Polyether monool

Abstract

This polyether monool has a polyoxyalkylene chain and an initiator residue derived from a C10 or higher monohydric alcohol, the ratio of the molecular weight of the polyoxyalkylene chain to the molecular weight of the initiator residue is 7.0 or less, and the content of at least one metal selected from the group consisting of Zn, Co, Fe, Ni, Al, Sr, Mn, Cr, Cu, Sn, Pb, Mo, W and V is 1.0 ppm or more.

Description

Polyether monool

[0001] This invention relates to polyether monools.

[0002] By utilizing basic catalysts such as KOH, polyether monools can be synthesized by ring-opening addition polymerization of alkylene oxide to an initiator having active hydrogen, such as an alcohol. For example, the polyoxypropylene monool described in paragraph

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

[0003] Patent No. 7240489

[0004] However, conventional polyether monools have room for improvement in their compatibility with hydrophobic compounds. In addition, when synthesizing polyether monools using a KOH catalyst, a side reaction can occur in which water generated in the alkoxide reaction acts as an initiator, potentially producing diol components such as polyether diols, which raises concerns about quality degradation.

[0005] This invention provides a polyether monool with improved compatibility with hydrophobic compounds and reduced risk of quality degradation due to diol components.

[0006] The present invention has the following embodiments: [1] A polyether monool having an initiator residue derived from a monohydric alcohol having 10 or more carbon atoms and a polyoxyalkylene chain, wherein the ratio of the molecular weight of the polyoxyalkylene chain to the molecular weight of the initiator residue is 7.0 or less, and the content of at least one metal selected from the group consisting of Zn, Co, Fe, Ni, Al, Sr, Mn, Cr, Cu, Sn, Pb, Mo, W, and V is 1.0 ppm or more. [2] The polyether monool according to [1], wherein the number of carbon atoms in the alkylene oxide-based unit in the polyoxyalkylene chain is 3 or more. [3] The polyether monool according to [1] or [2], wherein the cloud point is 10°C or less. [4] The polyether monool according to any one of [1] to [3], wherein the molecular weight on a hydroxyl value basis is 500 to 3000. [5] The polyether monool according to any one of [1] to [4], wherein the monohydric alcohol having 10 or more carbon atoms is derived from biomass.

[0007] According to the present invention, it is possible to provide a polyether monool with improved compatibility with hydrophobic compounds and reduced risk of quality degradation due to diol components.

[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 the hydrogen atom based on the active hydrogen-containing group and the hydrogen atom based on the hydroxyl group of water. An "initiator residue" is the residue obtained by removing the active hydrogen from the initiator.

[0011] Polyether monools and reactive silicon-containing oxyalkylene polymers are polymers consisting of a main chain and end groups. In polyether monools and reactive silicon-containing oxyalkylene polymers, the "end group" refers to the group of atoms containing the oxygen atom closest to the molecular end among the oxygen atoms in the polyoxyalkylene chain. If the group of atoms contains an initiator residue, it is not considered an end group but rather part of the main chain. The term "polyether compound" encompasses polyether polyols such as polyetherdiols, polyethertriols, and polyetherpolyols, as well as polyether monools. "Biomass" refers to renewable, biologically derived organic resources.

[0012] A "silylation agent" is a compound that can react with an unsaturated group to introduce a reactive silicon group. A "plasticizer" is a compound used to reduce the viscosity of a polymer, and refers to a compound that is not chemically incorporated into the polymer molecule but exerts a plasticizing effect on the polymer.

[0013] The hydroxyl value of polyether monool is measured according to Method B (phthalation method) described in JIS K 1557-1:2007. The hydroxyl value-based molecular weight of polyether monool is calculated as 56,100 / (hydroxyl value of polyether monool).

[0014] The number average molecular weight (Mn) and the weight average molecular weight (Mw) are polystyrene-equivalent molecular weights measured by using GPC (Gel Permeation Chromatography) with tetrahydrofuran as an eluent and creating a calibration curve using a polystyrene polymer with a known molecular weight. Mw / Mn is an index of the molecular weight distribution and is the ratio of Mw to Mn. The viscosity of the polyether monoalcohol is measured using an E-type viscometer. The numerical range represented by "~" means a numerical range with the numerical values before and after ~ as the lower limit value and the upper limit value, respectively.

[0015] [Polyether Monoalcohol] The polyether monoalcohol of the present invention has an initiator residue A derived from a monohydric alcohol having 10 or more carbon atoms and a polyoxyalkylene chain. The main chain of the polyether monoalcohol is a polymer chain composed of an initiator residue A and an oxyalkylene chain having one or more alkylene oxide units (hereinafter referred to as "AO units").

[0016] The initiator A in the synthesis of the polyether monoalcohol is a monohydric alcohol having 10 or more carbon atoms. The initiator A has a hydroxyl group as an active hydrogen-containing group. From the viewpoint of further improving the compatibility with hydrophobic compounds, the carbon number of the initiator A is preferably 10 or more, more preferably 11 or more, still more preferably 12 or more, particularly preferably 13 or more, and most preferably 14 or more.

[0017] The initiator having one hydroxyl group is not particularly limited. A monohydric alcohol having a linear or branched hydrocarbon group is preferred. For example, decyl alcohol, lauryl alcohol, tridecanol, cetyl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol can be mentioned. Further, the initiator A is preferably derived from biomass. The initiator A may be used alone or in combination of two or more.

[0018] 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 most preferably 3. One type of AO may be used alone, or two or more types may be used in combination.

[0019] An oxyalkylene chain has one or more types of AO units. In the case of an oxyalkylene chain having two or more types of AO units, these AO units may form block polymers or random polymers. Examples of oxyalkylene chains include polymer chains having EO units, polymer chains having PO units, polymer chains having EO units 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 units and PO units, and polymer chains consisting of PO units and butylene oxide units. As for the oxyalkylene chain, polymer chains consisting of AO units with 3 or more carbon atoms are preferred, and polymer chains consisting of PO units are particularly preferred.

[0020] The terminal group of a polyether monool is a hydroxyl group. The number of terminal groups in a polyether monool (i.e., the number of hydroxyl groups) is one, the same as the number of active hydrogen atoms in initiator A.

[0021] Molecular weight of initiator residue A (m ２ The molecular weight (m) of the polyoxyalkylene chain relative to ) １ ) ratio (m １ / m ２ ) is 7.0 or less. In terms of improved compatibility with hydrophobic compounds, m １ / m ２ m is preferably 0.5 to 7.0, more preferably 1.0 to 7.0, and even more preferably 1.4 to 7.0. １ / m ２ If the value is above the lower limit of the aforementioned numerical range, the hydrophilicity of the polyether monool improves.１ / m ２ When it is below the upper limit value within the numerical range, the compatibility with the hydrophobic compound is further improved.

[0022] In the polyether monool, the content of at least one metal selected from the group consisting of Zn, Co, Fe, Ni, Al, Sr, Mn, Cr, Cu, Sn, Pb, Mo, W and V (hereinafter simply referred to as "metal content") is 1.0 ppm or more. In the present invention, a polyether monool obtained by reacting an initiator having 10 or more carbon atoms with an AO in the presence of a double metal cyanide complex catalyst (hereinafter also referred to as "DMC catalyst") described later is preferable. As a trace produced by using the DMC catalyst, the metal content can be detected from the polyether monool.

[0023] In the polyether monool of the present invention, the metal content may be 5.0 ppm or more, may be 10.0 ppm or more, may be 15.0 ppm or more, may be 20.0 ppm or more, or may be 25.0 ppm or more. In order to suppress the precipitation of the metal and enhance the chemical stability, the metal content is preferably 1,000 ppm or less, more preferably 500 ppm or less, and even more preferably 200 ppm or less. After obtaining the polyether monool using the DMC catalyst, the metal content can be reduced by purification.

[0024] The cloud point of the polyether monool is preferably 10°C or lower, more preferably 7°C or lower, and even more preferably less than 5°C. When the cloud point of the polyether monool is below the upper limit value, the compatibility with the hydrophobic compound tends to be improved.

[0025] The hydroxyl value of the polyether monool is preferably 15 to 200 mgKOH / g, more preferably 25 to 150 mgKOH / g, and even more preferably 28 to 120 mgKOH / g. When the hydroxyl value is at least the lower limit value within the numerical range, sufficient curability is easily obtained when resinification occurs. When the hydroxyl value is below the upper limit value within the numerical range, sufficient flexibility can be imparted to the resin, and good elongation properties are easily obtained.

[0026] 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.

[0027] The Mw / Mn of the polyether monool is preferably 1.00 to 1.20, more preferably 1.00 to 1.17, even more preferably 1.00 to 1.15, 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.

[0028] 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.

[0029] (Method for producing polyether monools) A preferred method for producing polyether monools is, for example, a method in which AO is polymerized with initiator A, which is a monohydric alcohol having 10 or more carbon atoms, in the presence of a DMC catalyst. Initiator A and AO have already been described.

[0030] The DMC catalyst functions as a polymerization catalyst for alkylene oxides. The DMC catalyst is a crystalline solid containing 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, present in the metal salt and metal compound, as well as water other than crystal water. Known metal halides, cyanide transition metal compounds, and organic ligands can be used in the production of the DMC catalyst.

[0031] The DMC catalyst is thought to be represented by the following equation 1. １ａ [M ２ (CN) ｂ ] ｃ d(M １ ｅ X ｆ )・g(Ligand)・h(H ２ O) Formula 1

[0032] In Equation 1, M １ ｅ X ｆ It is a metal halide salt, M １ X is a metal atom that forms a cation, X is a halogen atom that forms a counter anion, and M ２ is a transition metal atom that is an active site in cyanide transition metal compounds, and is an organic ligand. a, b, c, d, e, f, g, and h are integers, and a, b, c and e, f are numbers that result in electrical neutrality.

[0033] M 1 Examples include Zn(II), Fe(II), Fe(III), Co(II), Ni(II), Al(III), Sr(II), Mn(II), Cr(III), Cu(II), Sn(II), Pb(II), Mo(IV), Mo(VI), W(IV), and W(VI). 1 In terms of catalyst life, Zn(II) and Co(II) are preferred.

[0034] M ２ Examples include Co(III), Fe(II), Fe(III), Co(II), Cr(II), Cr(III), Mn(II), Mn(III), V(IV), and V(V). ２ In terms of the properties of the catalyst, Co(III) and Co(II) are preferred because they extend the catalyst life of the DMC catalyst.

[0035] Examples of X include Cl, Br, and I. １ ｅ X ｆ The metal halide salt is preferably one or more selected from zinc fluoride, zinc chloride, zinc bromide, zinc iodide, zinc sulfate, zinc nitrate, and zinc acetate. ２In terms of the interatomic distance between X and the material, it is more preferable to include one or more selected from zinc chloride and zinc bromide.

[0036] 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.

[0037] 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).

[0038] 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.

[0039] 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.

[0040] 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.

[0041] 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 compounds, are preferred.

[0042] 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.

[0043] The content of the DMC catalyst relative to the total mass of the slurry catalyst is preferably, for example, 0.001 to 60% by mass, more preferably 0.003 to 50% by mass, and even more preferably 0.006 to 30% by mass. In particular, when the dispersion medium is a polyether monool, the content of the DMC catalyst relative to the total mass of the slurry catalyst is preferably 1 to 60% by mass, more preferably 3 to 40% by mass, and even more preferably 5 to 30% by mass.

[0044] 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.

[0045] 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.

[0046] 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. The obtained solid is dried so that its moisture content is within the above-mentioned specific range, and may be pulverized if necessary.

[0047] 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.

[0048] 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.

[0049] 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.

[0050] 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.

[0051] 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.

[0052] 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.

[0053] In the presence of a DMC catalyst, an initiator A having 10 or more carbon atoms can be brought into contact with AO, thereby enabling ring-opening addition polymerization of AO to initiator A.

[0054] For example, if the polyoxyalkylene chain of a 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.

[0055] 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.

[0056] 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 of the above numerical range, the polymerization reaction proceeds easily. If the amount of DMC catalyst used is below the upper limit of the above numerical range, the amount of DMC catalyst used is reduced, making it more economical.

[0057] 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 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.

[0058] 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.

[0059] 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. 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, is sometimes produced by extraction from plants. Such biomass-derived monohydric alcohols inevitably contain impurity alcohols with a larger or smaller number of carbon atoms than the desired number. When AO is added to a biomass-derived monohydric alcohol using a basic catalyst such as KOH, a molecular weight distribution arises due to the difference in the number of carbon atoms of the impurities in the biomass-derived monohydric alcohol, making it difficult to obtain a polyether monool with a narrow molecular weight distribution. In contrast, when a DMC catalyst is used as the polymerization catalyst for AO, a polyether monool with a narrow molecular weight distribution is easily obtained, even if impurity alcohols with different numbers of carbon atoms are mixed into initiator A.

[0060] 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 polyether monool composition obtained in this way 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.

[0061] 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 chain in other polyether monools are the same as those already described for the polyether monools of the present invention.

[0062] 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.

[0063] (Mechanism of Action) The polyether monool of the present invention described above has an initiator residue A derived from a monohydric alcohol having 10 or more carbon atoms, and the ratio of the molecular weight of the polyoxyalkylene chain to the molecular weight of initiator residue A is 7.0 or less, thus improving compatibility with hydrophobic compounds. In addition, the content of at least one metal selected from the group consisting of Zn, Co, Fe, Ni, Al, Sr, Mn, Cr, Cu, Sn, Pb, Mo, W, and V is 1.0 ppm or more, making it highly likely that it was produced using a DMC catalyst. When polyether monool is synthesized using a DMC catalyst, there is no influence from side reactions in which water generated in the alkoxide reaction reacts as an initiator, thus reducing the risk of quality degradation due to diol components.

[0064] (Applications) The applications of the polyether monool of the present invention described above are not particularly limited. Because its compatibility with hydrophobic compounds has been improved, it can be used in combination with various hydrophobic compounds. Several examples of applications of the polyether monool are described below, but the applications of the polyether monool of the present invention are not limited to those described below.

[0065] [Lubricating Oil Composition] The lubricating oil composition contains the polyether monool of the present invention described above and a refrigerant. In the lubricating oil composition, the polyether monool is blended as a lubricating oil base oil. The lubricating oil base oil is used for the smooth circulation of the refrigerant in a compression type refrigerator.

[0066] The type of refrigerant is not particularly limited. Examples of refrigerants include hydrocarbon compounds having 1 to 8 carbon atoms and unsaturated fluorinated hydrocarbon compounds. However, the refrigerant is not limited to the following examples.

[0067] Considering the boiling point suitable for use as a refrigerant, the number of carbon atoms in the hydrocarbon compound is preferably 1 to 5, more preferably 3 to 5, even more preferably 3 or 4, and most preferably 3. Examples of hydrocarbon compounds used as refrigerants include methane, ethane, ethylene, propane, cyclopropane, propylene, n-butane, isobutane, n-pentane, and isopentane. Among the many hydrocarbon compounds, propane and propylene are preferred. A single hydrocarbon compound may be used, or two or more may be used in combination by mixing them.

[0068] As the unsaturated fluorinated hydrocarbon compound, the compound represented by the following formula 2 is preferred. ｘ F ｙ H ｚ ...Formula 2

[0069] In formula 2, x is an integer from 2 to 6, y is an integer from 1 to 11, and z is an integer from 1 to 11, and the molecule has one or more carbon-carbon unsaturated bonds. The compound represented by formula 2 represents a fluoride (unsaturated fluorinated hydrocarbon compound) in which y of the hydrogen atoms of an unsaturated hydrocarbon compound having x carbon atoms and one or more carbon-carbon unsaturated bonds are replaced with fluorine atoms. The carbon chain constituting the compound represented by formula 2 may be linear, branched, or cyclic. The number of carbon-carbon unsaturated bonds is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1.

[0070] Examples of compounds represented by formula 2 include compounds in which some of the hydrogen atoms of a linear or branched chain olefin having 2 to 6 carbon atoms are substituted with fluorine atoms, and compounds in which some of the hydrogen atoms of a cyclic olefin having 4 to 6 carbon atoms are substituted with fluorine atoms.

[0071] Examples of compounds represented by formula 2 include ethylene fluoride with 1 to 3 fluorine atoms introduced, propene fluoride with 1 to 5 fluorine atoms introduced, butene fluoride with 1 to 7 fluorine atoms introduced, pentene fluoride with 1 to 9 fluorine atoms introduced, hexene fluoride with 1 to 11 fluorine atoms introduced, cyclobutene fluoride with 1 to 5 fluorine atoms introduced, cyclopentene fluoride with 1 to 7 fluorine atoms introduced, and cyclohexene fluoride with 1 to 9 fluorine atoms introduced.

[0072] Among the many unsaturated fluorinated hydrocarbon compounds, ethylene fluoride and propene fluoride are preferred, with propene having 3 to 5 fluorine atoms introduced being more preferred. Examples of suitable unsaturated fluorinated hydrocarbon compounds include 1,1,2-trifluoroethylene (HFO-1123), 2,3,3,3-tetrafluoropropene (R1234yf), 1,3,3,3-tetrafluoropropene (R1234ze), and 1,2,3,3-tetrafluoropropene (R1234ye).

[0073] The lubricating oil composition may further contain other components as additives besides the polyether monool and refrigerant of the present invention. These other components are not particularly limited, but include, for example, antioxidants, extreme pressure agents, stabilizers, copper deactivators, defoamers, load-bearing additives, chlorine scavengers, oxygen scavengers, detergent dispersants, viscosity index improvers, oiliness agents, rust inhibitors, corrosion inhibitors, and pour point depressants. However, the additives are not limited to these examples. These other components may be used individually or in combination of two or more.

[0074] Examples of antioxidants include phenolic antioxidants and amine antioxidants. Examples of phenolic antioxidants include 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, and 2,2'-methylenebis(4-methyl-6-tert-butylphenol). Examples of amine antioxidants include phenyl-α-naphthylamine and N.N'-diphenyl-p-phenylenediamine.

[0075] Examples of extreme pressure agents include phosphorus-based extreme pressure agents such as phosphate esters, acidic phosphate esters, phosphite esters, acidic phosphite esters, and their amine salts.

[0076] Examples of stabilizers include phenyl glycidyl ether, alkyl glycidyl ether, alkylene glycol glycidyl ether, cyclohexene oxide, α-olefin oxide, and epoxy compounds such as epoxidized soybean oil.

[0077] Examples of copper deactivators include benzotriazole and its derivatives. For example, N-[N,N'-dialkyl (alkyl group with 3 to 12 carbon atoms)aminomethyl]triazole is an example.

[0078] Examples of defoaming agents include silicone oil and fluorinated silicone oil.

[0079] [Curable Composition] The curable composition contains either or both of a reactive silicon group-containing oxyalkylene polymer and a reactive silicon group-containing (meth)acrylic acid ester polymer, and a plasticizer, wherein at least a portion of the plasticizer is the polyether monool of the present invention described above.

[0080] (Reactive silicon group-containing oxyalkylene polymer) A reactive silicon group-containing oxyalkylene polymer has a reactive silicon group and an oxyalkylene monomer unit.

[0081] Reactive silicon group-containing oxyalkylene polymers consist of a main chain and terminal groups. The main chain of a reactive silicon group-containing oxyalkylene polymer has repeating units based on initiator residue B and oxyalkylene monomers. Examples of oxyalkylene monomers in reactive silicon group-containing oxyalkylene polymers include ethylene oxide monomer, propylene oxide monomer, butylene oxide monomer, and tetramethylene oxide monomer. When the polyoxyalkylene chain in the main chain of an unsaturated group-containing oxyalkylene polymer is a copolymer chain of two or more oxyalkylene monomers, it may be a block polymerization chain or a random polymerization chain.

[0082] In reactive silicon group-containing oxyalkylene polymers, oxyalkylene monomers having 3 or more carbon atoms are preferred from the viewpoint of reactivity. Among the oxyalkylene monomers having 3 or more carbon atoms, oxyalkylene monomers having 3 to 5 carbon atoms are preferred, and propylene oxide monomers are more preferred.

[0083] The initiator B of the reactive silicon group-containing oxyalkylene polymer is not particularly limited. The number of active hydrogen atoms in initiator B may be one or more, two to ten, two to eight, or two to six. Initiator B may be used alone or in combination of two or more types.

[0084] Initiator B preferably has a hydroxyl group as an active hydrogen-containing group. As initiator B having one hydroxyl group, a monohydric alcohol having a linear or branched hydrocarbon group is preferred. Examples include methyl alcohol, ethyl alcohol, 1-propyl alcohol, 2-propyl alcohol, n-butyl alcohol, isobutyl alcohol, 2-butyl alcohol, tert-butyl alcohol, 2-ethylhexanol, decyl alcohol, lauryl alcohol, tridecanol, cetyl alcohol, stearyl alcohol, and oleyl alcohol.

[0085] Examples of initiator B having two hydroxyl groups include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, triethylene glycol, tripylene glycol, neopentyl glycol, 1,4-butanediol, and 1,6-hexanediol. Water can also be an example of initiator B having two hydroxyl groups.

[0086] Examples of initiator B having three hydroxyl groups include glycerin, trimethylolpropane, and trimethylolethane.

[0087] Examples of initiator B having four or more hydroxyl groups include pentaerythritol, diglycerin, meso-erythritol, methyl glucoside, sucrose, glucose, sorbitol, dipentaerythritol, trehalose, and diglycerin.

[0088] Initiator B may be a low molecular weight polymer obtained by polymerizing alkylene oxides onto these initiators in the presence of alkali metal hydroxides.

[0089] The hydroxyl value of initiator B may be, for example, 3 to 842 mg KOH / g, 7 to 561 mg KOH / g, etc.

[0090] The terminal groups of reactive silicon-containing oxyalkylene polymers have reactive silicon groups. Therefore, reactive silicon-containing oxyalkylene polymers yield crosslinked products through hydrolysis of silyl groups due to moisture in the air, and subsequent silanol condensation reactions with other polymer molecules.

[0091] Reactive silicon groups have hydrolyzable groups bonded to silicon atoms and can crosslink by forming siloxane bonds. The reaction that forms siloxane bonds is accelerated by a curing catalyst. Reactive silicon groups are represented by the following formula 3: -SiR ａ X ３－ａ ...Formula 3

[0092] In formula 3, R represents a monovalent organic group having 1 to 20 carbon atoms, excluding hydrolyzable groups, and X represents a hydroxyl group, a halogen atom, or a hydrolyzable group. a is an integer from 0 to 2. When a is 2, R may be the same or different from each other, and when a is 0 or 1, X may be the same or different from each other.

[0093] In formula 3, R is preferably at least one selected from the group consisting of hydrocarbon groups having 1 to 20 carbon atoms and triorganosiloxy groups.

[0094] R is preferably at least one 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 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 from the viewpoint of good curability of the reactive silicon group-containing oxyalkylene polymer and stability of the curable composition. α-chloromethyl groups are preferred from the viewpoint of a fast curing rate of the cured product. Methyl groups are particularly preferred from the viewpoint of being readily available.

[0095] In formula 3, X represents a halogen atom, a hydroxyl group, or a hydrolyzable group. X may be the same or different from each other. Examples of hydrolyzable groups include alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, acid amide groups, aminooxy groups, sulfanyl groups, and alkenyloxy groups. Alkoxy groups are preferred because they are mildly hydrolyzable and easy to handle. Methoxy groups, ethoxy groups, and isopropoxy groups are preferred, with methoxy or ethoxy groups being more preferred. When the alkoxy group is a methoxy or ethoxy group, siloxane bonds are quickly formed, making it easy to form a crosslinked structure in the cured product, and the elongation properties of the cured product tend to be good.

[0096] In Equation 3, 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 0 or 1, X may be the same or different from each other. Since the cured product tends to have excellent ductility, a is preferably 0 or 1, and more preferably a is 1.

[0097] Examples of reactive silicon groups represented by formula 3 include trimethoxysilyl group, triethoxysilyl group, triisopropoxysilyl group, tris(2-propenyloxy)silyl group, triacetoxysilyl group, dimethoxymethylsilyl group, diethoxymethylsilyl group, dimethoxyethylsilyl group, diethoxyethylsilyl group, methyldiisopropoxysilyl group, (α-chloromethyl)dimethoxysilyl group, and (α-chloromethyl)diethoxysilyl group. From the viewpoint of high activity and good curability, trimethoxysilyl group, triethoxysilyl group, dimethoxymethylsilyl group, and diethoxymethylsilyl group are preferred, and dimethoxymethylsilyl group and trimethoxysilyl group are more preferred.

[0098] The number of terminal groups in one molecule of the reactive silicon group-containing oxyalkylene polymer may be 0.8 to 1.2, etc. The number of reactive silicon groups per molecule of the reactive silicon group-containing oxyalkylene polymer may be 0.5 to 2.0, 0.60 to 1.94, etc. The number of reactive silicon groups per terminal group of the reactive silicon group-containing oxyalkylene polymer may be 0.6 to 1.2, 0.8 to 1.2, 0.9 to 1.2, etc. The Mn of the reactive silicon group-containing oxyalkylene polymer may be 2,000 to 100,000, 5,000 to 50,000, etc. The Mw / Mn of the reactive silicon group-containing oxyalkylene polymer may be 1.80 or less, 1.50 or less, 1.40 or less, 1.20 or less, etc.

[0099] Reactive silicon group-containing oxyalkylene polymers can be produced, for example, by reacting an unsaturated group-containing oxyalkylene polymer with a silylating agent. An unsaturated group-containing oxyalkylene polymer is a polymer having repeating units based on an unsaturated group and an oxyalkylene monomer. An unsaturated group-containing oxyalkylene polymer consists of a main chain and terminal groups. The main chain has repeating units based on an initiator residue B and an oxyalkylene monomer, and the terminal groups have unsaturated groups. Preferably, the main chain consists of repeating units based on an initiator residue B and an oxyalkylene monomer, and the terminal groups have an oxygen atom and an unsaturated group.

[0100] The method for producing an unsaturated group-containing oxyalkylene polymer is not particularly limited. It can be produced by ring-opening addition polymerization of one or more oxyalkylene monomers to initiator B, and then converting the hydroxyl groups of the terminal groups of the polymer obtained to alkenyloxy or alkynyloxy groups. The auxiliary materials such as initiators required for polymerization are not particularly limited, and reaction conditions such as reaction temperature and reaction pressure can be appropriately selected.

[0101] The ring-opening polymerization catalyst used when ring-opening addition polymerization of one or more oxyalkylene monomers to initiator B is not particularly limited. Examples include alkaline catalysts such as KOH, metal compound-porphyrin complex catalysts such as complexes obtained by reacting organoaluminum compounds with porphyrins, DMC catalysts, and catalysts consisting of phosphazene compounds.

[0102] DMC catalysts are preferred because they allow for a narrower molecular weight distribution and facilitate the acquisition of curable compositions with low viscosity. The DMC catalyst is not particularly limited, and its details have already been described.

[0103] Methods for converting the hydroxyl groups at the end of a polymer to alkenyloxy or alkynyloxy groups include, for example, a method in which the polymer is reacted with an alkali metal salt and then with a halogenated hydrocarbon compound having a carbon-carbon double bond; a method in which an epoxy compound having an unsaturated group is reacted with an alkali metal salt and then with an alkali metal salt and then with a halogenated hydrocarbon compound having an unsaturated group; and a method in which the polymer is reacted with an alkali metal salt and then with a halogenated hydrocarbon compound having a carbon-carbon triple bond.

[0104] 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 3, and hydrosilane compounds (e.g., HSiR ａ X ３－ａ The definitions of R, X, and a are the same as in Equation 3.

[0105] Examples of silylation agents include trimethoxysilane, triethoxysilane, triisopropoxysilane, tris(2-propenyloxy)silane, triacetoxysilane, dimethoxymethylsilane, diethoxymethylsilane, dimethoxyethylsilane, diethoxyethylsilane, diisopropoxymethylsilane, (α-chloromethyl)dimethoxysilane, and (α-chloromethyl)diethoxysilane. Trimethoxysilane, triethoxysilane, dimethoxymethylsilane, and diethoxymethylsilane are preferred due to their high activity and good curability, with dimethoxymethylsilane and trimethoxysilane being more preferred.

[0106] (Reactive silicon group-containing (meth)acrylic acid ester polymer) A reactive silicon group-containing (meth)acrylic acid ester polymer has a reactive silicon group and an alkyl (meth)acrylic acid ester monomer unit. The reactive silicon group-containing (meth)acrylic acid ester polymer may have repeating units based on other monomers copolymerizable with alkyl (meth)acrylic acid ester monomers. As the alkyl (meth)acrylic acid ester monomer, for example, various monomers described in Japanese Patent Application Publication No. 11-130931 can be used without particular limitation.

[0107] The proportion of alkyl (meth)acrylate monomer units may be 50% by mass or more, 70% by mass or more, or 100% by mass of the total monomer units. The number of reactive silicon groups per molecule of the reactive silicon group-containing (meth)acrylate polymer may be 0.8 to 8.0 or 0.8 to 6.0. The number of unsaturated groups per molecule of the reactive silicon group-containing (meth)acrylate polymer may be 1.0 to 8.0 or 1.0 to 6.0. The Mn of the reactive silicon group-containing (meth)acrylate polymer may be 500 to 100,000 or 1,000 to 80,000. The Mw / Mn of the reactive silicon group-containing (meth)acrylate polymer may be 1.80 or less, 1.50 or less, 1.40 or less.

[0108] Reactive silicon group-containing (meth)acrylic acid ester polymers can be produced by hydrosilylation of unsaturated group-containing (meth)acrylic acid ester polymers using a silylating agent. Unsaturated group-containing (meth)acrylic acid ester polymers have an unsaturated group and an alkyl (meth)acrylate monomer unit.

[0109] The method for producing unsaturated group-containing (meth)acrylic acid ester polymers is not particularly limited. For example, methods include polymerizing an alkyl (meth)acrylic acid ester monomer with a compound having an unsaturated group, and a method using living radical polymerization in which a compound having two alkenyl groups is reacted at the end of the polymerization reaction. In particular, living radical polymerization is preferred because it yields polymers with arbitrary molecular weights, a narrow molecular weight distribution, and low viscosity.

[0110] As a living radical polymerization method, for example, atom transfer radical polymerization (ATRP method) is used to polymerize alkyl (meth)acrylate monomers using an organic halide or sulfonyl halogenated compound as an initiator and a transition metal complex as a catalyst. As an atom transfer radical polymerization (ATRP method), polymerization can be carried out by the polymerization method described in Japanese Patent Application Publication No. 11-130931, for example, but various other polymerization methods may also be used.

[0111] Unsaturated group-containing (meth)acrylic acid ester polymers are obtained by introducing unsaturated groups by polymerizing alkyl (meth)acrylic acid ester monomers using atom transfer radical polymerization (ATRP), followed by reaction with a compound having at least two alkenyl groups, such as 1,5-hexadiene, 1,7-octadiene, or 1,9-decadien. In (meth)acrylic acid ester polymers obtained by the ATRP method, the "end group" refers to the group of carbon atoms in the chain of the (meth)acrylic acid ester polymer that is closest to the molecular end. If the group of carbon atoms contains an initiator residue, it is not considered an end group.

[0112] (Other components) The curable composition may further contain other components other than the polyether monool of the present invention, the reactive silicon group-containing oxyalkylene polymer, and the reactive silicon group-containing (meth)acrylic acid ester polymer. The curable composition may further contain other plasticizers other than the polyether monool of the present invention, but is not particularly limited.

[0113] Other components in the curable composition include, for example, curable compounds other than reactive silicon group-containing organic polymers, curing catalysts (silanol condensation catalysts), fillers (hollow bodies), plasticizers (excluding polyether monools of the present invention), thixotropic agents (anti-sagging agents), stabilizers, adhesion promoters, property modifiers, dehydrating agents, adhesion-improving 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. Other components may be used individually or in combination of two or more.

[0114] Applications of the curable composition include, for example, 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). It is particularly suitable for adhesive applications where a high modulus, good tensile strength, and elongation properties of the cured product are required.

[0115] 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, 2, and 8 are comparative examples, and Examples 3 to 7 are examples.

[0116] [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".

[0117] (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.

[0118] (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. With the column temperature 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).

[0119] (Metal Content) After purifying 20 g of polyether monool from each example, it was completely ashed using a burner. The ashed powder residue was mixed with 100 mL of hydrochloric acid aqueous solution to prepare the measurement sample. The Zn and Co content was measured using an ICP emission spectrometer (SPS3500 from SII Nanotechnology (Hitachi High-Tech Science)). The total amount of these detected metal elements was determined as the metal content of the polyol.

[0120] (Cloud Point) For each example, an aqueous solution of polyether monool was prepared by mixing 1 mL of polyether monool with 89 mL of water and 10 mL of 2-propanol. The aqueous solution of polyether monool was heated, and once the turbidity of the liquid became uniform, it was slowly cooled in air while monitoring the liquid temperature. The temperature at which the liquid changed from a cloudy state to a clear state was measured as the cloud point.

[0121] (Compatibility with hydrophobic compounds) The polyether monool and polybutadiene polyol of each example were mixed in a 20 mL vial in a volume ratio (polyether monool:polybutadiene polyol = 1:1). The compatibility of the mixture with hydrophobic compounds was evaluated according to the following criteria: A: The mixture is clear immediately after mixing and does not undergo phase separation even after being stored at room temperature (25°C) for two weeks. B: The mixture becomes cloudy immediately after mixing, or undergoes phase separation after being stored at room temperature (25°C) for two weeks.

[0122] (Diol component amount) The diol component corresponds to a molecular weight range of approximately twice the Mw value of the polyether monool determined by GPC. Therefore, the amount of diol component was calculated based on the value of (area of ​​molecular weight range from 1.8 × Mw to 2.2 × Mw) / (total area). The amount of diol component was evaluated according to the following criteria: A: Polyether diol component amount is less than 10% by mass. B: Polyether diol component amount is 10% by mass or more.

[0123] [Raw Materials] Initiator 1: n-butanol (a saturated monoalcohol with 4 carbon atoms, manufactured by Junsei Chemical Co., Ltd.) Initiator 2: Behenyl alcohol (a saturated higher monoalcohol with 22 carbon atoms derived from biomass, manufactured by Higher Alcohol Industry Co., Ltd., Hynol 22SS) Initiator 3: Cetanol (a saturated higher monoalcohol with 16 carbon atoms derived from biomass, manufactured by Higher Alcohol Industry Co., Ltd., cetyl alcohol NX-600) Initiator 4: Behenyl alcohol (containing 65% by mass of biomass-derived behenyl alcohol with 22 carbon atoms, manufactured by Higher Alcohol Industry Co., Ltd., NIKKOL Behenyl Alcohol 65) Initiator 5: Tridecanol (a saturated higher monoalcohol with 13 carbon atoms, manufactured by KH Neochem Co., Ltd.)

[0124] [Example 1] 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 polymerization in initiator 1 to obtain the polyether monool of Example 1. 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.

[0125] [Examples 2-7] Polyether monools for each example were obtained using the same procedure and conditions as in Example 1, except that the initiator was changed as shown in Table 1.

[0126] [Example 8] After alkoxideizing initiator 4, PO was subjected to ring-opening polymerization of the alkoxideized initiator 4 in the presence of a KOH catalyst. Subsequent neutralization and purification yielded the polyether monool of Example 8.

[0127]

[0128] In Table 1, m １ / m ２ The molecular weight (m) of the initiator residue is ２ ) Molecular weight of the PO chain (m １ It means the ratio of m. １ This value is obtained by subtracting the molecular weight of the initiator from the hydroxyl value-based molecular weight of the polyether monool. ２This value is obtained by subtracting 1 from the molecular weight of the initiator.

[0129] In Examples 3-7, the compatibility with polybutadiene polyols was better compared to Examples 1 and 2. In addition, since polyether monools were obtained using a DMC catalyst in Examples 3-7, the metal content was 1 ppm or more. In these Examples 3-7, the amount of diol impurities was reduced compared to Example 8, and high-quality polyether monools were obtained.

[0130] According to the present invention, it is possible to provide a polyether monool with improved compatibility with hydrophobic compounds and reduced risk of quality degradation due to diol components.

[0131] This application claims priority based on Japanese Patent Application No. 2024-201695, filed on 19 November 2024, and the entire contents of the said Japanese application are incorporated herein by reference.

Claims

1. A polyether monool having an initiator residue derived from a monohydric alcohol having 10 or more carbon atoms and a polyoxyalkylene chain, wherein the ratio of the molecular weight of the polyoxyalkylene chain to the molecular weight of the initiator residue is 7.0 or less, and the content of at least one metal selected from the group consisting of Zn, Co, Fe, Ni, Al, Sr, Mn, Cr, Cu, Sn, Pb, Mo, W, and V is 1.0 ppm or more.

2. The polyether monool according to claim 1, wherein the number of carbon atoms in the alkylene oxide-based unit in the polyoxyalkylene chain is 3 or more.

3. The polyether monool according to claim 1, wherein the cloud point is 10°C or lower.

4. The polyether monool according to claim 1, wherein the molecular weight on a hydroxyl value basis is 500 to 3000.

5. The polyether monool according to claim 1, wherein the monohydric alcohol having 10 or more carbon atoms is derived from biomass.

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