JP2017160132A - Method for producing carbonic acid ester - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing carbonic acid esters that increases the concentration of carbonic acid esters produced in the system.SOLUTION: A method for producing carbonic acid esters includes making an alcohol and carbon dioxide react with each other in the presence of a porous metal complex composed of a metal and an organic ligand, to produce a carbonic acid ester.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a carbonate ester by reacting alcohol and carbon dioxide in the presence of a catalyst.

Carbonic acid ester is a general term for compounds in which one or two of hydrogen atoms of carbonic acid CO (OH) ₂ is substituted with an alkyl group or an aryl group, and RO—C (═O) —OR ′ (R , R ′ represents a saturated hydrocarbon group or an unsaturated hydrocarbon group).

  Carbonate esters are used as additives such as gasoline additives to improve octane number and diesel fuel additives to reduce particles in exhaust gas, as well as resins and organic compounds such as polycarbonate, urethane, pharmaceuticals and agricultural chemicals. It is an extremely useful compound such as an alkylating agent, a carbonylating agent, a solvent, or the like, or a lithium battery electrolyte, a lubricating oil raw material, or a raw material for an oxygen scavenger for rust prevention of boiler piping.

  For example, Patent Document 1 describes “a method for producing a carbonate ester, wherein a carbonate ester is produced by reacting a monohydric alcohol and carbon dioxide in the presence of a solid catalyst and acetonitrile”. ([Claim 1]).

JP 2009-132673 A

  The inventors of the present invention have studied the method for producing a carbonate ester described in Patent Document 1. As a result, hydration of water and acetonitrile (wetting agent) by-produced when synthesizing dimethyl carbonate from methanol and carbon dioxide is performed. Acetamide is produced by the reaction, and methyl acetate is produced from the reaction between this acetamide and the raw material methanol, and further, trimethyl orthoacetate is produced from the reaction between the raw material methanol and acetonitrile. It was found that there was a problem that the concentration of the carbonate ester produced was low and the recovery efficiency was poor.

  Then, this invention makes it a subject to provide the manufacturing method of the carbonate ester from which the density | concentration of the carbonate ester produced | generated in a system becomes high.

As a result of intensive investigations to achieve the above-mentioned problems, the present inventors have used a porous metal complex composed of a metal and an organic ligand in place of a solid catalyst, thereby producing a carbonate ester produced in the system. The present inventors have found that the concentration is high and completed the present invention.
That is, it has been found that the above-described problem can be achieved by the following configuration.

[1] A method for producing a carbonate ester, wherein an alcohol and carbon dioxide are reacted in the presence of a porous metal complex composed of a metal and an organic ligand to produce a carbonate ester.
[2] The method for producing a carbonate ester according to [1], wherein the metal is at least one metal selected from Group 3 and Group 4 of the periodic table and a lanthanoid element.
[3] The method for producing a carbonate ester according to [1] or [2], wherein the organic ligand is an organic ligand capable of coordination at bidentate or higher.
[4] The method for producing a carbonate ester according to any one of [1] to [3], wherein the metal is a Group 4 metal.
[5] The organic ligand is any one of [1] to [4], which is at least one ligand selected from the group consisting of dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids, and amine compounds. Of carbonic acid ester.
[6] The method for producing a carbonate ester according to any one of [1] to [5], wherein the metal is at least one metal selected from the group consisting of zirconium and hafnium.
[7] The organic ligand is terephthalic acid, isophthalic acid, 2-aminoterephthalic acid, 2,5-diaminoterephthalic acid, 2,5-dihydroxyterephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalene. Dicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 3,3'-biphenyldicarboxylic acid, fumaric acid, malonic acid, adipic acid, biphenyl-3,4 ', 5-tricarboxylic acid, 1,3,5-tris ( 4'-carboxy [1,1'-biphenyl] -4-yl) benzene, 1,3,5-tris (4-carboxyphenyl) benzene, 1,3,5-benzenetricarboxylic acid and their derivatives The method for producing a carbonate ester according to any one of [1] to [6], which is at least one ligand selected from the group consisting of:
[8] The method for producing a carbonate ester according to any one of [1] to [7], wherein the porous metal complex has a BET specific surface area of 500 m ² / g or more and 3000 m ² / g or less.
[9] The method for producing a carbonate ester according to any one of [1] to [8], wherein the alcohol is a monohydric alcohol.
[10] The method for producing a carbonate ester according to any one of [1] to [9], wherein the carbonate ester is dimethyl carbonate.
[11] The method for producing a carbonate ester according to any one of [1] to [10], wherein alcohol and carbon dioxide are reacted at a pressure of 2.5 MPa or less.
[12] The method for producing a carbonate ester according to any one of [1] to [11], wherein the alcohol and carbon dioxide are reacted at a temperature of 50 ° C. or higher and 150 ° C. or lower.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the carbonate ester from which the density | concentration of the carbonate ester produced | generated in a system becomes high can be provided.

Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

  The method for producing a carbonate ester of the present invention (hereinafter also referred to as “the production method of the present invention”) reacts alcohol and carbon dioxide in the presence of a porous metal complex composed of a metal and an organic ligand. And a carbonate ester is produced.

[Porous metal complex]
A porous metal complex composed of a metal and an organic ligand is a porous metal complex composed of metal ions or metal ion clusters that occupy the central position of the structure coordinated with a bidentate or multidentate organic ligand. It is a crystalline substance, and is also a material called a porous coordination polymer (PoP) or a metal organic framework (MOF).
In the present invention, by using such a porous metal complex, the concentration of the carbonate ester generated in the system is increased.
Although this is not clear in detail, the present inventors presume as follows.
That is, carbon dioxide is adsorbed in the pores (possibly metal sites) of the porous metal complex, and as a result of the local concentration of carbon dioxide, the reaction between carbon dioxide and alcohol is promoted, and the concentration of carbonate ester It is thought that became higher.

In the present invention, BET specific surface area of the porous metal complex is preferably at 500 meters ² / g or more, more preferably from 500~10000m ² / g, in the range of 500~3000m ² / g Further preferred.
Here, the BET specific surface area means a specific surface area obtained by the BET method, and a value can be obtained from the amount of adsorbed nitrogen molecules by adsorbing nitrogen molecules to the porous metal complex. In the present specification, the BET specific surface area is a value measured in accordance with “Measurement method of gas adsorption amount by multipoint method” defined in JIS Z8830: 2013.

<Metal>
The metal constituting the porous metal complex is preferably at least one metal selected from Group 3 and Group 4 of the periodic table and lanthanoid elements.
Of these, metals of Group 4 elements such as titanium (Ti), zirconium (Zr), and hafnium (Hf) are more preferable, because a porous metal complex having a stable structure is easily obtained. More preferably, it is at least one metal selected from the group consisting of zirconium (Zr) and hafnium (Hf).

<Organic ligand>
As the organic ligand constituting the porous metal complex, it is desirable to use at least one organic ligand capable of coordinating at a bidentate or higher.
Examples of organic ligands that can be coordinated at bidentate or higher include dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids, amine compounds, etc., and these may be used alone or in combination of two or more. May be.

(Dicarboxylic acid)
Specific examples of the dicarboxylic acid include terephthalic acid, isophthalic acid, 2-aminoterephthalic acid, 2,5-diaminoterephthalic acid, 2,5-dihydroxyterephthalic acid, 1,4-naphthalenedicarboxylic acid, 2, Examples include 6-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 3,3′-biphenyldicarboxylic acid, fumaric acid, malonic acid, adipic acid, and derivatives thereof, and these may be used alone. In addition, two or more kinds may be used in combination.

(Tricarboxylic acid)
Specific examples of the tricarboxylic acid include biphenyl-3,4 ′, 5-tricarboxylic acid and 1,3,5-tris (4′-carboxy [1,1′-biphenyl] -4-yl) benzene. 1,3,5-tris (4-carboxyphenyl) benzene, 1,3,5-benzenetricarboxylic acid (hereinafter also abbreviated as “BTC”), derivatives thereof, and the like. You may use, and may use 2 or more types together.

(Tetracarboxylic acid)
Specific examples of the tetracarboxylic acid include p-terphenyl-3,3 ′, 5,5′-tetracarboxylic acid [another name: 5,5 ′-(1,4-phenylene) bisisophthalic acid. ], Tetracarboxylic acids such as 1,2,4,5-tetrakis (4-carboxyphenyl) benzene, derivatives thereof, and the like. These may be used alone or in combination of two or more. Also good.

(Amine compound)
Specific examples of the amine compound include imidazoles such as imidazole, 2-methylimidazole and 2-phenylimidazole and derivatives thereof; 4,4′-bipyridine, 1,4-bis (4-pyridyl) benzene, 2,2′-dimethyl-4,4′-bipyridine, 1,4-bis (4-pyridyl) butadiyne, 1,2-bis (4-pyridyl) ethane, 3,6-di (4-pyridyl) -1 , 2,4,5-tetrazine and the like having a pyridine ring and derivatives thereof; pyrazine, 2,5-dimethylpyrazine and the like having a pyrazine ring and derivatives thereof; and 1,4-diazabicyclo [2. 2.2] cyclic amines such as octane and derivatives thereof;

  Of these organic ligands, the above-mentioned dicarboxylic acids and tricarboxylic acids are preferable, and dicarboxylic acids are more preferable because porous metal complexes having a stable structure are easily obtained.

As said porous metal complex, what combined the example of the metal mentioned above and the organic ligand is mentioned, for example, These may be used individually by 1 type and may use 2 or more types together.
Of these, porous metal complexes using zirconium or hafnium as a metal and terephthalic acid as an organic ligand (UiO-66); using zirconium or hafnium as a metal and using biphenyldicarboxylic acid as an organic ligand Suitable porous metal complexes (UiO-67); porous metal complexes using zirconium or hafnium as a metal and 1,3,5-benzenetricarboxylic acid as an organic ligand;

Further, the shape of the porous metal complex is not particularly limited, and it may be used as a powder or a molded body.
In the case of a molded body, any of a spherical shape, a pellet shape, a cylinder shape, a ring shape, a wheel shape, a granular shape and the like may be used.

  In the present invention, the method for preparing the porous metal complex is not particularly limited, and a conventionally known method can be appropriately employed as a method for preparing POP or MOF. For example, the above-described solution containing metal ions of the metal and Diffusion method of gradually diffusing and reacting two kinds of solutions with the above-mentioned solution containing an organic ligand at the liquid-liquid interface; the above-mentioned organic coordination while stirring the solution containing the metal ion of the above-mentioned metal It can be prepared by using a stirring method in which a solution containing a child is dropped; a solvothermal method in which a solution containing a metal ion of the above-described metal and the above-described organic ligand is reacted in a pressure vessel;

〔alcohol〕
Although the alcohol used for the raw material of the manufacturing method of this invention is not specifically limited, A monohydric alcohol is preferable from a viewpoint that the usefulness of the carbonate ester obtained is high.
Examples of the monohydric alcohol include methanol, ethanol, n-propanol, n-butanol, methylcyclohexanol, cyclohexanol, and benzyl alcohol.
Note that what is used for the monohydric alcohol may be appropriately determined according to the type of carbonate to be produced. For example, when dimethyl carbonate is produced as the carbonate, methanol may be used.

〔carbon dioxide〕
The carbon dioxide used as a raw material for the production method of the present invention is not limited to industrially purified carbon dioxide, but may be gas separated and recovered from various factories, steelworks, power plants and the like.

[Reaction conditions]
Carbonate ester synthesis reaction using the porous metal complex is not particularly limited with respect to the reactor and reaction form used, for example, batch reactor, semi-batch reactor, continuous tank reactor, tubular reactor, etc. Any of the flow reactors such as
In addition, in the synthesis reaction of carbonic acid ester, it is preferable that the porous metal complex and the raw material alcohol are introduced into the reaction vessel, and then the carbon dioxide which is the other raw material is introduced to advance the reaction.

  The reaction pressure is preferably 2.5 MPa or less, more preferably 2 MPa or less, from the viewpoint of manufacturing equipment costs and the like. Moreover, it is preferable to set it as 0.1 Mpa or more from a viewpoint of the yield of carbonate ester.

  About reaction temperature, it is preferable to set it as the temperature of 50 to 150 degreeC from a viewpoint of productivity, manufacturing cost, etc., and it is more preferable to set it as the temperature of 100 to 150 degreeC.

  The reaction time is preferably 0.5 hours or more and 24 hours or less, more preferably 12 hours or less from the viewpoint of productivity, production cost, and the like.

  Hereinafter, the present invention will be described in more detail based on examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the following examples.

(Synthesis of porous metal complex)
<Synthesis of UiO-66 (Zr)>
In a glove box in a nitrogen atmosphere, 7.5 ml of acetic acid (CH ₃ COOH, manufactured by Wako Pure Chemical Industries, reagent special grade), 0.703 g of zirconium chloride (ZrCl ₄ , manufactured by Wako Pure Chemical Industries, 95.0 +%) ( 3 mmol), and after removing from the glove box, ultrasonic treatment was performed for several minutes to prepare a zirconium chloride solution in which zirconium chloride was dissolved in acetic acid.
To the prepared zirconium chloride solution, 50 mL of N, N-dimethylformamide (manufactured by Wako Pure Chemical Industries, Wako First Grade) was added, and sonication was performed again for several minutes.
Next, 0.501 g (3 mmol) of terephthalic acid (C ₆ H ₄ (COOH) ₂ , manufactured by Wako Pure Chemical Industries, Wako First Grade) and 200 μL of purified water are added, and ultrasonic treatment is performed for 10 minutes. A UiO-66 (Zr) precursor solution was prepared.
The prepared UiO-66 (Zr) precursor solution was sealed in a Teflon autoclave, heated to 120 ° C. at a heating rate of 4 ° C./min while stirring, and then kept at 120 ° C. for 24 hours. Then, it was naturally cooled to room temperature.
Next, the reaction solution was centrifuged to obtain only a white precipitate, stirred for 10 minutes with ethanol, and then centrifuged again to obtain a precipitate.
The obtained precipitate was soaked in acetone for 24 hours and centrifuged again for 3 times, and further immersed in water for 24 hours and centrifuged again for 3 times, thereby remaining N, N- Impurities such as dimethylformamide were removed.
The obtained white precipitate was dried on a hot plate at 60 ° C. for 2 hours and then vacuum-dried at 200 ° C. for 12 hours in a vacuum dryer to obtain UiO-66 (Zr) which is a porous metal complex. Of powder was obtained.
When the BET specific surface area of the obtained UiO-66 (Zr) was measured with an automatic specific surface area / pore distribution measuring device (BELSORP-miniII, manufactured by Microtrack Bell), as shown in Table 1 below, 1280 m ² / G.

<Synthesis of UiO-66 (Hf)>
In a glove box in a nitrogen atmosphere, 7.5 ml of acetic acid (CH ₃ COOH, manufactured by Wako Pure Chemical Industries, reagent special grade) and 0.962 g of hafnium chloride (HfCl ₄ , manufactured by Wako Pure Chemical Industries, 99.5%) ( 3 mmol), and after removing from the glove box, ultrasonic treatment was performed for several minutes to prepare a hafnium chloride solution in which hafnium chloride was dissolved in acetic acid.
To the prepared hafnium chloride solution, 50 mL of N, N-dimethylformamide (manufactured by Wako Pure Chemical Industries, Wako First Grade) was added, and sonication was performed again for several minutes.
Next, 0.501 g (3 mmol) of terephthalic acid (C ₆ H ₄ (COOH) ₂ , manufactured by Wako Pure Chemical Industries, Wako First Grade) and 200 μL of purified water are added, and ultrasonic treatment is performed for 10 minutes. A UiO-66 (Hf) precursor solution was prepared.
The prepared UiO-66 (Hf) precursor solution was placed in a Teflon autoclave, sealed, heated to 120 ° C. at a rate of 4 ° C./min while stirring, and then kept at 120 ° C. for 24 hours. Then, it was naturally cooled to room temperature.
Next, the reaction solution was centrifuged to obtain only a white precipitate, stirred for 10 minutes with ethanol, and then centrifuged again to obtain a precipitate.
The obtained precipitate was soaked in acetone for 24 hours and centrifuged again for 3 times, and further immersed in water for 24 hours and centrifuged again for 3 times, thereby remaining N, N- Impurities such as dimethylformamide were removed.
The obtained white precipitate was dried on a hot plate at 60 ° C. for 2 hours and then vacuum-dried at 200 ° C. for 12 hours in a vacuum dryer to obtain UiO-66 (Hf) which is a porous metal complex. Of powder was obtained.
The BET specific surface area of the obtained UiO-66 (Hf) was measured with an automatic specific surface area / pore distribution measuring device (BELSORP-miniII, manufactured by Microtrack Bell). As shown in Table 1 below, 1180 m ² / G.

<Synthesis of UiO-66 (Zr) -NH ₂ >
In a glove box in a nitrogen atmosphere, 7.5 ml of acetic acid (CH ₃ COOH, manufactured by Wako Pure Chemical Industries, reagent special grade), 0.703 g of zirconium chloride (ZrCl ₄ , manufactured by Wako Pure Chemical Industries, 95.0 +%) ( 3 mmol), and after removing from the glove box, ultrasonic treatment was performed for several minutes to prepare a zirconium chloride solution in which zirconium chloride was dissolved in acetic acid.
To the prepared zirconium chloride solution, 50 mL of N, N-dimethylformamide (manufactured by Wako Pure Chemical Industries, Wako First Grade) was added, and sonication was performed again for several minutes.
Then, 2-amino-terephthalic acid _{(C 8} H 7 NO _4, manufactured by Tokyo Kasei Kogyo, 98%) and 0.501 g (3 mmol), and purified water 200μL addition, by performing sonication for 10 minutes, transparent A UiO-66 (Zr) -NH ₂ precursor solution was prepared.
The prepared UiO-66 (Zr) -NH ₂ precursor solution was sealed in a Teflon autoclave, heated to 120 ° C. at a heating rate of 4 ° C./min while stirring, and then heated at 120 ° C. It was kept for 24 hours and naturally cooled to room temperature.
Next, the reaction solution was centrifuged to obtain only a white precipitate, stirred for 10 minutes with ethanol, and then centrifuged again to obtain a precipitate.
The obtained precipitate was soaked in acetone for 24 hours and centrifuged again for 3 times, and further immersed in water for 24 hours and centrifuged again for 3 times, thereby remaining N, N- Impurities such as dimethylformamide were removed.
The obtained white precipitate was dried on a hot plate at 60 ° C. for 2 hours and then vacuum-dried at 200 ° C. for 12 hours in a vacuum dryer to obtain UiO-66 (Zr) which is a porous metal complex. A powder of —NH ₂ was obtained.
The BET specific surface area of the obtained UiO-66 (Zr) -NH ₂ was measured with an automatic specific surface area / pore distribution measuring device (BELSORP-miniII, manufactured by Microtrac Bell Co.), as shown in Table 1 below. 1170 m ² / g.

<Synthesis of UiO-67 (Zr)>
In a glove box in a nitrogen atmosphere, 0.368 g (1.58 mmol) of zirconium chloride (ZrCl ₄ , Wako Pure Chemical Industries, 95.0 +%) is weighed and dissolved by adding 60 mL of N, N-dimethylformamide. A zirconium chloride solution was prepared.
To the prepared zirconium chloride solution, 5.654 g (46.3 mmol) of benzoic acid (C ₆ H ₅ COOH, manufactured by Wako Pure Chemical Industries, Ltd., reagent grade) was added and subjected to ultrasonic treatment for 5 minutes.
Then, 0.375 g (1.55 mmol) of 4,4-biphenyldicarboxylic acid (C ₁₄ H ₁₀ O ₄ , manufactured by Tokyo Chemical Industry Co., Ltd., 95.0% or more) and 36 μL of purified water were added, and sonication was performed for 10 times. A UiO-67 (Zr) precursor solution was prepared by performing for a minute.
The prepared UiO-66 (Zr) precursor solution was placed in a Teflon autoclave, sealed, heated to 120 ° C. at a rate of 3 ° C./min with stirring, and then kept at 120 ° C. for 24 hours. Then, it was naturally cooled to room temperature.
Next, the reaction solution was centrifuged to obtain only a white precipitate, stirred for 10 minutes with ethanol, and then centrifuged again to obtain a precipitate.
The resulting precipitate is immersed in N, N-dimethylformamide for 24 hours, centrifuged again three times, then immersed in acetone for 24 hours, and then centrifuged again three times for residual impurities. Was removed.
The obtained white precipitate was dried on a hot plate at 60 ° C. for 2 hours to obtain a powder of UiO-67 (Zr), which is a porous metal complex.
The BET specific surface area of the obtained UiO-67 (Zr) was measured with an automatic specific surface area / pore distribution measuring device (BELSORP-miniII, manufactured by Microtrack Bell). As shown in Table 1 below, 2480 m ² / G.

<Synthesis of Zr-BTC>
In a glove box under a nitrogen atmosphere, 16.8 ml of acetic acid (CH ₃ COOH, manufactured by Wako Pure Chemical Industries, reagent special grade), 0.703 g of zirconium chloride (ZrCl ₄ , manufactured by Wako Pure Chemical Industries, 95.0 +%) ( 3 mmol), and after removing from the glove box, ultrasonic treatment was performed for several minutes to prepare a zirconium chloride solution in which zirconium chloride was dissolved in acetic acid.
To the prepared zirconium chloride solution, 0.210 g (1 mmol) of 1,3,5-benzenetricarboxylic acid (manufactured by Wako Pure Chemical Industries, Wako Special Grade) was added, and sonication was performed for 5 minutes.
Next, 30 mL of N, N-dimethylformamide (manufactured by Wako Pure Chemical Industries, Wako No. 1) was added, and ultrasonic treatment was performed again for 20 minutes to prepare a transparent Zr-BTC precursor solution.
The prepared UiO-66 (Zr) precursor solution was sealed in a Teflon autoclave, heated to 135 ° C. at a rate of 4 ° C./min while stirring, and then kept at 135 ° C. for 24 hours. Then, it was naturally cooled to room temperature.
Subsequently, only white precipitate was obtained by centrifuging the reaction solution.
The obtained precipitate was immersed in N, N-dimethylformamide for 24 hours and centrifuged again three times, then immersed in acetone for 24 hours, centrifuged again, further immersed in ethanol for 24 hours, and centrifuged again. By performing the separation, the remaining impurities were removed.
The obtained white precipitate was dried on a hot plate at 60 ° C. for 2 hours to obtain a powder of Zr—BTC which is a porous metal complex.
When the BET specific surface area of the obtained Zr-BTC was measured with an automatic specific surface area / pore distribution measuring device (BELSORP-miniII, manufactured by Microtrack Bell), it was 576 m ² / g as shown in Table 1 below. there were.

[Example 1: UiO-66 (Zr)]
Methanol (super dehydration, Wako Pure Chemical Industries, Ltd., for organic synthesis) 19.75 mL (488 mmol) and 0.28 g (1/6 mmol) of UiO-66 (Zr) powder obtained by the above method were added to 100 mL Teflon. It put into the reaction container made, and set to the gas displacement type | mold reaction apparatus.
Next, after flowing CO ₂ gas into the gas displacement reactor for 10 minutes, the inside of the reaction vessel was pressurized and filled with CO ₂ gas to 0.5 MPa.
Next, the gas displacement reactor is heated with stirring, heated to 150 ° C. at 15 ° C./min, held at 150 ° C. for 2 hours, reacted with methanol and carbon dioxide, and then naturally cooled. A reaction solution was obtained.
The ultimate pressure in the reaction vessel during the reaction was 2.5 MPa.

[Example 2: UiO-66 (Zr)]
A reaction solution was obtained by carrying out the reaction in the same manner as in Example 1 except that the holding time (reaction time) at 150 ° C. was changed to 12 hours.

[Example 3: UiO-66 (Zr)]
A reaction solution was obtained by performing the reaction in the same manner as in Example 1 except that the inside of the reaction vessel was pressurized and filled with CO ₂ gas to 0.2 MPa.

[Example 4: UiO-66 (Zr)]
A reaction solution was obtained by carrying out the reaction in the same manner as in Example 1 except that the temperature (reaction temperature) maintained for 2 hours was changed to 100 ° C.

[Example 5: UiO-66 (Hf)]
A reaction solution was obtained in the same manner as in Example 1 except that 0.364 g (1/6 mmol) of UiO-66 (Hf) powder was used instead of UiO-66 (Zr).

Example 6: UiO-66 (Zr) -NH 2 ]
Instead of UiO-66 (Zr), the reaction was conducted in the same manner as in Example 1 except that 0.292 g (1/6 mmol) of UiO-66 (Zr) -NH ₂ powder was used, and the reaction solution was Obtained.

[Example 7: UiO-67 (Zr)]
A reaction solution was obtained in the same manner as in Example 1 except that 0.353 g (1/6 mmol) of UiO-67 (Zr) powder was used instead of UiO-66 (Zr).

[Example 8: Zr-BTC]
A reaction solution was obtained in the same manner as in Example 1 except that 0.243 g (1/6 mmol) of Zr-BTC powder was used instead of UiO-66 (Zr).

[Comparative Example 1: ZrO ₂ ]
The reaction was performed in the same manner as in Example 1 except that 0.123 g (1 mmol) of zirconium oxide (ZrO ₂ , Wako Pure Chemical Industries, Wako Special Grade) was used instead of UiO-66 (Zr). A solution was obtained.
In addition, when the BET specific surface area of the used zirconium oxide was measured with an automatic specific surface area / pore distribution measuring device (BELSORP-miniII, manufactured by Microtrack Bell), as shown in Table 1 below, 2.7 m ² / g.

  About each reaction solution prepared in Example 1 and 5-8 and the comparative example 1, the dimethyl carbonate density | concentration was measured using the gas chromatograph apparatus (The Shimadzu Corporation make, GC-2014). The results are shown in Table 1 below.

From the results shown in Table 1, it was found that when zirconium oxide (solid catalyst) described in Patent Document 1 was used, the concentration of dimethyl carbonate produced was as low as 10 ppm or less (Comparative Example 1).
On the other hand, when a porous metal complex was used, it turned out that all the density | concentrations of the dimethyl carbonate to produce | generate become as high as 30 ppm or more (Examples 1 and 5-8).
In addition, when the dimethyl carbonate density | concentration was measured also about each reaction solution prepared in Examples 2-4, it has confirmed that all the density | concentrations of the produced | generated dimethyl carbonate become 30 ppm or more like Example 1.

Claims (12)

  A method for producing a carbonate ester, wherein an alcohol and carbon dioxide are reacted to form a carbonate ester in the presence of a porous metal complex composed of a metal and an organic ligand.   The method for producing a carbonate ester according to claim 1, wherein the metal is at least one metal selected from Group 3, Group 4 and lanthanoid elements of the periodic table.   The method for producing a carbonate ester according to claim 1, wherein the organic ligand is an organic ligand capable of coordinating at a bidentate or higher.   The method for producing a carbonate ester according to any one of claims 1 to 3, wherein the metal is a Group 4 metal.   The carbonic acid according to any one of claims 1 to 4, wherein the organic ligand is at least one ligand selected from the group consisting of dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids, and amine compounds. Ester production method.   The method for producing a carbonate ester according to any one of claims 1 to 5, wherein the metal is at least one metal selected from the group consisting of zirconium and hafnium.   The organic ligand is terephthalic acid, isophthalic acid, 2-aminoterephthalic acid, 2,5-diaminoterephthalic acid, 2,5-dihydroxyterephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid. 4,4'-biphenyldicarboxylic acid, 3,3'-biphenyldicarboxylic acid, fumaric acid, malonic acid, adipic acid, biphenyl-3,4 ', 5-tricarboxylic acid, 1,3,5-tris (4' -Carboxy [1,1'-biphenyl] -4-yl) benzene, 1,3,5-tris (4-carboxyphenyl) benzene, 1,3,5-benzenetricarboxylic acid and their derivatives The method for producing a carbonate ester according to any one of claims 1 to 6, which is at least one kind of ligand. The method for producing a carbonate ester according to claim 1, wherein the porous metal complex has a BET specific surface area of 500 m ² / g or more and 3000 m ² / g or less.   The method for producing a carbonate ester according to any one of claims 1 to 8, wherein the alcohol is a monohydric alcohol.   The method for producing a carbonate ester according to claim 1, wherein the carbonate ester is dimethyl carbonate.   The method for producing a carbonate ester according to any one of claims 1 to 10, wherein the alcohol and the carbon dioxide are reacted at a pressure of 2.5 MPa or less.   The manufacturing method of the carbonate ester of any one of Claims 1-11 with which the said alcohol and the said carbon dioxide are made to react at the temperature of 50 to 150 degreeC.