Process for producing polycarboxylate compounds

Abstract

The present application provides a method for producing a polycarboxylate compound, which can be produced more rapidly, and in which the content of specific impurities is reduced, and the purity is further improved. As a solution, a method for producing a polycarboxylate compound (1) represented by general formula (1), characterized by including an etherification reaction step in which an etherification reaction is performed using a polyhydroxy aromatic compound (2) represented by general formula (2), a halogenated carboxylate compound (3) represented by general formula (3), and potassium carbonate, the specific surface area of the potassium carbonate being in the range of 0.1 m 2 / g or more and 2.0 m 2 / g or less.

Description

Technical Field

[0001] This invention relates to a method for manufacturing polycarboxylate compounds. More specifically, it relates to a method for manufacturing polycarboxylate compounds with improved purity, characterized by a more rapid etherification reaction to obtain the target polycarboxylate compound, reduced content of specific impurities, and improved purity. Background Technology

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

[0003] In recent years, the requirements for improving various properties have become increasingly stringent in the application fields of these materials. In order to achieve the desired characteristics, the raw materials used in the materials are required to have further improved quality.

[0004] As a method for manufacturing dicarboxylic acid compounds using bisphenol compounds as raw materials, one known method is to use bisphenol compounds and halocarboxylic acids or their esters as raw materials to carry out an etherification reaction to synthesize dicarboxylic acid compounds or their esters.

[0005] Patent documents Patent Document 1: Japanese Patent Application Publication No. 62-292819 Patent Document 2: Japanese Patent Application Publication No. 05-170702 Summary of the Invention Given the known manufacturing methods described above, further research was conducted to improve the quality of dicarboxylic acid ester compounds using bisphenol compounds as raw materials. The results showed that in the etherification reaction process using bisphenol compounds, halocarboxylic acid esters, and potassium carbonate as raw materials, the reaction proceeded differently depending on the potassium carbonate used, resulting in a slower formation of the target dicarboxylic acid ester compound. Furthermore, it was found that there was a problem where the formation of certain impurities increased without any improvement in purity.

[0006] In light of the aforementioned problems discovered by the inventors, the object of the present invention is to provide a method for more rapidly manufacturing the target polycarboxylate compound (1), and further to provide a method for manufacturing a polycarboxylate compound (1) with further improved purity by reducing the content of specific impurities.

[0007] The inventors conducted in-depth research and discovered byproducts of polycarboxylic acid compounds obtained by hydrolysis of the ester group of the target compound (1), as well as byproducts obtained by excess reaction of halocarboxylic acid esters during etherification.

[0008] If the target polycarboxylic acid ester compound (1) contains impurities with different substituents, there is a risk that the manufacture of the material obtained by using the compound will not be smooth or that the material's physical properties will be adversely affected.

[0009] Furthermore, it was discovered that the difference in the etherification reaction was due to the specific surface area of ​​potassium carbonate. By using potassium carbonate with a specific surface area within a specific range, the above-mentioned problem can be solved, thus completing the present invention.

[0010] The present invention is as follows.

[0011] 1. A method for manufacturing a polycarboxylate compound (1) represented by general formula (1), characterized in that it includes an etherification reaction step of using a polyhydroxy aromatic compound (2) represented by general formula (2), a halocarboxylate compound (3) represented by general formula (3), and potassium carbonate to carry out an etherification reaction, wherein the potassium carbonate has a specific surface area of ​​0.1 m². 2 / g or more 2.0m 2 The range below / g [Chemistry 1]

[0012] In formula (1), each Ar independently represents a monooxy aromatic hydrocarbon group with a "2+m valence" of 6 to 20 carbon atoms; each R1 independently represents a straight-chain or branched alkyl group with 1 to 6 carbon atoms, a cyclic alkyl group with 5 to 6 carbon atoms, or a straight-chain or branched alkoxy group with 1 to 6 carbon atoms; each R2 independently represents a straight-chain or branched alkylene group with 1 to 4 carbon atoms; each R3 independently represents an alkyl group with 1 to 10 carbon atoms or an alkenyl group with 2 to 10 carbon atoms; each m independently represents 0, 1, or 2; each 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 addition, in general formula (1), the oxygen atom of Ar is bonded to the aromatic hydrocarbon group contained in Ar and R2. [Chemistry 2]

[0013] In general formula (1a), R5 and R6 each independently represent a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, a haloalkyl group with 1 to 10 carbon atoms, or an aryl group with 6 to 12 carbon atoms. R5 and R6 can be bonded to each other to form a cycloalkane group with 5 to 20 carbon atoms as a whole. In general formula (1b), Ar1 each independently represents an aryl group with 6 to 12 carbon atoms. The asterisks in general formulas (1a), (1b), and (1c) each represent a bonding position. [Chemistry 3]

[0014] In general formula (1d), R7 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms. In general formula (1e), R8 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms. The asterisks in general formulas (1d) and (1e) respectively indicate the bonding positions. [Chemistry 4]

[0015] The definitions of Ar, R1, m, n, and X in general formula (2) are the same as those in general formula (1). In addition, in general formula (2), the oxygen atom in Ar is bonded to the aromatic hydrocarbon group contained in Ar and the hydrogen atom (H) recorded in general formula (2). [Chemistry 5]

[0016] The definitions of R2 and R3 in general formula (3) are the same as those in general formula (1), and Y represents a halogen atom.

[0017] 2. The manufacturing method according to 1., characterized in that each of the Ar is independently selected from 1-oxyphenyl-4-yl, 1-oxyphenyl-3-yl, 1-oxyphenyl-2-yl, 1-oxynaphthyl-2-yl, 1-oxynaphthyl-4-yl, 1-oxynaphthyl-5-yl, 2-oxynaphthyl-1-yl, 2-oxynaphthyl-6-yl, 2-oxynaphthyl-7-yl, 4-oxy-3-phenylphenyl-1-yl, 9-oxyphenanthrene-3-yl, 10-oxyphenanthrene-9-yl, 2-oxyanthracene-7-yl, 1-oxy-3-phenylnaphthyl-4-yl, 1-oxy-3-phenylnaphthyl-5-yl, 2-oxy-1-phenylnaphthyl Any one of the following groups: -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, 4-oxy-3-(2-naphthyl)phenyl-1-yl, 4-oxy-3,5-diphenylphenyl-1-yl, 4-oxy-2-phenylphenanthrene-6-yl, 4-oxy-2-phenylphenanthrene-7-yl, 4-oxy-2-phenylphenanthrene-8-yl, 4-oxy-2-phenylphenanthrene-9-yl, 4-oxy-2-phenylphenanthrene-10-yl, and 2-oxy-3-phenylanthracene-7-yl.

[0018] 3. The manufacturing method according to 1. is characterized in that the polycarboxylate compound (1) represented by general formula (1) is a polycarboxylate compound selected from any one of general formulas (1A) to (1F), and the polyhydroxy aromatic compound (2) represented by general formula (2) is a polyhydroxy aromatic compound selected from any one of general formulas (2A) to (2F). [Chemistry 6]

[0019] [Chemistry 7]

[0020] [Chemistry 8]

[0021] [Chemistry 9]

[0022] [Chemistry 10]

[0023] [Chemistry 11]

[0024] In general formulas (1A) to (1F), R1, R2, R3, m, n, and X are defined in the same way as in general formula (1). [Chemistry 12]

[0025] [Chemistry 13]

[0026] [Chemistry 14]

[0027] [Chemistry 15]

[0028] [Chemistry 16]

[0029] [Chemistry 17]

[0030] In general formulas (2A) to (2F), R1, m, n, and X are defined in the same way as in general formula (1).

[0031] 4. The manufacturing method according to 3. is characterized in that n is 1 for the polycarboxylate compounds represented by general formulas (1C), (1D), (1E) and (1F), n is 2 for the polycarboxylate compounds 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 compounds represented by general formula (2B).

[0032] According to the manufacturing method of the present invention, the etherification reaction step to obtain the target polycarboxylate compound (1) can be carried out more quickly, thus the polycarboxylate compound (1) can be manufactured efficiently. Furthermore, since the generation of certain impurities can be reduced, the polycarboxylate compound (1) with improved quality can be manufactured efficiently. Detailed Implementation

[0033] <Manufacturing Method of the Invention> The method for manufacturing the polycarboxylate compound (1) represented by general formula (1) of the present invention includes an etherification reaction step of using a polyhydroxy aromatic compound (2) represented by general formula (2), a halocarboxylate compound (3) represented by general formula (3), and potassium carbonate to carry out an etherification reaction, wherein the potassium carbonate has a specific surface area of ​​0.1 m². 2 / g or more 2.0m 2 The range below / g.

[0034] <The polycarboxylate compound (1) represented by general formula (1)> In general formula (1), each Ar independently represents a monooxy aromatic hydrocarbon group with a "2+m valence" of 6 to 20 carbon atoms. In addition, in general formula (1), the oxygen atom of Ar is bonded to the aromatic hydrocarbon group and R2 contained in Ar.

[0035] First, we will address the case where m is 0, specifically for divalent monooxy aromatic hydrocarbon groups with 6 to 20 carbon atoms.

[0036] Among divalent monooxy aromatic hydrocarbon groups with 6 to 20 carbon atoms, divalent monooxy aromatic hydrocarbon groups with 6 to 16 carbon atoms are preferred, divalent monooxy aromatic hydrocarbon groups with 6 to 14 carbon atoms are more preferred, divalent monooxy aromatic hydrocarbon groups with 6, 10 or 14 carbon atoms are even more preferred, and divalent monooxy aromatic hydrocarbon groups with 10 or 14 carbon atoms are particularly preferred.

[0037] Specific examples of divalent monooxy aromatic hydrocarbon groups with 6 carbon atoms include: 1-oxyphenyl-4-yl, 1-oxyphenyl-3-yl, and 1-oxyphenyl-2-yl.

[0038] Specific examples of divalent monooxy aromatic hydrocarbon groups with 10 carbon atoms include: 1-oxynaphth-2-yl, 1-oxynaphth-4-yl, 1-oxynaphth-5-yl, 2-oxynaphth-1-yl, 2-oxynaphth-6-yl, and 2-oxynaphth-7-yl.

[0039] Specific examples of divalent monooxy aromatic hydrocarbon groups with 12 carbon atoms include: 4-oxy-3-phenylphenyl-1-yl.

[0040] Specific examples of divalent monooxy aromatic hydrocarbon groups with 14 carbon atoms include: 9-oxyphenanthrene-3-yl, 10-oxyphenanthrene-9-yl, and 2-oxyanthracene-7-yl. Among these, monooxyphenanthrene groups are more preferred, and 9-oxyphenanthrene-3-yl or 10-oxyphenanthrene-9-yl are even more preferred.

[0041] Specific examples of divalent monooxy aromatic hydrocarbon groups with 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.

[0042] Specific examples of divalent monooxy aromatic hydrocarbon groups with 18 carbon atoms include: 4-oxy-3,5-diphenylphenyl-1-yl.

[0043] Specific examples of divalent monooxy aromatic hydrocarbon groups with 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-phenylanthracene-7-yl.

[0044] Alternatively, any one of the specific examples of divalent monooxy aromatic hydrocarbon groups having 6 to 20 carbon atoms may be selected. That is, Ar in general formula (1) may also be independently 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-oxyphenanthrene-3-yl, 10-oxyphenanthrene-9-yl, 2-oxyanthracene-7-yl, 1-oxy-3-phenylnaphthene-4-yl, 1-oxy-3-phenylnaphthene-5-yl, 2-oxy-1-phenylnaphthene-6-yl, etc. The group consisting of 1, 2-oxy-1-phenylnaphthyl-7-yl, 2-oxy-3-phenylnaphthyl-6-yl, 2-oxy-3-phenylnaphthyl-7-yl, 4-oxy-3-(1-naphthyl)phenyl-1-yl, 4-oxy-3-(2-naphthyl)phenyl-1-yl, 4-oxy-3,5-diphenylphenyl-1-yl, 4-oxy-2-phenylphenanthroline-6-yl, 4-oxy-2-phenylphenanthroline-7-yl, 4-oxy-2-phenylphenanthroline-8-yl, 4-oxy-2-phenylphenanthroline-9-yl, 4-oxy-2-phenylphenanthroline-10-yl, and 2-oxy-3-phenylanthracene-7-yl.

[0045] In general formula (1), Ar is preferably each independently selected from 1-oxyphenyl-4-yl, 1-oxyphenyl-2-yl, 2-oxynaphth-1-yl, 2-oxynaphth-6-yl, 4-oxy-3-phenylphenyl-1-yl, 9-oxyphenanthrene-3-yl and 10-oxyphenanthrene-9-yl, more preferably each independently selected from 1-oxyphenyl-4-yl, 1-oxyphenyl-2-yl, 2-oxynaphthene-1-yl and 10-oxyphenanthrene-9-yl, further preferably all of them are 1-oxyphenyl-4-yl, having 1-oxyphenyl-4-yl and 1-oxyphenyl-2-yl, all of them are 2-oxynaphthene-1-yl or all of them are 10-oxyphenanthrene-9-yl, particularly preferably having 1-oxyphenyl-4-yl and 1-oxyphenyl-2-yl, all of them are 2-oxynaphthene-1-yl or all of them are 10-oxyphenanthrene-9-yl.

[0046] Next, when m is 1 or 2, that is, trivalent or tetravalent monooxy aromatic hydrocarbon groups with 6 to 20 carbon atoms, it refers to the group in which one or two hydrogen atoms of the aromatic hydrocarbon group corresponding to the number m are substituted at the bonding position in a manner that can bond with the R1 group.

[0047] The polycarboxylate compound (1) represented by general formula (1) is preferably a polycarboxylate compound represented by any one of the general formulas (1A) to (1F) described below, more preferably a polycarboxylate compound represented by general formula (1A), (1B), (1C), (1E) or (1F), even more preferably a polycarboxylate compound represented by general formula (1A), (1B), (1E) or (1F), and particularly preferably a polycarboxylate compound represented by general formula (1B), (1E) or (1F).

[0048] In general formula (1), R1 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 alkoxy group having 1 to 6 carbon atoms. Preferably, each is a linear or branched alkyl group having 1 to 4 carbon atoms, a cyclohexyl group, or a methoxy group; more preferably, each is a methyl group, a tert-butyl group, or a cyclohexyl group; and particularly preferably, a methyl group.

[0049] In general formula (1), R2 each independently represents a linear or branched alkylene group having 1 to 4 carbon atoms. Preferably, each is a linear or branched alkylene group having 1 to 3 carbon atoms, more preferably methylene, 1,2-ethylene, or 1,3-propylene, and particularly preferably methylene or 1,3-propylene.

[0050] In general formula (1), R3 independently represents an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. Preferably, it is a linear or branched alkyl group having 1 to 6 carbon atoms or a cyclic alkyl group having 5 to 8 carbon atoms; more preferably, it is a linear or branched alkyl group having 1 to 4 carbon atoms or a cyclic alkyl group having 6 to 8 carbon atoms; further preferably, it is methyl, ethyl, tert-butyl, 1-methylcyclopentyl or 1-ethylhexyl; and particularly preferably, it is methyl, ethyl or tert-butyl.

[0051] Each m can independently represent 0, 1, or 2.

[0052] Regarding the position of R1 when m is 1, 1-oxyphenyl-4-yl is preferably at position 2, 1-oxyphenyl-2-yl is preferably at position 2 or 4, 2-oxynaphthyl-1-yl is preferably at position 6, 2-oxynaphthyl-6-yl is preferably at position 5, 4-oxy-3-phenylphenyl-1-yl is preferably at position 5, 9-oxyphenanthrene-3-yl is preferably at position 10, and 10-oxyphenanthrene-9-yl is preferably at position 6.

[0053] Regarding the position of R1 bonded when m is 2, 1-oxyphenyl-4-yl is preferably at positions 2 and 5.

[0054] n represents 1 or 2.

[0055] When n is 1, X in 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 general formula (1a), (1b), or (1c). Preferably, it is a single bond, a divalent group represented by general formula (1a), a divalent group represented by general formula (1b), or a divalent group represented by general formula (1c). More preferably, it is a single bond, a divalent group represented by general formula (1b), or a divalent group represented by general formula (1c). In particular, it is a single bond.

[0056] When n is 2, X in general formula (1) is the trivalent base represented by general formula (1d) or (1e), preferably the trivalent base represented by general formula (1d).

[0057] When X in general formula (1) is a divalent group represented by general formula (1a), R5 and R6 are more preferably hydrogen atoms, alkyl groups having 1 to 6 carbon atoms, haloalkyl groups having 1 to 6 carbon atoms, or aryl groups having 6 to 12 carbon atoms, and are even more preferably hydrogen atoms, alkyl groups having 1 to 4 carbon atoms, and are particularly preferably hydrogen atoms, methyl or ethyl.

[0058] Furthermore, R5 and R6 can be bonded to each other to form a cycloalkane group with 5 to 20 carbon atoms as a whole. The cycloalkane group with 5 to 20 carbon atoms may also contain an alkyl group as a substituent. The cycloalkane group preferably has 5 to 15 carbon atoms, more preferably 6 to 12 carbon atoms, and particularly preferably 6 to 9 carbon atoms.

[0059] As cycloalkylidene groups, specific examples include: cyclopentylidene (5 carbon atoms), cyclohexylidene (6 carbon atoms), 3-methylcyclohexylidene (7 carbon atoms), 4-methylcyclohexylidene (7 carbon atoms), 3,3,5-trimethylcyclohexylidene (9 carbon atoms), cycloheptylidene (7 carbon atoms), bicyclo[2.2.1]heptane-2,2-diyl (7 carbon atoms), 1,7,7-trimethylbicyclo[2.2.1]heptane-2,2-diyl (10 carbon atoms), 4,7,7-trimethylbicyclo[2.2.1]heptane-2,2-diyl (10 carbon atoms), tricyclo[5.2.1.0]heptane-2,2-diyl (10 carbon atoms), and tricyclo[5.2.1.0]heptane-2,2-diyl (10 carbon atoms). 2,6 Decane-8,8-diyl (10 carbon atoms), 2,2-adamantane-idel (10 carbon atoms), cyclododecane-idel (12 carbon atoms), etc. are preferred. Cyclohexidel (6 carbon atoms), 3-methylcyclohexidel (7 carbon atoms), 4-methylcyclohexidel (7 carbon atoms), 3,3,5-trimethylcyclohexidel (9 carbon atoms), cyclododecane-idel (12 carbon atoms) are more preferred, cyclohexidel (6 carbon atoms), 3,3,5-trimethylcyclohexidel (9 carbon atoms), cyclododecane-idel (12 carbon atoms) are more particularly preferred, and cyclohexidel (6 carbon atoms) and 3,3,5-trimethylcyclohexidel (9 carbon atoms) are especially preferred.

[0060] When X in general formula (1) is a divalent group represented by general formula (1b), Ar1 is preferably 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 fluorene group.

[0061] As the preferred form when X in general formula (1) is a divalent base represented by general formula (1c), the preferred form is a divalent base represented by formula (1c') or formula (1c'').

[0062] [Chemistry 18]

[0063] As a preferred form when X in general formula (1) is a trivalent group represented by general formula (1d), R7 is preferably a hydrogen atom, an alkyl group with 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.

[0064] As a preferred form when X in general formula (1) is a trivalent group represented by general formula (1e), R8 is preferably a hydrogen atom or a methyl group, and particularly preferably R8 is a methyl group.

[0065] When all Ar in general formula (1) are 1-oxyphenyl-4-yl, it will become a polycarboxylic acid ester compound represented by general formula (1A).

[0066] [Chemistry 19]

[0067] (In general formula (1A), R1, R2, R3, m, n, and X are defined in the same way as in general formula (1).) As specific examples of compounds in which Ar in general formula (1) is 1-oxyphenyl-4-yl, compounds (1-1) to (1-9) can be listed.

[0068] [Chemistry 20]

[0069]

[0070]

[0071] When Ar in general formula (1) is 1-oxyphenyl-4-yl or 1-oxyphenyl-2-yl, as an example, a polycarboxylate compound represented by general formula (1B) can be listed, and this compound is preferred. In the polycarboxylate compound represented by general formula (1B), n is preferably 2.

[0072] [Chemistry 21]

[0073] (In general formula (1B), R1, R2, R3, m, n, and X are defined in the same way as in general formula (1).) Specific examples of compounds in which Ar in general formula (1) has 1-oxyphenyl-4-yl and 1-oxyphenyl-2-yl can be listed as compounds (1-10) to (1-12).

[0074] [Chemistry 22]

[0075] When all Ar in general formula (1) are 2-oxynaphth-1-yl, it becomes a polycarboxylate compound represented by general formula (1C). In the polycarboxylate compound represented by general formula (1C), n is preferably 1.

[0076] [Chemistry 23]

[0077] (In general formula (1C), R1, R2, R3, m, n, and X are defined in the same way as in general formula (1).) As specific examples of compounds in which Ar in general formula (1) is 2-oxynaphth-1-yl, compounds (1-13) or (1-14) can be listed.

[0078] [Chemistry 24]

[0079] When all Ar in general formula (1) are 2-oxynaphth-6-yl, it becomes a polycarboxylate compound represented by general formula (1D). In the polycarboxylate compound represented by general formula (1D), n is preferably 1.

[0080] [Chemistry 25]

[0081] (In general formula (1D), R1, R2, R3, m, n, and X are defined in the same way as in general formula (1).) As specific examples of compounds in which Ar in general formula (1) is 2-oxynaphth-6-yl, compounds (1-15) can be listed.

[0082] [Chemistry 26]

[0083] When all Ar in general formula (1) are 4-oxy-3-phenylphenyl-1-yl, it becomes a polycarboxylate compound represented by general formula (1E). In the polycarboxylate compound represented by general formula (1E), n is preferably 1.

[0084] [Chemistry 27]

[0085] (In general formula (1E), R1, R2, R3, m, n, and X are defined in the same way as in general formula (1).) Specific examples of compounds in which Ar in general formula (1) is 4-oxy-3-phenylphenyl-1-yl can be listed as compounds (1-16) or (1-17).

[0086] [Chemistry 28]

[0087] When all Ar in general formula (1) are 10-oxyphenanthrene-9-yl, it becomes a polycarboxylate compound represented by general formula (1F). In the polycarboxylate compound represented by general formula (1F), n is preferably 1.

[0088] [Chemistry 29]

[0089] (In general formula (1F), R1, R2, R3, m, n, and X are defined in the same way as in general formula (1).) As specific examples of compounds in general formula (1) where Ar is 10-oxyphenanthrene-9-yl, compounds (1-18) to (1-23) can be listed.

[0090] [Chemistry 30]

[0091]

[0092] <The polyhydroxy aromatic compound (2) represented by general formula (2)> The definitions of Ar, R1, m, n and X in general formula (2) are the same as those in general formula (1), and their specific examples or preferred forms are also the same.

[0093] In addition, in general formula (2), the oxygen atom of Ar is bonded to the aromatic hydrocarbon group contained in Ar and the hydrogen atom (H) recorded in general formula (2).

[0094] Furthermore, regarding the polyhydroxy aromatic compound (2) represented by general formula (2), it is preferred to select the polyhydroxy aromatic compound represented by any one of the general formulas (2A) to (2F) described below, more preferably the polyhydroxy aromatic compound represented by general formulas (2A), (2B), (2C), (2E) or (2F), even more preferably the polyhydroxy aromatic compound represented by general formulas (2A), (2B), (2E) or (2F), and particularly preferably the polyhydroxy aromatic compound represented by general formulas (2B), (2E) or (2F).

[0095] When all Ar in general formula (2) are 1-oxyphenyl-4-yl, it will become a polyhydroxy aromatic compound represented by general formula (2A).

[0096] [Chemistry 31]

[0097] (In general formula (2A), R1, m, n, and X are defined in the same way as in general formula (1).) As specific examples of compounds in which Ar in general formula (2) is 1-oxyphenyl-4-yl, compounds (2-1) to (2-8) can be listed.

[0098] [Chemistry 32]

[0099]

[0100] When Ar in general formula (2) is 1-oxyphenyl-4-yl or 1-oxyphenyl-2-yl, as an example, polyhydroxy aromatic compounds represented by general formula (2B) can be listed, and this form is preferred. In polyhydroxy aromatic compounds represented by general formula (2B), n is preferably 2.

[0101] [Chemistry 33]

[0102] (In general formula (2B), R1, m, n, and X are defined in the same way as in general formula (1).) As specific examples of compounds in general formula (2) having 1-oxyphenyl-4-yl and 1-oxyphenyl-2-yl, compounds (2-9) can be listed.

[0103] [Chemistry 34]

[0104] When all Ar in general formula (2) are 2-oxynaphth-1-yl, it becomes a polyhydroxy aromatic compound represented by general formula (2C). In the polyhydroxy aromatic compound represented by general formula (2C), n is preferably 1.

[0105] [Chemistry 35]

[0106] (In general formula (2C), R1, m, n, and X are defined in the same way as in general formula (1).) As specific examples of compounds in which Ar in general formula (2) is 2-oxynaphth-1-yl, compounds (2-10) or (2-11) can be listed.

[0107] [Chemistry 36]

[0108] When all Ar in general formula (2) are 2-oxynaphth-6-yl, it becomes a polyhydroxy aromatic compound represented by general formula (2D). In the polyhydroxy aromatic compound represented by general formula (2D), n is preferably 1.

[0109] [Chemistry 37]

[0110] (In general formula (2D), R1, m, n, and X are defined in the same way as in general formula (1).) As specific examples of compounds in which Ar in general formula (2) is 2-oxynaphth-6-yl, compounds (2-12) can be listed.

[0111] [Chemistry 38]

[0112] When all Ar in general formula (2) are 4-oxy-3-phenylphenyl-1-yl, it becomes a polyhydroxy aromatic compound represented by general formula (2E). In the polyhydroxy aromatic compound represented by general formula (2E), n is preferably 1.

[0113] [Chemistry 39]

[0114] (In general formula (2E), R1, m, n, and X are defined in the same way as in general formula (1).) As specific examples of compounds in which Ar in general formula (2) is 4-oxy-3-phenylphenyl-1-yl, compounds (2-13) or (2-14) can be listed.

[0115] [Chemistry 40]

[0116] When all Ar in general formula (2) are 10-oxyphenanthrene-9-yl, it becomes a polyhydroxy aromatic compound represented by general formula (2F). In the polyhydroxy aromatic compound represented by general formula (2F), n is preferably 1.

[0117] [Chemistry 41]

[0118] (In general formula (2F), R1, m, n, and X are defined in the same way as in general formula (1).) As specific examples of compounds in which Ar in general formula (2) is 10-oxyphenanthrene-9-yl, compounds (2-15) or (2-16) can be listed.

[0119] [Chemistry 42]

[0120] <The halocarboxylic acid ester compound (3) represented by general formula (3)> The definitions of R2 and R3 in general formula (3) are the same as those in general formula (1), and their specific examples or preferred forms are also the same.

[0121] In general formula (3), Y represents a halogen atom, wherein a chlorine atom or a bromine atom is preferred, and a chlorine atom is particularly preferred.

[0122] Specific examples of halocarboxylic acid ester compounds (3) include: 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, 1-ethylcyclohexyl bromoacetate, etc., halocarboxylic acid alkyl esters; vinyl chloroacetate, allyl chloroacetate, vinyl bromoacetate, allyl bromoacetate, etc., halocarboxylic acid alkenyl esters; methyl 3-chloropropionate, ethyl 3-chloropropionate, methyl 3-bromopropionate, 3-bromopropionic acid Alkyl halogenated propionic acid esters such as ethyl ester; alkenyl halogenated propionic acid esters such as vinyl 3-chloropropionate, allyl 3-chloropropionate, vinyl 3-bromopropionate, and allyl 3-bromopropionate; alkyl halogenated butyrate esters such as methyl 4-chlorobutyrate, ethyl 4-chlorobutyrate, n-propyl 4-chlorobutyrate, isopropyl 4-chlorobutyrate, n-butyl 4-chlorobutyrate, isobutyl 4-chlorobutyrate, 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-bromobutyrate, tert-butyl 4-bromobutyrate, 1-methylcyclopentyl 4-bromobutyrate, and 1-ethylcyclohexyl 4-bromobutyrate, etc.

[0123] Preferably, the alkyl esters of haloacetic acid or alkyl esters of halobutyrate are used; more preferably, the alkyl esters are selected from 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-methylcyclopent ...hexyl 4-bromobutyrate, methyl 4-bromobutyrate, ethyl 4-bromobutyrate, tert-butyl 4-bromoacetate, 1-methylcyclopentyl 4-chlorobutyrate, methyl 4-bromobutyrate, ethyl 4-bromobutyrate, tert-butyl 4-bromoacetate, 1-methylcyclopentyl 4-bromobutyrate, methyl 4-bromobutyrate, ethyl 4-bromobutyrate, tert-butyl 4-bromoacetate The compound is selected from any one of methylcyclopentyl ester and 1-ethylcyclohexyl 4-bromoacetic acid, and is further preferably selected from any one of 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. The compound is particularly preferably selected from any one of methyl chloroacetate, ethyl chloroacetate, tert-butyl chloroacetate, methyl 4-chlorobutyrate, ethyl 4-chlorobutyrate, and tert-butyl 4-chlorobutyrate.

[0124] <Etherification Reaction Process> In the etherification reaction step of the manufacturing method of the present invention, the molar ratio of the halocarboxylic acid ester compound (3) to the polyhydroxy aromatic compound (2) is not particularly limited as long as it is at least the theoretical value (1.0+n). It is generally used in the range of 2 to 20 times the molar amount, preferably in the range of 2 to 10 times the molar amount, and more preferably in the range of 2 to 6 times the molar amount. In addition, the theoretical value "n" is the number of "n" in the general formula (1).

[0125] (Potassium carbonate) The etherification reaction step in the manufacturing method of this invention uses a specific surface area of ​​0.1 m². 2 Potassium carbonate of at least / g. The specific surface area is 0.1m². 2 When the concentration is above / g, it is similar to that of less than 0.1m. 2 Compared to the previous method, the etherification reaction proceeds more rapidly, further suppressing the formation of specific impurities, and is therefore preferred. In the etherification reaction step of the manufacturing method of the present invention, potassium carbonate forms a salt with the polyhydroxy aromatic compound (2), and the mixture becomes a slurry before reacting 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), and therefore the larger the better. From the perspective of obtaining potassium carbonate, the upper limit of the specific surface area can be 2.0 m². 2 / g or less. That is, a specific surface area of ​​0.1m² can be used. 2 / g or more 2.0m 2 Potassium carbonate in the range of less than / g. The lower limit of the specific surface area of ​​the potassium carbonate used is preferably 0.2m². 2 / g or more, preferably 0.3m 2 / g or more, further preferably 0.5m 2 / g or more, with 0.7m being particularly preferred. 2 / g or more. Furthermore, the upper limit of the specific surface area is preferably 1.5m². 2 / g or less, more preferably 1.2m 2 / g or less.

[0126] In addition, the specific surface area in this invention refers to the value obtained by analyzing potassium carbonate using a mercury porosimetry analyzer via the BET method.

[0127] The molar ratio of potassium carbonate to the total amount of the halocarboxylic acid ester compound (3) used is typically in the range of 0.8 to 4 times the molar amount, preferably in the range of 0.85 to 3 times the molar amount, and more preferably in the range of 0.9 to 2 times the molar amount.

[0128] (catalyst) The etherification reaction in the manufacturing method of the present invention can also use a catalyst, such as: sodium bromide or potassium bromide or other alkali metal bromide salts, sodium iodide or potassium iodide or other alkali metal iodide salts, ammonium bromide or ammonium iodide, etc.

[0129] The amount of catalyst used relative to the polyhydroxy aromatic compound (2) is typically 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.

[0130] (Etherification reaction temperature) The reaction temperature is typically in the range of 25–120°C, preferably in the range of 40–100°C, more preferably in the range of 50–90°C, and particularly preferably in the range of 60–80°C. Higher reaction temperatures result in lower yields, while lower reaction temperatures slow down the reaction rate, and are therefore not preferred.

[0131] (Etherification reaction pressure) The reaction pressure is not limited and can be atmospheric pressure, reduced pressure, or pressurized pressure. Atmospheric pressure or reduced pressure is preferred. In a pressurized reaction, for example, the reaction can be carried out under pressure by allowing a gas that is inactive relative to the reaction, such as nitrogen, to pass through. That is, an inactive gas can be introduced into the reaction system, and the reaction can proceed while the gas in the reaction system is being discharged. This promotes the reaction because carbon dioxide generated from potassium carbonate used in the reaction can be discharged outside the reaction system. Examples of inactive gases include nitrogen, argon, and helium; from an economic point of view, nitrogen is the most preferred.

[0132] From the perspective of shortening reaction time, it is more preferable to conduct the reaction under reduced pressure. By conducting the reaction under reduced pressure, carbon dioxide generated from the potassium carbonate used can be discharged from the reaction system, thus promoting the reaction and shortening the reaction time compared to the reaction under normal pressure. Furthermore, by distilling the solvent out of the reaction system while conducting the reaction under reduced pressure, the formation of byproducts 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 set to reduced pressure by a pressure reducing device. When the reaction pressure is maintained within the aforementioned range, the pressure reducing device can be operated intermittently or continuously, more preferably continuously. From the start of the reaction to the end of the reaction, it is preferable to conduct the reaction under reduced pressure, specifically, under a pressure maintained within the aforementioned range.

[0133] (solvent) While a reaction solvent may not be used during the reaction, its use is preferred for reasons such as ease of operation in industrial production and increased reaction rate. There are no particular restrictions on the type of reaction solvent, provided it does not distill off 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 can be used individually, or more than one can be used in combination to adjust polarity. Preferably, ketone solvents with 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, are preferred. More preferably, ketone solvents with 3 to 9 carbon atoms, dimethylformamide, N-methylpyrrolidone, or acetonitrile are preferred. Further preferred are ketone solvents with 3 to 6 carbon atoms, dimethylformamide, or N-methylpyrrolidone. Particularly preferred are acetone, methyl isobutyl ketone, dimethylformamide, or N-methylpyrrolidone. When methyl isobutyl ketone is used as the reaction solvent, a water wash to remove water-soluble impurities such as salts can be performed after the reaction, which is preferable. The solvent used in the etherification reaction is preferably dehydrated.

[0134] There are no particular restrictions on the amount of solvent used as long as it does not hinder the reaction. Generally, it is preferred to use 1 to 7 times the weight of the polyhydroxy aromatic compound (2), more preferably 2 to 4 times the weight, and even more preferably 2 to 3 times the weight.

[0135] When the reaction is carried out under reduced pressure while the solvent is distilled out of the reaction system, the amount of solvent used is preferably 1.5 to 10 times the weight of the polyhydroxy aromatic compound (2), more preferably 2 to 8 times the weight, and even more preferably 2 to 6 times the weight.

[0136] The distillation amount per hour during the reaction, which is carried out by distilling the solvent out of the reaction system, is preferably in the range of 0.05 to 1.5 times the weight of the polyhydroxy aromatic compound (2), more preferably in the range of 0.1 to 1.0 times the weight, even more preferably in the range of 0.3 to 1.0 times the weight, and particularly preferably in the range of 0.3 to 0.8 times the weight. During the reaction, the distillation amount per hour may vary within the above range, and the distillation amount may also temporarily exceed the upper or lower limit of the above range.

[0137] (End point of etherification reaction) The endpoint of the etherification reaction can be confirmed by liquid chromatography or gas chromatography. Preferably, the endpoint is defined as the point at which the unreacted polyhydroxy aromatic compound (2) disappears, and when n in the target polycarboxylic acid ester compound (1) is 2, a monoetheride is formed as an intermediate; and when n is 3, a dietheride is formed as an intermediate, after which the reaction is almost no longer observed. Specifically, the point at which the reaction intermediate is almost no longer observed is defined as the point at which the area percentage (APS) becomes 1.5% or less in liquid chromatography or gas chromatography, more preferably 1.0% or less, even more preferably 0.8% or less, and particularly preferably 0.5% or less. The reaction time varies depending on the type of raw materials used or the reaction conditions such as the reaction temperature, and typically ends in about 1 to 30 hours.

[0138] <The polycarboxylic acid compound (5) represented by general formula (5)> [Chemistry 43]

[0139] The definitions of Ar, R1, R2, m, n and X in general formula (5) are the same as those in general formula (1), and their specific examples or preferred forms are also the same.

[0140] Regarding polycarboxylic acid compounds (5), specific examples of compounds in which Ar in general formula (5) is 1-oxyphenyl-4-yl can be listed as compounds (5-1) to (5-8).

[0141] [Chemistry 44]

[0142]

[0143] Compounds (5-9) can be listed as specific examples of compounds in which Ar of general formula (5) has 1-oxyphenyl-4-yl and 1-oxyphenyl-2-yl.

[0144] [Chemistry 45]

[0145] As specific examples of compounds in which Ar in general formula (5) is 2-oxynaphth-1-yl, compounds (5-10) or (5-11) can be listed.

[0146] [Chemistry 46]

[0147] As specific examples of compounds in which Ar in general formula (5) is 2-oxynaphth-6-yl, compounds (5-12) can be listed.

[0148] [Chemistry 47]

[0149] As specific examples of compounds in which Ar in general formula (5) is 4-oxy-3-phenylphenyl-1-yl, compounds (5-13) or (5-14) can be listed.

[0150] [Chemistry 48]

[0151] As specific examples of compounds in general formula (5) where Ar is 10-oxyphenanthrene-9-yl, compounds (5-15) to (5-18) can be listed.

[0152] [Chemistry 49]

[0153] The polycarboxylic acid compound (5) is generated by hydrolyzing the ester group of the polycarboxylic acid ester compound (1) produced by the etherification reaction process with water, as shown in the following reaction formula.

[0154] [Transformation 50]

[0155] As a specific example of such a reaction, as shown in the following reaction formula, it can be cited that in the method of producing compound (1-13) by carrying out an etherification reaction, compound (1-13) is hydrolyzed by water to generate compound (5-10) as a byproduct.

[0156] [Chemistry 51]

[0157] <The polycarboxylate compound (6) represented by general formula (6)> [Chemistry 52]

[0158] The definitions of Ar, R1, R2, m, n, X and R3 in general formula (6) are the same as those in general formula (1), and their specific examples or preferred forms are also the same.

[0159] r can independently represent integers from 1 to 4. However, at least one r can be 2, 3, or 4.

[0160] Regarding polycarboxylate compounds (6), specific examples of compounds in which Ar in general formula (6) is 1-oxyphenyl-4-yl can be listed as compounds (6-1)~(6-9), (6-6'), (6-7'), (6-8'), (6-8''), (6-8''') and (6-9').

[0161] [Chemistry 53]

[0162]

[0163]

[0164]

[0165] As specific examples of compounds in which Ar of general formula (6) has 1-oxyphenyl-4-yl and 1-oxyphenyl-2-yl, compounds (6-10)~(6-12), (6-10')~(6-12'), (6-10'')~(6-12'') and (6-10''')~(6-12''') can be listed.

[0166] [Chemistry 54]

[0167]

[0168]

[0169] As specific examples of compounds in which Ar in general formula (6) is 2-oxynaphth-1-yl, compounds (6-13) or (6-14) can be listed.

[0170] [Chemistry 55]

[0171] As specific examples of compounds in which Ar in general formula (6) is 2-oxynaphth-6-yl, compounds (6-15) can be listed.

[0172] [Chemistry 56]

[0173] As specific examples of compounds in which Ar in general formula (6) is 4-oxy-3-phenylphenyl-1-yl, compounds (6-16) or (6-17) can be listed.

[0174] [Chemistry 57]

[0175] As specific examples of compounds in general formula (6) where Ar is 10-oxyphenanthrene-9-yl, compounds (6-18) to (6-23) can be listed.

[0176] [Chem.58]

[0177]

[0178]

[0179] As shown in the following reaction formula, it can be seen that in the etherification reaction process of using polyhydroxy aromatic compound (2) and halocarboxylic acid ester compound (3) to carry out the etherification reaction, the polycarboxylic acid ester compound (6) is generated due to the excess reaction of halocarboxylic acid ester compound (3) and its generation is promoted by water.

[0180] [Chemistry 59]

[0181] As a specific example of this reaction, as shown in the following reaction formula, it can be cited that in the method of producing compound (1-13) by etherification reaction of compound (2-10) as polyhydroxy aromatic compound (2) and ethyl chloroacetate as halocarboxylic acid ester compound (3), compound (6-13) is generated as a byproduct due to the excessive reaction of ethyl chloroacetate.

[0182] [Transformation 60]

[0183] <Isolation and purification of polycarboxylate compounds (1)> The reaction mixture obtained through the etherification reaction can be separated and purified using common methods to obtain a polycarboxylate compound (1) from the reaction mixture. For example, post-processing steps such as neutralization, washing, crystallization, filtration, distillation, and column chromatography can be performed. Furthermore, to improve purity, purification can be further carried out using common methods such as distillation or recrystallization and column chromatography.

[0184] In addition to the etherification reaction process, all processes involved in this manufacturing method, such as mixing, neutralizing, distilling, crystallizing, filtering, and drying of raw materials, are preferably carried out in an atmosphere with low oxygen content, which may lead to oxidation, deterioration, or discoloration, or electrostatic ignition caused by volatile solvents, or in an atmosphere of inactive gases such as nitrogen or argon.

[0185] Example The present invention will be described in more detail below through embodiments, but the present invention is not limited to these embodiments. The analysis method is shown below.

[0186] <Analytical Methods> 1. Compositional analysis of polycarboxylate compounds The composition of the reaction products was analyzed by high performance liquid chromatography (HPLC) under the following apparatus and conditions. The percentages (%) in the analytical results represent area percentages.

[0187] (1) The ratio of compounds (1-13), monoethers, and compounds (5-10) Measurement Apparatus: High Performance Liquid Chromatography (HPLC) System (manufactured by Shimadzu Corporation) Pump: LC-20AD Column oven: CTO-20A Detector: SPD-20A Column: HALO-C18 Incubator temperature: 50℃ Flow rate: 0.7 mL / min. Detection wavelength: 280nm Gradient conditions Mobile phase: (A) 0.1 vol% aqueous phosphoric acid solution, (B) acetonitrile (B) Volume % (from the start of analysis) 30% (0 minutes) → 100% (12 minutes) → 100% (15 minutes) (2) The proportion of compounds (6-13) Measurement Apparatus: High Performance Liquid Chromatography (HPLC) System (manufactured by Shimadzu Corporation) Pump: LC-20AD Column oven: CTO-20A Detector: SPD-20A Column: HALO-C18 Incubator temperature: 50℃ Flow rate: 0.7 mL / min. Detection wavelength: 280nm Gradient conditions Mobile phase: (A) 0.2 vol% aqueous acetic acid, (B) methanol (B) Volume % (from the start of analysis) 50% (0 minutes) → 100% (10 minutes) → 100% (13 minutes) (3) The proportions of compounds (1-20), (1-21), monoether, compound (5-17), compound (6-20), and compound (6-21). Measurement apparatus: Prominence UFLC high-performance liquid chromatography analyzer (manufactured by Shimadzu Corporation). Pump: LC-20AD Column oven: CTO-20A Detector: SPD-20A Column: HALO-C18 (3mm inner diameter, 75mm length) Incubator temperature: 50℃ Flow rate: 0.7 mL / min. Sample injection volume: 5 μL Detection wavelength: 280nm Mobile phase: (A) 0.1 v / v phosphoric acid aqueous solution, (B) acetonitrile Gradient conditions: (B) Volume % (from the start of analysis) 40% (0 min.) → 100% (17 min.) → 100% (20 min.) (4) The ratio of compounds (1-10), diethers, compounds (5-9), compounds (6-10), and (6-10') Measurement apparatus: Prominence liquid chromatography analysis system (manufactured by Shimadzu Corporation) Pump: LC-20AT Column oven: CTO-20A Detector: SPD-20A Column: Shim-Pack CLC-ODS (6mm inner diameter, 150mm length) Incubator temperature: 50℃ Flow rate: 1.0 mL / min. Sample injection volume: 20 μL Detection wavelength: 280nm Mobile phase: (A) 0.2 vol% aqueous acetic acid solution, (B) methanol Gradient conditions: (B) Volume % (from the start of analysis) 85% (0 min.) → 100% (30 min.) → 100% (40 min.) 2. Analysis of the specific surface area of ​​potassium carbonate The specific surface area of ​​potassium carbonate was analyzed using a mercury porosimetry pore size analyzer via the BET method.

[0188] <Comparative Example 1> 30.0 g (0.10 mol) of 1,1'-binaphthyl-2,2'-diol (compound (2-10)) and potassium carbonate (specific surface area 0.03 m²) were added. 2 30.4 g of N-methyl isobutyl ketone (N-methylpyrrolidone) and 0.6 g of potassium iodide were placed in a four-necked flask. After purging with nitrogen, 75.0 g of N-methyl isobutyl ketone was added. The temperature was then raised to 90-100°C, and 31.0 g of N-methyl isobutyl ketone was distilled off under reduced pressure at 46 kPa to obtain a slurry. The slurry was then restored to atmospheric pressure with nitrogen, and while maintaining this temperature, 32.1 g (0.25 mol) of ethyl chloroacetate containing 0.3 g of N-methylpyrrolidone was added dropwise over 2 hours. The etherification reaction was then carried out at 100°C for 20 hours.

[0189] Analysis of the slurry after the etherification reaction by HPLC showed that it contained 93.2% compounds (1-13), 2.9% monoethers as reaction intermediates, 0.8% compounds (5-10), and 8.1% compounds (6-13). Even after 20 hours of reaction, a large amount of monoethers as reaction intermediates remained, indicating that the reaction was not yet complete.

[0190] <Example 1> 30.0 g (0.10 mol) of 1,1'-binaphthyl-2,2'-diol (compound (2-10)) and potassium carbonate (specific surface area 1.00 m²) were added. 2 30.4 g of N-methyl isobutyl ketone (N-methylpyrrolidone) and 0.6 g of potassium iodide were placed in a four-necked flask. After purging with nitrogen, 75.0 g of N-methyl isobutyl ketone was added. The temperature was then raised to 90-100°C, and 31.0 g of N-methyl isobutyl ketone was distilled off under reduced pressure of 50 kPa to obtain a slurry. The slurry was then restored to atmospheric pressure with nitrogen, and while maintaining this temperature, 32.1 g (0.25 mol) of ethyl chloroacetate containing 0.3 g of N-methylpyrrolidone was added dropwise over 2 hours. The etherification reaction was then carried out at 100°C for 8 hours.

[0191] Analysis of the slurry after the etherification reaction by HPLC showed that it contained 96.8% compounds (1-13), 0.2% monoethers (intermediates), 0.4% compounds (5-10), and 6.9% compounds (6-13). The monoethers (intermediates) were sufficiently reduced, indicating the reaction was complete.

[0192] <Example 2> 50.0 g (0.17 mol) of 1,1'-binaphthyl-2,2'-diol (compound (2-10)) and potassium carbonate (specific surface area 0.76 m²) were added. 2 50.7 g of N-methyl isobutyl ketone (N-methylpyrrolidone) and 1.0 g of potassium iodide were placed in a four-necked flask. After purging with nitrogen, 125.0 g of N-methyl isobutyl ketone was added. The mixture was then heated to 90 °C and distilled off 55.6 g of N-methyl isobutyl ketone under reduced pressure at 42 kPa to obtain a slurry. The pressure was then restored to atmospheric pressure with nitrogen, and while maintaining this temperature, 53.5 g (0.43 mol) of ethyl chloroacetate containing 0.5 g of N-methylpyrrolidone was added dropwise over 2 hours. The etherification reaction was then carried out at 100 °C for 8 hours.

[0193] Analysis of the slurry after the etherification reaction by HPLC showed that it contained 97.2% compounds (1-13), 0.1% monoethers (intermediates), 0.2% compounds (5-10), and 6.6% compounds (6-13). The monoethers (intermediates) were sufficiently reduced, indicating that the reaction was complete.

[0194] The results of Comparative Example 1 confirmed that in the liquid following the etherification reaction of compounds (1-13) after 20 hours of dropwise addition, the amount of monoether as a reaction intermediate was 2.9%, indicating that the monoether was not sufficiently reduced and the reaction was not yet complete. Furthermore, the liquid contained 0.8% of compounds (5-10) generated by the hydrolysis of compounds (1-13) and 8.1% of compounds (6-13) as byproducts.

[0195] On the other hand, as can be clearly seen from the results of Examples 1 and 2 of the present invention, in the liquid following the etherification reaction process of producing compounds (1-13) after dropwise addition for 8 hours, the amount of monoether as a reaction intermediate is 0.2% or less, indicating that the amount of monoether as a reaction intermediate has been sufficiently reduced and the reaction has ended. Furthermore, it was confirmed that in Examples 1 and 2, the formation of compounds (5-10) as hydrolysates of compounds (1-13) and compounds (6-13) as byproducts was suppressed.

[0196] The results above clearly show that the reaction time required to terminate the reaction in Examples 1 and 2 is significantly shorter than that in Comparative Example 1. Furthermore, since the reaction time is also shorter, the generation of byproducts can also be suppressed.

[0197] <Example 3> 100.2 g (0.26 mol) of 9,9'-biphenanthrene-10,10'-diol (compound (2-15)), 151 g of N-methylpyrrolidone, and potassium carbonate (specific surface area 0.76 m²) were added. 2 75.7 g of potassium iodide and 6.2 g of chlorobutyrate were placed in a four-necked flask and purged with nitrogen. The mixture was then heated to 90°C, and 97.5 g (0.65 mol) of ethyl chlorobutyrate was added dropwise over 1 hour while maintaining the temperature at 90°C. The mixture was then stirred while maintaining the temperature at 90°C. The reaction was terminated after 11 hours of stirring. HPLC analysis of the reaction mixture showed a 99.8% selectivity for the target compounds (compounds (1-21)). No monoethers or compounds (5-17) were detected as reaction intermediates, and compounds (6-21) were present in less than 0.1% of the mixture.

[0198] Then, add 75g of water, cool the mixture, and continue to cool and stir at 25°C overnight. Filter out the precipitated solids.

[0199] 206.8 g of the obtained solid and 927 g of methyl isobutyl ketone were placed in a four-necked flask, purged with nitrogen, and then heated to dissolve. Then, 207 g of water was added and the mixture was washed at 80°C to remove the aqueous layer. This process was repeated four times.

[0200] Then, distillation was performed to remove 555 g of methyl isobutyl ketone and water. The liquid was then cooled and stirred continuously at 25 °C overnight, and the precipitated solid was filtered off. The filtered solid was dried under reduced pressure at 80 °C to give 145.9 g of 10,10'-bis(ethoxycarbonylpropoxy)-9,9'-biphenanthrene (compound (1-21)) (yield 91.5%).

[0201] The obtained compounds were analyzed by liquid chromatography-mass spectrometry and... 1 H-NMR and 13 C-NMR analysis confirmed that it is 10,10'-bis(ethoxycarbonylpropoxy)-9,9'-biphenanthrene (compound (1-21)).

[0202] Liquid chromatography-mass spectrometry (mass spectrometry / electrospray ionization): Mass 637.25 [M+Na] 1 ¹H-NMR analysis (400MHz, 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), 3.51-3.57 (m, 2H), 1.86-1.94 (m, 2H), 1.56-1.72 (m, 6H), 1.05-1.09 (t, 6H).

[0203] 13 C-NMR (400MHz, 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.

[0204] The purity of the obtained bifenthrin dicarboxylic acid compound was determined to be 99.6% by high performance liquid chromatography, and the hue of the 10% THF solution prepared according to the above analytical method was APHA20.

[0205] The crystallization of the obtained compound (1-21) showed an endothermic peak starting temperature of 134 °C, as determined by differential scanning calorimetry (DSC).

[0206] <Example 4> 80.4 g (0.21 mol) of 9,9'-biphenanthrene-10,10'-diol (compound (2-15)), 123 g of N-methylpyrrolidone, and potassium carbonate (specific surface area 0.76 m²) were added. 2 60.5 g of methyl chlorobutyrate (0.52 mol) and 4.0 g of potassium iodide were placed in a four-necked flask and purged with nitrogen. The mixture was then heated to 90 °C, and 70.9 g of methyl chlorobutyrate (0.52 mol) was added dropwise over 1 hour while maintaining the temperature at 90 °C. The mixture was then stirred while maintaining the temperature at 90 °C. The reaction was terminated after 18 hours of stirring. HPLC analysis of the reaction mixture showed a 99.7% selectivity for the target compounds (compounds (1-20)). No monoethers or compounds (5-17) were detected as reaction intermediates, and compounds (6-20) were present in less than 0.1% of their components.

[0207] Then, add 240g of water, cool at 25°C and stir overnight, then filter out the precipitated solids.

[0208] The obtained solid 157.0g and methyl isobutyl ketone 367g were placed in a four-necked flask, purged with nitrogen, and then heated to dissolve.

[0209] Then, 249g of water was added and washed at 80°C to remove the aqueous layer. This operation was repeated four times. Then, 141g of methyl isobutyl ketone and water were removed by distillation.

[0210] The liquid was then cooled and stirred continuously at 25°C overnight, and the precipitated solid was filtered off. The filtered solid was dried under reduced pressure at 80°C to give 108.4 g of 10,10'-bis(methoxycarbonylpropoxy)-9,9'-biphenanthrene (compound (1-20)) (yield 90.7%).

[0211] The obtained compounds were analyzed by liquid chromatography-mass spectrometry and... 1 H-NMR and 13 C-NMR analysis confirmed that it is 10,10'-bis(methoxycarbonylpropoxy)-9,9'-biphenanthrene (compound (1-20)).

[0212] Liquid chromatography-mass spectrometry (mass spectrometry / electrospray ionization): Mass 609.23 [M+Na] 1¹H-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).

[0213] 13 C-NMR (400MHz, 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.

[0214] The purity of the obtained compounds (1-20) was determined to be 99.5% by high performance liquid chromatography, and the hue of the 10% THF solution prepared according to the above analytical method was APHA20.

[0215] The endothermic peaks of the obtained compounds (1-20) were determined by differential scanning calorimetry (DSC) to have an onset temperature of 155 °C.

[0216] <Example 5> 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 m²) were added. 2 47.9 g of butyl chloroacetate and 80.0 g of dimethylformamide were placed in a four-necked flask, which was then purged with nitrogen. The mixture was then heated to 50°C, and while stirring, a mixture of 49.7 g of butyl chloroacetate and 2.5 g of dimethylformamide was added dropwise over 2 hours. The etherification reaction was then carried out at 100°C for 2 hours.

[0217] The slurry after etherification was analyzed by HPLC. The results showed that at 1 hour of etherification, compound (1-10) was present in 99.0% of the slurry, the dietherified intermediate was present in 0.5%, compound (5-9) was not detected, and compounds (6-10) and (6-10') were present in 0.2%. At 2 hours of etherification, compound (1-10) was present in 99.5% of the slurry, the dietherified intermediate was not detected, compound (5-9) was not detected, and compounds (6-10) and (6-10') were present in 0.3%.

[0218] <Example 6> 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 m²) were added. 2 47.9 g of butyl chloroacetate and 80.0 g of dimethylformamide were placed in a four-necked flask, which was then purged with nitrogen. The mixture was then heated to 50°C, and while stirring, a mixture of 49.7 g of butyl chloroacetate and 2.5 g of dimethylformamide was added dropwise over 2 hours. The etherification reaction was then carried out at 100°C for 3.5 hours.

[0219] The liquid after the etherification reaction was analyzed by HPLC. The results showed that at 2 hours of etherification, the content of compound (1-10) was 93.5%, the dietherified intermediate was 5.8%, compound (5-9) was not detected, and compounds (6-10) and (6-10') were present at 0.2%. At 3.5 hours of etherification, the content of compound (1-10) was 99.4%, the dietherified intermediate was not detected, compound (5-9) was not detected, and compounds (6-10) and (6-10') were present at 0.3%.

[0220] <Comparative Example 2> 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 0.03 m²) were added. 2 47.9 g of butyl chloroacetate and 80.0 g of dimethylformamide were placed in a four-necked flask, which was then purged with nitrogen. The mixture was then heated to 50°C, and while stirring, a mixture of 49.7 g of butyl chloroacetate and 2.5 g of dimethylformamide was added dropwise over 2 hours. The etherification reaction was then carried out at 100°C for 5 hours.

[0221] HPLC analysis of the slurry after etherification showed that at 2 hours of etherification, compound (1-10) accounted for 30.0%, the dietherified intermediate for 28.1%, compound (5-9) was not detected, and compounds (6-10) and (6-10') were present at 0.1%. At 3.5 hours of etherification, compound (1-10) accounted for 41.0%, the dietherified intermediate for 28.7%, compound (5-9) was not detected, and compounds (6-10) and (6-10') were present at 0.2%. At 5 hours of etherification, compound (1-10) accounted for 48.4%, and the dietherified intermediate for 28.0%. Even after 5 hours of reaction, a large amount of dietherified intermediate remained, indicating that the reaction was not complete.

[0222] As can be seen from the above, the etherification reaction process to obtain the target polycarboxylate compound (1) can be carried out more quickly according to the manufacturing method of the present invention. It is further clarified that since the formation of polycarboxylate compound (5) and polycarboxylate compound (6) can be reduced, the polycarboxylate compound (1) with improved quality can be manufactured more efficiently.

Claims

1. A method for manufacturing a polycarboxylate compound (1) represented by general formula (1), characterized in that, The process includes an etherification reaction step 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 carry out an etherification reaction, wherein the potassium carbonate has a specific surface area of ​​0.1 m². 2 / g or more 2.0m 2 The range below / g [Chemistry 1] In formula (1), each Ar independently represents a monooxy aromatic hydrocarbon group with a "2+m valence" of 6 to 20 carbon atoms; each R1 independently represents a straight-chain or branched alkyl group with 1 to 6 carbon atoms, a cyclic alkyl group with 5 to 6 carbon atoms, or a straight-chain or branched alkoxy group with 1 to 6 carbon atoms; each R2 independently represents a straight-chain or branched alkylene group with 1 to 4 carbon atoms; each R3 independently represents an alkyl group with 1 to 10 carbon atoms or an alkenyl group with 2 to 10 carbon atoms; each m independently represents 0, 1, or 2; each 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 addition, in general formula (1), the oxygen atom of Ar is bonded to the aromatic hydrocarbon group contained in Ar and R2. [Chemistry 2] In general formula (1a), R5 and R6 each independently represent a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, a haloalkyl group with 1 to 10 carbon atoms, or an aryl group with 6 to 12 carbon atoms. R5 and R6 can be bonded to each other to form a cycloalkane group with 5 to 20 carbon atoms as a whole. In general formula (1b), Ar1 each independently represents an aryl group with 6 to 12 carbon atoms. The asterisks in general formulas (1a), (1b), and (1c) each represent a bonding position. [Chemistry 3] In general formula (1d), R7 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms. In general formula (1e), R8 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms. The asterisks in general formulas (1d) and (1e) respectively indicate the bonding positions. [Chemistry 4] The definitions of Ar, R1, m, n, and X in general formula (2) are the same as those in general formula (1). In addition, in general formula (2), the oxygen atom in Ar is bonded to the aromatic hydrocarbon group contained in Ar and the hydrogen atom (H) recorded in general formula (2). [Chemistry 5] The definitions of R2 and R3 in general formula (3) are the same as those in general formula (1), and Y represents a halogen atom.

2. The manufacturing method according to claim 1, characterized in that, Each of the Ars is independently selected from 1-oxyphenyl-4-yl, 1-oxyphenyl-3-yl, 1-oxyphenyl-2-yl, 1-oxynaphthyl-2-yl, 1-oxynaphthyl-4-yl, 1-oxynaphthyl-5-yl, 2-oxynaphthyl-1-yl, 2-oxynaphthyl-6-yl, 2-oxynaphthyl-7-yl, 4-oxy-3-phenylphenyl-1-yl, 9-oxyphenanthrene-3-yl, 10-oxyphenanthrene-9-yl, 2-oxyanthracene-7-yl, 1-oxy-3-phenylnaphthyl-4-yl, 1-oxy-3-phenylnaphthyl-5-yl, 2-oxy-1-phenylnaphthyl-6-yl, 2- The group consisting of 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, 4-oxy-3-(2-naphthyl)phenyl-1-yl, 4-oxy-3,5-diphenylphenyl-1-yl, 4-oxy-2-phenylphenanthroline-6-yl, 4-oxy-2-phenylphenanthroline-7-yl, 4-oxy-2-phenylphenanthroline-8-yl, 4-oxy-2-phenylphenanthroline-9-yl, 4-oxy-2-phenylphenanthroline-10-yl, and 2-oxy-3-phenylanthracene-7-yl.

3. The manufacturing method according to claim 1, characterized in that, The polycarboxylate compound (1) represented by general formula (1) is selected from any one of the polycarboxylate compounds represented by general formulas (1A) to (1F), and the polyhydroxy aromatic compound (2) represented by general formula (2) is selected from any one of the polyhydroxy aromatic compounds represented by general formulas (2A) to (2F). [Chemistry 6] [Chemistry 7] [Chemistry 8] [Chemistry 9] [Chemistry 10] [Chemistry 11] In general formulas (1A) to (1F), R1, R2, R3, m, n, and X are defined in the same way as in general formula (1). [Chemistry 12] [Chemistry 13] [Chemistry 14] [Chemistry 15] [Chemistry 16] [Chemistry 17] In general formulas (2A) to (2F), R1, m, n, and X are defined in the same way as in general formula (1).

4. The manufacturing method according to claim 3, characterized in that, The n of the polycarboxylate compounds represented by general formulas (1C), (1D), (1E) and (1F) is 1, the n of the polycarboxylate compounds represented by general formula (1B) is 2, the n of the polyhydroxy aromatic compounds represented by general formulas (2C), (2D), (2E) and (2F) is 1, and the n of the polyhydroxy aromatic compounds represented by general formula (2B) is 2.

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