Method for producing polycarboxylate compound

Abstract

The present invention addresses the problem of providing a method whereby it is possible to produce a polycarboxylic acid ester compound having a reduced content of specific impurities and further improved purity. As a solution, provided is a method for producing a polycarboxylic acid ester compound (1) represented by general formula (1), which is characterized by comprising an etherification reaction step in which a polyhydroxyaromatic compound represented by general formula (2) and a halogenated carboxylic acid ester compound represented by general formula (3) are subjected to an etherification reaction in the presence of a ketone solvent, the content of a monovalent aliphatic alcohol in the ketone solvent is 0.04 mass% or less, and the content of water is 2 mass% or less.

Description

Technical Field

[0001] The present invention relates to a method for producing a polycarboxylate compound. More specifically, it relates to a method for producing a polycarboxylate compound with an increased purity by reducing the content of specific impurities. Background Art

[0002] Polycarboxylic compounds are generally used as raw materials for polyamides or allyl ester compounds, additives such as plasticizers and curing agents, and a dicarboxylic compound using a bisphenol compound as a raw material is also known (Patent Documents 1, 2, etc.).

[0003] In recent years, in the application fields of these materials, there has been an increasing demand for various performance improvements. In order to exhibit the desired properties, the raw materials used for the materials are required to have further improved quality.

[0004] As a method for producing a dicarboxylic compound using a bisphenol compound as a raw material, a method is known in which an etherification reaction is carried out using a bisphenol compound and a halo carboxylic acid or its ester as raw materials to synthesize a dicarboxylic acid or its ester compound. As a method for the etherification reaction to obtain a dicarboxylic compound with improved quality, for example, it is known that when the etherification reaction is carried out in a state where the water remaining in the reaction vessel has increased, the reaction rate is retarded and the yield of the target compound is reduced due to an increase in impurities (Patent Document 3).

[0005] Patent Documents Patent Document 1: Japanese Patent Application Laid-Open No. 62-292819 Patent Document 2: Japanese Patent Application Laid-Open No. 05-170702 Patent Document 3: International Publication No. 2021 / 054309 Summary of the Invention Against the background of the above-known manufacturing methods, in order to further improve the quality of a dicarboxylic ester compound using a bisphenol compound as a raw material, in-depth research was carried out. As a result, it was found that in the process of carrying out an etherification reaction using a bisphenol compound and a halo carboxylic acid ester as raw materials, when a ketone solvent is used as the solvent, there is sometimes a problem that impurities increase and the purity cannot be improved.

[0006] After in-depth research by the present inventors, as one of the impurities, a by-product of the overreaction of the halo carboxylic acid ester was found, and this impurity was generated due to the water contained in the ketone solvent used in the raw materials. In addition, it was found that the ketone solvent used in the raw materials contains an alcohol as an impurity, and this alcohol impurity generates a by-product having an ester group different from the ester group of the target compound. That is, it was found that the by-products generated thereby hinder the improvement of the purity of the target dicarboxylic ester compound.

[0007] As a method for reducing the by-product, for example, a purification method by crystallization operation and recrystallization operation can be cited. However, as shown in the comparative examples described later, it is known that in the purification method by recrystallization operation, the impurity cannot be sufficiently reduced.

[0008] When the target polycarboxylate compound contains impurities with different substituents, there is a risk that problems may occur during the manufacture of the material obtained by using the compound, or that the physical properties of the material may be adversely affected.

[0009] Against the background of the above problems discovered by the present inventors, an object of the present invention is to provide a method for producing a polycarboxylate compound in which the content of specific impurities is reduced and the purity is further improved.

[0010] The present inventors have found that in a method for producing a polycarboxylate compound using a ketone solvent in an etherification reaction, the above problems can be solved by using a ketone solvent having a specific composition, and thus the present invention has been completed.

[0011] The present invention is as follows.

[0012] 1. A method for producing a polycarboxylate compound (1) represented by the general formula (1), characterized by including an etherification reaction step of using a polyhydroxy aromatic compound represented by the general formula (2) and a haloalkanoate compound represented by the general formula (3) to perform an etherification reaction in the presence of a ketone solvent, wherein the content of monohydric aliphatic alcohol in the ketone solvent is 0.04% by mass or less, and the content of water is 2% by mass or less. [Chemical formula 1]

[0013] In the formula (1), each Ar independently represents a "2 + m-valent" monooxy aromatic hydrocarbon group having 6 to 20 carbon atoms, each R1 independently represents a linear or branched alkyl group having 1 to 6 carbon atoms or a cyclic alkyl group having 5 to 6 carbon atoms, each R2 independently represents a linear or branched alkylene group having 1 to 4 carbon atoms, R3 represents a linear or branched alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, each m independently represents 0, 1 or 2, n represents 1 or 2, X represents a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, a divalent group represented by the general formula (1a), (1b) or (1c), or a trivalent group represented by the general formula (1d) or (1e). In addition, in the general formula (1), the oxygen atom possessed by Ar is bonded to the aromatic hydrocarbon group and R2 contained in Ar. [Chemical formula 2]

[0014] In general formula (1a), R5 and R6 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms. R5 and R6 may be bonded to each other to form a cycloalkanediyl group having 5 to 20 carbon atoms as a whole. In general formula (1b), Ar1 each independently represents an aryl group having 6 to 12 carbon atoms. In general formulas (1a), (1b), and (1c), * each represents a bonding position. [Chemical formula 3]

[0015] In general formula (1d), R7 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms. In general formula (1e), R8 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. In general formulas (1d) and (1e), * each represents a bonding position. [Chemical formula 4]

[0016] The definitions of Ar, R1, m, n, and X in general formula (2) are the same as those in general formula (1). Additionally, in general formula (2), the oxygen atom possessed by Ar is bonded to the aromatic hydrocarbon group contained in Ar and the hydrogen atom (H) described in general formula (2). [Chemical formula 5]

[0017] The definitions of R2 and R3 in general formula (3) are the same as those in general formula (1). Y represents a halogen atom.

[0018] 2. The manufacturing method according to 1., characterized in that the ketone solvent is a ketone solvent having 3 to 9 carbon atoms.

[0019] 3. The manufacturing method according to 2., characterized in that the ketone solvent is acetone or methyl isobutyl ketone.

[0020] 4. The production method according to any one of 1. to 3., characterized in that the Ar is any one selected from 1-oxyphenyl-4-yl, 1-oxyphenyl-3-yl, 1-oxyphenyl-2-yl, 1-oxynaphthalen-2-yl, 1-oxynaphthalen-4-yl, 1-oxynaphthalen-5-yl, 2-oxynaphthalen-1-yl, 2-oxynaphthalen-6-yl, 2-oxynaphthalen-7-yl, 4-oxy-3-phenylphenyl-1-yl, 9-oxyphenanthren-3-yl, 10-oxyphenanthren-9-yl, 2-oxyanthren-7-yl, 1-oxy-3-phenylnaphthalen-4-yl, 1-oxy-3-phenylnaphthalen-5-yl, 2-oxy-1-phenylnaphthalen-6-yl, 2-oxy-1-phenylnaphthalen-7-yl, 2-oxy-3-phenylnaphthalen-6-yl, 2-oxy-3-phenylnaphthalen-7-yl, 4-oxy-3-(1-naphthyl)phenyl-1-yl, 4-oxy-3-(2-naphthyl)phenyl-1-yl, 4-oxy-3,5-diphenylphenyl-1-yl, 4-oxy-2-phenylphenanthren-6-yl, 4-oxy-2-phenylphenanthren-7-yl, 4-oxy-2-phenylphenanthren-8-yl, 4-oxy-2-phenylphenanthren-9-yl, 4-oxy-2-phenylphenanthren-10-yl, and 2-oxy-3-phenylanthren-7-yl.

[0021] 5. The production method according to 4., characterized in that n is 2 and X is a direct bond.

[0022] 6. The production method according to 5., characterized in that R3 is a linear or branched alkyl group having 1 to 10 carbon atoms.

[0023] According to the production method of the present invention, since specific impurities contained in the polycarboxylate compound (1) that cannot be removed by crystallization or recrystallization operations or have a small removal effect can be reduced, a polycarboxylate compound (1) with improved quality can be produced. Detailed implementation mode

[0024] <Production method of the present invention> The production method of the polycarboxylate compound (1) represented by the general formula (1) of the present invention includes an etherification reaction step of using a polyhydroxy aromatic compound represented by the general formula (2) and a haloalkyl carboxylate compound represented by the general formula (3) to carry out an etherification reaction in the presence of a ketone solvent, wherein the content of monohydric aliphatic alcohol in the ketone solvent is 0.04% by mass or less and the water content is 2% by mass or less.

[0025] <Polycarboxylate compound (1) represented by the general formula (1)> In the general formula (1), each Ar independently represents a "2 + m-valent" monoxy aromatic hydrocarbon group having 6 to 20 carbon atoms. In addition, in the general formula (1), the oxygen atom possessed by Ar is bonded to the aromatic hydrocarbon group and R2 contained in Ar.

[0026] First, the case where m is 0 will be described, that is, a divalent monoxy aromatic hydrocarbon group having 6 to 20 carbon atoms will be described.

[0027] Among the divalent monoxy aromatic hydrocarbon groups having 6 to 20 carbon atoms, a divalent monoxy aromatic hydrocarbon group having 6 to 16 carbon atoms is preferred, a divalent monoxy aromatic hydrocarbon group having 6 to 14 carbon atoms is more preferred, a divalent monoxy aromatic hydrocarbon group having 6, 10 or 14 carbon atoms is further preferred, and a divalent monoxy aromatic hydrocarbon group having 10 or 14 carbon atoms is particularly preferred.

[0028] Specific examples of the divalent monoxy aromatic hydrocarbon group having 6 carbon atoms include: 1-oxybenzene-4-yl, 1-oxybenzene-3-yl, 1-oxybenzene-2-yl.

[0029] Specific examples of the divalent monoxy aromatic hydrocarbon group having 10 carbon atoms include: 1-oxynaphthalene-2-yl, 1-oxynaphthalene-4-yl, 1-oxynaphthalene-5-yl, 2-oxynaphthalene-1-yl, 2-oxynaphthalene-6-yl, 2-oxynaphthalene-7-yl.

[0030] Specific examples of the divalent monoxy aromatic hydrocarbon group having 12 carbon atoms include: 4-oxy-3-phenylbenzene-1-yl.

[0031] Specific examples of the divalent monoxy aromatic hydrocarbon group having 14 carbon atoms include: 9-oxyphenanthrene-3-yl, 10-oxyphenanthrene-9-yl, 2-oxyanthracene-7-yl.

[0032] Among them, the divalent monoxy aromatic hydrocarbon group having 14 carbon atoms is more preferably a monoxyphenanthryl group. Therefore, 9-oxyphenanthrene-3-yl or 10-oxyphenanthrene-9-yl is further preferred.

[0033] Specific examples of the divalent monoxy aromatic hydrocarbon group having 16 carbon atoms include: 1-oxy-3-phenylnaphthalene-4-yl, 1-oxy-3-phenylnaphthalene-5-yl, 2-oxy-1-phenylnaphthalene-6-yl, 2-oxy-1-phenylnaphthalene-7-yl, 2-oxy-3-phenylnaphthalene-6-yl, 2-oxy-3-phenylnaphthalene-7-yl, 4-oxy-3-(1-naphthyl)benzene-1-yl, 4-oxy-3-(2-naphthyl)benzene-1-yl.

[0034] Specific examples of the divalent monoxy aromatic hydrocarbon group having 18 carbon atoms include: 4-oxy-3,5-diphenylbenzene-1-yl.

[0035] Specific examples of the divalent mono-oxy aromatic hydrocarbon group having 20 carbon atoms include: 4-oxy-2-phenylphenanthren-6-yl, 4-oxy-2-phenylphenanthren-7-yl, 4-oxy-2-phenylphenanthren-8-yl, 4-oxy-2-phenylphenanthren-9-yl, 4-oxy-2-phenylphenanthren-10-yl, 2-oxy-3-phenylanthracen-7-yl.

[0036] It is also possible to select any one of the above specific examples of the divalent mono-oxy aromatic hydrocarbon group having 6 to 20 carbon atoms. That is, it is also possible to select any one of 1-oxybenzene-4-yl, 1-oxybenzene-3-yl, 1-oxybenzene-2-yl, 1-oxynaphthalene-2-yl, 1-oxynaphthalene-4-yl, 1-oxynaphthalene-5-yl, 2-oxynaphthalene-1-yl, 2-oxynaphthalene-6-yl, 2-oxynaphthalene-7-yl, 4-oxy-3-phenylbenzene-1-yl, 9-oxyphenanthrene-3-yl, 10-oxyphenanthrene-9-yl, 2-oxyanthracene-7-yl, 1-oxy-3-phenylnaphthalene-4-yl, 1-oxy-3-phenylnaphthalene-5-yl, 2-oxy-1-phenylnaphthalene-6-yl, 2-oxy-1-phenylnaphthalene-7-yl, 2-oxy-3-phenylnaphthalene-6-yl, 2-oxy-3-phenylnaphthalene-7-yl, 4-oxy-3-(1-naphthyl)benzene-1-yl, 4-oxy-3-(2-naphthyl)benzene-1-yl, 4-oxy-3,5-diphenylbenzene-1-yl, 4-oxy-2-phenylphenanthren-6-yl, 4-oxy-2-phenylphenanthren-7-yl, 4-oxy-2-phenylphenanthren-8-yl, 4-oxy-2-phenylphenanthren-9-yl, 4-oxy-2-phenylphenanthren-10-yl, and 2-oxy-3-phenylanthracen-7-yl.

[0037] Among them, it is preferably any one selected from 1-oxybenzene-4-yl, 2-oxynaphthalene-1-yl, 2-oxynaphthalene-6-yl, 4-oxy-3-phenylbenzene-1-yl, 9-oxyphenanthrene-3-yl, and 10-oxyphenanthrene-9-yl, more preferably any one selected from 1-oxybenzene-4-yl, 2-oxynaphthalene-1-yl, and 10-oxyphenanthrene-9-yl, and particularly preferably 2-oxynaphthalene-1-yl or 10-oxyphenanthrene-9-yl.

[0038] Next, when m is 1 or 2, that is, the trivalent or tetravalent mono-oxy aromatic hydrocarbon group having 6 to 20 carbon atoms, it means that one or two of the partial hydrogen atoms of the aromatic hydrocarbon group when m is 0 are substituted at the bonding position in a manner that can bond with the R1 group.

[0039] Each R1 in the general formula (1) independently represents a linear or branched alkyl group having 1 to 6 carbon atoms or a cyclic alkyl group having 5 to 6 carbon atoms. Among them, it is preferably independently a linear or branched alkyl group having 1 to 4 carbon atoms or cyclohexyl, more preferably independently methyl, tert-butyl, or cyclohexyl, and particularly preferably methyl.

[0040] Each R2 in the general formula (1) independently represents a linear or branched alkylene group having 1 to 4 carbon atoms. Among them, methylene is particularly preferred.

[0041] R3 in the general formula (1) represents a linear or branched alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. Among them, a linear or branched alkyl group having 1 to 10 carbon atoms is preferred, a linear or branched alkyl group having 1 to 6 carbon atoms is more preferred, methyl or ethyl is further preferred, and ethyl is particularly preferred.

[0042] Each m independently represents 0, 1 or 2. Among them, 0 or 1 is preferred, and 0 is particularly preferred.

[0043] Regarding the position to which R1 is bonded when m is 1, for 1-oxyphenyl-4-yl, the 2-position is preferred; for 2-oxynaphthalen-1-yl, the 6-position is preferred; for 2-oxynaphthalen-6-yl, the 5-position is preferred; for 4-oxo-3-phenylphenyl-1-yl, the 5-position is preferred; for 9-oxyphenanthren-3-yl, the 10-position is preferred; for 10-oxyphenanthren-9-yl, the 6-position is preferred.

[0044] Regarding the position to which R1 is bonded when m is 2, for 1-oxyphenyl-4-yl, the 2-position and the 5-position are preferred.

[0045] n represents 1 or 2, and 1 is preferred.

[0046] When n is 1, X in the general formula (1) is a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group or a divalent group represented by the general formula (1a), (1b) or (1c). Among them, a single bond, the divalent group represented by the general formula (1a), the divalent group represented by (1b) or the divalent group represented by (1c) is preferred, a single bond, the divalent group represented by (1b) or the divalent group represented by (1c) is more preferred, and a single bond is particularly preferred.

[0047] When n is 2, X in the general formula (1) is a trivalent group represented by the general formula (1d) or (1e), and the trivalent group represented by (1e) is preferred.

[0048] When X in the general formula (1) is the divalent group represented by the general formula (1a), R5 and R6 are more preferably each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, further preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and particularly preferably a hydrogen atom, methyl or ethyl.

[0049] In addition, R5 and R6 may be bonded to each other to form a cycloalkanediyl group having 5 to 20 carbon atoms as a whole. The cycloalkanediyl group having 5 to 20 carbon atoms may also contain an alkyl group as a side chain. The cycloalkanediyl group preferably has 5 to 15 carbon atoms, more preferably 6 to 12 carbon atoms, and particularly preferably 6 to 9 carbon atoms.

[0050] As the cycloalkanediyl group, specifically, for example, cyclopentanediyl (5 carbon atoms), cyclohexanediyl (6 carbon atoms), 3-methylcyclohexanediyl (7 carbon atoms), 4-methylcyclohexanediyl (7 carbon atoms), 3,3,5-trimethylcyclohexanediyl (9 carbon atoms), cycloheptanediyl (7 carbon atoms), bicyclo[2.2.1]heptane-2,2-diyl (7 carbon atoms), 1,7,7-trimethylbicyclo[2.2.1]heptane-2,2-diyl (10 carbon atoms), 4,7,7-trimethylbicyclo[2.2.1]heptane-2,2-diyl (10 carbon atoms), tricyclo[5.2.1.0 2,6 decane-8,8-diyl (10 carbon atoms), 2,2-adamantanediyl (10 carbon atoms), cyclododecanediyl (12 carbon atoms), etc. are exemplified. Preferred are cyclohexanediyl (6 carbon atoms), 3-methylcyclohexanediyl (7 carbon atoms), 4-methylcyclohexanediyl (7 carbon atoms), 3,3,5-trimethylcyclohexanediyl (9 carbon atoms), cyclododecanediyl (12 carbon atoms), etc., more preferred are cyclohexanediyl (6 carbon atoms), 3,3,5-trimethylcyclohexanediyl (9 carbon atoms), cyclododecanediyl (12 carbon atoms), and particularly preferred are cyclohexanediyl (6 carbon atoms), 3,3,5-trimethylcyclohexanediyl (9 carbon atoms).

[0051] When X in the general formula (1) is a divalent group represented by the general formula (1b), Ar1 is preferably independently a benzene ring or a naphthalene ring, and more preferably both Ar1 are benzene rings. For example, when both Ar1 are benzene rings, the group represented by the general formula (1b) is a fluorenediyl group.

[0052] As a preferred form when X in the general formula (1) is a divalent group represented by the general formula (1c), a divalent group represented by the formula (1c') or the formula (1c'') is preferred.

[0053] [Chemical formula 6]

[0054] As a preferred form when X in the general formula (1) is a trivalent group represented by the general formula (1d), R7 is preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, more preferably R7 is a hydrogen atom, a methyl group, or a phenyl group, and particularly preferably R7 is a hydrogen atom or a methyl group.

[0055] When X in the general formula (1) is a trivalent group represented by the general formula (1e), preferably R8 is a hydrogen atom or a methyl group, and particularly preferably R8 is a methyl group.

[0056] Regarding specific examples of the polycarboxylate compound (1), as specific examples of the compound in which Ar in the general formula (1) is 1-oxyphenyl-4-yl, compounds (1-1) to (1-6) can be cited.

[0057] [Chemical formula 7]

[0058] As specific examples of the compound in which Ar in the general formula (1) is 2-oxynaphthalen-1-yl, compounds (1-7) or (1-8) can be cited.

[0059] [Chemical formula 8]

[0060] As specific examples of the compound in which Ar in the general formula (1) is 2-oxynaphthalen-6-yl, compound (1-9) can be cited.

[0061] [Chemical formula 9]

[0062] As specific examples of the compound in which Ar in the general formula (1) is 4-oxy-3-phenylphenyl-1-yl, compounds (1-10) or (1-11) can be cited.

[0063] [Chemical formula 10]

[0064] As specific examples of the compound in which Ar in the general formula (1) is 10-oxyphenanthren-9-yl, compounds (1-12) or (1-13) can be cited.

[0065] [Chemical formula 11]

[0066] <Polyhydroxy aromatic compound (2) represented by the general formula (2)> The definitions of Ar, R1, m, n, and X in the general formula (2) are the same as those in the general formula (1), and their specific examples or preferred forms are also the same.

[0067] In addition, in the general formula (2), the oxygen atom of Ar is bonded to the aromatic hydrocarbon group contained in Ar and the hydrogen atom (H) described in the general formula (2).

[0068] Regarding specific examples of the polyhydroxy aromatic compound (2), as specific examples of the compound in which Ar in the general formula (2) is 1-oxybenzene-4-yl, compounds (2-1) to (2-6) can be cited.

[0069] [Chemical formula 12]

[0070] As specific examples of the compound in which Ar in the general formula (2) is 2-oxynaphthalene-1-yl, compounds (2-7) or (2-8) can be cited.

[0071] [Chemical formula 13]

[0072] As specific examples of the compound in which Ar in the general formula (2) is 2-oxynaphthalene-6-yl, compound (2-9) can be cited.

[0073] [Chemical formula 14]

[0074] As specific examples of the compound in which Ar in the general formula (2) is 4-oxy-3-phenylbenzene-1-yl, compounds (2-10) or (2-11) can be cited.

[0075] [Chemical formula 15]

[0076] As specific examples of the compound in which Ar in the general formula (2) is 10-oxyphenanthrene-9-yl, compounds (2-12) or (2-13) can be cited.

[0077] [Chemical formula 16]

[0078] <Halogenated carboxylic acid ester compound (3) represented by the general formula (3)> The definitions of R2 and R3 in the general formula (3) are the same as those in the general formula (1), and their specific examples or preferred forms are also the same.

[0079] Y in the general formula (3) represents a halogen atom, preferably a chlorine atom or a bromine atom, and particularly preferably a chlorine atom.

[0080] As specific examples of the halo-carboxylic acid ester compound (3), for example, the following can be cited: alkyl haloacetates such as methyl chloroacetate, ethyl chloroacetate, n-propyl chloroacetate, isopropyl chloroacetate, n-butyl chloroacetate, isobutyl chloroacetate, tert-butyl chloroacetate, methyl bromoacetate, ethyl bromoacetate, n-propyl bromoacetate, isopropyl bromoacetate, n-butyl bromoacetate, isobutyl bromoacetate, tert-butyl bromoacetate; alkenyl haloacetates such as vinyl chloroacetate, allyl chloroacetate, vinyl bromoacetate, allyl bromoacetate; alkyl halopropionates such as methyl 3-chloropropionate, ethyl 3-chloropropionate, methyl 3-bromopropionate, ethyl 3-bromopropionate; alkenyl halopropionates such as vinyl 3-chloropropionate, allyl 3-chloropropionate, vinyl 3-bromopropionate, allyl 3-bromopropionate, etc. Among them, alkyl haloacetates or alkenyl haloacetates are preferred, compounds selected from methyl chloroacetate, ethyl chloroacetate, methyl bromoacetate, ethyl bromoacetate, vinyl chloroacetate and allyl chloroacetate are more preferred, compounds selected from methyl chloroacetate, ethyl chloroacetate, methyl bromoacetate and ethyl bromoacetate are further preferred, and methyl chloroacetate or ethyl chloroacetate is particularly preferred.

[0081] <Etherification reaction step> In the etherification reaction step involved in the production method of the present invention, the molar ratio of the halo-carboxylic acid ester compound (3) added relative to the polyhydroxy aromatic compound (2) is not particularly limited as long as it is (1.0 + n) or more of the theoretical value, and it is usually used in the range of 2 to 20 times the molar amount, preferably in the range of 2 to 10 times the molar amount, and more preferably in the range of 2 to 6 times the molar amount. In addition, "n" in the theoretical value is the number of "n" in the general formula (1).

[0082] The etherification reaction is carried out in the presence of a base. Examples of the base used include: triethylamine, pyridine, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, etc. Among them, sodium carbonate or potassium carbonate is preferred. The molar ratio of the base added relative to the total amount of the halo-carboxylic acid ester compound used is usually in the range of 0.8 to 4 times the molar amount, preferably in the range of 0.85 to 3 times the molar amount, and more preferably in the range of 0.9 to 2 times the molar amount.

[0083] In addition, a catalyst can also be used. For example, the following can be cited: alkali metal bromides such as sodium bromide or potassium bromide, alkali metal iodides such as sodium iodide or potassium iodide, ammonium bromide or ammonium iodide, etc. The amount of the catalyst used relative to the polyhydroxy aromatic compound (2) is usually in the range of 0.1 to 100% by weight, preferably in the range of 0.1 to 20% by weight, and more preferably in the range of 0.1 to 10% by weight.

[0084] (Etherification reaction temperature) The reaction temperature is generally in the range of 25~120°C, preferably in the range of 40~100°C, more preferably in the range of 50~90°C, and particularly preferably in the range of 60~80°C. If the reaction temperature is high, the yield decreases; if the reaction temperature is low, the reaction rate slows down, so this is not preferred.

[0085] (Etherification reaction pressure) The reaction pressure is not limited and can be under normal pressure, reduced pressure, or increased pressure. It is preferably under normal pressure or reduced pressure. In the reaction under increased pressure, for example, the reaction can be carried out under a pressurized state in which a gas inert to the reaction such as nitrogen is circulated. That is, an inert gas can be introduced into the reaction system, and the reaction can be carried out while discharging the gas in the reaction system. Thus, since the carbon dioxide generated from the carbonate or bicarbonate used in the reaction can be discharged out of the reaction system, the reaction can be promoted. Specific examples of the gas inert to the reaction include nitrogen, argon, helium, etc. From the perspective of economy, nitrogen is most preferred.

[0086] From the perspective of shortening the reaction time, it is more preferably under reduced pressure. By carrying out the reaction under reduced pressure, the carbon dioxide generated from the carbonate or bicarbonate used can be discharged out of the reaction system, so the reaction can be promoted, and the reaction time can be shortened compared with the reaction under normal pressure. Further, by carrying out the reaction under reduced pressure and distilling out the solvent out of the reaction system at the same time, the generation of by-products can be inhibited. Specifically, the reaction pressure is preferably in the range of 5 kPa or more and 80 kPa or less, more preferably in the range of 10 kPa or more and 80 kPa or less, and further preferably in the range of 30 kPa or more and 60 kPa or less. The reaction pressure can be set under reduced pressure by a decompression device. When the reaction pressure is maintained within the above range, the decompression device can operate intermittently or continuously, and it is more preferably continuous operation. From the start to the end of the reaction, it is preferably under reduced pressure, specifically, the reaction is carried out while maintaining the pressure within the above range.

[0087] (Ketone solvent in the etherification reaction) Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Ketone solvents having 3 to 9 carbon atoms are preferred. Among them, ketone solvents having 3 to 6 carbon atoms are further preferred, and acetone or methyl isobutyl ketone is particularly preferred. When methyl isobutyl ketone is used as the reaction solvent, it is preferred because water washing for removing water-soluble impurities such as salts can be carried out after the reaction.

[0088] These organic solvents can be used alone respectively. In addition, in order to adjust the polarity, two or more of them can also be used in combination as appropriate.

[0089] The content of the monohydric aliphatic alcohol in the ketone solvent is 0.04% by mass or less. This content is preferably 0.03% by mass or less, more preferably 0.02% by mass or less, still more preferably 0.01% by mass or less, and particularly preferably 0.005% by mass or less. The lower limit value of this content is preferably as low as possible, and there is no particular limitation. However, from the perspective of the economy of reducing the content or the perspective of being difficult to detect or quantify by analysis, it can be 0.0005% by mass or more, or can be 0.001% by mass or more.

[0090] In addition to being a by-product or impurity during the production of the ketone solvent, the aforementioned monohydric aliphatic alcohol is sometimes also an impurity contained in the regenerated ketone solvent.

[0091] The present inventors found that, as the monohydric aliphatic alcohol that is a by-product during the production of the ketone solvent, for example, in the case of acetone, it contains methanol, and in the case of methyl isobutyl ketone, it contains methyl isobutyl carbinol. Moreover, in the etherification reaction step of the production method of the present invention, since the monohydric aliphatic alcohol as an impurity is contained in the ketone solvent, the ester groups of the halogenated carboxylic acid ester compound (3) and the target polycarboxylate compound (1) react with this monohydric aliphatic alcohol, thereby generating a by-product having an ester group different from that of the target compound. This by-product is the polycarboxylate compound (5) represented by the general formula (5), which will be described in detail later.

[0092] Moreover, the present inventors found that by setting the amount of the monohydric aliphatic alcohol contained in the used ketone solvent within a specific range, a polycarboxylate compound (1) with further improved quality can be produced.

[0093] As the aforementioned monohydric aliphatic alcohol, the monohydric aliphatic alcohol (4) represented by the general formula (4) can be exemplified.

[0094] [Chemical Formula 17]

[0095] (In the formula, R4 represents a linear or branched alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. However, it is a group different from R3 in the general formula (1).) R4 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably a linear or branched alkyl group having 1 to 6 carbon atoms, still more preferably methyl or 4-methylpentan-2-yl, and particularly preferably methyl.

[0096] As the monohydric aliphatic alcohol, specifically, in addition to the above-mentioned methanol and methyl isobutyl carbinol, examples include: ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, hexanol, cyclohexanol, 1-octanol, lauryl alcohol, allyl alcohol, etc.

[0097] The water content in the ketone solvent is 2% by mass or less. This content is preferably 1% by mass or less, more preferably 0.5% by mass or less, still more preferably 0.3% by mass or less, and particularly preferably 0.1% by mass or less. The lower limit value of this content is preferably as low as possible, and there is no particular limitation. However, from the perspective of the economy for reducing the content or from the perspective that it is difficult to detect or quantify by analysis, it can be 0.0001% by mass (1 mass ppm) or more.

[0098] The present inventors have found that in the etherification reaction step, the water contained in the ketone solvent causes the halo-carboxylic acid ester compound (3) to react in an excessive amount compared to the target polycarboxylic acid ester compound (1) to form a by-product. This by-product is the polycarboxylic acid ester compound (6) represented by the general formula (6), which will be described in detail later.

[0099] Furthermore, the present inventors have found that by setting the amount of water contained in the used ketone solvent within a specific range, a polycarboxylic acid ester compound (1) with further improved quality can be produced.

[0100] The usage amount of the ketone solvent is not particularly limited as long as it does not hinder the reaction. Generally, it is preferably used in a range of 1 to 7 times by weight relative to the polyhydroxy aromatic compound (2), more preferably in a range of 2 to 4 times by weight, and still more preferably in a range of 2 to 3 times by weight.

[0101] When the reaction is carried out while distilling the solvent out of the reaction system under reduced pressure, regarding the usage amount of the solvent, it is preferably used in a range of 1.5 to 10 times by weight relative to the polyhydroxy aromatic compound (2), more preferably in a range of 2 to 8 times by weight, and still more preferably in a range of 2 to 6 times by weight.

[0102] As the distillation amount per hour during the reaction by distilling the solvent out of the reaction system, relative to the polyhydroxy aromatic compound (2), a range of 0.05 to 1.5 times by weight is preferred, a range of 0.1 to 1.0 times by weight is more preferred, a range of 0.3 to 1.0 times by weight is still more preferred, and a range of 0.3 to 0.8 times by weight is particularly preferred. During the reaction, the distillation amount per hour can vary within the above range, and the distillation amount can also temporarily exceed the upper or lower limit values of the above range.

[0103] (Etherification reaction end point) The end point of the etherification reaction can be confirmed by liquid chromatography or gas chromatography analysis. It is preferable to use the following time points as the end point of the reaction: the time point at which the unreacted polyhydroxy aromatic compound (2) disappears, and when n in the polycarboxylate compound (1) as the target compound is 2, a monoetherified product is formed, and when n is 3, a dietherified product is formed and almost no further formation is observed. Regarding the time point at which almost no further formation is observed after the formation of the reaction intermediate, specifically, it is the time point at which it becomes 1.5 area% or less in liquid chromatography or gas chromatography analysis, more preferably the time point at which it becomes 1.0 area% or less, further preferably the time point at which it becomes 0.8 area% or less, and particularly preferably the time point at which it becomes 0.5 area% or less. The reaction time varies depending on reaction conditions such as reaction temperature and usually ends in about 1 to 30 hours.

[0104] <Polycarboxylate compound (5) represented by general formula (5)> [Chemical formula 18]

[0105] Ar, R1, R2, R in general formula (5) 3、 The definitions of m, n and X are the same as those in general formula (1), and their specific examples or preferred forms are also the same.

[0106] Each R4 independently represents a linear or branched alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms different from R3. Among them, a linear or branched alkyl group having 1 to 10 carbon atoms is preferred, a linear or branched alkyl group having 1 to 6 carbon atoms is more preferred, methyl or 4-methylpentan-2-yl is further preferred, and methyl is particularly preferred.

[0107] Regarding the polycarboxylate compound (5), as specific examples of the compound in which Ar in general formula (5) is 1-oxyphen-4-yl and R3 and R4 are ethyl and methyl, compounds (5-1) to (5-6), (5-6') can be cited.

[0108] [Chemical formula 19]

[0109] As specific examples of the compound in which Ar in general formula (5) is 2-oxynaphth-1-yl and R3 and R4 are ethyl and methyl, compounds (5-7) or (5-8) can be cited.

[0110] [Chemical formula 20]

[0111] As specific examples of the compound in which Ar in general formula (5) is 2-oxynaphth-6-yl and R3 and R4 are ethyl and methyl, compound (5-9) can be cited.

[0112] [Chemical formula 21]

[0113] As specific examples of the compound in which Ar in the general formula (5) is 4-oxy-3-phenylbenzene-1-yl and R3 and R4 are ethyl and methyl, compounds (5-10) or (5-11) can be cited.

[0114] [Chemical formula 22]

[0115] As specific examples of the compound in which Ar in the general formula (5) is 10-oxy-phenanthrene-9-yl and R3 and R4 are ethyl and methyl, compounds (5-12) or (5-13) can be cited.

[0116] [Chemical formula 23]

[0117] As shown in the following reaction formula, in order to obtain the polycarboxylate compound (1), in the etherification reaction step of using the polyhydroxy aromatic compound (2) and the halo-carboxylate compound (3) to carry out the etherification reaction, the halo-carboxylate compound (3) and the polycarboxylate compound (1) react with the monohydric aliphatic alcohol (for example, the monohydric aliphatic alcohol represented by the general formula (4)) contained in the ketone solvent to generate the polycarboxylate compound (5).

[0118] [Chemical formula 24]

[0119] (In the formula, R4 represents a linear or branched alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms different from R3.) As a specific example of this reaction, as shown in the following reaction formula, it can be cited: in the method of using the compound (2-7) as the polyhydroxy aromatic compound (2) and using ethyl chloroacetate as the halo-carboxylate compound (3) to carry out the etherification reaction to produce the compound (1-7), since methanol is contained as the monohydric aliphatic alcohol contained in the used ketone solvent, the compound (5-7) is by-produced.

[0120] [Chemical formula 25]

[0121] <Polycarboxylate compound (6) represented by the general formula (6)> [Chemical formula 26]

[0122] The definitions of Ar, R1, R2, m, n, X and R3 in the general formula (6) are the same as those in the general formula (1), and their specific examples or preferred forms are also the same.

[0123] Each r independently represents an integer from 1 to 4. However, at least one r is 2, 3, or 4.

[0124] Regarding the polycarboxylate compound (6), as specific examples of the compound in which Ar in the general formula (6) is 1-oxyphenyl-4-yl, compounds (6-1) to (6-6), (6-6') can be cited.

[0125] [Chemical formula 27]

[0126] As specific examples of the compound in which Ar in the general formula (6) is 2-oxynaphthalen-1-yl, compounds (6-7) or (6-8) can be cited.

[0127] [Chemical formula 28]

[0128] As specific examples of the compound in which Ar in the general formula (6) is 2-oxynaphthalen-6-yl, compound (6-9) can be cited.

[0129] [Chemical formula 29]

[0130] As specific examples of the compound in which Ar in the general formula (6) is 4-oxy-3-phenylphenyl-1-yl, compounds (6-10) or (6-11) can be cited.

[0131] [Chemical formula 30]

[0132] As specific examples of the compound in which Ar in the general formula (6) is 10-oxyphenanthren-9-yl, compounds (6-12) or (6-13) can be cited.

[0133] [Chemical formula 31]

[0134] As shown in the following reaction formula, it can be known that in the etherification reaction step of using the polyhydroxy aromatic compound (2) and the haloalkyl carboxylate compound (3) for the etherification reaction, the polycarboxylate compound (6) is generated due to the excessive reaction of the haloalkyl carboxylate compound (3), and its generation is promoted by water.

[0135] [Chemical formula 32]

[0136] As a specific example of this reaction, as shown in the following reaction formula, the following can be cited: In the method of producing compound (1-7) by subjecting compound (2-7) as the polyhydroxy aromatic compound (2) and ethyl chloroacetate as the halo carboxylic acid ester compound (3) to an etherification reaction, compound (6-7) is by-produced due to the excessive reaction of ethyl chloroacetate.

[0137] [Chemical Formula 33]

[0138] <Separation and Purification of Polycarboxylate Compound (1)> The reaction-terminated mixture obtained through the etherification reaction step can be separated and purified according to common methods, and thus the polycarboxylate compound (1) can be obtained from the reaction mixture. For example, post-treatment steps such as separation steps carried out by a neutralization step, a water washing step, a crystallization step, a filtration step, a distillation step, column chromatography, etc. can be performed. Further, in order to improve the purity, purification carried out by distillation or recrystallization, column chromatography can also be further performed according to common methods.

[0139] In addition, except for the etherification reaction step, all steps such as mixing, neutralization, distillation, crystallization, filtration, drying, etc. of the raw materials involved in this production method are preferably carried out in an environment with less oxygen that may cause oxidative deterioration or coloring, or electrostatic ignition caused by volatile solvents, or in an inert gas environment such as nitrogen or argon.

[0140] Examples The present invention will be described more specifically below through examples, but the present invention is not limited by these examples. The analysis methods are as follows.

[0141] <Analysis Methods> 1. Composition Analysis of Polycarboxylate Compound The composition analysis of the polycarboxylate compound is carried out by high performance liquid chromatography (HPLC) under the following apparatus and conditions. The “%” of the obtained analysis results is the area percentage.

[0142] Measuring Apparatus: High Performance Liquid Chromatography Analyzer (manufactured by Shimadzu Corporation) Pump: LC-20AD Column Oven: CTO-20A Detector: SPD-20A Chromatographic Column: HALO-C18 Oven Temperature: 50 °C Flow Rate: 0.7 mL / min. Detection Wavelength: 280 nm · Gradient Conditions Mobile Phase: (A) 0.2 vol% acetic acid aqueous solution, (B) methanol (B)Volume % (time since analysis) 50% (0 minutes) → 100% (10 minutes) → 100% (13 minutes) <Comparative Example 1> Using the crystal of 2,2'-bis(2-ethoxycarbonylmethoxy)-1,1'-binaphthalene with the results analyzed by HPLC being 98.8% of 2,2'-bis(2-ethoxycarbonylmethoxy)-1,1'-binaphthalene (Compound (1-7)), 0.6% of Compound (5-7), and 0.5% of Compound (6-7), 50.0 g of this crystal and 32.0 g of methyl isobutyl ketone were charged into a four-necked flask, and the temperature was raised to 73 °C to dissolve the crystal. Then, 32.0 g of n-heptane was added at the same temperature, and cooling was started while continuously stirring. Seed crystals were added at 70 °C, and after maintaining the temperature at 50 °C for 1 hour, it was cooled to 25 °C and continuously stirred overnight. Then the crystal was filtered out by filtration. The obtained crystal was dried and refined by recrystallization to obtain 47.4 g of the crystal of Compound (1-7).

[0143] The obtained crystal was analyzed by HPLC, and as a result, Compound (1-7) was 99.0%, Compound (5-7) was 0.6%, and Compound (6-7) was 0.3%.

[0144] In the refinement by recrystallization, the content ratio of Compound (6-7) decreased by 0.2%, which is 40% of the original content ratio, but the content ratio of Compound (5-7) did not change, indicating that it cannot be removed by the refinement by recrystallization.

[0145] The difference in the structures of Compound (5-7) and Compound (1-7) is only that one ester group is different between ethyl and methyl, and the difference in solubility is not significant. It is speculated that this impurity and the target compound cannot be separated in the refinement by recrystallization.

[0146] <Comparative Example 2> 15.0 g (0.05 mol) of 1,1'-binaphthalene-2,2'-diol (Compound (2-7)), 25.0 g of potassium carbonate, and 1.3 g of potassium iodide were charged into a four-necked flask. After purging with nitrogen, 22.5 g of acetone (water content: 2.5 mass%, methanol content: 0.05 mass%) was added. Then the temperature was raised to 60 °C, and while maintaining this temperature, 16.1 g (0.13 mol) of ethyl chloroacetate to which 0.1 g of N-methylpyrrolidone had been added was added dropwise over 1 hour and 20 minutes. Then the etherification reaction was carried out for 17 hours while maintaining 60 °C.

[0147] The liquid after the etherification reaction was analyzed by HPLC, and the results showed that the content of compound (1-7) was 97.3%, the content of compound (5-7) was 0.5%, and the content of compound (6-7) was 1.5%.

[0148] Next, while maintaining the liquid temperature at 55-60 °C, 60.0 g of water was added to the liquid after the etherification reaction. Then, cooling was started and seed crystals were mixed at 50 °C, and the mixture was cooled to 25 °C to precipitate crystals. Then, the crystals were filtered out by filtration.

[0149] The filtered crystals were analyzed by HPLC, and the results showed that the content of compound (1-7) was 97.9%, the content of compound (5-7) was 0.5%, and the content of compound (6-7) was 1.3%.

[0150] The filtered crystals and 15.0 g of methyl isobutyl ketone were placed in a four-necked flask and heated to 70 °C to dissolve the crystals. 15.0 g of water was added to the flask, and the mixture was stirred at 78 °C for 30 minutes, then allowed to stand and the separated aqueous layer was removed. This water washing operation was repeated 2 times. 30.0 g of n-heptane was added to the oil layer after water washing, and the mixture was cooled to 25 °C while continuously stirring. Seed crystals were mixed at the time point of 70 °C midway. After continuous stirring overnight, the precipitated crystals were filtered out. The obtained crystals were dried to obtain 15.7 g of crystals of compound (1-7).

[0151] The obtained crystals were analyzed by HPLC, and the results showed that the content of compound (1-7) was 98.6%, the content of compound (5-7) was 0.5%, and the content of compound (6-7) was 0.9%.

[0152] The hue of the obtained crystals of compound (1-7) in a 30 wt% tetrahydrofuran (THF) solution was APHA 30.

[0153] <Example 1> 15.0 g (0.05 mol) of compound (2-7), 15.0 g of potassium carbonate, and 0.8 g of potassium iodide were placed in a four-necked flask. After purging with nitrogen, 22.5 g of acetone (water content: 4 mass ppm, methanol content: less than 0.002 mass%) was added. Then, the temperature was raised to 60 °C, and while maintaining this temperature, 16.1 g (0.13 mol) of ethyl chloroacetate to which 0.1 g of N-methylpyrrolidone had been added was added dropwise over 2 hours. Then, the etherification reaction was carried out for 19 hours while maintaining 60 °C.

[0154] The liquid after the etherification reaction was analyzed by HPLC, and the results showed that the content of compound (1-7) was 98.0%, the content of compound (5-7) was 0.2%, and the content of compound (6-7) was 1.3%.

[0155] Next, while maintaining the liquid temperature at 60 °C, 60.0 g of water was added to the liquid after the etherification reaction, and then it was cooled with stirring to 30 °C to precipitate crystals. Thereafter, the crystals were filtered out.

[0156] The filtered crystals were analyzed by HPLC, and as a result, the compound (1-7) was 98.5%, the compound (5-7) was 0.2%, and the compound (6-7) was 1.2%.

[0157] The filtered crystals and 15.0 g of methyl isobutyl ketone were placed in a four-necked flask and the crystals were dissolved. 15.0 g of water was added to the flask and stirred at 75 °C for 30 minutes, then allowed to stand and the separated aqueous layer was removed, and this washing operation was repeated 3 times. 21.0 g of n-heptane was added to the washed oil layer, and it was cooled to 25 °C while continuously stirring. After stirring overnight, the precipitated crystals were filtered out. The obtained crystals were dried to obtain 17.6 g of crystals of the compound (1-7).

[0158] The obtained crystals were analyzed by HPLC, and as a result, the compound (1-7) was 99.2%, the compound (5-7) was 0.2%, and the compound (6-7) was 0.6%.

[0159] The hue of the obtained crystals of the compound (1-7) in a 30 wt% tetrahydrofuran (THF) solution was APHA 20.

[0160] From the results of Comparative Example 2, it was confirmed that even when the compound (5-7) was refined twice by crystallization, it could not be reduced from the content ratio in the liquid after the etherification reaction step, and it was a by-product that could not be reduced by the operations of crystallization or recrystallization as in Comparative Example 1.

[0161] On the other hand, it was clarified that, compared with the composition after recrystallization of Comparative Example 1, the liquid after the etherification reaction step of Example 1 had a 0.3% reduction in the compound (5-7) as a reaction by-product and a 0.2% reduction in the compound (6-7).

[0162] From the above results, it can be seen that the content of the compound (5-7) is due to the amount of methanol contained in the acetone of the solvent used, and when its content is small, the generation of by-products can be suppressed.

[0163] In addition, it can be seen that the compound (6-7) is due to the amount of water contained in the acetone of the solvent used, and when its content is small, the generation of by-products can be suppressed.

[0164] From these, it can be seen that for specific impurities that cannot be removed or have a small removal effect by recrystallization operations, according to the production method of the present invention, the generation of such impurities can be reduced, and thus a compound (1-7) with further improved quality can be obtained.

[0165] From the above, it can be seen that according to the manufacturing method of the present invention, since specific impurities contained in the polycarboxylate compound that cannot be removed or have a small removal effect by crystallization operation or recrystallization operation can be reduced, a polycarboxylate compound with improved quality can be manufactured.

Claims

1. A method for producing a polycarboxylate compound (1) represented by the general formula (1), characterized in that, An etherification reaction step including using a polyhydroxy aromatic compound represented by the general formula (2) and a halo carboxylic acid ester compound represented by the general formula (3) to carry out an etherification reaction in the presence of a ketone solvent, wherein the content of monohydric aliphatic alcohol in the ketone solvent is 0.04% by mass or less, and the water content is 2% by mass or less. [Chemical formula 1] In the formula (1), each Ar independently represents a "2 + m-valent" monoxy aromatic hydrocarbon group having 6 to 20 carbon atoms, each R1 independently represents a linear or branched alkyl group having 1 to 6 carbon atoms or a cyclic alkyl group having 5 to 6 carbon atoms, each R2 independently represents a linear or branched alkylene group having 1 to 4 carbon atoms, R3 represents a linear or branched alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, each m independently represents 0, 1 or 2, n represents 1 or 2, X represents a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, a divalent group represented by the general formula (1a), (1b) or (1c), or a trivalent group represented by the general formula (1d) or (1e). Additionally, in the general formula (1), the oxygen atom possessed by Ar is bonded to the aromatic hydrocarbon group contained in Ar and R2. [Chemical formula 2] In the general formula (1a), each of R5 and R6 independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms. R5 and R6 may be bonded to each other to form a cycloalkanediyl group having 5 to 20 carbon atoms as a whole. In the general formula (1b), each Ar1 independently represents an aryl group having 6 to 12 carbon atoms. In the general formula (1a), (1b) and (1c), each * represents a bonding position. [Chemical formula 3] In the general formula (1d), R7 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms. In the general formula (1e), R8 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms. In the general formula (1d) and (1e), each * represents a bonding position. [Chemical formula 4] The definitions of Ar, R1, m, n and X in the general formula (2) are the same as those in the general formula (1). Additionally, in the general formula (2), the oxygen atom possessed by Ar is bonded to the aromatic hydrocarbon group contained in Ar and the hydrogen atom (H) described in the general formula (2). [Chemical formula 5] The definitions of R2 and R3 in the general formula (3) are the same as those in the general formula (1), and Y represents a halogen atom.

2. The manufacturing method according to claim 1, wherein The ketone solvent is a ketone solvent having 3 to 9 carbon atoms.

3. The manufacturing method according to claim 2, characterized in that, The ketone solvent is acetone or methyl isobutyl ketone.

4. The manufacturing method according to any one of claims 1 to 3, characterized in that, Ar is any one of the groups selected from 1-oxyphenyl-4-yl, 1-oxyphenyl-3-yl, 1-oxyphenyl-2-yl, 1-oxynaphthalen-2-yl, 1-oxynaphthalen-4-yl, 1-oxynaphthalen-5-yl, 2-oxynaphthalen-1-yl, 2-oxynaphthalen-6-yl, 2-oxynaphthalen-7-yl, 4-oxo-3-phenylphenyl-1-yl, 9-oxophenanthren-3-yl, 10-oxophenanthren-9-yl, 2-oxoanthracen-7-yl, 1-oxo-3-phenylnaphthalen-4-yl, 1-oxo-3-phenylnaphthalen-5-yl, 2-oxo-1-phenylnaphthalen-6-yl, 2-oxo-1-phenylnaphthalen-7-yl, 2-oxo-3-phenylnaphthalen-6-yl, 2-oxo-3-phenylnaphthalen-7-yl, 4-oxo-3-(1-naphthyl)phenyl-1-yl, 4-oxo-3-(2-naphthyl)phenyl-1-yl, 4-oxo-3,5-diphenylphenyl-1-yl, 4-oxo-2-phenylphenanthren-6-yl, 4-oxo-2-phenylphenanthren-7-yl, 4-oxo-2-phenylphenanthren-8-yl, 4-oxo-2-phenylphenanthren-9-yl, 4-oxo-2-phenylphenanthren-10-yl, and 2-oxo-3-phenylanthracen-7-yl.

5. The manufacturing method according to claim 4, wherein n is 2 and X is a direct bond.

6. The manufacturing method according to claim 5, characterized in that, R3 is a linear or branched alkyl group having 1 to 10 carbon atoms.

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