Method for producing polycarboxylate compound

Abstract

The present invention addresses the problem of providing a method whereby it is possible to produce a polycarboxylic acid ester compound having a reduced content of specific impurities and further improved purity. As a solution, provided is a method for producing a polycarboxylic acid ester compound (1) represented by general formula (1), which is characterized by comprising a step for reacting with an aliphatic alcohol (4), in which at least one type selected from the group consisting of polycarboxylic acid ester compounds (2) represented by general formula (2) and polycarboxylic acid ester compounds (3) represented by general formula (3) is reacted with an aliphatic alcohol (4). A polycarboxylic acid ester compound (1) represented by general formula (1) is obtained by reacting with an aliphatic alcohol (4) represented by general formula (4).

Description

Technical Field

[0001] The present invention relates to a method for producing a polycarboxylate compound, and more particularly to a method for producing a polycarboxylate compound having a reduced content of specific impurities and improved purity. Background Art

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

[0003] In recent years, the requirements for various performance improvements in the application fields of these materials have become increasingly higher. In order to exhibit the desired characteristics, the raw materials used in 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 is known in which a bisphenol compound and a halogenated carboxylic acid or its ester are used as raw materials to conduct an etherification reaction to synthesize a dicarboxylic acid or its ester compound. As an etherification reaction method for obtaining a dicarboxylic acid compound of improved quality, for example, it is known that the etherification reaction is conducted with an increased water content, resulting in a decrease in the reaction rate and a decrease in the yield of the target compound due to an increase in impurities (Patent Document 3).

[0005] Patent Literature Patent Document 1: Japanese Patent Application Laid-Open No. 62-292819 Patent Document 2: Japanese Patent Application Laid-Open No. 05-170702 Patent Document 3: International Publication No. 2021 / 054309 Summary of the Invention Against the backdrop of the aforementioned production method, intensive research to further improve the quality of dicarboxylic acid ester compounds using bisphenol compounds as raw materials has led to the discovery that, in the etherification reaction process using bisphenol compounds and halogenated carboxylic acid esters as raw materials, the halogenated carboxylic acid esters may overreact, resulting in the formation of by-products. Furthermore, the halogenated carboxylic acid esters used as raw materials contain halogenated carboxylic acid esters with different ester groups as impurities, which can undergo etherification reactions, resulting in the formation of by-products with ester groups different from those of the target dicarboxylic acid ester compound.

[0006] That is, the problem that the by-products thus produced hinder the improvement of the purity of the target dicarboxylic acid ester compound was discovered.

[0007] Examples of methods for reducing these by-products include purification methods by crystallization and recrystallization. However, as shown in the comparative examples described below, it was found that the purification method by recrystallization could not sufficiently reduce these impurities.

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

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

[0010] The present inventors have conducted intensive studies on various methods for reducing these by-products and have found that these by-products can be sufficiently reduced by reacting them with an alcohol having an alkoxy group corresponding to the ester group of the target dicarboxylic acid ester compound, thereby completing the present invention.

[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 it includes a step of reacting with an aliphatic alcohol (4), wherein at least one selected from a polycarboxylate compound (2) represented by the general formula (2) and a polycarboxylate compound (3) represented by the general formula (3) is reacted with an aliphatic alcohol (4) represented by the general formula (4) to obtain a polycarboxylate compound (1) represented by the general formula (1). [Chemistry 1]

[0013] In formula (1), Ar each independently represents a "2+m-valent" monooxy aromatic hydrocarbon group having 6 to 20 carbon atoms, R1 each 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, R2 each 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, m each 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), and in general formula (1), the oxygen atom contained in Ar is bonded to the aromatic hydrocarbon group contained in Ar and R2. [Chemistry 2]

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

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

[0016] In the general formula (2), Ar, R1, R2, R3, m, n, and X are defined the same as in the general formula (1), and 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, which is different from R3. [Chemistry 5]

[0017] In the general formula (3), Ar, R1, R2, m, n, X, and R3 are defined the same as in the general formula (1), and each r independently represents an integer of 1 to 4, but at least one r is 2, 3, or 4. [Chemistry 6]

[0018] The definition of R3 in the general formula (4) is the same as that in the general formula (1).

[0019] 2. The production method according to 1., characterized in that the polycarboxylate compound (2) represented by the general formula (2) and the polycarboxylate compound (3) represented by the general formula (3) are compounds obtained by an etherification reaction step, wherein the etherification reaction step is performed using a polyhydroxy aromatic compound (5) represented by the general formula (5) and a halogenated carboxylate compound composition containing a halogenated carboxylate compound (6) represented by the general formula (6) and a halogenated carboxylate compound (7) represented by the general formula (7), [Chemistry 7]

[0020] The definitions of Ar, R1, m, n, and X in the general formula (5) are the same as those in the general formula (1). In addition, in the general formula (5), 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 (5). [Chemistry 8]

[0021] In the general formula (6), R2 and R3 are defined the same as in the general formula (1), and Y represents a halogen atom. [Chemistry 9]

[0022] In the general formula (7), R2 and R4 are defined as in the general formula (2), and Y is defined as in the general formula (6).

[0023] 3. The production method according to 1., characterized in that the polycarboxylate compound (2) is a compound obtained by an etherification reaction step, wherein the etherification reaction step is performed using a polyhydroxy aromatic compound (5) represented by the general formula (5) and a halogenated carboxylate compound composition comprising a halogenated carboxylate compound (6) represented by the general formula (6) and a halogenated carboxylate compound (7) represented by the general formula (7). [Chemistry 10]

[0024] The definitions of Ar, R1, m, n, and X in the general formula (5) are the same as those in the general formula (1). In addition, in the general formula (5), 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 (5). [Chemistry 11]

[0025] In the general formula (6), R2 and R3 are defined the same as in the general formula (1), and Y represents a halogen atom. [Chemistry 12]

[0026] In the general formula (7), R2 and R4 are defined as in the general formula (2), and Y is defined as in the general formula (6).

[0027] 4. The production method according to 1., characterized in that the polycarboxylate compound (3) is a compound obtained by an etherification reaction step, wherein the etherification reaction step is an etherification reaction using a polyhydroxy aromatic compound (5) represented by the general formula (5) and a halogenated carboxylate compound (6) represented by the general formula (6). [Chemistry 13]

[0028] The definitions of Ar, R1, m, n, and X in the general formula (5) are the same as those in the general formula (1). In addition, in the general formula (5), 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 (5). [Chemistry 14]

[0029] In the general formula (6), R2 and R3 are defined the same as in the general formula (1), and Y represents a halogen atom.

[0030] 5. The production method according to any one of 1. to 4., characterized in that Ar is selected from 1-oxyphenyl-4-yl, 1-oxyphenyl-3-yl, 1-oxyphenyl-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-phenylphenyl-1-yl, 9-oxyphenanthren-3-yl, 10-oxyphenanthren-9-yl, 2-oxyanthracene-7-yl, 1-oxy-3-phenylnaphthalene-4-yl, 1-oxy-3-phenylnaphthalene-5-yl, 2-oxy-1 any one of 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)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-phenylanthracen-7-yl.

[0031] 6. The manufacturing method according to 5., characterized in that n is 2 and X is a direct bond.

[0032] 7. The production method according to 6., characterized in that R3 is a linear or branched alkyl group having 1 to 10 carbon atoms.

[0033] According to the production method of the present invention, since specific impurities contained in the polycarboxylate compound (1) that cannot be removed by crystallization or recrystallization or that are only slightly removed can be reduced, a polycarboxylate compound (1) of improved quality can be produced. DETAILED DESCRIPTION

[0034] <Production method of the present invention> The method for producing a polycarboxylate compound (1) represented by the general formula (1) of the present invention is characterized in that it includes a step of reacting with an aliphatic alcohol (4), wherein at least one selected from a polycarboxylate compound (2) represented by the general formula (2) and a polycarboxylate compound (3) represented by the general formula (3) is reacted with an aliphatic alcohol (4) represented by the general formula (4) to obtain a polycarboxylate compound (1) represented by the general formula (1).

[0035] The following methods can be mentioned: a method comprising a step of reacting with an aliphatic alcohol (4), in which the polycarboxylate compound (2) is reacted with the aliphatic alcohol (4) to obtain the polycarboxylate compound (1); a method comprising a step of reacting with an aliphatic alcohol (4), in which the polycarboxylate compound (3) is reacted with the aliphatic alcohol (4) to obtain the polycarboxylate compound (1); a method comprising a step of reacting with an aliphatic alcohol (4), in which the polycarboxylate compound (2) and the polycarboxylate compound (3) are reacted with the aliphatic alcohol (4) to obtain the polycarboxylate compound (1).

[0036] <Polycarboxylate compound (1) represented by general formula (1)> Ar in the general formula (1) each independently represents a monooxy aromatic hydrocarbon group having a valence of 2+m and having a carbon number of 6 to 20. In the general formula (1), the oxygen atom contained in Ar is bonded to the aromatic hydrocarbon group contained in Ar and R2.

[0037] First, the case where m is 0, that is, a divalent monooxy aromatic hydrocarbon group having 6 to 20 carbon atoms, will be described.

[0038] Among the divalent monooxy aromatic hydrocarbon groups having 6 to 20 carbon atoms, a divalent monooxy aromatic hydrocarbon group having 6 to 16 carbon atoms is preferred, a divalent monooxy aromatic hydrocarbon group having 6 to 14 carbon atoms is more preferred, a divalent monooxy aromatic hydrocarbon group having 6, 10 or 14 carbon atoms is further preferred, and a divalent monooxy aromatic hydrocarbon group having 10 or 14 carbon atoms is particularly preferred.

[0039] Specific examples of the divalent monooxy aromatic hydrocarbon group having 6 carbon atoms include 1-oxyphen-4-yl, 1-oxyphen-3-yl, and 1-oxyphen-2-yl.

[0040] Specific examples of the divalent monooxy aromatic hydrocarbon group having 10 carbon atoms include 1-oxynaphthyl-2-yl, 1-oxynaphthyl-4-yl, 1-oxynaphthyl-5-yl, 2-oxynaphthyl-1-yl, 2-oxynaphthyl-6-yl, and 2-oxynaphthyl-7-yl.

[0041] Specific examples of the divalent monooxy aromatic hydrocarbon group having 12 carbon atoms include 4-oxy-3-phenylphenyl-1-yl.

[0042] Specific examples of the divalent monooxy aromatic hydrocarbon group having 14 carbon atoms include 9-oxyphenanthren-3-yl, 10-oxyphenanthren-9-yl, and 2-oxyanthracen-7-yl.

[0043] Among them, the divalent monooxy aromatic hydrocarbon group having 14 carbon atoms is more preferably a monooxyphenanthryl group. Therefore, among them, 9-oxyphenanthrene-3-yl or 10-oxyphenanthrene-9-yl is more preferred.

[0044] Specific examples of the divalent monooxy aromatic hydrocarbon group having 16 carbon atoms include 1-oxy-3-phenylnaphth-4-yl, 1-oxy-3-phenylnaphth-5-yl, 2-oxy-1-phenylnaphth-6-yl, 2-oxy-1-phenylnaphth-7-yl, 2-oxy-3-phenylnaphth-6-yl, 2-oxy-3-phenylnaphth-7-yl, 4-oxy-3-(1-naphthyl)phenyl-1-yl, and 4-oxy-3-(2-naphthyl)phenyl-1-yl.

[0045] Specific examples of the divalent monooxy aromatic hydrocarbon group having 18 carbon atoms include a 4-oxy-3,5-diphenylbenzene-1-yl group.

[0046] Specific examples of the divalent monooxy aromatic hydrocarbon group having 20 carbon atoms include 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-phenylanthracen-7-yl.

[0047] Any one of the above-mentioned specific examples of divalent monooxy aromatic hydrocarbon groups having 6 to 20 carbon atoms may be selected. Specifically, a group selected from 1-oxyphenyl-4-yl, 1-oxyphenyl-3-yl, 1-oxyphenyl-2-yl, 1-oxynaphth-2-yl, 1-oxynaphth-4-yl, 1-oxynaphth-5-yl, 2-oxynaphth-1-yl, 2-oxynaphth-6-yl, 2-oxynaphth-7-yl, 4-oxy-3-phenylphenyl-1-yl, 9-oxyphenanthren-3-yl, 10-oxyphenanthren-9-yl, 2-oxyanthracen-7-yl, 1-oxy-3-phenylnaphth-4-yl, 1-oxy-3-phenylnaphth-5-yl, 2-oxy-1-phenylnaphth-6-yl, 2-oxynaphth-7-yl, 4-oxy-3-phenylphenyl-1-yl, 9-oxyphenanthren-3-yl, 10-oxyphenanthren-9-yl, 2-oxyanthracen-7-yl, 1-oxy-3-phenylnaphth-4-yl, 1-oxy-3-phenylnaphth-5-yl, 2-oxy-1-phenylnaphth-6-yl, 2-oxy any one of 1-phenylnaphthyl-7-yl, 2-oxy-3-phenylnaphthyl-6-yl, 2-oxy-3-phenylnaphthyl-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-phenylanthracen-7-yl.

[0048] Among them, any one selected from 1-oxyphen-4-yl, 2-oxynaphthalene-1-yl, 2-oxynaphthalene-6-yl, 4-oxy-3-phenylphen-1-yl, 9-oxyphenanthren-3-yl and 10-oxyphenanthren-9-yl is preferred, any one selected from 1-oxyphen-4-yl, 2-oxynaphthalene-1-yl and 10-oxyphenanthren-9-yl is more preferred, and 2-oxynaphthalene-1-yl or 10-oxyphenanthren-9-yl is particularly preferred.

[0049] Next, when m is 1 or 2, that is, a trivalent or tetravalent monooxy aromatic hydrocarbon group having 6 to 20 carbon atoms, means a group in which one or two of the hydrogen atoms corresponding to the number m in the aromatic hydrocarbon group when m is 0 are substituted at the bonding position so as to be bonded to the R1 group.

[0050] In the general formula (1), R1 each independently represents an alkyl group having 1 to 6 carbon atoms or a cyclic alkyl group having 5 to 6 carbon atoms. Among them, each independently represents an alkyl group having 1 to 4 carbon atoms or a cyclohexyl group, more preferably each independently represents a methyl group, a tert-butyl group, or a cyclohexyl group, and particularly preferably a methyl group.

[0051] In the general formula (1), R2 each independently represents a linear or branched alkylene group having 1 to 4 carbon atoms. Among them, a methylene group is particularly preferred.

[0052] 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, a methyl group or an ethyl group is further preferred, and an ethyl group is particularly preferred.

[0053] m each independently represents 0, 1 or 2. Among them, 0 or 1 is preferred, and 0 is particularly preferred.

[0054] Regarding the position to which R1 is bonded when m is 1, 1-oxyphen-4-yl is preferably at the 2-position, 2-oxynaphthalen-1-yl is preferably at the 6-position, 2-oxynaphthalen-6-yl is preferably at the 5-position, 4-oxy-3-phenylphen-1-yl is preferably at the 5-position, 9-oxyphenanthren-3-yl is preferably at the 10-position, and 10-oxyphenanthren-9-yl is preferably at the 6-position.

[0055] When m is 2, the position to which R1 bonds is preferably the 2-position and the 5-position of the 1-oxyphen-4-yl group.

[0056] n represents 1 or 2, preferably 1.

[0057] 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, a divalent group represented by the general formula (1a), a divalent group represented by (1b), or a divalent group represented by (1c) is preferred, a single bond, a divalent group represented by (1b), or a divalent group represented by (1c) is more preferred, and a single bond is particularly preferred.

[0058] When n is 2, X in the general formula (1) is a trivalent group represented by the general formula (1d) or (1e), preferably a trivalent group represented by (1e).

[0059] When X in the general formula (1) is a divalent group represented by the general formula (1a), R3 and R4 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 or an alkyl group having 1 to 4 carbon atoms, and particularly preferably a hydrogen atom, a methyl group, or an ethyl group.

[0060] Furthermore, R3 and R4 may 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 also contain an alkyl group as a branch. The cycloalkylidene group preferably has 5 to 15 carbon atoms, more preferably 6 to 12 carbon atoms, and particularly preferably 6 to 9 carbon atoms.

[0061] Specific examples of the cycloalkylidene group include a cyclopentylidene group (carbon number 5), a cyclohexylidene group (carbon number 6), a 3-methylcyclohexylidene group (carbon number 7), a 4-methylcyclohexylidene group (carbon number 7), a 3,3,5-trimethylcyclohexylidene group (carbon number 9), a cycloheptylidene group (carbon number 7), a bicyclo[2.2.1]heptane-2,2-diyl group (carbon number 7), a 1,7,7-trimethylbicyclo[2.2.1]heptane-2,2-diyl group (carbon number 10), a 4,7,7-trimethylbicyclo[2.2.1]heptane-2,2-diyl group (carbon number 10), a tricyclo[5.2.1.0 2,6 ] decane-8,8-diyl (carbon number 10), 2,2-adamantylidene (carbon number 10), cyclododecylidene (carbon number 12), etc. Preferred are cyclohexylidene (carbon number 6), 3-methylcyclohexylidene (carbon number 7), 4-methylcyclohexylidene (carbon number 7), 3,3,5-trimethylcyclohexylidene (carbon number 9), cyclododecylidene (carbon number 12), etc. More preferred are cyclohexylidene (carbon number 6), 3,3,5-trimethylcyclohexylidene (carbon number 9), and cyclododecylidene (carbon number 12), and particularly preferred are cyclohexylidene (carbon number 6) and 3,3,5-trimethylcyclohexylidene (carbon number 9).

[0062] When X in general formula (1) is a divalent group represented by general formula (1b), Ar1 is preferably independently a benzene ring or a naphthalene ring, and more preferably all Ar1 are benzene rings. For example, when all Ar1 are benzene rings, the group represented by general formula (1b) is a fluorenylidene group.

[0063] As a preferred embodiment 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.

[0064] [Chemistry 15]

[0065] In a preferred embodiment 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 a hydrogen atom, a methyl group, or a phenyl group, and particularly preferably a hydrogen atom or a methyl group.

[0066] As a preferred embodiment when X in the general formula (1) is a trivalent group represented by the general formula (1e), R8 is preferably a hydrogen atom or a methyl group, and particularly preferably R8 is a methyl group.

[0067] Specific examples of the polycarboxylate compound (1) include compounds (1-1) to (1-6) as specific examples of compounds wherein Ar in the general formula (1) is a 1-oxyphenyl-4-yl group.

[0068] [Chemistry 16]

[0069] Specific examples of the compound wherein all Ars in the general formula (1) are 2-oxynaphthalene-1-yl include compound (1-7) or (1-8).

[0070] [Chemistry 17]

[0071] Specific examples of the compound wherein all Ars in the general formula (1) are 2-oxynaphthalene-6-yl include compound (1-9).

[0072] [Chemistry 18]

[0073] Specific examples of the compound wherein all Ars in the general formula (1) are 4-oxy-3-phenylphenyl-1-yl include compound (1-10) or (1-11).

[0074] [Chemistry 19]

[0075] Specific examples of the compound wherein Ar in the general formula (1) is a 10-oxyphenanthrene-9-yl group include compound (1-12) or (1-13).

[0076] [Chemistry 20]

[0077] <Polycarboxylate compound (2) represented by general formula (2)> [Chemistry 21]

[0078] Ar, R1, R2, R in the general formula (2) 3、 The definitions of m, n, and X are the same as those in the general formula (1), and the specific examples and preferred embodiments thereof are also the same.

[0079] R4 each independently represents a linear or branched alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, which is 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, a methyl group or an ethyl group is further preferred, and a methyl group is particularly preferred.

[0080] Specific examples of the polycarboxylate compound (2) in which Ar in the general formula (2) is 1-oxyphenyl-4-yl, and R3 and R4 are ethyl and methyl include compounds (2-1) to (2-6) and (2-6').

[0081] [Chemistry 22]

[0082] Specific examples of the compound wherein Ar in the general formula (2) is a 2-oxynaphthalen-1-yl group, and R3 and R4 are an ethyl group and a methyl group include compound (2-7) or (2-8).

[0083] [Chemistry 23]

[0084] Specific examples of the compound in the general formula (2) wherein Ar is a 2-oxynaphthalen-6-yl group, and R3 and R4 are an ethyl group and a methyl group include compound (2-9).

[0085] [Chemistry 24]

[0086] Specific examples of the compound wherein Ar in the general formula (2) is a 4-oxy-3-phenylphenyl-1-yl group, and R3 and R4 are an ethyl group and a methyl group include compound (2-10) or (2-11).

[0087] [Chemistry 25]

[0088] Specific examples of the compound wherein Ar in the general formula (2) is a 10-oxyphenanthren-9-yl group, and R3 and R4 are an ethyl group and a methyl group include compound (2-12) or (2-13).

[0089] [Chemistry 26]

[0090] The polycarboxylate compound (2) used in the production method of the present invention is not limited, and the production method for obtaining the polycarboxylate compound (2) is also not limited. As a production method, for example, as shown in the following reaction formula, the polycarboxylate compound (2) can be produced by a method including an etherification reaction step, wherein the etherification reaction step is an etherification reaction of a polyhydroxyaromatic compound (5) represented by the general formula (5) with a halogenated carboxylate compound composition containing a halogenated carboxylate compound (6) represented by the general formula (6) and a halogenated carboxylate compound (7) represented by the general formula (7). The polycarboxylate compound (2) obtained by this method is preferred. Although the polycarboxylate compound (1) may be produced by the etherification reaction step, the production of the polycarboxylate compound (1) is preferred.

[0091] [Chemistry 27]

[0092] A specific example of this method is a method for producing compound (2-7) using a halogenated carboxylate compound composition comprising compound (5-7) as a polyhydroxyaromatic compound (5), ethyl chloroacetate (6-2) as a halogenated carboxylate compound (6), and methyl chloroacetate (7-1) as a halogenated carboxylate compound (7), as shown in the following reaction formula. Although compound (1-7) as a polycarboxylate compound (1) represented by general formula (1) may be produced in this etherification reaction step, it is preferred that compound (1-7) be produced.

[0093] [Chemistry 28]

[0094] Alternatively, it can be produced by carboxylation, wherein a polycarboxylic acid compound in which R3 and R4 in the polycarboxylic acid ester compound (2) are both hydrogen atoms is reacted with an alcohol corresponding to R3 and R4. This reaction may produce a polycarboxylic acid ester compound (1), but it is preferred that the polycarboxylic acid ester compound (1) be produced.

[0095] A specific example of this method is a method for producing compound (2-7) by reacting 2,2'-bis(2-carboxymethoxy)-1,1'-binaphthyl with ethanol and methanol as shown in the following reaction formula. Although compound (1-7) which is a polycarboxylate compound (1) is produced by this reaction, it is preferred that compound (1-7) be produced.

[0096] [Chemistry 29]

[0097] <Polycarboxylate compound (3) represented by general formula (3)> The definitions of Ar, R1, R2, m, n, X, and R3 in the general formula (3) are the same as those in the general formula (1), and the specific examples and preferred embodiments thereof are also the same.

[0098] Each r independently represents an integer of 1 to 4. However, at least one r is 2, 3 or 4.

[0099] Regarding the polycarboxylate compound (3), specific examples of the compound wherein Ar in the general formula (3) is all 1-oxyphenyl-4-yl include compounds (3-1) to (3-6) and (3-6′).

[0100] [Chemistry 30]

[0101] Specific examples of the compound wherein all Ars in the general formula (3) are 2-oxynaphthalene-1-yl include compound (3-7) or (3-8).

[0102] [Chemistry 31]

[0103] Specific examples of the compound wherein all Ars in the general formula (3) are 2-oxynaphthalene-6-yl groups include compound (3-9).

[0104] [Chemistry 32]

[0105] Specific examples of the compound wherein all Ars in the general formula (3) are 4-oxy-3-phenylbenzene-1-yl include compound (3-10) or (3-11).

[0106] [Chemistry 33]

[0107] Specific examples of the compound wherein Ar in the general formula (3) is a 10-oxyphenanthrene-9-yl group include compound (3-12) and (3-13).

[0108] [Chemistry 34]

[0109] The polycarboxylate compound (3) used in the production method of the present invention is not limited, and the production method for obtaining the polycarboxylate compound (3) is also not limited. As a production method, for example, as shown in the following reaction formula, the polycarboxylate compound (3) can be produced by a method including an etherification reaction step, wherein the etherification reaction step is an etherification reaction using a polyhydroxyaromatic compound (5) and a halogenated carboxylate compound (6), or a halogenated carboxylate compound composition containing a halogenated carboxylate compound (6) and a halogenated carboxylate compound (7). The polycarboxylate compound (3) obtained by this method is preferred. Although the polycarboxylate compound (1) may be produced by the etherification reaction step, the production of the polycarboxylate compound (1) is preferred.

[0110] [Chemistry 35]

[0111] A specific example of this method is a method for producing compound (3-7) using compound (5-7) as the polyhydroxyaromatic compound (5) and ethyl chloroacetate (6-2) as the halogenated carboxylate compound (6), as shown in the following reaction formula. Although compound (1-7) of the polycarboxylate compound (1) may be produced by this etherification reaction step, it is preferred that compound (1-7) be produced.

[0112] [Chemistry 36]

[0113] In the method for producing a polycarboxylate compound (1) of the present invention, at least one compound selected from the group consisting of the polycarboxylate compound (2) and the polycarboxylate compound (3) may be the polycarboxylate compound (2) alone, the polycarboxylate compound (3) alone, or both the polycarboxylate compound (2) and the polycarboxylate compound (3).

[0114] When both the polycarboxylate compound (2) and the polycarboxylate compound (3) are present, among the methods for obtaining the above compounds, the compound obtained by a method comprising an etherification reaction step, as shown in the following reaction formula, wherein the etherification reaction step is performed using a polyhydroxyaromatic compound (5) and a halogenated carboxylate compound composition comprising a halogenated carboxylate compound (6) and a halogenated carboxylate compound (7). Although the polycarboxylate compound (1) may be produced by the etherification reaction step, the production of the polycarboxylate compound (1) is preferred.

[0115] [Chemistry 37]

[0116] A specific example of this method is a method for producing compounds (2-7) and (3-7) using a halogenated carboxylate compound composition comprising a compound (5-7) described later as a polyhydroxyaromatic compound (5), ethyl chloroacetate (6-2) as a halogenated carboxylate compound (6), and methyl chloroacetate (7-1) as a halogenated carboxylate compound (7), as shown in the following reaction formula. Although compound (1-7) as a polycarboxylate compound (1) may be produced by this etherification reaction step, it is preferred that the polycarboxylate compound (1) be produced.

[0117] [Chemistry 38]

[0118] The polycarboxylate compound (2) and the polycarboxylate compound (3) may be used alone or in combination of two or more.

[0119] <Polyhydroxyaromatic compound (5) represented by general formula (5)> The definitions of Ar, R1, m, n, and X in the general formula (5) are the same as those in the general formula (1), and the specific examples and preferred embodiments thereof are also the same.

[0120] In the general formula (5), the oxygen atom contained in Ar is bonded to the aromatic hydrocarbon group contained in Ar and the hydrogen atom (H) described in the general formula (5).

[0121] Specific examples of the polycarboxylate compound (5) include compounds (5-1) to (5-6) as specific examples of compounds wherein Ar in the general formula (5) is a 1-oxyphenyl-4-yl group.

[0122] [Chemistry 39]

[0123] Specific examples of the compound wherein all Ars in the general formula (5) are 2-oxynaphthalene-1-yl include compound (5-7) or (5-8).

[0124] [Chemistry 40]

[0125] Specific examples of the compound wherein all Ars in the general formula (5) are 2-oxynaphthalene-6-yl include compound (5-9).

[0126] [Chemistry 41]

[0127] Specific examples of the compound wherein Ar in the general formula (5) is 4-oxy-3-phenylbenzene-1-yl include compound (5-10) or (5-11).

[0128] [Chemistry 42]

[0129] Specific examples of the compound wherein Ar in the general formula (5) is a 10-oxyphenanthrene-9-yl group include compound (5-12) and (5-13).

[0130] [Chemistry 43]

[0131] <Halogenated carboxylic acid ester compound composition> The halogenated carboxylate compound composition comprises a halogenated carboxylate compound (6) represented by the general formula (6) and a halogenated carboxylate compound (7) represented by the general formula (7).

[0132] The definitions of R2 and R3 in the general formula (6) are the same as those in the general formula (1), and their specific examples and preferred embodiments are also the same.

[0133] Y in the general formula (6) represents a halogen atom, preferably a chlorine atom or a bromine atom, and particularly preferably a chlorine atom.

[0134] The definitions of R2 and R4 in the general formula (7) are the same as those in the general formula (2), and their specific examples and preferred embodiments are also the same.

[0135] The definition of Y in the general formula (7) is the same as that in the general formula (6), and its specific examples and preferred embodiments are also the same.

[0136] The specific compounds of the halogenated carboxylic acid ester compound (6) and the halogenated carboxylic acid ester compound (7) are common, and examples thereof include: alkyl haloacetates such as methyl chloroacetate, ethyl chloroacetate, n-propyl chloroacetate, isopropyl chloroacetate, n-butyl chloroacetate, isobutyl chloroacetate, tert-butyl chloroacetate, methyl bromoacetate, ethyl bromoacetate, n-propyl bromoacetate, isopropyl bromoacetate, n-butyl bromoacetate, isobutyl bromoacetate, and tert-butyl bromoacetate; alkenyl haloacetates such as vinyl chloroacetate, allyl chloroacetate, vinyl bromoacetate, and allyl bromoacetate; alkyl halopropionates such as methyl 3-chloropropionate, ethyl 3-chloropropionate, methyl 3-bromopropionate, and ethyl 3-bromopropionate; and alkenyl halopropionates such as vinyl 3-chloropropionate, allyl 3-chloropropionate, vinyl 3-bromopropionate, and allyl 3-bromopropionate.

[0137] Among them, alkyl haloacetates or alkenyl haloacetates are preferred, more preferably compounds selected from methyl chloroacetate, ethyl chloroacetate, methyl bromoacetate, ethyl bromoacetate, vinyl chloroacetate and allyl chloroacetate, further preferably compounds selected from methyl chloroacetate, ethyl chloroacetate, methyl bromoacetate and ethyl bromoacetate, particularly preferably methyl chloroacetate or ethyl chloroacetate.

[0138] The halogenated carboxylate compound (6) is a compound selected such that the group of R3 in the polycarboxylate compound (1) to be produced is the same.

[0139] Particularly preferably, the halocarboxylate compound (6) is ethyl chloroacetate, and the halocarboxylate compound (7) is methyl chloroacetate.

[0140] In the halogenated carboxylate compound composition according to the production method of the present invention, the total component ratio of the halogenated carboxylate compound (6) to the halogenated carboxylate compound (7) is preferably 95 area % or more, more preferably 97 area % or more, further preferably 99 area % or more, and particularly preferably 99.5 area % or more, relative to the entire halogenated carboxylate compound composition, as determined by gas chromatography.

[0141] In the halogenated carboxylate compound composition, the component ratio of the halogenated carboxylate compound (6) as determined by gas chromatography analysis is not particularly limited, but is preferably from 90 area % to 99.99 area %, more preferably from 95 area % to 99.99 area %, further preferably from 97 area % to 99.99 area %, and particularly preferably from 98 area % to 99.99 area %.

[0142] In the halogenated carboxylate compound composition, the component ratio of the halogenated carboxylate compound (7) as determined by gas chromatography analysis is not particularly limited, but is preferably from 0.001 area % to 10 area %, more preferably from 0.001 area % to 5 area %, further preferably from 0.001 area % to 1 area %, and particularly preferably from 0.001 area % to 0.1 area %.

[0143] In the halogenated carboxylate compound composition, other components of the halogenated carboxylate compound (6) and the halogenated carboxylate compound (7) may include, for example, a hydroxycarboxylate compound or an aliphatic alcohol.

[0144] The total component ratio of the halogenated carboxylate compound (6), the halogenated carboxylate compound (7), and other components obtained by gas chromatography analysis of the halogenated carboxylate compound composition is 100 area %.

[0145] <Etherification reaction step> In the etherification reaction step of the production method of the present invention, the molar ratio of the halogenated carboxylic acid ester compound (6) to the polyhydroxyaromatic compound (5) is not particularly limited as long as it is at least the theoretical value (1.0 + n). It is usually used in a range of 2 to 20 times the molar amount, preferably in a range of 2 to 10 times the molar amount, and more preferably in a range of 2 to 6 times the molar amount. The theoretical value of "n" is the number of "n" in the general formula (1).

[0146] The etherification reaction is carried out in the presence of a base. Examples of the base include triethylamine, pyridine, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate. Sodium carbonate and potassium carbonate are preferred. The molar ratio of the base added is generally in the range of 0.8 to 4 times the total amount of the halogenated carboxylic acid ester compound (6), 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.

[0147] In addition, a catalyst may be used, for example, an alkali metal bromide such as sodium bromide or potassium bromide, an alkali metal iodide such as sodium iodide or potassium iodide, ammonium bromide or ammonium iodide, etc. The amount of the catalyst used is usually in the range of 0.1 to 100% by weight, preferably in the range of 0.1 to 20% by weight, and more preferably in the range of 0.1 to 10% by weight relative to the polyhydroxyaromatic compound (5).

[0148] (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 decreases the yield, while a low reaction temperature slows the reaction rate, which is not preferred.

[0149] (Etherification reaction pressure) The reaction pressure is not limited and can be normal pressure, reduced pressure or pressurized pressure. It is preferably normal pressure or reduced pressure. In the reaction under pressure, for example, the reaction can be carried out under a pressurized state in which nitrogen or the like is circulated as an inactive gas relative to the reaction. That is, the inactive gas can be introduced into the reaction system and reacted 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 outside the reaction system, the reaction can be promoted. As a gas that is inactive for the reaction, specifically, for example, nitrogen, argon, helium, etc. can be listed, and from the perspective of economy, nitrogen is most preferred.

[0150] From the perspective of shortening the reaction time, it is more preferably under reduced pressure. By reacting under reduced pressure, the carbon dioxide generated from the carbonate or bicarbonate used for the reaction can be discharged outside the reaction system, so the reaction can be promoted, and the reaction time can be shortened compared with the reaction at normal pressure. Further, by reacting under reduced pressure while distilling the solvent outside the reaction system, the generation of by-products can be suppressed. Specifically, its reaction pressure is preferably the scope of more than 5kPa and less than 80kPa, more preferably the scope of more than 10kPa and less than 70kPa, more preferably the scope of more than 30kPa and less than 60kPa. The reaction pressure can be set to under reduced pressure by a pressure reducer. When the reaction pressure is maintained in the aforementioned range, the pressure reducer can be intermittently or continuously operated, more preferably continuously operated. From the start of the reaction to the end of the reaction, it is preferably under reduced pressure, specifically to react under the pressure maintained in the aforementioned range.

[0151] (Etherification reaction solvent) The reaction may be performed without a reaction solvent, but it is preferred to use a reaction solvent for reasons such as operability during industrial production and improvement of reaction speed. The reaction solvent is not particularly limited as long as it does not distill from the reaction vessel at the reaction temperature and is inactive for the reaction. Examples 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 may be used in combination to adjust the polarity. Among these, preferred are ketone solvents having 3 to 9 carbon atoms, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, and cyclooctanone, or aprotic polar solvents such as acetonitrile, dimethyl sulfoxide, dimethylformamide, and N-methylpyrrolidone. Ketone solvents having 3 to 9 carbon atoms or acetonitrile are more preferred, ketone solvents having 3 to 6 carbon atoms are even more preferred, and acetone or methyl isobutyl ketone are particularly preferred. Methyl isobutyl ketone is preferably used as the reaction solvent because it allows for water washing after the reaction to remove water-soluble impurities such as salts.

[0152] The solvent used in the etherification reaction is preferably dehydrated.

[0153] The amount of the solvent used is not particularly limited as long as it does not inhibit the reaction. Generally, it is preferably used 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 polyhydroxyaromatic compound (5).

[0154] 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 the range of 1.5 to 10 times by weight, more preferably in the range of 2 to 8 times by weight, and even more preferably in the range of 2 to 6 times by weight relative to the polyhydroxyaromatic compound (5).

[0155] During the reaction by distilling the solvent out of the reaction system, the distillate amount per hour is preferably in the range of 0.05 to 1.5 times by weight, more preferably in the range of 0.1 to 1.0 times by weight, further preferably in the range of 0.3 to 1.0 times by weight, and particularly preferably in the range of 0.3 to 0.8 times by weight relative to the polyhydroxyaromatic compound (5). During the reaction, the distillate amount per hour may be varied within the above range, and the distillate amount may temporarily exceed the upper or lower limit of the above range.

[0156] The water content of the reaction liquid in the etherification reaction step is preferably set to a range of 0.01% by weight to 2.0% by weight relative to the polyhydroxyaromatic compound (5). By setting the water content in the reaction liquid to 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 of the 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. Examples of methods for setting the water content of the reaction liquid to the above range include a method of using a pre-dehydrated raw material or solvent, and a method of distilling off the water before the etherification reaction.

[0157] (End point of etherification reaction) The endpoint of the etherification reaction can be confirmed by liquid chromatography or gas chromatography analysis. The endpoint of the reaction is preferably defined as the time point when the unreacted polyhydroxyaromatic compound (5) disappears and the intermediate monoether product (when n is 2) and the intermediate bisether product (when n is 3) in the polycarboxylate compound (1) as the target compound are almost no longer observed. The time point when the intermediate product is almost no longer observed after the reaction is generated is specifically the time point when the concentration in the above analysis is 1.5 area % or less, more preferably 1.0 area % or less, further preferably 0.8 area % or less, and particularly preferably 0.5 area % or less.

[0158] The reaction time varies depending on reaction conditions such as reaction temperature, but is usually completed in about 1 to 30 hours.

[0159] <Aliphatic alcohol (4) represented by general formula (4)> The definition of R3 in the general formula (4) is the same as that in the general formula (1), and its specific examples and preferred embodiments are also the same.

[0160] Specific examples of the aliphatic alcohol (4) represented by the general formula (4) include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, octanol, and allyl alcohol.

[0161] <Reaction step with aliphatic alcohol (4)> (Raw material usage) The amount of the aliphatic alcohol (4) used is preferably in the range of 5 to 500 times by weight, more preferably in the range of 10 to 300 times by weight, further preferably in the range of 10 to 200 times by weight, and particularly preferably in the range of 15 to 150 times by weight, relative to the total weight of at least one selected from the polycarboxylate compound (2) and the polycarboxylate compound (3).

[0162] (Solvent for reaction with aliphatic alcohol (4)) In the reaction step with the aliphatic alcohol (4), the reaction is usually carried out in the presence of a solvent. The solvent is not particularly limited as long as it does not inhibit the reaction, but an aprotic polar solvent is preferably used. Specific examples include: chain aliphatic ketones having 3 to 9 carbon atoms, such as acetone (3 carbon atoms), methyl ethyl ketone (4 carbon atoms), diethyl ketone (5 carbon atoms), methyl isobutyl ketone (6 carbon atoms), methyl amyl ketone (7 carbon atoms), and methyl hexyl ketone (8 carbon atoms); chain nitrile solvents having 2 to 6 carbon atoms, such as acetonitrile and propionitrile; ether solvents such as diethyl ether and tetrahydrofuran; ester solvents such as ethyl acetate; dimethylformamide, dimethyl sulfoxide, etc. Among these, chain aliphatic ketones having 3 to 9 carbon atoms or acetonitrile are preferred, chain aliphatic ketones having 3 to 9 carbon atoms are more preferred, chain aliphatic ketones having 3 to 6 carbon atoms are further preferred, and acetone or methyl isobutyl ketone are particularly preferred. When methyl isobutyl is used as the reaction solvent, water washing can be performed to remove water-soluble impurities such as salts, so it is preferred. These solvents may be used alone or in combination of two or more.

[0163] The solvent used in the reaction with the aliphatic alcohol (4) is preferably dehydrated.

[0164] The amount of the solvent used in the reaction is not particularly limited as long as it does not cause difficulty in operability or handling. However, it is preferably in the range of 1.5 to 5 times by weight, more preferably 1.5 to 3.5 times by weight, and even more preferably 1.5 to 2.5 times by weight relative to the solid content used in the reaction.

[0165] (Catalyst for reaction with aliphatic alcohol (4)) In the reaction step with the aliphatic alcohol (4), a catalyst for promoting the reaction is not particularly required, and an acid catalyst or a base catalyst may be used as needed. In this case, examples of usable acid catalysts include concentrated hydrochloric acid, hydrogen chloride gas, trifluoroacetic acid, methanesulfonic acid, p-toluenesulfonic acid, benzoic acid, and mixtures thereof. Examples of usable salt catalysts include, but are not limited to, sodium hydroxide, sodium carbonate, triethylamine, triethanolamine, and mixtures thereof.

[0166] (Temperature, pressure, and time during reaction with aliphatic alcohol (4)) The reaction temperature in the reaction step with the aliphatic alcohol (4) is carried out at a temperature lower than the boiling point of the aliphatic alcohol (4) used. The upper limit also depends on the boiling point, but is preferably in the range of 30 to 100°C, more preferably in the range of 30 to 80°C, further preferably in the range of 40 to 80°C, and particularly preferably in the range of 40 to 60°C.

[0167] The reaction pressure in the reaction step with the aliphatic alcohol (4) may be normal pressure, increased pressure, or reduced pressure.

[0168] The reaction time in the reaction step with the aliphatic alcohol (4) varies depending on the reaction conditions such as the reaction temperature, but is usually completed in about 1 to 48 hours.

[0169] <Other aspects of the production method of the present invention> As other aspects of the production method of the present invention, the following aspects can also be mentioned.

[0170] (Method 1) A method for producing a polycarboxylate compound (1), characterized by comprising: an etherification reaction step in which a polyhydroxyaromatic compound (5) is subjected to an etherification reaction with a halogenated carboxylate compound composition comprising a halogenated carboxylate compound (6) and a halogenated carboxylate compound (7) to obtain a polycarboxylate compound (2); and a reaction step with an aliphatic alcohol (4), in which the polycarboxylate compound (2) obtained in the etherification step is reacted with an aliphatic alcohol (4) to obtain a polycarboxylate compound (1).

[0171] (Method 2) A method for producing a polycarboxylate compound (1), characterized by comprising: an etherification reaction step in which a polyhydroxyaromatic compound (5) and a halogenated carboxylate compound (6) are subjected to an etherification reaction to obtain a polycarboxylate compound (3); and a reaction step with an aliphatic alcohol (4), in which the polycarboxylate compound (3) obtained in the etherification step is reacted with an aliphatic alcohol (4) to obtain a polycarboxylate compound (1).

[0172] (Method 3) A method for producing a polycarboxylate compound (1) is characterized by comprising: an etherification reaction step in which a polyhydroxyaromatic compound (5) is subjected to an etherification reaction with a halogenated carboxylate compound composition comprising a halogenated carboxylate compound (6) and a halogenated carboxylate compound (7) to obtain a polycarboxylate compound (2) and a polycarboxylate compound (3); and a reaction step with an aliphatic alcohol (4) in which the polycarboxylate compound (2) and the polycarboxylate compound (3) obtained in the etherification step are reacted with an aliphatic alcohol (4) to obtain a polycarboxylate compound (1).

[0173] In the above-mentioned embodiments 1 to 3, although the polycarboxylate compound (1) represented by the general formula (1) may be produced in the etherification reaction step, it is preferred that the polycarboxylate compound (1) be produced.

[0174] <Separation and purification of polycarboxylate compound (1)> The reaction mixture obtained from the reaction step with the aliphatic alcohol (4) can be separated and purified according to conventional methods, thereby obtaining the polycarboxylate compound (1) from the reaction mixture. For example, post-treatment operations such as separation by washing with water, crystallization, filtration, distillation, column chromatography, etc. can be performed. Furthermore, in order to increase the purity, further purification by distillation, recrystallization, or column chromatography can be performed according to conventional methods.

[0175] In addition, except for the reaction step with the aliphatic alcohol (4) or the etherification reaction step, all steps involved in the present production method, such as mixing of raw materials, neutralization, distillation, crystallization, filtration, and drying, are preferably carried out in an environment with little oxygen, which may cause oxidative degradation or coloring, or static ignition caused by volatile solvents, or in an inert gas environment such as nitrogen or argon.

[0176] Example The present invention will be described in more detail below with reference to the following examples, but the present invention is not limited to these examples. The analysis method is as follows.

[0177] <Analysis Method> 1. Composition analysis of polycarboxylate compounds The composition analysis of the polycarboxylate compound was performed by high performance liquid chromatography (HPLC) using the following apparatus and conditions. The "%" in the obtained analysis results represents area percentage.

[0178] Measuring device: High performance liquid chromatography analyzer (manufactured by Shimadzu Corporation) Pump: LC-20AD Column oven: CTO-20A Detector: SPD-20A Column: HALO-C18 Incubator temperature: 50°C Flow rate: 0.7mL / min. Detection wavelength: 280nm ・Gradient conditions Mobile phase: (A) 0.2 vol% acetic acid in water, (B) methanol (B) Volume % (from the start of analysis): 50% (0 min) → 100% (10 min) → 100% (13 min) 2. Composition analysis of halogenated carboxylic acid esters Measuring device: Gas chromatograph (GC) Injection mode: split flow Vaporization chamber temperature: 300.0℃ Pressure: 164.0kPa Flow rate: 33.7 mL / min. Column flow rate: 1.46ml / min. Split ratio: 20.0 Chromatographic column: TC-1 0.25mm×60m Detector: FID Detector temperature: 300.0℃ Temperature program: 40°C (0 minutes) → 40°C (5 minutes) → 250°C (15.5 minutes) → 250°C (20.5 minutes) Comparative Example 1 HPLC analysis revealed 2,2'-bis(2-ethoxycarbonylmethoxy)-1,1'-binaphthyl crystals (98.8% 2,2'-bis(2-ethoxycarbonylmethoxy)-1,1'-binaphthyl (Compound (1-7)), 0.6% Compound (2-7), and 0.5% Compound (3-7). 50.0 g of these crystals and 32.0 g of methyl isobutyl ketone were placed in a four-necked flask and heated to 73°C to dissolve the crystals. Subsequently, 32.0 g of n-heptane was added at the same temperature, and cooling began while stirring. Seed crystals were added at 70°C, and after maintaining the temperature at 50°C for 1 hour, the mixture was cooled to 25°C and stirred overnight. The crystals were then filtered off. The resulting crystals were dried and purified by recrystallization to yield 47.4 g of 2,2'-bis(2-ethoxycarbonylmethoxy)-1,1'-binaphthyl crystals.

[0179] The obtained crystals were analyzed by HPLC. The results showed that the content of compound (1-7) was 99.0%, compound (2-7) was 0.6%, and compound (3-7) was 0.3%.

[0180] The content of compound (3-7) decreased by 0.2% during purification by recrystallization, representing a 40% reduction from the original content. However, the content of compound (2-7) remained unchanged, indicating that it could not be removed by purification by recrystallization.

[0181] The structural difference between compound (2-7) and the target compound, 2,2'-bis(2-ethoxycarbonylmethoxy)-1,1'-binaphthyl (compound (1-7)), lies only in the presence of an ester group, which differs between the ethyl and methyl groups. The difference in solubility is not significant, and it is speculated that this impurity could not be separated from the target compound during purification by recrystallization.

[0182] Comparative Example 2 A four-necked flask was charged with 15.0 g (0.05 mol) of 1,1'-binaphthyl-2,2'-diol (Compound (5-7)), 15.0 g of potassium carbonate, and 0.8 g of potassium iodide. After nitrogen substitution, 22.5 g of superdehydrated acetone was added. The temperature was then raised to 60°C and, while maintaining this temperature, 16.1 g of ethyl chloroacetate (GC analysis: 99.50 area % ethyl chloroacetate, 0.05 area % methyl chloroacetate) (0.13 mol) to which 0.1 g of N-methylpyrrolidone had been added was added dropwise over 2 hours. An etherification reaction was then carried out while maintaining the temperature at 60°C for 19 hours.

[0183] Analysis of the liquid after the etherification reaction by HPLC revealed that the liquid contained 98.0% of Compound (1-7), 0.2% of Compound (2-7), and 1.3% of Compound (3-7).

[0184] Next, 60.0 g of water was added to the etherification reaction liquid containing Compound (2-7) and Compound (3-7) while maintaining the liquid temperature at 60° C., and then cooled and stirred to 30° C. to precipitate crystals. The crystals were then filtered off.

[0185] The filtered crystals were analyzed by HPLC. The concentrations of compound (1-7) were 98.5%, compound (2-7) were 0.2%, and compound (3-7) were 1.2%.

[0186] The filtered crystals and 15.0 g of methyl isobutyl ketone were placed in a four-necked flask and the crystals were dissolved. 15.0 g of water was added to the flask and stirred at 75°C for 30 minutes. The mixture was then allowed to stand and the separated aqueous layer was removed. This water washing process was repeated three times. 21.0 g of n-heptane was added to the washed oil layer and the mixture was cooled to 25°C while stirring continuously. After stirring overnight, the precipitated crystals were filtered. The resulting crystals were dried to obtain 17.6 g of crystals of compound (1-7) (yield: 73%).

[0187] The obtained crystals were analyzed by HPLC. The concentrations of compound (1-7) were 99.2%, compound (2-7) were 0.2%, and compound (3-7) were 0.6%.

[0188] The color of the obtained crystals of compound (1-7) in a 30 wt % tetrahydrofuran (THF) solution was APHA20.

[0189] <Example 1> Example 1 is a method for producing 2,2'-bis(2-ethoxycarbonylmethoxy)-1,1'-binaphthyl (Compound (1-7)) by including a step of reacting with an aliphatic alcohol after the etherification reaction step in the production method of Comparative Example 2.

[0190] A four-necked flask was charged with 25.0 g (0.09 mol) of compound (5-7), 25.0 g of potassium carbonate, and 1.3 g of potassium iodide, and the atmosphere was purged with nitrogen. Then, 37.5 g of superdehydrated acetone was added, and the temperature was raised to 60°C. While maintaining this temperature, 26.8 g (0.22 mol) of ethyl chloroacetate (GC analysis showed a content of 99.50 area% ethyl chloroacetate and 0.05 area% methyl chloroacetate) to which 0.2 g of N-methylpyrrolidone had been added was added dropwise over 2 hours. An etherification reaction was then carried out while maintaining the temperature at 60°C for 21 hours.

[0191] The reaction liquid obtained by the etherification reaction was analyzed by HPLC. As a result, it contained 98.4% of the compound (1-7), 0.2% of the compound (2-7), and 0.9% of the compound (3-7).

[0192] The area percentage of each compound calculated by HPLC analysis of the reaction solution was regarded as the weight ratio in the reaction solution. Furthermore, the theoretical yield of 40.0 g of compound (1-7) obtained in the etherification reaction was regarded as the total amount of components detected by HPLC produced by the etherification reaction, and the yield (g) of compound (2-7) and compound (3-7) obtained in the etherification reaction was estimated. As a result, it was estimated that 0.08 g (40 (g) × 0.2 (%) = 0.08 (g)) of compound (2-7) and 0.36 g (40 (g) × 0.9 (%) = 0.36 (g)) of compound (3-7) were produced.

[0193] Then, 48.0 g of superdehydrated ethanol was added to the liquid containing Compound (2-7) and Compound (3-7) after the etherification reaction, and the mixture was stirred for 6 hours while maintaining the liquid temperature at 50° C. to allow reaction with the aliphatic alcohol.

[0194] HPLC analysis of the reaction solution obtained from the reaction with the aliphatic alcohol revealed a decrease in the detection levels (peak sizes) of Compounds (2-7) and (3-7) after the reaction, comparing the peaks before and after the reaction. The peaks for Compound (1-7) were 99.2%, for Compound (2-7) 0.1%, and for Compound (3-7) less than 0.1%.

[0195] Then, while maintaining the liquid temperature at 50° C., 100.0 g of water was added to the liquid after the reaction with the alcohol, and then the mixture was cooled to 25° C. and stirred to precipitate crystals. The crystals were then collected by filtration.

[0196] The filtered crystals and 25.0 g of methyl isobutyl ketone were added to a four-necked flask to dissolve the crystals. The washing operation of adding 25.0 g of water to the flask, stirring at 80°C for 30 minutes, allowing to stand, and removing the separated aqueous layer was repeated three times.

[0197] 30.0 g of n-heptane was added to the washed oil layer, and the liquid was cooled to 25°C while stirring. After stirring overnight, the precipitated crystals were filtered and dried to obtain 35.7 g of crystals of compound (1-7) (yield: 89%).

[0198] The obtained crystals were analyzed by HPLC. The content of compound (1-7) was 99.9%, that of compound (2-7) was 0.1%, and that of compound (3-7) was less than 0.1%.

[0199] The color of the obtained crystals of compound (1-7) in a 30 wt % THF solution was APHA10.

[0200] As described above, it was found that 2,2'-bis(2-ethoxycarbonylmethoxy)-1,1'-binaphthyl (Compound (1-7)) with a low impurity content, high purity, and improved quality can be produced.

[0201] In Example 1, the reaction with the aliphatic alcohol was carried out. Before the reaction with the aliphatic alcohol, the content ratios of compound (2-7) were 0.2% and compound (3-7) were 0.9%. However, after the reaction with the aliphatic alcohol, the content ratios decreased to 0.1% for compound (2-7) and less than 0.1% for compound (3-7).

[0202] Compared to the results of Comparative Example 2, the results of Example 1 showed that the amount of compound (2-7) contained in the obtained compound (1-7) decreased by 0.1%, the amount of compound (3-7) decreased by 0.6%, and the amount of compound (3-7) was almost completely eliminated. As a result, a higher purity of compound (1-7) was obtained.

[0203] This clearly shows that, for specific impurities that cannot be removed by recrystallization or whose removal effect is low, the production method of the present invention can reduce the specific impurities and obtain compound (1-7) with further improved quality.

[0204] <Example 2> A four-necked flask was charged with 35.0 g (0.12 mol) of compound (5-7), 35.5 g of potassium carbonate, and 1.8 g of potassium iodide, and the atmosphere was purged with nitrogen. 87.5 g of methyl isobutyl ketone was then added, and the temperature was raised to 92°C. Under reduced pressure of 43 kPa, 35.3 g of methyl isobutyl ketone was distilled off. The pressure was then returned to normal with nitrogen, and while maintaining this temperature, 37.5 g (0.31 mol) of ethyl chloroacetate (99.57 area % ethyl chloroacetate, 0.10 area % methyl chloroacetate according to GC analysis) to which 0.3 g of N-methylpyrrolidone had been added was added dropwise over 2 hours. The etherification reaction was then carried out while maintaining the temperature at 90°C for 13 hours.

[0205] The liquid obtained by the etherification reaction was analyzed by HPLC. As a result, it contained 93.2% of compound (1-7), 0.7% of compound (2-7), and 4.0% of compound (3-7).

[0206] The area percentage of each compound calculated by HPLC analysis of the reaction solution was regarded as the weight ratio in the reaction solution. Furthermore, the theoretical yield of 56.0 g of compound (1-7) obtained in the etherification reaction was regarded as the total amount of components detected by HPLC produced by the etherification reaction, and the yield (g) of compound (2-7) and compound (3-7) obtained in the etherification reaction was estimated. The estimated yield of compound (2-7) was 0.39 g (56.0 (g) × 0.7 (%) ≈ 0.39 (g)), and compound (3-7) was 2.24 g (56.0 (g) × 4.0 (%) = 2.24 (g)).

[0207] Then, 34.0 g of super-dehydrated ethanol was added to the liquid containing Compound (2-7) and Compound (3-7) after the etherification reaction, and the mixture was stirred for 3 hours while maintaining the liquid temperature at 65 to 70°C. Then, 22.0 g of super-dehydrated ethanol was further added, and the mixture was stirred for 2 hours while maintaining the liquid temperature at 65 to 70°C.

[0208] HPLC analysis of the liquid after the reaction with the aliphatic alcohol revealed a decrease in the detection levels (detection peak sizes) of Compound (2-7) and Compound (3-7) after the reaction compared to before and after the reaction with the aliphatic alcohol. The detection levels for Compound (1-7) were 97.4%, for Compound (2-7) 0.2%, and for Compound (3-7) 0.2%.

[0209] Next, while maintaining the liquid temperature at 76°C, 140.0 g of water was added to the liquid after the reaction with the aliphatic alcohol, the oil layer was washed with water, and the water layer was removed. While maintaining the liquid temperature at 76°C, 17.5 g of water was added and stirred, and then the water layer was removed in the same manner as the previous operation.

[0210] After washing with water, 52.5 g of n-heptane was added to the oil layer at 76°C. The solution was cooled while stirring continuously, and then seed crystals were added to the solution at 60°C. A large amount of crystals precipitated at 52°C. The solution was then cooled to 25°C and stirred continuously, and the precipitated crystals were filtered out.

[0211] Analysis of the filtered crystals by HPLC revealed that the content of compound (1-7) was 99.5%, compound (2-7) was 0.2%, and compound (3-7) was 0.1%.

[0212] The filtered crystals and 28.0 g of methyl isobutyl ketone were placed in a four-necked flask and replaced with nitrogen. The temperature was then raised to 78°C to dissolve the crystals. The washing operation of adding 18.0 g of water to the flask, stirring at 80°C for 30 minutes, letting it stand and removing the separated water layer was repeated twice. 35.0 g of n-heptane was added to the oil layer after washing with water, and the liquid was cooled while continuing to stir. Seed crystals were added at 70°C and finally cooled to 25°C. The precipitated crystals were filtered out and the obtained crystals were dried to obtain 47.0 g of crystals of compound (1-7) (yield: 83.9%).

[0213] The obtained crystals were analyzed by HPLC. The content of compound (1-7) was 99.8%, compound (2-7) was 0.2%, and compound (3-7) was less than 0.1%.

[0214] The color of the obtained crystals of compound (1-7) in a 30 wt % tetrahydrofuran (THF) solution was APHA 40.

[0215] <Example 3> A four-necked flask was charged with 300.4 g (0.78 mol) of 9,9'-biphenylene-10,10'-diol (Compound (5-12)), 225.4 g (1.63 mol) of potassium carbonate, and 15.1 g (0.09 mol) of potassium iodide, and the atmosphere was purged with nitrogen. Subsequently, 798 g of superdehydrated acetone was added, the temperature was raised to 55°C, and 239.1 g (1.95 mol) of ethyl chloroacetate (GC analysis showed 99.63 area % of ethyl chloroacetate and 0.01 area % of methyl chloroacetate) was added dropwise over 2 hours. After the addition, stirring was continued for 14 hours while maintaining the temperature at 55°C to allow for an etherification reaction.

[0216] The reaction liquid obtained by the etherification reaction was analyzed by HPLC. The content of 10,10'-bis(2-ethoxycarbonylmethoxy)-9,9'-biphenanthrene (Compound (1-12)) was 98.3%, Compound (2-12) was 0.3%, and Compound (3-12) was 0.7%.

[0217] The area percentages of each compound calculated by HPLC analysis of the reaction solution were considered as the weight ratios in the reaction solution, and the theoretical yield of 434.5 g of compound (1-12) obtained in the etherification reaction was considered as the total amount of components detected by HPLC produced by the etherification reaction. The yields (g) of compound (2-12) and compound (3-12) obtained in the etherification reaction were estimated. The results showed that 1.30 g (434.5 (g) × 0.3 (%) ≈ 1.30 (g)) of compound (2-12) and 3.04 g (434.5 (g) × 0.7 (%) ≈ 3.04 (g)) of compound (3-12) were produced.

[0218] To the liquid containing Compound (2-12) and Compound (3-12), 431.3 g (9.36 mol) of superdehydrated ethanol was added, and stirring was continued for 2 hours while maintaining the liquid temperature at 50° C. to allow reaction with the aliphatic alcohol.

[0219] HPLC analysis of the reaction solution obtained from the reaction with the aliphatic alcohol revealed that the detected amounts (detection peak sizes) of Compound (2-12) and Compound (3-12) decreased after the reaction, while the detected amount of the target compound (1-12) increased. The concentrations of Compound (1-12) were 99.2%, Compound (2-12) 0.1%, and Compound (3-12) 0.1%.

[0220] Then, the liquid after the reaction with the aliphatic alcohol was cooled, and after continuing stirring at 25° C. overnight, the precipitated crystals were filtered out.

[0221] The filtered crystals, 1358 g of methyl isobutyl ketone, and 900 g of water were placed in a four-necked flask, the atmosphere was purged with nitrogen, and the flask was heated to dissolve the crystals. The oil layer was then washed with water at 80°C, and the water layer was removed. This oil layer washing process was repeated four times.

[0222] To the washed oil layer, 600 g of n-heptane was added, and the solution was cooled to 25°C while stirring. After stirring overnight, the precipitated crystals were filtered out. The filtered crystals were dried at 80°C under reduced pressure to obtain 356.3 g of crystals of compound (1-12) (yield: 82%).

[0223] The obtained crystals were analyzed by HPLC. The concentration of compound (1-12) was 99.6%, compound (2-12) was 0.1%, and compound (3-12) was 0.1%.

[0224] Comparative Example 3 A four-necked flask was charged with 30.1 g (0.08 mol) of compound (5-12), 22.6 g (0.16 mol) of potassium carbonate, and 1.7 g (0.01 mol) of potassium iodide, and the atmosphere was purged with nitrogen. Subsequently, 75.0 g of methyl isobutyl ketone was added, and the temperature was raised to 95°C. Under reduced pressure of 50 kPa, 28.0 g of methyl isobutyl ketone was distilled off. The pressure was then returned to normal with nitrogen, and while maintaining this temperature, 24.0 g (0.20 mol) of ethyl chloroacetate (content according to GC analysis: 99.57 area % ethyl chloroacetate, 0.10 area % methyl chloroacetate) was added dropwise over 2 hours. The etherification reaction was then carried out while maintaining the temperature at 90°C for 10 hours.

[0225] The reaction liquid obtained by the etherification reaction was analyzed by HPLC. The content of compound (1-12) was 96.0%, compound (2-12) was 0.5%, and compound (3-12) was 0.8%.

[0226] Then, without going through the reaction step with the aliphatic alcohol, 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 more. Then, 92 g of n-heptane was added to the washed oil layer, and the liquid was cooled to 25°C while continuously stirring. After continuing stirring overnight, the precipitated crystals were filtered out.

[0227] Analysis of the filtered crystals by HPLC revealed that the content of compound (1-12) was 98.9%, that of compound (2-12) was 0.5%, and that of compound (3-12) was 0.4%.

[0228] The filtered crystals, 184 g of methyl isobutyl ketone, and 100 g of water were placed in a four-necked flask, replaced with nitrogen, and heated to dissolve the crystals. The oil layer was then washed with water at 80°C, and the water layer was removed. The oil layer was washed with water once more. 107 g of n-heptane was added to the washed oil layer, the liquid was cooled to 25°C, and after continuous 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) (yield: 78%).

[0229] The obtained crystals were analyzed by HPLC. The concentrations of compound (1-12) were 99.0%, compound (2-12) were 0.5%, and compound (3-12) were 0.4%.

[0230] As is clear from the above, according to the production method of the present invention, specific impurities contained in the polycarboxylate compound (1) that cannot be removed or can be removed only with little effect by crystallization or recrystallization can be reduced, thereby producing a polycarboxylate compound (1) with improved quality.

Claims

1. A method for producing a polycarboxylate compound (1) represented by the general formula (1), characterized in that: The process comprises the step of reacting at least one selected from a polycarboxylate compound (2) represented by the general formula (2) and a polycarboxylate compound (3) represented by the general formula (3) with the aliphatic alcohol (4) represented by the general formula (4) to obtain a polycarboxylate compound (1) represented by the general formula (1), [Chemistry 1] In formula (1), Ar each independently represents a "2+m-valent" monooxy aromatic hydrocarbon group having 6 to 20 carbon atoms, R1 each 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, R2 each 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, m each 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), and in general formula (1), the oxygen atom contained in Ar is bonded to the aromatic hydrocarbon group contained in Ar and R2. [Chemistry 2] In the general formula (1a), R5 and R6 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms. R5 and R6 may be bonded to each other to form a cycloalkylidene group having 5 to 20 carbon atoms as a whole. In the general formula (1b), Ar1 each independently represents an aryl group having 6 to 12 carbon atoms. * in the general formulas (1a), (1b), and (1c) each represents a bonding position. [Chemistry 3] In the general formula (1d), R7 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms. In the general formula (1e), R8 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms. * in the general formulas (1d) and (1e) each represents a bonding position. [Chemistry 4] In the general formula (2), Ar, R1, R2, R3, m, n, and X are defined the same as in the general formula (1), and 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, which is different from R3. [Chemistry 5] In the general formula (3), Ar, R1, R2, m, n, X, and R3 are defined the same as in the general formula (1), and each r independently represents an integer of 1 to 4, but at least one r is 2, 3, or 4. [Chemistry 6] The definition of R3 in the general formula (4) is the same as that in the general formula (1).

2. The manufacturing method according to claim 1, characterized in that The polycarboxylate compound (2) represented by the general formula (2) and the polycarboxylate compound (3) represented by the general formula (3) are compounds obtained by an etherification reaction step, wherein the etherification reaction step is performed using a polyhydroxy aromatic compound (5) represented by the general formula (5) and a halogenated carboxylate compound composition containing a halogenated carboxylate compound (6) represented by the general formula (6) and a halogenated carboxylate compound (7) represented by the general formula (7). [Chemistry 7] The definitions of Ar, R1, m, n, and X in the general formula (5) are the same as those in the general formula (1). In addition, in the general formula (5), 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 (5). [Chemistry 8] In the general formula (6), R2 and R3 are defined the same as in the general formula (1), and Y represents a halogen atom. [Chemistry 9] In the general formula (7), R2 and R4 are defined as in the general formula (2), and Y is defined as in the general formula (6).

3. The manufacturing method according to claim 1, characterized in that The polycarboxylate compound (2) is a compound obtained by an etherification reaction step, wherein the etherification reaction step is performed using a polyhydroxy aromatic compound (5) represented by the general formula (5) and a halogenated carboxylate compound composition comprising a halogenated carboxylate compound (6) represented by the general formula (6) and a halogenated carboxylate compound (7) represented by the general formula (7). [Chemistry 10] The definitions of Ar, R1, m, n, and X in the general formula (5) are the same as those in the general formula (1). In addition, in the general formula (5), 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 (5). [Chemistry 11] In the general formula (6), R2 and R3 are defined the same as in the general formula (1), and Y represents a halogen atom. [Chemistry 12] In the general formula (7), R2 and R4 are defined as in the general formula (2), and Y is defined as in the general formula (6).

4. The manufacturing method according to claim 1, characterized in that The polycarboxylate compound (3) is a compound obtained by an etherification reaction step, wherein the etherification reaction step is performed using a polyhydroxy aromatic compound (5) represented by the general formula (5) and a halogenated carboxylate compound (6) represented by the general formula (6). [Chemistry 13] The definitions of Ar, R1, m, n, and X in the general formula (5) are the same as those in the general formula (1). In addition, in the general formula (5), 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 (5). [Chemistry 14] In the general formula (6), R2 and R3 are defined the same as in the general formula (1), and Y represents a halogen atom.

5. The manufacturing method according to any one of claims 1 to 4, characterized in that The Ar is selected from 1-oxyphen-4-yl, 1-oxyphen-3-yl, 1-oxyphen-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-phenylphen-1-yl, 9-oxyphenanthren-3-yl, 10-oxyphenanthren-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- Any one of 1-phenylnaphthyl-7-yl, 2-oxy-3-phenylnaphthyl-6-yl, 2-oxy-3-phenylnaphthyl-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-phenylanthracen-7-yl.

6. The manufacturing method according to claim 5, characterized in that The n is 2, and the X is a direct bond.

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

Images