Method for producing polycarboxylate compound

Abstract

The present invention addresses the problem of providing a method capable of producing a polycarboxylate compound having a reduced impurity content and further improved purity. As a solution, provided is a method for producing a polycarboxylate compound (1) represented by general formula (1), composition using polyhydroxyaromatic compound (2) represented by general formula (2) and halogenated carboxylic acid ester compound in the following component ratio range (wherein the total of the component ratios of halogenated carboxylic acid ester compound (3), halogenated carboxylic acid ester compound (4) and other components as determined by gas chromatography is 100% by area)) The component ratio as determined by gas chromatography > the halogenated carboxylic acid ester compound (3) represented by general formula (3) is in the range of from 99.50% by area to 99.99% by area (inclusive), and the halogenated carboxylic acid ester compound (4) represented by general formula (4) is in the range of from 0.01% by area to 0.09% by area (inclusive).

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 reduced content of specific impurities and improved purity. 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 acid 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 have been increasing demands for various performance improvements. In order to exhibit desired properties, the raw materials used for the materials are required to have further improved quality.

[0004] As a method for producing a dicarboxylic acid compound using a bisphenol compound as a raw material, a method of synthesizing a dicarboxylic acid or its ester compound by subjecting a bisphenol compound and a halo carboxylic acid or its ester to an etherification reaction is known. As a method for the etherification reaction to obtain a dicarboxylic acid 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 Laid-Open No. 62-292819 Patent Document 2: Japanese Patent 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 the dicarboxylic acid 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 subjecting a bisphenol compound and a halo carboxylic acid ester to an etherification reaction, there are sometimes problems of increased impurities and inability to improve purity.

[0006] The present inventors conducted in-depth research and found that the halo carboxylic acid ester compound used contains a halo carboxylic acid ester compound with a different ester group as an impurity, and it was found that a by-product having an ester group different from that of the target dicarboxylic acid ester compound is generated from this impurity, which is the main reason for the reduction in purity.

[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] Based on 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 conducted in-depth research and as a result, found that in the method for producing the target polycarboxylate compound, the problem can be solved by using a halogenated carboxylate compound composition having a specific composition, and thus the present invention was 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 in that an etherification reaction is carried out using a polyhydroxy aromatic compound (2) represented by the general formula (2) and a halogenated carboxylate compound composition within the following component ratio range, <Component ratio obtained by gas chromatography analysis> Halogenated carboxylate compound (3) represented by the general formula (3): in the range of 99.50 area% or more and 99.99 area% or less, Halogenated carboxylate compound (4) represented by the general formula (4): in the range of 0.01 area% or more and 0.09 area% or less, In addition, the total of the component ratios of the halogenated carboxylate compound (3), the halogenated carboxylate compound (4), and other components in the halogenated carboxylate compound composition obtained by gas chromatography analysis is 100 area%, [Chemical formula 1]

[0013] In formula (1), each Ar independently represents a "2 + m-valent" monoxoaromatic 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 general formula (1a), (1b) or (1c), or a trivalent group represented by general formula (1d) or (1e). Additionally, in general formula (1), the oxygen atom possessed by Ar is bonded to the aromatic hydrocarbon group contained in Ar and R2. [Chemical formula 2]

[0014] In general formula (1a), each of R5 and R6 independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl 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), each Ar1 independently represents an aryl group having 6 to 12 carbon atoms. In general formula (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 formula (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), and Y represents a halogen atom. [Chemical formula 6]

[0018] The definition of R2 in the general formula (4) is the same as that in the general formula (1), the definition of Y is the same as that in the general formula (3), R4 represents an alkyl group having 1 to 10 carbon atoms in a straight chain or branched chain or an alkenyl group having 2 to 10 carbon atoms, provided that R4 is a group different from the R3 group of the halogenated carboxylic acid ester compound represented by the general formula (3).

[0019] 2. The manufacturing method according to 1., characterized in that the Ar is any one group 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.

[0020] 3. The manufacturing method according to 2., characterized in that the n is 2 and the X is a direct bond.

[0021] 4. The manufacturing method according to 3., characterized in that the R3 is an alkyl group having 1 to 10 carbon atoms in a straight chain or branched chain.

[0022] According to the manufacturing method of the present invention, specific impurities contained in the polycarboxylate compound (1) that cannot be removed by crystallization operation or recrystallization operation can be reduced, and thus a polycarboxylate compound (1) with improved quality can be manufactured. Detailed Description

[0023] The manufacturing method of the polycarboxylate compound (1) represented by the general formula (1) of the present invention is characterized in that an etherification reaction is carried out using a polyhydroxy aromatic compound (2) represented by the general formula (2) and a halogenated carboxylic acid ester compound composition within a specific component ratio range.

[0024] The polycarboxylate compound (1) represented by the general formula (1) of the target compound of the production method of the present invention is produced by using the polyhydroxy aromatic compound (2) represented by the general formula (2) and the halogenated carboxylate compound (3) represented by the general formula (3) as raw materials and carrying out an etherification reaction.

[0025] [Chemical formula 7]

[0026] However, in the halogenated carboxylate compound (3), the halogenated carboxylate (4) represented by the general formula (4) having a different ester group may be contained as an impurity. In the above-mentioned etherification step, it has been found that the polyhydroxy aromatic compound (2) reacts with the halogenated carboxylate compound (3) and the halogenated carboxylate (4), and a polycarboxylate compound (5) represented by the general formula (5) is by-produced. The polycarboxylate compound (5) represented by the general formula (5) will be described in detail later.

[0027] [Chemical formula 8]

[0028] Furthermore, as shown in Comparative Example 1 described later, it has been found that the by-produced polycarboxylate compound (5) cannot be removed from the target polycarboxylate compound (1) by crystallization or recrystallization operations.

[0029] Therefore, it has been found that by using a halogenated carboxylate compound composition in which the component ratio of the halogenated carboxylate compound (3) and the halogenated carboxylate compound (4) is within a specific range as a raw material for the etherification reaction step, the content of this specific impurity can be reduced, and a method for producing a polycarboxylate compound (1) with further improved purity can be obtained.

[0030] As a specific example of such an etherification reaction step, the following reaction step can be cited as shown in the following reaction formula: An etherification reaction is carried out using the compound (2-7) as the polyhydroxy aromatic compound (2) and a halogenated carboxylate compound composition containing ethyl chloroacetate as the halogenated carboxylate compound (3) and methyl chloroacetate as the halogenated carboxylate compound (4) to produce the compound (1-7) as the polycarboxylate compound (1), and the polycarboxylate compound (5-7) as the by-product polycarboxylate compound (5).

[0031] In this reaction, by using a specific halogenated carboxylate compound composition, the generation of the compound (5-7) having an ester group different from that of the target compound (1-7) and which cannot be removed by crystallization or recrystallization operations can be suppressed, and the compound (1-7) with further improved purity can be produced.

[0032] [Chemical formula 9]

[0033] <Polycarboxylate compound (1) represented by general formula (1)> In general formula (1), each Ar independently represents a “2 + m-valent” monoxy aromatic hydrocarbon group having 6 to 20 carbon atoms. Further, in general formula (1), the oxygen atom possessed by Ar is bonded to the aromatic hydrocarbon group and R2 contained in Ar.

[0034] First, the case where m is 0, that is, a divalent monoxy aromatic hydrocarbon group having 6 to 20 carbon atoms will be described.

[0035] 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.

[0036] 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.

[0037] 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.

[0038] Specific examples of the divalent monoxy aromatic hydrocarbon group having 12 carbon atoms include: 4-oxy-3-phenylbenzene-1-yl.

[0039] 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.

[0040] 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.

[0041] 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.

[0042] As a specific example of the divalent mono-oxy aromatic hydrocarbon group having 18 carbon atoms, the following can be cited: 4-oxy-3,5-diphenylbenzene-1-yl.

[0043] As a specific example of the divalent mono-oxy aromatic hydrocarbon group having 20 carbon atoms, the following can be cited: 4-oxy-2-phenylphenanthrene-6-yl, 4-oxy-2-phenylphenanthrene-7-yl, 4-oxy-2-phenylphenanthrene-8-yl, 4-oxy-2-phenylphenanthrene-9-yl, 4-oxy-2-phenylphenanthrene-10-yl, 2-oxy-3-phenylanthracene-7-yl.

[0044] 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-phenylphenanthrene-6-yl, 4-oxy-2-phenylphenanthrene-7-yl, 4-oxy-2-phenylphenanthrene-8-yl, 4-oxy-2-phenylphenanthrene-9-yl, 4-oxy-2-phenylphenanthrene-10-yl, and 2-oxy-3-phenylanthracene-7-yl.

[0045] Among them, it is preferable to select any one of 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 to select any one of 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.

[0046] 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 to the R1 group.

[0047] 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, each is preferably independently a linear or branched alkyl group having 1 to 4 carbon atoms or cyclohexyl, more preferably each is independently methyl, tert-butyl or cyclohexyl, and particularly preferably methyl.

[0048] 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.

[0049] 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.

[0050] Each m independently represents 0, 1 or 2. Among them, 0 or 1 is preferred, and 0 is particularly preferred.

[0051] Regarding the position where 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-oxy-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.

[0052] Regarding the positions where R1 is bonded when m is 2, for 1-oxyphenyl-4-yl, the 2-position and the 5-position are preferred.

[0053] n represents 1 or 2, and 1 is preferred.

[0054] 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.

[0055] 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.

[0056] 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 halogenated alkyl 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.

[0057] 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.

[0058] 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).

[0059] 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.

[0060] 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.

[0061] [Chemical formula 10]

[0062] 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.

[0063] 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.

[0064] Regarding specific examples of the polycarboxylate compound (1), as specific examples of the compound in which Ar in the general formula (1) is 1-oxybenzene-4-yl, compounds (1-1) to (1-6) can be cited.

[0065] [Chemical formula 11]

[0066] As specific examples of the compound in which Ar in the general formula (1) is 2-oxynaphthalene-1-yl, compounds (1-7) or (1-8) can be cited.

[0067] [Chemical formula 12]

[0068] As specific examples of the compound in which Ar in the general formula (1) is 2-oxynaphthalene-6-yl, compound (1-9) can be cited.

[0069] [Chemical formula 13]

[0070] As specific examples of the compound in which Ar in the general formula (1) is 4-oxy-3-phenylbenzene-1-yl, compounds (1-10) or (1-11) can be cited.

[0071] [Chemical formula 14]

[0072] As specific examples of the compound in which Ar in the general formula (1) is 10-oxyphenanthrene-9-yl, compounds (1-12) or (1-13) can be cited.

[0073] [Chemical formula 15]

[0074] <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 modes are also the same.

[0075] In addition, 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).

[0076] Regarding specific examples of the polyhydroxy aromatic compound (2) represented by the general formula (2), as specific examples of the compound in which Ar in the general formula (2) is all 1-oxybenzene-4-yl, compounds (2-1) to (2-6) can be cited.

[0077] [Chemical Formula 16]

[0078] As specific examples of the compound in which Ar in the general formula (2) is all 2-oxynaphthalene-1-yl, compounds (2-7) or (2-8) can be cited.

[0079] [Chemical Formula 17]

[0080] As specific examples of the compound in which Ar in the general formula (2) is all 2-oxynaphthalene-6-yl, compound (2-9) can be cited.

[0081] [Chemical Formula 18]

[0082] As specific examples of the compound in which Ar in the general formula (2) is all 4-oxy-3-phenylbenzene-1-yl, compounds (2-10) or (2-11) can be cited.

[0083] [Chemical Formula 19]

[0084] As specific examples of the compound in which Ar in the general formula (2) is all 10-oxyphenanthrene-9-yl, compounds (2-12) or (2-13) can be cited.

[0085] [Chemical Formula 20]

[0086] <Halogenated Carboxylic Acid Ester Compound Composition> The halogenated carboxylic acid ester compound composition contains the halogenated carboxylic acid ester compound (3) represented by the general formula (3) and the halogenated carboxylic acid ester compound (4) represented by the general formula (4) within the following range of component ratios.

[0087] <Component Ratio Obtained by Gas Chromatography Analysis> The halogenated carboxylic acid ester compound (3) represented by the general formula (3): 99.50 area% or more and 99.99 area% or less.

[0088] The halogenated carboxylic acid ester compound (4) represented by the general formula (4): 0.01 area% or more and 0.09 area% or less.

[0089] In addition, the halo-carboxylic acid ester compound composition in the present invention refers to a composition constituted by the sum of the component ratios of the halo-carboxylic acid ester compound (3), the halo-carboxylic acid ester compound (4), and other components obtained by the above gas chromatography analysis being 100 area %.

[0090] The definitions of R2 and R3 in the general formula (3) are the same as those in the general formula (1), and the specific examples or preferred modes are also the same.

[0091] In the general formula (3), Y represents a halogen atom, preferably a chlorine atom or a bromine atom, and particularly preferably a chlorine atom.

[0092] The definition of R2 in the general formula (4) is the same as that in the general formula (1), and the specific examples or preferred modes are also the same.

[0093] The definition of Y in the general formula (4) is the same as that in the general formula (3), and the specific examples or preferred modes are also the same.

[0094] In the general formula (4), 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, R4 is a group different from the R3 group of the halo-carboxylic acid ester compound represented by the general formula (3). 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 methyl is particularly preferred.

[0095] The specific compounds of the halo-carboxylic acid ester compound (3) and the halo-carboxylic acid ester compound (4) are common. For example, halo-acetic acid alkyl esters 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; halo-acetic acid alkenyl esters such as vinyl chloroacetate, allyl chloroacetate, vinyl bromoacetate, allyl bromoacetate; halo-propionic acid alkyl esters such as methyl 3-chloropropionate, ethyl 3-chloropropionate, methyl 3-bromopropionate, ethyl 3-bromopropionate; halo-propionic acid alkenyl esters such as vinyl 3-chloropropionate, allyl 3-chloropropionate, vinyl 3-bromopropionate, allyl 3-bromopropionate, etc.

[0096] Among them, halo-acetic acid alkyl esters or halo-acetic acid alkenyl esters 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.

[0097] The halo-carboxylic acid ester compound (3) is selected to be the same as the compound of the R3 group in the target polycarboxylic acid ester compound (1) to be manufactured.

[0098] Particularly preferably, the halogenated carboxylic acid ester compound (3) is ethyl chloroacetate, and the halogenated carboxylic acid ester compound (4) is methyl chloroacetate.

[0099] Regarding the composition ratio of the halogenated carboxylic acid ester compound composition obtained by gas chromatography, the halogenated carboxylic acid ester compound (3) is in the range of 99.50 area% or more and 99.99 area% or less, preferably in the range of 99.6 area% or more and 99.99 area% or less, more preferably in the range of 99.7 area% or more and 99.99 area% or less, and particularly preferably in the range of 99.8 area% or more and 99.99 area% or less.

[0100] The halogenated carboxylic acid ester compound (4) is in the range of 0.01 area% or more and 0.09 area% or less, preferably in the range of 0.01 area% or more and 0.07 area% or less, more preferably in the range of 0.01 mass% or more and 0.05 area% or less, and particularly preferably in the range of 0.01 area% or more and 0.03 area% or less.

[0101] In addition, the halogenated carboxylic acid ester compound composition refers to a composition in which the total of the composition ratios of the halogenated carboxylic acid ester compound (3), the halogenated carboxylic acid ester compound (4), and other components obtained by the above gas chromatography is 100 area%.

[0102] As other components, for example, hydroxycarboxylic acid ester compounds or aliphatic alcohols may be contained.

[0103] <Polycarboxylic acid ester compound (5) represented by general formula (5)> The definitions of Ar, R1, R2, R3, m, n, and X in general formula (5) are the same as those in general formula (1), and the specific examples or preferred modes are also the same.

[0104] 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 ethyl is further preferred, and methyl is particularly preferred.

[0105] Regarding the polycarboxylic acid ester compound (5), as specific examples of the compound in which Ar in general formula (5) is 1-oxybenzene-4-yl and R3 and R4 are ethyl and methyl, compounds (5-1) to (5-6), (5-6') can be cited.

[0106] [Chemical formula 21]

[0107] Specific examples of the compound in which Ar in the general formula (5) is 2-oxynaphthalen-1-yl and R3 and R4 are ethyl and methyl include compound (5-7) or (5-8).

[0108] [Chemical formula 22]

[0109] Specific examples of the compound in which Ar in the general formula (5) is 2-oxynaphthalen-6-yl and R3 and R4 are ethyl and methyl include compound (5-9).

[0110] [Chemical formula 23]

[0111] Specific examples of the compound in which Ar in the general formula (5) is 4-oxo-3-phenylbenzene-1-yl and R3 and R4 are ethyl and methyl include compound (5-10) or (5-11).

[0112] [Chemical formula 24]

[0113] Specific examples of the compound in which Ar in the general formula (5) is 10-oxophenanthren-9-yl and R3 and R4 are ethyl and methyl include compound (5-12) or (5-13).

[0114] [Chemical formula 25]

[0115] <Etherification reaction step> In the etherification reaction step involved in the production method of the present invention, the molar ratio of the total amount of the halogenated carboxylic acid ester compound added relative to the polyhydroxy aromatic compound (2) represented by the general formula (2) is not particularly limited as long as it is (1.0 + n) or more of the theoretical value, and is usually 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).

[0116] 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 halogenated 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.

[0117] In addition, a catalyst can also be used, for example, alkali metal bromide salts such as sodium bromide or potassium bromide, alkali metal iodide salts such as sodium iodide or potassium iodide, ammonium bromide or ammonium iodide, etc. The usage amount of the catalyst is generally in the range of 0.1 to 100% by weight, preferably in the range of 0.1 to 20% by weight, more preferably in the range of 0.1 to 10% by weight, relative to the polyhydroxy aromatic compound (2).

[0118] (Etherification reaction temperature) The reaction temperature is generally in the range of 25 to 120 °C, preferably in the range of 40 to 100 °C, more preferably in the range of 50 to 90 °C, and particularly preferably in the range of 60 to 80 °C. If the reaction temperature is high, the yield decreases; if the reaction temperature is low, the reaction rate becomes slow, so it is not preferred.

[0119] (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 in a pressurized state where a gas inactive to the reaction such as nitrogen is circulated. That is, an inactive 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 inactive to the reaction include nitrogen, argon, helium, etc. From the perspective of economy, nitrogen is most preferred.

[0120] 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 while distilling the solvent out of the reaction system, the generation of by-products can be suppressed. 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 70 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 to reduced pressure by a decompression device. When the reaction pressure is maintained within the aforementioned range, the decompression device can operate intermittently or continuously, and more preferably continuously. 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 aforementioned range.

[0121] (Etherification reaction solvent) The reaction may also be carried out without using a reaction solvent. However, from the viewpoints of operability during industrial production or improvement of reaction rate, it is preferred to use a reaction solvent. As the reaction solvent, there is no particular limitation as long as it does not distill out from the reaction vessel at the reaction temperature and is inactive towards the reaction. For example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ethers such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane, diethoxyethane; aprotic polar solvents such as acetonitrile, dimethyl sulfoxide, dimethylformamide, N-methylpyrrolidone; aromatic hydrocarbon solvents such as toluene, xylene, mesitylene, etc. These organic solvents can be used alone respectively. In addition, two or more of them can be used in combination as appropriate to adjust the polarity. Among them, ketone solvents having 3 to 9 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone or aprotic polar solvents such as acetonitrile, dimethyl sulfoxide, dimethylformamide, N-methylpyrrolidone are preferred. Ketone solvents having 3 to 9 carbon atoms or acetonitrile are more preferred. Ketone solvents having 3 to 6 carbon atoms are further preferred. Acetone or methyl isobutyl ketone is particularly preferred. When methyl isobutyl ketone is used as the reaction solvent, after the reaction is completed, water washing can be carried out to remove water-soluble impurities such as salts. From this point of view, it is preferred.

[0122] The solvent used in the etherification reaction is preferably dehydrated.

[0123] The amount of the solvent used 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 further preferably in a range of 2 to 3 times by weight.

[0124] When the reaction is carried out under reduced pressure while distilling the solvent out of the reaction system, the amount of the solvent used is preferably 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 further preferably in a range of 2 to 6 times by weight.

[0125] During the reaction with the solvent distilled out of the reaction system, as the distillation amount per hour, 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 further 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 be changed within the above range, and the distillation amount can also temporarily exceed the upper or lower limit values of the above range.

[0126] The water content of the reaction solution in the etherification reaction step is preferably in the range of 0.01% by weight or more and 2.0% by weight or less with respect to the polyhydroxy aromatic compound (2). By setting the water content of the reaction solution within the above range, the polycarboxylate compound (1) which is the target compound of the production method of the present invention can be produced with a good reaction yield. The upper limit value of this water content is more preferably in the range of 1.5% by weight or less, further preferably in the range of 1.0% by weight or less, and particularly preferably in the range of 0.5% by weight or less. As a method for setting the water content of the reaction solution within this range, for example, a method of using a raw material or a solvent that has been dehydrated in advance, or a method of distilling off water before carrying out the etherification reaction can be cited.

[0127] (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 point 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) which is the target compound is 2, a monoetherified product which is an intermediate is generated, and when n is 3, after a dietherified product which is an intermediate is generated, it is hardly observed any more. Regarding the time point at which it is hardly observed any more after the production 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.

[0128] The reaction time varies depending on reaction conditions such as the reaction temperature, and usually ends in about 1 to 30 hours.

[0129] <Separation and purification of polycarboxylate compound (1)> The reaction-terminated mixture obtained from the etherification reaction step can be separated and purified according to a conventional method, and thus the polycarboxylate compound (1) can be obtained from the reaction mixture. For example, post-treatment operations such as separation by washing with water, crystallization, filtration, distillation, column chromatography, etc. can be carried out. Further, in order to improve the purity, it can also be further purified by distillation or recrystallization, column chromatography according to a conventional method.

[0130] In addition, in addition to 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 a volatile solvent, or in an inert gas environment such as nitrogen or argon.

[0131] Examples The present invention will be described in more detail below by way of examples, but the present invention is not limited by these examples. The analysis methods are as follows.

[0132] <Analysis Method> 1. Composition Analysis of Polycarboxylate Compounds The composition analysis of polycarboxylate compounds is carried out by high performance liquid chromatography (HPLC) using the following apparatus and conditions. The “%” in the obtained analysis results is the area percentage.

[0133] Measuring apparatus: High performance liquid chromatography analysis apparatus (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 Volume % of (B) (from the start time of analysis) 50% (0 minute) → 100% (10 minutes) → 100% (13 minutes) 2. Composition Analysis of Halogenated Carboxylic Esters Measuring apparatus: Gas chromatograph (GC) Injection mode: Split Vaporization chamber temperature: 300.0 °C Pressure: 164.0 kPa Flow rate: 33.7 mL / min. Chromatographic column flow rate: 1.46 ml / min. Split ratio: 20.0 Chromatographic column: TC-1 0.25 mm × 60 m Detector: FID Detector temperature: 300.0 °C Temperature program: 40 °C (0 minute) → 40 °C (5 minutes) → 250 °C (15.5 minutes) → 250 °C (20.5 minutes) <Comparative Example 1> Using the crystal of 2,2'-bis(2-ethoxycarbonylmethoxy)-1,1'-binaphthyl with the result analyzed by HPLC being 98.8% of 2,2'-bis(2-ethoxycarbonylmethoxy)-1,1'-binaphthyl (Compound (1-7)) and 0.6% of Compound (5-7), 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. A seed crystal was 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 purified by recrystallization to obtain 47.4 g of the crystal of 2,2'-bis(2-ethoxycarbonylmethoxy)-1,1'-binaphthyl.

[0134] The obtained crystal was analyzed by HPLC, and as a result, Compound (1-7) was 99.0% and Compound (5-7) was 0.6%.

[0135] In the purification by recrystallization, the content ratio of Compound (5-7) did not change, and it was found that it could not be removed by the purification by recrystallization.

[0136] The difference in the structure between Compound (5-7) and 2,2'-bis(2-ethoxycarbonylmethoxy)-1,1'-binaphthyl (Compound (1-7)) as the target compound is only that one ester group is different between ethyl and methyl, and the difference in solubility is not large. It is speculated that this impurity and the target substance cannot be separated in the purification by recrystallization.

[0137] <Comparative Example 2> 25.0 g (0.09 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, 37.5 g of super-dehydrated acetone was added. Then, the temperature was raised to 55 - 60 °C, and while maintaining this temperature, 26.8 g (0.22 mol) of ethyl chloroacetate (component ratio analyzed by GC: ethyl chloroacetate 99.60 area%, methyl chloroacetate 0.10 area%) to which 0.3 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 55 - 60 °C.

[0138] The liquid after the etherification reaction was analyzed by HPLC, and as a result, Compound (1-7) was 97.9% and Compound (5-7) was 0.6%.

[0139] <Example 1> Place 15.0 g (0.05 mol) of compound (2-7), 15.0 g of potassium carbonate, and 0.8 g of potassium iodide into a four-necked flask. After purging with nitrogen, add 22.5 g of super-dehydrated acetone. Then, heat to 60 °C and, while maintaining this temperature, add dropwise 16.1 g (0.13 mol) of ethyl chloroacetate (composition ratio determined by GC: ethyl chloroacetate 99.50 area%, methyl chloroacetate 0.05 area%) to which 0.1 g of N-methylpyrrolidone has been added over 2 hours. Then, carry out an etherification reaction for 19 hours while maintaining 60 °C.

[0140] Analyze the liquid after the etherification reaction by HPLC. As a result, compound (1-7) is 98.0% and compound (5-7) is 0.2%.

[0141] <Comparative Example 3> Place 35.0 g (0.12 mol) of compound (2-7), 35.5 g of potassium carbonate, and 1.8 g of potassium iodide into a four-necked flask. After purging with nitrogen, add 87.5 g of methyl isobutyl ketone. Then, heat to 92 °C and distill off 35.3 g of methyl isobutyl ketone under a reduced pressure of 43 kPa. Then, return to atmospheric pressure with nitrogen and, while maintaining this temperature, add dropwise 37.5 g (0.31 mol) of ethyl chloroacetate (composition ratio determined by GC: ethyl chloroacetate 99.57 area%, methyl chloroacetate 0.10 area%) to which 0.3 g of N-methylpyrrolidone has been added over 2 hours. Then, carry out an etherification reaction for 13 hours while maintaining 90 °C.

[0142] Analyze the liquid obtained from the etherification reaction by HPLC. As a result, compound (1-7) is 93.2% and compound (5-7) is 0.7%.

[0143] <Example 2> Place 50.0 g (0.17 mol) of compound (2-7), 50.7 g of potassium carbonate, and 2.5 g of potassium iodide into a four-necked flask. After purging with nitrogen, add 125.0 g of methyl isobutyl ketone. After heating to 92 °C, distill off 55.4 g of methyl isobutyl ketone under a reduced pressure of 50 kPa. Then, return to atmospheric pressure with nitrogen and, while maintaining this temperature, add dropwise 53.5 g (0.44 mol) of ethyl chloroacetate (composition ratio determined by GC: ethyl chloroacetate 99.90 area%, methyl chloroacetate 0.01 area%) to which 0.5 g of N-methylpyrrolidone has been added over 2 hours. Then, carry out an etherification reaction for 12 hours while maintaining 90 °C.

[0144] Analyze the liquid obtained from the etherification reaction by HPLC. As a result, compound (1-7) is 93.5% and compound (5-7) is less than 0.1%.

[0145] When comparing the reaction results of Comparative Example 2 where the content of the halogenated carboxylic acid ester compound (4) represented by the general formula (4) deviated from the present invention with the reaction results of Example 1 which is a specific example of the present invention, in Example 1 which is a specific example of the present invention, the content ratio of the compounds (5-7) decreased by 0.4%.

[0146] Furthermore, when comparing the reaction results of Comparative Example 3 where the content of the halogenated carboxylic acid ester compound (4) represented by the general formula (4) deviated from the present invention with the reaction results of Example 2 which is a specific example of the present invention, it was confirmed that in Example 2 which is a specific example of the present invention, the content ratio of the compounds (5-7) decreased by about 0.7% and was less than 0.1% and thus was regarded as almost not contained.

[0147] From the results of Comparative Example 1, it can be known that according to the method of the present invention, since the generation of the compounds (5-7) that cannot be removed in the purification by recrystallization can be suppressed, the present invention exhibits the remarkable effect of being able to manufacture the compounds (1-7) with improved purity and more excellent quality.

[0148] <Comparative Example 4> 30.1 g (0.08 mol) of 9,9'-biphenanthrene-10,10'-diol (compound (2-12)), 22.6 g (0.16 mol) of potassium carbonate, and 1.7 g (0.01 mol) of potassium iodide were charged into a four-necked flask and purged with nitrogen. Then, 75.0 g of methyl isobutyl ketone was added, and after heating to 95°C, 28.0 g of methyl isobutyl ketone was distilled off under a reduced pressure of 50 kPa. Then, it was returned to normal pressure with nitrogen, and while maintaining this temperature, 24.0 g (0.20 mol) of ethyl chloroacetate (component ratio obtained by GC analysis: ethyl chloroacetate 99.57 area%, methyl chloroacetate 0.10 area%) was added dropwise over 2 hours. Then, while maintaining 90°C, an etherification reaction was carried out for 10 hours.

[0149] The reaction solution obtained from the etherification reaction was analyzed by HPLC, and as a result, 10,10'-bis(2-ethoxycarbonylmethoxy)-9,9'-biphenanthrene (compound (1-12)) was 96.0% and the compound (5-12) was 0.5%.

[0150] 120 g of water and 45 g of methyl isobutyl ketone were added to the liquid after the etherification reaction, and the oil layer was washed with water at 80°C, and the water layer was removed. The oil layer washing operation was repeated once. Then, 92 g of n-heptane was added to the washed oil layer, and while continuously stirring, the liquid was cooled to 25°C, and after continuously stirring overnight, the precipitated crystals were filtered out by filtration.

[0151] The filtered crystals were analyzed by HPLC. As a result, the content of compound (1-12) was 98.9% and that of compound (5-12) was 0.5%.

[0152] The filtered crystals, 184 g of methyl isobutyl ketone and 100 g of water were charged into a four-necked flask, purged with nitrogen, and heated to dissolve the crystals. Then, the oil layer was washed with water at 80°C, and the aqueous layer was removed. The washing operation of the oil layer was repeated once. 107 g of n-heptane was added to the washed oil layer, the liquid was cooled to 25°C, and after stirring overnight, the precipitated crystals were filtered out. The filtered crystals were dried at 80°C under reduced pressure to obtain 33.8 g of crystals of compound (1-12).

[0153] The obtained crystals were analyzed by HPLC. As a result, the content of compound (1-12) was 99.0% and that of compound (5-12) was 0.5%.

[0154] <Example 3> 300.4 g (0.78 mol) of compound (2-12), 225.4 g (1.63 mol) of potassium carbonate and 15.1 g (0.09 mol) of potassium iodide were charged into a four-necked flask and purged with nitrogen. Then, 798 g of super-dehydrated acetone was added, and the temperature was raised to 55°C. Then, 239.1 g (1.95 mol) of ethyl chloroacetate (composition ratio analyzed by GC: ethyl chloroacetate 99.63 area%, methyl chloroacetate 0.01 area%) was added dropwise over 2 hours. After the addition, the mixture was continuously stirred at 55°C for 14 hours to carry out the etherification reaction.

[0155] The reaction solution obtained from the etherification reaction was analyzed by HPLC. As a result, the content of compound (1-12) was 98.3% and that of compound (5-12) was 0.3%.

[0156] It can be clearly understood from the above that according to the production method of the present invention, specific impurities contained in the polycarboxylate compound (1) that cannot be removed by crystallization operation and recrystallization operation can be reduced. Therefore, a polycarboxylate compound (1) with improved quality can be produced.

Claims

1. A method for producing a polycarboxylate compound (1) represented by the general formula (1), characterized in that, The polyhydroxy aromatic compound (2) represented by the general formula (2) and a halo-carboxylic acid ester compound composition within the following component ratio range are subjected to an etherification reaction. <Component ratio obtained by gas chromatography analysis> The halo-carboxylic acid ester compound (3) represented by the general formula (3): in the range of 99.50 area% or more and 99.99 area% or less. The halo-carboxylic acid ester compound (4) represented by the general formula (4): in the range of 0.01 area% or more and 0.09 area% or less. In addition, the total of the component ratios of the halo-carboxylic acid ester compound (3), the halo-carboxylic acid ester compound (4), and other components in the halo-carboxylic acid ester compound composition obtained by gas chromatography analysis is 100 area%. [Chemical formula 1] In 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). In addition, 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 or 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). In addition, 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. [Chemical formula 6] The definition of R2 in the general formula (4) is the same as that in the general formula (1), the definition of Y is the same as that in the general formula (3), and R4 represents a linear or branched alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, provided that R4 is a group different from the R3 group of the halo-carboxylic acid ester compound represented by the general formula (3).

2. The manufacturing method according to claim 1, 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-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.

3. The manufacturing method according to claim 2, characterized in that, n is 2 and X is a direct bond.

4. The manufacturing method according to claim 3, characterized in that, R3 is a linear or branched alkyl group having 1 to 10 carbon atoms.

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