CN111286024A - Imidazole functionalized covalent triazine framework material and preparation method and application thereof - Google Patents
Imidazole functionalized covalent triazine framework material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides an imidazole functionalized covalent triazine framework material, and a preparation method and application thereof, and belongs to the technical field of catalysts. The imidazole functionalized covalent triazine framework material provided by the invention has a repeating structural unit with a structure shown in a formula I, wherein the covalent triazine framework contains abundant nitrogen, and the mesoporous structure of the covalent triazine framework is helpful for the diffusion of a substrate and fully plays the role of an active site. Under the assistance of no promoter, the covalent triazine framework is only used as a catalyst to catalyze the cycloaddition reaction of carbon dioxide and epichlorohydrin, the epichlorohydrin is difficult to open the ring, and the catalytic effect is not obvious. The imidazole group is introduced into the imidazole functionalized covalent triazine framework material, has certain nucleophilic capacity, can attack epoxide to cause ring opening of epoxide, can activate carbon dioxide, and can realize high-efficiency catalysis of cycloaddition reaction of carbon dioxide and epoxy chloropropane without adding other cocatalyst.
Description
Technical Field
The invention relates to the technical field of catalysts, and particularly relates to an imidazole functionalized covalent triazine framework material and a preparation method and application thereof.
Background
Covalent Triazine Framework (CTF) is a porous organic material newly developed in recent years, and the material has the advantages of extremely large specific surface area, uniform porous structure, stable chemical structure and the like, so that the material is widely applied to the technical fields of gas storage and separation, adsorption, catalysis and the like. For example, document 1(Arindam Modak, Malay Pramanik, Shinji Inagaki and Asim Bhaunik, J.Mater.chem.A,2014,2,11642-3In the presence of 4,4', 4' - (1,3, 5-triazine-2, 4, 6-triphenyl) tri (oxy) benzaldehyde and pyrrole, the covalent triazine framework material shows good CO2Storage capacity. The literature (Yan He, Qinqin Liu, Fei Liu, Chensheng Huang, Changjun Pen, Qiang Yang, Hualin Wang, Jun Hu, Honglai Liu, Micropor.MeOpor.Mat., 2016,233,10-15.) discloses a covalent triazine skeleton structure synthesized by friedel-crafts alkylation of cyanuric chloride with aromatic compounds, which has a good effect on removing Cu (II) in aqueous solution. Chinese patent CN 109880087A discloses covalent triazine organic framework materials CTF-TPN and CTF-TDPN with triphenylamine structures, which are obtained by respectively condensing 4,4 '-nitrotris (aminoformamidine) chloride with 1, 4-phenyldicarboxaldehyde or 4,4' -biphenyldicarboxaldehyde with benzene ring chains of different lengths for photocatalysis of CO2The reduction to CO has good catalytic performance. However, the above-mentioned covalent triazine framework materials are mostly used for the adsorption of CO2Photocatalytic CO2Reducing to CO or adsorbing heavy metals, but has poor catalytic performance for the cycloaddition reaction of carbon dioxide and epichlorohydrin.
Disclosure of Invention
The invention aims to provide an imidazole functionalized covalent triazine framework material, and a preparation method and application thereof. The imidazole functionalized covalent triazine framework material provided by the invention has excellent catalytic performance on the cycloaddition reaction of carbon dioxide and epichlorohydrin.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an imidazole functionalized covalent triazine framework material, which has a repeating structural unit with a structure shown in a formula I:
the wavy lines in formula I represent repeating structural units.
The invention provides a preparation method of an imidazole functionalized covalent triazine framework material, which comprises the following steps:
mixing a covalent triazine framework, N' -carbonyl diimidazole and furan organic solvent, and performing addition reaction to obtain an imidazole functionalized covalent triazine framework material;
a repeating structural unit of the covalent triazine framework having a structure represented by formula II:
the wavy lines in formula II represent repeating structural units.
Preferably, the mass ratio of the covalent triazine framework to the N, N' -carbonyldiimidazole is 1: (1.5-2.2).
Preferably, the temperature of the addition reaction is 60-70 ℃, and the time is 12-48 h.
Preferably, the method for preparing the covalent triazine framework comprises the following steps: p-phenylenediamine, an alkaline reagent, water, cyanuric chloride and a solvent are mixed for polymerization reaction to obtain the covalent triazine framework.
Preferably, the molar ratio of the p-phenylenediamine to the cyanuric chloride is 1 (0.2-0.7).
Preferably, the temperature of the polymerization reaction is 20-35 ℃, and the time is 8-24 h.
The invention provides an imidazole functionalized covalent triazine framework material in the technical scheme or an application of the imidazole functionalized covalent triazine framework material prepared by the preparation method in the technical scheme in catalyzing cycloaddition reaction of carbon dioxide and epichlorohydrin.
Preferably, the method of application comprises the steps of: under the catalytic action of an imidazole functionalized covalent triazine framework material, performing cycloaddition reaction on carbon dioxide and epoxy chloropropane to obtain propylene carbonate.
Preferably, the temperature of the cycloaddition reaction is 110-140 ℃ and the time is 2-4 h.
The invention provides an imidazole functionalized covalent triazine framework material which has a repeating structural unit with a structure shown in a formula I. The covalent triazine framework in the imidazole functionalized covalent triazine framework material provided by the invention contains abundant nitrogen, and the mesoporous structure of the covalent triazine framework material is helpful for the diffusion of epoxide substrates, fully plays the role of active sites (imidazole groups) and is helpful for promoting the progress of cycloaddition reaction. The imidazole group is introduced into the imidazole functionalized covalent triazine framework material, has certain nucleophilic capacity, can attack epoxide to cause ring opening of epoxide, can activate carbon dioxide, and can realize high-efficiency catalysis of cycloaddition reaction of carbon dioxide and epoxy chloropropane without adding other cocatalyst.
According to the preparation method of the imidazole functionalized covalent triazine framework material, imidazole groups capable of activating carbon dioxide are introduced into the covalent triazine framework through a post-modification method, the synthetic process is simple, no catalyst is required to be additionally added, and the preparation method is suitable for industrial production.
Drawings
FIG. 1 is an IR spectrum of CTF and CTF-IM prepared in example 1;
FIG. 2 is a graph showing the catalytic effects of applications 1 to 4 and comparative example 1;
FIG. 3 is a graph showing the catalytic effects of applications 5 to 8 and comparative example 2;
FIG. 4 is a graph showing the catalytic effects of applications 9 to 12 and comparative example 3;
FIG. 5 is a graph showing the catalytic effects of applications 13 to 16 and comparative example 4.
Detailed Description
The invention provides an imidazole functionalized covalent triazine framework material, which has a repeating structural unit with a structure shown in a formula I:
in formula I, the wavy line represents a repeating basic unit.
The covalent triazine framework in the imidazole functionalized covalent triazine framework material provided by the invention contains abundant nitrogen, and the mesoporous structure of the covalent triazine framework material is beneficial to the diffusion of epoxide, so that the function of an active site is fully exerted; furthermore, the covalent triazine framework may activate carbon dioxide, and a small portion of the unreacted primary and secondary amines and unsaturated nitrogen in the covalent triazine framework may activate carbon dioxide. The imidazole group is introduced into the imidazole functionalized covalent triazine framework material, has certain nucleophilic capacity, can attack epoxide to cause ring opening of epoxide, can form carboxylate radical intermediate with carbon dioxide to realize activation of the carbon dioxide, and can realize high-efficiency catalysis of cycloaddition reaction of the carbon dioxide and epoxy chloropropane without adding other cocatalyst.
The invention provides a preparation method of an imidazole functionalized covalent triazine framework material, which comprises the following steps:
mixing a covalent triazine framework, N' -carbonyl diimidazole and furan organic solvent, and performing addition reaction to obtain an imidazole functionalized covalent triazine framework material;
a repeating structural unit of the covalent triazine framework having a structure represented by formula II:
in formula II, the wavy line represents a repeating basic unit.
In the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.
In the present invention, the method for preparing the Covalent Triazine Framework (CTF) at room temperature preferably comprises the following steps: p-phenylenediamine, an inorganic alkaline reagent, water, cyanuric chloride and a solvent are mixed for polymerization reaction to obtain the covalent triazine framework.
In the present invention, the molar ratio of p-phenylenediamine to cyanuric chloride is preferably 1: (0.2 to 0.7), more preferably 1: (0.26 to 0.67), most preferably 1: (0.3-0.6). In the present invention, the inorganic alkaline agent preferably includes one or more of sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide. In the present invention, the molar ratio of the p-phenylenediamine to the inorganic alkaline agent is preferably 1: (0.4 to 1).
In the present invention, the mixing of p-phenylenediamine, an alkaline agent, water, cyanuric chloride and a solvent preferably comprises the steps of: mixing p-phenylenediamine, an alkaline reagent and water to obtain a p-phenylenediamine solution; mixing cyanuric chloride with a solvent to obtain a cyanuric chloride solution; and dropwise adding the cyanuric chloride solution into the p-phenylenediamine solution. In the present invention, the mixing is preferably performed by stirring; the stirring and mixing speed and time in the present invention are not particularly limited, and the raw materials can be uniformly mixed by using the stirring speed and time known in the art. The amount of water used in the present invention is not particularly limited, and may be any amount of water known in the art, and in the embodiment of the present invention, the ratio of the amount of water to the amount of p-phenylenediamine is preferably (1 to 3) mL:1 mmol. In the present invention, the solvent preferably includes acetone or tetrahydrofuran; the dosage of the solvent is not specially limited, and cyanuric chloride can be dissolved; in the embodiment of the invention, the ratio of the solvent volume to the amount of the cyanuric chloride substance is preferably (12.5-20) mL:1 mmol. The dropping rate in the present invention is not particularly limited, and a dropping rate well known in the art may be used.
In the invention, the temperature of the polymerization reaction is preferably 25-35 ℃, and in the embodiment of the invention, the temperature of the polymerization reaction is preferably room temperature; the time of the polymerization reaction is preferably 8-24 hours, and more preferably 10-15 hours. In the present invention, the reaction occurring during the polymerization reaction is represented by the formula (1):
after the polymerization reaction is completed, the method preferably further comprises the steps of carrying out solid-liquid separation on a system obtained by the polymerization reaction, and sequentially carrying out water washing, acetone washing, methanol washing and drying on an obtained solid product to obtain the covalent triazine framework. The solid-liquid separation mode is not particularly limited in the invention, and a solid-liquid separation mode well known in the field, such as suction filtration, can be adopted. In the present invention, the number of washing with water is not particularly limited, and the alkaline agent may be removed, specifically, washing with water 3 times. The frequency of the acetone washing and the methanol washing is not particularly limited, and the unreacted p-phenylenediamine can be removed, specifically, the acetone washing is carried out for 3 times, and the methanol washing is carried out for 3 times. The drying method is not particularly limited, and drying methods known in the art, such as vacuum drying, may be used. In the invention, the drying temperature is preferably 60-90 ℃, and more preferably 70-80 ℃; the drying time is preferably 10-24 hours, and more preferably 15-20 hours.
After obtaining the covalent triazine framework, N' -carbonyl diimidazole and furan organic solvent are mixed for addition reaction to obtain the imidazole functionalized covalent triazine framework material (CTF-IM).
In the present invention, the mass ratio of the covalent triazine framework to the N, N' -carbonyldiimidazole is preferably 1: (1.5-2.2), more preferably 1: (1.5 to 2.262), and most preferably (1.6 to 2.0).
In the present invention, the covalent triazine framework, N' -carbonyldiimidazole and furan-based organic solvent mixing preferably comprises mixing the covalent triazine framework and a part of furan-based organic solvent to obtain a covalent triazine framework solution; mixing N, N '-carbonyl diimidazole with the residual furan organic solvent to obtain an N, N' -carbonyl diimidazole solution; mixing the covalent triazine framework solution and the N, N' -carbonyldiimidazole solution. In the present invention, the mixing is preferably performed by stirring; the stirring and mixing speed and time in the present invention are not particularly limited, and the raw materials can be uniformly mixed by using the stirring speed and time known in the art. In the present invention, the furan-based organic solvent preferably includes tetrahydrofuran; the amount of the furan organic solvent used in the present invention is not particularly limited, and the covalent triazine framework or N, N' -carbonyldiimidazole can be dissolved. In the embodiment of the invention, the ratio of the mass of the covalent triazine framework to the volume of part of the furan organic solvent is preferably 1g (33-54) mL, and the ratio of the mass of the N, N' -carbonyldiimidazole to the volume of the rest furan organic solvent is preferably 1g (15-23) mL.
In the invention, the temperature of the addition reaction is preferably 60-70 ℃, more preferably 60-65 ℃, and the time of the addition reaction is preferably 12-48 h, more preferably 15-24 h. In the present invention, the reaction occurring during the addition reaction is represented by formula (2):
after the addition reaction is finished, the method preferably further comprises the steps of carrying out solid-liquid separation on a system obtained by the addition reaction, and sequentially carrying out tetrahydrofuran washing, dichloromethane washing, methanol washing and drying on an obtained solid product to obtain the imidazole functionalized covalent triazine framework material. The solid-liquid separation mode is not particularly limited in the invention, and a solid-liquid separation mode well known in the field, such as suction filtration, can be adopted. In the present invention, the number of the tetrahydrofuran washes is not particularly limited, and unreacted N, N' -carbonyldiimidazole can be removed, specifically, the number of the tetrahydrofuran washes is 3. The number of washing with dichloromethane and washing with methanol is not particularly limited, and impurities can be removed, specifically, the washing with dichloromethane is performed 3 times, and the washing with methanol is performed 3 times. The drying method is not particularly limited, and drying methods known in the art, such as vacuum drying, may be used. In the invention, the drying temperature is preferably 60-70 ℃, and the drying time is preferably 12-24 h.
According to the preparation method of the imidazole functionalized covalent triazine framework material, imidazole groups capable of activating carbon dioxide are introduced into the covalent triazine framework through a post-modification method, the synthesis process is simple, and the preparation method is suitable for industrial production. Under the assistance of no promoter, the cycloaddition reaction of carbon dioxide and epichlorohydrin is catalyzed only by taking the covalent triazine framework as the catalyst, the epichlorohydrin is difficult to open the ring, and the catalytic effect is not obvious. The imidazole group is introduced into the imidazole functionalized covalent triazine framework material prepared by the invention, has certain nucleophilic ability, can attack epoxide to cause ring opening of epoxide, can activate carbon dioxide, and can realize high-efficiency catalysis of cycloaddition reaction of carbon dioxide and epoxy chloropropane without adding other cocatalyst.
The invention provides an imidazole functionalized covalent triazine framework material in the technical scheme or an application of the imidazole functionalized covalent triazine framework material prepared by the preparation method in the technical scheme in catalyzing cycloaddition reaction of carbon dioxide and epichlorohydrin.
In the present invention, the method of application preferably comprises the steps of: under the catalytic action of an imidazole functionalized covalent triazine framework material, performing cycloaddition reaction on carbon dioxide and epoxy chloropropane to obtain propylene carbonate.
In the invention, the ratio of the mass of the imidazole functionalized covalent triazine framework material to the amount of the epichlorohydrin substance is preferably (2-4.5) mg: 1mmol, more preferably (2.5-4.2) mg: 1mmol, most preferably (2.6-4) mg: 1 mmol. In the present invention, the initial pressure of the carbon dioxide is preferably 1.5 to 3.0MPa, more preferably 2 to 3.0MPa, and most preferably 2.5 to 3.0 MPa.
In the invention, the temperature of the cycloaddition reaction is preferably 110-140 ℃, more preferably 120-140 ℃, and most preferably 130-140 ℃; the time of the cycloaddition reaction is preferably 2-4 h, more preferably 2.5-4 h, and most preferably 3-4 h.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Mixing p-phenylenediamine (0.81g), sodium carbonate (0.3175g) and deionized water (10mL) to obtain a p-phenylenediamine solution; mixing cyanuric chloride (0.3688g) and acetone (25mL) to obtain cyanuric chloride solution; and dropwise adding the p-phenylenediamine solution into the cyanuric chloride solution, reacting for 8h at room temperature, then carrying out suction filtration on the obtained reaction system, washing the obtained solid product with water for 3 times, washing with acetone for 3 times and washing with methanol for 3 times in sequence, and placing the solid product in a vacuum drying oven to carry out vacuum drying for 10h at 90 ℃ to obtain the Covalent Triazine Framework (CTF).
Mixing a covalent triazine framework (0.75g) and tetrahydrofuran (25mL) to give a covalent triazine framework solution; mixing N, N '-carbonyldiimidazole (1.6215g) and tetrahydrofuran (20mL) to obtain a solution of N, N' -carbonyldiimidazole; and (2) mixing the covalent triazine framework solution and the N, N' -carbonyldiimidazole solution, carrying out reflux reaction for 24h at 65 ℃, then carrying out suction filtration on the obtained reaction system, washing the obtained solid product with tetrahydrofuran for 3 times, washing the solid product with dichloromethane for 3 times and washing the solid product with methanol for 3 times in sequence, and placing the solid product in a vacuum drying oven to carry out vacuum drying for 12h at 60 ℃ to obtain the imidazole functionalized covalent triazine framework (CTF-IM).
Infrared spectra of CTF and CTF-IM prepared in this exampleAs shown in FIG. 1, it can be seen from FIG. 1 that CTF and CTF-IM are 1397cm-1And 1500cm-1The absorption peaks appeared at the positions correspond to C-N and C-N stretching vibration in the triazine ring respectively; at 3393cm-1And 1213cm-1The absorption peak is caused by the stretching vibration of secondary ammonium (-NH-); CTF-IM at 1213cm compared to CTF-1The characteristic peak intensity of secondary ammonium is reduced, indicating that part of the secondary amine is consumed; in addition, the CTF-IM is at 1060cm-1And 902cm-1The new absorption peak generated in (b) is ascribed to imidazole.
The structural parameters of CTF and CTF-IM prepared in this example are shown in Table 1:
TABLE 1 structural parameters of CTF and CTF-IM
| Compound (I) | BET specific surface area (m)2/g) | Pore volume (m)3/g) | Average pore diameter (nm) |
| CTF | 35.4 | 0.13 | 14.46 |
| CTF-IM | 16.6 | 0.073 | 17.47 |
Example 2
Mixing p-phenylenediamine (0.324g), sodium carbonate (0.3175g) and deionized water (10mL) to obtain a p-phenylenediamine solution; mixing cyanuric chloride (0.3688g) and acetone (20mL) to obtain cyanuric chloride solution; and dropwise adding the p-phenylenediamine solution into the cyanuric chloride solution, reacting for 12h at room temperature, then carrying out suction filtration on the obtained reaction system, washing the obtained solid product with water for 3 times, washing with acetone for 3 times and washing with methanol for 3 times in sequence, and placing the solid product in a vacuum drying oven to carry out vacuum drying for 12h at 80 ℃ to obtain the covalent triazine framework.
Mixing a covalent triazine framework (0.75g) and tetrahydrofuran (25mL) to give a covalent triazine framework solution; mixing N, N '-carbonyldiimidazole (1.2g) and tetrahydrofuran (20mL) to obtain a solution of N, N' -carbonyldiimidazole; and (2) mixing the covalent triazine framework solution and the N, N' -carbonyldiimidazole solution, carrying out reflux reaction for 24 hours at the temperature of 60 ℃, then carrying out suction filtration on the obtained reaction system, washing the obtained solid product with tetrahydrofuran for 3 times, washing the solid product with dichloromethane for 3 times and washing the solid product with methanol for 3 times in sequence, and placing the solid product in a vacuum drying oven for vacuum drying for 24 hours at the temperature of 65 ℃ to obtain the imidazole functionalized covalent triazine framework.
Example 3
Mixing p-phenylenediamine (0.54g), sodium carbonate (0.3175g) and deionized water (10mL) to obtain a p-phenylenediamine solution; mixing cyanuric chloride (0.3688g) and acetone (20mL) to obtain cyanuric chloride solution; and dropwise adding the p-phenylenediamine solution into the cyanuric chloride solution, reacting for 12h at room temperature, then carrying out suction filtration on the obtained reaction system, washing the obtained solid product with water for 3 times, washing with acetone for 3 times and washing with methanol for 3 times in sequence, and placing the solid product in a vacuum drying oven to carry out vacuum drying for 24h at 70 ℃ to obtain the covalent triazine framework.
Mixing a covalent triazine framework (0.75g) and tetrahydrofuran (25mL) to give a covalent triazine framework solution; mixing N, N '-carbonyldiimidazole (1.4g) and tetrahydrofuran (20mL) to obtain a solution of N, N' -carbonyldiimidazole; and (2) mixing the covalent triazine framework solution and the N, N' -carbonyldiimidazole solution, carrying out reflux reaction for 24 hours at 65 ℃, then carrying out suction filtration on the obtained reaction system, washing the obtained solid product with tetrahydrofuran for 3 times, washing the solid product with dichloromethane for 3 times and washing the solid product with methanol for 3 times in sequence, and placing the solid product in a vacuum drying oven to carry out vacuum drying for 12 hours at 70 ℃ to obtain the imidazole functionalized covalent triazine framework.
Application example 1
Under the catalytic action of CTF-IM (0.075g), carbon dioxide (the initial pressure is 2.0MPa) and epichlorohydrin (35.7mmol) react for 2.5h at the temperature of 120 ℃ to obtain propylene carbonate.
Application examples 2 to 16
Propylene carbonate was prepared according to the method of application example 1, and the reaction conditions of application examples 2 to 16 are shown in table 2.
Comparative examples 1 to 4
Propylene carbonate was prepared according to the method of application example 1, and the reaction conditions of comparative examples 1 to 4 are shown in table 2.
Comparative example 5
Using CTF as a catalyst, propylene carbonate was produced according to the method of application example 1, and the reaction conditions of comparative example 5 are shown in Table 2.
TABLE 2 reaction conditions and catalytic effects of application examples 1 to 16 and comparative examples 1 to 5
The yield of the chloropropylene carbonate and the selectivity to cyclic chloropropylene carbonate results of application examples 1 to 4 and comparative example 1 are shown in Table 2 and FIG. 1. As can be seen from Table 2 and FIG. 1, when the amount of CTF-IM used was in the range of 0.050 to 0.125g, the selectivity to cyclic propylene carbonate was 100% with the increase in the amount of CTF-IM used, and the yield of propylene carbonate remained unchanged. The increase of the dosage of the CTF-IM can improve the catalytic performance of the CTF-IM.
The results of the yields of the chloropropylene carbonate and the selectivity to cyclic chloropropylene carbonate in application examples 5 to 8 and comparative example 2 are shown in Table 2 and FIG. 2. As can be seen from Table 2 and FIG. 2, when the temperature of the cycloaddition reaction is in the range of 100 to 140 ℃, the selectivity to the cyclic propylene carbonate is 100% with the increase of the temperature of the cycloaddition reaction, and the yield of the propylene carbonate is increased. The improvement of the temperature of the cycloaddition reaction is shown to improve the catalytic performance of CTF-IM.
The yield of the chloropropylene carbonate and the selectivity to cyclic chloropropylene carbonate results of application examples 9 to 12 and comparative example 3 are shown in Table 2 and FIG. 3. As can be seen from Table 2 and FIG. 3, when the cycloaddition reaction time is in the range of 1.5 to 3.5 hours, the selectivity to cyclic propylene carbonate is 100% with the increase of the cycloaddition reaction time, and the yield of propylene carbonate is increased. It is shown that the prolonged cycloaddition reaction time can improve the catalytic performance of CTF-IM.
The results of the yields of chloropropylene carbonate and the selectivity to cyclic chloropropylene carbonate in application examples 13 to 16 and comparative example 4 are shown in Table 2 and FIG. 4. As can be seen from Table 2 and FIG. 4, when the initial pressure of carbon dioxide is in the range of 1.0 to 3.0MPa, the selectivity to cyclic propylene carbonate is 100% with the increase of the initial pressure of carbon dioxide, and the yield of propylene carbonate is increased while maintaining the same. It is shown that an increase in the initial pressure of carbon dioxide can improve the catalytic performance of CTF-IM.
In conclusion, the imidazole functionalized covalent triazine framework prepared by the invention has excellent catalytic performance for the cycloaddition reaction of carbon dioxide and epichlorohydrin.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. An imidazole functionalized covalent triazine framework material having a repeating structural unit having a structure represented by formula I:
in formula I, the wavy line represents a repeating structural unit.
2. A process for the preparation of imidazole-functionalized covalent triazine framework material as claimed in claim 1, comprising the steps of:
mixing a covalent triazine framework, N' -carbonyl diimidazole and furan organic solvent, and performing addition reaction to obtain an imidazole functionalized covalent triazine framework material;
a repeating structural unit of the covalent triazine framework having a structure represented by formula II:
in formula II, the wavy line represents a repeating structural unit.
3. The method according to claim 2, wherein the mass ratio of the covalent triazine framework to the N, N' -carbonyldiimidazole is 1: (1.5-2.2).
4. The method according to claim 2, wherein the temperature of the addition reaction is 60 to 70 ℃ and the time is 12 to 48 ℃.
5. A method of preparation according to claim 2 or 3, wherein the method of preparation of the covalent triazine framework comprises the steps of: p-phenylenediamine, an alkaline reagent, water, cyanuric chloride and a solvent are mixed for polymerization reaction to obtain the covalent triazine framework.
6. The preparation method of claim 5, wherein the molar ratio of p-phenylenediamine to cyanuric chloride is 1 (0.2-0.7).
7. The method according to claim 5, wherein the polymerization reaction is carried out at a temperature of 20 to 35 ℃ for 8 to 24 hours.
8. Use of the imidazole-functionalized covalent triazine framework material according to claim 1 or the imidazole-functionalized covalent triazine framework material prepared by the preparation method according to any one of claims 2 to 7 for catalyzing the cycloaddition reaction of carbon dioxide and epichlorohydrin.
9. The application according to claim 8, characterized in that the method of application comprises the steps of: under the catalytic action of an imidazole functionalized covalent triazine framework material, performing cycloaddition reaction on carbon dioxide and epoxy chloropropane to obtain propylene carbonate.
10. Use according to claim 8 or 9, wherein the temperature of the cycloaddition reaction is 110 to 140 ℃ for 2 to 4 hours.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| CN113117745A (en) * | 2021-04-13 | 2021-07-16 | 昆明理工大学 | Preparation method and application of metal-free catalyst |
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