Method for producing polycarboxylic acid ester compound

Abstract

The present invention addresses the problem of providing a polycarboxylic acid ester compound production method for producing a target polycarboxylic acid ester compound more rapidly and with further improved purity by reducing the content of a specific impurity. The above problem is solved by providing a method for producing a polycarboxylic acid ester compound (1) represented by general formula (1), wherein the method comprises an etherification reaction step for using a polyhydroxy aromatic compound (2) represented by general formula (2), a halocarboxylic acid ester compound (3) represented by general formula (3), and potassium carbonate to initiate an etherification reaction, and the specific surface area of the potassium carbonate is in the range of 0.1-2.0 m2 / g<sp / >.

Description

Method for producing polycarboxylic acid ester compound

[0001] The present invention relates to a method for producing a polycarboxylic acid ester compound. More specifically, the present invention relates to a method for producing a polycarboxylic acid ester compound having improved purity by more quickly carrying out an etherification reaction to obtain a target polycarboxylic acid ester compound, thereby reducing the content of specific impurities.

[0002] Polycarboxylic acid compounds are used as raw materials for polyamides, raw materials for allyl ester compounds, and additives such as plasticizers and curing agents, and dicarboxylic acid compounds using bisphenol compounds as raw materials are also known (Patent Documents 1 and 2, etc.). In recent years, in the application fields of such materials, demands for improvements in various performances have become increasingly sophisticated, and raw materials used in materials to exhibit desired properties are required to have improved quality. As a method for producing dicarboxylic acid compounds using bisphenol compounds as raw materials, a method is known in which a bisphenol compound and a halocarboxylic acid or an ester thereof are used as raw materials and an etherification reaction is carried out to synthesize a dicarboxylic acid or an ester compound thereof.

[0003] JP-A-62-292819 JP-A-05-170702

[0004] While the above-mentioned production methods are known, the present inventors have conducted extensive research to improve the quality of dicarboxylic acid ester compounds produced using bisphenol compounds as raw materials. As a result, they have discovered a problem in that, in the step of carrying out an etherification reaction using a bisphenol compound, a halocarboxylic acid ester, and potassium carbonate as raw materials, the reaction progresses differently depending on the potassium carbonate used, slowing down the production of the target dicarboxylic acid ester compound. Furthermore, they have discovered a problem in that the amount of specific impurities produced increases, sometimes preventing improvement in purity. In light of the above-mentioned problems discovered by the present inventors, the present invention aims to provide a method for more quickly producing the target polycarboxylic acid ester compound (1), and a method for producing a polycarboxylic acid ester compound (1) with improved purity by reducing the content of specific impurities.

[0005] As a result of intensive research, the present inventors have discovered by-products of polycarboxylic acid compounds in which the ester groups of the target compound, polycarboxylic acid ester compound (1), are hydrolyzed, and by-products in which halocarboxylic acid esters are excessively reacted during the etherification reaction. If the target polycarboxylic acid ester compound (1) contains impurities with different substituents, there is a risk of malfunction during the production of materials obtained using this compound, or adverse effects on the physical properties of the materials. Furthermore, they have discovered that the difference in the progress of the etherification reaction is due to the specific surface area of ​​the potassium carbonate used, and that the above problems can be solved by using potassium carbonate with a specific surface area within a certain range, thereby completing the present invention.

[0006] The present invention is as follows: 1. An etherification reaction process includes an etherification reaction using a polyhydroxy aromatic compound (2) represented by general formula (2), a halocarboxylic acid ester compound (3) represented by general formula (3), and potassium carbonate, wherein the potassium carbonate has a specific surface area of ​​0.1 m ２ / g or more 2.0m ２ / g or less. (In formula (1), each Ar independently represents a monooxy aromatic hydrocarbon group having 6 to 20 carbon atoms and a valence of 2+m, and R １ each independently represents a linear or branched alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 5 to 6 carbon atoms, or a linear or branched alkoxyl group having 1 to 6 carbon atoms; R ２ each independently represents a linear or branched alkylene group having 1 to 4 carbon atoms; R ３ each independently represents an 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, and 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). In general formula (1), the oxygen atom contained in Ar is in contact with the aromatic hydrocarbon group contained in Ar and R ２ Binds to (In general formula (1a), R ５ and R ６ each 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; R ５ and R ６ may be bonded to each other to form a cycloalkylidene group having 5 to 20 carbon atoms as a whole, and in general formula (1b), Ar １ each independently represents an aryl group having 6 to 12 carbon atoms. * in general formulas (1a), (1b), and (1c) indicates the bonding position. (In general formula (1d), R ７ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms. ８ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. * in general formulas (1d) and (1e) respectively indicates the bonding position.) (Ar and R in general formula (2) １ The definitions of m, n, and X are the same as in general formula (1). In general formula (2), the oxygen atom of Ar bonds to the aromatic hydrocarbon group contained in Ar and the hydrogen atom (H) described in general formula (2). (R in general formula (3) ２ and R ３is defined as in general formula (1), and Y represents a halogen atom.) 2. Each Ar independently represents a 1-oxybenzene-4-yl group, a 1-oxybenzene-3-yl group, a 1-oxybenzene-2-yl group, a 1-oxynaphthalen-2-yl group, a 1-oxynaphthalen-4-yl group, a 1-oxynaphthalen-5-yl group, a 2-oxynaphthalen-1-yl group, a 2-oxynaphthalen-6-yl group, a 2-oxynaphthalen-7-yl group, a 4-oxy-3-phenylbenzene-1-yl group, a 9-oxyphenanthren-3-yl group, a 10-oxyphenanthren-9-yl group, a 2-oxyanthracen-7-yl group, a 1-oxy-3-phenylnaphthalen-4-yl group, a 1-oxy-3-phenylnaphthalen-5-yl group, a 2-oxy-1-phenylnaphthalen-6-yl group, a 2-oxy-1-phenyl ... 2. The method according to 1., wherein the hydroxyl group is any one group selected from the group consisting of a 2-oxy-3-phenylanthracen-7-yl group, a 2-oxy-3-phenylnaphthalen-6-yl group, a 2-oxy-3-phenylnaphthalen-7-yl group, a 4-oxy-3-(1-naphthyl)benzene-1-yl group, a 4-oxy-3-(2-naphthyl)benzene-1-yl group, a 4-oxy-3,5-diphenylbenzene-1-yl group, a 4-oxy-2-phenylphenanthren-6-yl group, a 4-oxy-2-phenylphenanthren-7-yl group, a 4-oxy-2-phenylphenanthren-8-yl group, a 4-oxy-2-phenylphenanthren-9-yl group, a 4-oxy-2-phenylphenanthren-10-yl group, and a 2-oxy-3-phenylanthracen-7-yl group. 1. The production method according to Item 1, wherein the polycarboxylic acid ester compound (1) represented by the general formula (1) is a polycarboxylic acid ester compound represented by any one of general formulae (1A) to (1F), and the polyhydroxy aromatic compound (2) represented by the general formula (2) is a polyhydroxy aromatic compound represented by any one of general formulae (2A) to (2F). (In general formulas (1A) to (1F), R １ , R ２ , R３ , m, n, and X are the same as those defined in general formula (1). (In general formulas (2A) to (2F), R １ , m, n, and X are defined as in general formula (1). 4. The production method according to 3., wherein n is 1 for the polycarboxylic acid ester compounds represented by general formulas (1C), (1D), (1E), and (1F), n is 2 for the polycarboxylic acid ester compound represented by general formula (1B), n is 1 for the polyhydroxy aromatic compounds represented by general formulas (2C), (2D), (2E), and (2F), and n is 2 for the polyhydroxy aromatic compound represented by general formula (2B).

[0007] According to the production method of the present invention, the etherification reaction step for obtaining the target polycarboxylic acid ester compound (1) can be carried out more quickly, thereby enabling efficient production of the polycarboxylic acid ester compound (1). Furthermore, the production of specific impurities can be reduced, allowing efficient production of the polycarboxylic acid ester compound (1) with improved quality.

[0008] <Production Method of the Present Invention> The method of the present invention for producing a polycarboxylic acid ester compound (1) represented by general formula (1) includes an etherification reaction step of carrying out an etherification reaction using a polyhydroxy aromatic compound (2) represented by general formula (2), a halocarboxylic acid ester compound (3) represented by general formula (3), and potassium carbonate, wherein the potassium carbonate has a specific surface area of ​​0.1 m ２ / g or more 2.0m ２ / g or less.

[0009] <Polycarboxylic acid ester compound (1) represented by general formula (1)> In general formula (1), Ar each independently represents a monooxy aromatic hydrocarbon group having a valence of 2+m and having 6 to 20 carbon atoms. In general formula (1), the oxygen atom contained in Ar is in a state where it ... ２ Combine with.

[0010] First, the case where m is 0, i.e., a divalent monooxy aromatic hydrocarbon group having 6 to 20 carbon atoms, will be described. Among divalent monooxy aromatic hydrocarbon groups having 6 to 20 carbon atoms, divalent monooxy aromatic hydrocarbon groups having 6 to 16 carbon atoms are preferred, divalent monooxy aromatic hydrocarbon groups having 6 to 14 carbon atoms are more preferred, divalent monooxy aromatic hydrocarbon groups having 6, 10 or 14 carbon atoms are even more preferred, and divalent monooxy aromatic hydrocarbon groups having 10 or 14 carbon atoms are particularly preferred. Specific examples of divalent monooxy aromatic hydrocarbon groups having 6 carbon atoms include a 1-oxybenzene-4-yl group, a 1-oxybenzene-3-yl group, and a 1-oxybenzene-2-yl group. Specific examples of divalent monooxy aromatic hydrocarbon groups having 10 carbon atoms include 1-oxynaphthalen-2-yl, 1-oxynaphthalen-4-yl, 1-oxynaphthalen-5-yl, 2-oxynaphthalen-1-yl, 2-oxynaphthalen-6-yl, and 2-oxynaphthalen-7-yl groups. Specific examples of divalent monooxy aromatic hydrocarbon groups having 12 carbon atoms include 4-oxy-3-phenylbenzene-1-yl groups. Specific examples of divalent monooxy aromatic hydrocarbon groups having 14 carbon atoms include monooxyphenanthrenyl groups such as 9-oxyphenanthren-3-yl and 10-oxyphenanthren-9-yl groups, and 2-oxyanthracen-7-yl groups. Of these, monooxyphenanthrenyl groups are more preferred, and 9-oxyphenanthren-3-yl and 10-oxyphenanthren-9-yl groups are even more preferred. Specific examples of the divalent monooxy aromatic hydrocarbon group having 16 carbon atoms include a 1-oxy-3-phenylnaphthalen-4-yl group, a 1-oxy-3-phenylnaphthalen-5-yl group, a 2-oxy-1-phenylnaphthalen-6-yl group, a 2-oxy-1-phenylnaphthalen-7-yl group, a 2-oxy-3-phenylnaphthalen-6-yl group, a 2-oxy-3-phenylnaphthalen-7-yl group, a 4-oxy-3-(1-naphthyl)benzene-1-yl group, and a 4-oxy-3-(2-naphthyl)benzene-1-yl group.A specific example of a divalent monooxy aromatic hydrocarbon group having 18 carbon atoms is a 4-oxy-3,5-diphenylbenzene-1-yl group. Specific examples of a divalent monooxy aromatic hydrocarbon group having 20 carbon atoms are a 4-oxy-2-phenylphenanthrene-6-yl group, a 4-oxy-2-phenylphenanthrene-7-yl group, a 4-oxy-2-phenylphenanthrene-8-yl group, a 4-oxy-2-phenylphenanthrene-9-yl group, a 4-oxy-2-phenylphenanthrene-10-yl group, and a 2-oxy-3-phenylanthracen-7-yl group. It is also possible to select any one group selected from the group consisting of the above specific examples of divalent monooxy aromatic hydrocarbon groups having 6 to 20 carbon atoms. That is, Ar in the general formula (1) each independently represents a 1-oxybenzene-4-yl group, a 1-oxybenzene-3-yl group, a 1-oxybenzene-2-yl group, a 1-oxynaphthalen-2-yl group, a 1-oxynaphthalen-4-yl group, a 1-oxynaphthalen-5-yl group, a 2-oxynaphthalen-1-yl group, a 2-oxynaphthalen-6-yl group, a 2-oxynaphthalen-7-yl group, a 4-oxy-3-phenylbenzene-1-yl group, a 9-oxyphenanthren-3-yl group, a 10-oxyphenanthren-9-yl group, a 2-oxyanthracen-7-yl group, a 1-oxy-3-phenylnaphthalen-4-yl group, a 1-oxy-3-phenylnaphthalen-5-yl group, a 2-oxy-1-phenylnaphthalen-6-yl group, a 2-oxy- It is also possible to select any one group selected from the group consisting of a 1-phenylnaphthalen-7-yl group, a 2-oxy-3-phenylnaphthalen-6-yl group, a 2-oxy-3-phenylnaphthalen-7-yl group, a 4-oxy-3-(1-naphthyl)benzene-1-yl group, a 4-oxy-3-(2-naphthyl)benzene-1-yl group, a 4-oxy-3,5-diphenylbenzene-1-yl group, a 4-oxy-2-phenylphenanthren-6-yl group, a 4-oxy-2-phenylphenanthren-7-yl group, a 4-oxy-2-phenylphenanthren-8-yl group, a 4-oxy-2-phenylphenanthren-9-yl group, a 4-oxy-2-phenylphenanthren-10-yl group, and a 2-oxy-3-phenylanthracen-7-yl group.Among these, Ar in general formula (1) is preferably any one group selected from the group consisting of 1-oxybenzene-4-yl group, 1-oxybenzene-2-yl group, 2-oxynaphthalen-1-yl group, 2-oxynaphthalen-6-yl group, 4-oxy-3-phenylbenzene-1-yl group, 9-oxyphenanthrene-3-yl group and 10-oxyphenanthrene-9-yl group, and each independently is preferably 1-oxybenzene-4-yl group, 1-oxybenzene-2-yl group, 2-oxynaphthalen-1-yl group and 10-oxyphenanthrene-9-yl group. and m is 1 or 2, that is, in the case of a trivalent or tetravalent monooxy aromatic hydrocarbon group having 6 to 20 carbon atoms, when m is 0, one or two of the hydrogen atoms in the aromatic hydrocarbon group are R. １ It is a group that has been substituted at the bonding position so that it can bond to the group.

[0011] The polycarboxylic acid ester compound (1) represented by general formula (1) is preferably a polycarboxylic acid ester compound represented by any one selected from general formulas (1A) to (1F) described below, more preferably a polycarboxylic acid ester compound represented by general formula (1A), (1B), (1C), (1E) or (1F), still more preferably a polycarboxylic acid ester compound represented by general formula (1A), (1B), (1E) or (1F), and particularly preferably a polycarboxylic acid ester compound represented by general formula (1B), (1E) or (1F).

[0012] R in general formula (1) １each independently represents a linear or branched alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 5 to 6 carbon atoms, or a linear or branched alkoxyl group having 1 to 6 carbon atoms. Among these, each independently represents a linear or branched alkyl group having 1 to 4 carbon atoms, a cyclohexyl group, or a methoxy group, and each independently represents a methyl group, a t-butyl group, or a cyclohexyl group, more preferably, a methyl group.

[0013] R in general formula (1) ２ each independently represent a linear or branched alkylene group having 1 to 4 carbon atoms. Among these, each independently represents a linear or branched alkylene group having 1 to 3 carbon atoms, more preferably a methylene group, a 1,2-ethylene group, or a 1,3-propylene group, and particularly preferably a methylene group or a 1,3-propylene group.

[0014] R in general formula (1) ３ each independently represents an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. Among these, a linear or branched alkyl group having 1 to 6 carbon atoms or a cyclic alkyl group having 5 to 8 carbon atoms is preferred, a linear or branched alkyl group having 1 to 4 carbon atoms or a cyclic alkyl group having 6 to 8 carbon atoms is more preferred, a methyl group, an ethyl group, a t-butyl group, a 1-methylcyclopentyl group or a 1-ethylhexyl group is even more preferred, and a methyl group, an ethyl group or a t-butyl group is particularly preferred.

[0015] Each m independently represents 0, 1 or 2. When m is 1, R １ Regarding the position to which R is bonded, the 1-oxybenzene-4-yl group is preferably the 2-position, the 1-oxybenzene-2-yl group is preferably the 2- or 4-position, the 2-oxynaphthalen-1-yl group is preferably the 6-position, the 2-oxynaphthalen-6-yl group is preferably the 5-position, the 4-oxy-3-phenylbenzene-1-yl group is preferably the 5-position, the 9-oxyphenanthren-3-yl group is preferably the 10-position, and the 10-oxyphenanthren-9-yl group is preferably the 6-position. １Regarding the bonding positions, the 1-oxybenzene-4-yl group is preferably bonded to positions 2 and 5. n is 1 or 2.

[0016] In the general formula (1), when n is 1, X 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), and among these, a single bond, a divalent group represented by the general formula (1a), a divalent group represented by the general formula (1b), or a divalent group represented by the general formula (1c) is preferred, a single bond, a divalent group represented by the general formula (1b), or a divalent group represented by the general formula (1c) is more preferred, and a single bond is particularly preferred. In the general formula (1), when n is 2, X is a trivalent group represented by the general formula (1d) or (1e), and a trivalent group represented by the general formula (1d) is preferred.

[0017] When X in the general formula (1) is a divalent group represented by the general formula (1a), more preferred R ５ and R ６ are 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, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and particularly preferably a hydrogen atom, a methyl group, or an ethyl group. ５ and R ６may be bonded to each other to form a cycloalkylidene group having 5 to 20 carbon atoms as a whole. The cycloalkylidene group having 5 to 20 carbon atoms may contain an alkyl group as a substituent. The cycloalkylidene group preferably has 5 to 15 carbon atoms, more preferably has 6 to 12 carbon atoms, and particularly preferably has 6 to 9 carbon atoms. Specific examples of the cycloalkylidene group include a cyclopentylidene group (5 carbon atoms), a cyclohexylidene group (6 carbon atoms), a 3-methylcyclohexylidene group (7 carbon atoms), a 4-methylcyclohexylidene group (7 carbon atoms), a 3,3,5-trimethylcyclohexylidene group (9 carbon atoms), a cycloheptylidene group (7 carbon atoms), a bicyclo[2.2.1]heptane-2,2-diyl group (7 carbon atoms), a 1,7,7-trimethylbicyclo[2.2.1]heptane-2,2-diyl group (10 carbon atoms), a 4,7,7-trimethylbicyclo[2.2.1]heptane-2,2-diyl group (10 carbon atoms), a tricyclo[5.2.1.0 ２，６ ]decane-8,8-diyl group (10 carbon atoms), 2,2-adamantylidene group (10 carbon atoms), cyclododecanylidene group (12 carbon atoms), etc. Preferred are cyclohexylidene group (6 carbon atoms), 3-methylcyclohexylidene group (7 carbon atoms), 4-methylcyclohexylidene group (7 carbon atoms), 3,3,5-trimethylcyclohexylidene group (9 carbon atoms), and cyclododecanylidene group (12 carbon atoms), more preferred are cyclohexylidene group (6 carbon atoms), 3,3,5-trimethylcyclohexylidene group (9 carbon atoms), and cyclododecanylidene group (12 carbon atoms), and particularly preferred are cyclohexylidene group (6 carbon atoms) and 3,3,5-trimethylcyclohexylidene group (9 carbon atoms).

[0018] Preferred Ar when X in general formula (1) is a divalent group represented by general formula (1b) １ are each independently a benzene ring or a naphthalene ring, and Ar １ It is more preferable that both of Ar and Ar are benzene rings. １When both are benzene rings, the group represented by general formula (1b) is a fluorenylidene group.

[0019] When X in general formula (1) is a divalent group represented by general formula (1c), a preferred embodiment is a divalent group represented by formula (1c') or formula (1c'').

[0020] In the case where X in the general formula (1) is a trivalent group represented by the general formula (1d), a preferred embodiment is R ７ is preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and R ７ is more preferably a hydrogen atom, a methyl group, or a phenyl group, and R ７ is particularly preferably a hydrogen atom or a methyl group.

[0021] In the case where X in the general formula (1) is a trivalent group represented by the general formula (1e), a preferred embodiment is R ８ is preferably a hydrogen atom or a methyl group, and R ８ is particularly preferably a methyl group.

[0022] When both Ar in general formula (1) are 1-oxybenzene-4-yl groups, the resulting polycarboxylic acid ester compound is represented by general formula (1A). (In general formula (1A), R １ , R ２ , R ３ , m, n, and X are defined as in general formula (1). Specific examples of the compound in which both Ar in general formula (1) are 1-oxybenzene-4-yl groups include compounds (1-1) to (1-9).

[0023] When Ar in general formula (1) is a 1-oxybenzene-4-yl group and a 1-oxybenzene-2-yl group, an example thereof is a polycarboxylic acid ester compound represented by general formula (1B), and this compound is preferred. In the polycarboxylic acid ester compound represented by general formula (1B), n is preferably 2. (In general formula (1B), R１ , R ２ , R ３ , m, n, and X are defined as in general formula (1). Specific examples of the compound in which Ar in general formula (1) has a 1-oxybenzene-4-yl group and a 1-oxybenzene-2-yl group include compounds (1-10) to (1-12).

[0024] When both Ar in general formula (1) are 2-oxynaphthalen-1-yl groups, the polycarboxylic acid ester compound is represented by general formula (1C). In the polycarboxylic acid ester compound represented by general formula (1C), n is preferably 1. (In general formula (1C), R １ , R ２ , R ３ , m, n, and X are defined as in general formula (1). Specific examples of the compound in which both Ar in general formula (1) are 2-oxynaphthalen-1-yl groups include compounds (1-13) and (1-14).

[0025] When both Ar in general formula (1) are 2-oxynaphthalen-6-yl groups, the polycarboxylic acid ester compound is represented by general formula (1D). In the polycarboxylic acid ester compound represented by general formula (1D), n is preferably 1. (In general formula (1D), R １ , R ２ , R ３ , m, n, and X are defined as in general formula (1). A specific example of a compound in which both Ar in general formula (1) are 2-oxynaphthalen-6-yl groups is compound (1-15).

[0026] When both Ar in general formula (1) are 4-oxy-3-phenylbenzene-1-yl groups, the polycarboxylic acid ester compound is represented by general formula (1E). In the polycarboxylic acid ester compound represented by general formula (1E), n is preferably 1. (In general formula (1E), R １ , R ２ , R３ , m, n, and X are defined as in general formula (1). Specific examples of the compound in which both Ar in general formula (1) are 4-oxy-3-phenylbenzene-1-yl groups include compounds (1-16) and (1-17).

[0027] When both Ar in general formula (1) are 10-oxyphenanthren-9-yl groups, the polycarboxylic acid ester compound is represented by general formula (1F). In the polycarboxylic acid ester compound represented by general formula (1F), n is preferably 1. (In general formula (1F), R １ , R ２ , R ３ , m, n, and X are defined as in general formula (1). Specific examples of the compound in which both Ar in general formula (1) are 10-oxyphenanthren-9-yl groups include compounds (1-18) to (1-23).

[0028] <Polyhydroxy aromatic compound (2) represented by general formula (2)> Ar and R in general formula (2) １ The definitions of m, n, and X are the same as those in general formula (1), and specific examples and preferred embodiments are also the same. In general formula (2), the oxygen atom in Ar bonds to the aromatic hydrocarbon group contained in Ar and the hydrogen atom (H) described in general formula (2). Among the polyhydroxy aromatic compounds (2) represented by general formula (2), polyhydroxy aromatic compounds represented by any one of general formulas (2A) to (2F) described below are preferred, polyhydroxy aromatic compounds represented by general formulas (2A), (2B), (2C), (2E), or (2F) are more preferred, polyhydroxy aromatic compounds represented by general formulas (2A), (2B), (2E), or (2F) are even more preferred, and polyhydroxy aromatic compounds represented by general formulas (2B), (2E), or (2F) are particularly preferred.

[0029] When both Ar in general formula (2) are 1-oxybenzene-4-yl groups, the resulting polyhydroxy aromatic compound is represented by general formula (2A). (In general formula (2A), R １ , m, n, and X are defined as in general formula (1). Specific examples of the compound in which both Ar in general formula (2) are 1-oxybenzene-4-yl groups include compounds (2-1) to (2-8).

[0030] When Ar in general formula (2) is a 1-oxybenzene-4-yl group and a 1-oxybenzene-2-yl group, an example thereof is a polyhydroxy aromatic compound represented by general formula (2B), and this embodiment is preferred. In the polyhydroxy aromatic compound represented by general formula (2B), n is preferably 2. (In general formula (2B), R １ , m, n, and X are defined as in general formula (1). A specific example of a compound in which Ar in general formula (2) has a 1-oxybenzene-4-yl group and a 1-oxybenzene-2-yl group is compound (2-9).

[0031] When both Ar in general formula (2) are 2-oxynaphthalen-1-yl groups, the polyhydroxy aromatic compound is represented by general formula (2C). In the polyhydroxy aromatic compound represented by general formula (2C), n is preferably 1. (In general formula (2C), R １ , m, n, and X are defined as in general formula (1). Specific examples of the compound in which both Ar in general formula (2) are 2-oxynaphthalen-1-yl groups include compounds (2-10) and (2-11).

[0032] When both Ar in general formula (2) are 2-oxynaphthalen-6-yl groups, the polyhydroxy aromatic compound is represented by general formula (2D). In the polyhydroxy aromatic compound represented by general formula (2D), n is preferably 1. (In general formula (2D), R １, m, n, and X are defined as in general formula (1). A specific example of a compound in which both Ar in general formula (2) are 2-oxynaphthalen-6-yl groups is compound (2-12).

[0033] When both Ar in general formula (2) are 4-oxy-3-phenylbenzene-1-yl groups, the polyhydroxy aromatic compound is represented by general formula (2E). In the polyhydroxy aromatic compound represented by general formula (2E), n is preferably 1. (In general formula (2E), R １ , m, n, and X are defined as in general formula (1). Specific examples of the compound in which both Ar in general formula (2) are 4-oxy-3-phenylbenzene-1-yl groups include compounds (2-13) and (2-14).

[0034] When both Ar in general formula (2) are 10-oxyphenanthren-9-yl groups, the polyhydroxy aromatic compound is represented by general formula (2F). In the polyhydroxy aromatic compound represented by general formula (2F), n is preferably 1. (In general formula (2F), R １ , m, n, and X are defined as in general formula (1). Specific examples of the compound in which both Ar in general formula (2) are 10-oxyphenanthren-9-yl groups include compounds (2-15) and (2-16).

[0035] <Halocarboxylic acid ester compound (3) represented by general formula (3)> R in general formula (3) ２ and R ３The definition of is the same as that of general formula (1), and specific examples and preferred embodiments are also the same. Y in general formula (3) represents a halogen atom, and among them, a chlorine atom or a bromine atom is preferred, and a chlorine atom is particularly preferred. Specific examples of the halocarboxylic acid ester compound (3) include halogenated alkyl acetates such as methyl chloroacetate, ethyl chloroacetate, n-propyl chloroacetate, isopropyl chloroacetate, n-butyl chloroacetate, isobutyl chloroacetate, tert-butyl chloroacetate, 1-methylcyclopentyl chloroacetate, 1-ethylcyclohexyl chloroacetate, methyl bromoacetate, ethyl bromoacetate, n-propyl bromoacetate, isopropyl bromoacetate, n-butyl bromoacetate, isobutyl bromoacetate, tert-butyl bromoacetate, 1-methylcyclopentyl bromoacetate, and 1-ethylcyclohexyl bromoacetate; halogenated alkenyl acetates such as vinyl chloroacetate, allyl chloroacetate, vinyl bromoacetate, and allyl bromoacetate; methyl 3-chloropropanoate, ethyl 3-chloropropanoate, methyl 3-bromopropanoate, and ethyl 3-bromopropanoate. halogenated alkyl propanoates such as vinyl 3-chloropropanoate, allyl 3-chloropropanoate, vinyl 3-bromopropanoate, and allyl 3-bromopropanoate; halogenated alkenyl propanoates such as methyl 4-chlorobutyrate, ethyl 4-chlorobutyrate, n-propyl 4-chlorobutyrate, isopropyl 4-chlorobutyrate, n-butyl 4-chlorobutyrate, isobutyl chloroacetate, tert-butyl 4-chlorobutyrate, 1-methylcyclopentyl 4-chlorobutyrate, 1-ethylcyclohexyl 4-chlorobutyrate, methyl 4-bromobutyrate, ethyl 4-bromobutyrate, n-propyl 4-bromobutyrate, isopropyl 4-bromobutyrate, n-butyl 4-bromobutyrate, isobutyl 4-bromoacetate, tert-butyl 4-bromobutyrate, 1-methylcyclopentyl 4-bromobutyrate, and 1-ethylcyclohexyl 4-bromobutyrate.Among these, halogenated alkyl acetates or halogenated alkyl butyrates are preferred, such as methyl chloroacetate, ethyl chloroacetate, tert-butyl chloroacetate, 1-methylcyclopentyl chloroacetate, 1-ethylcyclohexyl chloroacetate, methyl bromoacetate, ethyl bromoacetate, tert-butyl bromoacetate, 1-methylcyclopentyl bromoacetate, 1-ethylcyclohexyl bromoacetate, methyl 4-chlorobutyrate, ethyl 4-chlorobutyrate, tert-butyl 4-chlorobutyrate, 1-methylcyclopentyl 4-chlorobutyrate, 1-ethylcyclohexyl 4-chlorobutyrate, methyl 4-bromobutyrate, ethyl 4-bromobutyrate, tert-butyl 4-bromoacetate, 1-methylcyclopentyl 4-chlorobutyrate, ... and 1-ethylcyclohexyl 4-bromoacetate are more preferred, and any one compound selected from methyl chloroacetate, ethyl chloroacetate, tert-butyl chloroacetate, 1-methylcyclopentyl chloroacetate, 1-ethylcyclohexyl chloroacetate, methyl 4-chlorobutyrate, ethyl 4-chlorobutyrate, tert-butyl 4-chlorobutyrate, 1-methylcyclopentyl 4-chlorobutyrate, and 1-ethylcyclohexyl 4-chlorobutyrate are even more preferred, and any one compound selected from methyl chloroacetate, ethyl chloroacetate, tert-butyl chloroacetate, methyl 4-chlorobutyrate, ethyl 4-chlorobutyrate, and tert-butyl 4-chlorobutyrate are particularly preferred.

[0036] <Etherification Reaction Step> In the etherification reaction step according to the production method of the present invention, the molar ratio of the halocarboxylic acid ester compound (3) charged to the polyhydroxy aromatic compound (2) is not particularly limited as long as it is equal to or greater than the theoretical value (1.0 + n), but is usually in the range of 2 to 20 times the molar amount, preferably 2 to 10 times the molar amount, and more preferably 2 to 6 times the molar amount. Note that the theoretical value "n" is the number "n" in general formula (1).

[0037] (Potassium carbonate) In the etherification reaction step according to the production method of the present invention, potassium carbonate having a specific surface area of ​​0.1 m ２ The specific surface area of ​​potassium carbonate is 0.1 m / g or more. ２ / g or more, 0.1m２ This is preferable because the etherification reaction proceeds more quickly and the formation of specific impurities can be suppressed compared to when the specific surface area is less than 1 / g. In the etherification reaction step according to the production method of the present invention, potassium carbonate and the polyhydroxy aromatic compound (2) form a salt, and the prepared liquid is in a slurry state before the reaction with the halocarboxylic acid ester compound (3). In the reaction mechanism of the etherification reaction step, the specific surface area affects the frequency of interaction with the polyhydroxy aromatic compound (2), so the larger the specific surface area, the better. From the viewpoint of availability of potassium carbonate, the upper limit of the specific surface area is 2.0 m ２ / g or less. That is, the specific surface area may be 0.1 m ２ / g or more 2.0m ２ The lower limit of the specific surface area of ​​the potassium carbonate used is 0.2 m / g. ２ / g or more, and ２ / g or more, and 0.5m ２ / g or more, and more preferably 0.7m ２ The upper limit of the specific surface area is preferably 1.5 m / g or more. ２ / g or less, and ２ / g or less. The specific surface area in the present invention means a value obtained by analyzing potassium carbonate by the BET method using a mercury porosimetry apparatus. The molar ratio of potassium carbonate charged is usually in the range of 0.8 to 4 times, preferably 0.85 to 3 times, and more preferably 0.9 to 2 times, the total amount of halocarboxylic acid ester compound (3) used.

[0038] (Catalyst) The etherification reaction in the production method of the present invention may use a catalyst, and examples thereof include alkali metal bromides such as sodium bromide and potassium bromide, alkali metal iodides such as sodium iodide and potassium iodide, ammonium bromide, ammonium iodide, etc. The amount of the catalyst used is usually in the range of 0.1 to 100% by weight, preferably 0.1 to 20% by weight, and more preferably 0.1 to 10% by weight, based on the weight of the polyhydroxy aromatic compound (2).

[0039] (Etherification Reaction Temperature) The reaction temperature is usually 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. A high reaction temperature reduces the yield, while a low reaction temperature slows the reaction rate, which is undesirable.

[0040] (Etherification Reaction Pressure) The reaction pressure is not limited and may be atmospheric pressure, reduced pressure, or pressurized. Atmospheric pressure or reduced pressure is preferred. In a reaction under pressure, the reaction can be carried out under pressure by circulating an inert gas such as nitrogen through the reaction system. That is, the reaction can be carried out by introducing an inert gas into the reaction system and discharging the gas from the reaction system. This allows carbon dioxide gas generated from the potassium carbonate used in the reaction to be discharged from the reaction system, thereby accelerating the reaction. Specific examples of inert gases include nitrogen gas, argon gas, and helium gas. From an economical viewpoint, nitrogen gas is most preferred. From the viewpoint of shortening the reaction time, reduced pressure is more preferred. By carrying out the reaction under reduced pressure, carbon dioxide gas generated from the potassium carbonate used can be discharged from the reaction system, thereby accelerating the reaction and shortening the reaction time compared to a reaction under atmospheric pressure. Furthermore, by carrying out the reaction under reduced pressure and distilling the solvent out of the reaction system, the production of by-products can be suppressed. Specifically, the reaction pressure is preferably in the range of 5 kPa to 80 kPa, more preferably in the range of 10 kPa to 70 kPa, and even more preferably in the range of 30 kPa to 60 kPa. The reaction pressure can be reduced using a pressure reducing device, and when the reaction pressure is maintained within the above range, the pressure reducing device may be operated intermittently or continuously, but is more preferably operated continuously. It is preferable to carry out the reaction under reduced pressure, specifically by maintaining the pressure within the above range, from the start to the end of the reaction.

[0041] (Solvent) The reaction does not necessarily require the use of a reaction solvent, but it is preferable to use one for reasons such as improving operability and reaction rate during industrial production. The reaction solvent is not particularly limited as long as it does not distill out of the reaction vessel at the reaction temperature and is inert to the reaction. Examples of the reaction solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethers such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane, and diethoxyethane; aprotic polar solvents such as acetonitrile, dimethyl sulfoxide, dimethylformamide, and N-methylpyrrolidone; and aromatic hydrocarbon solvents such as toluene, xylene, and mesitylene. These organic solvents may be used alone, or two or more of them may be used in combination as appropriate to adjust the polarity. Among these, ketone solvents having 3 to 9 carbon atoms, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, and cyclooctanone, and aprotic polar solvents such as acetonitrile, dimethyl sulfoxide, dimethylformamide, and N-methylpyrrolidone are preferred; ketone solvents having 3 to 9 carbon atoms, dimethylformamide, N-methylpyrrolidone, and acetonitrile are more preferred; ketone solvents having 3 to 6 carbon atoms, dimethylformamide, and N-methylpyrrolidone are even more preferred; and acetone, methyl isobutyl ketone, dimethylformamide, and N-methylpyrrolidone are particularly preferred. Methyl isobutyl ketone is also preferred because it allows for washing with water to remove water-soluble impurities such as salts after completion of the reaction. It is preferable that the solvent used in the etherification reaction is dehydrated. The amount of solvent used is not particularly limited as long as it does not interfere with the reaction, but is usually preferably used in an amount in the range of 1 to 7 times by weight, more preferably 2 to 4 times by weight, and even more preferably 2 to 3 times by weight, relative to the polyhydroxy aromatic compound (2). When the reaction is carried out under reduced pressure and the solvent is distilled out of the reaction system, the amount of solvent used is preferably 1.5 to 10 times by weight, more preferably 2 to 8 times by weight, and even more preferably 2 to 6 times by weight, relative to the polyhydroxy aromatic compound (2).The amount of distillate per hour during the reaction by distilling the solvent out of the reaction system is preferably 0.05 to 1.5 times by weight, more preferably 0.1 to 1.0 times by weight, even more preferably 0.3 to 1.0 times by weight, and particularly preferably 0.3 to 0.8 times by weight, relative to the amount of polyhydroxy aromatic compound (2). During the reaction, the amount of distillate per hour may vary within the above range, or may temporarily exceed the upper or lower limit of the above range.

[0042] (End point of etherification reaction) The end point of the etherification reaction can be confirmed by liquid chromatography or gas chromatography analysis. The end point of the reaction is preferably the time when the unreacted polyhydroxy aromatic compound (2) has disappeared and the mono-etherified intermediate (when n is 2 in the target compound polycarboxylic acid ester compound (1)) has been produced and is almost no longer observed, or when n is 3, when the bis-etherified intermediate (when n is 3). The time when the reaction intermediate is produced and is almost no longer observed is specifically the time when the concentration of the reaction intermediate is 1.5 area % or less, more preferably 1.0 area % or less, even more preferably 0.8 area % or less, and particularly preferably 0.5 area % or less, as determined by liquid chromatography or gas chromatography analysis. The reaction time varies depending on the reaction conditions, such as the type of raw material used and the reaction temperature, but is usually completed within about 1 to 30 hours.

[0043] <Polycarboxylic acid compound (5) represented by general formula (5)> Ar and R in general formula (5) １ , R ２ The definitions of m, n and X are the same as those in formula (1), and specific examples and preferred embodiments are also the same.

[0044] Specific examples of the polycarboxylic acid compound (5) in which both Ars in the general formula (5) are 1-oxybenzene-4-yl groups include compounds (5-1) to (5-8).

[0045] A specific example of the compound in which Ar in general formula (5) has a 1-oxybenzene-4-yl group and a 1-oxybenzene-2-yl group is the compound (5-9).

[0046] Specific examples of the compound in which both Ars in general formula (5) are 2-oxynaphthalen-1-yl groups include compounds (5-10) and (5-11).

[0047] A specific example of the compound in which both Ars in general formula (5) are 2-oxynaphthalen-6-yl groups is the compound (5-12).

[0048] Specific examples of the compound in which both Ars in general formula (5) are 4-oxy-3-phenylbenzen-1-yl groups include compounds (5-13) and (5-14).

[0049] Specific examples of the compound in which both Ars in general formula (5) are 10-oxyphenanthren-9-yl groups include compounds (5-15) to (5-18).

[0050] As shown in the following reaction formula, the polycarboxylic acid compound (5) is produced by hydrolysis of the ester group of the polycarboxylic acid ester compound (1) produced in the etherification reaction step with water.

[0051] A specific example of such a reaction is a case where, in a method for producing compound (1-13) by carrying out an etherification reaction as represented by the following reaction formula, compound (1-13) is hydrolyzed with water to produce compound (5-10) as a by-product.

[0052] <Polycarboxylic acid ester compound (6) represented by general formula (6)> Ar and R in general formula (6) １ , R ２ , m, n, X and R ３The definition of is the same as in general formula (1), and specific examples and preferred embodiments are also the same. Each r independently represents an integer of 1 to 4, provided that at least one r is 2, 3, or 4.

[0053] Regarding the polycarboxylic acid ester compound (6), specific examples of the compound in which both Ars in general formula (6) are 1-oxybenzene-4-yl groups include compounds (6-1) to (6-9), (6-6'), (6-7'), (6-8'), (6-8"), (6-8'"), and (6-9').

[0054] Specific examples of the compound in which Ar in general formula (6) has a 1-oxybenzene-4-yl group and a 1-oxybenzene-2-yl group include compounds (6-10) to (6-12), (6-10') to (6-12'), (6-10") to (6-12"), and (6-10'") to (6-12'").

[0055] Specific examples of the compound in which both Ars in general formula (6) are 2-oxynaphthalen-1-yl groups include compounds (6-13) and (6-14).

[0056] A specific example of the compound in which both Ars in general formula (6) are 2-oxynaphthalen-6-yl groups is the compound (6-15).

[0057] Specific examples of the compound in which both Ars in general formula (6) are 4-oxy-3-phenylbenzen-1-yl groups include compounds (6-16) and (6-17).

[0058] Specific examples of the compound in which both Ars in general formula (6) are 10-oxyphenanthren-9-yl groups include compounds (6-18) to (6-23).

[0059] As shown in the following reaction formula, polycarboxylic acid ester compound (6) is produced by reacting an excess amount of halocarboxylic acid ester compound (3) during the etherification reaction step in which a polyhydroxy aromatic compound (2) and a halocarboxylic acid ester compound (3) are used for etherification, and it has been revealed that the production of polycarboxylic acid ester compound (6) is promoted by the presence of water.

[0060] A specific example of such a reaction is a process for producing compound (1-13) by carrying out an etherification reaction using compound (2-10) as polyhydroxy aromatic compound (2) and ethyl chloroacetate as halocarboxylic acid ester compound (3), as represented by the following reaction formula, in which compound (6-13) is by-produced due to an excess reaction of ethyl chloroacetate.

[0061] <Separation and Purification of Polycarboxylic Acid Ester Compound (1)> The reaction mixture obtained in the etherification reaction step can be separated and purified in accordance with a conventional method to obtain the polycarboxylic acid ester compound (1) from the reaction mixture. For example, post-treatment steps such as a neutralization step, a water washing step, a crystallization step, a filtration step, a distillation step, and a separation step by column chromatography can be performed. To further increase the purity, further purification by distillation, recrystallization, or column chromatography in accordance with a conventional method may be performed.

[0062] In addition to the etherification reaction step, all steps of the present production method, such as mixing of raw materials, neutralization, distillation, crystallization, filtration, and drying, are preferably carried out in an atmosphere with little oxygen, which can cause oxidative deterioration, discoloration, and electrostatic ignition due to volatile solvents, or in an inert gas atmosphere such as nitrogen or argon.

[0063] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Analytical methods are as follows. <Analytical Method> 1. Compositional Analysis of Polycarboxylic Acid Ester Compound Compositional analysis of the reaction product was carried out by high performance liquid chromatography (HPLC) using the following equipment and conditions. The "%" in the obtained analytical results represents area percentage. (1) Ratio of Compound (1-13), Monoetherified Product, and Compound (5-10) Measuring Equipment: High Performance Liquid Chromatography Analyzer (Shimadzu Corporation) Pump: LC-20AD Column Oven: CTO-20A Detector: SPD-20A Column: HALO-C18 Oven Temperature: 50°C Flow Rate: 0.7 mL / min. Detection wavelength: 280 nm Gradient conditions Mobile phase: (A) 0.1 vol% phosphoric acid aqueous solution, (B) acetonitrile (B) Volume % (time from start of analysis) 30% (0 min) → 100% (12 min) → 100% (15 min) (2) Ratio of compound (6-13) Measurement device: High-performance liquid chromatography analyzer (Shimadzu Corporation) Pump: LC-20AD Column oven: CTO-20A Detector: SPD-20A 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 from start of analysis) 50% (0 min) → 100% (10 min) → 100% (13 min) (3) Proportions of compounds (1-20), (1-21), monoetherified compounds, compound (5-17), compound (6-20), and compound (6-21) Measuring apparatus: High-performance liquid chromatography analyzer Prominence UFLC (manufactured by Shimadzu Corporation) Pump: LC-20AD Column oven: CTO-20A Detector: SPD-20A Column: HALO-C18 (inner diameter 3 mm, length 75 mm) Oven temperature: 50°C Flow rate: 0.7 mL / min. Sample injection volume: 5 μL Detection wavelength: 280 nm Mobile phase: (A) 0.1% by volume phosphoric acid aqueous solution, (B) acetonitrile Gradient conditions: (B) vol% (time from start of analysis) 40% (0 min) → 100% (17 min) → 100% (20 min)(4) Ratio of compound (1-10), dietherified product, ratio of compound (5-9), compound (6-10), and compound (6-10′) Measuring apparatus: Liquid chromatography analyzer Prominence (Shimadzu Corporation) Pump: LC-20AT Column oven: CTO-20A Detector: SPD-20A Column: Shim-Pack CLC-ODS (inner diameter 6 mm, length 150 mm) Oven temperature: 50°C Flow rate: 1.0 mL / min. Sample injection amount: 20 μL Detection wavelength: 280 nm Mobile phase: (A) 0.2 vol% acetic acid aqueous solution, (B) methanol Gradient conditions: (B) vol% (time from start of analysis) 85% (0 min) → 100% (30 min) → 100% (40 min) 2. Analysis of Specific Surface Area of ​​Potassium Carbonate The specific surface area of ​​potassium carbonate was analyzed by the BET method using a mercury porosimetry apparatus.

[0064] Comparative Example 1: 30.0 g (0.10 mol) of 1,1′-binaphthalene-2,2′-diol (compound (2-10)), potassium carbonate (specific surface area 0.03 m ２ 30.4 g of methyl isobutyl ketone (1-13 / g) and 0.6 g of potassium iodide were charged into a four-neck flask, and after nitrogen substitution, 75.0 g of methyl isobutyl ketone was added. The temperature was then raised to 90-100°C, and 31.0 g of methyl isobutyl ketone was distilled off under a reduced pressure of 46 kPa to obtain a slurry. The pressure was then returned to normal with nitrogen, and while maintaining the temperature, 32.1 g (0.25 mol) of ethyl chloroacetate containing 0.3 g of N-methylpyrrolidone was added dropwise over 2 hours. Thereafter, an etherification reaction was carried out for 20 hours while maintaining the temperature at 100°C. Analysis of the slurry after the etherification reaction by HPLC revealed that it contained 93.2% compound (1-13), 2.9% of the monoetherified product (a reaction intermediate), 0.8% compound (5-10), and 8.1% compound (6-13). Even after 20 hours of reaction, a large amount of the monoether compound, which is a reaction intermediate, still remained, and the reaction was not completed.

[0065] Example 1: 30.0 g (0.10 mol) of 1,1′-binaphthalene-2,2′-diol (compound (2-10)), potassium carbonate (specific surface area 1.00 m ２30.4 g of methyl isobutyl ketone (1 / g) and 0.6 g of potassium iodide were charged into a four-neck flask, and after nitrogen substitution, 75.0 g of methyl isobutyl ketone was added. The temperature was then raised to 90-100°C, and 31.0 g of methyl isobutyl ketone was distilled off under a reduced pressure of 50 kPa to obtain a slurry. The pressure was then returned to normal with nitrogen, and while maintaining the temperature, 32.1 g (0.25 mol) of ethyl chloroacetate containing 0.3 g of N-methylpyrrolidone was added dropwise over 2 hours. Thereafter, an etherification reaction was carried out for 8 hours while maintaining the temperature at 100°C. Analysis of the slurry after the etherification reaction by HPLC revealed that it contained 96.8% compound (1-13), 0.2% of the monoetherified product as a reaction intermediate, 0.4% of compound (5-10), and 6.9% of compound (6-13). The monoetherified product as a reaction intermediate had been sufficiently reduced, indicating that the reaction was complete.

[0066] Example 2: 50.0 g (0.17 mol) of 1,1′-binaphthalene-2,2′-diol (compound (2-10)), potassium carbonate (specific surface area 0.76 m ２ 50.7 g of methyl isobutyl ketone (1.0 g / g) and 1.0 g of potassium iodide were charged into a four-neck flask, and after nitrogen substitution, 125.0 g of methyl isobutyl ketone was added. The temperature was then raised to 90°C, and 55.6 g of methyl isobutyl ketone was distilled off under a reduced pressure of 42 kPa to obtain a slurry. The pressure was then returned to normal with nitrogen, and while maintaining the temperature, 53.5 g (0.43 mol) of ethyl chloroacetate containing 0.5 g of N-methylpyrrolidone was added dropwise over 2 hours. Thereafter, an etherification reaction was carried out for 8 hours while maintaining the temperature at 100°C. Analysis of the slurry after the etherification reaction by HPLC revealed that it contained 97.2% compound (1-13), 0.1% of the monoetherified product as a reaction intermediate, 0.2% of compound (5-10), and 6.6% of compound (6-13). The monoetherified product as a reaction intermediate had been sufficiently reduced, indicating that the reaction was complete.

[0067] The results of Comparative Example 1 showed that the amount of the monoether compound, a reaction intermediate, in the liquid after 20 hours of the etherification reaction step to produce compound (1-13) following dropwise addition was 2.9%, confirming that the monoether compound had not been sufficiently reduced and the reaction was not yet complete. Furthermore, the amount of compound (5-10), which was produced by hydrolysis of compound (1-13), was 0.8%, and the amount of the by-product compound (6-13) was 8.1%. On the other hand, the results of Examples 1 and 2, which are specific examples of the present invention, showed that the amount of the monoether compound, a reaction intermediate, in the liquid after 8 hours of the etherification reaction step to produce compound (1-13) following dropwise addition was 0.2% or less, demonstrating that the monoether compound, a reaction intermediate, had been sufficiently reduced and the reaction was complete. Additionally, it was confirmed that in Examples 1 and 2, the production of compound (5-10), a hydrolysis product of compound (1-13), and the by-product compound (6-13) were suppressed. From the above results, it was revealed that the reactions of Examples 1 and 2 required significantly shorter times to complete the reaction than the reaction of Comparative Example 1, and furthermore, the shorter reaction times made it possible to suppress the production of by-products.

[0068] Example 3: 100.2 g (0.26 mol) of 9,9'-biphenanthrene-10,10'-diol (compound (2-15)), 151 g of N-methylpyrrolidone, potassium carbonate (specific surface area 0.76 m), ２75.7 g of ethyl chlorobutyrate (1-21 / g) and 6.2 g of potassium iodide were charged into a four-neck flask and purged with nitrogen. The temperature was then raised to 90°C, and 97.5 g (0.65 mol) of ethyl chlorobutyrate was added dropwise over 1 hour while maintaining the temperature of the reaction solution at 90°C. The temperature in the flask was then maintained at 90°C while stirring. The reaction was completed after 11 hours of post-stirring. HPLC analysis of the reaction solution after the reaction showed that the reaction selectivity of the target compound (compound (1-21)) was 99.8%. Neither the monoetherified product nor compound (5-17), which are reaction intermediates, was detected, and compound (6-21) was present at less than 0.1%. 75 g of water was then added, cooled, and the mixture was stirred overnight at 25°C, after which the precipitated solid was filtered off. 206.8 g of the resulting solid and 927 g of methyl isobutyl ketone were charged into a four-neck flask, purged with nitrogen, and then heated to dissolve. Thereafter, 207 g of water was added, and the mixture was washed with water at 80°C, and the aqueous layer was extracted. This operation was repeated four times. Thereafter, distillation was carried out to distill off 555 g of methyl isobutyl ketone and water. Thereafter, the liquid was cooled and stirred overnight while maintaining the temperature at 25°C, and then the precipitated solid was filtered off. The filtered solid was dried at 80°C under reduced pressure to obtain 145.9 g of 10,10'-bis(ethoxycarbonylpropoxy)-9,9'-biphenanthryl (compound (1-21)) (yield 91.5%). The obtained compound was analyzed by liquid chromatography mass spectrometry and １ H-NMR and １３ C-NMR analysis revealed that the compound was 10,10'-bis(ethoxycarbonylpropoxy)-9,9'-biphenanthryl (compound (1-21)). Liquid chromatography mass spectrometry (mass spectrometry / electrospray ionization): mass 637.25 [M+Na] １H-NMR analysis (400 MHz, solvent: deuterated chloroform) δ (ppm): 8.81-8.83 (d, 2H), 8.75-8.76 (d, 2H), 8.30-8.32 (dd, 2H), 7.75-7.79 (dt, 2H), 7.69-7.73 (dt, 2H), 7.55-7 .59 (m, 2H), 7.32-7.33 (d, 4H), 3.88-3.94 (m, 2H), 3.80-3.87 (m, 4H), 3.5 1-3.57 (m, 2H), 1.86-1.94 (m, 2H), 1.56-1.72 (m, 6H), 1.05-1.09 (t, 6H). １３ C-NMR (400 MHz, solvent: deuterated chloroform) δ (ppm): 173.01, 151.74, 132.77, 131.81, 128.25, 128.13, 127.15, 126.92, 126.86, 126.83, 125.51, 123.44, 122.91, 122.65, 122.32, 72.43, 59.95, 30.28, 25.26, 12.06. The purity of the obtained biphenanthrene dicarboxylic acid compound measured by high performance liquid chromatography was 99.6%, and the hue when made into a 10% THF solution by the above analytical method was APHA20. The onset temperature of the endothermic peak by differential scanning calorimetry (DSC) of the obtained crystals of compound (1-21) was 134 ° C.

[0069] Example 4: 80.4 g (0.21 mol) of 9,9'-biphenanthrene-10,10'-diol (compound (2-15)), 123 g of N-methylpyrrolidone, potassium carbonate (specific surface area 0.76 m ２60.5 g of methyl chlorobutyrate (1-20 / g) and 4.0 g of potassium iodide were charged into a four-neck flask and purged with nitrogen. The temperature was then raised to 90°C, and 70.9 g (0.52 mol) of methyl chlorobutyrate was added dropwise over 1 hour while maintaining the temperature of the reaction solution at 90°C. The temperature inside the flask was then maintained at 90°C while stirring. The reaction was completed after 18 hours of post-stirring. HPLC analysis of the reaction solution after the reaction showed that the reaction selectivity of the target compound (compound (1-20)) was 99.7%. Neither the reaction intermediate monoetherified product nor compound (5-17) was detected, and compound (6-20) was present at less than 0.1%. 240 g of water was then added, cooled, and the mixture was stirred overnight at 25°C, after which the precipitated solid was filtered off. 157.0 g of the resulting solid and 367 g of methyl isobutyl ketone were charged into a four-neck flask, purged with nitrogen, and then heated to dissolve. Thereafter, 249 g of water was added, and the mixture was washed with water at 80°C, and the aqueous layer was extracted. This operation was repeated four times. Then, 141 g of methyl isobutyl ketone and water were distilled off by distillation. Thereafter, the liquid was cooled and stirred overnight while maintaining the temperature at 25°C, and then the precipitated solid was filtered off. The filtered solid was dried at 80°C under reduced pressure, and 108.4 g of 10,10'-bis(methoxycarbonylpropoxy)-9,9'-biphenanthryl (compound (1-20)) was obtained (yield 90.7%). The obtained compound was analyzed by liquid chromatography mass spectrometry and １ H-NMR and １３ C-NMR analysis revealed that the compound was 10,10'-bis(methoxycarbonylpropoxy)-9,9'-biphenanthryl (compound (1-20)). Liquid chromatography mass spectrometry (mass spectrometry / electrospray ionization): mass 609.23 [M+Na] １H-NMR analysis (400MHz, solvent: deuterated chloroform) δ (ppm): 8.81-8.83 (d, 2H), 8.75-8.77 (d, 2H), 8.29-8.31 (dd, 2H), 7.69-7.79 (dt, 2H), 7.69-7.73 (dt , 2H), 7.55-7.59 (m, 2H), 7.31-7.33 (d, 4H), 3.88-3.93 (m, 2H), 3.54-3.58 (m, 2H), 3.36 (s, 6H), 1.88-1.94 (m, 2H), 1.58-1.74 (m, 6H). １３ C-NMR (400 MHz, solvent: deuterated chloroform) δ (ppm): 173.42, 151.70, 132.75, 131.84, 128.22, 128.14, 127.16, 126.94, 126.88, 126.86, 125.54, 123.43, 122.93, 122.66, 122.32, 72.33, 51.21, 29.95, 25.25. The purity of the obtained compound (1-20) measured by high performance liquid chromatography was 99.5%, and the color of a 10% THF solution measured by the above analytical method was APHA20. The onset temperature of the endothermic peak of the obtained compound (1-20) measured by differential scanning calorimetry (DSC) was 155 ° C.

[0070] Example 5: A mixture of 40.0 g (0.083 mol) of bis(4-hydroxy-3-cyclohexyl-6-methyl)(2-hydroxyphenyl)methane (compound (2-9)) and potassium carbonate (specific surface area 0.26 m ２47.9 g of butyl chloroacetate (1-10 / g) and 80.0 g of dimethylformamide were charged into a four-neck flask, and the flask was purged with nitrogen. After that, the temperature was raised to 50 ° C., and a mixed solution of 49.7 g of butyl chloroacetate and 2.5 g of dimethylformamide was added dropwise over 2 hours while stirring and mixing. Thereafter, the etherification reaction was carried out for 2 hours while maintaining the temperature at 100 ° C. As a result of analyzing the slurry after the etherification reaction by HPLC, at 1 hour into the etherification reaction, compound (1-10) was 99.0%, the dietherified product (reaction intermediate) was 0.5%, compound (5-9) was not detected, and compound (6-10) and compound (6-10') were contained at 0.2%. At 2 hours into the etherification reaction, the content of compound (1-10) was 99.5%, the dietherified product, which was a reaction intermediate, was not detected, compound (5-9) was not detected, and compound (6-10) and compound (6-10′) were contained in an amount of 0.3%.

[0071] Example 6: A mixture of 40.0 g (0.083 mol) of bis(4-hydroxy-3-cyclohexyl-6-methyl)(2-hydroxyphenyl)methane (compound (2-9)) and potassium carbonate (specific surface area 1.00 m ２ 47.9 g of butyl chloroacetate (1-10 / g) and 80.0 g of dimethylformamide were charged into a four-neck flask, and the flask was purged with nitrogen. After that, the temperature was raised to 50 ° C., and a mixed solution of 49.7 g of butyl chloroacetate and 2.5 g of dimethylformamide was added dropwise over 2 hours while stirring and mixing. Thereafter, the etherification reaction was carried out for 3.5 hours while maintaining the temperature at 100 ° C. As a result of analyzing the liquid after the etherification reaction by HPLC, at the 2-hour point of the etherification reaction, compound (1-10) was 93.5%, the dietherified product as a reaction intermediate was 5.8%, compound (5-9) was not detected, and compound (6-10) and compound (6-10') were 0.2%. At 3.5 hours into the etherification reaction, the compound (1-10) was contained in an amount of 99.4%, the dietherified product, which was a reaction intermediate, was not detected, the compound (5-9) was not detected, and the compound (6-10) and the compound (6-10′) were contained in an amount of 0.3%.

[0072] Comparative Example 2: 40.0 g (0.083 mol) of bis(4-hydroxy-3-cyclohexyl-6-methyl)(2-hydroxyphenyl)methane (compound (2-9)), potassium carbonate (specific surface area 0.03 m ２ 47.9 g of butyl chloroacetate (1-10 / g) and 80.0 g of dimethylformamide were charged into a four-neck flask, and the atmosphere in the flask was replaced with nitrogen. After that, the temperature was raised to 50 ° C., and a mixed solution of 49.7 g of butyl chloroacetate and 2.5 g of dimethylformamide was added dropwise over 2 hours while stirring and mixing. Thereafter, the etherification reaction was carried out for 5 hours while maintaining the temperature at 100 ° C. As a result of analyzing the slurry after the etherification reaction by HPLC, at the 2-hour point in the etherification reaction, compound (1-10) was 30.0%, the dietherified product as a reaction intermediate was 28.1%, compound (5-9) was not detected, and compound (6-10) and compound (6-10') were 0.1%. At 3.5 hours into the etherification reaction, the compound (1-10) was 41.0%, the dietherified product, which is a reaction intermediate, was 28.7%, compound (5-9) was not detected, and compound (6-10) and compound (6-10') were 0.2%. At 5 hours into the etherification reaction, the compound (1-10) was 48.4%, and the dietherified product, which is a reaction intermediate, was 28.0%. Even after 5 hours of reaction, a large amount of the dietherified product, which is a reaction intermediate, still remained, and the reaction was not completed.

[0073] From the above, it has been revealed that the production method of the present invention can more quickly carry out the etherification reaction step to obtain the target polycarboxylic acid ester compound (1). Furthermore, it is possible to reduce the production of polycarboxylic acid compound (5) and polycarboxylic acid ester compound (6), thereby enabling efficient production of polycarboxylic acid ester compound (1) with improved quality.

Claims

1. An etherification reaction step is carried out using a polyhydroxy aromatic compound (2) represented by general formula (2), a halocarboxylic acid ester compound (3) represented by general formula (3), and potassium carbonate, wherein the potassium carbonate has a specific surface area of ​​0.1 m ２ / g or more 2.0m ２ / g or less, the method for producing a polycarboxylate compound (1) represented by general formula (1). In formula (1), each Ar independently represents a monooxy aromatic hydrocarbon group having 6 to 20 carbon atoms and a valence of 2+m; １ each independently represents a linear or branched alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 5 to 6 carbon atoms, or a linear or branched alkoxyl group having 1 to 6 carbon atoms; R ２ each independently represents a linear or branched alkylene group having 1 to 4 carbon atoms; R ３ each independently represents an 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, and 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). In general formula (1), the oxygen atom possessed by Ar is in contact with the aromatic hydrocarbon group contained in Ar and R ２ Binds to.) (In general formula (1a), R ５ and R ６ each 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; R ５ and R ６ may be bonded to each other to form a cycloalkylidene group having 5 to 20 carbon atoms as a whole, and in general formula (1b), Ar １ Each independently represents an aryl group having 6 to 12 carbon atoms. In general formulas (1a), (1b), and (1c), * indicates a bonding position. (In general formula (1d), R ７ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms. ８ 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.) (Ar and R in general formula (2) １ The definitions of m, n, and X are the same as those in the general formula (1). In the general formula (2), the oxygen atom of Ar bonds to the aromatic hydrocarbon group contained in Ar and to the hydrogen atom (H) described in the general formula (2). (R in general formula (3) ２ and R ３ is defined as the same as in general formula (1), and Y represents a halogen atom.

2. Each of the Ar's independently represents a 1-oxybenzene-4-yl group, a 1-oxybenzene-3-yl group, a 1-oxybenzene-2-yl group, a 1-oxynaphthalen-2-yl group, a 1-oxynaphthalen-4-yl group, a 1-oxynaphthalen-5-yl group, a 2-oxynaphthalen-1-yl group, a 2-oxynaphthalen-6-yl group, a 2-oxynaphthalen-7-yl group, a 4-oxy-3-phenylbenzene-1-yl group, a 9-oxyphenanthren-3-yl group, a 10-oxyphenanthren-9-yl group, a 2-oxyanthracen-7-yl group, a 1-oxy-3-phenylnaphthalen-4-yl group, a 1-oxy-3-phenylnaphthalen-5-yl group, a 2-oxy-1-phenylnaphthalen-6-yl group, a 2-oxy-1-phenylnaphthalen 2. The method according to claim 1, wherein the aryl group is any one selected from the group consisting of anthracene-7-yl group, 2-oxy-3-phenylnaphthalene-6-yl group, 2-oxy-3-phenylnaphthalene-7-yl group, 4-oxy-3-(1-naphthyl)benzene-1-yl group, 4-oxy-3-(2-naphthyl)benzene-1-yl group, 4-oxy-3,5-diphenylbenzene-1-yl group, 4-oxy-2-phenylphenanthren-6-yl group, 4-oxy-2-phenylphenanthren-7-yl group, 4-oxy-2-phenylphenanthren-8-yl group, 4-oxy-2-phenylphenanthren-9-yl group, 4-oxy-2-phenylphenanthren-10-yl group and 2-oxy-3-phenylanthracen-7-yl group.

3. The method according to claim 1, wherein the polycarboxylate compound (1) represented by the general formula (1) is a polycarboxylate compound represented by any one of general formulae (1A) to (1F), and the polyhydroxy aromatic compound (2) represented by the general formula (2) is a polyhydroxy aromatic compound represented by any one of general formulae (2A) to (2F). (In general formulas (1A) to (1F), R １ , R ２ , R ３ , m, n, and X are the same as those defined in general formula (1). (In general formulas (2A) to (2F), R １ , m, n, and X are the same as those defined in general formula (1).

4. The method according to claim 3, wherein n is 1 for the polycarboxylic acid ester compounds represented by the general formulae (1C), (1D), (1E) and (1F), n is 2 for the polycarboxylic acid ester compound represented by the general formula (1B), n is 1 for the polyhydroxy aromatic compounds represented by the general formulae (2C), (2D), (2E) and (2F), and n is 2 for the polyhydroxy aromatic compound represented by the general formula (2B).

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