Preparation method of covalent organic framework material

Abstract

The invention relates to a preparation method of a covalent organic framework material. Gamma rays are used for irradiating monomers to generate polymerization reaction to generate the covalent organic framework material. The reaction can be carried out at normal temperature and normal pressure, the reaction time is shortened, and industrial large-scale production is facilitated.

Description

Technical Field

[0001] The present invention relates to a method for preparing a covalent organic framework material, in particular to a method for preparing a covalent organic framework material using gamma ray irradiation. Background Art

[0002] The design and application of polymers is a field of considerable interest in modern materials science. The principle is to assemble and connect different small structural units using a variety of connection methods to form one-dimensional, two-dimensional or three-dimensional structures, and these connection methods include covalent bonding and pi-pi stacking. Common polymers such as polyethylene, nylon, polyester compounds or polyamine compounds formed by covalent polymerization of small structural units such as olefins, amines or organic acids are widely used in modern daily life.

[0003] Among the above polymers, the material called "covalent organic framework" has the characteristics of low density, high specific surface area, controllable pore structure, easy to adjust properties, high material strength, stable chemical properties, etc. It can be used in application fields such as gas storage, adsorption, photoelectricity, catalysis, or functional devices. Covalent organic framework is considered to be an excellent material after the current metal organic framework. Because covalent organic framework has the potential to be applied in many fields, many teams have invested in the research and development of this material.

[0004] The research on covalent organic framework materials was initially proposed by Professor Omar M. Yaghi and his team from the University of California, Berkeley. In 2005, the team successfully synthesized a three-dimensional covalent organic framework by condensing phenyldiboronic acid and hexahydroxytriphenylenebenzene.

[0005] So far, the preparation methods developed for the synthesis of covalent organic framework materials include solvothermal synthesis, ionothermal synthesis, microwave-assisted synthesis, mechanochemical synthesis, etc. Among them, the solvothermal synthesis method is the most widely used technology. In this method, the monomer solution is polymerized for several days under high temperature and high pressure in a closed container. However, the disadvantage of this method is that it requires high temperature and high pressure, which not only has high production costs, but also increases the requirements for machinery and equipment. In addition, batch production in a closed container is difficult to prepare on a large scale, and the reaction time is too long, which is not conducive to large-scale industrial production. Therefore, seeking a preparation method that can be highly efficient under general conditions is the current research and development goal of the industry. Summary of the invention

[0006] The purpose of the present invention is to provide a new method for preparing a covalent organic framework material, which can be reacted at room temperature and pressure, reduce production costs, and shorten reaction time to improve efficiency, so as to facilitate large-scale industrial production.

[0007] In order to achieve the above-mentioned object, the present invention provides a method for preparing a covalent organic framework material, the steps of which are to take at least one monomer in at least one form and put it into a container, then use a gamma ray to irradiate the monomer for a period of time, and use the gamma ray to cause the at least one monomer to undergo a polymerization reaction to form a covalent organic framework material through the reaction.

[0008] The present invention provides an embodiment, wherein in the step of taking at least one monomer and placing it in a container in at least one form, the at least one monomer is selected from the group consisting of a substituted triphenylbenzene, an unsubstituted triphenylbenzene, a substituted tetraphenylpyrene and an unsubstituted tetraphenylpyrene, or a combination thereof.

[0009] The present invention provides an embodiment, which includes a step of placing at least one monomer in at least one form into a container, wherein the at least one form is a solution of the at least one monomer prepared with at least one solvent or a powder form of the at least one monomer.

[0010] The present invention provides an embodiment, wherein the at least one solvent is an organic solvent, water, or a combination thereof.

[0011] The present invention provides an embodiment, wherein the at least one solvent is selected from the group consisting of p-dichlorobenzene (o-DCB), n-butanol (n-BuOH), mesitylene, The present invention is a group consisting of dioxane, N-methyl pyrrolidone (NMP), isoquinoline, acetic acid, or water.

[0012] The present invention provides an embodiment, wherein in the step of preparing a solution of at least one monomer with at least one solvent and then placing the solution in a container, the container is made of plastic, glass, ceramic or metal.

[0013] The present invention provides an embodiment, wherein in the step of irradiating the interior of the container with a gamma ray within a period of time, the radiation dose rate of the gamma ray is 0.001 to 1000 kGy / h.

[0014] The present invention provides an embodiment, wherein in the step of irradiating the interior of the container with a gamma ray within a time period greater than 0 seconds and less than 7 days.

[0015] The present invention provides an embodiment, wherein in the step of polymerizing the at least one monomer by means of the gamma ray, the polymerization temperature is -200 to 1000°C.

[0016] The present invention provides an embodiment, wherein in the step of polymerizing the at least one monomer by means of the gamma ray, the polymerization reaction is carried out under a pressure of 0 to 30 atmospheres. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 :It is a flow chart of the steps of the preparation method of the covalent organic framework material of the present invention; and Figures 2A-2F :It is a powder X-ray diffraction analysis result chart of the covalent organic framework material reaction product of the present invention; Figures 3A-3F : It is a graph showing the experimental results of the covalent organic framework material of the present invention. DETAILED DESCRIPTION

[0018] In order to further understand and appreciate the structural features and effects of the present invention, a preferred embodiment and detailed description are provided as follows:

[0019] Conventional methods for preparing covalent organic frameworks require high-pressure and high-temperature production conditions and containers that are resistant to high temperatures and high pressures. Only small batches can be produced during production, and the reaction takes several days, which is not conducive to large-scale industrial production.

[0020] The present invention is different from the conventional preparation method. It uses gamma rays to irradiate the reaction monomers to generate a reaction to generate a covalent organic skeleton, thereby solving the above-mentioned problem of being unfavorable for large-scale industrial production.

[0021] Hereinafter, the present invention will be described in detail by illustrating various embodiments of the present invention with reference to the drawings. However, the concept of the present invention may be embodied in many different forms and should not be construed as being limited to the exemplary embodiments described herein.

[0022] In the present invention, the term "gamma ray" refers to a type of penetrating electromagnetic radiation produced by the radioactive decay of atomic nuclei, which is generally defined as having a frequency range greater than 3×10 19 Hz, generally expressed as its radiation dose rate when used.

[0023] First, see Figure 1 , which is a flow chart of the preparation method of the covalent organic framework material of the present invention, and the steps are as follows:

[0024] Step S1: taking at least one monomer in at least one form and placing it in a container;

[0025] Step S2 uses a gamma ray to irradiate the solution for a period of time;

[0026] Step S3: The at least one monomer undergoes a polymerization reaction by means of the gamma ray to form a covalent organic framework material. The details of each step are described below.

[0027] In step S1, the present embodiment puts at least one monomer for preparing a covalent organic framework material into a container in at least one form. The at least one monomer used in the preparation method of the present invention refers to a small molecule compound that can be used to synthesize a covalent organic framework, and the at least one monomer is preferably selected from the group consisting of a substituted triphenylbenzene, an unsubstituted triphenylbenzene, a substituted tetraphenylpyrene and an unsubstituted tetraphenylpyrene, or a combination thereof, and is more preferably selected from the group consisting of 1,3,5-tris-(4-aminophenyl)triazine (TPT-3NH2), 2,4,6-Tris(4-formylphenyl)triazine (TPT-3CHO), 1,3,5-tris(4'-aldehyde phenyl)benzene (TPB-3CHO) and 4,4',4",4'-pyrene-1,3,6,8-tetrayl)tetraaniline (Py-4NH2) or a combination thereof.

[0028] Among them, the synthesis method of 1,3,5-tris-(4-aminophenyl)triazine (TPT-3NH2) is: The detailed process is to add 4-aminobenzonitrile (1.5g, 12.70mmol) to 20mL anhydrous chloroform (CHCl3) to form a suspension, and then put it into a 100mL double-necked bottle. After ice bathing under nitrogen environment, 4mL (0.045mmol) trifluoromethanesulfonic acid (trifluoromethanesulfonic acid) is added. The mixed suspension is stirred in an ice bath for 30 minutes and warmed to room temperature. After stirring at room temperature for 24 hours, ice water is added, and then the suspension is neutralized with ammonia water. Finally, it is dried overnight by vacuum filtration to obtain TPT-3NH2 white solid (yield 80%).

[0029] Its FT-IR (powder state): 3460, 3379, 3321, 3207, 1633, 1606, 1579, 1498, 1433, 1367, 1309, 1180, 1147, 813, 590, 513cm -1 . 1H NMR (DMSO-d6, 25°C, 600MHz): δ = 5.89 (s, 6H), 8.36 (d, J = 10.2Hz, 6H), 6.70 (d, J = 10.2Hz, 6H). 13 C NMR (DMSO-d6, 25℃, 500MHz): 170.45, 153.77, 130.82, 123.56, 113.69.

[0030] The synthesis method of 2,4,6-Tris(4-formylphenyl)triazine(TPT-3CHO) is: The detailed process is to add 4-bromobenzonitrile (1.5g, 12.70mmol) to 20mL anhydrous chloroform (CHCl3) to prepare a suspension, then put it into a 100mL double-necked bottle, and after ice bathing under nitrogen environment, add 4mL (0.045mmol) trifluoromethanesulfonic acid. The mixed suspension is stirred in an ice bath for 30 minutes and warmed to room temperature. After stirring at room temperature for 20 hours, ice water is added, and then the suspension is neutralized with ammonia water. Finally, it is dried overnight by vacuum filtration to obtain TPT-3Br as a white solid (yield 92%). Its FTIR (powder state): 2821, 2729, 1706, 1583, 1517, 1419, 1357, 1298, 1201, 1105, 1012, 806, 499cm -1 . 1 H NMR (CDCl3 and DMSO-d6, 25°C, 600MHz): 10.12 (s, 3H), 8.89 (d, J = 9.6 Hz, 6H), 8.06 (d, J = 9.6 Hz, 6H). 13 C NMR (CDCl3, 25°C, 500MHz): 192.48, 171.47, 140.77, 139.46, 130.03, 129.80.

[0031] Subsequently, the TPT-3Br product was added to 130 mL of anhydrous tetrahydrofuran (THF) to prepare a suspension, which was then placed in a 250 mL double-necked flask and cooled to -78°C in a nitrogen environment. 7.30 mL (18.6 mmol) of a 2.5 M hexane solution of n-butyl lithium (n-BuL) was then added. The mixed suspension was stirred at -70°C for 3 hours and returned to room temperature. After further stirring at room temperature for 16 hours, 50 mL of 2.88 M hydrochloric acid was added, and the product was extracted with chloroform, and filtered after dehydration with anhydrous magnesium sulfate. Finally, the solvent was removed by evaporation under reduced pressure and then centrifuged and purified to obtain TPT-3CHO as a white solid (yield 80%). Its FTIR (powder state): 2821, 2729, 1706, 1583, 1517, 1419, 1357, 1298, 1201, 1105, 1012, 806, 499 cm -1 . 1 H NMR (CDCl3 and DMSO-d6, 25°C, 600MHz): 10.12 (s, 3H), 8.89 (d, J = 9.6 Hz, 6H), 8.06 (d, J = 9.6 Hz, 6H). 13 C NMR (CDCl3, 25°C, 500MHz): 192.48, 171.47, 140.77, 139.46, 130.03, 129.80.

[0032] In addition, the synthesis method of 1,3,5-tris(4'-aldehyde phenyl)benzene(TPB-3CHO) is: The detailed process is to add 1,3,5-tribromobenzene (0.75 g, 2.38 mmol), 4-(Dihydroxyboryl)benzaldehyde (2.145 g, 14.32 mmol), tetrakis(triphenylphosphine)palladium(0) (138 mg, 0.12 mmol) and potassium carbonate (1.98 g, 14.32 mmol) into a 100 mL round-bottom flask, and then slowly add a mixture of 30 mL 1,4-dioxane and 5.5 mL water under nitrogen atmosphere after vacuuming for 15 minutes. The resulting mixture is heated at 110 ° C for 40 hours and then warmed to room temperature. After adding ice water to the mixture, a white precipitate is obtained, which is vacuum filtered and then rinsed with water and methanol several times. Finally, TPB-3CHO is purified by flash column chromatography (SiO2; EA / n-hexane, 1:9) to obtain a white solid (yield 80%).

[0033] The synthesis method of 4,4',4",4"'-pyrene-1,3,6,8-tetrayl)tetraaniline (Py-4NH2) is: The detailed process is to add 1,3,6,8-Tetrabromopyrene (2.0 g, 3.86 mmol), 4-bromoaniline (2.54 g, 18.53 mmol), tetrakis(triphenylphosphine)palladium(0) (452 ​​mg, 0.39 mmol) and potassium carbonate (2.95 g, 21.32 mmol) into a 100 mL round-bottom flask, and then slowly add 60 mL of DMF and 10 mL of water under nitrogen atmosphere after vacuuming for 30 minutes. The resulting mixture is heated at 120 ° C for 48 hours, and then warmed to room temperature after 1,3,6,8-Tetrabromopyrene is consumed. After adding ice water to the mixture, a yellow-green precipitate is obtained, which is vacuum filtered and then rinsed with water and methanol several times. Finally, Py-4NH2 solid (yield 80%) is obtained after purification. 1 H NMR (500MHz, DMSO-d6) δ (ppm): 8.12 (s, 4H), 7.79 (s, 2H), 7.35 (d, J = 12Hz, 8H), 6.78 (d, J = 12Hz, 8H), 5.30 (br s, 8H, 4NH2).

[0034] In addition, in the preparation method of the present invention, in the step of taking at least one monomer in at least one form and placing it in a container, the at least one form is not particularly limited, and is preferably a solution of the at least one monomer prepared with at least one solvent or a powder form of the at least one monomer.

[0035] In addition, the solvent used in the preparation method of the present invention is mainly a solvent that can dissolve or suspend the above-mentioned monomers, and the solvent includes but is not limited to p-dichlorobenzene (o-DCB), n-butanol (n-butanol, n-BuOH), mesitylene (Mesitylene), dioxane, N-methyl pyrrolidone (NMP), isoquinoline, acetic acid and water.

[0036] In addition, the container used in the preparation method of the present invention does not require a high temperature and high pressure environment, and the transparency or thickness of the material has no significant effect on the penetration ability of gamma rays. Therefore, there is no special material or shape restriction, and plastic, glass, ceramic or metal can be preferably used.

[0037] In step S2, the present embodiment uses a gamma ray to irradiate the solution for a period of time. The gamma ray has extremely high energy, so that the monomers mentioned above can be activated and react with each other to form bonds. The radiation dose rate of the gamma ray used in the present embodiment is preferably 0.001 to 1000 kGy / h, more preferably 0.11 to 0.809 kGy / h; and the irradiation time decreases as the radiation dose rate increases, preferably greater than 0 seconds and less than 7 days, more preferably 4 minutes to 4.0 hours.

[0038] In step S3, the present embodiment uses the gamma ray to cause the at least one monomer to undergo a polymerization reaction to form a covalent organic framework material. The at least one monomer irradiated with the gamma ray can be effectively activated and then undergo the polymerization reaction. The formed covalent organic framework material has several different stereo structures depending on the type of monomer used.

[0039] In this embodiment, the polymerization reaction when TPB-3NH2 and TPT-3CHO are used as monomers to synthesize TPT-TPB-COF is: The results of powder X-ray diffraction (PXRD) analysis of the polymer product are as follows: Figure 2A and Figure 2B ; When TPB-3NH2 and TPT-3CHO are used as monomers to synthesize Py-TPTγ-COF, the polymerization reaction is: When Py-4NH2 and TP-2CHO are used as monomers to synthesize Py-TP-γ-COF, the polymerization reaction is: The results of powder X-ray diffraction (PXRD) analysis of the polymer product are shown in the figure. Figure 2C and Figure 2D ; When Py-4NH2 and NTDA are used as monomers to synthesize Py-NTDA-γ-COF, the polymerization reaction is: The results of powder X-ray diffraction (PXRD) analysis of the polymer product are as follows: Figure 2E and Figure 2F The structure of the synthesized covalent organic framework material was verified by Fourier Transform IR Spectrum. The results are shown in FIG. 3A to FIG. 3F. From the test results, it can be seen that the products formed by the above-mentioned polymerization reactions all have the characteristic absorption peaks of C=N or C—N after bonding, indicating that the monomers can undergo the polymerization reaction to generate the covalent organic framework material after being irradiated with gamma rays. From the above results, it can be seen that the method for preparing the covalent organic framework material of the present invention can indeed react at room temperature and pressure, and shorten the reaction time, which is conducive to large-scale industrial production.

[0040] The order of execution of each step in the above embodiment does not mean the order of execution. The order of execution of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiment of the present application.

[0041] The above is only a preferred embodiment of the present invention and is not intended to limit the scope of the present invention. All equivalent changes and modifications to the shape, structure, characteristics and spirit described in the claims of the present invention should be included in the scope of the claims of the present invention.

Claims

1. A method for preparing a covalent organic framework material, characterized in that: The steps include: Taking at least one monomer in at least one form and placing it in a container; irradiating the solution with gamma rays for a period of time; and By means of the gamma ray, the at least one monomer undergoes a polymerization reaction to form a covalent organic framework material.

2. The method for preparing a covalent organic framework material according to claim 1, characterized in that: In the step of taking at least one monomer and placing it in a container in at least one form, the at least one monomer is selected from the group consisting of a substituted triphenylbenzene, an unsubstituted triphenylbenzene, a substituted tetraphenylpyrene and an unsubstituted tetraphenylpyrene, or a combination thereof.

3. The method for preparing a covalent organic framework material according to claim 1, characterized in that: In the step of taking at least one monomer and placing it in a container in at least one form, the at least one form is a solution of the at least one monomer prepared with at least one solvent or a powder form of the at least one monomer.

4. The method for preparing a covalent organic framework material according to claim 3, characterized in that: The at least one solvent is an organic solvent, water, or a combination thereof.

5. The method for preparing a covalent organic framework material according to claim 4, characterized in that: The at least one solvent is selected from the group consisting of p-dichlorobenzene (o-DCB), n-butanol (n-BuOH), mesitylene, The group consisting of dioxane, N-methyl pyrrolidone (NMP), isoquinoline, acetic acid, and water.

6. The method for preparing a covalent organic framework material according to claim 1, characterized in that: In the step of taking at least one monomer and placing it in at least one form into a container, the container is made of plastic, glass, ceramic or metal.

7. The method for preparing a covalent organic framework material according to claim 1, characterized in that: In the step of irradiating the interior of the container with a gamma ray within a period of time, the radiation dose rate of the gamma ray is 0.001 to 1000 kGy / h.

8. The method for preparing a covalent organic framework material according to claim 1, characterized in that: In the step of irradiating the interior of the container with gamma rays within a time period, the time period is greater than 0 seconds and less than 7 days.

9. The method for preparing a covalent organic framework material according to claim 1, characterized in that: In the step of polymerizing the at least one monomer by means of the gamma ray, the polymerization temperature is -200 to 1000°C. 10 . The method for preparing a covalent organic framework material as claimed in claim 1 , wherein in the step of polymerizing the at least one monomer by means of the gamma ray, the polymerization reaction is carried out under a pressure of 0 to 30 atmospheres.

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