Polyether-based polymer and method for producing polyether-based polymer

Abstract

Disclosed are a polyether-based polymer containing a structural unit represented by general formula (1), and a method for producing the polyether-based polymer.

Description

Polyether polymers and methods for producing polyether polymers

[0001] This invention relates to polyether polymers and methods for producing polyether polymers.

[0002] Polyether polymers are widely used in various industrial fields, for example, as raw materials for compounds, additives, and solvents. For instance, due to their excellent hydrophilicity resulting from the presence of ether bonds, polyether polymers are used as surfactants and dispersants. Because polyether polymers can exhibit diverse properties depending on the selection of monomer types and synthesis conditions, various studies are being conducted on their molecular structure and manufacturing methods.

[0003] Patent Document 1 discloses a polyol with a molecular weight distribution Mw / Mn of 4 or more, obtained by reacting a compound containing an alkylene oxide compound (II) having a hydroxyl group in a base polyol (I) with a molecular weight of 2000 or more. The objective is to provide a polyol useful for producing a flexible polyurethane foam that has a good balance of excellent rebound elasticity, moderate hardness, and excellent durability.

[0004] Patent Document 2 discloses a method for producing superbranched polyols, characterized by polymerizing epoxy alcohol in the presence of phosphine, with the objective of developing an improved method for producing superbranched polyols.

[0005] International Publication No. 2012 / 018135, JP 2012-531511

[0006] Polyether polymers are often used by dissolving them in various solvents, and their solubility in solvents is one of the important properties that affects the range of applications of polyether polymers. Therefore, polyether polymers are required to exhibit solubility in a wide range of solvents (hereinafter referred to as "solvent solubility"), but polyether polymers have sometimes lacked sufficient solubility in some organic solvents.

[0007] An object of the present invention is to solve the above-mentioned problems, and an object of the present invention is to provide a polyether polymer excellent in solvent solubility and a method for producing the same.

[0008] As a result of studies conducted by the present inventors to solve the above problems, they have found that the problems can be solved by the following embodiments [1] to [7]. [1] A polyether polymer comprising a structural unit represented by the following general formula (1). (In the formula, R １ is a monovalent hydrocarbon group having 1 to 6 carbon atoms, and may have a substituent that does not contain active hydrogen. R ２ is a divalent hydrocarbon group having 1 to 6 carbon atoms, and may have a substituent that does not contain active hydrogen. * １ is a bond bonding to a carbon atom, and * ２ is a bond bonding to an etheric oxygen atom. ) [2] The polymer does not contain a structural unit represented by the following general formula (2), or contains a structural unit represented by the following general formula (2), and with respect to the structural unit represented by the following general formula (2), the molar ratio of the structural unit represented by the general formula (1) [structural unit represented by general formula (1) / structural unit represented by general formula (2)] is more than 1.0, The polyether polymer according to [1] above. (In the formula, R １ and R ２ are R in the general formula (1) １ and R ２ are the same as above. R ａ and R ｂ are each independently a hydroxyl group or a bond bonding to an etheric oxygen atom. * ３ is a bond bonding to a carbon atom. ) [3] The polyether polymer according to [1] or [2] above, wherein the peak top molecular weight in the molecular weight distribution is from 150 to 1,000,000. [4] R in the general formula (1) １ is a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, and may have a substituent that does not contain active hydrogen, and R in the general formula (1) ２ is a divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, and may have a substituent that does not contain active hydrogen, The polyether polymer according to any one of [1] to [3] above. [5] R in the general formula (1)１ and R ２ A polyether polymer according to any of [1] to [4] above, wherein the total number of carbon atoms is 2 to 4. [6] R in the general formula (1) １ is a methyl group, and R in the general formula (1) ２ ga-CH ２ - or -CH ２ -CH ２ - A polyether polymer according to any of [1] to [5] above. [7] A method for producing a polyether polymer according to any of [1] to [6] above, comprising ring-opening polymerization of an epoxy alcohol monomer represented by the following general formula (5) in the presence of an alkaline catalyst. (In the formula, R １ and R ２ R in the general formula (1) is １ and R ２ It is the same as this.

[0009] According to the present invention, a polyether polymer with excellent solvent solubility and a method for producing the same can be provided.

[0010] The following description is based on an example of an embodiment of the present invention. However, the embodiments shown below are illustrative examples for realizing the technical concept of the present invention, and the present invention is not limited to the following description.

[0011] In this specification, preferred forms of embodiments are shown, but combinations of two or more individual preferred forms are also preferred forms. When there are several numerical ranges for a given item, a preferred form can be created by selectively combining the lower and upper limits of those ranges. For example, from a statement like "preferably 10 to 90, more preferably 30 to 60," the "preferred lower limit (10)" and the "more preferred upper limit (60)" can be combined to become "10 to 60." Also, in numerical ranges described in this specification, the upper or lower limit of that numerical range may be replaced with the values ​​shown in the examples. In this specification, when a numerical range is described as "XX to YY," it means "XX or more and YY or less."

[0012] In this invention, "structural unit" refers to the structure in a polymer formed by the reaction of one monomer molecule. Furthermore, in this invention, "monomer" refers to a polymerizable compound that is a raw material for a polymer, and initiators and catalysts are not included in the concept of monomer.

[0013] [Polyether Polymer] The polyether polymer of the present invention is a polyether polymer containing a structural unit represented by the above general formula (1). The reason why the polyether polymer of the present invention has excellent solvent solubility is not clear, but it is presumed that the polyether polymer of the present invention has ether bonds that contribute to hydrophilicity, as well as specific hydrocarbon groups contained in the structural unit represented by the above general formula (1), and that these hydrocarbon groups contribute to improved hydrophobicity, resulting in a good balance between hydrophilicity and hydrophobicity, which is one of the reasons for its excellent solvent solubility.

[0014] <Structural unit represented by general formula (1)> The polyether polymer of the present invention contains a structural unit represented by the following general formula (1).

[0015] (In the formula, R １ R is a monovalent hydrocarbon group having 1 to 6 carbon atoms, and may have substituents that do not contain active hydrogen. ２ This is a divalent hydrocarbon group having 1 to 6 carbon atoms, and may have substituents that do not contain active hydrogen. １ This is a bond that connects to a carbon atom, * ２ (This is a bonding bond that attaches to an etheric oxygen atom.)

[0016] The structural unit represented by the general formula (1) in the polyether polymer of the present invention may be one type alone or two or more types.

[0017] In the above general formula (1), R １ The number of carbon atoms in the monovalent hydrocarbon group having 1 to 6 carbon atoms represented by is preferably 1 to 4, more preferably 1 to 3, even more preferably 1 or 2, and particularly preferably 1, from the viewpoint of the solvent solubility of the polyether polymer. Note that the number of carbon atoms of substituents is not included in this number.

[0018] Substituents that a monovalent hydrocarbon group having 1 to 6 carbon atoms may have are substituents that do not contain active hydrogen. In this specification, "active hydrogen" means a hydrogen atom bonded to an atom other than a carbon atom. Examples of substituents that do not contain active hydrogen include halogen atoms, cyano groups, nitro groups, alkoxy groups, aryloxy groups, acyloxy groups, etc. From the viewpoint of the solvent solubility of the polyether polymer, the carbon number of the substituent is preferably 6 or less, more preferably 3 or less, even more preferably 1 or less, and particularly preferably 0. Note that the following R １ In the explanation of this, "substituted or unsubstituted" means "having substituents that do not contain active hydrogen or having no substituents."

[0019] Examples of monovalent hydrocarbon groups having 1 to 6 carbon atoms include substituted or unsubstituted monovalent aliphatic hydrocarbon groups having 1 to 6 carbon atoms, and substituted or unsubstituted monovalent aromatic hydrocarbon groups having 6 carbon atoms. Among these, substituted or unsubstituted monovalent aliphatic hydrocarbon groups having 1 to 6 carbon atoms are preferred from the viewpoint of solvent solubility of polyether polymers. The substituted or unsubstituted monovalent aliphatic hydrocarbon groups having 1 to 6 carbon atoms may be linear, branched, or cyclic. The substituted or unsubstituted monovalent aliphatic hydrocarbon groups having 1 to 6 carbon atoms are preferably substituted or unsubstituted alkyl groups having 1 to 6 carbon atoms.

[0020] Examples of substituted or unsubstituted C1-C6 alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, 1-ethylpropyl group, 2-ethylpropyl group, 1-ethyl-2-methylpropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, 1-methylbutyl group, 2-methylbutyl group, 1,1-dimethylbutyl group, 2,2-dimethylbutyl group, 3,3-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, n-pentyl group, isopentyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, and n-hexyl group. Among these, the methyl group is preferred from the viewpoint of solvent solubility of the polyether polymer.

[0021] In the above general formula (1), R ２ This is a divalent hydrocarbon group having 1 to 6 carbon atoms, and may have substituents that do not contain active hydrogen. From the viewpoint of the solvent solubility of the polyether polymer, the number of carbon atoms in the divalent hydrocarbon group having 1 to 6 carbon atoms is preferably 1 to 4, more preferably 1 to 3, even more preferably 1 or 2, and particularly preferably 2. Note that the number of carbon atoms of substituents is not included in this number.

[0022] The substituents that a divalent hydrocarbon group having 1 to 6 carbon atoms may have are substituents that do not contain active hydrogen. Examples of substituents that do not contain active hydrogen include the above R １ Examples include substituents that do not contain active hydrogen, which may be present in the following R ２ In the explanation of this, "substituted or unsubstituted" means "having substituents that do not contain active hydrogen or having no substituents."

[0023] Examples of divalent hydrocarbon groups having 1 to 6 carbon atoms include substituted or unsubstituted divalent aliphatic hydrocarbon groups having 1 to 6 carbon atoms, and substituted or unsubstituted divalent aromatic hydrocarbon groups having 6 carbon atoms. Among these, substituted or unsubstituted divalent aliphatic hydrocarbon groups having 1 to 6 carbon atoms are preferred from the viewpoint of solvent solubility of polyether polymers. The substituted or unsubstituted divalent aliphatic hydrocarbon groups having 1 to 6 carbon atoms may be linear, branched, or cyclic. The substituted or unsubstituted divalent aliphatic hydrocarbon groups having 1 to 6 carbon atoms are preferably substituted or unsubstituted alkylene groups having 1 to 6 carbon atoms.

[0024] Examples of substituted or unsubstituted alkylene groups having 1 to 6 carbon atoms include methylene group, methylmethylene group, ethylene group (dimethylene group), 1-methylethylene group, 1-ethylethylene group, 1,2-dimethylethylene group, 1,1-dimethylethylene group, 1-ethyl-1-methylethylene group, 1-ethyl-2-methylethylene group, 1,1,2-trimethylethylene group, 1-ethyl-1,2-dimethylethylene group, 1-ethyl-2,2-dimethylethylene group, and 1,1,2,2-tetramethylethylene group. Diethylethylene group, 1,1-diethylethylene group, 1,2-diethylethylene group, 1-methyl-1-propylethylene group, 1-methyl-2-propylethylene group, 2-methyl-2-propylethylene group, 1-butylethylene group, trimethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 1-ethyltrimethylene group, 2-ethyltrimethylene group, 1,1-dimethyltrimethylene group, 1,2-dimethyltrimethylene group, 1,3-dimethyltrimethylene group, 1-propyl 2-propyltrimethylene group, 1-ethyl-1-methyltrimethylene group, 1-ethyl-2-methyltrimethylene group, 1-ethyl-3-methyltrimethylene group, 2-ethyl-1-methyltrimethylene group, 2-ethyl-2-methyltrimethylene group, 1,1,2-trimethyltrimethylene group, 1,1,3-trimethyltrimethylene group, 1,2,2-trimethyltrimethylene group, 1,2,3-trimethyltrimethylene group, tetramethylene group, 1-methyltetramethylene Examples include the ethylene group, 2-methyltetramethylene group, 1-ethyltetramethylene group, 2-ethyltetramethylene group, 1,1-dimethyltetramethylene group, 1,2-dimethyltetramethylene group, 1,3-dimethyltetramethylene group, 1,4-dimethyltetramethylene group, 2,2-dimethyltetramethylene group, 2,3-dimethyltetramethylene group, pentamethylene group, 1-methylpentamethylene group, 2-methylpentamethylene group, 3-methylpentamethylene group, and hexamethylene group. Among these, the ethylene group is preferred from the viewpoint of solvent solubility of the polyether polymer.

[0025] Among the above options, from the viewpoint of the solvent solubility of polyether polymers, R １However, it is a substituted or unsubstituted monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, and R ２ However, it is preferable that it be a substituted or unsubstituted divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, R １ However, it is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and R ２ However, it is more preferable that it be a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, R １ However, it is an unsubstituted alkyl group having 1 to 6 carbon atoms, and R ２ However, it is more preferable that it be an unsubstituted alkylene group having 1 to 6 carbon atoms, R １ is a methyl group, and R ２ ga-CH ２ - or -CH ２ -CH ２ - is particularly preferable.

[0026] In the above general formula (1), R １ and R ２ The total number of carbon atoms is preferably 2 to 4, more preferably 2 or 3, from the viewpoint of the solvent solubility of the polyether polymer.

[0027] * in the above general formula (1) ２ The etheric oxygen atom to which it can bond is the * ２ Examples include etheric oxygen atoms in structural units represented by the above general formula (1), which are different from structural units having *, and etheric oxygen atoms in structural units represented by the general formula (2), which will be described later. １ The carbon atom to which it is bonded is the * １ * in a structural unit represented by the above general formula (1), which is different from the structural unit having ２ The carbon atom to which it is bonded (i.e., R in general formula (1)) ２ The carbon atoms contained in, and the R in the structural unit represented by the general formula (2) described later. ａ The carbon atom to which it is bonded (i.e., R in general formula (2)) ２ (The carbon atoms contained in) or R ｂ Examples include carbon atoms to which the compound is bonded (i.e., the methylene group in general formula (2)), and carbon atoms derived from the initiator.

[0028] (Content of structural units represented by general formula (1)) The content of the structural units represented by the above general formula (1) in the polyether polymer of the present invention, based on the number of carbon atoms, is preferably 50% or more, more preferably 60% or more, even more preferably 70% or more, even more preferably 80% or more, and particularly preferably 90% or more, and may also be 100% or less, or 97% or less. In the present invention, the content of each structural unit based on the number of carbon atoms means the ratio (%) of the total number of carbon atoms of the structural unit to the total number of carbon atoms of the polyether polymer, and can be measured by the method described in the examples.

[0029] <Structural unit represented by general formula (2)> The polyether polymer of the present invention may or may not contain the structural unit represented by the following general formula (2).

[0030] (In the formula, R １ and R ２ R in the general formula (1) is １ and R ２ It is the same as R ａ and R ｂ These are bonds that independently attach to a hydroxyl group or an etheric oxygen atom. ３ (This is a bonding bond that attaches to a carbon atom.)

[0031] When the polyether polymer of the present invention contains a structural unit represented by the above general formula (2), the structural unit represented by the above general formula (2) may be one type or two or more types. ３ The carbon atom to which it is bonded is the * ３ R in a structural unit represented by the above general formula (2), which is different from the structural unit having R ａ The carbon atom to which it is bonded (i.e., R in general formula (2)) ２ (The carbon atoms contained in) or R ｂ The carbon atom to which it is bonded (i.e., the methylene group in general formula (2)), and the * in the structural unit represented by the above general formula (1) ２ The carbon atom to which it is bonded (i.e., R in general formula (1))２ Examples include carbon atoms contained in the compound, and carbon atoms derived from the initiator.

[0032] In the above general formula (2), R ａ and R ｂ These are bonds that independently attach to a hydroxyl group or an etheric oxygen atom. That is, the structural unit represented by the above general formula (2) is represented by the following general formula (2a), R ａ and R ｂ A structural unit in which all are hydroxyl groups, represented by the following general formula (2b), R ａ and R ｂ These are structural units in which bonds are attached to etheric oxygen atoms, represented by the following general formula (2c), R ａ is a hydroxyl group, R ｂ R is a structural unit in which a bond is attached to an etheric oxygen atom, represented by the following general formula (2d), ｂ is a hydroxyl group, R ａ This represents one of the structural units in which a bond is attached to an etheric oxygen atom.

[0033] (In the formula, * １ This is a bond that connects to a carbon atom. ４ (This is a bonding bond that attaches to an etheric oxygen atom.)

[0034] When the polyether polymer of the present invention contains a structural unit represented by the above general formula (2), the molar ratio of the structural unit represented by the above general formula (1) to the structural unit represented by the above general formula (2) [structural unit represented by general formula (1) / structural unit represented by general formula (2)] (hereinafter also referred to as "molar ratio [(1) / (2)]") is preferably greater than 1.0, more preferably 5.0 or more, even more preferably 8.0 or more, even more preferably 10.0 or more, particularly preferably 16.0 or more, and may also be 100.0 or less, 50.0 or less, or 30.0 or less. The above molar ratio [(1) / (2)] can be measured by the method described in the examples.

[0035] (Content of Structural Unit Represented by General Formula (2)) From the viewpoint of increasing entanglement of molecular chains to improve strength, the content based on the number of carbon atoms of the structural unit represented by general formula (2) above in the polyether polymer of the present invention is preferably 50% or less, more preferably 40% or less, still more preferably 30% or less, even more preferably 20% or less, particularly preferably 10% or less, and may be 0% or more, or 3% or more.

[0036] (Total Content of Structural Unit Represented by General Formula (1) and Structural Unit Represented by General Formula (2)) From the viewpoint of solvent solubility of the polyether polymer, the total content based on the number of carbon atoms of the structural unit represented by general formula (1) above and the structural unit represented by general formula (2) above in the polyether polymer of the present invention is preferably 50% or more, more preferably 60% or more, still more preferably 80% or more, even more preferably 90% or more, particularly preferably 95% or more, and may be 100% or 99% or less.

[0037] <Structure Represented by General Formula (3)> The polyether polymer of the present invention may or may not contain a structure represented by the following general formula (3).

[0038] (wherein, R １ and R ２ are the same as R １ and R ２ in general formula (1) above. R ３ is a monovalent hydrocarbon group, and may have a substituent that does not contain active hydrogen. L is an ester bond (-C(=O)-O-) or an ether bond (-O-). * ４ is a bond that binds to an etheric oxygen atom. )

[0039] When the polyether polymer of the present invention contains the structure represented by general formula (3) above, the structure represented by general formula (3) may be of one type alone or two or more types. The structure represented by general formula (3) above is attached to the bond * １ of the structural unit represented by general formula (1) above as R ３ - or R ３This corresponds to a structure in which -C(=O)- is bonded, and is a structure that includes the structural unit represented by the general formula (1) above.

[0040] In the above general formula (3), R ３ R is a monovalent hydrocarbon group and may have substituents that do not contain active hydrogen. ３ The number of carbon atoms in the monovalent hydrocarbon group represented by is preferably 1 to 30, more preferably 3 to 25, even more preferably 5 to 22, and particularly preferably 7 to 20, from the viewpoint of ease of manufacture and enhanced surface activity. Note that the number of carbon atoms of substituents is not included in this number.

[0041] The substituents that the above monovalent hydrocarbon group may have are substituents that do not contain active hydrogen. Examples of substituents that do not contain active hydrogen include the above R １ Examples include substituents that do not contain active hydrogen, which may be present in the following R ３ In the explanation of this, "substituted or unsubstituted" means "having substituents that do not contain active hydrogen or having no substituents."

[0042] Examples of monovalent hydrocarbon groups include substituted or unsubstituted monovalent aliphatic hydrocarbon groups and substituted or unsubstituted monovalent aromatic hydrocarbon groups. Among these, substituted or unsubstituted monovalent aliphatic hydrocarbon groups are preferred. Examples of substituted or unsubstituted monovalent aliphatic hydrocarbon groups include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, and hexadecyl groups; alkenyl groups; alkynyl groups; and so on. These aliphatic hydrocarbon groups may be in linear, branched, or cyclic form. Among these, R ３ The monovalent hydrocarbon group represented is preferably a substituted or unsubstituted alkyl group, more preferably a substituted or unsubstituted linear alkyl group, and even more preferably an unsubstituted linear alkyl group, from the viewpoint of ease of manufacture and enhanced surface activity.

[0043] (Content of the structure represented by general formula (3)) When the polyether polymer of the present invention contains the structure represented by the general formula (3) above, the content of the structure represented by the general formula (3) in the polyether polymer of the present invention is preferably 0.001 to 50 mol%, more preferably 0.005 to 30 mol%, even more preferably 0.01 to 20 mol%, and particularly preferably 0.05 to 10 mol%, of the total structural units (100 mol%) of the polyether polymer.

[0044] <Other Structural Units> The polyether polymer of the present invention may or may not contain structural units other than the structural unit represented by the above general formula (1) and the structural unit represented by the above general formula (2) (hereinafter also referred to as "other structural units"). From the viewpoint of the solvent solubility of the polyether polymer of the present invention, the total content of other structural units based on the number of carbon atoms is preferably 50% or less, more preferably 40% or less, even more preferably 20% or less, even more preferably 10% or less, and particularly preferably 5% or less, and may be 0% or 1% or more.

[0045] <Peak Top Molecular Weight of Molecular Weight Distribution> The peak top molecular weight of the molecular weight distribution of the polyether polymer of the present invention is preferably 150 to 1,000,000, more preferably 160 to 700,000, even more preferably 170 to 300,000, even more preferably 180 to 100,000, even more preferably 190 to 30,000, and particularly preferably 200 to 10,000, from the viewpoint of the handlingability and solvent solubility of the polyether polymer. The peak top molecular weight of the molecular weight distribution can be measured by the method described in the examples.

[0046] [Method for producing polyether polymers] The present invention provides a method for producing polyether polymers, which involves ring-opening polymerization of an epoxy alcohol monomer represented by the following general formula (5) in the presence of an alkaline catalyst.

[0047] (In the formula, R １ and R２ is the same as R １ and R ２ in the above general formula (1).)

[0048] R in the above general formula (5) １ and R ２ are the same as R １ and R ２ in the general formula (1), and preferred embodiments are also the same. Among the epoxy alcohol monomers represented by the above general formula (5), 3,4-epoxy-3-methylbutan-1-ol and 2,3-epoxy-2-methyl-1-propanol are preferred from the viewpoints of availability and solvent solubility of the polyether polymer. 3,4-epoxy-3-methylbutan-1-ol and 2,3-epoxy-2-methyl-1-propanol are commercially available. In addition, 3,4-epoxy-3-methylbutan-1-ol and 2,3-epoxy-2-methyl-1-propanol can be synthesized, for example, by the method described in Japanese Patent Application Laid-Open No. 2003-2697. One epoxy alcohol monomer may be used alone, or two or more epoxy alcohol monomers may be used in combination.

[0049] In the method for producing the polyether polymer of the present invention, a monomer other than the epoxy alcohol monomer represented by the above general formula (5) may or may not be used. In 100 mol% of the monomers used in the method for producing the polyether polymer of the present invention, from the viewpoint of the solvent solubility of the polyether polymer, the content of the epoxy alcohol monomer represented by the above general formula (5) is preferably 60 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, even more preferably 95 mol% or more, even more preferably 97 mol% or more, particularly preferably 99 mol% or more, and may be 100 mol%.

[0050] In the method for producing polyether polymers of the present invention, an alkaline catalyst is used as a catalyst for ring-opening polymerization. By using an alkaline catalyst, cleavage of the bond (C-O) between the unsubstituted secondary carbon atom and the oxygen atom among the two carbon atoms constituting the oxirane ring in the epoxy alcohol monomer represented by the general formula (5) above is facilitated, and the structural unit represented by the general formula (1) above is suitably formed. As the alkaline catalyst, known alkaline catalysts can be used, for example, alkali metal hydroxides such as potassium hydroxide and sodium hydroxide; alkali metal alkoxides such as potassium methoxide and sodium methoxide; quaternary ammonium hydroxide salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide; anion exchange resins; and the like. Among these, potassium methoxide, sodium methoxide, tetrabutylammonium hydroxide, and anion exchange resins are preferred. These alkaline catalysts may be used individually or in combination of two or more. The molar ratio of the alkali catalyst to the epoxy alcohol monomer [alkali catalyst / epoxy alcohol monomer] is preferably 0.005 to 20, more preferably 0.01 to 15, and even more preferably 0.02 to 10.

[0051] When performing ring-opening polymerization, initiators may be used as needed. Examples of initiators include water, alcohols, and organic acids. Examples of alcohols include monoalcohols such as methanol, ethanol, octanol, decanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, and arachidyl alcohol; epoxy alcohols such as 2-methyl-2,3-epoxy-1-propanol and 3,4-epoxy-3-methylbutan-1-ol; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-cyclohexanediol, and 1,3-butanediol. Examples of initiators include diols such as 1,4-butanediol, 1,6-hexanediol, and 1,4-cyclohexanediol; polyhydric alcohols obtained by the reaction of monoalcohols such as 2-dodecyloxy-2-methyl-1,4-butanediol with epoxy alcohols; polyhydric alcohols obtained by the reaction of monocarboxylic acids such as lauric acid-2,4-dihydroxy-2-methylbutyl with epoxy alcohols; and polyhydric alcohols of three or higher valencies such as glycerin, diglycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, and tripentaerythritol. Examples of organic acids include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, and arachidic acid. These initiators may be used individually or in combination of two or more. Among the above initiators, alcohols are preferred, with methanol, lauryl alcohol, 2,4-dihydroxy-2-methylbutyl laurate, 3,4-epoxy-3-methylbutan-1-ol, and ethylene glycol being more preferred. These initiators may be used individually or in combination of two or more. The molar ratio of the initiator to the epoxy alcohol monomer [initiator / epoxy alcohol monomer] is preferably 0.01 to 60, more preferably 0.05 to 50, and even more preferably 0.1 to 40.

[0052] The mixing order of the epoxy alcohol monomer, alkaline catalyst, and initiator is not particularly limited, but from the viewpoint of ensuring a homogeneous reaction, it is preferable to sequentially add the epoxy alcohol monomer to the initiator under heating or to a mixture of the initiator and alkaline catalyst under heating. Ring-opening polymerization is preferably carried out under an inert atmosphere such as nitrogen with stirring. Ring-opening polymerization may also be carried out under heating. The polymerization temperature is preferably 15 to 200°C, more preferably 30 to 150°C, and even more preferably 50 to 100°C.

[0053] After polymerization is complete, the product may be purified by washing, concentration, or other methods as needed.

[0054] The present invention will be described in more detail below with reference to examples, but the present invention is not limited in any way by these examples.

[0055] [Production of Polyether Polymers] Example 1 A separable flask equipped with a stirrer, thermometer, condenser, and nitrogen inlet tube was mixed with 4.35 moles of methanol as an initiator and 0.87 moles of potassium methoxide as an alkaline catalyst. The mixture was heated to 60°C while stirring and flowing nitrogen. Subsequently, while continuing the nitrogen flow and stirring, 100 moles of e-IPEA (3,4-epoxy-3-methylbutan-1-ol) as a monomer was added dropwise at a rate of 3.9 moles / hour to carry out ring-opening polymerization of e-IPEA. During the polymerization reaction, the internal temperature of the reaction mixture (polymerization temperature) was maintained at 60°C. After 8 hours, the conversion rate of e-IPEA was confirmed to be 99% or higher by gas chromatography (GC), and the reaction mixture was cooled to room temperature to obtain a polyether polymer.

[0056] Examples 2-9, Comparative Examples 1-3 In Example 1, polyether polymers were obtained in the same manner as in Example 1, except that the type of raw material, the amount charged, the dropping rate, and the polymerization temperature were changed as shown in Table 1. However, in Example 3, a dimethylacetamide (DMA) solution containing 20% ​​by mass of the monomer e-IPEA was added dropwise.

[0057] [Measurement of the content and molar ratio of each structural unit [(1) / (2)]] The polyether polymers obtained in each example were used as the target of measurement and measured using a nuclear magnetic resonance spectrometer (Bruker BioSpin, Inc., product name "AVANCE 600") by the reverse gate decoupling method. １３ ¹³C-NMR measurement (solvent: deuterium methanol) was performed. １３ In the 1C-NMR spectrum, the R of the structural unit represented by the above general formula (1) １ The integral value of the peak attributable to the methyl group (in the polyether polymer obtained in the examples) is 1, and the R of the structural unit represented by the general formula (2) above is also R. １ The integral value 2 of the peak attributed to the methyl group (in the polyether polymer obtained in the examples) and the integral value 2 were determined. For example, in Example 1, the signal attributed to the methyl group of the structural unit represented by the general formula (1) was observed at 25 ppm, and the signal attributed to the methyl group of the structural unit represented by the general formula (2) was observed at 20-23 ppm. The ratio of integral value 1 and integral value 2 obtained above [integral value 1 / integral value 2] was taken as the molar ratio of the structural unit represented by the general formula (1) to the structural unit represented by the general formula (2) [(1) / (2)]. １３In the 1C-NMR spectrum, the integral value 3 of the peak originating from all carbon atoms in the polyether polymer and the integral value 4 of the peak originating from all carbon atoms in the structural unit represented by general formula (1) and the structural unit represented by general formula (2) were determined, respectively, and [integral value 4 × 100 / integral value 3] was taken as the total content (%) of the structural unit represented by general formula (1) and the structural unit represented by general formula (2) in the polyether polymer, based on the number of carbon atoms. From this total content and the molar ratio [(1) / (2)] obtained above, the content based on the number of carbon atoms of the structural unit represented by general formula (1) and the content based on the number of carbon atoms of the structural unit represented by general formula (2) were calculated, respectively, using the following formulas. The percentage of the structural unit represented by general formula (1) based on the number of carbon atoms = A × [B / (1 + B)] The percentage of the structural unit represented by general formula (2) based on the number of carbon atoms = A × [1 / (1 + B)] (In the formulas, A means the total percentage of the structural unit represented by general formula (1) and the structural unit represented by general formula (2) based on the number of carbon atoms, and B means the molar ratio [(1) / (2)].)

[0058] [Method for Measuring Peak Top Molecular Weight] The peak top molecular weight of the polyether polymers obtained in each example and comparative example was measured using the following procedure. First, GPC measurements were performed on the polyether polymers obtained in each example and comparative example under the following conditions. For those for which a peak top molecular weight could be obtained, that peak top molecular weight was adopted as the peak top molecular weight of the polyether polymer. On the other hand, for those for which the peak top molecular weight could not be identified in the GPC measurement, matrix-assisted laser desorption / ionization-time-of-flight mass spectrometry (MALDI-TOF-MS) measurements were performed under the following conditions, and the peak top molecular weight of the obtained mass spectrum was adopted as the peak top molecular weight of the polyether polymer. Cases in which the peak top molecular weight could not be identified in the GPC measurement refer to either the appearance of a negative peak in the GPC elution curve or the overlapping of multiple peaks originating from low molecular weight components, making it impossible to identify the peak top. (GPC measurement conditions) Measurement device: Size exclusion high-performance liquid chromatography system "HLC-8320GPC" (manufactured by Tosoh Corporation) Column: Methacrylic polymer column "TSKgel α-M" (manufactured by Tosoh Corporation) Standard sample: Polymethyl methacrylate solvent and mobile phase: DMSO (containing 5 mM sodium nitrate) Flow rate: 0.8 mL / min Temperature: 50°C Sample solution concentration: 0.1% by mass (filtered with a 0.45 μm aperture filter) Injection volume: 100 μL Detector: Attached RI detector (MALDI-TOF-MS measurement conditions) Measurement device: Bruker Japan, product name "ultraflextreme" Analysis mode: Positive, reflectron mode Matrix: α-cyano-4-hydroxycinnamate Cationizing agent: Sodium trifluoroacetate Measurement method: A mixture of sample / methanol solution and matrix / cationizing agent / THF solution was dropped onto a MALDI target plate, dried, and then subjected to measurement.

[0059] [Evaluation of Solvent Solubility] The solubility (mass of dissolved polyether polymer (g) / volume of solvent (mL)) of the polyether polymers obtained in each example and comparative example in the solvent (isopropanol (IPA), acetone, tetrahydrofuran (THF), or water) was measured at 25°C and judged as follows: (Evaluation criteria for IPA, acetone, and THF) A: Solubility is greater than 0.1 g / mL. B: Solubility is 0.003 g / mL or more and 0.1 g / mL or less. C: Solubility is less than 0.003 g / mL. (Evaluation criteria for water) A: At 0.001 g / mL, it was possible to dissolve or disperse uniformly in water. C: At 0.001 g / mL, the polyether polymer aggregated and precipitated.

[0060] *1: This refers to the carbon number-based content (%) of the structural units represented by each general formula. *2: This refers to the molar ratio of the structural units represented by general formula (1) to the structural units represented by general formula (2) [structural units represented by general formula (1) / structural units represented by general formula (2)].

[0061] Table 1 details the alkaline catalyst and monomers as follows. Note that the amount of alkaline catalyst charged in Table 1 is the amount of solids charged. (Alkaline Catalyst) ・Potassium methoxide: 30% by mass methanol solution ・Sodium methoxide: 28% by mass methanol solution ・Tetrabutylammonium hydroxide: 37% by mass methanol solution ・Ion exchange resin: Manufactured by Fujifilm Wako Chemical Co., Ltd., product name "Strongly Basic Anion Exchange Resin No. 8 (OH type)" (Monomers) ・e-IPEA: 3,4-epoxy-3-methylbutan-1-ol ・e-MALY: 2-methyl-2,3-epoxy-1-propanol ・Glycidol: 2,3-epoxy-1-propanol

[0062] Table 1 shows that the polyether polymers of Examples 1 to 9 exhibit excellent solvent solubility.

Claims

1. A polyether polymer containing a structural unit represented by the following general formula (1). (In the formula, R １ R is a monovalent hydrocarbon group having 1 to 6 carbon atoms, and may have substituents that do not contain active hydrogen. ２ This is a divalent hydrocarbon group having 1 to 6 carbon atoms, and may have substituents that do not contain active hydrogen. １ This is a bond that connects to a carbon atom, * ２ (This is a bonding bond that attaches to an etheric oxygen atom.) 2. The polyether polymer according to claim 1, which does not comprise a structural unit represented by the following general formula (2), or comprises a structural unit represented by the following general formula (2), and the molar ratio of the structural unit represented by the general formula (1) to the structural unit represented by the following general formula (2) [structural unit represented by general formula (1) / structural unit represented by general formula (2)] is more than 1.

0. (wherein R １ and R ２ are R in said general formula (1) １ and R ２ are the same as defined above. R ａ and R ｂ are each independently a bonding hand bonding to a hydroxyl group or an etheric oxygen atom. * ３ is a bonding hand bonding to a carbon atom.) 3. The polyether polymer according to claim 1 or 2, wherein the peak top molecular weight of the molecular weight distribution is 150 to 1,000,000.

4. R in the general formula (1) １ However, it is a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, and may have substituents that do not contain active hydrogen, and R in the general formula (1) ２ The polyether polymer according to claim 1 or 2, wherein the substituent is a divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms and does not contain active hydrogen.

5. R in the general formula (1) １ and R ２ The polyether polymer according to claim 1 or 2, wherein the total number of carbon atoms is 2 to 4.

6. R in the general formula (1) １ is a methyl group, and R in the general formula (1) ２ ga-CH ２ - or -CH ２ -CH ２ - The polyether polymer according to claim 1 or 2.

7. A method for producing a polyether polymer according to claim 1 or 2, comprising ring-opening polymerization of an epoxy alcohol monomer represented by the following general formula (5) in the presence of an alkaline catalyst. (In the formula, R １ and R ２ R in the general formula (1) is １ and R ２ It is the same as this.

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