Method for producing polyether compound having urethane bond

Abstract

To provide a method for producing a urethane bond-containing polyether compound having excellent curability.SOLUTION: Contacting an initiator having active hydrogen with an alkylene oxide-containing starting material, polymerizing alkylene oxides in the alkylene oxide-containing starting material with the initiator, and reacting the obtained hydroxyl group-containing starting material with a polyisocyanate, wherein the methyl formate 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 having a urethane bond. [Background technology]

[0002] Polyether compounds having urethane bonds, such as urethane prepolymers, are used as raw materials for adhesives, paints, sealants, coatings, etc. Polyether compounds having urethane bonds are produced using 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.

[0003] Patent Document 1 discloses a urethane prepolymer composition (G) containing a hydroxyl-terminated urethane prepolymer (E) and a polyalkylene oxide (B). It also discloses that the urethane prepolymer (E) is a reaction product of a polyol and a polyisocyanate (C) and has at least one urethane group and at least one hydroxyl group per molecule. It also discloses that the polyol can be produced using a double metal cyanide complex catalyst. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2023-155601 Summary of the Invention [Problem to be solved by the invention]

[0005] However, according to the investigations of the present inventors, the curability of polyether compounds having urethane bonds obtained from polyether compounds having hydroxyl groups obtained using a double metal cyanide complex catalyst may be reduced.

[0006] An object of the present invention is to provide a production method that can yield a polyether compound having a urethane bond and excellent curability. [Means for solving the problem]

[0007] The present invention has the following aspects. [1] A method for producing a polyether compound having a urethane bond, comprising the steps of: contacting an initiator having active hydrogen with an alkylene oxide-containing raw material in the presence of a composite metal cyanide complex catalyst to polymerize the alkylene oxide in the alkylene oxide-containing raw material with the initiator; and reacting the resulting polyether compound having a hydroxyl group with a polyisocyanate; The alkylene oxide-containing feedstock has a methyl formate 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 alkylene oxide-containing raw material has a propionaldehyde content of less than 20 ppm. [Effects of the Invention]

[0008] According to the present invention, a production method can be provided that can obtain a polyether compound having a urethane bond and excellent curability. DETAILED DESCRIPTION OF THE INVENTION

[0009] The meanings and definitions of terms used in this specification are as follows: A numerical range indicated by "to" means that the numerical values ​​before and after "to" are the lower and upper limits of the numerical range.

[0010] 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 case of a polyether compound having a hydroxyl 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 is a polymer consisting of a main chain and terminal groups. The "end group" of a polyether compound having a hydroxyl 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 is the same as the number of active hydrogen atoms in the initiator, which will be described later. 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.

[0011] 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.

[0012] 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 the formula: 56,100 / hydroxyl value of the polyether compound having hydroxyl groups×number of hydroxyl groups of the polyether compound having hydroxyl groups.

[0013] The degree of unsaturation of a polyether compound having a hydroxyl group can be measured in accordance with JIS K 1557-3:2007. The viscosity of the polyether compound is measured using an E-type viscometer. The ultra-high molecular weight component of a polyether compound means a component having a molecular weight ranging from 12 times (12W) to 46 times (46W) the molecular weight of a polyether compound, where W is the Mn of the polyether compound. The content of the ultra-high molecular weight component is measured by the method described in JP 2019-137810 A. Details are as described in the Examples.

[0014] The content of isocyanate groups relative to the total mass of the polyether compound having a urethane bond is a value measured in accordance with Method A described in JIS K 1603-1:2007.

[0015] The methyl formate content and propionaldehyde content of the alkylene oxide-containing raw material are measured by gas chromatography, as described in detail in the Examples. "ppm" is by mass unless otherwise specified.

[0016] In the method for producing a polyether compound having a urethane bond of the present embodiment, an initiator having active hydrogen is brought into contact with an alkylene oxide-containing raw material in the presence of a composite metal cyanide complex catalyst, the alkylene oxide in the alkylene oxide-containing raw material is polymerized with the initiator, and the resulting polyether compound having a hydroxyl group is reacted with a polyisocyanate.

[0017] Hereinafter, a polyether compound having a hydroxyl group will be referred to as "polyether compound A." Furthermore, a polyether compound having a urethane bond will be referred to as "polyether compound B." Below, the methods for producing polyether compound A and polyether compound B will be described in order.

[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 methyl formate 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 methyl formate content is equal to or less than the upper limit, the curability of polyether compound B obtained from polyether compound A is excellent. The detection limit for methyl formate is typically 0.1 ppm.

[0021] The propionaldehyde content of the AO-containing raw material is preferably less than 20 ppm, more preferably less than 18 ppm, even more preferably less than 16 ppm, particularly preferably less than 14 ppm, and most preferably below the detection limit, relative to the total mass of the AO-containing raw material. When the propionaldehyde content is equal to or less than the upper limit, odor and coloration of products produced using the polyether compound A can be reduced. The detection limit for propionaldehyde is typically 0.1 ppm.

[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 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 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 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.

[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 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.

[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 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").

[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 having a hydroxyl group is preferred, since it does not become an impurity in the product (polyether compound A) obtained by polymerization of alkylene oxide. The Mn of the polyether compound A 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 polyether compound A, 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 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.

[0042] 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.

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

[0044] After coordinating the organic ligand, it is preferable to perform solid-liquid separation. Solid-liquid separation can adopt 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 multiple times.

[0045] When manufacturing 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. 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 with the AO-containing raw material in the presence of a 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 A is likely to be smaller, and the unsaturation degree of the polyether compound A is likely to be smaller.

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

[0048] 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.

[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 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.

[0052] <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.

[0053] The Mn of the 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 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 A can be kept low, making it easy to handle.

[0054] 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.

[0055] The hydroxyl value-equivalent molecular weight of the 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-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 A can be kept low, making it easy to handle.

[0056] The Mw of the 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 the polyether compound A can be kept low, making it easy to handle.

[0057] The Mw / Mn of the polyether compound A is preferably from 1.00 to 1.15, more preferably from 1.00 to 1.12, and even more preferably from 1.00 to 1.10. When the Mw / Mn is not more than the above upper limit, the viscosity of the polyether compound A can be kept low, making it easy to handle.

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

[0059] The content of the ultra-high molecular weight component in the polyether compound is preferably less than 2,900 ppm, more preferably 2,800 ppm or less, and even more preferably 2,700 ppm or less, based on the total mass of the polyether compound. When the content of the ultra-high molecular weight component is equal to or less than the upper limit, the physical properties (e.g., stability, strength, etc.) of the article produced using the polyether compound are better.

[0060] 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.

[0061] <Method of producing polyether compound having urethane bond> In the production process of polyether compound B, polyether compound A is reacted with polyisocyanate. If necessary, a urethane catalyst may be used. One type of polyether compound A may be used, or two or more types may be used in combination.

[0062] 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.

[0063] 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.

[0064] 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.

[0065] 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.

[0066] Examples of the araliphatic polyisocyanate include dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, and α,α,α,α-tetramethylxylylene diisocyanate.

[0067] As the polyisocyanate, alicyclic polyisocyanates and aromatic polyisocyanates are preferred, and IPDI and MDI are more preferred. One type of polyisocyanate may be used alone, or two or more types may be used in combination.

[0068] 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 polyether compound A (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.

[0069] 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.

[0070] Examples of tertiary amine compounds include triethylamine, triethylenediamine, and 1,8-diazabicyclo(5,4,0)-undecene-7.

[0071] 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.

[0072] 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 0.001 to 0.1 parts by mass per 100 parts by mass of the polyether compound A, for example.

[0073] 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 A.

[0074] Examples of methods for producing the polyether compound B include a method of mixing the polyether compound A, a polyisocyanate, and, if necessary, a urethanization catalyst and a solvent. Alternatively, a method may be used in which the polyisocyanate is added dropwise to a mixed liquid obtained by mixing the polyether compound A, and, if necessary, a urethanization catalyst and a solvent.

[0075] The reaction temperature is preferably 50 to 100° C., more preferably 50 to 90° 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.

[0076] 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.

[0077] If unreacted polyisocyanate remains after the reaction, it is preferable to purify polyether compound B by removing the polyisocyanate by distillation.

[0078] <Polyether compounds with urethane bonds> Polyether compound B is a reaction product of polyether compound A and polyisocyanate. A urethane bond is formed between polyether compound A and polyisocyanate through a urethane reaction between the hydroxyl groups of polyether compound A 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 B 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.

[0079] 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.

[0080] 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.

[0081] 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 1 to 20 mass%, more preferably 1 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.

[0082] 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 %.

[0083] 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.

[0084] (Polyurethane composition containing a polyether compound having a urethane bond) 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 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 50% by mass or more and 100% by mass or less, and preferably 60 to 100% by mass. The polyurethane composition may further contain optional components other than polyether compound B.

[0085] 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.

[0086] 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.

[0087] Examples of the curing agent having a hydroxyl group include the initiators and water described in the production method of polyether compound A. Examples of the curing agent having an isocyanate group include the above-mentioned polyisocyanates.

[0088] 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.

[0089] 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%.

[0090] (Use of polyurethane composition containing polyether compound having urethane bond) 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. [Example]

[0091] 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 3 are examples, and Examples 4 to 6 are comparative examples.

[0092] [Methyl formate content and propionaldehyde content of AO-containing raw materials] The methyl formate content (ppm) and propionaldehyde content (ppm) relative to the total mass of the AO-containing raw material were 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

[0093] [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.

[0094] [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).

[0095] [Ultra high molecular weight component] The content of ultra-high molecular weight components was determined by CAD-HPLC under the following measurement conditions: Apparatus and detector: High-performance liquid chromatography apparatus (ThemoFisher SCIENTIFIC product name U3000HPLC system, degasser: SRD-3600, pump: DGP3600SD, autosampler: WPS-3000TSL, column compartment: TCC-3000SD, UV-Vis detector: VWD-3400RS, charged aerosol detector: Corona Veo) Eluent: THF for HPLC Eluent flow rate: 0.2 mL / min Sample injection volume: 20 μL Columns: One upstream column and one downstream column were connected in series in the following order. The exclusion limit molecular weight of each column is the exclusion limit molecular weight when the molecular weight of polystyrene is measured using HPLC-grade THF as the eluent. Upstream column: Showa Denko product name Shodex KF-404HQ (a column for organic solvent liquid chromatography, with a packing material of styrene-divinylbenzene copolymer with an average particle size of 3 μm, an inner diameter of 4.6 mm, a length of 250 mm, a theoretical plate count of 25,000 or more TP / column, and an exclusion limit molecular weight of 1,000,000) Downstream column: Showa Denko product name Shodex KF-403HQ (a column for organic solvent liquid chromatography, with a packing material of styrene-divinylbenzene copolymer with an average particle size of 3 μm, an inner diameter of 4.6 mm, a length of 250 mm, a theoretical plate count of 25,000 or more per column, and an exclusion limit molecular weight of 70,000)

[0096] The details of the measurement operations are as follows. (1) Polyether compound A in each example was dissolved in HPLC-grade THF to a concentration of 0.6% by mass, and then filtered through a syringe filter with a pore size of 0.45 μm to prepare a sample. The sample was analyzed under the above-mentioned HPLC conditions to obtain a chromatogram with retention time on the X-axis and signal intensity on the Y-axis. (2) A calibration curve showing the relationship between molecular weight and retention time was prepared using polystyrene standard samples (Agilent Technologies product name Easyal PS-2, molecular weight range 580 to 400,000). (3) Using the calibration curve created in (2), the retention time X1 corresponding to the above 12 W and the retention time X2 corresponding to the above 46 W were determined. (4) The area enclosed by the above chromatogram, the baseline, the line X=X1, and the line X=X2 was calculated by electronic integration. (5) A polystyrene standard sample with a molecular weight of 92,600 (Gaschromatography Co., Ltd. product name PSS-05 No. 500-16) was dissolved in HPLC-grade THF to concentrations of 1, 6, 20, and 60 ppm. This standard solution was analyzed under the above HPLC conditions to obtain a chromatogram. The area enclosed by the resulting chromatogram and the baseline was taken as the area. The area at each concentration was calculated, and a calibration curve with an intercept of zero was created, showing the relationship between the concentration of polystyrene with a molecular weight of 92,600 and the area. (6) Using the calibration curve prepared in (5), the area determined in (4) was converted into the concentration of polystyrene with a molecular weight of 92,600, which was used as the concentration of the ultra-high molecular weight component in the sample prepared in (1). (7) From the concentration value of the ultra-high molecular weight component obtained in (6), the mass of the ultra-high molecular weight component in the sample prepared in (1) was calculated, and further, the content of the ultra-high molecular weight component relative to the mass of the test substance (polyether compound A) used to prepare the sample was calculated.

[0097] [Adhesive strength] The polyurethane composition was applied to a substrate film (a 25 μm-thick polyethylene terephthalate (PET) film) using an applicator to a thickness of 10 μm, and then left to dry and harden in a thermostatic chamber at 130°C to form an adhesive layer. The substrate film with the adhesive layer formed thereon was cut into a width of 25 mm and a length of 150 mm to prepare an evaluation sample. The adhesive layer of the evaluation sample was bonded to a glass plate (float glass) at 23°C and 50% RH. The evaluation sample was placed on a horizontal surface with the substrate film side facing up, and a 2.0 kg roller was rolled back and forth from the substrate film side to press the adhesive layer to the glass plate. After 30 minutes of curing at 23°C and 50% RH, the adhesive layer of the evaluation sample was peeled from the interface with the glass plate using a universal tensile tester (A&D, product name: Tensilon RTG-1310) at a peel angle of 180° and a pulling rate of 300 mm / min, and the adhesive strength of the adhesive layer was measured. The measured adhesive strength was evaluated according to the following criteria. A: Adhesive strength is 0.10N / 25mm or less. B: Adhesive strength exceeds 0.10N / 25mm.

[0098] [Coatability] The polyurethane composition was applied to a 25 μm thick PET film using an applicator to a thickness of 10 μm. The polyurethane composition applied to the PET film was visually inspected for the presence or absence of foreign matter and cissing, and evaluated according to the following criteria. A: The coating was done cleanly without any foreign matter or repelling (smooth). B: Foreign matter and cissing occurred, making it impossible to coat cleanly (unevenness).

[0099] [Curability] The polyurethane composition was applied to a 25 μm thick PET film using an applicator to a thickness of 10 μm, and then left to dry and harden in a thermostatic chamber at 130°C to form an adhesive layer. 16 hours and 24 hours after the adhesive layer was formed, the presence or absence of tack on the surface of the adhesive layer was checked and evaluated according to the following criteria. AA...No tack after 16 hours. A: No tack after 24 hours. B...There will be a tack in 24 hours.

[0100] [AO-containing raw materials] Six types of PO (PO(1) to (6)) from different sources and lots were used as AO-containing raw materials. The methyl formate content and propionaldehyde content of each of the six types of PO are shown in Table 1 below. The PO content (PO purity) of each of the six types of PO was 99% or more.

[0101] [Production Example 1: Preparation of Polyol P1 (Initiator)] In the presence of a KOH catalyst, sorbitol was polymerized with PO(1), followed by dealkalization and purification to obtain polyoxypropylene hexaol (hereinafter also referred to as "polyol P1"). Polyol P1 had an average of 6 hydroxyl groups per molecule and an OHV-equivalent molecular weight of 880.

[0102] [Production Example 2: Preparation of Polyol P2 (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 P2"). Polyol P2 had an average of 2 hydroxyl groups per molecule and an OHV-equivalent molecular weight of 1,000.

[0103] [Production Example 3: Preparation of Polyol P3 (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 P3"). Polyol P3 had an average of 3 hydroxyl groups per molecule and an OHV-equivalent molecular weight of 1,000.

[0104] [Manufacturing example (a-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 42,000, yielding a polyether compound (a-1) 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 (a-1).

[0105] [Manufacturing example (a-2)] Using polyol P2 as an initiator, PO (2) was polymerized in the presence of TBA-DMC catalyst until the OHV-equivalent molecular weight reached 10,000, yielding a polyether compound (a-2) 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 (a-2).

[0106] [Manufacturing example (a-3)] Using polyol P3 as an initiator, PO (3) was polymerized in the presence of a TBA-DMC catalyst until the OHV-equivalent molecular weight reached 10,000, yielding a polyether compound (a-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 the polyether compound (a-3).

[0107] [Manufacturing example (b-1)] A polyether compound (b-1) having a hydroxyl group was produced in the same manner as in Production Example (a-1), except that PO(4) was used instead of PO(1).

[0108] [Manufacturing example (b-2)] A polyether compound (b-2) having a hydroxyl group was produced in the same manner as in Production Example (a-2), except that PO(5) was used instead of PO(2).

[0109] [Manufacturing example (b-3)] A polyether compound (b-3) having a hydroxyl group was produced in the same manner as in Production Example (a-3), except that PO(6) was used instead of PO(3).

[0110] Table 1 shows the evaluation results of the number of functional groups, OHV-equivalent molecular weight, and Mw / Mn of the initiator of each polyether compound.

[0111] [Table 1]

[0112] [Example 1] 100 parts by mass of polyether compound (a-1), 7.0 parts by mass of a polyisocyanate compound (Coronate HX, manufactured by Tosoh Corporation, isocyanate group content 21.3% by mass), 0.04 parts by mass of Narcem ferric iron manufactured by Nippon Chemical Industry Co., Ltd. as a catalyst, and an amount of ethyl acetate as a solvent such that the overall solids concentration became 50% by mass were uniformly mixed and subjected to a urethane reaction to obtain a polyurethane composition containing a polyether compound having a urethane bond.

[0113] [Examples 2-6] A polyurethane composition containing a polyether compound having a urethane bond was obtained in the same manner as in Example 1, except that polyether compound A shown in Table 2 was used instead of 100 parts by mass of polyether compound (a-1).

[0114] The average number of functional groups, Mn, and Mn per average number of functional groups of the polyether compound having urethane bonds in each example are shown in Table 2. The results of evaluating the adhesion, coatability, and curability of the polyurethane composition in each example are also shown in Table 2. In Table 2, the values ​​for "Properties of Polyether Compound A" in Examples 2 and 5 are average values ​​for a mixture of two types of polyether compound A.

[0115] [Table 2]

[0116] Comparing Examples 1 and 4, in which polyurethane compositions were produced under the same conditions except for the AO-containing raw materials, the curability was superior in Example 1. Similar trends were confirmed in comparing Examples 2 and 5, and Examples 3 and 6. [Industrial Applicability]

[0117] According to the present invention, a production method can be provided that can obtain a polyether compound having a urethane bond and excellent curability.

Claims

1. A method for producing a polyether compound having a urethane bond, comprising the steps of: contacting an initiator having active hydrogen with an alkylene oxide-containing raw material in the presence of a composite metal cyanide complex catalyst to polymerize the alkylene oxide in the alkylene oxide-containing raw material with the initiator; and reacting the resulting polyether compound having a hydroxyl group with a polyisocyanate; The alkylene oxide-containing feedstock has a methyl formate content of less than 20 ppm based on the total mass of the alkylene oxide-containing feedstock.

2. 2. The process according to claim 1, wherein the alkylene oxide-containing feedstock has a propionaldehyde content of less than 20 ppm.

Images