the total mass of the alkylene oxide-containing feedstock.

2. 2. The process of claim 1, wherein the alkylene oxide-containing feedstock has a total aldehyde content of less than 15 ppm based on the total mass of the alkylene oxide-containing feedstock.

3. 3. The method according to claim 1, wherein the hydroxyl group of the polyether compound having a hydroxyl group obtained by polymerizing the alkylene oxide with the initiator is converted into a group having a reactive silicon group represented by the following formula 2: -SiR ａ X ３－ａ Formula 2 In the formula 2, R represents a monovalent organic group having 1 to 20 carbon atoms other than a hydrolyzable group, and X represents a hydroxyl group, a halogen atom, or a hydrolyzable group. a is an integer of 0 to 2. When a is 2, R may be the same or different from each other, and when a is 0 or 1, X may be the same or different from each other.

Images