CN112961299A - Covalent-organic framework material and preparation method thereof - Google Patents
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Abstract
The invention relates to the technical field of covalent-organic framework materials, and provides a covalent-organic framework material and a preparation method thereof. The covalent-organic framework material provided by the invention is obtained by polymerizing 1,3,5 (4-aldehyde pyridyl) triazine chloride and 2,4, 6-trimethyl-1, 3, 5-triazine, and is a novel covalent-organic framework material. The covalent-organic framework material has wider pore channels, is a porous crystal structure material, has higher thermal stability, and has wide application prospect in the fields of photocatalysis, storage, gas adsorption and heat-resistant materials. The preparation method provided by the invention has simple steps and is easy to operate.
Description
Technical Field
The invention relates to the technical field of covalent-organic framework materials, in particular to a covalent-organic framework material and a preparation method thereof.
Background
The porous material refers to an organic material having interconnected pores or a closed network-like spatial structure. In a plurality of chemical material researches, the porous material can be widely applied to the fields of storage, gas adsorption, sensing, interface chemistry, separation, catalysis, energy storage, photovoltaic materials and the like due to the special surface area and the low skeleton density of the porous material. Porous materials can be classified into three types according to the size of pore size: micropores, mesopores, and macropores. The difference in pore size also results in differences in various properties.
Metal organic framework Materials (MOFs) originated in the last 90 th century and consisted of metals and organic ligands, and are therefore also called metal-organic polymers, which have great scientific interest and research due to their characteristics of large specific surface area, high porosity, etc. Therefore, in the last two decades, ordered porous metal organic framework materials mainly comprising inorganic and organic hybrid substances have gradually emerged. The material has the characteristics of large specific surface area, adjustable physical and chemical properties, and easy application to functional areas in new fields of nonlinear optics, magnetic materials, superconducting materials, hydrogen storage materials and the like, and has potential application prospects.
Covalent organic framework materials (COFs) have a larger specific surface area, higher porosity, and lower density than metal organic framework materials, and can store gases more easily. COFs are composed entirely of nonmetallic elements such as C, H, O, N, B, and have a regular pore structure and uniform pore distribution, as well as good heat resistance and a very high surface area. In 2005, the Cote group used the topological design principle to synthesize COF-1 and COF-5 from self-condensing covalent organic backbone polymers using 1, 4-phenylboronic acid (BDBA) polycondensation and 1, 4-hexahydroxybenzene and phenylboronic acid and/or fe (hhtp) for the first time. Subsequently, significant progress has been made in the study of organic covalent backbone polymers. In 2005, Yaghi et al prepared schiff base-linked COF-300 using an aldehyde-amine condensation reaction, followed by synthesis of COF-102 and COF-103 using three-dimensional configuration monomers. In 2008, Kuhn et al expressed as ZnCl2As a catalyst, the triazine group covalent organic framework polymer CTFs is prepared by adopting a high-temperature ionothermal synthesis technology at the temperature of more than 400 ℃, and the obtained material has a crystal structure similar to COF-1.
In recent years, the construction of covalent organic framework materials with different structures becomes a research hotspot, and the research of covalent-organic framework materials with novel structures has important significance.
Disclosure of Invention
In view of the above, the present invention provides a covalent-organic framework material and a method for preparing the same. The covalent-organic framework material provided by the invention is obtained by polymerizing 1,3,5 (4-aldehyde pyridyl) triazine chloride and 2,4, 6-trimethyl-1, 3, 5-triazine, and is a novel covalent-organic framework material.
In order to achieve the above object, the present invention provides the following technical solutions:
a covalent-organic framework material obtained by polymerizing 1,3,5 (4-formylpyridyl) triazine chloride and 2,4, 6-trimethyl-1, 3, 5-triazine, having the structure shown in formula I:
the invention provides a preparation method of the covalent-organic framework material, which comprises the following steps:
1,3,5 (4-aldehyde pyridyl) triazine and 2,4, 6-trimethyl-1, 3, 5-triazine are polymerized to obtain the covalent-organic framework material with the structure shown in formula I.
Preferably, the preparation method of the chlorinated 1,3,5 (4-aldehyde pyridyl) triazine comprises the following steps: nucleophilic substitution reaction is carried out on 4-pyridine aldehyde and cyanuric chloride to obtain chlorinated 1,3,5 (4-aldehyde pyridyl) triazine.
Preferably, the solvent for nucleophilic substitution reaction includes one or more of tetrahydrofuran, dimethyl sulfoxide, N-dimethylformamide and dioxane.
Preferably, the molar ratio of the 4-pyridylaldehyde to the cyanuric chloride is (2-4): 0.8-1.2.
Preferably, the nucleophilic substitution reaction is carried out under anaerobic conditions; the nucleophilic substitution reaction is carried out under the reflux condition, and the reaction time is 46-50 h.
Preferably, the solvent for polymerization reaction comprises one or more of methanol, n-butanol, mesitylene and dichlorobenzene.
Preferably, the molar ratio of the 1,3,5 (4-aldehyde pyridyl) triazine chloride to the 2,4, 6-trimethyl-1, 3, 5-triazine is (0.9-1.1): 0.9-1.1.
Preferably, the polymerization reaction is carried out under anaerobic conditions.
Preferably, the polymerization reaction is carried out under a reflux condition, and the reaction time is 13-15 h.
The present invention provides a covalent-organic framework material. The covalent-organic framework material provided by the invention is obtained by polymerizing 1,3,5 (4-aldehyde pyridyl) triazine chloride and 2,4, 6-trimethyl-1, 3, 5-triazine, has a structure shown in a formula I, and is a novel covalent-organic framework material. The covalent-organic framework material provided by the invention has wider pore channels, is a porous crystal structure material, has higher thermal stability, and has wide application prospects in the fields of photocatalysis, storage, gas adsorption and heat-resistant materials.
The invention also provides a preparation method of the covalent-organic framework material. The preparation method provided by the invention has simple steps and is easy to operate.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of chlorinated 1,3,5 (4-aldehyde pyridyl) triazine;
FIG. 2 is an infrared spectrum of 1,3,5 (4-aldehyde pyridine) triazine chloride;
FIG. 3 is an infrared spectrum of YZL-POP;
FIG. 4 is a UV spectrum of YZL-POP;
FIG. 5 is a scanning electron micrograph of YZL-POP;
FIG. 6 is a thermogravimetric plot of YZL-POP.
Detailed Description
The invention provides a covalent-organic framework material, which is obtained by polymerizing 1,3,5 (4-aldehyde pyridyl) triazine chloride and 2,4, 6-trimethyl-1, 3, 5-triazine, and has a structure shown in a formula I:
in formula I:
the three-terminal-linked group of (A) is
The three-terminal-linked group of (A) is
The invention also provides a preparation method of the covalent-organic framework material, which comprises the following steps:
1,3,5 (4-aldehyde pyridyl) triazine and 2,4, 6-trimethyl-1, 3, 5-triazine are polymerized to obtain the covalent-organic framework material with the structure shown in formula I.
In the present invention, the preparation method of the chlorinated 1,3,5 (4-aldehyde pyridyl) triazine preferably comprises the following steps: nucleophilic substitution reaction is carried out on 4-pyridine aldehyde and cyanuric chloride to obtain chlorinated 1,3,5 (4-aldehyde pyridyl) triazine. In the present invention, the solvent for nucleophilic substitution reaction preferably includes one or more of tetrahydrofuran, dimethyl sulfoxide, N-dimethylformamide and dioxane; the mol ratio of the 4-pyridylaldehyde to the cyanuric chloride is preferably (2-4): (0.8-1.2), and more preferably 3: 1; the invention has no special requirements on the dosage of the solvent, and can ensure the smooth reaction.
In the present invention, the nucleophilic substitution reaction is preferably carried out under an anaerobic condition; the nucleophilic substitution reaction is preferably carried out under the reflux condition, and the reaction time is preferably 46-50 h, and more preferably 48 h; the nucleophilic substitution reaction is preferably carried out under magnetic stirring conditions.
In the specific embodiment of the invention, preferably, 4-pyridylaldehyde and cyanuric chloride are added into a solvent (after the 4-pyridylaldehyde and the cyanuric chloride are added into the solvent, the color of the solution is gradually changed from colorless to yellow brown, and then the color is continuously deepened), then magnetons are added, a reaction device is sealed, vacuumized, filled with nitrogen, the operations of vacuumizing and filling with nitrogen are repeated for more than three times, oxygen in the device is exhausted, then magnetic stirring is started, and the temperature is raised to the reflux temperature for reaction.
In the present invention, the nucleophilic substitution reaction has the formula shown in formula A:
after the nucleophilic substitution reaction is completed, the present invention preferably performs post-treatment on the obtained product liquid. In the present invention, the post-treatment preferably comprises the steps of: and filtering the obtained product liquid, and sequentially washing and drying a filter cake to obtain the chlorinated 1,3,5 (4-aldehyde pyridyl) triazine. In the present invention, the filtration is preferably a reduced pressure filtration; the washing is preferably carried out by sequentially using tetrahydrofuran and ethanol, and the washing times by using tetrahydrofuran and ethanol are independently 2-3 times; the drying is preferably vacuum drying, the drying temperature is preferably 50 ℃, the drying time is preferably 24 hours, and a light-brown red solid product, namely the chlorinated 1,3,5 (4-aldehyde pyridyl) triazine (the structural formula is shown in the formula A), is obtained after the drying.
After 1,3,5 (4-aldehyde pyridyl) triazine chloride is obtained, the invention carries out polymerization reaction on the 1,3,5 (4-aldehyde pyridyl) triazine chloride and 2,4, 6-trimethyl-1, 3, 5-triazine to obtain the covalent-organic framework material with the structure shown in formula I. In the invention, the solvent for polymerization reaction comprises one or more of methanol, n-butanol, mesitylene and dichlorobenzene; the mol ratio of the chlorinated 1,3,5 (4-aldehyde pyridyl) triazine to the 2,4, 6-trimethyl-1, 3, 5-triazine is preferably (0.9-1.1): (0.9-1.1), and more preferably 1: 1; the invention has no special requirements on the dosage of the solvent, and can ensure the smooth reaction.
In the present invention, the polymerization reaction is preferably carried out under oxygen-free conditions; the polymerization reaction is preferably carried out under the reflux condition, and the reaction time is preferably 13-15 h, and more preferably 14 h; the polymerization is preferably carried out under magnetic stirring.
In the specific embodiment of the invention, 1,3,5 (4-aldehyde pyridyl) triazine chloride and 2,4, 6-trimethyl-1, 3, 5-triazine are preferably dissolved in a solvent, then magnetons are placed in the solvent, the reaction device is sealed and then vacuumized, nitrogen is filled in the reaction device, oxygen in the reaction device is exhausted, then magnetic stirring is started, and the temperature is raised to the reflux temperature for reaction.
In the present invention, the reaction formula of the polymerization reaction is shown as formula B:
after the polymerization reaction is finished, the invention preferably carries out post-treatment on the obtained product liquid to obtain the covalent-organic framework material with the structure shown in the formula I. In the present invention, the post-treatment preferably comprises the steps of: and cooling the obtained product liquid to separate out a solid product, filtering the cooled product liquid, washing a filter cake, and drying to obtain the covalent-organic framework material with the structure shown in the formula I. In the present invention, the filtration is preferably a reduced pressure filtration; the washing is preferably carried out for 2 times by sequentially using methanol, water and N, N-dimethylformamide and then for 3 times by using ethanol; the drying is preferably vacuum drying, the temperature of the drying is preferably 50 ℃, and the time is preferably 24 hours; drying to obtain a dark reddish brown solid product, namely the covalent-organic framework material with the structure shown in the formula I.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.
Example 1
(1) 4-pyridylaldehyde (1.742g,16.260mmol) and cyanuric chloride (1.000g,5.420mmol) were weighed on an electronic balance into a single-neck flask containing 50mL of tetrahydrofuran (the solution gradually changed from colorless to yellowish brown with increasing color in the flask), and then magnetons were added. Sealing the device which is put in advance by using vaseline to ensure that the device is airtight, vacuumizing the device, filling nitrogen, vacuumizing and filling nitrogen, and performing the operation for three times. The magnetic stirrer was turned on to stir, and the reaction was heated at 70 ℃ under reflux for 48h, after which time the solution in the flask was observed to turn dark brown. And (3) filtering the mixture in the single-neck flask under reduced pressure, washing the mixture for 3 times by using tetrahydrofuran and ethanol respectively to obtain a brown product, and then putting the brown product into a vacuum drying oven (at 50 ℃) to dry for 24 hours to obtain a light-brown red solid product, namely chlorinated 1,3,5 (4-aldehyde pyridyl) triazine. A little product was taken in a test tube, and distilled water was added thereto for shaking, and the product was found to be completely dissolved in water.
(2) 1.5020g of intermediate chlorinated 1,3,5 (4-aldehyde pyridyl) triazine obtained by the reaction in the step (1) is taken, 0.462g of 2,4, 6-trimethyl-1, 3, 5-triazine is weighed and added into a single-neck flask containing 60mL of methanol, a magneton is placed after the full dissolution, a device put in advance is sealed by Vaseline, the vacuum pumping is carried out, nitrogen is filled to ensure oxygen-free and anhydrous state, a magnetic stirrer is opened, the reflux reaction is carried out for 14h at 65 ℃, the solution is observed to become reddish brown after the reaction is finished, a large amount of dark brown solid is separated out after the cooling, the pressure is reduced and the filtration is carried out, methanol, water and N, N-dimethylformamide are used for washing for 2 times in sequence, and finally, the ethanol is used for washing for 3 times, so that a dark reddish brown product is. And (3) putting the mixture into a vacuum drying oven at 50 ℃ for drying for 24 hours to finally obtain a dark reddish brown solid, namely the covalent-organic framework material with the structure shown in the formula I, which is marked as YZL-POP.
Structural characterization:
FIG. 1 shows nuclear magnetic hydrogen spectrum of 1,3,5 (4-aldehyde pyridyl) triazine chloride (deuterated chloroform is used as solvent). In fig. 1, δ 10.096(1H, s) is aldehyde hydrogen (H δ is about 10.0 in aldehyde group), δ 7.471(2H, s), δ 8.922(2H, s) are two kinds of hydrogen of benzene ring (H δ 6.0-9.0 at two different positions on benzene ring). Wherein, the delta 3.700(1H, s) and the delta 7.244(1H, s) may not be pure and have impurity proton peaks.
FIG. 2 is an infrared spectrum of 1,3,5 (4-aldehyde pyridine) triazine chloride. According to the relevant documents, the infrared characteristic peak benzene ring C-C, C-N (1680-1450 cm)-1)，Ar-H(3300～3000cm-1) Aldehyde group C ═ O (1740-1720 cm)-1) Aldehyde group C-H (2900-2700 cm)-1) And C-Cl (600-500 cm)-1) And the like. As can be seen from fig. 2, the characteristic peak of C ═ C and C ═ N is 1363.39cm-1，1613.28cm-1The characteristic peak of the benzene ring C-H is 3057.25cm-1Characteristic peak of C-Cl is 537.36cm-1The characteristic peak of aldehyde group C ═ O is 1722.71cm-1The aldehyde group C-H is 2785.88cm-1Therefore, it was preliminarily judged that the resulting product was 1,3,5 (4-formylpyridyl) triazine chloride.
FIG. 3 is an infrared spectrum of YZL-POP. As can be seen from fig. 3, the characteristic peak of C ═ C and C ═ N is (1363.63 cm)-1,1549.24cm-1) The characteristic peak of the benzene ring C-H is 3113.63cm-1Characteristic peak of C-Cl is 530.32cm-1The characteristic peak of C ═ C is 1662.87cm-1(document C ═ C1650-1640 cm-1). Compared with 1,3,5 (4-aldehyde pyridyl) triazine chloride shown in figure 2, the aldehyde group is reduced (C ═ O1740-1720 cm)-1,C-H2900～2700cm-1) 1662.87cm with C ═ C added-1Characteristic peaks, which indicate the disappearance of aldehyde groups, forming C ═ C, with all other key characteristic peaks, can be concluded that the resulting polymer is the expected product.
FIG. 4 is a UV spectrum of YZL-POP. As can be seen from FIG. 4, the medium and low intensity absorption is shown at 250-290 nm, which indicates the existence of heteroaromatic ring; the segment of 300 nm-400 nm shows a larger conjugated system, which is basically consistent with the structure of the product.
FIG. 5 is a scanning electron micrograph of YZL-POP. As can be seen from FIG. 5, YZL-POP is rich in multiple pores and has wider pore passage size.
FIG. 6 is a thermogravimetric plot of YZL-POP. As can be seen from FIG. 6, YZL-POP has a significant decrease in product quality during the temperature range of 16.36-350 ℃, and may have solvent or monomer residues therein. During the period of 350-550 ℃, the quality of the product is reduced more stably, and a small part of the space structure is collapsed, which indicates that the structure of the product is more stable in the temperature range. During the period of 550-800 ℃, the quality of the product is more stably reduced, the space structure is firmer, and the quality of the product reaches 64.36% at 789.16 ℃, which shows that the product material has better heat resistance, and the product with considerable quantity exists at about 800 ℃, which shows that the product has a wider application prospect in the aspect of heat resistance.
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. A covalent-organic framework material derived from the polymerization of 1,3,5 (4-aldehydiyl) triazine chloride and 2,4, 6-trimethyl-1, 3, 5-triazine having the structure of formula I:
2. a method of preparing a covalent-organic framework material according to claim 1, comprising the steps of:
1,3,5 (4-aldehyde pyridyl) triazine and 2,4, 6-trimethyl-1, 3, 5-triazine are polymerized to obtain the covalent-organic framework material with the structure shown in formula I.
3. The method for preparing 1,3,5 (4-aldehydiyl) triazine chloride according to claim 2, comprising the steps of: nucleophilic substitution reaction is carried out on 4-pyridine aldehyde and cyanuric chloride to obtain chlorinated 1,3,5 (4-aldehyde pyridyl) triazine.
4. The process according to claim 3, wherein the solvent for nucleophilic substitution reaction comprises one or more selected from the group consisting of tetrahydrofuran, dimethylsulfoxide, N-dimethylformamide and dioxane.
5. The method according to claim 3, wherein the molar ratio of the 4-pyridylaldehyde to the cyanuric chloride is (2-4) to (0.8-1.2).
6. The production method according to claim 3, wherein the nucleophilic substitution reaction is performed under an oxygen-free condition; the nucleophilic substitution reaction is carried out under the reflux condition, and the reaction time is 46-50 h.
7. The method according to claim 2, wherein the solvent for polymerization comprises one or more selected from methanol, n-butanol, mesitylene and dichlorobenzene.
8. The method according to claim 2, wherein the molar ratio of 1,3,5 (4-formylpyridyl) triazine chloride to 2,4, 6-trimethyl-1, 3, 5-triazine is (0.9-1.1): 0.9-1.1.
9. The method of claim 2, wherein the polymerization reaction is carried out in the absence of oxygen.
10. The preparation method according to claim 2, wherein the polymerization reaction is carried out under reflux conditions for 13-15 h.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114427657A (en) * | 2022-01-30 | 2022-05-03 | 北京东方红升新能源应用技术研究院有限公司 | High-pressure hydrogen storage method and gas cylinder |
| CN116966759A (en) * | 2023-08-08 | 2023-10-31 | 山东中盛药化设备有限公司 | Preparation method and application of organic framework mixed membrane for VOCs recovery |
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| CN109251285A (en) * | 2018-09-21 | 2019-01-22 | 台州学院 | Conjugation microporous polymer and preparation method thereof based on 1,3,5- tri- (4- aldehyde radical pyridyl group) triazine |
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| CN114427657A (en) * | 2022-01-30 | 2022-05-03 | 北京东方红升新能源应用技术研究院有限公司 | High-pressure hydrogen storage method and gas cylinder |
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| CN116966759A (en) * | 2023-08-08 | 2023-10-31 | 山东中盛药化设备有限公司 | Preparation method and application of organic framework mixed membrane for VOCs recovery |
| CN116966759B (en) * | 2023-08-08 | 2024-01-30 | 山东中盛药化设备有限公司 | Preparation method and application of organic framework mixed membrane for VOCs recovery |
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