WO2018074675A1 - Novel zinc-containing metal organic framework compound, and method for preparing five-membered cyclic carbonate compound using same as catalyst - Google Patents

Abstract

The present invention relates to a method for preparing a five-membered cyclic carbonate compound, characterized in that carbon dioxide and an epoxy compound are reacted under relatively mild reaction conditions by using, as a catalyst, a metal organic framework which is a novel zinc-containing porous coordination compound. The zinc-containing metal organic framework compound ZnTi (taz) according to the present invention is advantageous in that the ZnTi (taz) can synthesize a five-membered cyclic carbonate compound with a high yield under relatively low pressure and low temperature conditions since ZnTi (taz) is a safe porous catalyst having a regular structure and a large surface area, and that when ZnTi (taz) is used as a catalyst in a synthesis reaction of a five-membered cyclic carbonate compound, zinc and titanium atoms can easily interact with oxygen atoms of an epoxy compound as a Lewis acid, and a nitrogen atom of triazole facilitates the adsorption of carbon dioxide, and thus the reactivity is excellent.

Description

Novel zinc-containing metalorganic framework compounds and preparation method of 5-membered ring carbonate compounds using the catalyst

The present invention is characterized in that a five-membered ring carbonate compound can be easily synthesized under low temperature and pressure conditions using carbon dioxide and an epoxy compound as a catalyst using zinc-containing metal organic frameworks, which are novel porous coordination compounds. The present invention relates to a novel zinc-containing metalorganic skeleton compound and a method for preparing a 5-membered ring carbonate compound using the same as a catalyst.

In general, a technique of using carbon dioxide as a raw material for organic synthesis has been studied for a long time, and a technique of synthesizing a 5-membered ring carbonate compound by reacting an epoxy compound and carbon dioxide has attracted much attention in terms of monomer production of functional polymer materials.

Conventionally, a method of using diol and phosgene is used to obtain a 5-membered ring carbonate compound in high yield. However, due to the toxicity of phosgene, it is difficult to handle, resulting in many difficulties in the process. Therefore, there is an urgent need for a method of synthesizing a 5-membered ring carbonate compound in high yield under safe conditions.

On the other hand, the techniques of the synthesis of the 5-membered ring carbonate compound in high yield, US Patent Publication No. 2773881 ("glycol carbonate", registered December 11, 1956), alkylamine, dialkylamine, triethylamine A method of synthesizing ethylene carbonate or propylene carbonate from carbon dioxide and ethylene oxide or propylene oxide using amines such as catalysts is disclosed. However, the conditions of the synthesis reaction is high reaction conditions of the reaction pressure is more than 34 atm and the reaction temperature is 100 ~ 400 ℃.

In addition, in Polymerization of propylene carbonate [K. Soga et al., J. Polymer Science: Polymer Chemistry Edition, 15 (1997) 219], K. Soga et al. Are organometallic compounds ZnEt ₂ , AlCl ₃ , Ti (OBu). It is known that polypropylene carbonate having a molecular weight of 1800 to 3600 was synthesized by reacting propylene oxide and carbon dioxide at 40 atmospheres and 120 to 180 ° C. for 3 days using ₄ ) as a catalyst.

Solid-state catalytic incorporation of carbon dioxide into oxirane-polymer. Conversion of poly (glycidyl methacrylate) to carbonate-polymer under atomospheric pressure [N. In Kihara et al., J. Chemical Society: Chemical Communication, (1994) 937], N. Kihara et al. Reacted polyglycityl methacrylate with gaseous carbon dioxide at 120 to 160 ° C. Oxo-1,3-dioxolan-4-yl) methyl methacrylate)] (hereinafter referred to as 'poly DOMA') is also reported. Incorporation of Carbon Dioxide into Poly (glycidyl methacrylate) [N. Kihara et al., Macromolecules, 25 (1992) 4824], a mixture of polyglycidyl methacrylate and atmospheric carbon dioxide with NaI, an alkali metal halogen compound, and triphenylphosphine was used as a catalyst to react polyDOMA at 100 ° C. It is also known to have obtained.

Insoluble polystyrene-bound quaternary onium salt catalysts for the synthesis of cyclic carbonates by the reaction of oxiranes with carbon dioxide [T. In Nishikubo et al., J. Polymer Science, 31 (1993) 939], T. Nishikubo et al. Are quaternary ammonium chlorides or quaternary chlorides on polystyrenes prepared by the simultaneous copolymerization of styrene, divinylbenzene and vinylbenzene chloride. It is known that a yield of phenoxymethyl ethylene carbonate is obtained by reacting carbon dioxide and phenylglycidyl ether at atmospheric pressure at 80 ° C. for 24 hours using a salt attached as a catalyst and toluene as a solvent. However, even in this case, the structure of the catalyst is too dense to cause diffusion resistance, which makes it difficult for the reactant to approach the active point of the catalyst, resulting in low reaction yield and long time for the reaction.

Meanwhile, Chitosan functionalized ionic liquid as a recyclable biopolymer-supported catalyst for cycloaddition of CO2 [J. In Sun et al., Green Chem., 14 (2012) 14], J. Sun et al. Reported that hydrogen bonding of the hydroxyl groups of catalysts is characterized by synergistic effects with halogen anions. In addition reaction of epoxy compound promotes ring opening of epoxy compound, it is reported to increase reactivity.

The present inventors researched and developed a method for preparing a phase transfer catalyst and a 5-membered ring carbonate compound using the catalyst prepared by the method in order to improve the problems described above, and the Republic of Korea Patent Publication No. 10-239222 ("Production of phase transfer catalyst Method and a method of preparing a 5-membered ring carbonate compound using a catalyst prepared by the method ", registered on Jan. 15, 2000). The difficulty in recovering the catalyst during synthesis was not easy to reuse.

In addition, the inventors of the present invention relates to a method for producing a five-membered ring carbonate compound using an ionic liquid catalyst, Korean Patent Publication No. 10-0911494 ("MCM-41 of the hybrid MC-41 catalyst carrying an ionic liquid catalyst) 5) using a hybrid MC-41 catalyst in which an ionic liquid catalyst was supported in a MC-41 (Mobil Composition of Matter No 41). Registered method for preparing cyclic carbonate compound, and Korean Patent Publication No. 10-0999360 ("Method for preparing ionic liquid catalyst supported on porous amorphous silica and method for preparing 5-membered cyclic carbonate compound using the same", 2010. 12. 09 registration Although a method for manufacturing a 5-membered ring carbonate compound using an ionic liquid catalyst supported on porous amorphous silica has been developed and registered, a patent has been registered. Publication No. 10-0911494 ("Manufacturing Method of Hybrid MC-41 Catalyst Supported with Ionic Liquid Catalyst in MC-41 and Method of Manufacturing 5-membered Ring Carbonate Compound Using the Same", Registered on Aug. 11, 2009) Publication No. 10-0999360 ("Method for Preparing Ionic Liquid Catalyst Supported in Porous Amorphous Silica and Method for Preparing Five-membered Ring Carbonate Compound Using the Same", Dec. 09, 2010) of MC-41 or porous amorphous silica In the case of using the carrier, there is a disadvantage in that the manufacturing process of the carrier is complicated and the manufacturing cost is high.

As the above-mentioned conventional epoxy compound and carbon dioxide addition reaction mainly use expensive organometallic catalyst or quaternary ammonium salt catalyst as liquid phase transfer catalyst, it is difficult to separate and recover the catalyst after the reaction. There is a costly problem, and in the case of the catalyst prepared according to the method of Nishikubo (T. Nishikubo) and the like, there are problems such as a low diffusion resistance to the reactants and a low stability, lowering the yield.

In addition, the present inventors are able to combine the metal and the organic material to an infinite range depending on the type of the metal, the metal cluster, the type of the organic material, and the degree of coordination bond. Zn ₂ (HIP) ₂ (bipy) (H ₂ O) ₂ .H ₂ O (hereinafter referred to as 'ZnHIPbipy') metal organic framework in metal organic frameworks (hereinafter referred to as 'MOF') Korean Patent Publication No. 10-1536351 ("Manufacturing Method of Five-membered Ring Carbonate Compound Using Zinc-Containing Metal Organic Framework" as a Catalyst), 2015. 07. 07 registration).

In addition, the present inventors have developed a technique for synthesizing a five-membered ring carbonate compound by using a zinc-glutamate metal organic framework catalyst, and has already used Korean Patent Publication No. 10-1635756 (“Zinc-glutamate metal organic framework” as a catalyst). "How to prepare 5-membered cyclic carbonate compound", 2016. 06. 28 registered).

For reference, MOF, the porous inorganic coordination compound applied to the present invention, was first named in 1995 as the Metal-Organic Framework, and those who gave academic value were Omar M. Yaghi of UCLA and Michael O'Keefe of Arizona State University. O'Keeffe).

Firstly, MOF can vary the pore size from several microseconds to 3 nm. Second, MOF skeleton does not collapse even if solvent or template is removed like zeolite. Third, despite the inclusion of organic matter, thermal stability reaches 300-400 ° C., which has the potential of being a high temperature catalyst.

The inventor of the present invention is a zinc used in the Republic of Korea Patent Publication No. 10-1635756 ("Manufacturing method of 5-membered ring carbonate compound using a zinc- glutamate metal organic skeleton" as a catalyst, registered on June 28, 2016) [Zn (L-Glutamate) (H ₂ O)], a metal organic skeleton containing 2H ₂ O, is a novel porous coordination compound with a different composition, structure, and performance than the metal organic framework. The present invention was completed by preparing by a hydrothermal synthesis method and synthesizing a five-membered ring carbonate compound using it as a catalyst.

In order to overcome the above problems, the present invention uses a novel porous coordination compound, a zinc-containing metalorganic framework compound as a catalyst, to easily prepare a 5-membered ring carbonate compound in high yield under mild reaction conditions. One An object of the present invention is to provide a zinc-containing metal organic framework compound and a method for producing a 5-membered ring carbonate compound using the same as a catalyst.

In addition, the present invention is the novel porous coordination compound zinc Zinc fluoride tetrahydrate and titanium isopropoxide are selected as the metal sources that form the skeleton in the metal-organic skeleton-containing compound, and 1,2,4-triazole (1,2,4) is used as the organic material. -triazole) to prepare by hydrothermal synthesis method zinc Another object is to provide a metal-organic skeleton-containing compound and a method for producing a 5-membered ring carbonate compound using the same as a catalyst.

As such, the zinc-containing metalorganic framework compound, a novel porous coordination compound developed in the present invention, is a three-dimensional structure prepared using 1,2,4-triazole as an organic material. The metalorganic skeleton compound according to the present invention has a zinc and titanium valence when used as a catalyst in the synthesis reaction of a 5-membered ring carbonate compound. Lewis acid can easily interact with the oxygen atoms of the epoxy compound, and the nitrogen atom of the triazole promotes the adsorption of carbon dioxide.

The present invention for solving the above problems is to use a zinc fluoride (zincfluoridetetrahydrate) and titanium isopropoxide (titaniumisopropoxide) as a metal source forming a skeleton, 1,2,4-triazole (1,2) as an organic compound And a zinc-containing metalorganic framework compound, which is a porous coordination compound, characterized in that it is synthesized using (4-triazole).

The zinc-containing metal organic framework compound is characterized in that the structural unit of the compound of the following [Formula 1] is repeated to have a three-dimensional network structure.

[Formula 1]

[Zn ₄ (TiO ₆ ) _x (TiF ₆ ) _y (1,2,4-triazole) _z ]

In the above,

x: 0.4 ~ 1.2

y: 0.1 ~ 0.3

z: 30 ~ 38

In addition, the present invention is a porous coordination compound, characterized in that the metal source of zinc fluoride and titanium isopropoxide is dissolved in distilled water and then mixed with 1,2,4-triazole, which is a structure-forming organic compound, to hydrothermally react. The manufacturing method of a zinc containing metal organic framework compound is made into another solution of the subject.

In addition, the present invention provides a method for producing a 5-membered ring carbonate compound characterized by carbonylation of carbon dioxide and an epoxy compound by using a zinc-containing metalorganic framework compound as a catalyst.

The present invention by means of solving the above problems is to prepare a zinc-containing metal organic framework compound, a novel porous coordination compound having a regular and stable structure by hydrothermal synthesis method and by using this catalyst to synthesize a 5-membered ring carbonate compound, according to the present invention Since zinc-containing metalorganic framework compounds have a regular structure, a large surface area, and a stable porous catalyst, they can synthesize 5-membered ring carbonate compounds at high yields under relatively low pressure and low temperature conditions, and as catalysts for the synthesis reaction of 5-membered ring carbonate compounds. When used, Zn (HIP) containing a single metal of the Republic of Korea Patent Publication No. 10-1536351 ("Manufacturing method of 5-membered ring carbonate compound using a zinc-containing metal organic skeleton as a catalyst", registered on 07. 07. 2015) Oxygen atoms can interact with metal atoms much more easily than bipy metalorganic framework catalysts, Nitrogen atom, it is superior in reactivity advantage to promote the adsorption of carbon dioxide.

1 is a view showing a skeleton structure of a zinc-containing metalorganic skeleton compound according to a preferred embodiment of the present invention.

Hereinafter, a novel porous coordination compound, a zinc-containing metalorganic skeletal compound and a method of preparing a 5-membered ring carbonate compound using the catalyst, according to a preferred embodiment of the present invention will be described in detail, and are not directly related to the technical features of the present invention. The description of the specific technical configuration and operation of the non-element is omitted, and only the technical configuration related to the present invention has been briefly described.

The metal organic framework compound, which is a novel zinc-containing porous coordination compound according to the present invention, is characterized by having a three-dimensional structure by a structural unit represented by the following [Formula 1].

[Formula 1]

[Zn ₄ (TiO ₆ ) _x (TiF ₆ ) _y (1,2,4-triazole) _z ]

In the above,

x: 0.4 ~ 1.2

y: 0.1 ~ 0.3

z: 30 ~ 38

Thus, in the present invention, a novel zinc-containing metalorganic skeleton compound represented by the above [Formula 1] {[Zn ₄ (TiO ₆ ) _x (TiF ₆ ) _y (1,2,4-triazole) _z ]}} ( Hereinafter, 'ZnTi (taz)') is a porous coordination compound, a compound having a three-dimensional network structure by repeating the structural unit of [Formula 1], a tablet measured by purifying the compound of [Formula 1] The component ratio of the chemical composition is as described in Table 1 below.

X, Y, Z defined in [Formula 1] is not necessarily limited only to the range of the numerical values defined above, zinc fluoride hydrate and titanium isopropoxide and 1, which is a compound used in the synthesis of ZnTi (taz); It is limited depending on the amount of the 2,4-triazole used or the reaction conditions, and may be appropriately adjusted according to the needs of the manufacturer.

ZnTi (taz), a novel porous coordination compound according to the present invention, selects zinc fluoride tetrahydrate and titanium isopropoxide as a metal source forming a skeleton, and 1,2,4- as an organic compound. It is prepared by hydrothermal synthesis using triazole (1,2,4-triazole).

3 mmol of zinc fluoride hydrate and 1.0 to 3 mmol of titanium isopropoxide were dissolved in 50 to 70 mL of distilled water, and then mixed with 3 to 6 mmol of 1,2,4-triazole, a structural organic substance, and then synthesized. The product prepared by hydrothermal synthesis at 140-150 ° C. for 60-72 hours was filtered, thoroughly washed with distilled water and methanol, and then vacuum-dried at 120-140 ° C. under vacuum pressure of 10-20 mmHg for 12-14 hours. do.

In the above synthetic conditions, when the amount of titanium isopropoxide to zinc fluoride, the mixed amount of the structure-forming organic substance 1,2,4-triazole, and the amount of distilled water used are outside of the above-mentioned ranges, ZnTi (taz) metal There exists a possibility that the yield of an organic framework compound may fall.

 In addition, when the ZnTi (taz) metal organic skeleton compound is less than the reaction conditions defined above in the synthesis of the hydrothermal synthesis method, the yield of the ZnTi (taz) metal organic skeleton compound may be reduced, and the above limitation is limited. If the reaction conditions are exceeded, the product may decompose or the yield may decrease.

After the reaction, the synthesized product is filtered by a conventional method such as filter filtration, washed thoroughly with distilled water and methanol, and then vacuum dried at a pressure of 10-20 mmHg at 120-140 ° C.

At this time, if the vacuum drying conditions are less than the above-described conditions, there is a fear that the resulting metal organic framework is not sufficiently dried, if the above-mentioned conditions are exceeded there is a risk that the product is lost by rapid drying. .

Meanwhile, the present invention uses carbon dioxide and an epoxy compound by using ZnTi (taz), a zinc-containing metalorganic skeleton compound, which is a novel porous coordination compound having a three-dimensional structure, by the structural unit represented by [Formula 1] as a catalyst. By addition reaction, a 5-membered ring carbonate compound is produced.

In particular, the present invention is characterized in that the reaction of producing a five-membered ring carbonate compound using only carbon dioxide and an epoxy compound, and does not use an additional solvent.

In the present invention, carbon dioxide and an epoxy compound are added and reacted, and the catalyst to be added is novel zinc represented by the above [Formula 1]. It is a ZnTi (taz) metal organic framework compound which is a porous coordination compound.

When the ZnTi (taz) metal organic framework compound is used as a catalyst, a mol ratio of an epoxy compound to a metal organic framework compound is added at a ratio of 100 to 0.5 to 5 when preparing a 5-membered ring carbonate compound. If the amount of the added catalyst is less than 0.5, the carbon dioxide and the epoxy compound do not sufficiently react, and there is a possibility that the unreacted epoxy compound remains in the reactant. If the amount of the catalyst exceeds 5, the reactant and Poor mixing of the catalysts may reduce the catalytic activity.

Tetrabutylammonium bromide (hereinafter referred to as 'TBAB') as a cocatalyst is added in a ratio of 1 to 1 mol of ZnTi (taz) to TBAB. If the amount of TBAB, the added promoter, is less than 1, the carbon dioxide and the epoxy compound may not react sufficiently, so that unreacted epoxy compound may remain in the reactant, and the amount of TBAB, the promoter, may exceed 3 In this case, the mixing of the reactants and the catalyst is not good, there is a fear that the catalytic activity is reduced.

The reaction conditions of the epoxy compound synthesis in the above is preferably reacted for 4 to 20 hours at a reaction temperature of 80 ~ 150 ℃, the pressure of carbon dioxide 0.8 ~ 1.6 MPa, when the reaction conditions are less than the range defined above There is a possibility that the yield of the product may decrease, and when it exceeds the range defined above, there is a fear that the product decomposes or the yield decreases.

In the present invention, the amount of carbon dioxide used in the synthesis of the 5-membered ring carbonate compound requires a mol ratio equal to the mol ratio of the epoxy compound. In the present invention, since the carbon dioxide charged in the reactor is pressurized and filled in the reactor, the number of mol of carbon dioxide is not particularly limited. In this case, the epoxy compound to be reacted with carbon dioxide is considered by considering the number of mol of carbon dioxide charged in the reactor. What is necessary is just to supply suitably.

The epoxy compound is selected from propylene oxide, allyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, glycidyl methacrylate, and vinyl cyclohexene oxide. desirable.

Thus zinc prepared according to the invention It is characterized by high yield when synthesizing 5-membered ring carbonate compound by using ZnTi (taz) as a catalyst.

The ZnTi (taz) catalyst is a coordination compound with regular structure and high crystallinity. ZnTi (taz) has both acidity and basicity, and is excellent in reactivity and stability. Zinc and titanium atoms are Lewis acids than the metal-organic framework catalysts, and oxygen atoms of epoxy compounds can interact much more easily with zinc and titanium atoms, and carbon dioxide is more likely to adsorb to nitrogen atoms of triazoles. It is characterized by excellent reactivity.

Hereinafter, the present invention will be described in detail through examples. However, the scope of the present invention is not limited only to these Examples.

1. Preparation of ZnTi (taz) metal organic framework compounds

zinc The ZnTi (taz) metal organic framework catalyst, a porous coordination compound containing, firstly, a structure-forming organic substance 1,2,4-tria obtained by dissolving 3 mmol of metal fluoride zinc hydrate and 1 mmol of titanium isopropoxide in 50 mL of distilled water. After mixing with 6 mmol of sol, the product prepared by hydrothermal synthesis for 72 hours at a synthesis temperature of 140 ° C. was slowly cooled to room temperature, filtered, and then sufficiently washed with distilled water and methanol, followed by 12 hours in a vacuum of 140 ° C. and 20 mmHg. After drying, ZnTi (taz) was finally prepared as a white solid.

[Structure Analysis of ZnTi (taz)]

Structural analysis of ZnTi (taz) was performed by Synchrotron powder X-ray diffraction (XRD) measurement using monochromatic radiation with λ = 1.4862 Å at beamline 9B of Pohang Accelerator Center in Pohang University of Science and Technology.

The detector arm of the vertical scan diffractometer consists of seven sets of slurts, a flat window 111 crystal analyzer, an anti-scattering divider and a scintillation detector, each set of 20 Separated by °

Data were collected in a flat mode at room temperature with a step size of 0.01 ° and an overlap for the next detector bank of 2 ° through 2θ ranging from 4.0 to 124 °.

Diffraction patterns were indexed using the DICVOL04 program implemented in the Fullprof program suite, and Le Bail refinement was performed to obtain profile parameters for other purifications.

Structure analysis results for ZnTi (taz) according to a preferred embodiment of the present invention are as described in Table 1 below.

Analysis item	ZnTi (taz)
Refined chemical composition	'C 225.86 F 24 N 338.79 O 56 Ti 8 Zn 64 '
Crystal system	Cubic
Space group	F 4 3 2
Cell parameters
a (Å)	17.07037 (7)
Cell volume (Å 3 )	4974.26 (4)
Diffraction Geometry	Reflection
X-ray source	Synchrotron radiation (l = 1.4862Å)
2q scan range (°)	4-124
Scan step size (°)	0.01
Data collection temperature (K)	298
Number of contributing reflections	285
Number of parameters	45
Profile function	Pseudo-Voigt
Rp (%)	12.17
Rwp (%)	18.66
R exp (%)	3.17
GOF	5.95

The structure of ZnTi (taz) according to the present invention predicts the structure of ZnTi (taz) samples analyzed at Pohang Accelerator Center attached to Pohang University of Science and Technology based on the analysis results of [Table 1]. As a metal organic skeleton compound having a three-dimensional structure having a unit structure as shown, the unit structures are combined to have a three-dimensional network as a whole. In the compound illustrated in FIG. 1, red represents oxygen, gray represents zinc, blue represents nitrogen, and black represents carbon, and a titanium atom, which is not illustrated in FIG. 1, is TiO _6. It is assumed that the fluorine atom exists in a form substituted with a part of the oxygen atom in the form of pores.

2. Preparation of 5-membered ring carbonate compound using ZnTi (taz) as catalyst

(Example 1)

zinc Using a catalyst of 0.2 mmol of ZnTi (taz), a metalorganic skeletal compound of the porous coordination compound, and using 0.6 mmol of the co-catalyst TBAB, a relatively low temperature was maintained at 80 ° C. After filling carbon dioxide to a reaction condition of a pressure of 1.0 MPa, without using a solvent, 40 mmol of propylene oxide (PO), an epoxy compound, was added and reacted with carbon dioxide for 4 hours to produce propylene carbonate (PC), a 5-membered ring carbonate compound. Synthesized.

(Comparative Examples 1-4)

Comparative Examples 1 to 4 proceeded with the synthesis of propylene carbonate (PC) which is a 5-membered ring carbonate compound by the same method as in Example 1, Comparative Examples 1 to 4 below [Table 2], [Table 3] and [ As described in Table 6, the reaction temperature, the reaction time and the type of the carrier were limited.

(Examples 1-5 and Comparative Example 1)

Examples 2 to 5 and Comparative Example 1 are carried out under the same conditions as in Example 1, but the results of measuring the yield of the PC by changing only the reaction temperature is shown in Table 2 below.

division	Reaction temperature (℃)	PC yield (%)
Comparative Example 1	60	89
Example 1	80	94
Example 2	100	97
Example 3	120	98
Example 4	140	97
Example 5	150	94

  As can be seen in Table 2, Examples 1 to 5 were PC yield of 94% or more within the range of the reaction temperature 80 ~ 150 ℃ and showed a maximum value at 120 ℃. This is because if the temperature is too high, the side reaction of converting PC into oligomer proceeds.

(Examples 6 to 8 and Comparative Example 2)

Examples 6 to 8 and Comparative Example 2 are carried out under the same conditions as in Example 1, but the results of measuring the yield of the PC by changing only the reaction time is shown in Table 3 below. Table 3 below shows the yield of PC according to the change of reaction time.

division	Response time (hours)	PC yield (%)
Comparative Example 2	3	82
Example 1	4	94
Example 6	12	97
Example 7	16	97
Example 8	20	97

As can be seen in Table 3, the reaction time increases steadily from 4 hours to 12 hours. However, it was judged that the equilibrium reaction was reached with almost constant yield over 12 hours.

(Examples 9-12)

In Examples 9 to 12, the reaction was performed under the same conditions as in Example 1, but the reaction was performed by changing only the carbon dioxide pressure, and the results of measuring the yield of the PC are shown in the following [Table 4]. Table 4 below shows the yield of PC according to carbon dioxide pressure.

division	CO2 pressure (MPa)	PC yield (%)
Example 9	0.8	93
Example 10	1.2	97
Example 11	1.4	98
Example 12	1.6	95

As can be seen in Table 4, as the carbon dioxide pressure increased to 1.4 MPa, the yield of PC increased. However, it decreased slightly at 1.6 MPa. This may be due to the dilution effect of poor contact between the PO and the catalyst at high pressure.

(Examples 13-16)

Examples 13 to 16 carried out the reaction under the same conditions as in Example 1, to prepare a five-membered ring carbonate compound by changing the type of epoxide used, the yield of the five-membered ring carbonate compound according to the change of the epoxy compound [Table 5 ].

division	Epoxide	Yield of 5-membered ring carbonate (%)
Example 1	Propylene oxide	94
Example 13	Butyl glycidyl ether	94
Example 14	Phenylglycidyl ether	96
Example 15	Allyl glycidyl ether	97
Example 16	Vinyl cyclohexene oxide	92

As shown in Table 5, it can be seen that the catalyst of the present invention is effective for the addition reaction of various types of epoxide and carbon dioxide.

(Comparative Examples 3 and 4)

Comparative Examples 3 and 4 were carried out under the same conditions as in Example 1, except that the catalyst was obtained by supporting tetrabutylammonium bromide ionic liquid on silica or alumina instead of ZnTi (taz) metalorganic framework catalyst. After the synthesis, the yield of PC according to the catalyst was measured and shown in the following [Table 6].

division	carrier	PC yield (%)
Comparative Example 3	SiO 2	73
Comparative Example 4	γ-Al 2 O 3	62

As can be seen from Table 6 above, when a catalyst obtained by supporting tetrabutylammonium bromide ionic liquid on a silica or alumina carrier is used, the catalyst of the ZnTi (taz) metalorganic framework compound according to the present invention is used. Compared to the PC yield is much lower.

Therefore, the coordination compound ZnTi (taz) metalorganic framework catalyst prepared according to the present invention as described through the above examples has excellent reactivity and stability, and can be synthesized with high yield under relatively mild reaction conditions. Confirmed.

The present invention described above is not necessarily limited only to the above configuration, and various substitutions, modifications, and changes can be made without departing from the technical spirit of the present invention.

The present invention uses zinc fluoride and titanium isopropoxide as the metal source forming the skeleton, and 1,2,4-triazole (1,2,4-triazole) as the organic compound. A zinc-containing metalorganic framework compound, which is a porous coordination compound, which is synthesized by the above, is in the form for carrying out the invention.

The zinc-containing metal organic framework compound is preferably a structural unit of the compound of the formula [1] is repeated to have a three-dimensional network structure.

[Formula 1]

[Zn ₄ (TiO ₆ ) _x (TiF ₆ ) _y (1,2,4-triazole) _z ]

In the above,

x: 0.4 ~ 1.2

y: 0.1 ~ 0.3

z: 30 ~ 38

In addition, the present invention is a porous coordination compound, characterized in that the metal source of zinc fluoride and titanium isopropoxide is dissolved in distilled water and then mixed with 1,2,4-triazole, which is a structure-forming organic compound, to hydrothermally react. A method for producing a zinc-containing metal organic framework compound is another embodiment for carrying out the invention.

In another aspect, the present invention provides a method for producing a 5-membered cyclic carbonate compound characterized by carbonylation of carbon dioxide and an epoxy compound using a zinc-containing metalorganic framework compound as a catalyst.

The present invention provides a zinc-containing metal organic framework according to the present invention by preparing a zinc-containing metal organic framework compound, a novel porous coordination compound having a regular structure and stable structure, by hydrothermal synthesis and synthesizing a 5-membered ring carbonate compound using this catalyst. Since the compound has a regular structure, a large surface area, and a stable porous catalyst, it is possible to synthesize a 5-membered ring carbonate compound at a high yield under relatively low pressure and low temperature conditions, and when used as a catalyst for the synthesis reaction of the 5-membered ring carbonate compound. Zn (HIP) bipy metalorganic framework catalyst containing a single metal of Publication No. 10-1536351 ("Method for preparing 5-membered ring carbonate compound using zinc-containing metal organic framework as catalyst", registered on 07/07/2015) Oxygen atoms can interact with metal atoms much more easily than nitrogen atoms. It promotes the complex is excellent in reactivity benefits, it is expected to be widely used in the industry.

Claims (7)

1. Synthesis using zinc fluoride tetrahydrate and titanium isopropoxide as a skeleton metal source and 1,2,4-triazole as organic compound Zinc is a porous coordination compound characterized in that Containing metalorganic framework compounds.
2. The method of claim 1,

   Zinc The metal-organic framework compound containing zinc is a porous coordination compound, characterized in that the structural unit of the compound of the formula [1] below has a three-dimensional network structure.

   [Formula 1]

   [Zn ₄ (TiO ₆ ) _x (TiF ₆ ) _y (1,2,4-triazole) _z ]

   In the above,

   x: 0.4 ~ 1.2

   y: 0.1 ~ 0.3

   z: 30 ~ 38
3. Zinc-containing metalorganic, which is a porous coordination compound, characterized by dissolving zinc fluoride hydrate and titanium isopropoxide, which are metal sources, in distilled water, followed by hydrothermal reaction by mixing with 1,2,4-triazole, which is a structural organic compound Method for preparing a skeletal compound.
4. A method for producing a five-membered ring carbonate compound, wherein the carbonylation reaction of carbon dioxide and an epoxy compound is carried out using the zinc-containing metalorganic framework compound according to any one of claims 1 and 2 as a catalyst.
5. The method of claim 4, wherein

   The carbonylation reaction is a method for producing a 5-membered ring carbonate compound, characterized in that the reaction temperature is 80 ~ 150 ℃, the pressure of carbon dioxide is reacted for 4 to 20 hours under the conditions of 0.8 ~ 1.6 MPa.
6. The method of claim 4, wherein

   The addition amount of the metal organic skeleton compound is a method for producing a five-membered ring carbonate compound, characterized in that the mol ratio of the epoxy compound to the metal organic framework compound is 100 to 0.5 to 5.
7. The method of claim 4, wherein

   The epoxy compound is an epoxide derivative, and is selected from allyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, proylene oxide, and vinyl cyclohexene oxide. Manufacturing method.

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