KR102864153B1 - Novel copper metal organic frameworks compound and method of preparation of five-membered cyclic carbonates by using the same as catalyst - Google Patents

Abstract

The present invention relates to a novel copper-containing metal-organic framework compound and a method for producing the same, a five-membered ring carbonate compound using the novel copper-containing metal-organic framework compound as a catalyst, and a method for producing the same. The novel metal-organic framework is characterized by comprising copper hydrate, an organic linker connecting the framework, and a structural linker.

Description

Novel copper-containing metal organic framework compound and preparation method thereof, five-membered cyclic carbonate compound using the novel copper-containing metal organic framework compound as a catalyst and preparation method thereof {Novel copper metal organic frameworks compound and method of preparation of five-membered cyclic carbonates by using the same as catalyst}

The present invention relates to a novel copper-containing metal-organic framework compound and a method for producing the same, and a five-membered ring carbonate compound using the novel copper-containing metal-organic framework compound as a catalyst and a method for producing the same.

In general, the technology of using carbon dioxide as a raw material for organic synthesis has been studied for a long time, and in particular, the technology of synthesizing a five-membered ring carbonate compound by reacting an epoxy compound and carbon dioxide has attracted much attention in terms of producing monomers for functional polymer materials.

Traditionally, methods utilizing diols and phosgene have been used to obtain five-membered ring carbonate compounds in high yields. However, phosgene's toxicity makes it difficult to handle, resulting in significant process challenges. Therefore, there is a pressing need for a method for synthesizing five-membered ring carbonate compounds in high yields under safe conditions.

Meanwhile, looking at technologies for synthesizing 5-membered ring carbonate compounds in high yields, a method for synthesizing ethylene carbonate or propylene carbonate from carbon dioxide and ethylene oxide or propylene oxide using amines such as dialkylamines, dialkylamines, and triethylamine as catalysts is disclosed. However, the conditions for this synthesis reaction are relatively high, with a reaction pressure of 34 atm or higher and a reaction temperature of 100 to 400°C.

In addition, a technology has been reported in which a quaternary ammonium chloride or quaternary phosphorus chloride was attached to polystyrene manufactured by simultaneously copolymerizing styrene, divinylbenzene, and vinylbenzene chloride, and used as a catalyst, and carbon dioxide and phenyl glycidyl ether were reacted for 24 hours to obtain a yield of 30 to 95% of phenoxymethyl ethylene carbonate. However, in this case, the structure of the catalyst is too dense, causing diffusion resistance, making it difficult for the reactants to approach the active site of the catalyst, and thus, there is a disadvantage in that the reaction takes a long time and the yield is low.

In addition, a method for producing a five-membered ring carbonate compound using a hybrid MCM-41 catalyst in which an ionic liquid catalyst is supported on MCM-41 or an ionic liquid catalyst supported on porous amorphous silica has been reported. However, when the carrier of MCM-41 or porous amorphous silica is used, the manufacturing process of the carrier is complicated, expensive organic metals are used, so the manufacturing cost is high, and separation and recovery of the catalyst are difficult, so there are problems in that the process costs are high.

In addition, when quaternary ammonium chloride or quaternary phosphorus chloride is attached to polystyrene manufactured by simultaneously copolymerizing styrene, divinylbenzene, and vinylbenzene chloride and used as a catalyst, and carbon dioxide and phenyl glycidyl ether are reacted for 24 hours using toluene as a solvent to manufacture phenoxymethyl ethylene carbonate, the yield is very low at 30-95%. This is because the structure of the catalyst is too dense, causing diffusion resistance, making it difficult for the reactants to approach the active site of the catalyst, so the reaction yield is low and the reaction takes a long time. However, in this case, there is also a disadvantage that a separation process must be added due to the use of a solvent.

Accordingly, the present invention aims to provide a catalyst that improves the above-mentioned problems, a five-membered ring carbonate compound using the catalyst, and a method for producing the same.

The purpose of the present invention is to provide a metal organic framework compound containing copper, which is a novel porous coordination compound, and a method for producing the same.

In addition, the present invention aims to provide a 5-membered ring carbonate compound and a method for producing the same using the above-mentioned copper-containing metal-organic framework compound as a catalyst.

However, these tasks are exemplary and the scope of the present invention is not limited thereby.

According to one aspect of the present invention for achieving the above object, a metal-organic framework compound catalyst is provided, which comprises a metal-organic framework including copper hydride and an organic linker and a structural linker connecting the metal-organic framework.

According to one embodiment of the present invention, the polyol may include a primary amine polyol or a secondary amine polyol.

According to one embodiment of the present invention, the organic linker may include bispyridyldiazabutadiene ([1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene, BPDB]).

According to one embodiment of the present invention, the structural linker may include 4,4'-benzenedicarboxylic acid (BDC).

According to one embodiment of the present invention, the structural linker may further include an amine functional group.

According to one embodiment of the present invention, the metal-organic framework compound is represented by the following chemical formula 1, and may be a three-dimensional network structure in which the structural unit of the compound of the chemical formula 1 is repeated.

[Chemical Formula 1]

[Cu(BPDB) _0.5 (BDC)] _n

According to another aspect of the present invention, a method for producing a metal-organic framework compound catalyst is provided, comprising the steps of forming a mixture by mixing an organic linker, a structural linker, and a metal-organic framework including copper hydride, and dissolving the mixture in a solvent and reacting to synthesize a metal-organic framework compound.

According to one embodiment of the present invention, the organic linker may include bispyridyldiazabutadiene ([1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene, BPDB]).

According to one embodiment of the present invention, the structural linker may further include a structural linker having an amine functional group formed thereon.

According to one embodiment of the present invention, the structural linker may include one selected from benzenedicarboxylic acid (4,4'-benzenedicarboxylic acid, BDC) and benzenedicarboxylic acid-NH ₂ (BDC-NH ₂ ).

According to one embodiment of the present invention, the step of forming the mixture may be to prepare a ligand solution by mixing the organic linker and the structural linker, and to mix the ligand solution with copper hydrate.

According to one embodiment of the present invention, the solvent may be at least one selected from dimethylformamide, methanol, distilled water, and mixtures thereof.

According to another aspect of the present invention, there is provided a method for producing a 5-membered ring carbonate compound using a metal organic framework compound catalyst, wherein the method comprises synthesizing a 5-membered ring carbonate compound by reacting an epoxy compound and carbon dioxide in the presence of the metal organic framework compound catalyst.

According to one embodiment of the present invention, the epoxy compound may include one selected from propylene oxide, butylene oxide, epichlorohydrin, allyl glycidyl ether, glycidol, and styrene oxide.

According to one embodiment of the present invention, the epoxy compound may react with the metal organic framework compound catalyst at a ratio of 30:0.15 to 30:3.

According to one embodiment of the present invention, the step of reacting and synthesizing the epoxy compound and carbon dioxide further includes a cocatalyst, and the cocatalyst may be one selected from among tetrabutylammonium bromide (TBAB), tetrabutylammonium chloride (TBAC), and tetrabutylammonium iodide (TBAI).

According to one embodiment of the present invention, the metal-organic framework compound catalyst may be recovered and reused after the reaction is completed.

According to another aspect of the present invention, a five-membered ring carbonate compound produced by a method for producing a five-membered ring carbonate compound is provided.

The present invention has the effect of providing a novel copper-containing metal-organic framework compound catalyst and a method for producing the same.

In addition, by using the copper-containing metal organic framework compound catalyst, there is an effect of being able to produce a five-membered ring carbonate compound in a high yield from carbon dioxide and an epoxy compound under relatively mild reaction conditions.

In addition, the catalyst can be recovered by a relatively simple method after manufacturing the five-membered ring carbonate compound, and it has the effect of being reusable.

Further scope of the applicability of the present invention will become apparent from the detailed description below. However, since various modifications and variations within the spirit and scope of the present invention will become apparent to those skilled in the art, it should be understood that the detailed description and specific examples, such as preferred embodiments of the present invention, are given by way of example only.

Figure 1 is a schematic diagram showing a metal-organic framework compound catalyst according to one embodiment.
Figure 2 is a schematic diagram showing a method for manufacturing a catalyst according to one embodiment and a process for manufacturing a five-membered ring carbonate compound using the catalyst.
Figure 3 is a graph showing the XRD results of a catalyst according to one embodiment.
Figure 4 is a graph showing the FT-IR results of a catalyst according to one embodiment.
Fig. 5 is an SEM image of a catalyst according to one embodiment.
Figure 6 is a graph showing the XRD results of a catalyst recovered after manufacturing a 5-membered ring carbonate according to one embodiment.
Figure 7 is a graph showing the FT-IR results of a catalyst recovered after manufacturing a 5-membered ring carbonate according to one embodiment.
Figure 8 is a graph showing the conversion rate of a five-membered ring carbonate according to reuse before and after catalyst recovery according to one embodiment.
Figure 9 is a SEM image of a catalyst recovered after manufacturing a five-membered ring carbonate according to one embodiment.

Hereinafter, the present invention will be described in detail with reference to embodiments and drawings. These embodiments are merely illustrative and intended to illustrate the present invention more specifically, and it will be apparent to those skilled in the art that the scope of the present invention is not limited by these embodiments.

Additionally, unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, and in case of conflict, the description in this specification, including definitions, shall prevail.

To clearly explain the invention proposed in the drawings, parts irrelevant to the description have been omitted, and similar parts have been designated with similar drawing reference numerals throughout the specification. Furthermore, when a part is said to "include" a certain component, this does not mean that other components are excluded, but rather that other components may be included, unless otherwise specifically stated. Furthermore, a "part" described in the specification refers to a single unit or block that performs a specific function.

The identification codes (1, 2, etc.) for each step are used for convenience of explanation and do not describe the order of each step. Each step may be performed in a different order than specified unless the context clearly indicates a specific order.

That is, the steps may be performed in the same order as specified, may be performed substantially simultaneously, or may be performed in the opposite order.

The metal-organic framework compound catalyst according to the present invention comprises a metal-organic framework, an organic linker connecting the metal-organic framework, and a structural linker.

Specifically, the metal-organic framework compound catalyst is characterized by including a metal-organic framework including copper hydrate, an organic linker including bis-pyridyl-diaza-butadiene ([1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene, BPDB]), and a structural linker including 4,4'-benzenedicarboxylic acid (BDC). In this case, the structural linker may further include an amine functional group.

For example, the metal-organic framework compound is preferably represented by the following chemical formula 1 or chemical formula 2. In addition, the metal-organic framework compound is characterized by a three-dimensional network structure in which the structural units of the compound of the following chemical formula 1 or chemical formula 2 are repeated. In addition, as disclosed in Fig. 1, the metal-organic framework compound catalyst is characterized by a porous catalyst with a regular structure and a large surface area.

[Chemical Formula 1]

[Cu(BPDB) _0.5 (BDC)] _n

[Chemical Formula 2]

[Cu(BPDB) _0.5 (BDC-NH ₂ )] _n

At this time, the above BPDB is the organic linker, and BDC or BDC-NH ₂ is a structural linker.

Below, a method for producing the above metal-organic framework compound is described in detail.

The method for producing the above metal-organic framework compound includes a step of mixing a metal-organic framework including an organic linker, a structural linker, and copper hydride to form a mixture, and a step of dissolving the mixture in a solvent and reacting to synthesize the metal-organic framework compound.

The step of forming the above mixture is characterized by mixing the organic linker and the structural linker to prepare a ligand solution, and mixing the ligand solution with copper hydrate.

At this time, the structural linker is characterized in that it includes one selected from among benzenedicarboxylic acid (4,4'-benzenedicarboxylic acid, BDC) and benzenedicarboxylic acid-NH ₂ (BDC-NH ₂ ).

In addition, the organic linker is characterized by including bispyridyldiazabutadiene ([1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene, BPDB]).

The step of synthesizing the above metal-organic framework compound is characterized in that the mixture is dissolved in a solvent and then synthesized using a solvent-thermal synthesis method, and the solvent is at least one selected from dimethylformamide, methanol, distilled water, and a mixture thereof.

Figure 2 is a schematic diagram showing a method for manufacturing a catalyst according to one embodiment and a process for manufacturing a five-membered ring carbonate compound using the catalyst.

Below, a method for producing a 5-membered ring carbonate compound using a metal-organic framework compound catalyst will be described in detail with reference to FIG. 2.

Referring to FIG. 2, the method for producing the 5-membered ring carbonate compound is characterized by synthesizing the compound by reacting an epoxy compound and carbon dioxide in the presence of the metal-organic framework compound catalyst. Specifically, the method is characterized by reacting the epoxy compound and carbon dioxide to convert an epoxide group present in the epoxy compound into a carbonate group, thereby producing the 5-membered ring carbonate.

At this time, the epoxy compound and the metal organic framework compound catalyst react at a molar ratio of 30:0.15 to 30:3. If the molar ratio of the epoxy compound and the metal organic framework compound catalyst is less than 30:0.15, the addition reaction with carbon dioxide may not proceed well, and if the molar ratio of the epoxy compound and the metal complex catalyst exceeds 30:3, the diffusion of the reactant may be hindered, thereby lowering the efficiency of the catalyst and reducing the yield of the 5-membered ring carbonate compound.

In addition, it is preferable that the epoxy compound includes one selected from propylene oxide, butylene oxide, epichlorohydrin, allyl glycidyl ether, glycidol, and styrene oxide.

In addition, the step of reacting and synthesizing the epoxy compound and carbon dioxide is characterized by further including a cocatalyst. Preferably, the cocatalyst is a quaternary ammonium halide compound.

For example, the cocatalyst may be one selected from among quaternary ammonium halogen compounds such as tetrabutylammonium bromide (TBAB), tetrabutylammonium chloride (TBAC), and tetrabutylammonium iodide (TBAI).

In addition, the epoxy compound can be activated by adding the cocatalyst, and it is preferable that the epoxy compound and the cocatalyst are added in a molar ratio of 30:0.15 to 30:3. At this time, if the molar ratio of the epoxy compound and the cocatalyst is included in a ratio of less than 30:0.15, the epoxy compound and carbon dioxide may not sufficiently react, and unreacted epoxy compound may remain in the reactant, and if the cocatalyst is included in a ratio exceeding 30:3, diffusion of the reactant may be hindered, thereby reducing catalytic activity.

In addition, the metal-organic framework compound catalyst can be recovered and reused after producing the five-membered ring carbonate compound. Specifically, the method is characterized in that the catalyst is precipitated and separated by adding ether to the reactant to separate the five-membered ring carbonate compound and the catalyst. At this time, the separated five-membered ring carbonate compound can be recovered by evaporation, and the precipitated catalyst can be recovered through filtration. In addition, it is preferable to wash the recovered catalyst and reuse it to produce the five-membered ring carbonate compound.

Hereinafter, the present invention will be described in detail through examples and experimental examples. However, the following examples and experimental examples are only illustrative of the present invention, and the present invention is not limited to the following examples and experimental examples.

Example.

Example 1. Preparation of a metal-organic framework compound catalyst. (PNU-25)

Benzenedicarboxylic acid (BDC), bis-pyridyl-diaza-butadiene (BPDB), and Cu(NO ₃ ) ₂ ·3H ₂ O were added to a solvent containing dimethylformamide:water:methanol in a ratio of 0.5:0.5:4, stirred for 15 minutes, and then placed in an autoclave for reaction at 85°C for 48 hours. The metal-organic framework compound catalyst thus manufactured is denoted as PNU-25 below.

Example 2. Preparation of a metal-organic framework compound catalyst containing an amine functional group. (PNU-25-NH ₂ )

A catalyst was prepared in the same manner as in Example 1, except that benzenedicarboxylic acid (BDC-NH ₂ ) having an amine functional group was used instead of benzenedicarboxylic acid (BDC). The metal-organic framework compound catalyst thus prepared is referred to as PNU-25-NH ₂ .

Fig. 3 is a graph showing the XRD results of a catalyst according to one embodiment, and Fig. 4 is a graph showing the FT-IR results of a catalyst according to one embodiment.

Referring to Fig. 3, it can be confirmed that both PNU-25 and PNU-25-NH ₂ have the same PNU-25 single crystal profile. In addition, referring to Fig. 4, peaks corresponding to BDC were observed in the range of 1655-1500 cm ^-1 , and peaks corresponding to BPDB were observed in the range of 1385-1580 cm ^-1 . In addition, peaks corresponding to Cu-N and Cu-O were observed in the range of 460-657 cm ^-1 .

That is, it can be confirmed that PNU-25 and PNU25-NH ₂ were synthesized through FIGS. 3 and 4.

Fig. 5 is a SEM image of a catalyst according to one embodiment.

It can be confirmed through Fig. 5(a) and Fig. 5(b) that PNU-25 and PNU-25-NH ₂ were formed into block-shaped particles. In addition, Fig. 5(C) shows the EDX analysis results for PNU-25-NH _2, which confirms that it contains nitrogen, oxygen, carbon, and copper.

Example 3. Preparation of a five-membered ring carbonate compound in the presence of a PNU-25 catalyst.

A five-membered ring carbonate compound was prepared by reacting an epoxy compound and carbon dioxide at 55°C for 12 hours under a pressure of 1 bar in the presence of 1 mol% of PNU-25 catalyst.

Example 4. Preparation of a five-membered ring carbonate compound in the presence of a PNU-25 catalyst and a cocatalyst.

A five-membered ring carbonate compound was prepared by reacting an epoxy compound and carbon dioxide at 80°C for 12 hours in the presence of a PNU-25 catalyst and a cocatalyst, TBAB.

Example 5. PNU-25-NH ₂ Preparation of five-membered ring carbonate compounds in the presence of a catalyst.

It was prepared in the same manner as in Example 3, except that the PNU-25-NH ₂ catalyst was used.

Example 6. PNU-25-NH ₂ Preparation of five-membered ring carbonate compounds in the presence of catalysts and cocatalysts.

It was prepared in the same manner as in Example 4, except that the PNU-25-NH ₂ catalyst was used.

Comparative example

Comparative Example 1.

A five-membered ring carbonate compound was prepared by reacting an epoxy compound and carbon dioxide at 80°C for 12 hours without adding a catalyst.

Comparative Examples 2 to 6

By changing the type of catalyst, a five-membered ring carbonate compound was prepared by reacting an epoxy compound and carbon dioxide at 80°C for 12 hours.

Table 1 below shows the conversion rate and selectivity of the five-membered ring carbonate compounds synthesized according to Examples 3 to 6 and Comparative Examples 1 to 6.

Conversion rate (%) Selectivity (%) Example 3 35 >99 Example 4 46 >99 Example 5 70 >99 Example 6 92 >99 Comparative Example 1 - - Comparative Example 2 33 >99 Comparative Example 3 22 >99 Comparative Example 4 18 >99 Comparative Example 5 12 >99 Comparative Example 6 21 >99

Referring to Table 1, it can be confirmed that the conversion rate of the 5-membered ring carbonate compound in Example 4 using PNU-25-NH ₂ as a catalyst is higher than that in Example 3 using PNU-25 as a catalyst. That is, it can be confirmed that the catalytic properties were improved by activating the adsorption of carbon dioxide by adding an amine functional group.

In addition, it can be confirmed that the conversion rate was significantly improved in Examples 5 and 6 by adding a cocatalyst together with the PNU-25 catalyst or the PNU-25-NH ₂ catalyst during the synthesis of a 5-membered ring carbonate compound. In particular, the conversion rate of Example 6 was the highest, which is because the activation of the epoxide compound and carbon dioxide was simultaneously promoted due to the synergistic effect of the PNU-25-NH ₂ catalyst and the cocatalyst.

Examples 7 to 12. Preparation of five-membered ring carbonate compounds using epoxide compounds.

A five-membered ring carbonate compound was prepared by reacting an epoxy compound and carbon dioxide at 55°C for 12 hours under a pressure of 1 bar in the presence of a 1 mol% PNU-25-NH ₂ catalyst and a 0.5 mol% TBAB cocatalyst. Table 2 below shows the five-membered ring carbonate compounds prepared according to the type of epoxy compound, and Table 3 shows the conversion and selectivity according to the synthesis. At this time, the epoxy compound was synthesized using epichlorohydrin, propylene oxide, allyl glycidyl ether, butylene oxide, styrene oxide, and cyclohexene oxide.

epoxide compounds 5-membered ring carbonate compound Example 6



Example 7



Example 8



Example 9



Example 10



Example 11

Conversion rate (%) Selectivity (%) Example 6 92% >99 Example 7 93% >99 Example 8 81% >99 Example 9 62% >99 Example 10 35% >99 Example 11 12% >99

It can be confirmed that the above Examples 6 to 9 have a high conversion rate to aliphatic epoxide. This can be because the ring of the epoxide group of the epoxide compound is rapidly opened, promoting the conversion to a cyclic carbonate, thereby increasing the conversion rate.

Meanwhile, Examples 10 and 11 are cases of terminal epoxide compounds with large structures, and it can be confirmed that the conversion rate to epoxide is relatively low.

Example 12. Recovery and reuse of catalyst

After preparing the above five-membered ring carbonate compound, in order to separate the product and the catalyst, a small amount of ether was added, and the catalyst was recovered by re-precipitation and filtration, and the residue was distilled to separate the ether, thereby finally obtaining the product.

In addition, a five-membered ring carbonate compound was prepared by reacting an epoxy compound and carbon dioxide in the presence of the recovered catalyst at 55°C and a reaction pressure of 1 bar for 12 hours.

FIG. 6 is a graph showing the XRD results of a catalyst recovered after manufacturing a 5-membered ring carbonate according to one embodiment, and FIG. 7 is a graph showing the FT-IR results of a catalyst recovered after manufacturing a 5-membered ring carbonate according to one embodiment.

Through Figures 6 and 7, it can be confirmed that the XRD results and FT-IR results of the synthesized catalyst and the recovered catalyst are identical. In other words, it can be confirmed that the catalyst can be recovered without affecting the catalyst.

Figure 8 is a SEM image of a catalyst recovered after manufacturing a 5-membered ring carbonate according to one embodiment.

Referring to Fig. 8, it can be confirmed that the recovered catalyst also contains carbon, nitrogen, oxygen, and copper.

Figure 9 is a graph showing the conversion rate and selectivity of a five-membered ring carbonate according to the number of times the catalyst is reused after recovery according to one embodiment.

Referring to Fig. 9, a high conversion rate of over 91% was observed when repeated three times, and a high conversion rate of over 86% was observed when repeated five or more times, confirming that the conversion rate and selectivity did not decrease significantly even when the catalyst was reused. In other words, it can be confirmed through this that the metal-organic framework compound catalyst manufactured according to the present invention can be recovered and reused.

Although this specification describes only a few examples among various embodiments performed by the inventors of the present invention, the technical idea of the present invention is not limited or restricted thereto, and can be modified and implemented in various ways by those skilled in the art.

Claims (17)

Metal-organic frameworks containing copper hydride;
It comprises an organic linker and a structural linker connecting the above metal-organic framework;
The above organic linker
Contains bispyridyldiazabutadiene ([1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene, BPDB]),
The above structural connector
Contains 4,4'-benzenedicarboxylic acid (BDC),
It is for the production of a 5-membered ring carbonate compound by reacting and synthesizing an epoxy compound and carbon dioxide.
The reaction conditions of the epoxy compound and carbon dioxide are 55°C to 80°C and 1 bar.
Metal-organic framework compound catalysts. delete delete In the first paragraph,
The above structural connector
which further contains an amine functional group,
Metal-organic framework compound catalysts. In the first paragraph,
The above metal organic framework compound is represented by the following chemical formula 1 or chemical formula 2,
The structural unit of the compound of the following chemical formula 1 is a three-dimensional network structure in which it repeats.
Metal-organic framework compound catalysts.
[Chemical Formula 1]
[Cu(BPDB) _0.5 (BDC)] _n
[Chemical Formula 2]
[Cu(BPDB) _0.5 (BDC-NH ₂ )] _n
(In the above chemical formulas 1 and 2, BPDB is bispyridyldiazabutadiene ([1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene]), and BDC is benzenedicarboxylic acid (4,4'-benzenedicarboxylic acid). A step of forming a mixture by mixing a metal organic framework including an organic linker, a structural linker and copper hydride; and
A step of dissolving the above mixture in a solvent and reacting to synthesize a metal-organic framework compound;
The above organic linker
Contains bispyridyldiazabutadiene ([1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene, BPDB]),
The above structural connector
Contains 4,4'-benzenedicarboxylic acid (BDC),
It is for the production of a 5-membered ring carbonate compound by reacting and synthesizing an epoxy compound and carbon dioxide.
The reaction conditions of the epoxy compound and carbon dioxide are 55°C to 80°C and 1 bar.
Method for preparing a metal-organic framework compound catalyst. In paragraph 6,
The step of forming the mixture is,
A ligand solution is prepared by mixing the above organic linker and structural linker,
Mixing the above ligand solution with copper hydrate,
Method for preparing a metal-organic framework compound catalyst. In paragraph 6,
The above structural connector is,
It further includes a structural linker in which an amine functional group is formed.
Method for preparing a metal-organic framework compound catalyst. delete delete In paragraph 6,
The above solvent is at least one selected from dimethylformamide, methanol, distilled water, and mixtures thereof.
Method for preparing a metal-organic framework compound catalyst. A method for producing a five-membered ring carbonate compound using the metal organic framework compound catalyst of Article 1,
A step of synthesizing an epoxy compound and carbon dioxide by reacting them in the presence of the metal-organic framework compound catalyst;
Method for producing a five-membered ring carbonate compound. In Article 12,
The above epoxy compound comprises one selected from propylene oxide, butylene oxide, epichlorohydrin, allyl glycidyl ether, glycidol, and styrene oxide.
Method for producing a five-membered ring carbonate compound. In Article 12,
The above epoxy compound reacts with the metal organic framework compound catalyst at a molar ratio of 30:0.15 to 30:3.
Method for producing a five-membered ring carbonate compound. In Article 12,
The step of synthesizing by reacting the above epoxy compound and carbon dioxide is:
By including more co-catalysts,
The above cocatalyst is one selected from among tetrabutylammonium bromide (TBAB), tetrabutylammonium chloride (TBAC), and tetrabutylammonium iodide (TBAI).
Method for producing a five-membered ring carbonate compound. In Article 12,
The above metal-organic framework compound catalyst is,
It is possible to recover and reuse the 5-membered ring carbonate compound after manufacturing it.
Method for producing a five-membered ring carbonate compound. delete