Patent Application
20250214922
The present invention relates to a method for producing 4,4′-dihydroxybiphenyl-3,3′-dicarboxylic acid.
Carboxylated biphenol compounds are compounds useful as raw materials for producing aromatic polyesters superior in thermal characteristics, mechanical characteristics, and the like. In recent years, applications as organic ligands for metal-organic frameworks (MOFs) used for gas storage, solid catalysts, and the like are expected. MOFs are one of the porous materials in which a metal and an organic ligand are combined, and Patent Documents 1 and 2 propose to use 4,4′-dihydroxybiphenyl-3,3′-dicarboxylic acid (BPDC) as an organic ligand.
MOFs containing BPDC are attracting attention because of their high carbon dioxide adsorptivity, and as the demand for MOFs increases, the demand for BPDC also increases.
As a method for producing BPDC, a so-called Kolbe-Schmitt reaction is known, and Patent Document 3 describes a method for producing BPDC by reacting 4,4′-dihydroxybiphenyl disodium salt with carbon dioxide in benzyl alcohol.
Patent Document 1: JP-A-2020-527455
Patent Document 2: JP-A-2020-531248
Patent Document 3: JP-A-H11-140015
However, the method described in Patent Document 3 affords a low yield and is not suitable for production on an industrial scale. Therefore, a method for producing BPDC in a high yield has been required.
An object of the present invention is to provide a production method which can yield BPDC in a high yield.
As a result of intensive studies in view of the above problems, the present inventors have found that BPDC is obtained at a high generation rate by reacting a 4,4′-dihydroxybiphenyl dialkali metal salt with carbon dioxide in light oil in the presence of an alkali metal salt of acetic acid, and have accomplished the present invention.
That is, the present invention includes the following preferred embodiments.
[1] A method for producing 4,4′-dihydroxybiphenyl-3,3′-dicarboxylic acid represented by formula (2),
[4] The method according to any one of [1] to [3], wherein the reaction step is performed under a condition of a temperature of 100 to 300° C.
[5] The method according to any one of [1] to [4], wherein the alkali metal salt of acetic acid is potassium acetate.
[6] The method according to any one of [1] to [5], comprising a step of adding water to a reaction liquid obtained in the reaction step, then separating the obtained mixture into an organic layer and an aqueous layer, and conducting acid precipitation of the obtained aqueous layer to obtain a crude composition containing 4,4′-dihydroxybiphenyl-3,3′-dicarboxylic acid represented by the formula (2).
[7] The method according to [6], comprising a step of further purifying the crude composition.
[8] The method according to [7], wherein the purification step includes one or more steps selected from the group consisting of suspension washing, recrystallization, and reprecipitation.
[9] The method according to [7] or [8], wherein the purification step includes a suspension washing step.
[10] The method according to any one of [7] to [9], wherein the solvent to be used in the purification step is one or more selected from the group consisting of water, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, 2-ethylhexanol, ethylene glycol, glycerin, acetic acid, N-methyl-2-pyrrolidone, N,N-dimethylformamide, acetonitrile, acetone, xylene, toluene, methyl ethyl ketone, methyl isobutyl ketone, hexane, heptane, cyclohexanone, tetrahydrofuran, 4-methyltetrahydropyran, chloroform, dioxane, ethyl acetate, propyl acetate, and butyl acetate.
[11] 4,4′-Dihydroxybiphenyl-3,3′-dicarboxylic acid represented by the formula (2), wherein the content of an alkali metal is less than 1000 ppm.
[12] The 4,4′-dihydroxybiphenyl-3,3′-dicarboxylic acid according to [11]. wherein the alkali metal is sodium and/or potassium.
[13] The 4,4′-dihydroxybiphenyl-3,3′-dicarboxylic acid according to [11], wherein the alkali metal is sodium.
[14] The 4,4′-Dihydroxybiphenyl-3,3′-dicarboxylic acid according to [13], wherein the content of sodium is less than 100 ppm.
According to the present invention, BPDC can be obtained at a high generation rate.
In the method for producing BPDC represented by the formula (2) of the present invention, a so-called Kolbe-Schmitt reaction in which the 4,4′-dihydroxybiphenyl dialkali metal salt represented by the formula (1) is reacted with carbon dioxide is used. In the present invention, the reaction is usually carried out with stirring.
The reactor to be used in the present invention may be any reactor used in an ordinary Kolbe-Schmitt reaction, and for example, an autoclave equipped with a stirrer and capable of coping with a high-pressure reaction can be suitably used. Furthermore, the reactor is more preferably one having a temperature control function and having an introduction tube for carbon dioxide gas or inert gas, a thermometer support tube, a pressure gauge, an exhaust pipe, and the like.
Examples of the 4,4′-dihydroxybiphenyl dialkali metal salt represented by the formula (1) to be used in the present invention include 4,4′-dihydroxybiphenyl dipotassium salt, 4,4′-dihydroxybiphenyl dilithium salt, 4,4′-dihydroxybiphenyl dirubidium salt, and 4,4′-dihydroxybiphenyl dicesium salt. From the viewpoint of easy availability, cost, and reactivity, 4,4′-dihydroxybiphenyl dipotassium salt is preferable.
The 4,4′-dihydroxybiphenyl dialkali metal salt can be obtained by converting 4,4′-dihydroxybiphenyl into a dialkali metal salt thereof using an alkali metal hydroxide or an alkali metal alkoxide such as alkali metal tert-butoxide, alkali metal methoxide, alkali metal ethoxide, or alkali metal iso-propoxide. In particular, in consideration of economic efficiency, it is preferable to use 4,4′-dihydroxybiphenyl and an alkali metal hydroxide to form a dialkali metal salt.
More specifically, the 4,4′-dihydroxybiphenyl dipotassium salt can be obtained by converting 4,4′-dihydroxybiphenyl into a dipotassium salt thereof using potassium hydroxide or a potassium alkoxide such as potassium tert-butoxide, potassium methoxide, potassium ethoxide, or potassium iso-propoxide. In particular, in consideration of economic efficiency, it is preferable to form a dipotassium salt using 4,4′-dihydroxybiphenyl and potassium hydroxide.
The 4,4′-dihydroxybiphenyl dialkali metal salt to be subjected to the reaction and the alkali metal salt of acetic acid to be made present in the reaction system are preferably sufficiently dehydrated, and when the dehydration is incomplete, the reaction yield may decrease. The dehydration is performed, for example, by heating in a vacuum state using such a device as an evaporator. The 4,4′-dihydroxybiphenyl dialkali metal salt and the alkali metal salt of acetic acid subjected to the reaction preferably have a water content of 3 mass % or less, preferably 2 mass % or less, and more preferably 1 mass % or less.
In the present invention, the reaction of 4,4′-dihydroxybiphenyl dialkali metal salt with carbon dioxide is carried out in the presence of an alkali metal salt of acetic acid.
Examples of the alkali metal salt of acetic acid include one or more selected from the group consisting of potassium acetate, lithium acetate. rubidium acetate, and cesium acetate. Potassium acetate is preferable from the viewpoint of being superior in reactivity.
It is preferable that the alkali metal salt of acetic acid be present in an amount of usually 0.1 to 10 mol, preferably 0.3 to 5 mol, more preferably 0.5 to 4.5 mol, and still more preferably 1 to 3 mol, per 1 mol of the 4,4′-dihydroxybiphenyl dialkali metal salt.
In the method of the present invention, light oil is used as a solvent. By using light oil as a solvent, the generation rate of BPDC is greatly improved.
The use amount of the light oil to be used in the present invention is preferably 100 to 3000 parts by mass based on 100 parts by mass of the 4,4′-dihydroxybiphenyl dialkali metal salt represented by the formula (1) (1 to 30 mass times based on the 4,4′-dihydroxybiphenyl dialkali metal salt), more preferably 150 to 2000 parts by mass, still more preferably 200 to 1500 parts by mass, and particularly preferably 300 to 1000 parts by mass. When the use amount of the light oil is within the above range, the generation rate of BPDC can be efficiently improved.
The reaction of the 4,4′-dihydroxybiphenyl dialkali metal salt with carbon dioxide is carried out usually at 100 to 300° C., and can be carried out preferably at a temperature of 150 to 280° C., and more preferably at a temperature of 200 to 270° C. At a temperature lower than 100° C., the reaction tends to hardly proceed, and at a temperature higher than 300° C., the reaction reaches a plateau, so that energy is lost, and side reactions such as decomposition may occur.
The reaction of the 4,4′-dihydroxybiphenyl dialkali metal salt with carbon dioxide is carried out usually under a pressure of 10 MPa or less, preferably 0.1 to 5 MPa, more preferably 0.2 to 1 MPa, and preferably under a pressure with carbon dioxide. If the pressure during the reaction exceeds 10 MPa, it may be not industrially advantageous, for example, a device that withstands high pressure is required.
The reaction time can be appropriately selected usually between 30 minutes and 24 hours, preferably between 1 hour and 20 hours, more preferably between 2 hours and 16 hours, and particularly preferably between 3 to 12 hours.
The dialkali metal salt of BPDC obtained by such a reaction can afford the targeted BPDC by being converted into an acid by means known to those skilled in the art, such as acid precipitation.
Before the acid precipitation, washing with an organic solvent in a state where the dialkali metal salt of BPDC is dissolved in a water-soluble solvent, a filtration treatment for removing insoluble foreign matters, and an adsorbent treatment with activated carbon or the like for removing a coloring substance, a metal, or the like may be performed, as necessary.
By the step of reacting the 4,4′-dihydroxybiphenyl dialkali metal salt represented by the formula (1) with carbon dioxide in light oil in the presence of an alkali metal salt of acetic acid, a reaction liquid containing the BPDC dialkali metal salt is obtained.
Water is added to the reaction liquid containing the BPDC dialkali metal salt (the liquid after the addition is sometimes referred to as reaction liquid), and the aqueous layer obtained by liquid separation is subjected to acid precipitation with an acid to afford a crude composition containing BPDC.
Before the acid precipitation, a water-soluble medium may be further added separately to the aqueous layer. Examples of the water-soluble medium that can be added include one or more selected from the group consisting of methanol, ethanol, n-propyl alcohol, isopropyl alcohol, ethylene glycol, glycerin, N-methyl-2-pyrrolidone, N,N-dimethylformamide, acetonitrile, acetone, tetrahydrofuran, and dioxane, and it is preferable to add methanol from the viewpoint of making it possible to improve the filterability at the time of solid-liquid separation after the acid precipitation. In addition, for example, when methanol is added, the aqueous layer to be subjected to acid precipitation is preferably prepared to be an aqueous solution containing 20 to 80 mass % of methanol, more preferably an aqueous solution containing 35 to 65 mass % of methanol, and still more preferably an aqueous solution containing 45 to 55 mass % of methanol.
The amount of the medium of the solution to be subjected to the acid precipitation is preferably 1 to 20 mass times, more preferably 2 to 15 mass times, and still more preferably 3 to 10 mass times the mass of BPDC.
The temperature during the acid precipitation is preferably 20 to 95° C., more preferably 30 to 90° C., and still more preferably 40 to 85° C. When the temperature during the acid precipitation is within the above range, side reactions are less prone to occur, and the filterability at the time of solid-liquid separation after the acid precipitation is improved.
In the present invention, the acid to be used for the acid precipitation is not particularly limited, but a mineral acid is suitably used. Examples of the mineral acid include binary acids such as hydrochloric acid and hydrofluoric acid, and oxoacids such as sulfuric acid, nitric acid, phosphoric acid, and perchloric acid. Organic acids such as acetic acid and propionic acid can also be used.
The acid to be used for the acid precipitation is preferably in the form of an aqueous solution from the viewpoint of easily controlling the reaction temperature and the like, and for example, a 62 mass % aqueous sulfuric acid solution is suitably used.
The crude composition containing BPDC means a composition containing impurities such as a reaction raw material, a catalyst, and a reaction by-product in addition to BPDC as a target product. The content of impurities varies depending on the reaction method, but is usually 1 to 30 mass % in the crude composition, and is 3 to 25 mass % in another case. In the present description, the crude composition containing BPDC is also simply referred to as “crude BPDC”.
The obtained crude composition containing BPDC may be further subjected to a purification step to have a higher purity.
The purification step preferably includes one or more steps selected from the group consisting of suspension washing, recrystallization, and reprecipitation, and more preferably includes a suspension washing step.
Examples of the solvent to be used in the purification step include one or more selected from the group consisting of water, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, 2-ethylhexanol, ethylene glycol, glycerin, acetic acid, N-methyl-2-pyrrolidone, N,N-dimethylformamide, acetonitrile, acetone, xylene, toluene, methyl ethyl ketone, methyl isobutyl ketone, hexane, heptane, cyclohexanone, tetrahydrofuran, 4-methyltetrahydropyran, chloroform, dioxane, ethyl acetate, propyl acetate, and butyl acetate.
The suspension washing step is performed by adding a suspension washing solvent to the crude composition containing BPDC and stirring the mixture in a suspended state.
The amount of the solvent in the suspension washing varies depending on the type of the solvent, but the amount of the solvent is preferably 1 to 50 mass times, more preferably 3 to 40 mass times, and most preferably 5 to 30 mass times the amount of the crude composition containing BPDC.
The temperature at the time of the suspension washing is not particularly limited because it varies depending on the type and mixing ratio of the solvent to be used, but is preferably 15° C. to 200° C., more preferably 20° C. to 150° C., and still more preferably 30° C. to 100° C.
The recrystallization step is performed by dissolving the crude composition containing BPDC in a recrystallization solvent and then crystallizing the solution.
The amount of the solvent in the recrystallization step varies depending on the type of the solvent, but the amount of the solvent is preferably 1 to 50 mass times, more preferably 3 to 40 mass times, and most preferably 5 to 30 mass times the amount of the crude composition containing BPDC.
In the recrystallization, the temperature at which the crude composition containing BPDC is dissolved in the solvent is not particularly limited because it varies depending on the type and mixing ratio of the solvent to be used, but is preferably 20 to 200° C., more preferably 40 to 150° C., and still more preferably 60 to 130° C.
Crystallization in the recrystallization step is performed with stirring at a temperature of preferably 0 to 80° C., more preferably 5 to 60° C., and still more preferably 10 to 40° C. Incidentally, it is preferable to remove insoluble matters by filtration before the crystallization.
The reprecipitation step is performed by adding a poor solvent to a solution obtained by dissolving the crude composition containing BPDC in a good solvent to precipitate a solid of BPDC.
The good solvent and the poor solvent to be used in the reprecipitation step each can be appropriately selected from the solvents to be used in the purification step.
After the purification step, solid-liquid separation is performed by a conventional means such as filtration to recover BPDC as the target product. In the solid-liquid separation, it is preferable to wash crystals by appropriately pouring an organic solvent or water. The solvent to be used for washing in the solid-liquid separation is preferably 1 to 50 mass times, more preferably 3 to 40 mass times, and most preferably 5 to 30 mass times the crude BPDC.
The crystals recovered by the solid-liquid separation are forced air-dried under normal pressure or dried under reduced pressure, and the solvent is distilled off, whereby highly pure BPDC can be obtained.
The highly pure BPDC obtained by the method of the present invention has a low alkali metal content, which is less than 1,000 ppm, preferably less than 500 ppm, more preferably less than 300 ppm, and still more preferably less than 250 ppm. Such an alkali metal may exist in the form of a hydrochloride, a sulfate, a nitrate, a phosphate, and the like. Examples of the alkali metal include sodium and/or potassium.
Thus, the present invention provides BPDC having an alkali metal content of less than 1,000 ppm, preferably less than 500 ppm, more preferably less than 300 ppm, and still more preferably less than 250 ppm. Examples of the alkali metal include sodium and/or potassium. In one embodiment of the present invention, the content of the alkali metal is usually 5 ppm or more.
The highly pure BPDC obtained by the method of the present invention provides BPDC which has a low content of sodium especially among the alkali metals, wherein the content of sodium is less than 100 ppm, preferably less than 75ppm, and more preferably less than 50 ppm. In one embodiment of the present invention, the content of sodium is usually 1 ppm or more.
In the following, the present invention is described in detail by way of Examples, but the present invention is not limited to them.
Each compound was analyzed by the following method.
A 120 mL autoclave was charged with 13.4 g (0.05 mol) of 4,4′-dihydroxybiphenyl dipotassium salt (BP-K2), 10.4 g (0.11 mol, 2.1 eq/BP-K2) of potassium acetate, and 67.7 g of light oil, sealed, and then heated to 260° C. with stirring. After reaching 260° C., a reaction was carried out for 6 hours under the condition of carbon dioxide pressure of 0.4 MPa. After completion of the reaction, the mixture was cooled to 80° C. 201.3 g of water was added, and the resulting mixture was stirred and allowed to stand, affording a reaction liquid.
The reaction liquid obtained was subjected to quantitative analysis using UPLC for the conversions of BPDC and BPMC (4,4′-dihydroxybiphenyl-3-carboxylic acid) as an intermediate, and the residual rate of BP (4,4′-dihydroxybiphenyl). The results are shown in Table 1.
A reaction liquid was obtained in the same manner as in Example 1 except that the reaction temperature was changed from 260° C. to 250° C. The reaction liquid obtained was subjected to quantitative analysis for the conversions to BPDC and BPMC and the residual rate of BP by UPLC. The results are shown in Table 1.
A reaction liquid was obtained in the same manner as in Example 2 except that potassium acetate was not added. The reaction liquid obtained was subjected to quantitative analysis for the conversions to BPDC and BPMC and the residual rate of BP by UPLC. The results are shown in Table 1.
A reaction liquid was obtained in the same manner as in Comparative Example 1 except that 67.3 g of benzyl alcohol (BnOH) was used instead of light oil, and the reaction temperature was changed from 250° C. to 200° C. The reaction liquid obtained was subjected to quantitative analysis for the conversions to BPDC and BPMC and the residual rate of BP by UPLC. The results are shown in Table 1.
A reaction liquid was obtained in the same manner as in Comparative Example 2 except that 10.0 g (0.10 mol, 2.0 eq/BP-K2) of potassium acetate was added. The reaction liquid obtained was subjected to quantitative analysis for the conversions to BPDC and BPMC and the residual rate of BP by UPLC. The results are shown in Table 1.
A reaction liquid was obtained in the same manner as in Example 2 except that potassium acetate was changed to 8.6 g (0.10 mol, 2.0 eq/BP-K2) of potassium formate. The reaction liquid obtained was subjected to quantitative analysis for the conversions to BPDC and BPMC and the residual rate of BP by UPLC. The results are shown in Table 1.
A reaction liquid was obtained in the same manner as in Example 2 except that potassium acetate was changed to 7.1 g (0.05 mol, 1.0 eq/BP-K2) of potassium carbonate. The reaction liquid obtained was subjected to quantitative analysis for the conversions to BPDC and BPMC and the residual rate of BP by UPLC. The results are shown in Table 1.
A reaction liquid was obtained in the same manner as in Example 2 except that 11.8 g (0.05 mol) of 4,4′-dihydroxybiphenyl disodium salt (BP-Na2) was used in place of BP-K2 and 8.4 g (0.10 mol) of sodium acetate was used in place of potassium acetate. The reaction liquid obtained was subjected to quantitative analysis for the conversions to BPDC and BPMC and the residual rate of BP by UPLC. The results are shown in Table 1.
The reaction liquid obtained in Example 2 was subjected to liquid-liquid separation, and only the aqueous layer was taken out. The aqueous layer taken out was transferred to a 1 L four-neck flask with a bottom outlet equipped with a stirrer, a temperature sensor and a reflux tube, 395.1 g of water was added thereto, and then the temperature was raised to 85° C. After the raising of the temperature, 72% sulfuric acid was added until the pH reached 6.0, and then washing was performed three times with 235.4 g of 2-ethylhexanol (EHA). To the aqueous layer was added 72% sulfuric acid, and the resulting mixture was subjected to acid precipitation at 80° C. (pH 2.0). The solid precipitated was collected by filtration and then forced air-dried at 80° C., affording crude BPDC (11.5 g, yield: 99.7 mol %). The crude BPDC obtained was subjected to quantitative analysis by UPLC and crystal inductively coupled plasma (ICP) emission spectrometry. The composition is shown in Table 2.
A 500 mL four-necked flask equipped with a stirrer, a temperature sensor, and a reflux tube was charged with 11.5 g of the crude BPDC obtained, 143.9 g of methanol, and 143.9 g of water, and the resulting mixture was subjected to suspension washing at 60° C. for 3 hours under a nitrogen stream. The suspension was subjected to solid-liquid separation, then washed with 153.0 g of water, and the collected crystals were forced air-dried at 80° C., affording 9.6 g of BPDC (yield: 95.4 mol %). The composition of the BPDC obtained is shown in Table 2.
As shown in Table 1, it is found that in Examples 1 and 2 of the present invention, in which the reaction was carried out with the raw material BP being in the form of a potassium salt in the presence of an alkali metal salt of acetic acid in light oil, the BPDC generation rate has been greatly improved as compared with Comparative Examples 1, 4, and 5, in which the alkali metal salt of acetic acid was not added, Comparative Examples 2 and 3, in which the reaction was carried out in benzyl alcohol, and Comparative Example 6, in which the raw material BP was a sodium salt. In addition. as shown in Table 2. it is found that impurities can be significantly removed by further performing a purification step.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2022-057074 | Mar 2022 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2023/009689 | 3/13/2023 | WO |
