Method for producing polyether compound having reactive silicon group

Abstract

To provide a method for producing a polyether compound having a reactive silicon group, which has low viscosity and excellent workability.SOLUTION: A method for producing a polyether compound having a reactive silicon group, wherein an initiator having an active hydrogen is brought into contact with an alkylene oxide-containing starting material in the presence of a double metal cyanide complex catalyst to polymerize the alkylene oxide in the alkylene oxide-containing starting material into a group having a reactive silicon group, and the hydroxyl group of the obtained polyether compound having a hydroxyl group is converted into a group having a reactive silicon group, wherein the acid value of the alkylene oxide-containing starting material is 0.0001 to 0.008 mgKOH / g.SELECTED DRAWING: None

Description

[Technical Field]

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

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

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

[0004] Patent Document 1 discloses 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 investigations of the present inventors, even when a composite metal cyanide complex catalyst is used, the molecular weight distribution of the polyether compound having a hydroxyl group may not be sufficiently narrow. Polyether compounds having reactive silicon groups obtained from polyether compounds with a broader molecular weight distribution may have high viscosity, which may deteriorate workability.

[0007] An object of the present invention is to provide a production method for producing a polyether compound having a reactive silicon group, which has low viscosity and excellent workability. [Means for solving the problem]

[0008] A preferred embodiment of the present invention provides the following means: [1] A method for producing a polyether compound having a reactive silicon group, comprising the steps of: In the presence of a composite metal cyanide complex catalyst, an initiator having active hydrogen is brought into contact with an alkylene oxide-containing raw material, and the alkylene oxide in the alkylene oxide-containing raw material is polymerized with the initiator, and the hydroxyl group of the resulting polyether compound having a hydroxyl group is converted into a group having a reactive silicon group represented by the following formula 1: The production method, wherein the alkylene oxide-containing raw material has an acid value of 0.001 to 0.008 mgKOH / g. -SiR a X 3-a formula 1 In formula 1, R represents a monovalent organic group having 1 to 20 carbon atoms other than a hydrolyzable group, and X represents a hydroxyl group, a halogen atom, or a hydrolyzable group. a is an integer of 0 to 2. When a is 2, R may be the same or different from each other, and when a is 0 or 1, X may be the same or different from each other. [2] The production method according to [1], wherein the amount of the double metal cyanide complex catalyst used is 5 to 60 ppm based on the total mass of the polyether compound having a hydroxyl group. [Effects of the Invention]

[0009] According to the present invention, there can be provided a production method that can produce a polyether compound having a reactive silicon group, which has low viscosity and excellent workability. DETAILED DESCRIPTION OF THE INVENTION

[0010] The meanings and definitions of terms used in this specification are as follows: A numerical range expressed as "to" means a numerical range with the numbers before and after "to" as the lower and upper limits. The lower and upper limits of the numerical ranges disclosed in this specification can be combined in any way to create a new numerical range.

[0011] The "unit" constituting the polyether compound having a hydroxyl group means an atomic group formed directly by polymerization of a monomer. The term "main chain" refers to a polymer chain formed by polymerization of two or more monomers. In the polyether compounds having a hydroxyl group and the polyether compounds having a reactive silicon group, which will be described later, the "main chain" refers to a residue obtained by removing active hydrogen from an initiator and a portion containing a repeating unit based on alkylene oxide (polyoxyalkylene chain). The polyether compound having a hydroxyl group and the polyether compound having a reactive silicon group are polymers consisting of a main chain and terminal groups. The "end group" of a polyether compound having a hydroxyl group and a polyether compound having a reactive silicon group means an atomic group containing the oxygen atom closest to the molecular end among the oxygen atoms in the polyoxyalkylene chain. However, if the atomic group contains a residue of an initiator, it is not considered to be an end group but is considered to be part of the main chain. The "number of end groups" in a polyether compound having a hydroxyl group and a polyether compound having a reactive silicon group is the same number as the number of active hydrogen atoms in the initiator, as described below. The "active hydrogen-containing group" refers to at least one group selected from the group consisting of a hydroxyl group bonded to a carbon atom, a carboxyl group, an amino group, a monovalent functional group obtained by removing one hydrogen atom from a primary amine, a hydrazide group, and a sulfanyl group. "Active hydrogen" refers to a hydrogen atom derived from an active hydrogen-containing group and a hydrogen atom derived from a 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 in the silylating agent added to the number of terminal groups of a polyether compound having a hydroxyl group when reactive silicon groups are introduced into the terminal groups of the hydroxyl group-containing polyether compound using the silylating agent described below. In this case, however, a diisocyanate compound is used as the polyisocyanate compound in the method (c1) described below. The term "silylating agent" refers to a compound having a reactive silicon group and a functional group that reacts with an active hydrogen-containing group, an unsaturated group, or an isocyanate group.

[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 a polyether compound having a hydroxyl group is a value measured in accordance with Method B (phthalation method) described in JIS K 1557-1:2007. The hydroxyl value-based molecular weight is a value calculated by multiplying the hydroxyl value of the hydroxyl-containing polyether compound by the number of hydroxyl groups in the hydroxyl-containing polyether compound (the number of active hydrogen atoms in the initiator). When two or more types of hydroxyl-containing polyether compounds with different numbers of hydroxyl groups are contained, the number of hydroxyl groups in the hydroxyl-containing 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 acid value of the alkylene oxide-containing raw material is the number of milligrams of potassium hydroxide required to neutralize 1 g of the alkylene oxide-containing raw material, and is measured by the method described 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. Details are as described in the Examples. The alkylene oxide content of the alkylene oxide-containing raw material is measured by gas chromatography, as described in detail in the Examples. "ppm" is by mass unless otherwise specified.

[0017] <Method for producing polyether compound having reactive silicon group> The method for producing a polyether compound having a reactive silicon group of this embodiment involves contacting an initiator having active hydrogen with an alkylene oxide-containing raw material in the presence of a composite metal cyanide complex catalyst, polymerizing the alkylene oxide in the alkylene oxide-containing raw material with the initiator, and converting the hydroxyl groups of the resulting polyether compound having a hydroxyl group into a group having a reactive silicon group represented by Formula 1 described below.

[0018] Hereinafter, the polyether compound having a hydroxyl group will be referred to as "polyether compound A," and the polyether compound having a reactive silicon group will be referred to as "polyether compound B." The production process for polyether compound A and the production process for polyether compound B will be described in order below.

[0019] <Production process of polyether compound having hydroxyl groups> In the process for producing polyether compound A of this 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.

[0020] (Alkylene oxide-containing raw material) The alkylene oxide-containing raw material contains alkylene oxide (hereinafter also referred to as "AO"), which is selected depending on the structural unit of the polyoxyalkylene chain of the polyether compound A 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.

[0021] 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.

[0022] The AO content (AO purity) of the AO-containing raw material is preferably 97% by mass or more, more preferably 98% by mass or more, and even more preferably 99% by 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 acid content of the AO-containing raw material is 0.001 to 0.008 mg KOH / g, preferably 0.001 to 0.007 mg KOH / g, and more preferably 0.001 to 0.006 mg KOH / g, as expressed in terms of the acid value of the AO-containing raw material. When the acid value is within the above range, the molecular weight distribution of the polyether compound A becomes narrow. Furthermore, while the catalytic activity of a composite metal cyanide complex catalyst (hereinafter also referred to as a "DMC catalyst") used in the production of polyether compound A has traditionally declined over time, the use of an AO-containing raw material with an acid value within the above range can prevent this decline in catalytic activity. Suppressing this decline in catalytic activity reduces the amount of DMC catalyst used, which is economical. Furthermore, when the acid value is within the above range, the odor and coloration of products produced using the polyether compound A can be reduced.

[0024] 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 polyether compound A can be reduced. The total aldehyde content of the AO-containing raw material is preferably 0 ppm or more, and 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 polyether compound B obtained from the obtained polyether compound A is superior. The upper limit and the lower limit can be combined as appropriate.

[0025] The AO-containing raw material may be selected from commercially available AO-containing raw materials so that the impurity content falls 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 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.

[0026] 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.

[0027] (initiator) The number of active hydrogens in the initiator is preferably 1 or more, more preferably 1 to 10, even more preferably 1 to 8, and particularly preferably 1 to 6. The number of active hydrogens in the initiator is preferably selected depending on the number of hydroxyl groups per molecule of the polyether compound A to be obtained. The number of active hydrogens in the initiator and the number of terminal groups in the polyether compound A are the same. The initiator may be used alone or in combination of two or more kinds.

[0028] 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.

[0029] (Double metal cyanide complex catalyst) The DMC catalyst functions as a polymerization catalyst for alkylene oxide. The DMC catalyst is a crystalline solid and contains a reaction product of a metal halide salt and a transition metal cyanide compound, an organic ligand, and water of crystallization (such as coordinated water) contained within the crystal. In addition, the catalyst may contain trace amounts of impurities unavoidable during production and moisture other than water of crystallization contained in the metal salt, metal compound, etc. The metal halide salt, transition metal cyanide compound, and organic ligand that can be used are those known in the production of DMC catalysts.

[0030] The DMC catalyst is believed to be represented by Formula 2 below. M 1 a [M 2 (CN) b ] c d(M 1 e X f )·g(Ligand)·h(H2O) Equation 2 In Equation 2, 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 2is 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.

[0031] M 1 Examples of such metals 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). 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.

[0032] 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).

[0033] The DMC catalyst is preferably a zinc hexacyanocobaltate (Zn3[Co(CN)6]2) complex with tert-butyl alcohol as the ligand. The complex may be coordinated with water and zinc chloride.

[0034] The DMC catalyst may be used in the production of polyether compound A, for example, in a solid state, or in the production of polyether compound A 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").

[0035] 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.

[0036] As the dispersion medium for the slurry catalyst, a known organic solvent for slurry catalysts can be used. For example, the hardly volatile hydroxy compound described in Japanese Patent No. 3194255 can be used. The hydroxy compound is a hydroxyl group-containing compound having 1 to 8 hydroxyl groups and a molecular weight of 100 to 8000, and a compound having an alcoholic hydroxyl group, such as a polyether compound having a hydroxyl group, is preferred. The dispersion medium for the slurry catalyst is preferably a second polyether compound having a hydroxyl group, since it does not become an impurity for the product (polyether compound A) obtained by polymerization of alkylene oxide. That is, the dispersion medium for the slurry catalyst preferably contains a second polyether compound having a hydroxyl group. The Mn of the second polyether compound having a hydroxyl group used as a dispersion medium is preferably 100 to 8,000, more preferably 600 to 3,000. When Mn is equal to or greater than the lower limit, the compound does not act as a catalyst poison, and when Mn is equal to or less than the upper limit, the slurry catalyst is easy to handle. An initiator for polymerizing alkylene oxide may be used as part of the dispersion medium.

[0037] 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.

[0038] 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 second polyether compound having a hydroxyl group, 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 an initiator, the content of the DMC catalyst relative to the total mass of the slurry catalyst is preferably 0.003 to 0.020 mass%, more preferably 0.004 to 0.015 mass%, and even more preferably 0.006 to 0.010 mass%.

[0039] 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.

[0040] 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.

[0041] 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.

[0042] The concentration of the metal halide salt in the aqueous solution of the metal halide salt is preferably 10% by mass or more, more preferably 30% by mass or more, and even more preferably 50% by mass or more, and is preferably equal to or less than the saturated concentration. The concentration of the transition metal cyanide compound in the aqueous solution of the transition metal cyanide 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, and more preferably 1.8 to 8.

[0043] The reaction temperature in the reaction between the aqueous solution of the metal halide salt and the aqueous solution of the transition metal cyanide compound is preferably 10 to 65°C, more preferably 20 to 60°C, and even more preferably 30 to 55°C.

[0044] The concentration of the organic ligand in the aqueous solution of the organic ligand is preferably 10 to 90% by mass, more preferably 25 to 75% by mass, and even more preferably 35 to 65% by mass.

[0045] The temperature at which the organic ligand is coordinated is preferably 10 to 90°C, more preferably 20 to 80°C, and even more preferably 30 to 70°C.

[0046] After the organic ligand is coordinated, it is preferable to carry out solid-liquid separation. For solid-liquid separation, methods known in the art, such as filtration and centrifugation, can be used. The obtained solid contains the DMC catalyst as well as 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, the mixture is stirred, and then solid-liquid separation is carried out again. The washing time is preferably 10 to 90 minutes, more preferably 20 to 60 minutes. It is preferable to carry out washing multiple times.

[0047] When producing a slurry catalyst, a method can be used in which a mixed liquid containing a DMC catalyst and water is obtained as described above, impurities and water are removed from the obtained mixed liquid, and then a dispersion medium is added to prepare a slurry containing the DMC catalyst and the dispersion medium. Before adding the dispersion medium, washing with an aqueous solution of an organic ligand may be performed.

[0048] (AO polymerization) By contacting the initiator with the AO-containing raw material in the presence of a DMC catalyst, the AO in the AO-containing raw material is polymerized with the initiator (ring-opening addition polymerization). When a DMC catalyst is used as the polymerization catalyst for AO, the Mw / Mn of the polyether compound A tends to be smaller and the degree of unsaturation of the polyether compound A tends to be smaller than when a polymerization catalyst other than a DMC catalyst is used.

[0049] When the polyoxyalkylene chain of the polyether compound A is a random copolymer chain consisting of PO units and EO units, a preferred method is to contact an initiator with an AO-containing raw material containing PO and EO in the presence of a DMC catalyst to obtain the polyether compound A. The same applies to combinations of two or more AOs other than the combination of PO and EO.

[0050] When the polyoxyalkylene chain of polyether compound A is a block copolymer chain having a block of PO units and a block of EO units, a precursor may be obtained by reacting an initiator with an AO-containing raw material containing PO in the presence of a DMC catalyst, and then the precursor may be reacted with an AO-containing raw material containing EO to obtain polyether compound A. Alternatively, a precursor may be obtained by reacting an initiator with an AO-containing raw material containing EO in the presence of a DMC catalyst, and then the precursor may be reacted with an AO-containing raw material containing PO to obtain polyether compound A. The same applies to combinations of two or more AOs other than the combination of PO and EO.

[0051] 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, relative to the total mass of the polyether compound A finally obtained. When the amount of the DMC catalyst used is equal to or greater than the lower limit, the polymerization reaction proceeds easily. When the amount of the DMC catalyst used is equal to or less than the upper limit, the storage stability of products using the polyether compound or its modified product is improved. In addition, the amount of metal impurities in the product can be reduced.

[0052] 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 fed to the reactor at a rate that maintains the reaction temperature. The reaction atmosphere is preferably one that is less susceptible to moisture contamination, and more preferably an inert gas atmosphere such as nitrogen.

[0053] The reaction solution after polymerization contains polyether compound A 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.

[0054] <Polyether compounds having hydroxyl groups> The main chain of the polyether compound A is a polymer chain consisting of a residue obtained by removing active hydrogen from an initiator and an oxyalkylene chain containing one or more repeating units based on alkylene oxide (hereinafter, a repeating unit based on a monomer will be simply referred to as a "monomer unit", for example, a repeating unit based on AO will be referred to as an "AO unit"). 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 A are hydroxyl groups. The number of terminal groups of the polyether compound A (i.e., the number of hydroxyl groups) is the same as the number of active hydrogens of the initiator.

[0055] The Mn of polyether compound A is preferably 1,000 to 100,000, more preferably 1,500 to 80,000, and even more preferably 2,000 to 60,000. When Mn is equal to or greater than the lower limit, sufficient flexibility is imparted when used as an adhesive or coating material, and good elongation properties are likely to be obtained. When Mn is equal to or less than the upper limit, the viscosity of polyether compound A and polyether compound B can be kept low, making them easy to handle.

[0056] The hydroxyl value of the polyether compound A is preferably 0.5 to 350 mgKOH / g, more preferably 1 to 200 mgKOH / g, and even more preferably 5 to 100 mgKOH / g. When the hydroxyl value is equal to or greater than the lower limit, sufficient curing is likely to be achieved when resinified. When the hydroxyl value is equal to or less than the upper limit, sufficient flexibility is imparted to the resin, and good elongation properties are likely to be achieved.

[0057] The hydroxyl value-based molecular weight of polyether compound A is preferably 1,000 to 100,000, more preferably 1,500 to 80,000, and even more preferably 2,000 to 60,000. When the hydroxyl value-based molecular weight is equal to or greater than the lower limit, sufficient flexibility is imparted when used as an adhesive or coating material, and good elongation properties are likely to be obtained. When the hydroxyl value-based molecular weight is equal to or less than the upper limit, the viscosity of polyether compound A and polyether compound B can be kept low, making them easy to handle.

[0058] The Mw of polyether compound A is preferably 1,200 to 120,000, more preferably 2,000 to 90,000, and even more preferably 3,000 to 70,000. When the Mw is equal to or greater than the lower limit, sufficient flexibility is imparted when used as an adhesive or coating material, and good elongation properties are likely to be obtained. When the Mw is equal to or less than the upper limit, the viscosity of polyether compound A and polyether compound B can be kept low, making them easy to handle.

[0059] The Mw / Mn of the polyether compound A is preferably 1.00 to 1.15, more preferably 1.00 to 1.12, and even more preferably 1.00 to 1.10. When the Mw / Mn is equal to or less than the upper limit, the viscosity of the polyether compound A and the polyether compound B can be kept low, making them easy to handle.

[0060] The degree of unsaturation of polyether compound A is preferably 0.001 to 0.040 meq / g, more preferably 0.002 to 0.030 meq / g, and even more preferably 0.003 to 0.010 meq / g. When the degree of unsaturation is not more than the upper limit, polyether compound B obtained from polyether compound A tends to have good physical properties when used in the applications described below.

[0061] The viscosity of the polyether compound A 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.

[0062] <Production process of polyether compound having reactive silicon group> In the process for producing polyether compound B, the hydroxyl groups of polyether compound A are converted into groups having a reactive silicon group.

[0063] (reactive silicon group) The reactive silicon group has a hydroxyl group, a halogen atom, or a hydrolyzable group bonded to a silicon atom, and can form a siloxane bond to crosslink. The reaction to form the siloxane bond is accelerated by a curing catalyst. The reactive silicon group in polyether compound B is represented by the following formula 1: -SiR a X 3-a formula 1

[0064] In formula 1, R represents a monovalent organic group having 1 to 20 carbon atoms other than a hydrolyzable group. R is preferably at least one group selected from the group consisting of hydrocarbon groups having 1 to 20 carbon atoms and triorganosiloxy groups.

[0065] 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 because of the good curability of the polymer having a reactive silicon group and the stability of the curable composition. An α-chloromethyl group is preferred because of the fast curing rate of the cured product. A methyl group is particularly preferred because of its easy availability.

[0066] In formula 1, X represents a hydroxyl group, a halogen atom, or a hydrolyzable group. Examples of the hydrolyzable group include an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a sulfanyl group, and an alkenyloxy group. An alkoxy group is preferred because it is mildly hydrolyzable and easy to handle. The alkoxy group is preferably a methoxy group, an ethoxy group, or an isopropoxy group, and more preferably a methoxy group or an ethoxy group. When the alkoxy group is a methoxy group or an ethoxy group, it is easy to 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.

[0067] In formula 1, 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. If the crosslinking density due to siloxane bonds is low, the modulus of the cured product will decrease, so a is preferably 2 or less, and more preferably 1 or less.

[0068] Examples of the reactive silicon group represented by formula 1 include a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a tris(2-propenyloxy)silyl group, a triacetoxysilyl group, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, a dimethoxyethylsilyl group, a methyldiisopropoxysilyl group, an (α-chloromethyl)dimethoxysilyl group, and an (α-chloromethyl)diethoxysilyl group. In terms of high activity and good curability, a trimethoxysilyl group, a triethoxysilyl group, a dimethoxymethylsilyl group, and a diethoxymethylsilyl group are preferred, and a trimethoxysilyl group and a dimethoxymethylsilyl group are more preferred.

[0069] The method for producing the polyether compound B may be the following method (a1), (b1) or (c1). Method (a1): Converting the hydroxyl groups of polyether compound A to 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 Formula 1. a X 3-a A method of converting an alkenyloxy group or an alkynyloxy group into a group having a reactive silicon group represented by formula 1 by reacting the alkenyloxy group or the alkynyloxy group with a silylating agent capable of introducing the following formula: Method (b1): A method in which a silylating agent having a functional group reactive with a hydroxyl group and a reactive silicon group represented by formula 1 is reacted with the hydroxyl group of polyether compound A to convert the hydroxyl group into a group having a reactive silicon group represented by formula 1. Method (c1): A method in which the hydroxyl groups of polyether compound A are converted to groups having an isocyanate group, and then the hydroxyl groups are converted to groups having a reactive silicon group represented by formula 1 by reacting with a silylating agent having a functional group reactive with an isocyanate group and a reactive silicon group represented by formula 1.

[0070] In method (a1), polyether compound A is subjected to the action of an alkali metal salt to form an alcoholate, and then reacted with a halogenated hydrocarbon compound having a carbon-carbon double bond 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 polyether compound A 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.

[0071] 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.

[0072] 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

[0073] Next, a reactive silicon group, -SiR, represented by Formula 1, is attached 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 formula 1 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 1). 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.

[0074] In the method (b1), a silylating agent is reacted with the polyether compound A. It is preferable to use an isocyanate silane compound represented by the following formula 3 as the silylating agent. OCN-(CH2) n -SiR a X 3-a ...Formula 3 -SiR in Equation 3 a X 3-a is the same as in formula 1. n is an integer of 1 to 8, and preferably 1 to 3. The reaction between the hydroxyl group of polyether compound A and the isocyanate silane compound converts the hydroxyl group of polyether compound A to -OC(=O)NH-(CH2) n -SiR a X 3-a The urethane bond (-OC(=O)NH-) and -SiR a X 3-a is converted to an end group having the formula: Examples of the isocyanate silane compound include 3-isocyanate propyl 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.

[0075] The active hydrogen of the polyether compound A reacts with the isocyanate group of the isocyanate silane compound represented by formula 3, thereby introducing a reactive silicon group into the polyether compound A. When the active hydrogen-containing group of the polyether compound A is a hydroxyl group, the polyoxyalkylene chain (-(R 5 O) m -, R 5 represents an alkylene group, and m represents the number of moles of oxyalkylene groups.) to which a reactive silicon group is bonded via a urethane bond and an organic group is obtained. 5 O) m -C(=O)NH-(CH2) n -SiR a X 3-a A linked structure represented by the following formula is formed.

[0076] 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.

[0077] The molar ratio of the total number of isocyanate groups in the isocyanate silane compound represented by formula 3 to the total number of active hydrogens in polyether compound A is preferably set according to the number of reactive silicon groups per molecule of the polyether compound B to be obtained. It is preferable to react the isocyanate silane compound represented by formula 3 so that the number of reactive silicon groups per molecule of the resulting polyether compound B is at least 0.7. For example, when the active hydrogen-containing group of polyether compound A is a hydroxyl group, NCO / OH, which represents the molar ratio of the total number of isocyanate groups (NCO) of the isocyanate silane compound represented by formula 3 to the total number of active hydrogens (total number of hydroxyl groups) of polyether compound A, is preferably 0.7 to 1.0, more preferably 0.8 to 1.0, and even more preferably 0.9 to 1.0. When NCO / OH is at least the lower limit, the strength of the cured product is excellent, and when it is at most the upper limit, the elongation of the cured product is excellent.

[0078] In method (c1), a polyisocyanate compound is reacted with the hydroxyl groups of polyether compound A to convert the hydroxyl groups into monovalent organic groups containing an isocyanate group (hereinafter also referred to as "isocyanate-containing groups") that have a urethane bond (-O-C(=O)NH-) at the bond terminal with polyether compound A. Next, a silylating agent having a functional group reactive with an isocyanate group and a reactive silicon group represented by formula 1 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 formula 1 is a compound represented by the following formula 5, but the present invention is not limited thereto.

[0079] OCN-R 3 -NCO...Formula 4 R in Equation 4 3 represents a divalent organic group.

[0080] WR 4 -SiR a X 3-a ...Formula 5 In formula 5, W represents a functional group (a group having one or more active hydrogen atoms) capable of reacting with a monovalent isocyanate group, R 4 is a divalent organic group, -SiR a X 3-a is the same as Equation 1.

[0081] When the hydroxyl group of polyether compound A is reacted with the diisocyanate compound represented by formula 4, the isocyanate-containing group is -OC(=O)NH-R 3 When an isocyanate-containing group is reacted with a silylating agent represented by formula 5, the urethane bond and the reactive silicon-containing group are formed as follows: -OC(=O)NH-R 3 -NHC(=O)-W'-R 4 -SiR a X 3-a (wherein W' is a divalent group obtained by removing one active hydrogen from W.) For example, when W is a hydroxyl group, the urethane bond and the 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 the reactive silicon group-containing group have two urethane bonds. For example, when W is an amino group (-NH), the urethane bond and the reactive silicon group-containing group are represented by -OC(=O)NH-R 3 -NHC(=O)-NH-R 4 -SiR a X 3-a It is a group represented by the formula:

[0082] R 3is preferably a divalent organic group having 2 to 20 carbon atoms, and examples thereof include an alkylene group, a cycloalkylene group, a bicycloalkylene group, a monocyclic or polycyclic divalent aromatic hydrocarbon group, a divalent group obtained by removing two hydrogen atoms from a cycloalkane having an alkyl group as a substituent, a divalent group obtained by removing two hydrogen atoms from an aromatic hydrocarbon having an alkyl group as a substituent, a divalent group obtained by removing two hydrogen atoms from two or more cycloalkanes which 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.

[0083] Examples of the diisocyanate compound represented by 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 constituting an aromatic ring), aliphatic polyisocyanates, alicyclic polyisocyanates, and urethane-modified, biuret-modified, allophanate-modified, carbodiimide-modified, and isocyanurate-modified 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.

[0084] 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 4 is preferably a divalent organic group having 1 to 20 carbon atoms, more preferably a group obtained by removing two hydrogen atoms from an aromatic hydrocarbon having 6 to 10 carbon atoms, a group obtained by removing two hydrogen atoms from an aromatic hydrocarbon having 6 to 10 carbon atoms and substituted with an alkyl group having 1 to 4 carbon atoms, a group obtained by removing two hydrogen atoms from a cyclic hydrocarbon having 3 to 10 carbon atoms, or a group obtained by removing two hydrogen atoms from a straight-chain hydrocarbon having 1 to 12 carbon atoms, still more preferably a group obtained by removing two hydrogen atoms from a straight-chain hydrocarbon having 1 to 8 carbon atoms, and particularly preferably a group obtained by removing two hydrogen atoms from a straight-chain hydrocarbon having 1 to 6 carbon atoms. W is preferably a group having one or two active hydrogen atoms selected from 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.

[0085] In the methods (b1) and (c1), the reactive silicon group in the resulting polyether compound B is formed via one or more organic groups represented by the following formula (i). That is, the polyether compound B obtained by methods (b1) and (c1) contains one or more organic groups represented by the following formula (i). The polyether compound B obtained by method (b1) contains only one organic group represented by the following formula (i), and the polyether compound B obtained by method (c1) contains two or more organic groups represented by the following formula (i). -C(=O)NH- Formula (i)

[0086] The organic group (i) is a divalent group derived from a urethane bond or a urea bond. When the isocyanate silane compound represented by Formula 3 is used as a silylating agent, the number of organic groups (i) is one.

[0087] The organic group (i) preferably forms a urethane bond (-OC(=O)NH-, where -O- represents the oxygen atom at the terminal of the polyoxyalkylene chain) with the polyoxyalkylene chain. That is, it is preferable that one organic group (i) is present between the polyoxyalkylene chain and the reactive silicon group in the polyether compound B. When the polyether compound B is produced by the above-mentioned method (b1), the number of organic groups represented by formula (i) contained in the polyether compound B is one. When the polyether compound B is produced by the method (b1), a polyether compound B with a high silylation rate is easily obtained. When the polyether compound B is produced by the method (b1), a polyether compound B with a narrow molecular weight distribution is easily obtained. The viscosity of the polyether compound B is suppressed, resulting in good workability. When the isocyanate silane compound represented by formula 3 contains one isocyanate group and one reactive silicon group, the number of reactive silicon groups per molecule of polyether compound B is the same as the number of groups (i) per molecule.

[0088] The silylation rate of polyether compound B is preferably 50 to 100 mol %, more preferably 60 to 98 mol %. When the silylation rate is at least the lower limit of the above range, the cured product has excellent tensile strength and a high modulus. When the curable composition contains two or more types of polyether compounds B, it is sufficient that the average silylation rate of all the polyether compounds B is within the above range.

[0089] <Polyether compound having reactive silicon group> The polyether compound B has a reactive silicon group represented by formula 1.

[0090] Polyether compound B is a polyether compound having an average of 1.0 or more terminal groups per molecule and having a reactive silicon group represented by formula 1, wherein the terminal group is a reactive silicon group, an unsaturated group, an isocyanate group, or a hydroxyl group.

[0091] Polyether compound B has an average of 1.0 or more terminal groups per molecule. The average number of terminal groups is preferably 1.0 to 8.0, more preferably 1.0 to 6.0, and even more preferably 1.0 to 4.0, since this results in a cured product with higher tensile strength and better modulus and elongation. The number of terminal groups of polyether compound B is the same as the number of terminal groups of the polyether compound. The terminal groups of polyether compound B have any of a reactive silicon group, an unsaturated group, an isocyanate group, or a hydroxyl group represented by formula 1. The respective terminal groups may be the same or different.

[0092] The average number of reactive silicon groups represented by formula 1 per terminal group of polyether compound B is preferably 0.5 to 2.0, more preferably 0.60 to 1.94. 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, and a good cured product with a high modulus can be obtained.

[0093] The average number of reactive silicon groups represented by formula 1 per molecule of polyether compound B is preferably 0.6 to 8.0, more preferably 0.8 to 6.0, and even more preferably 1.2 to 4.0. When the average number of reactive silicon groups is equal to or greater than the above lower limit, the crosslinking density due to siloxane bonds increases, and a good cured product with a high modulus can be obtained.

[0094] The Mn of the polyether compound B 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.

[0095] The Mw / Mn of the polyether compound B is preferably 1.00 to 1.50, more preferably 1.00 to 1.45, even more preferably 1.00 to 1.40, and most preferably 1.00 to 1.20. When the Mw / Mn is equal to or less than the upper limit, good elongation properties are easily obtained, and the viscosity is reduced, resulting in good workability.

[0096] The viscosity of polyether compound B 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.

[0097] (Curable composition containing a polyether compound having a reactive silicon group) The polyether compound B is used in a curable composition. The curable composition is obtained by mixing the polyether compound B with other necessary components. As the polyether compound B, only one type may be used, or two or more types may be used in combination. The content of polyether compound B relative to the total mass of the curable composition is preferably 1 to 90 mass%, more preferably 10 to 80 mass%, and even more preferably 20 to 70 mass%. When it is equal to or less than the upper limit of the above range, the cured product has better tensile strength and elongation properties.

[0098] Examples of other components contained in the curable composition include curable compounds other than polyether compound B, such as epoxy resins, epoxy resin curing agents, curing catalysts (silanol condensation catalysts), fillers, plasticizers, thixotropy-imparting agents, stabilizers, adhesion-imparting agents, physical property adjusters, dehydrating agents, adhesion-imparting resins, reinforcing materials such as fillers, surface modifiers, flame retardants, foaming agents, solvents, and silicates. Other components can be used in combination without limitation with conventionally known components described in International Publication No. 2013 / 180203, International Publication No. 2014 / 192842, International Publication No. 2016 / 002907, JP 2014-88481 A, JP 2015-10162 A, JP 2015-105293 A, JP 2017-039728 A, JP 2017-214541 A, etc. Two or more types of each component may be used in combination.

[0099] The curable composition may be a one-component type in which polyether compound B and all other components are mixed in advance, sealed, and stored, and then cured by moisture in the air after application, or a two-component type in which a base composition containing at least polyether compound B and a curing agent composition containing at least a curing catalyst are stored separately, and the curing agent composition and the base composition are mixed before use. The one-component curable composition preferably does not contain water. It is preferable that the components containing water are dehydrated and dried in advance, or that the components are dehydrated under reduced pressure during mixing and kneading. In the two-component curable composition, the curing agent composition may contain water. The base composition is unlikely to gel even if it contains a small amount of water, but from the viewpoint of storage stability, it is preferable to dehydrate and dry the blended components in advance. In order to improve storage stability, a dehydrating agent may be added to the one-component curable composition or the two-component base composition.

[0100] (Use of curable composition containing polyether compound having reactive silicon group) Suitable applications of the curable composition containing polyether compound B include adhesives, sealants (for example, elastic sealants for construction, sealants for double glazing, anti-rust and waterproof sealants for glass edges, sealants for the backside of solar cells, sealants for buildings, sealants for ships, sealants for automobiles, and sealants for roads), and electrical insulating materials (insulating coating materials for electric wires and cables). [Example]

[0101] Hereinafter, the embodiments will be described in more detail with reference to examples, but the present invention is not limited to the following descriptions. Examples 1 to 4, 9, and 10 are working examples, and Examples 5 to 8 and 11 are comparative examples.

[0102] [Total aldehydes in 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 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 0-10°C for 15 minutes. 4) Add 150 mL of distilled water, which has been cooled to 0-10°C in advance, to a measuring cylinder and approximately 2 mL of the starch solution. 5) Titrate with 0.05 mol / L iodine solution until just before the end point, and then continue titrating with 0.005 mol / L iodine solution until the blue color no longer disappears within 1 minute. 6) Add 1g 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.

[0103] [Acid value of AO-containing raw materials] The acid value of the AO-containing raw material was measured using the following reagents and by the following procedure. (1) Reagents Phenolphthalein solution (10g / L) 0.01 mol / L (N / 100) sodium hydroxide solution CO2-free water: Prepare by purging 5 L of water with nitrogen gas at a rate of 1 L / min for approximately 30 minutes or more. (2) Operation 1) Place 100 mL of decarbonated water in a 300 mL Erlenmeyer flask, add 48 mL of sample, and mix well. 2) Using phenolphthalein solution (10 g / L) as an indicator, titrate with 0.01 mol / L (N / 100) sodium hydroxide solution, and the endpoint is when the faint red color does not disappear for more than 15 seconds. 3) As a blank test, place 100 mL of CO2-depleted water in a separate 300 mL Erlenmeyer flask and repeat step 2. 4) Calculate the acid value using the following formula: A = ((VB) × 0.561) / (48 × 0.83) Here, A represents the acid value (as KOH) (mgKOH / g), V represents the amount (mL) of 0.01 mol / L (N / 100) sodium hydroxide solution consumed in the titration of the sample, and B represents the amount (mL) of 0.01 mol / L (N / 100) sodium hydroxide solution consumed in the blank test.

[0104] [AO content in AO-containing raw materials] The AO content (mass %) relative to the total mass of the AO-containing raw material was measured using a gas chromatograph (detector: flame ionization detector (FID)) under the following conditions. Column: Capillary, 60 m x 0.32 mm φ, DB-1301ms, film thickness 1.0 μm Oven temperature: 35℃ (12 min) → 10℃ / min → 100℃ (12 min) INJ / DET temperature: 180 / 180℃ Carrier gas: He Air flow rate: 400mL / min H2 flow rate: 30mL / min Carrier flow rate (pressure): 1.3609 mL / min (24.056 psi) Septum purge flow rate: 5 mL / min Split ratio: 50:1 Split flow rate: 68.047 mL / min Total flow: 74.407mL / min Gas saver: 20mL / min Inlet: Back Injection method: Microsyringe, injection volume 2 μL

[0105] [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 hydroxyl-containing polyether compound x number of hydroxyl groups of hydroxyl-containing polyether compound." The number of hydroxyl groups of the hydroxyl-containing polyether compound is the number of hydroxyl groups of the initiator used.

[0106] [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 x 150 mm) columns and two Super HZ2500 (4.6 mm x 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).

[0107] [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.

[0108] [Silylation rate] The silylation rate of polyether compound B is 1 Measurement was performed using the internal standard method of H-NMR.

[0109] [Storage stability] Polyether compound B 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.

[0110] [AO-containing raw materials] Eleven types of PO (PO(1)-(11)) from different sources and lots were used as AO-containing raw materials. The total aldehyde content and acid value of each of PO(1)-(11) are shown in Table 1 below. "ND" indicates not detected. The PO content (PO purity) of each of PO(1)-(11) was 99% or higher.

[0111] [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.

[0112] [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.

[0113] [Production Example 3: Preparation of Polyol P3 (Initiator)] In the presence of a KOH catalyst, PO(1) was polymerized with n-butyl alcohol, followed by dealkalization and purification to obtain polyoxypropylene monool (hereinafter also referred to as "Polyol P3"). Polyol P3 had an average of 1 hydroxyl group per molecule and an OHV-equivalent molecular weight of 400.

[0114] [Production Example 4: Preparation of Polyol P4 (Initiator)] In the presence of a KOH catalyst, sorbitol was polymerized with PO(1), followed by dealkalization and purification to obtain polyoxypropylene polyol (hereinafter also referred to as "Polyol P4"). Polyol P4 had an average of 6 hydroxyl groups per molecule and an OHV-equivalent molecular weight of 880.

[0115] [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 A1 having hydroxyl groups. 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 A1.

[0116] To 150 g of polyether compound A1, 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 A1 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 B1 having a reactive silicon group.

[0117] [Example 2] Using polyol P1 as an initiator, PO(2) was polymerized in the presence of TBA-DMC catalyst until the OHV-equivalent molecular weight reached 18,000, yielding polyether compound A2 having hydroxyl groups. 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 TBA-DMC catalyst was 50 ppm relative to the total mass of polyether compound A2. Next, polyether compound B2 having a reactive silicon group was obtained in the same manner as in Example 1, except that polyether compound A2 was used instead of polyether compound A1 and the amount of 3-isocyanatopropyltriethoxysilane added was 3.31 g.

[0118] [Example 3] Using polyol P2 as an initiator, PO(3) was polymerized in the presence of TBA-DMC catalyst until the OHV-equivalent molecular weight reached 15,000, yielding polyether compound A3 having hydroxyl groups. 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 TBA-DMC catalyst was 50 ppm relative to the total mass of polyether compound A3. Next, polyether compound B3 having a reactive silicon group was obtained in the same manner as in Example 1, except that polyether compound A3 was used instead of polyether compound A1 and the amount of 3-isocyanatopropyltriethoxysilane added was 5.96 g.

[0119] [Example 4] Using polyol P1 as an initiator, PO(4) was polymerized in the presence of TBA-DMC catalyst until the OHV-equivalent molecular weight reached 22,000, yielding polyether compound A4 having hydroxyl groups. 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 TBA-DMC catalyst was 50 ppm relative to the total mass of polyether compound A4. Next, polyether compound B4 having a reactive silicon group was obtained in the same manner as in Example 1, except that polyether compound A4 was used instead of polyether compound A1 and the amount of 3-isocyanatopropyltriethoxysilane added was 2.71 g.

[0120] [Example 5] Polyether compound A5 having a hydroxyl group and polyether compound B5 having a reactive silicon group were prepared in the same manner as in Example 1, except that PO(5) was used instead of PO(1).

[0121] [Example 6] Polyether compound A6 having a hydroxyl group and polyether compound B6 having a reactive silicon group were prepared in the same manner as in Example 2, except that PO(6) was used instead of PO(2).

[0122] [Example 7] Polyether compound A7 having a hydroxyl group and polyether compound B7 having a reactive silicon group were prepared in the same manner as in Example 3, except that PO(7) was used instead of PO(3).

[0123] [Example 8] Polyether compound A8 having a hydroxyl group and polyether compound B8 having a reactive silicon group were prepared in the same manner as in Example 4, except that PO(8) was used instead of PO(4).

[0124] [Example 9] Using polyol P3 as an initiator, PO (9) was polymerized in the presence of a TBA-DMC catalyst until the OHV-equivalent molecular weight reached 4,000, yielding polyether compound A9. 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 A9. Next, polyether compound B9 having a reactive silicon group was obtained in the same manner as in Example 1, except that polyether compound A9 was used instead of polyether compound A1 and the amount of 3-isocyanatopropyltriethoxysilane added was 7.46 g.

[0125] [Example 10] Using polyol P4 as an initiator, PO(10) was polymerized in the presence of a TBA-DMC catalyst until the OHV-equivalent molecular weight reached 42,000, yielding polyether compound A10. 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 A10. Next, polyether compound B10 having a reactive silicon group was obtained in the same manner as in Example 1, except that polyether compound A10 was used instead of polyether compound A1 and the amount of 3-isocyanatopropyltriethoxysilane added was 4.26 g.

[0126] [Example 11] A polyether compound A11 having a hydroxyl group and a polyether compound B11 having a reactive silicon group were prepared in the same manner as in Example 10, except that PO(11) was used instead of PO(10).

[0127] Table 1 shows the number of functional groups, OHV-equivalent molecular weight, Mw / Mn, and viscosity of the initiator of each polyether compound A, and the silylation rate, viscosity, and storage stability of each polyether compound B.

[0128] [Table 1]

[0129] Comparing Example 1 and Example 5, in which polyether compound B was produced under the same conditions except for the AO-containing raw material, the polyether compound B in Example 1 had a lower viscosity. Furthermore, Example 1 had better storage stability. Similar trends were also observed in comparisons between Example 2 and Example 6, between Example 3 and Example 7, between Example 4 and Example 8, and between Example 10 and Example 11.

Claims

1. A method for producing a polyether compound having a reactive silicon group, comprising the steps of: In the presence of a composite metal cyanide complex catalyst, an initiator having active hydrogen is brought into contact with an alkylene oxide-containing raw material to polymerize the alkylene oxide in the alkylene oxide-containing raw material with the initiator, and the hydroxyl group of the resulting polyether compound having a hydroxyl group is converted into a group having a reactive silicon group represented by the following formula 1: The alkylene oxide-containing raw material has an acid value of 0.001 to 0.008 mgKOH / g. -SiR ａ X ３－ａ Formula 1 In formula 1, R represents a monovalent organic group having 1 to 20 carbon atoms other than a hydrolyzable group, and X represents a hydroxyl group, a halogen atom, or a hydrolyzable group. a is an integer of 0 to 2. When a is 2, R may be the same or different from each other, and when a is 0 or 1, X may be the same or different from each other.

2. 2. The method according to claim 1, wherein the amount of the double metal cyanide complex catalyst used is 5 to 60 ppm based on the total mass of the polyether compound having a hydroxyl group.

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