Method for preparing polycarboxylic acid ester compounds

Abstract

The present invention aims to provide a method for producing a polycarboxylic acid ester compound with improved purity by reducing the content of specific impurities. As a means of solving the above problem, the present invention provides a method for manufacturing a polycarboxylic acid ester compound (1) represented by Formula 1, comprising an etherification reaction process in which an etherification reaction is performed using a polyhydroxy aromatic compound (2) represented by Formula 2, a halocarboxylic acid ester compound (3) represented by Formula 3, and potassium carbonate, wherein the amount of water contained in the potassium carbonate is in the range of 0.01 weight% or more and 1.5 weight% or less.

Description

Technology Field

[0001] The present invention relates to a method for manufacturing a polycarboxylic acid ester compound. More specifically, it relates to a method for manufacturing a polycarboxylic acid ester compound having improved purity and reduced content of specific impurities. Background Technology

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

[0003] Recently, as the demand for various performance improvements in the application fields of these materials has become increasingly sophisticated, raw materials used in the materials are required to have higher quality in order to exhibit the desired characteristics.

[0004] A method for producing a dicarboxylic acid compound using a bisphenol compound as a raw material is known, which involves performing an etherification reaction using a bisphenol compound and a halocarboxylic acid or its ester as raw materials to synthesize a dicarboxylic acid or its ester compound. Prior art literature

[0005] Japanese Patent Publication No. Sho 62-292819 Japanese Patent Publication No. Hei 05-170702 The problem to be solved

[0006] While the aforementioned manufacturing method is known, as a result of careful consideration to improve the quality of dicarboxylic acid ester compounds using bisphenol compounds as raw materials, it was discovered that in a process of performing an etherification reaction using bisphenol compounds, halocarboxylic acid esters, and potassium carbonate as raw materials, depending on the potassium carbonate used, the amount of impurities generated increases and the purity is not improved.

[0007] Based on the above-mentioned problem discovered by the inventors, the present invention aims to provide a method for producing a polycarboxylic acid ester compound with improved purity by reducing the content of specific impurities. means of solving the problem

[0008] As a result of careful examination by the inventors, we discovered a byproduct of a polycarboxylic acid compound in which the ester group of the target compound, polycarboxylic acid ester compound (1), was hydrolyzed, and a byproduct in which the halocarboxylic acid ester reacted in excess during the etherification reaction, and we discovered that these byproducts are due to the amount of water contained in potassium carbonate.

[0009] If the target polycarboxylic acid ester compound (1) contains other impurities such as these substituents, there is a risk of adverse effects on the physical properties of the material obtained using this compound or during the manufacturing process.

[0010] And, by using potassium carbonate with a moisture content within a specific range, it was discovered that the above problem could be solved, and the present invention was completed.

[0011] The present invention is as follows.

[0012] 1. A method for preparing a polycarboxylic acid ester compound (1) represented by Chemical Formula 1, comprising an etherification reaction process in which an etherification reaction is performed using a polyhydroxy aromatic compound (2) represented by Chemical Formula 2, a halocarboxylic acid ester compound (3) represented by Chemical Formula 3, and potassium carbonate, wherein the amount of water contained in the potassium carbonate is in the range of 0.01 weight% or more and 1.5 weight% or less.

[0013]

[0014] (In Formula 1, Ar independently represents a “2+m” monooxyaromatic hydrocarbon group having 6 to 20 carbon atoms, R1 independently represents a straight-chain or branched-chain alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 5 to 6 carbon atoms, or a straight-chain or branched-chain alkoxy group having 1 to 6 carbon atoms, R2 independently represents a straight-chain or branched-chain alkylene group having 1 to 4 carbon atoms, R3 independently represents an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, m independently represents 0, 1, or 2, n represents 1 or 2, and X represents a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, a divalent group represented by Formula 1a, 1b, or 1c, or represented by Formula 1d or 1e It represents a trivalent group. Also, in Chemical Formula 1, the oxygen atom of Ar is bonded to the aromatic hydrocarbon group contained in Ar and R2.

[0015] [Chemical Formulas 1a–1c]

[0016]

[0017] (In Formula 1a, R5 and R6 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms; R5 and R6 may each bond to form a cycloalkylidene group having 5 to 20 carbon atoms as a whole; in Formula 1b, Ar1 each independently represents an aryl group having 6 to 12 carbon atoms. * in Formulas 1a, 1b, and 1c each indicate a bonding position.)

[0018] [Chemical formula 1d, 1e]

[0019]

[0020] (In 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 Formula 1e, R8 represents a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms. * in Formulas 1d and 1e each indicate a bonding position.)

[0021]

[0022] (The definitions of Ar, R1, m, n, and X in Chemical Formula 2 are the same as those in Chemical Formula 1. Additionally, in Chemical Formula 2, the oxygen atom of Ar is bonded to the aromatic hydrocarbon group contained in Ar and the hydrogen atom (H) described in Chemical Formula 2.)

[0023]

[0024] (The definitions of R2 and R3 in Chemical Formula 3 are the same as in Chemical Formula 1, and Y represents a halogen atom.)

[0025] 2. Each of the above Ars independently 1-oxybenzene-4-digroup, 1-oxybenzene-3-digroup, 1-oxybenzene-2-digroup, 1-oxynaphthalene-2-digroup, 1-oxynaphthalene-4-digroup, 1-oxynaphthalene-5-digroup, 2-oxynaphthalene-1-digroup, 2-oxynaphthalene-6-digroup, 2-oxynaphthalene-7-digroup, 4-oxy-3-phenylbenzene-1-digroup, 9-oxyphenanthrene-3-digroup, 10-oxyphenanthrene-9-digroup, 2-oxyanthracene-7-digroup, 1-oxy-3-phenylnaphthalene-4-digroup, 1-oxy-3-phenylnaphthalene-5-digroup, 2-oxy-1-phenylnaphthalene-6-digroup, A manufacturing method described in 1, comprising any one of the group consisting of 2-oxy-1-phenylnaphthalene-7-di, 2-oxy-3-phenylnaphthalene-6-di, 2-oxy-3-phenylnaphthalene-7-di, 4-oxy-3-(1-naphthyl)benzene-1-di, 4-oxy-3-(2-naphthyl)benzene-1-di, 4-oxy-3,5-diphenylbenzene-1-di, 4-oxy-2-phenylphenanthrene-6-di, 4-oxy-2-phenylphenanthrene-7-di, 4-oxy-2-phenylphenanthrene-8-di, 4-oxy-2-phenylphenanthrene-9-di, 4-oxy-2-phenylphenanthrene-10-di, and 2-oxy-3-phenylanthracene-7-di.

[0026] 3. A method of manufacturing as described in 1, wherein the polycarboxylic acid ester compound (1) represented by the above chemical formula 1 is a polycarboxylic acid ester compound represented by any one selected from chemical formulas 1A to 1F, and the polyhydroxy aromatic compound (2) represented by the above chemical formula 2 is a polyhydroxy aromatic compound represented by any one selected from chemical formulas 2A to 2F.

[0027] [Chemical Formula 1A]

[0028]

[0029] [Chemical Formula 1B]

[0030]

[0031] [Chemical Formula 1C]

[0032]

[0033] [Chemical Formula 1D]

[0034]

[0035] [Chemical Formula 1E]

[0036]

[0037] [Chemical Formula 1F]

[0038]

[0039] (In Chemical Formulas 1A–1F, R1, R2, R3, m, n, and X are identical to the definitions in Chemical Formula 1.)

[0040] [Chemical Formula 2A]

[0041]

[0042] [Chemical Formula 2B]

[0043]

[0044] [Chemical Formula 2C]

[0045]

[0046] [Chemical Formula 2D]

[0047]

[0048] [Chemical Formula 2E]

[0049]

[0050] [Chemical Formula 2F]

[0051]

[0052] (In chemical formulas 2A–2F, R1, m, n, and X are identical to the definitions in chemical formula 1.)

[0053] 4. A method for manufacturing as described in 3, wherein the polycarboxylic acid ester compound represented by the above chemical formulas 1C, 1D, 1E, and 1F has n 1, the polycarboxylic acid ester compound represented by the above chemical formula 1B has n 2, the polyhydroxy aromatic compound represented by the above chemical formulas 2C, 2D, 2E, and 2F has n 1, and the polyhydroxy aromatic compound represented by the above chemical formula 2B has n 2. Effects of the invention

[0054] According to the manufacturing method of the present invention, in the etherification reaction process for obtaining the desired polycarboxylic acid ester compound (1), the generation of specific impurities can be reduced, so a polycarboxylic acid ester compound (1) of improved quality can be manufactured. Specific details for implementing the invention

[0055] <Manufacturing method of the present invention>

[0056] The method for preparing a polycarboxylic acid ester compound (1) represented by Formula 1 of the present invention comprises an etherification reaction process in which an etherification reaction is performed using a polyhydroxy aromatic compound (2) represented by Formula 2, a halocarboxylic acid ester compound (3) represented by Formula 3, and potassium carbonate, wherein the amount of water contained in the potassium carbonate is in the range of 0.01% by weight or more and 1.5% by weight or less.

[0057] <Polycarboxylic acid ester compound represented by chemical formula 1 (1)>

[0058] In Chemical Formula 1, Ar each independently represents a “2+m” monooxyaromatic hydrocarbon group having 6 to 20 carbon atoms. In addition, in Chemical Formula 1, the oxygen atom of Ar is bonded to the aromatic hydrocarbon group contained in Ar and R2.

[0059] First, we will explain the case where m is 0, that is, a divalent monooxy aromatic hydrocarbon group with 6 to 20 carbon atoms.

[0060] Among the divalent monooxyaromatic hydrocarbon groups having 6 to 20 carbon atoms, a divalent monooxyaromatic hydrocarbon group having 6 to 16 carbon atoms is preferred, a divalent monooxyaromatic hydrocarbon group having 6 to 14 carbon atoms is more preferred, a divalent monooxyaromatic hydrocarbon group having 6, 10, or 14 carbon atoms is even more preferred, and a divalent monooxyaromatic hydrocarbon group having 10 or 14 carbon atoms is particularly preferred.

[0061] Specific examples of divalent monooxy aromatic hydrocarbon groups having 6 carbon atoms include 1-oxybenzene-4-yl group, 1-oxybenzene-3-yl group, and 1-oxybenzene-2-yl group.

[0062] Specific examples of divalent monooxy aromatic hydrocarbon groups having 10 carbon atoms include 1-oxynaphthalene-2-1 group, 1-oxynaphthalene-4-1 group, 1-oxynaphthalene-5-1 group, 2-oxynaphthalene-1-1 group, 2-oxynaphthalene-6-1 group, and 2-oxynaphthalene-7-1 group.

[0063] Specific examples of divalent monooxy aromatic hydrocarbon groups having 12 carbon atoms include the 4-oxy-3-phenylbenzene-1-yl group.

[0064] Specific examples of a divalent monooxy aromatic hydrocarbon group having 14 carbon atoms include a monooxyphenanthrenyl group such as a 9-oxyphenanthren-3-yl group or a 10-oxyphenanthren-9-yl group, and a 2-oxyanthracene-7-yl group. Among these, a monooxyphenanthrenyl group is more preferred, and furthermore, among these, a 9-oxyphenanthren-3-yl group or a 10-oxyphenanthren-9-yl group is preferred.

[0065] Specific examples of divalent monooxy aromatic hydrocarbon groups having 16 carbon atoms include 1-oxy-3-phenylnaphthalene-4-yl group, 1-oxy-3-phenylnaphthalene-5-yl group, 2-oxy-1-phenylnaphthalene-6-yl group, 2-oxy-1-phenylnaphthalene-7-yl group, 2-oxy-3-phenylnaphthalene-6-yl group, 2-oxy-3-phenylnaphthalene-7-yl group, 4-oxy-3-(1-naphthyl)benzene-1-yl group, and 4-oxy-3-(2-naphthyl)benzene-1-yl group.

[0066] Specific examples of divalent monooxy aromatic hydrocarbon groups with 18 carbon atoms include the 4-oxy-3,5-diphenylbenzene-1-yl group.

[0067] Specific examples of divalent monooxy aromatic hydrocarbon groups having 20 carbon atoms include 4-oxy-2-phenylphenanthrene-6-yl group, 4-oxy-2-phenylphenanthrene-7-yl group, 4-oxy-2-phenylphenanthrene-8-yl group, 4-oxy-2-phenylphenanthrene-9-yl group, 4-oxy-2-phenylphenanthrene-10-yl group, and 2-oxy-3-phenylanthracene-7-yl group.

[0068] It is also possible to select any one of the groups selected from the above specific examples of divalent monooxy aromatic hydrocarbon groups having 6 to 20 carbon atoms. That is, Ar in Chemical Formula 1 is independently 1-oxybenzene-4-di group, 1-oxybenzene-3-di group, 1-oxybenzene-2-di group, 1-oxynaphthalene-2-di group, 1-oxynaphthalene-4-di group, 1-oxynaphthalene-5-di group, 2-oxynaphthalene-1-di group, 2-oxynaphthalene-6-di group, 2-oxynaphthalene-7-di group, 4-oxy-3-phenylbenzene-1-di group, 9-oxyphenanthrene-3-di group, 10-oxyphenanthrene-9-di group, 2-oxyanthracene-7-di group, 1-oxy-3-phenylnaphthalene-4-di group, 1-oxy-3-phenylnaphthalene-5-di group, 2-oxy-1-phenylnaphthalene-6-di group, It is also possible to select any one group from the group consisting of 2-oxy-1-phenylnaphthalene-7-yl group, 2-oxy-3-phenylnaphthalene-6-yl group, 2-oxy-3-phenylnaphthalene-7-yl group, 4-oxy-3-(1-naphthyl)benzene-1-yl group, 4-oxy-3-(2-naphthyl)benzene-1-yl group, 4-oxy-3,5-diphenylbenzene-1-yl group, 4-oxy-2-phenylphenanthrene-6-yl group, 4-oxy-2-phenylphenanthrene-7-yl group, 4-oxy-2-phenylphenanthrene-8-yl group, 4-oxy-2-phenylphenanthrene-9-yl group, 4-oxy-2-phenylphenanthrene-10-yl group and 2-oxy-3-phenylanthracene-7-yl group.

[0069] Among these, Ar in Formula 1 is preferably one group independently selected from the group consisting of 1-oxybenzene-4-di, 1-oxybenzene-2-di, 2-oxynaphthalene-1-di, 2-oxynaphthalene-6-di, 4-oxy-3-phenylbenzene-1-di, 9-oxyphenanthrene-3-di, and 10-oxyphenanthrene-9-di, and is more preferably one group independently selected from the group consisting of 1-oxybenzene-4-di, 1-oxybenzene-2-di, 2-oxynaphthalene-1-di, and 10-oxyphenanthrene-9-di, all of which are 1-oxybenzene-4-di, have 1-oxybenzene-4-di and 1-oxybenzene-2-di, and all of which are 1-oxybenzene-4-di, have 1-oxybenzene-4-di and 1-oxybenzene-2-di, and all of which It is more preferable that it is 2-oxynaphthalene-1-diary or all 10-oxyphenanthrene-9-diary, and particularly preferable that it has 1-oxybenzene-4-diary and 1-oxybenzene-2-diary, all 2-oxynaphthalene-1-diary or all 10-oxyphenanthrene-9-diary.

[0070] Next, when m is 1 or 2, that is, when the number of carbon atoms is 6 to 20, the trivalent or tetravalent monooxy aromatic hydrocarbon group is a group in which one or two of the hydrogen atoms of the aromatic hydrocarbon group in the case where m is 0 are substituted at bonding positions according to the number of m so as to bond with the group of R1.

[0071] The polycarboxylic acid ester compound represented by Chemical Formula 1 is preferably a polycarboxylic acid ester compound represented by any one selected from Chemical Formulas 1A to 1F described below, more preferably a polycarboxylic acid ester compound represented by Chemical Formulas 1A, 1B, 1C, 1E, or 1F, even more preferably a polycarboxylic acid ester compound represented by Chemical Formulas 1A, 1B, 1E, or 1F, and particularly preferably a polycarboxylic acid ester compound represented by Chemical Formulas 1B, 1E, or 1F.

[0072] R1 in Chemical Formula 1 represents, respectively, a straight-chain or branched-chain alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 5 to 6 carbon atoms, or a straight-chain or branched-chain alkoxyl group having 1 to 6 carbon atoms. Among these,, a straight-chain or branched-chain alkyl group having 1 to 4 carbon atoms, a cyclohexyl group, or a methoxy group is preferred, and a methyl group, a t-butyl group, or a cyclohexyl group is more preferred, and a methyl group is particularly preferred.

[0073] R2 in Chemical Formula 1 each independently represents a straight-chain or branched-chain alkylene group having 1 to 4 carbon atoms. Among these, a straight-chain or branched-chain alkylene group having 1 to 3 carbon atoms is preferred, a methylene group, a 1,2-ethylene group, or a 1,3-propylene group is more preferred, and a methylene group or a 1,3-propylene group is particularly preferred.

[0074] R3 in Formula 1 each independently represents an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. Among these, a straight-chain or branched-chain alkyl group having 1 to 6 carbon atoms or a cyclic alkyl group having 5 to 8 carbon atoms is preferred, a straight-chain or branched-chain alkyl group having 1 to 4 carbon atoms or a cyclic alkyl group having 6 to 8 carbon atoms is more preferred, a methyl group, an ethyl group, a t-butyl group, a 1-methylcyclopentyl group, or a 1-ethylhexyl group is even more preferred, and a methyl group, an ethyl group, or a t-butyl group is particularly preferred.

[0075] m represents 0, 1, or 2 independently, respectively.

[0076] Regarding the binding position of R1 when m is 1, the 1-oxybenzene-4-diyl group is preferably at position 2, the 1-oxybenzene-2-diyl group is preferably at position 2 or 4, the 2-oxynaphthalene-1-diyl group is preferably at position 6, the 2-oxynaphthalene-6-diyl group is preferably at position 5, the 4-oxy-3-phenylbenzene-1-diyl group is preferably at position 5, the 9-oxyphenanthrene-3-diyl group is preferably at position 10, and the 10-oxyphenanthrene-9-diyl group is preferably at position 6.

[0077] For the binding positions of R1 when m is 2, the 1-oxybenzene-4-yl group is preferably at positions 2 and 5.

[0078] n represents 1 or 2.

[0079] X in Formula 1 is, when n is 1, a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, or a divalent group represented by Formula 1a, 1b, or 1c, among which a single bond, a divalent group represented by Formula 1a, a divalent group represented by Formula 1b, or a divalent group represented by Formula 1c is preferred, a single bond, a divalent group represented by Formula 1b, or a divalent group represented by Formula 1c is more preferred, and a single bond is particularly preferred.

[0080] X in Chemical Formula 1 is a trivalent group represented by Chemical Formula 1d or 1e when n is 2, and a trivalent group represented by Chemical Formula 1d is preferred.

[0081] In the case where X in Formula 1 is a divalent group represented by Formula 1a, more preferred R5 and R6 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkyl halide group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, more preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and particularly preferably a hydrogen atom, a methyl group, or an ethyl group.

[0082] In addition, R5 and R6 may each bond 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 include an alkyl group as a substituent. The cycloalkylidene group is preferably 5 to 15 carbon atoms, more preferably 6 to 12 carbon atoms, and particularly preferably 6 to 9 carbon atoms.

[0083] As for the cycloalkylidene group, specifically, for example, the cyclopentylidene group (5 carbon atoms), the cyclohexylidene group (6 carbon atoms), the 3-methylcyclohexylidene group (7 carbon atoms), the 4-methylcyclohexylidene group (7 carbon atoms), the 3,3,5-trimethylcyclohexylidene group (9 carbon atoms), the cycloheptylidene group (7 carbon atoms), the bicyclo[2.2.1]heptane-2,2-diyl group (7 carbon atoms), the 1,7,7-trimethylbicyclo[2.2.1]heptane-2,2-diyl group (10 carbon atoms), the 4,7,7-trimethylbicyclo[2.2.1]heptane-2,2-diyl group (10 carbon atoms), the tricyclo[5. 2. 1. 0 2,6 Examples include decane-8,8-diyl group (10 carbon atoms), 2,2-adamantylidene group (10 carbon atoms), cyclododecanylidene group (12 carbon atoms). Preferably, it is a cyclohexylidene group (6 carbon atoms), a 3-methylcyclohexylidene group (7 carbon atoms), a 4-methylcyclohexylidene group (7 carbon atoms), a 3,3,5-trimethylcyclohexylidene group (9 carbon atoms), and a cyclododecanylidene group (12 carbon atoms); more preferably, it is a cyclohexylidene group (6 carbon atoms), a 3,3,5-trimethylcyclohexylidene group (9 carbon atoms), and a cyclododecanylidene group (12 carbon atoms); and particularly preferably, it is a cyclohexylidene group (6 carbon atoms) and a 3,3,5-trimethylcyclohexylidene group (9 carbon atoms).

[0084] In the case where X in Chemical Formula 1 is a divalent group represented by Chemical Formula 1b, the preferred Ar1 is independently a benzene ring and a naphthalene ring, and it is more preferable that all Ar1 are benzene rings. For example, when all Ar1 are benzene rings, the group represented by Chemical Formula 1b is a fluorenylidene group.

[0085] As a preferred embodiment in the case where X in Chemical Formula 1 is a divalent group represented by Chemical Formula 1c, a divalent group represented by Chemical Formula 1c' or Chemical Formula 1c" is preferred.

[0086] [Chemical Formula 1c', Chemical Formula 1c"]

[0087]

[0088] As a preferred embodiment in which X in Chemical Formula 1 is a trivalent group represented by Chemical Formula 1d, it is preferable that R7 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, more preferable that R7 is a hydrogen atom, a methyl group, or a phenyl group, and particularly preferable that R7 is a hydrogen atom or a methyl group.

[0089] As a preferred embodiment in which X in Chemical Formula 1 is a trivalent group represented by Chemical Formula 1e, it is preferable that R8 is a hydrogen atom or a methyl group, and particularly preferable that R8 is a methyl group.

[0090] When all the Ar in Chemical Formula 1 are 1-oxybenzene-4-yl groups, it becomes a polycarboxylic acid ester compound represented by Chemical Formula 1A.

[0091] [Chemical Formula 1A]

[0092]

[0093] (In Chemical Formula 1A, R1, R2, R3, m, n, and X are identical to the definitions in Chemical Formula 1.)

[0094] Specific examples of compounds in which all Ar in Chemical Formula 1 is a 1-oxybenzene-4- group include compounds (1-1) to (1-9).

[0095]

[0096]

[0097]

[0098] In the case where Ar in Chemical Formula 1 is a 1-oxybenzene-4-yl group and a 1-oxybenzene-2-yl group, an example is a polycarboxylic acid ester compound represented by Chemical Formula 1B, and this compound is preferred. In the polycarboxylic acid ester compound represented by Chemical Formula 1B, it is preferred that n is 2.

[0099] [Chemical Formula 1B]

[0100]

[0101] (In Chemical Formula 1B, R1, R2, R3, m, n, and X are identical to the definitions in Chemical Formula 1.)

[0102] Specific examples of compounds in which Ar in Chemical Formula 1 has a 1-oxybenzene-4-yl group and a 1-oxybenzene-2-yl group include compounds (1-10) to (1-12).

[0103]

[0104] When all the Ar in Chemical Formula 1 are 2-oxynaphthalene-1- di groups, it becomes a polycarboxylic acid ester compound represented by Chemical Formula 1C. In the polycarboxylic acid ester compound represented by Chemical Formula 1C, it is preferable that n is 1.

[0105] [Chemical Formula 1C]

[0106]

[0107] (In Chemical Formula 1C, R1, R2, R3, m, n, and X are identical to the definitions in Chemical Formula 1.)

[0108] Specific examples of compounds in which all Ar in Chemical Formula 1 is a 2-oxynaphthalene-1-di group include compounds (1-13) and (1-14).

[0109]

[0110] When all the Ar in Chemical Formula 1 are 2-oxynaphthalene-6-yl groups, it becomes a polycarboxylic acid ester compound represented by Chemical Formula 1D. In the polycarboxylic acid ester compound represented by Chemical Formula 1D, it is preferable that n is 1.

[0111] [Chemical Formula 1D]

[0112]

[0113] (In Chemical Formula 1D, R1, R2, R3, m, n, and X are identical to the definitions in Chemical Formula 1.)

[0114] A specific example of a compound in which all Ar in Chemical Formula 1 is a 2-oxynaphthalene-6-yl group is compound (1-15).

[0115]

[0116] When all Ar in Chemical Formula 1 are 4-oxy-3-phenylbenzene-1-yl groups, it becomes a polycarboxylic acid ester compound represented by Chemical Formula 1E. In the polycarboxylic acid ester compound represented by Chemical Formula 1E, it is preferable that n is 1.

[0117] [Chemical Formula 1E]

[0118]

[0119] (In Chemical Formula 1E, R1, R2, R3, m, n, and X are identical to the definitions in Chemical Formula 1.)

[0120] Specific examples of compounds in which all Ar in Chemical Formula 1 is a 4-oxy-3-phenylbenzene-1-yl group include compounds (1-16) and (1-17).

[0121]

[0122] When all Ar in Chemical Formula 1 are 10-oxyphenanthrene-9-yl groups, it becomes a polycarboxylic acid ester compound represented by Chemical Formula 1F. In the polycarboxylic acid ester compound represented by Chemical Formula 1F, it is preferable that n is 1.

[0123] [Chemical Formula 1F]

[0124]

[0125] (In Chemical Formula 1F, R1, R2, R3, m, n, and X are identical to the definitions in Chemical Formula 1.)

[0126] Specific examples of compounds in which all of the Ar in Chemical Formula 1 are 10-oxyphenanthrene-9-di groups include compounds (1-18) to (1-23).

[0127]

[0128] <Polyhydroxy aromatic compound represented by chemical formula 2 (2)>

[0129] The definitions of Ar, R1, m, n, and X in Chemical Formula 2 are the same as those in Chemical Formula 1, and their specific examples and preferred embodiments are also the same.

[0130] In addition, in Chemical Formula 2, the oxygen atom of Ar is bonded to the aromatic hydrocarbon group contained in Ar and the hydrogen atom (H) described in Chemical Formula 2.

[0131] In addition, among the polyhydroxy aromatic compounds represented by Chemical Formula 2, a polyhydroxy aromatic compound represented by any one selected from Chemical Formulas 2A to 2F described below is preferred, a polyhydroxy aromatic compound represented by Chemical Formulas 2A, 2B, 2C, 2E, or 2F is more preferred, a polyhydroxy aromatic compound represented by Chemical Formulas 2A, 2B, 2E, or 2F is even more preferred, and a polyhydroxy aromatic compound represented by Chemical Formulas 2B, 2E, or 2F is particularly preferred.

[0132] When all the Ar in Chemical Formula 2 are 1-oxybenzene-4-yl groups, it becomes a polyhydroxy aromatic compound represented by Chemical Formula 2A.

[0133] [Chemical Formula 2A]

[0134]

[0135] (In Chemical Formula 2A, R1, m, n, and X are identical to the definitions in Chemical Formula 1.)

[0136] Specific examples of compounds in which all Ar in Chemical Formula 2 is a 1-oxybenzene-4-di group include compounds (2-1) to (2-8).

[0137]

[0138] In the case where Ar in Chemical Formula 2 is a 1-oxybenzene-4-yl group and a 1-oxybenzene-2-yl group, as an example, a compound represented by Chemical Formula 2B can be cited, and this embodiment is preferred. In the polyhydroxy aromatic compound represented by Chemical Formula 2B, it is preferred that n is 2.

[0139] [Chemical Formula 2B]

[0140]

[0141] (In Chemical Formula 2B, R1, m, n, and X are identical to the definitions in Chemical Formula 1.)

[0142] A specific example of a compound in which Ar in Chemical Formula 2 has a 1-oxybenzene-4- and a 1-oxybenzene-2- group is compound (2-9).

[0143]

[0144] When all the Ar in Chemical Formula 2 are 2-oxynaphthalene-1- di groups, it becomes a polyhydroxy aromatic compound represented by Chemical Formula 2C. For the polyhydroxy aromatic compound represented by Chemical Formula 2C, it is preferable that n is 1.

[0145] [Chemical Formula 2C]

[0146]

[0147] (In Chemical Formula 2C, R1, m, n, and X are identical to the definitions in Chemical Formula 1.)

[0148] Specific examples of compounds in which all Ar in Chemical Formula 2 is a 2-oxynaphthalene-1-di group include compounds (2-10) and (2-11).

[0149]

[0150] When all the Ar in Chemical Formula 2 are 2-oxynaphthalene-6-yl groups, it becomes a polyhydroxy aromatic compound represented by Chemical Formula 2D. For the polyhydroxy aromatic compound represented by Chemical Formula 2D, it is preferable that n is 1.

[0151] [Chemical Formula 2D]

[0152]

[0153] (In Chemical Formula 2D, R1, m, n, and X are identical to the definitions in Chemical Formula 1.)

[0154] A specific example of a compound in which all of the Ar in Chemical Formula 2 are 2-oxynaphthalene-6-di groups is compound (2-12).

[0155]

[0156] When all Ar in Chemical Formula 2 are 4-oxy-3-phenylbenzene-1-yl groups, it becomes a polyhydroxy aromatic compound represented by Chemical Formula 2E. For the polyhydroxy aromatic compound represented by Chemical Formula 2E, it is preferable that n is 1.

[0157] [Chemical Formula 2E]

[0158]

[0159] (In Chemical Formula 2E, R1, m, n, and X are identical to the definitions in Chemical Formula 1.)

[0160] Specific examples of compounds in which all Ar in Chemical Formula 2 is a 4-oxy-3-phenylbenzene-1-yl group include compounds (2-13) and (2-14).

[0161]

[0162] When all the Ar in Chemical Formula 2 are 10-oxyphenanthrene-9-yl groups, it becomes a compound represented by Chemical Formula 2F.

[0163] [Chemical Formula 2F]

[0164]

[0165] (In Chemical Formula 2F, R1, m, n, and X are identical to the definitions in Chemical Formula 1.)

[0166] Specific examples of compounds in which all of the Ar in Chemical Formula 2 are 10-oxyphenanthrene-9-di groups include compounds (2-15) and (2-16).

[0167]

[0168] <Halocarboxylic acid ester compound represented by chemical formula 3 (3)>

[0169] The definitions of R2 and R3 in Chemical Formula 3 are the same as those in Chemical Formula 1, and their specific examples and preferred embodiments are also the same.

[0170] Y in Chemical Formula 3 represents a halogen atom, and among them, a chlorine atom or a bromine atom is preferred, and a chlorine atom is particularly preferred.

[0171] Specific examples of halocarboxylic acid ester compounds (3) include, for example, alkyl halides of acetate such as methyl chloroacetate, ethyl chloroacetate, n-propyl chloroacetate, isopropyl chloroacetate, n-butyl chloroacetate, isobutyl chloroacetate, tertiary butyl chloroacetate, 1-methylcyclopentyl chloroacetate, 1-ethylcyclohexyl chloroacetate, methyl bromoacetate, ethyl bromoacetate, n-propyl bromoacetate, isopropyl bromoacetate, n-butyl bromoacetate, isobutyl bromoacetate, tertiary butyl bromoacetate, 1-methylcyclopentyl bromoacetate, and 1-ethylcyclohexyl bromoacetate; alkenyl halides of acetate such as vinyl chloroacetate, allyl chloroacetate, vinyl bromoacetate, and allyl bromoacetate; and methyl 3-chloropropanoate. Alkyl halides of propanoates such as 3-ethyl chloropropanoate, 3-methyl bromopropanoate, 3-ethyl bromopropanoate; alkenyl halides of propanoates such as 3-vinyl chloropropanoate, 3-allyl chloropropanoate, 3-vinyl bromopropanoate, 3-allyl bromopropanoate; methyl 4-chlorobutyrate, 4-ethyl chlorobutyrate, n-propyl 4-chlorobutyrate, isopropyl 4-chlorobutyrate, n-butyl chlorobutyrate, isobutyl chloroacetate, tertiarybutyl 4-chlorobutyrate, 1-methylcyclopentyl 4-chlorobutyrate, 1-ethylcyclohexyl 4-chlorobutyrate, methyl bromobutyrate, 4-ethyl bromobutyrate, Examples include alkyl butyrate halides such as 4-bromobutyrate n-propyl, 4-bromobutyrate isopropyl, 4-bromobutyrate n-butyl, 4-bromoacetate isobutyl, 4-bromobutyrate tertiarybutyl, 4-bromobutyrate 1-methylcyclopentyl, and 4-bromobutyrate 1-ethylcyclohexyl.Among these, alkyl halides of acetate or alkyl butyrates of butyrate are preferred, and methyl chloroacetate, ethyl chloroacetate, tertiary butyl chloroacetate, 1-methylcyclopentyl chloroacetate, 1-ethylcyclohexyl chloroacetate, methyl bromoacetate, ethyl bromoacetate, tertiary butyl bromoacetate, 1-methylcyclopentyl bromoacetate, 1-ethylcyclohexyl bromoacetate, 4-methyl chlorobutyrate, 4-ethyl chlorobutyrate, 4-tertiary butyl chlorobutyrate, 4-methylcyclopentyl chlorobutyrate, 4-ethylcyclohexyl chlorobutyrate, 4-methyl bromobutyrate, 4-ethylbromobutyrate, 4-methyl bromobutyrate, 4-ethylbromobutyrate, 4-tertiary butyl bromoacetate Any one compound selected from 1-methylcyclopentyl and 4-bromoacetic acid 1-ethylcyclohexyl is more preferred, any one compound selected from methyl chloroacetate, ethyl chloroacetate, tertiary butyl chloroacetate, 1-methylcyclopentyl chloroacetate, 1-ethylcyclohexyl chloroacetate, 4-methyl chlorobutyrate, 4-ethyl chlorobutyrate, 4-tertiary butyl chlorobutyrate, 4-methylcyclopentyl chlorobutyrate, and 4-ethylcyclohexyl chlorobutyrate is even more preferred, and any one compound selected from methyl chloroacetate, ethyl chloroacetate, tertiary butyl chloroacetate, 4-methyl chlorobutyrate, 4-ethyl chlorobutyrate, and 4-tertiary butyl chlorobutyrate is particularly preferred.

[0172] <Etherization Reaction Process>

[0173] In the etherification reaction process of the manufacturing method of the present invention, the molar ratio of the addition of the halocarboxylic acid ester compound (3) to the polyhydroxy aromatic compound (2) is not particularly limited as long as it is greater than or equal to the theoretical value (1.0 + n), but is typically used in the range of 2 to 20 times molar amount, preferably in the range of 2 to 10 times molar amount, and more preferably in the range of 2 to 6 times molar amount. Also, the "n" of the theoretical value is the number of "n" in Chemical Formula 1.

[0174] (Potassium carbonate)

[0175] The etherification reaction process of the manufacturing method of the present invention uses potassium carbonate having a water content of 1.5 weight% or less.

[0176] In the etherification reaction process of the manufacturing method of the present invention, it is preferable that the amount of water contained in the potassium carbonate be as small as within the above range, so that the amount of polycarboxylic acid compound (5) and polycarboxylic acid ester compound (6) described later can be suppressed; however, from the perspective of ease of obtaining potassium carbonate, such water amount may be 0.01 weight% or more. That is, potassium carbonate having a water content in the range of 0.01 weight% or more and 1.2 weight% or less may be used. The amount of water contained in the potassium carbonate used is preferably in the range of 0.01 weight% or more and 1.2 weight% or less, more preferably in the range of 0.01 weight% or more and 1.0 weight% or less, and particularly preferably in the range of 0.01 weight% or more and 0.5 weight% or less.

[0177] In the present invention, the amount of moisture contained in potassium carbonate means a value measured by the drying method.

[0178] Since potassium carbonate is hygroscopic, it absorbs moisture from the air, which can lead to an increase in moisture content. Potassium carbonate containing a moisture content exceeding this upper limit can be dried under heating and reduced pressure to reduce the moisture content.

[0179] Potassium carbonate used in the manufacturing method of the present invention is preferably stored by wrapping it in a container or bag by means of a method in which a dry gas with a low moisture content (such as dry air and an inert gas such as nitrogen) is sealed in a container or bag that does not allow moisture to pass through, or by a method of degassing by sealing it in a container or bag that does not allow moisture to pass through, in order to avoid the moisture content increasing by absorbing moisture from the air.

[0180] Potassium carbonate used in the manufacturing method of the present invention preferably has a specific surface area of ​​0.1 m² / g or more. In the etherification reaction process of the manufacturing method of the present invention, potassium carbonate and the polyhydroxy aromatic compound (2) form a salt, and before the reaction with the halocarboxylic acid ester compound (3), the mixture becomes a slurry. In the reaction mechanism of the etherification reaction process, since the specific surface area affects the frequency of interaction with the polyhydroxy aromatic compound (2), it is better if it is larger. From the perspective of obtaining potassium carbonate, the upper limit of the specific surface area may be 2.0 m² / g or less. That is, potassium carbonate with a specific surface area in the range of 0.1 m² / g or more and 2.0 m² / g or less may be used. The lower limit of the specific surface area of ​​the potassium carbonate used is preferably 0.2 m² / g or more, more preferably 0.3 m² / g or more, even more preferably 0.5 m² / g or more, and particularly preferably 0.7 m² / g or more. In addition, the upper limit of the specific surface area is preferably 1.5 m² / g or less, and more preferably 1.2 m² / g or less.

[0181] In addition, the specific surface area in the present invention refers to a value obtained by analyzing potassium carbonate by the BET method using a mercury intrusion type pore distribution measuring device.

[0182] It is preferable that the specific surface area of ​​the potassium carbonate used is within the above range, as the etherification reaction proceeds quickly compared to the case where potassium carbonate outside the above range is used, thereby shortening the reaction time, so that the target compound, the polycarboxylic acid ester compound (1), can be efficiently produced.

[0183] The molar ratio of potassium carbonate added is typically in the range of 0.8 to 4 times the molar amount relative to the total amount of the halocarboxylic acid ester compound (3) used, 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.

[0184] (catalyst)

[0185] In the manufacturing method of the present invention, the etherification reaction may use a catalyst, and examples include alkali metal salts of bromate such as sodium bromate and potassium bromate, alkali metal salts of iodide such as sodium iodide and potassium iodide, ammonium bromate and ammonium iodide.

[0186] The amount of catalyst used is typically in the range of 0.1 to 100 weight%, preferably in the range of 0.1 to 20 weight%, and more preferably in the range of 0.1 to 10 weight% with respect to the polyhydroxy aromatic compound (2).

[0187] (Etherization reaction temperature)

[0188] The reaction temperature is typically in the range of 25 to 120°C, preferably in the range of 40 to 100°C, more preferably in the range of 50 to 90°C, and particularly preferably in the range of 60 to 80°C. If the reaction temperature is high, the yield decreases, and if the reaction temperature is low, the reaction rate slows down, which is undesirable.

[0189] (Etherization reaction pressure)

[0190] There are no restrictions on the reaction pressure, and it may be at atmospheric pressure, reduced pressure, or pressurized. At atmospheric pressure or reduced pressure is preferred. In the case of a reaction under pressurized pressure, the reaction can be carried out in a pressurized state while circulating an inert gas, such as nitrogen, for example. That is, the reaction can be carried out by introducing an inert gas into the reaction system and simultaneously discharging the gas within the reaction system. By doing so, the carbon dioxide generated from the potassium carbonate used in the reaction can be discharged outside the reaction system, thereby accelerating the reaction. Specifically, examples of inert gases include nitrogen gas, argon gas, and helium gas, and from an economic perspective, nitrogen gas is the most preferred.

[0191] From the perspective of shortening the reaction time, it is more desirable to perform the reaction under reduced pressure. By carrying out the reaction under reduced pressure, carbon dioxide generated from the potassium carbonate used can be discharged outside the reaction system, thereby accelerating the reaction and making it possible to shorten the reaction time compared to a reaction under atmospheric pressure. In addition, by carrying out the reaction under reduced pressure and simultaneously discharging the solvent outside the reaction system, the formation of by-products can be suppressed. Specifically, the reaction pressure is preferably in the range of 5 kPa or more and 80 kPa or less, more preferably in the range of 10 kPa or more and 70 kPa or less, and even more preferably in the range of 30 kPa or more and 60 kPa or less. The reaction pressure can be reduced by a pressure reduction device, and when the reaction pressure is maintained within the above range, the pressure reduction device may be operated intermittently or continuously, but it is more desirable to operate it continuously. It is desirable to carry out the reaction under reduced pressure, specifically maintaining a pressure within the above range, from the start of the reaction to the end of the reaction.

[0192] (menstruum)

[0193] Although a reaction solvent may not be used during the reaction, it is desirable to use one for reasons such as improving operability and reaction speed during industrial production. As for the reaction solvent, there are no particular restrictions as long as it does not leak out of the reaction vessel at the reaction temperature and is inert to 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 each be used individually, or two or more may be used in combination to adjust polarity. Among these, ketone solvents having 3 to 9 carbon atoms, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, and cyclooctanone, or aprotic polar solvents such as acetonitrile, dimethyl sulfoxide, dimethylformamide, and N-methylpyrrolidone are preferred, ketone solvents having 3 to 9 carbon atoms, dimethylformamide, N-methylpyrrolidone, or acetonitrile are more preferred, ketone solvents having 3 to 6 carbon atoms, dimethylformamide, or N-methylpyrrolidone are even more preferred, and acetone, methyl isobutyl ketone, dimethylformamide, or N-methylpyrrolidone are particularly preferred. When methyl isobutyl ketone is used as a reaction solvent, it is also preferred that water washing can be performed to remove water-soluble impurities such as salts after the reaction is completed.

[0194] It is preferable that the solvent used in the etherification reaction be dehydrated.

[0195] There is no particular limit on the amount of solvent used as long as it does not interfere with the reaction, but generally, it is preferable to use it in the range of 1 to 7 times by weight relative to the polyhydroxy aromatic compound (2), more preferable to use it in the range of 2 to 4 times by weight, and even more preferable to use it in the range of 2 to 3 times by weight.

[0196] When the reaction is carried out under reduced pressure and the solvent is discharged out of the reaction system, the amount of solvent used is preferably in the range of 1.5 to 10 times by weight relative to the polyhydroxy aromatic compound (2), 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.

[0197] As for the amount of effluent per hour during the reaction by effluent of the solvent out of the reaction system, a range of 0.05 to 1.5 times by weight with respect to the polyhydroxy aromatic compound (2) is preferred, a range of 0.1 to 1.0 times by weight is more preferred, a range of 0.3 to 1.0 times by weight is even more preferred, and a range of 0.3 to 0.8 times by weight is particularly preferred. During the reaction, the amount of effluent per hour may fluctuate within the above range, and the amount of effluent may temporarily exceed the upper or lower limit of the above range.

[0198] (Etherization reaction endpoint)

[0199] The endpoint of the etherification reaction can be confirmed by liquid chromatography or gas chromatography analysis. It is preferable to define the endpoint of the reaction as the point in time when the unreacted polyhydroxy aromatic compound (2) disappears, and when n is 2, the intermediate monoether product is formed in the target compound polycarboxylic acid ester compound (1), and when n is 3, the intermediate biether product is formed and then almost invisible. Specifically, regarding the point in time when the reaction intermediate is formed and then almost invisible, it is the point in time when the liquid chromatography or gas chromatography analysis becomes 1.5 area% or less, more preferably 1.0 area% or less, even more preferably 0.8 area% or less, and particularly preferably 0.5 area% or less. The reaction time varies depending on the type of raw material used and reaction conditions such as the reaction temperature, but it is usually completed in about 1 to 30 hours.

[0200] <Polycarboxylic acid compound represented by chemical formula 5 (5)>

[0201]

[0202] The definitions of Ar, R1, R2, m, n, and X in Chemical Formula 5 are the same as those in Chemical Formula 1, and their specific examples and preferred embodiments are also the same.

[0203] Regarding polycarboxylic acid compounds (5), specific examples of compounds in which all Ar in chemical formula 5 is a 1-oxybenzene-4- group include compounds (5-1) to (5-8).

[0204]

[0205] A specific example of a compound in which Ar in Chemical Formula 5 has a 1-oxybenzene-4- and a 1-oxybenzene-2- group is compound (5-9).

[0206]

[0207] Specific examples of compounds in which all Ar in Chemical Formula 5 is a 2-oxynaphthalene-1-di group include compounds (5-10) and (5-11).

[0208]

[0209] A specific example of a compound in which all of the Ar in Chemical Formula 5 are 2-oxynaphthalene-6-di groups is compound (5-12).

[0210]

[0211] Specific examples of compounds in which all Ar in Chemical Formula 5 is a 4-oxy-3-phenylbenzene-1-yl group include compounds (5-13) and (5-14).

[0212]

[0213] Specific examples of compounds in which all of the Ar in Chemical Formula 5 are 10-oxyphenanthrene-9-di groups include compounds (5-15) to (5-18).

[0214]

[0215] The polycarboxylic acid compound (5) is produced by hydrolyzing the ester group of the polycarboxylic acid ester compound (1), which is produced by the etherification reaction process, with water, as shown in the reaction equation below.

[0216]

[0217] As a specific example of such a reaction, there is a method of producing compound (1-13) by carrying out an etherification reaction as shown in the reaction equation below, in which compound (1-13) is hydrolyzed by water and compound (5-10) is produced as a byproduct.

[0218]

[0219] <Polycarboxylic acid ester compound represented by chemical formula 6 (6)>

[0220]

[0221] The definitions of Ar, R1, R2, m, n, X, and R3 in Chemical Formula 6 are the same as those in Chemical Formula 1, and their specific examples and preferred embodiments are also the same.

[0222] r each independently represents an integer from 1 to 4, provided that at least one r is 2, 3, or 4.

[0223] Regarding polycarboxylic acid ester compounds (6), specific examples of compounds in which all Ar in chemical formula 6 is a 1-oxybenzene-4- group include compounds (6-1) to (6-9), (6-6'), (6-7'), (6-8') and (6-9').

[0224]

[0225]

[0226]

[0227] Specific examples of compounds in which Ar in Chemical Formula 6 has a 1-oxybenzene-4- group and a 1-oxybenzene-2- group include compounds (6-10) to (6-12), (6-10') to (6-12'), (6-10") to (6-12") and (6-10''') to (6-12''').

[0228]

[0229]

[0230]

[0231] Specific examples of compounds in which all Ar in Chemical Formula 6 is a 2-oxynaphthalene-1-di group include compounds (6-13) and (6-14).

[0232]

[0233] A specific example of a compound in which all of the Ar in chemical formula 6 are 2-oxynaphthalene-6-di groups is compound (6-15).

[0234]

[0235] Specific examples of compounds in which all Ar in Chemical Formula 6 is a 4-oxy-3-phenylbenzene-1-yl group include compounds (6-16) and (6-17).

[0236]

[0237] Specific examples of compounds in which all of the Ar in Chemical Formula 6 are 10-oxyphenanthrene-9-di groups include compounds (6-18) to (6-23).

[0238]

[0239]

[0240]

[0241] It has been made clear that the polycarboxylic acid ester compound (6) is produced by the reaction of the halocarboxylic acid ester compound (3) in excess during the etherification reaction process, in which the polyhydroxy aromatic compound (2) and the halocarboxylic acid ester compound (3) are used to perform the etherification reaction as shown in the reaction formula below, and that the production is promoted by water.

[0242]

[0243] As a specific example of such a reaction, in a method for producing compound (1-13) by performing an etherification reaction using compound (2-10) as a polyhydroxy aromatic compound (2) and ethyl chloroacetate as a halocarboxylic acid ester compound (3), as shown in the reaction formula below, a case can be cited in which compound (6-13) is produced as a byproduct due to the reaction of ethyl chloroacetate in excess.

[0244]

[0245] <Separation and purification of polycarboxylic acid ester compound (1)>

[0246] The reaction-finished mixture obtained by the etherification reaction process can be separated and purified in accordance with conventional methods to obtain a polycarboxylic acid ester compound (1) from the reaction mixture. For example, post-treatment processes such as a neutralization process, a washing process, a crystallization process, a filtration process, a distillation process, and a separation process by column chromatography can be performed. To further increase purity, additional distillation, recrystallization, and purification by column chromatography may be performed in accordance with conventional methods.

[0247] In addition, in addition to the etherification reaction process of the present manufacturing method, all processes such as mixing, neutralization, distillation, crystallization, filtration, and drying of the raw materials are preferably carried out in an atmosphere with low oxygen, which causes oxidative deterioration, discoloration, and electrostatic ignition by volatile solvents, or in an inert gas atmosphere such as nitrogen or argon.

[0248] Examples

[0249] The present invention is described in detail below by way of examples, but the present invention is not limited to these examples. The analysis method is as follows.

[0250] <Analysis Method>

[0251] 1. Composition analysis of polycarboxylic acid ester compounds

[0252] The composition of the reaction product was analyzed by high-speed liquid chromatography (HPLC) using the apparatus and conditions below. The “%” in the obtained analysis results represents the area percentage.

[0253] (1) Ratio of compound (1-13), monoetheride, and compound (5-10)

[0254] Measuring device: High-speed liquid chromatography analyzer (manufactured by Shimadzu Corporation)

[0255] Pump: LC-20AD

[0256] Column Oven: CTO-20A

[0257] Detector: SPD-20A

[0258] Column: HALO-C18

[0259] Oven temperature: 50℃

[0260] Flow rate: 0.7 mL / min.

[0261] Detection wavelength: 280 nm

[0262] · Gradient condition

[0263] Mobile phase: (A) 0.1 vol% aqueous phosphoric acid solution, (B) acetonitrile

[0264] (B) Volume % (Time since analysis start) 30% (0 min) → 100% (12 min) → 100% (15 min)

[0265] (2) Ratio of compound (6-13)

[0266] Measuring device: High-speed liquid chromatography analyzer (manufactured by Shimadzu Corporation)

[0267] Pump: LC-20AD

[0268] Column Oven: CTO-20A

[0269] Detector: SPD-20A

[0270] Column: HALO-C18

[0271] Oven temperature: 50℃

[0272] Flow rate: 0.7 mL / min.

[0273] Detection wavelength: 280 nm

[0274] · Gradient condition

[0275] Mobile phase: (A) 0.2 vol% aqueous acetic acid solution, (B) methanol

[0276] (B) Volume % (Time since analysis start) 50% (0 min) → 100% (10 min) → 100% (13 min)

[0277] (3) Ratio of compounds (1-20), (1-21), monoetheride, compounds (5-17), compounds (6-20), and compounds (6-21)

[0278] Measuring device: High-speed liquid chromatography analyzer Prominence UFLC (Manufactured by Shimadzu Corporation)

[0279] Pump: LC-20AD

[0280] Column Oven: CTO-20A

[0281] Detector: SPD-20A

[0282] Column: HALO-C18 (inner diameter 3 mm, length 75 mm)

[0283] Oven temperature: 50℃

[0284] Flow rate: 0.7 mL / min.

[0285] Sample injection volume: 5 μL

[0286] Detection wavelength: 280 nm

[0287] Mobile phase: (A) 0.1 vol% aqueous phosphoric acid solution, (B) acetonitrile

[0288] · Gradient Condition: (B) Volume % (Time from start of analysis) 40% (0 min.) → 100% (17 min.) → 100% (20 min.)

[0289] (4) Ratio of compound (1-10), dietheride, compound (5-9), compound (6-10), and (6-10')

[0290] Measuring device: Liquid chromatography analyzer Prominence (manufactured by Shimadzu Corporation)

[0291] Pump: LC-20AT

[0292] Column Oven: CTO-20A

[0293] Detector: SPD-20A

[0294] Column: Shim-Pack CLC-ODS (Inner diameter 6 mm, length 150 mm)

[0295] Oven temperature: 50℃

[0296] Flow rate: 1.0 mL / min.

[0297] Sample injection volume: 20 μL

[0298] Detection wavelength: 280 nm

[0299] Mobile phase: (A) 0.2 vol% aqueous acetic acid solution, (B) methanol

[0300] · Gradient Condition: (B) Volume % (Time from analysis start) 85% (0 min.) → 100% (30 min.) → 100% (40 min.)

[0301] 2. Analysis of the moisture content of potassium carbonate

[0302] Using 3 g of potassium carbonate, the moisture content of the potassium carbonate was analyzed using the following measuring device and measuring conditions.

[0303] Measuring device: Shimadzu moisture meter EB330MOC

[0304] Set temperature: 360°C

[0305] Dry point detection weight / width: 10 mg

[0306] Dry point monitoring time: 5 minutes

[0307] Maximum measurement time: 30 minutes

[0308] <Comparative Example 1>

[0309] 50.0 g (0.17 mol) of 1,1'-vinaphthalene-2,2'-diol (compound (2-10)), 50.7 g of potassium carbonate (water content 1.9 wt%), and 1.0 g of potassium iodide were placed in a 4-neck flask, and after nitrogen substitution, 125.0 g of methyl isobutyl ketone was added. After raising the temperature to 90–100°C, 55.6 g of methyl isobutyl ketone was distilled under reduced pressure of 42 kPa to obtain a slurry. Then, the pressure was returned to atmospheric pressure with nitrogen, and while maintaining the temperature, 53.5 g (0.43 mol) of ethyl chloroacetate, to which 0.5 g of N-methylpyrrolidone had been added, was added dropwise over 2 hours. Afterward, the etherification reaction was carried out for 8 hours while maintaining the temperature at 100°C.

[0310] As a result of analyzing the slurry liquid after the etherification reaction by HPLC, compound (1-13) was found to be 93.3%, the reaction intermediate monoetheride was 0.2%, compound (5-10) was 3.9%, and compound (6-13) was 9.6%.

[0311] <Example 1>

[0312] 30.0 g (0.10 mol) of 1,1'-vinaphthalene-2,2'-diol (compound (2-10)), 30.4 g of potassium carbonate (water content 0.9 wt%), and 0.6 g of potassium iodide were placed in a 4-neck flask, and after nitrogen substitution, 75.0 g of methyl isobutyl ketone was added. After raising the temperature to 90°C, 55.6 g of methyl isobutyl ketone was distilled under reduced pressure of 42 kPa to obtain a slurry. Then, the pressure was returned to atmospheric pressure with nitrogen, and while maintaining the temperature, 32.1 g (0.25 mol) of ethyl chloroacetate containing 0.5 g of N-methylpyrrolidone was added dropwise over 2 hours. Afterward, the etherification reaction was carried out for 10 hours while maintaining the temperature at 100°C.

[0313] As a result of analyzing the reaction solution in the slurry state in the etherification reaction process by HPLC, at the point where the etherification reaction was performed 8 hours after dropping, compound (1-13) was contained at 97.2%, the reaction intermediate monoether was contained at 0.1%, compound (5-10) at 0.2%, and compound (6-13) at 6.6%. The reaction intermediate monoether was sufficiently reduced, and the reaction was complete. In addition, at the point where the etherification reaction was performed 10 hours after dropping, compound (1-13) was contained at 97.0%, the reaction intermediate monoether was contained at 0.1%, compound (5-10) at 0.3%, and compound (6-13) at 7.1%.

[0314] <Example 2>

[0315] 50.0 g (0.17 mol) of 1,1'-vinaphthalene-2,2'-diol (compound (2-10)), 50.7 g of potassium carbonate (water content 0.6 wt%), and 1.0 g of potassium iodide were placed in a 4-neck flask, and after nitrogen substitution, 125.0 g of methyl isobutyl ketone was added. After raising the temperature to 90–100°C, 55.6 g of methyl isobutyl ketone was distilled under reduced pressure of 42 kPa to obtain a slurry. Then, the pressure was returned to atmospheric pressure with nitrogen, and while maintaining the temperature, 53.5 g (0.43 mol) of ethyl chloroacetate, to which 0.5 g of N-methylpyrrolidone had been added, was added dropwise over 2 hours. Afterward, the etherification reaction was carried out for 8 hours while maintaining the temperature at 100°C.

[0316] As a result of analyzing the slurry liquid after the etherification reaction by HPLC, compound (1-13) was found to be 96.8%, the reaction intermediate monoetheride was 0.2%, compound (5-10) was 0.4%, and compound (6-13) was 6.9%.

[0317] From the result of Comparative Example 1, in which the water content of the potassium carbonate used was 1.9 wt%, in the liquid after 8 hours of the etherification reaction process for producing compound (1-13) after dropping, compound (5-10), which is a hydrolyzate of compound (1-13), was contained at 3.9%, and compound (6-13), which is a byproduct, was contained at 9.6%.

[0318] In this regard, from the results of Examples 1 and 2, which are specific examples of the present invention, in the slurry liquid after 8 hours of etherification reaction process for producing compound (1-13) after dropping, in Example 1, where the water content of the potassium carbonate used was 0.9 wt%, compound (5-10) was 0.3% and compound (6-13) was 7.1%, and in Example 2, where the water content was 0.6 wt%, compound (5-10) was 0.4% and compound (6-13) was 6.9%.

[0319] In the etherification reaction of Examples 1 and 2 and Comparative Example 1, even though methyl isobutyl ketone is extracted under heating and reduced pressure from a prepared solution of compound (2-10), potassium carbonate, potassium iodide, and methyl isobutyl ketone before adding ethyl chloroacetate, it can be understood that the amount of hydrolysate and by-products produced is affected by the amount of water contained in the potassium carbonate used.

[0320] From this result, it became clear that, as a result of the influence of the amount of water in the potassium carbonate used, the less water there is, the more the formation of the compound (5-10), which is a hydrolysis product of the compound (1-13), and the byproduct compound (6-13) can be suppressed.

[0321] <Example 3>

[0322] 100.2 g (0.26 mol) of 9,9'-biphenanthrene-10,10'-diol (compound (2-15)), 151 g of N-methylpyrrolidone, 75.7 g of potassium carbonate (water content 0.9 wt%), and 6.2 g of potassium iodide were placed in a 4-neck flask and nitrogen was applied. Then, the temperature was raised to 90°C, and 97.5 g (0.65 mol) of ethyl chlorobutyrate was added dropwise over 1 hour while maintaining the temperature of the reaction mixture at 90°C. Afterward, stirring was performed while maintaining the temperature inside the flask at 90°C. The reaction was terminated after 11 hours of post-stirring. As a result of HPLC analysis of the reaction mixture after the reaction, the reaction selectivity of the target compound (compound (1-22)) was 99.8%. The reaction intermediate monoetheride and compound (5-17) were not detected, and compound (6-21) was contained in an amount of less than 0.1%.

[0323] After that, 75 g of water was added, and after cooling and stirring continued overnight at 25°C, the precipitated solid was filtered and separated.

[0324] 206.8 g of the obtained solid and 927 g of methyl isobutyl ketone were placed in a 4-neck flask, nitrogen was applied, and then heated to dissolve. Afterward, 207 g of water was added, and the mixture was washed at 80°C to extract the aqueous layer. This operation was repeated 4 times.

[0325] Afterwards, distillation was performed to remove 555 g of methyl isobutyl ketone and water. Then, the liquid was cooled and stirred overnight while maintaining the temperature at 25°C, after which the precipitated solid was filtered. The filtered solid was dried under reduced pressure at 80°C to obtain 145.9 g of 10,10'-bis(ethoxycarbonylpropoxy)-9,9'-biphenanthrile (compound (1-21)) (yield 91.5%).

[0326] The obtained compound, liquid chromatography mass spectrometry and 1 H-NMR and 13By C-NMR analysis, it was clear that it is 10,10'-bis(ethoxycarbonylpropoxy)-9,9'-biphenanthril (compound (1-21)).

[0327] Liquid chromatography mass spectrometry (mass spectrometry / electrospray ionization): mass 637.25 [M + Na]

[0328]

[0329]

[0330] The purity of the obtained biphenanthrendicarboxylic acid compound measured by high-speed liquid chromatography was 99.6%, and the color when measured with a 10% THF solution according to the above analysis method was APHA20.

[0331] The onset temperature of the endothermic peak by differential scanning calorimetry (DSC) of the crystal of the obtained compound (1-21) was 134°C.

[0332] <Example 4>

[0333] 80.4 g (0.21 mol) of 9,9'-biphenanthrene-10,10'-diol (compound (2-15)), 123 g of N-methylpyrrolidone, 60.5 g of potassium carbonate (water content 0.9 wt%), and 4.0 g of potassium iodide were placed in a 4-neck flask and nitrogen was applied. Then, the temperature was raised to 90°C, and 70.9 g (0.52 mol) of methyl chlorobutyrate was added dropwise over 1 hour while maintaining the temperature of the reaction mixture at 90°C. Afterward, stirring was performed while maintaining the temperature inside the flask at 90°C. The reaction was terminated after 18 hours of post-stirring. As a result of HPLC analysis of the reaction mixture after the reaction, the reaction selectivity of the target compound (compound (1-20)) was 99.7%. The reaction intermediate monoetheride and compound (5-17) were not detected, and compound (6-20) was contained in an amount of less than 0.1%.

[0334] After that, 240 g of water was added, and after cooling and stirring continued overnight at 25°C, the precipitated solid was filtered and separated.

[0335] 157.0 g of the obtained solid and 367 g of methyl isobutyl ketone were placed in a 4-neck flask, nitrogen was applied, and then heated to dissolve.

[0336] Afterwards, 249 g of water was added and washed at 80°C, and the aqueous layer was extracted. This operation was repeated 4 times. Subsequently, 141 g of methyl isobutyl ketone and water were removed by distillation.

[0337] Afterward, the liquid was cooled and stirred overnight while maintaining the temperature at 25°C, and the precipitated solid was filtered. The filtered solid was dried under reduced pressure at 80°C to obtain 10,10'-bis(methoxycarbonylpropoxy)-9,9'-biphenanthrile (compound (1-20)) 108.4 g (yield 90.7%).

[0338] The obtained compound, liquid chromatography mass spectrometry and 1 H-NMR and 13 It was clear by C-NMR analysis that it is 10,10'-bis(methoxycarbonylpropoxy)-9,9'-biphenanthril (compound (1-20)).

[0339] Liquid chromatography mass spectrometry (mass spectrometry / electrospray ionization): mass 609.23 [M + Na]

[0340]

[0341]

[0342] The purity of the obtained compound (1-20) measured by high-speed liquid chromatography was 99.5%, and the color when measured with a 10% THF solution according to the above analysis method was APHA20.

[0343] The onset temperature of the endothermic peak by differential scanning calorimetry (DSC) of the obtained compound (1-20) was 155°C.

[0344] <Example 5>

[0345] 40.0 g (0.083 mol) of bis(4-hydroxy-3-cyclohexyl-6-methyl)(2-hydroxyphenyl)methane (compound (2-9)), 47.9 g of potassium carbonate (water content 0.9 wt%), and 80.0 g of dimethylformamide were placed in a 4-neck flask, and the inside of the flask was purged with nitrogen. After that, the temperature was raised to 50°C, and while stirring, a mixed solution of 49.7 g of butyl chloroacetate and 2.5 g of dimethylformamide was added dropwise over 2 hours. Then, the etherification reaction was carried out for 2 hours while maintaining the temperature at 100°C.

[0346] As a result of analyzing the slurry liquid after the etherification reaction by HPLC, at 1 hour of the etherification reaction, compound (1-10) was 99.0%, the reaction intermediate dietherized was 0.5%, compound (5-9) was not detected, and compounds (6-10) and (6-10') were 0.2%. At 2 hours of the etherification reaction, compound (1-10) was 99.5%, the reaction intermediate dietherized was not detected, compound (5-9) was not detected, and compounds (6-10) and (6-10') were 0.3%.

[0347] From the above facts, it has become clear that by using potassium carbonate with low moisture content, the by-products of the polycarboxylic acid compound (5) and the polycarboxylic acid ester compound (6) can be suppressed in the etherification reaction process for obtaining the desired polycarboxylic acid ester compound (1).

Claims

Claim 1 A method for preparing a polycarboxylic acid ester compound (1) represented by Chemical Formula 1, comprising an etherification reaction process in which an etherification reaction is performed using a polyhydroxy aromatic compound (2) represented by Chemical Formula 2, a halocarboxylic acid ester compound (3) represented by Chemical Formula 3, and potassium carbonate, wherein the amount of water contained in the potassium carbonate is in the range of 0.01 weight% or more and 1.5 weight% or less. [Chemical Formula 1] (In Formula 1, Ar independently represents a “2+m” monooxyaromatic hydrocarbon group having 6 to 20 carbon atoms, R1 independently represents a straight-chain or branched-chain alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 5 to 6 carbon atoms, or a straight-chain or branched-chain alkoxy group having 1 to 6 carbon atoms, R2 independently represents a straight-chain or branched-chain alkylene group having 1 to 4 carbon atoms, R3 independently represents an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, m independently represents 0, 1, or 2, n represents 1 or 2, and X represents a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, a divalent group represented by Formula 1a, 1b, or 1c, or represented by Formula 1d or 1e It represents a trivalent group. Also, in Chemical Formula 1, the oxygen atom of Ar is bonded to the aromatic hydrocarbon group contained in Ar and R2.)[Chemical Formulas 1a–1c] (In Formula 1a, R5 and R6 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms; R5 and R6 may each bond to form a cycloalkylidene group having 5 to 20 carbon atoms as a whole; in Formula 1b, Ar1 each independently represents an aryl group having 6 to 12 carbon atoms. * in Formulas 1a, 1b, and 1c each indicate a bonding position.)[Formulas 1d, 1e] (In 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 Formula 1e, R8 represents a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms. * in Formulas 1d and 1e each indicate a bonding position.)[Formula 2] (The definitions of Ar, R1, m, n, and X in Chemical Formula 2 are the same as those in Chemical Formula 1. Also, in Chemical Formula 2, the oxygen atom of Ar is bonded to the aromatic hydrocarbon group contained in Ar and the hydrogen atom (H) described in Chemical Formula 2.)[Chemical Formula 3] (The definitions of R2 and R3 in Chemical Formula 3 are the same as in Chemical Formula 1, and Y represents a halogen atom.) Claim 2 In claim 1, the Ar are each independently 1-oxybenzene-4-digroup, 1-oxybenzene-3-digroup, 1-oxybenzene-2-digroup, 1-oxynaphthalene-2-digroup, 1-oxynaphthalene-4-digroup, 1-oxynaphthalene-5-digroup, 2-oxynaphthalene-1-digroup, 2-oxynaphthalene-6-digroup, 2-oxynaphthalene-7-digroup, 4-oxy-3-phenylbenzene-1-digroup, 9-oxyphenanthrene-3-digroup, 10-oxyphenanthrene-9-digroup, 2-oxyanthracene-7-digroup, 1-oxy-3-phenylnaphthalene-4-digroup, 1-oxy-3-phenylnaphthalene-5-digroup, 2-oxy-1-phenylnaphthalene-6-digroup, A method of manufacturing, comprising any one of the following: a group consisting of 2-oxy-1-phenylnaphthalene-7-di, 2-oxy-3-phenylnaphthalene-6-di, 2-oxy-3-phenylnaphthalene-7-di, 4-oxy-3-(1-naphthyl)benzene-1-di, 4-oxy-3-(2-naphthyl)benzene-1-di, 4-oxy-3,5-diphenylbenzene-1-di, 4-oxy-2-phenylphenanthrene-6-di, 4-oxy-2-phenylphenanthrene-7-di, 4-oxy-2-phenylphenanthrene-8-di, 4-oxy-2-phenylphenanthrene-9-di, 4-oxy-2-phenylphenanthrene-10-di, and 2-oxy-3-phenylanthracene-7-di. Claim 3 A method of manufacturing according to claim 1, wherein the polycarboxylic acid ester compound (1) represented by Chemical Formula 1 is a polycarboxylic acid ester compound represented by any one selected from Chemical Formulas 1A to 1F, and the polyhydroxy aromatic compound (2) represented by Chemical Formula 2 is a polyhydroxy aromatic compound represented by any one selected from Chemical Formulas 2A to 2F. [Chemical Formula 1A] [Chemical Formula 1B] [Chemical Formula 1C] [Chemical Formula 1D] [Chemical Formula 1E] [Chemical Formula 1F] (In Chemical Formulas 1A to 1F, R1, R2, R3, m, n, and X are identical to the definitions in Chemical Formula 1.)[Chemical Formula 2A] [Chemical Formula 2B] [Chemical Formula 2C] [Chemical Formula 2D] [Chemical Formula 2E] [Chemical Formula 2F] (In chemical formulas 2A–2F, R1, m, n, and X are identical to the definitions in chemical formula 1.) Claim 4 A method for manufacturing according to claim 3, wherein the polycarboxylic acid ester compound represented by formulas 1C, 1D, 1E, and 1F has n 1, the polycarboxylic acid ester compound represented by formula 1B has n 2, the polyhydroxy aromatic compound represented by formulas 2C, 2D, 2E, and 2F has n 1, and the polyhydroxy aromatic compound represented by formula 2B has n 2.

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