Method for producing polyether monool

Abstract

In the method for producing a polyether monool according to the present invention, an alkylene oxide is polymerized with an initiator that is a C10 or higher monohydric alcohol in the presence of a double metal cyanide catalyst. The double metal cyanide catalyst is represented by M1 a[M2(CN)b]c・d(M1 eXf)・g(Ligand)・h(H2O).

Description

Method for producing polyether monoalcohol

[0001] The present invention relates to a method for producing polyether monoalcohol.

[0002] By using a basic catalyst such as KOH, an alkylene oxide may be subjected to ring-opening polymerization with an initiator having active hydrogen such as an alcohol to synthesize a polyether monoalcohol. For example, the polyoxypropylene monoalcohol described in paragraph

[0216] of Patent Document 1 is considered to be synthesized by subjecting propylene oxide to ring-opening addition polymerization with n-butanol in the presence of a KOH catalyst.

[0003] Japanese Patent No. 7240489

[0004] Conventionally, when subjecting an alkylene oxide to ring-opening addition polymerization with a higher alcohol having 10 or more carbon atoms, a KOH catalyst is often used. However, when a KOH catalyst is used for the ring-opening addition polymerization of an alkylene oxide, as a result of a side reaction in which the water generated in the alcoholization reaction of the higher alcohol reacts as an initiator, a diol component may be generated. In this regard, in the conventional method, it is necessary to remove water during alcoholization. When removing the water generated in this alcoholization reaction, low molecular weight components are also removed from the starting initiator. As a result, there may be a problem of fouling of the production line.

[0005] The present invention provides a method for producing polyether monoalcohol in which fouling of the production line of polyether monoalcohol hardly occurs.

[0006] The present invention has the following embodiments: [1] A method for producing a polyether monool, comprising polymerizing an alkylene oxide onto an initiator which is a monohydric alcohol having 10 or more carbon atoms in the presence of a complex metal cyanide catalyst. [2] The method for producing the polyether monool according to [1], wherein the hydroxyl value-based molecular weight of the polyether monool is 500 to 3000. [3] The method for producing the polyether monool according to [1] or [2], wherein the Mw / Mn of the polyether monool is 1.15 or less. [4] The method for producing the polyether monool according to any one of [1] to [3], wherein the alkylene oxide has 3 or more carbon atoms. [5] The method for producing the polyether monool according to any one of [1] to [4], wherein the initiator is derived from biomass.

[0007] According to the present invention, a method for producing polyether monool that is less prone to contamination of the polyether monool production line is provided.

[0008] [Terminology] The meanings of the terms are as follows: The "units" that make up polyether monools, etc., refer to atomic groups directly formed by the polymerization of monomers. Repeating units based on monomers are simply called "monomer units," for example, repeating units based on alkylene oxide (AO) are called "AO units."

[0009] The term "main chain" refers to a polymer chain formed by the polymerization of two or more monomers. In the polyether monools and reactive silicon group-containing oxyalkylene polymers described later, the "main chain" includes an initiator residue from which the active hydrogen has been removed, and a polyoxyalkylene chain having repeating units based on alkylene oxide.

[0010] An "initiator" is a compound having an active hydrogen-containing group. An "active hydrogen-containing group" is at least one group selected from the group consisting of a hydroxyl group, carboxyl group, amino group, monovalent functional group obtained by removing one hydrogen atom from a primary amine, hydrazide group, and sulfanyl group, all bonded to a carbon atom. "Active hydrogen" refers to hydrogen atoms based on the active hydrogen-containing group and hydrogen atoms based on the hydroxyl group of water. An "initiator residue" is the residue obtained by removing the active hydrogen from the initiator. "Biomass" means renewable, biologically derived organic resources.

[0011] Polyether monools, polyether compounds having reactive silicon groups, and polyether compounds having polymerizable unsaturated groups are polymers consisting of a main chain and terminal groups. In polyether monools, polyether compounds having reactive silicon groups, and polyether compounds having polymerizable unsaturated groups, the "terminal group" refers to the group of oxygen atoms in the polyoxyalkylene chain that is closest to the molecular end. However, if the group of oxygen atoms includes an initiator residue, it is not considered a terminal group but rather part of the main chain.

[0012] The "silylation rate" in a polyether compound having reactive silicon groups is the ratio of the number of reactive silicon groups to the total number of reactive silicon groups, hydroxyl groups, unsaturated groups, and isocyanate groups at the terminal groups of the polyether compound having reactive silicon groups. The silylation rate is calculated by the following formula.

[0013] 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]

[0014] The silylation rate can be measured by NMR analysis. Alternatively, it may be the ratio (mol%) of the number of silyl groups of the added silylation agent to the number of terminal groups when introducing the reactive silicon groups to the terminal groups of the polyether monool using the silylation agent described later. However, in this case, a diisocyanate compound is used as the polyisocyanate compound in method (c1) described later.

[0015] A "silylation agent" refers to a compound having a functional group that reacts with an active hydrogen-containing group, an unsaturated group, or an isocyanate group, and a reactive silicon group. The isocyanate group content relative to the total mass of the prepolymer described later is a value measured in accordance with JIS K 7301:1995.

[0016] The hydroxyl value of polyether monool is measured according to Method B (phthalation method) described in JIS K 1557-1:2007. The molecular weight of polyether monool based on hydroxyl value is calculated as 56,100 / (hydroxyl value of polyether monool). The viscosity of polyether monool is measured using an E-type viscometer.

[0017] 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 the eluent, and a calibration curve created using polystyrene polymers with known molecular weights. Mw / Mn is an indicator of the molecular weight distribution and is the ratio of Mw to Mn.

[0018] "(meth)acryloyl group" is a general term for acryloyl group and methacryloyl group. "(meth)acryloyloxy group" is a general term for acryloyloxy group and methacryloyloxy group. "(meth)acrylate" is a general term for acrylate and methacrylate. A numerical range represented by "~" means a numerical range with the numbers before and after "~" as the lower and upper limits, respectively.

[0019] [Method for producing polyether monools] In the method for producing polyether monools of the present invention, an alkylene oxide (hereinafter also referred to as "AO") is polymerized on an initiator which is a monohydric alcohol having 10 or more carbon atoms in the presence of a complex metal cyanide catalyst.

[0020] In the method for producing polyether monools, an initiator (hereinafter also referred to as "initiator A") which is a monohydric alcohol having 10 or more carbon atoms is used. From the viewpoint of improving hydrophobicity, the number of carbon atoms in initiator A is 10 or more, preferably 11 or more, more preferably 12 or more, even more preferably 13 or more, and particularly preferably 14 or more. Initiator A is preferably derived from biomass.

[0021] Initiator A is not particularly limited. Monohydric alcohols having linear or branched hydrocarbon groups are preferred. Examples include decyl alcohol, lauryl alcohol, tridecanol, cetyl alcohol, stearyl alcohol, oleyl alcohol, and behenyl alcohol. Initiator A may be used alone or in combination of two or more types.

[0022] Examples of AOs 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. AOs with 3 or more carbon atoms are preferred. Among AOs with 3 or more carbon atoms, AOs with 3 to 5 carbon atoms are preferred, and PO is more preferred. The number of carbon atoms in the AO unit of the polyoxyalkylene chain is preferably 3 or more, more preferably 3 to 5, and even more preferably 3. One type of AO may be used alone, or two or more types may be used in combination.

[0023] The complex metal cyanide catalyst (hereinafter also referred to as "DMC catalyst") functions as a polymerization catalyst for alkylene oxides. The DMC catalyst is a crystalline solid and contains the reaction product of a metal halide salt and a cyanide transition metal compound, an organic ligand, and crystal water (coordinating water, etc.) encapsulated within the crystal. In addition to these, the DMC catalyst may contain trace amounts of impurities unavoidable during production, which are present in the above-mentioned metal salt and metal compound, as well as water other than crystal water. Known metal halide salts, cyanide transition metal compounds, and organic ligands can be used in the production of the DMC catalyst.

[0024] The DMC catalyst is thought to be represented by the following equation 1. １ ａ [M ２ (CN) ｂ ]ｃ ・d(M １ ｅ X ｆ )・g(Ligand)・h(H ２ O) Formula 1

[0025] In Formula 1, M １ ｅ X ｆ is a metal halide salt, M １ is a metal atom that becomes a cation, X is a halogen atom that becomes a counter anion, M ２ is a transition metal contained in a transition metal cyanide compound and is a metal atom that becomes an active site, Ligand is an organic ligand. a, b, c, d, e, f, g, h are integers, and a, b, c and e, f are electrically neutral numbers.

[0026] M 1 Examples of M 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), W(VI). M 1 Zn(II) and Co(II) are preferable in terms of the long catalyst life of the DMC catalyst.

[0027] M ２ Examples of M include Co(III), Fe(II), Fe(III), Co(II), Co(III), Cr(II), Cr(III), Mn(II), Mn(III), V(IV), V(V). M ２ Co(III) and Co(II) are preferable in terms of the long catalyst life of the DMC catalyst.

[0028] Examples of X include Cl, Br, and I. M １ ｅ X ｆ The metal halide salt that is X is preferably one or more selected from zinc fluoride, zinc chloride, zinc bromide, zinc iodide, zinc sulfate, zinc nitrate, and zinc acetate. In terms of the interatomic distance between M ２ and X described later, it is more preferable to contain one or more selected from zinc chloride and zinc bromide.

[0029] Examples of ligands (organic ligands) include alcohols, ethers, esters, aldehydes, ketones, amides, nitriles, sulfides, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, polyoxyalkylene polyols, and polyoxyalkylene monools. There may be one or more organic ligands. Examples of alcohols include tert-butyl alcohol, n-butyl alcohol, sec-butyl alcohol, iso-butyl alcohol, tert-pentyl alcohol, iso-pentyl alcohol, and ethylene glycol mono-tert-butyl ether. An example of a polyoxyalkylene polyol is polypropylene diol. Tert-butyl alcohol is preferred as the organic ligand.

[0030] A preferred example of a DMC catalyst is zinc hexacyanocobaltate (Zn), which contains an organic ligand, water, zinc chloride, or zinc bromide. ３ [Co(CN) ６ ] ２ ) Its chemical formula is Zn ３ [Co(CN) ６ ] ２ d(ZnCl) ２ )・g(Ligand)・h(H ２ O) or Zn ３ [Co(CN) ６ ] ２ ・d(ZnBr ２ )・g(Ligand)・h(H ２ It is thought to be O).

[0031] As a DMC catalyst, the ligand is zinc hexacyanocobaltate (Zn) with tert-butyl alcohol. ３ [Co(CN) ６ ] ２ A complex is preferred. Water and zinc chloride may be coordinated to the above complex.

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

[0033] The slurry catalyst comprises a DMC catalyst and a dispersion medium. A slurry containing a DMC catalyst and a dispersion medium, and possibly containing impurities and water that are unavoidable during production, is preferred.

[0034] As the dispersion medium for the slurry catalyst, organic solvents known for slurry catalysts can be used. For example, a non-volatile hydroxyl compound described in Japanese Patent Publication No. 3194255 can be used. The hydroxyl compound is a hydroxyl group-containing compound having 1 to 8 hydroxyl groups and a molecular weight of 100 to 8000, and compounds having alcoholic hydroxyl groups such as polyether monools are preferred.

[0035] The dispersion medium of the slurry catalyst is preferably substantially water-free. The water content of the dispersion medium is preferably 500 ppm or less, more preferably 200 ppm or less, and may even be undetectable. The water content of the dispersion medium is the water content measured by the Karl Fischer assay.

[0036] The content of the DMC catalyst relative to the total mass of the slurry catalyst is preferably, for example, 0.001 to 60% by mass, more preferably 0.003 to 50% by mass, and even more preferably 0.006 to 30% by mass.

[0037] DMC catalysts can be produced by known methods. For example, a DMC catalyst can be synthesized by coordinating an organic ligand to a reaction product obtained by reacting a metal halide salt with a cyanide transition metal compound. After the synthesis of the DMC catalyst, the water content of the DMC catalyst may be adjusted.

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

[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 is reacted with an aqueous solution of a cyanide transition metal compound to produce a reaction product. An aqueous solution of an organic ligand is added to this and stirred to coordinate the organic ligand, obtaining a mixture containing the DMC catalyst and water. The obtained mixture is subjected to solid-liquid separation to obtain a solid. The obtained solid is washed with an aqueous solution containing the organic ligand, and the solid-liquid separation operation is repeated one or more times, preferably two or more times. Alternatively, the obtained solid may be dried so that its moisture content is within the above-mentioned specific range, and pulverized if 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. It is also preferable that it be below the saturation concentration. The concentration of the cyanide transition metal compound in the aqueous solution of the cyanide transition metal compound is preferably 2 to 50% by mass, more preferably 2 to 20% by mass, and even more preferably 3 to 10% by mass. The molar ratio of the metal contained in the metal halide salt to the transition metal contained in the cyanide transition metal compound is preferably 1.6 to 12, and more preferably 1.8 to 8.

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

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

[0044] After coordinating the organic ligand, it is preferable to perform solid-liquid separation. Solid-liquid separation can be carried out using methods known in this field, such as filtration or centrifugation. The resulting solid contains the DMC catalyst as well as salts (alkali metal halides) produced in the reaction. Therefore, it is preferable to remove the salts by washing the resulting solid. Specifically, an aqueous solution of the organic ligand is added to the resulting solid, stirred, and then solid-liquid separation is performed again. The washing time is preferably 10 to 90 minutes, and more preferably 20 to 60 minutes. It is preferable to perform multiple washes.

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

[0046] By contacting the initiator with AO in the presence of a DMC catalyst, the AO is polymerized onto the initiator (ring-opening addition polymerization). When a DMC catalyst is used as the polymerization catalyst for AO, the Mw / Mn ratio of the polyether monool tends to be lower compared to when a basic catalyst such as KOH is used.

[0047] If the polyoxyalkylene chain of the polyether monool is a random copolymer chain consisting of PO units and EO units, the polyether monool can be obtained by contacting initiator A with PO and EO in the presence of a DMC catalyst. The same applies to combinations of two or more AO other than the combination of PO and EO.

[0048] If the polyoxyalkylene chain of the polyether monool is a block copolymer chain having a block consisting of PO units and a block consisting of EO units, a precursor may be obtained by reacting the initiator with PO in the presence of a DMC catalyst, and then the precursor may be reacted with EO to obtain the polyether monool. Alternatively, a precursor may be obtained by reacting the initiator with EO in the presence of a DMC catalyst, and then the precursor may be reacted with PO to obtain the polyether monool. The same applies to combinations of two or more AO other than the combination of PO and EO.

[0049] The amount of 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 final polyether monool. If the amount of DMC catalyst used is above the lower limit, the polymerization reaction proceeds easily. If the amount of DMC catalyst used is below the upper limit, the amount of DMC catalyst used is reduced, making it more economical.

[0050] Polymerization may be carried out in a continuous or batch manner, but batch polymerization is preferred. The polymerization temperature is preferably 30 to 180°C, more preferably 70 to 160°C, and even more preferably 90 to 140°C. The polymerization pressure is preferably 1.0 MPa or less, more preferably 0.8 MPa or less, and even more preferably 0.3 MPa or less. The supply of AO-containing raw materials to the reactor is preferably carried out at a rate that maintains the above reaction temperature. The reaction atmosphere is preferably one that is less susceptible to moisture contamination, and more preferably an inert gas atmosphere such as nitrogen.

[0051] The reaction solution after polymerization contains polyether monool and DMC catalyst. The reaction solution after polymerization may also contain stabilizers and may contain trace amounts of impurities. The reaction solution may be purified by filtration.

[0052] A polyether monool has an initiator residue with 10 or more carbon atoms derived from initiator A and a polyoxyalkylene chain. The main chain of the polyether monool is a polymerization chain consisting of an initiator residue and an oxyalkylene chain having one or more types of AO units. In the case of a polymerization chain having two or more types of AO units, these AO units may form a block polymer or a random polymer.

[0053] For example, oxyalkylene chains include polymer chains having EO units, polymer chains having PO units, polymer chains having EO and PO units, polymer chains consisting of EO units, polymer chains consisting of PO units, polymer chains consisting of butylene oxide units, polymer chains consisting of tetramethylene oxide units, polymer chains consisting of EO and PO units, and polymer chains consisting of PO units and butylene oxide units. As oxyalkylene chains, polymer chains consisting of AO units with 3 or more carbon atoms are preferred, and polymer chains consisting of PO units are particularly preferred. The terminal group of the polyether monool is a hydroxyl group. The number of terminal groups of the polyether monool (i.e., the number of hydroxyl groups) is 1, which is the same as the number of active hydrogens in the initiator.

[0054] The hydroxyl value of the polyether monool is preferably 15 to 200 mg KOH / g, more preferably 25 to 150 mg KOH / g, and even more preferably 28 to 120 mg KOH / g. If the hydroxyl value is above the lower limit of the above numerical range, sufficient curability is easily obtained when resin formation occurs. If the hydroxyl value is below the upper limit of the above numerical range, sufficient flexibility can be imparted to the resin, and good elongation properties are easily obtained.

[0055] The hydroxyl value-based molecular weight of the polyether monool is preferably 500 to 3000, more preferably 500 to 2500, and even more preferably 550 to 2000. If the hydroxyl value-based molecular weight is above the lower limit of the above numerical range, sufficient flexibility can be imparted when used as an adhesive or coating material, and good elongation properties can be easily obtained. If the hydroxyl value-based molecular weight is below the upper limit of the above numerical range, the viscosity of the polyether monool can be kept low.

[0056] The Mw / Mn of the polyether monool is preferably 1.00 to 1.15, more preferably 1.00 to 1.14, even more preferably 1.00 to 1.13, particularly preferably 1.00 to 1.12, and most preferably 1.00 to 1.10. When the Mw / Mn is below the upper limit of the above numerical range, the viscosity of the polyether monool can be kept low.

[0057] The viscosity of polyether monool at a measurement temperature of 25°C is not particularly limited and may be, for example, 30 to 3,000 mPa·s, 35 to 2,800 mPa·s, 35 to 2,500 mPa·s, 35 to 2,000 mPa·s, 35 to 1,500 mPa·s, 40 to 1,500 mPa·s, etc.

[0058] (Mechanism of Action) In the method for producing polyether monools of the present invention described above, AO is added polymerized to initiator A, which has 10 or more carbon atoms, in the presence of a DMC catalyst. Therefore, there is no influence from side reactions in which water generated in the alkoxide reaction reacts with the initiator. Consequently, there is no need to remove the water generated in the alkoxide reaction. As a result, the yield of polyether monools is improved, and contamination of the production line is less likely to occur.

[0059] Some initiators A, having 10 or more carbon atoms, are solid at room temperature. According to the present invention's method for producing polyether monools, AO can also be converted to a liquid state at room temperature by addition polymerization.

[0060] When a DMC catalyst is used as a polymerization catalyst for AO, the Mw / Mn ratio of the polyether monool tends to be lower compared to when a basic catalyst such as KOH is used. This is particularly advantageous when using a monohydric alcohol derived from biomass as an initiator, as explained below. Initiator A, a monohydric alcohol with 10 or more carbon atoms, can be produced by extraction from plants. Such monohydric alcohols derived from biomass inevitably contain impurity alcohols with a larger or smaller number of carbon atoms than the desired number. When AO is added to a monohydric alcohol derived from biomass using a basic catalyst such as KOH, it is difficult to obtain a polyether monool with a narrow molecular weight distribution due to the difference in the number of carbon atoms of the impurities in the monohydric alcohol derived from biomass. In addition, impurity alcohols with a small number of carbon atoms are removed along with water from the degassing line when water generated in the alkoxide reaction is removed, which is disadvantageous for increasing the yield. In contrast, if a DMC catalyst is used as the polymerization catalyst for AO, there is no need to remove the water produced in the alkoxide reaction. Therefore, even if the initiator A contains impurity alcohols with different numbers of carbon atoms, polyether monools with a narrow molecular weight distribution can be easily obtained in high yield.

[0061] As already mentioned, monohydric alcohols derived from biomass inevitably contain impurity alcohols with different numbers of carbon atoms. Therefore, when a monohydric alcohol derived from biomass with 10 or more carbon atoms is used as initiator A and AO is subjected to ring-opening addition polymerization in the presence of a DMC catalyst, multiple types of polyether monools with different numbers of carbon atoms in the initiator residue may be produced due to the differences in the number of carbon atoms in the impurity alcohols. The resulting polyether monool composition may contain the polyether monool of the present invention as described above, as well as other polyether monools having an initiator residue derived from a monohydric alcohol with 9 or fewer carbon atoms and a polyoxyalkylene chain.

[0062] Examples of monohydric alcohols having 9 or fewer carbon atoms include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, and 1-nonanol, but are not limited to these examples. Details of the polyoxyalkylene chains in other polyether monools have already been explained.

[0063] In the polyether monool composition of the present invention containing the polyether monool and another polyether monool, the proportion of the other polyether monool derived from impurity alcohol is not particularly limited, but may be, for example, 0 to 5% by mass, 0 to 4% by mass, 0 to 3% by mass, 0 to 2% by mass, 0 to 1% by mass, etc., of the total amount of the polyether monool composition.

[0064] (Uses of Polyether Monool) Polyether monool can be used as a lubricant, a raw material for polyurethane foam, an adhesive, a sealant, a coating material, etc. By reacting it with a compound that can react with the hydroxyl group of polyether monool, polyether compounds having reactive silicon groups, prepolymers, and polyether compounds having polymerizable unsaturated groups may be produced. Several examples of uses of polyether monool are described below, but the uses of the polyether monool of the present invention are not limited to those described below.

[0065] [Method for producing polyether compounds having reactive silicon groups] In the method for producing polyether compounds having reactive silicon groups (hereinafter also referred to as "polyether compound A"), the hydroxyl groups of the polyether monool are converted into groups having reactive silicon groups represented by the following formula 2. -SiR ａ X ３－ａ ...Formula 2

[0066] In formula 2, R is a monovalent organic group having 1 to 20 carbon atoms, and represents an organic group other than a hydrolyzable group. Preferably, R is at least one group selected from the group consisting of hydrocarbon groups and triorganosiloxy groups having 1 to 20 carbon atoms.

[0067] R is preferably at least one group selected from the group consisting of alkyl groups, cycloalkyl groups, aryl groups, α-chloroalkyl groups, and triorganosiloxy groups. More preferably, R is at least one group selected from the group consisting of linear or branched alkyl groups having 1 to 4 carbon atoms, cyclohexyl groups, phenyl groups, benzyl groups, α-chloromethyl groups, trimethylsiloxy groups, triethylsiloxy groups, and triphenylsiloxy groups. Methyl groups and ethyl groups are preferred in terms of improving the curability of polyether compound A and the stability of the curable composition. α-chloromethyl groups are preferred in terms of the fast curing rate of the cured product. Methyl groups are particularly preferred in terms of their readily available availability.

[0068] In formula 2, X represents a hydroxyl group, a halogen atom, or a hydrolyzable group. Examples of hydrolyzable groups include alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, acid amide groups, aminooxy groups, sulfanyl groups, and alkenyloxy groups.

[0069] Alkoxy groups are preferred because they are mildly hydrolyzable and easy to handle. Methoxy, ethoxy, and isopropoxy groups are preferred alkoxy groups, with methoxy and ethoxy groups being more preferred. When the alkoxy group is a methoxy or ethoxy group, siloxane bonds are quickly formed, making it easier to form a crosslinked structure in the cured product, which tends to result in good physical properties of the cured product.

[0070] In Equation 2, a is an integer between 0 and 2. When a is 2, R may be the same or different from each other. When a is 1 or less, X may be the same or different from each other. Since a lower crosslinking density due to siloxane bonds tends to decrease the modulus of the cured product, a is preferably 2 or less, and a is more preferably 1 or less.

[0071] Examples of reactive silicon groups include trimethoxysilyl group, triethoxysilyl group, triisopropoxysilyl group, tris(2-propenyloxy)silyl group, triacetoxysilyl group, dimethoxymethylsilyl group, diethoxymethylsilyl group, dimethoxyethylsilyl group, methyldiisopropoxysilyl group, (α-chloromethyl)dimethoxysilyl group, and (α-chloromethyl)diethoxysilyl group. From the standpoint of high activity and good curability, trimethoxysilyl group, triethoxysilyl group, dimethoxymethylsilyl group, and diethoxymethylsilyl group are preferred, and dimethoxymethylsilyl group is more preferred.

[0072] Polyether compound A preferably has an average of 0.8 to 1.2 terminal groups per molecule. The terminal groups of polyether compound A are either a reactive silicon group, an unsaturated group, an isocyanate group, or a hydroxyl group. Each terminal group may be the same or different from the others.

[0073] The average number of reactive silicon groups per terminal group of polyether compound A is preferably 0.5 to 2.0, and more preferably 0.60 to 1.94. When the average number of reactive silicon groups is above the lower limit, the crosslinking density due to siloxane bonds increases, and a good cured product with high modulus can be obtained.

[0074] The average number of reactive silicon groups per molecule of polyether compound A is preferably 0.6 to 1.2, more preferably 0.8 to 1.2, and even more preferably 0.9 to 1.2. When the average number of reactive silicon groups is above the lower limit, the crosslinking density due to siloxane bonds increases, and a good cured product with high modulus can be obtained.

[0075] Examples of methods for producing polyether compound A include the following methods (a1), (b1), and (c1).

[0076] Method (a1): Convert the hydroxyl group of the polyether monool to an alkenyloxy group having a carbon-carbon double bond or an alkynyloxy group having a carbon-carbon triple bond, and then attach a reactive silicon group represented by formula 2 -SiR to the carbon-carbon double bond of the alkenyloxy group or the carbon-carbon triple bond of the alkynyloxy group. ａ X ３－ａ A method for converting an alkenyloxy group or alkynyloxy group into a group having a reactive silicon group represented by formula 2 by reacting it with a silylating agent that can introduce a silyl group.

[0077] Method (b1): A method of converting a hydroxyl group of a polyether monool into a group having a reactive silicon group represented by formula 2 by reacting the hydroxyl group with a silylating agent having a functional group that can react with the hydroxyl group and a reactive silicon group represented by formula 2.

[0078] Method (c1): A method of converting the hydroxyl group of a polyether monool into a group having an isocyanate group, and then reacting it with a silylating agent having a functional group that can react with an isocyanate group and a reactive silicon group represented by formula 2, thereby converting the hydroxyl group into a group having a reactive silicon group represented by formula 2.

[0079] In method (a1), polyether compound A is reacted with an alkali metal salt to alkoxideize it, and then reacted with a halogenated hydrocarbon compound having a carbon-carbon double bond or a halogenated hydrocarbon compound having a carbon-carbon triple bond to convert the hydroxyl group of the polyether monool into an alkenyloxy group having a carbon-carbon double bond or an alkynyloxy group having a carbon-carbon triple bond.

[0080] Examples of alkali metal salts include sodium hydroxide, sodium alkoxide, potassium hydroxide, potassium alkoxide, lithium hydroxide, lithium alkoxide, cesium hydroxide, and cesium alkoxide. From the viewpoint of ease of handling and solubility, sodium hydroxide, sodium methoxide, sodium ethoxide, potassium hydroxide, potassium methoxide, and potassium ethoxide are preferred, with sodium methoxide and potassium ethoxide being more preferred. Sodium methoxide is particularly preferred from the viewpoint of availability. The alkali metal salt may be used in a dissolved state in a solvent.

[0081] Examples of halogenated hydrocarbon compounds containing a carbon-carbon double bond 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.

[0082] Examples of halogenated hydrocarbon compounds containing a carbon-carbon triple bond include propargyl chloride, 1-chloro-2-butyne, 4-chloro-1-butyne, 1-chloro-2-octine, 1-chloro-2-pentine, 1,4-dichloro-2-butyne, 5-chloro-1-pentine, 6-chloro-1-hexine, propargyl bromide, 1-bromo-2-butyne, 4-bromo-1-butyne, and 1-bromo-2-butyne. Examples include mo-2-octyne, 1-bromo-2-pentine, 1,4-dibromo-2-butine, 5-bromo-1-pentine, 6-bromo-1-hexine, propargyl iodide, 1-iodo-2-butine, 4-iodo-1-butine, 1-iodo-2-octyne, 1-iodo-2-pentine, 1,4-diiodo-2-butine, 5-iodo-1-pentine, and 6-iodo-1-hexine. Propargyl chloride, propargyl bromide, and propargyl iodide are preferred.

[0083] A halogenated hydrocarbon compound having a carbon-carbon double bond and a halogenated hydrocarbon compound having a carbon-carbon triple bond may be used in combination. The halogenated hydrocarbon compound having a carbon-carbon double bond may be used individually or in combination of two or more. The halogenated hydrocarbon compound having a carbon-carbon triple bond may be used individually or in combination of two or more.

[0084] Next, a reactive silicon group represented by formula 2, -SiR, is attached to the carbon-carbon double bond or carbon-carbon triple bond of the alkenyloxy group. ａ X ３－ａ The alkenyloxy group or alkynyloxy group is converted to a group having a reactive silicon group represented by formula 2 by reacting with a silylation agent that can introduce the reactive silicon group represented by formula 2. Examples of silylation agents include compounds having both a group that can react with an unsaturated group to form a bond (e.g., a sulfanyl group) and a reactive silicon group represented by formula 2, and hydrosilane compounds (e.g., HSiR ａ X ３－ａ (where R, X, and a are the same as in Equation 2) is one example.

[0085] Examples include dimethoxymethylsilane, diethoxymethylsilane, dimethoxyethylsilane, methyldiisopropoxysilane, (α-chloromethyl)dimethoxysilane, (α-chloromethyl)diethoxysilane, trimethoxysilane, triethoxysilane, triisopropoxysilane, tris(2-propenyloxy)silane, triacetoxysilane, and 3-mercaptopropyltrimethoxysilane. Trimethoxysilane, dimethoxymethylsilane, and diethoxymethylsilane are preferred, and dimethoxymethylsilane is more preferred, due to their high activity and good curability.

[0086] In method (b1), a polyether monool is reacted with a silylating agent. It is preferable to use an isocyanate silane compound represented by formula 3 below as the silylating agent: OCN-(CH ２ ) ｎ -SiR ａ X ３－ａ ...Formula 3

[0087] -SiR in Equation 3 ａ X ３－ａ This is the same as in formula 2. n is an integer from 1 to 8, preferably 1 to 3. The reaction between the hydroxyl group of the polyether monool and the above isocyanate silane compound results in the hydroxyl group of the polyether monool being -O-C(=O)NH-(CH ２ ) ｎ -SiR ａX ３－ａ Represented by a urethane bond (-O-C(=O)NH-) and -SiR ａ X ３－ａ It is converted to a terminal group having a .

[0088] Examples of isocyanate silane compounds include 3-isocyanate propyltrimethoxysilane, 3-isocyanate propyltriethoxysilane, isocyanate methyltrimethoxysilane, isocyanate methyltriethoxysilane, 3-isocyanate propylmethyldimethoxysilane, 3-isocyanate propylmethyldiethoxysilane, isocyanate methylmethyldimethoxysilane, and isocyanate methylmethyldiethoxysilane.

[0089] As isocyanate silane compounds, 3-isocyanate propyltrimethoxysilane, 3-isocyanate propyltriethoxysilane, 3-isocyanate propylmethyldimethoxysilane, isocyanate methylmethyldimethoxysilane, and isocyanate methyltrimethoxysilane are preferred due to their reactivity with polyether monools and ease of handling.

[0090] The active hydrogen of the polyether monool reacts with the isocyanate group of the isocyanate silane compound represented by formula 3, thereby introducing a reactive silicon group to the polyether monool.

[0091] When the active hydrogen-containing group of the polyether monool is a hydroxyl group, the polyoxyalkylene chain (-(R ５ O) ｍ -, R ５ represents an alkylene group, and m represents the number of moles of oxyalkylene groups. A polyether compound A is obtained in which a reactive silicon group is bonded to ) via a urethane bond and an organic group. That is, -(R ５ O) ｍ -C(=O)NH-(CH ２ ) ｎ -SiR ａ X ３－ａ A connected structure represented by is formed.

[0092] This reaction may be carried out in the presence of a urethane catalyst. The urethane catalyst is not particularly limited, and any known urethane catalyst can be used as appropriate. Examples include organotin compounds such as dibutyltin dilaurate and dioctyltin dilaurate, metal catalysts such as bismuth compounds, and base catalysts such as organic amines. The reaction temperature is preferably 20 to 200°C, and more preferably 50 to 150°C. Furthermore, the urethane reaction is preferably carried out under an inert gas atmosphere. Nitrogen is preferred as the inert gas.

[0093] The molar ratio of the total number of isocyanate groups in the isocyanate-silane compound represented by formula 3 to the total number of active hydrogens in the polyether monool is preferably set according to the number of reactive silicon groups per molecule of the polyether compound A to be obtained. It is preferable to react the isocyanate-silane compound represented by formula 3 such that at least 0.7 reactive silicon groups are found per molecule of the obtained polyether compound A.

[0094] For example, when the active hydrogen-containing group of the polyether monool is a hydroxyl group, the molar ratio NCO / OH, which represents the total number of isocyanate groups (NCO) of the isocyanate silane compound represented by formula 3 to the total number of active hydrogens (total number of hydroxyl groups) of the polyether monool, 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 above the lower limit, the strength of the cured product is excellent, and when it is below the upper limit, the elongation of the cured product is excellent.

[0095] In method (c1), a polyisocyanate compound is reacted with the hydroxyl group of a polyether monool to convert the hydroxyl group into a monovalent organic group containing an isocyanate group having a urethane bond (-O-C(=O)NH-) at the terminal end bonded to the polyether monool (hereinafter also referred to as the "isocyanate-containing group"). Then, the isocyanate-containing group is reacted with a silylation agent having a functional group that can react with an isocyanate group and a reactive silicon group represented by formula 2 to obtain a terminal group that is a monovalent organic group having one or more urethane bonds (-O-C(=O)NH-) and a silylation agent residue that has reacted with the isocyanate group (hereinafter also referred to as the "urethane-bonded and reactive silicon group-containing group").

[0096] Hereinafter, the polyisocyanate compound described above will be a diisocyanate compound represented by formula 4 below, and the silylation agent having a functional group that can react with an isocyanate group and a reactive silicon group represented by formula 2 will be a compound represented by formula 5 below, and method (c1) will be described below, but will not be limited thereto.

[0097] OCN-R ３ -NCO ...Equation 4 R in Equation 4 ３ This indicates a divalent organic group.

[0098] W-R ４ -SiR ａ X ３－ａ ...Formula 5 In Formula 5, W is a functional group that can react with a monovalent isocyanate group (a group having one or more active hydrogen atoms), R ４ This is a divalent organic group, -SiR ａ X ３－ａ This is the same as equation 2 above.

[0099] When a diisocyanate compound represented by formula 4 is reacted with the hydroxyl group of a polyether monool, the isocyanate-containing group is -O-C(=O)NH-R ３ -NCO is the group that is formed. When the above isocyanate-containing group is reacted with the silylating agent represented by formula 5, the above urethane bond and reactive silicon group-containing group are -O-C(=O)NH-R ３ -NHC(=O)-W'-R ４ -SiR ａ X ３－ａ(However, W' is a divalent group obtained by removing one active hydrogen from W.) It becomes a group represented by For example, when W is a hydroxyl group, the urethane bond and the reactive silicon group-containing group are -O-C(=O)NH-R ３ -NHC(=O)-O-R ４ -SiR ａ X ３－ａ It is a group represented by In this case, the urethane bond and the reactive silicon group-containing group have two urethane bonds. For example, when W is an amino group (-NH ２ ), the urethane bond and the reactive silicon group-containing group are -O-C(=O)NH-R ３ -NHC(=O)-NH-R ４ -SiR ａ X ３－ａ It is a group represented by

[0100] R ３ is preferably a divalent organic group having 2 to 20 carbon atoms, an alkylene group, a cycloalkylene group, a bicycloalkylene group, a monocyclic or polycyclic divalent aromatic hydrocarbon group, a divalent group obtained by removing two hydrogen atoms from a cycloalkane having an alkyl group as a substituent, a divalent group obtained by removing two hydrogen atoms from an aromatic hydrocarbon having an alkyl group as a substituent, a divalent group obtained by removing two hydrogen atoms from two or more cycloalkanes which may have an alkyl group as a substituent and are bonded via an alkylene group, and a divalent group obtained by removing two hydrogen atoms from two or more aromatic hydrocarbons which may have an alkyl group as a substituent and are bonded via an alkylene group.

[0101] Examples of the diisocyanate compound represented by Formula 4 and other polyisocyanate compounds include aromatic polyisocyanate, non-yellowing aromatic polyisocyanate (a compound having no isocyanate group directly bonded to a carbon atom constituting an aromatic ring), aliphatic polyisocyanate, alicyclic polyisocyanate, and urethane-modified products, burette-modified products, allophanate-modified products, carbodiimide-modified products, and isocyanurate-modified products obtained from the above polyisocyanates.

[0102] Examples of aromatic polyisocyanates include naphthalene-1,5-diisocyanate, polyphenylene-polymethylene-polyisocyanate, 4,4'-diphenylmethane-diisocyanate, 2,4-tolediisocyanate, and 2,6-tolediisocyanate.

[0103] Examples of non-yellowing aromatic polyisocyanates include xylylene diisocyanate and tetramethyl xylylene diisocyanate. Examples of aliphatic polyisocyanates include hexamethylene diisocyanate, 2,2,4-trimethyl-hexamethylene diisocyanate, and 2,4,4-trimethyl-hexamethylene diisocyanate.

[0104] Examples of alicyclic polyisocyanates include isophorone diisocyanate and 4,4'-methylenebis(cyclohexyl isocyanate). The polyisocyanate compound is preferably one having two isocyanate groups, with hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, and 2,6-tolylene diisocyanate being more preferred, and tolylene diisocyanate being even more preferred because it easily yields high tensile strength in the cured product. One polyisocyanate compound may be used, or two or more may be used in combination.

[0105] Functional groups that can react with the isocyanate group represented by formula 5 and -SiR ａ X ３－ａ In silylating agents having R ４ Preferably, the group is a divalent organic group having 1 to 20 carbon atoms; more preferably, a group obtained by removing two hydrogen atoms from an aromatic hydrocarbon having 6 to 10 carbon atoms; more preferably, a group obtained by removing two hydrogen atoms from an aromatic hydrocarbon having 6 to 10 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms; more preferably, a group obtained by removing two hydrogen atoms from a cyclic hydrocarbon having 3 to 10 carbon atoms; more preferably, a group obtained by removing two hydrogen atoms from a linear hydrocarbon having 1 to 12 carbon atoms; even more preferably, a group obtained by removing two hydrogen atoms from a linear hydrocarbon having 1 to 8 carbon atoms; and particularly preferably, a group obtained by removing two hydrogen atoms from a linear hydrocarbon having 1 to 6 carbon atoms.

[0106] The 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, or an amino group in which one hydrogen atom is substituted with an alkyl group having 1 to 6 carbon atoms. Hydroxyl groups, sulfanyl groups, amino groups, methylamino groups, ethylamino groups, and butylamino groups are preferred, and hydroxyl groups, amino groups, methylamino groups, ethylamino groups, and butylamino groups are more preferred.

[0107] In methods (b1) and (c1), the resulting polyether compound A has reactive silicon groups formed via one or more organic groups represented by the following formula (i). That is, the polyether compound A obtained by methods (b1) and (c1) contains one or more organic groups represented by the following formula (i). The polyether compound A obtained by method (b1) contains only one organic group represented by the following formula (i), while the polyether compound A obtained by method (c1) contains two or more organic groups represented by the following formula (i). -C(=O)NH- Formula (i)

[0108] Organic group (i) is a divalent group derived from a urethane bond or a urea bond. When an isocyanate silane compound represented by formula 3 is used as a silylating agent, there is one organic group (i).

[0109] It is preferable that the organic group (i) forms a urethane bond (-O-C(=O)NH-, where -O- represents the terminal oxygen atom of the polyoxyalkylene chain) with the polyoxyalkylene chain. That is, it is preferable that one organic group (i) exists between the polyoxyalkylene chain and the reactive silicon group in polyether compound A. When polyether compound A is produced by the above method (b1), the number of organic groups represented by formula (i) in polyether compound A is one. When polyether compound A is produced by method (b1), it is easy to obtain polyether compound A with a high silylation rate. When produced by method (b1), it is easy to obtain polyether compound A with a narrow molecular weight distribution. The viscosity of the polyether monool 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 A and the number of groups (i) per molecule are the same.

[0110] The silylation rate of polyether compound A is preferably 50 to 100 mol%, and more preferably 60 to 98 mol%. When the silylation rate is above the lower limit of the above range, the cured product exhibits excellent tensile strength and high modulus. If the curable composition contains two or more types of polyether compound A, it is sufficient if the average silylation rate of all polyether compounds A is within the above range.

[0111] (Curable composition containing polyether compound A) Polyether compound A can be used, for example, in a curable composition. The curable composition is obtained by mixing polyether compound A with other necessary components. One type of polyether compound A may be used, or two or more types may be used in combination.

[0112] The content of the polyether compound having reactive silicon groups relative to the total mass of the curable composition is preferably 1 to 90% by mass, more preferably 10 to 80% by mass, and even more preferably 20 to 70% by mass. If the content is below the upper limit of the above range, the tensile strength of the cured product is superior and the elongation properties are better.

[0113] Other components included in the curable composition include, for example, curable compounds other than polyether compound A such as epoxy resin, epoxy resin curing agents, curing catalysts (silanol condensation catalysts), fillers, plasticizers, thixotropic agents, stabilizers, adhesion modifiers, property modifiers, dehydrating agents, adhesion-imparting resins, reinforcing materials such as fillers, surface modifiers, flame retardants, foaming agents, solvents, and silicates. Other components can be used in any combination without limitation from those conventionally known as described in International Publication No. 2013 / 180203, International Publication No. 2014 / 192842, International Publication No. 2016 / 002907, Japanese Patent Publication No. 2014-88481, Japanese Patent Publication No. 2015-10162, Japanese Patent Publication No. 2015-105293, Japanese Patent Publication No. 2017-039728, Japanese Patent Publication No. 2017-214541, etc. Two or more of each ingredient may be used in combination.

[0114] The curable composition may be a one-component type in which polyether compound A and all other components are pre-mixed and sealed for storage, and cured by moisture in the air after application. Alternatively, it may be a two-component type in which a main component composition containing at least polyether compound A and a curing agent composition containing at least a curing catalyst are stored separately, and the curing agent composition and the main component composition are mixed before use. A one-component curable composition is preferably free of water. It is preferable to pre-dehydrate and dry any water-containing components, or to dehydrate them by reducing the pressure during mixing. In a two-component curable composition, the curing agent composition may contain water, and the main component composition is less likely to gel even if it contains a small amount of water, but from the viewpoint of storage stability, it is preferable to pre-dehydrate and dry the components. To improve storage stability, a dehydrating agent may be added to the one-component curable composition or the two-component main component composition.

[0115] (Uses of curable compositions containing polyether compound A) Suitable uses for curable compositions containing polyether compound A include adhesives, sealants (e.g., elastic sealants for buildings, sealants for double-glazed windows, sealing materials for rust prevention and waterproofing of glass edges, back-surface sealing materials for solar cells, sealing materials for buildings, sealing materials for ships, sealing materials for automobiles, sealing materials for roads), and electrical insulating materials (insulating coatings for electric wires and cables).

[0116] The embodiments will be described in more detail below with reference to examples, but the present invention is not limited to the following description. Examples 1 and 2 are comparative examples, and Examples 3 and 4 are examples.

[0117] [Measurement Method] (Hydrogen Value and Hydroxygen Value-Equivalent Molecular Weight) The hydroxyl value (OHV) of polyether monools was calculated in accordance with Method B of JIS K 1557-1:2007. The OHV-equivalent molecular weight of polyether monools was calculated using the formula "56,100 / hydroxyl value of polyether monool".

[0118] (Viscosity) The viscosity of polyether monool was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., product name: RE85U) at a measurement temperature of 25°C and rotor No. 1.

[0119] (Mw / Mn) The Mn and Mw of polyether monools were analyzed using a GPC system (Tosoh Corporation product name HLC-8320) and an RI detector. Two TSK-GEL Super HZ4000 (4.6 mm × 150 mm) columns and two Super HZ2500 (4.6 mm × 150 mm) columns were connected in series in that order. Tetrahydrofuran (THF) was used as the eluent at a flow rate of 0.35 ml / min, and the column temperature was set to 40°C. Mw, Mn, and Mw / Mn were determined by conversion using a calibration curve created with polystyrene standard samples (Agilent Technologies product name Easyal PS-2, molecular weight range 580 to 400,000).

[0120] (Contamination of the production line) In each example, the contamination of the degassing line of the production equipment after the synthesis of polyether monool is evaluated. In Examples 1 and 2, the piping used for dehydration in the alcoholation reaction is evaluated. In Examples 3 and 4, the piping used for degassing the raw material components is evaluated. Specifically, after cleaning the inside of the reactor, an organic solvent (such as methylene chloride) is overflowed from the degassing line. If turbidity occurs in the organic solvent after it passes through the degassing line, it is judged as "contamination present". If the organic solvent is colorless and transparent, it is judged as "contamination absent".

[0121] [Raw Materials] Initiator 1: Cetanol (a saturated higher monoalcohol with 16 carbon atoms derived from biomass, a product of Higher Alcohol Industry Co., Ltd., cetyl alcohol NX-600) Initiator 2: Behenyl alcohol (containing 65% by mass of behenyl alcohol with 22 carbon atoms derived from biomass, a product of Higher Alcohol Industry Co., Ltd., NIKKOL Behenyl Alcohol 65)

[0122] [Example 1] After alkoxideating initiator 1, a degassing step was performed to remove the water generated by alkoxideating. Subsequently, PO was subjected to ring-opening addition polymerization of the alkoxideated initiator 1 in the presence of a KOH catalyst. By neutralization purification, the polyether monool of Example 1 was obtained.

[0123] [Example 2] Polyether monools for each example were obtained using the same procedure and conditions as in Example 1, except that initiator 1 was changed to initiator 2.

[0124] [Example 3] In the presence of a tert-butyl alcohol zinc hexacyanocobaltate complex catalyst (hereinafter referred to as "TBA-DMC catalyst"), PO was subjected to ring-opening addition polymerization of initiator 1 to obtain the polyether monool of Example 3. For polymerization, 0.1% by mass of Irganox 1010 manufactured by BASF was added 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 the polyether monool. Since neither a degassing step to remove water nor a neutralization purification step is necessary in the polymerization reaction of PO using the TBA-DMC catalyst, these steps were not performed.

[0125] [Example 4] Polyether monools for each example were obtained using the same procedure and conditions as in Example 3, except that initiator 1 was changed to initiator 2.

[0126]

[0127] In Examples 1 and 2, polyether monools were synthesized using a KOH catalyst, resulting in the generation of water during the alkoxide reaction. This water reacts with the initiator to produce a polyether diol, which is undesirable for the synthesis of polyether monools. It is also likely that the piping used for dehydration in the alkoxide reaction will become contaminated with raw material components. As a result of the loss of raw material components due to dehydration in the alkoxide reaction, a problem of reduced yield of polyoxypropylene monool is also likely to occur.

[0128] In contrast, in Examples 3 and 4, polyether monools were synthesized using a TBA-DMC catalyst, eliminating the need for water removal. Therefore, it is believed that no contamination from raw material components will adhere to the piping of the manufacturing equipment. In addition, the yield of polyoxypropylene monools is also expected to improve. Because propylene oxide was ring-opening added to the initiator higher alcohol in the presence of a TBA-DMC catalyst, the molecular weight distribution of each polyether monool in Examples 3 and 4 is narrower compared to Examples 1 and 2. As already explained, higher alcohols with 10 or more carbon atoms derived from biomass inevitably contain impurity alcohols with a larger or smaller number of carbon atoms than desired. In Examples 3 and 4, even when using higher alcohols contaminated with impurity alcohols, it was possible to obtain polyether monools with a narrower molecular weight distribution compared to Examples 1 and 2.

[0129] According to the present invention, a method for producing polyether monool that is less prone to contamination of the polyether monool production line is provided.

[0130] This application claims priority based on Japanese Patent Application No. 2024-201703, filed on 19 November 2024, and the entire contents of the said Japanese application are incorporated herein by reference.

Claims

1. A method for producing a polyether monool, comprising polymerizing an alkylene oxide onto an initiator which is a monohydric alcohol having 10 or more carbon atoms, in the presence of a complex metal cyanide catalyst.

2. The manufacturing method according to claim 1, wherein the hydroxyl value-based molecular weight of the polyether monool is 500 to 3000.

3. The manufacturing method according to claim 1, wherein the Mw / Mn of the polyether monool is 1.15 or less.

4. The manufacturing method according to claim 1, wherein the alkylene oxide has three or more carbon atoms.

5. The manufacturing method according to claim 1, wherein the initiator is derived from biomass.

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