CN114752068A - Preparation method of structure-controllable and adjustable covalent triazine-based material - Google Patents
Preparation method of structure-controllable and adjustable covalent triazine-based material Download PDFInfo
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- CN114752068A CN114752068A CN202111639547.2A CN202111639547A CN114752068A CN 114752068 A CN114752068 A CN 114752068A CN 202111639547 A CN202111639547 A CN 202111639547A CN 114752068 A CN114752068 A CN 114752068A
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- C07D251/24—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to three ring carbon atoms
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Abstract
The invention discloses a preparation method of a covalent triazine-based material with a controllable and adjustable structure. In a glove box protected by inert gas, uniformly mixing a monomer and a catalyst, adding the mixture into a quartz tube, melting and sealing the quartz tube outside the glove box in a vacuum state, placing the sealed quartz tube in a muffle furnace for heating and reacting, opening the tube after the reaction is finished, collecting a product, and then sequentially grinding, washing and vacuum-drying the product to obtain the covalent triazine-based material powder. The method expands the synthetic method of the covalent triazine-based material, and has the characteristics of simple synthetic process, cheap and easily available raw materials and controllable material structure appearance; the prepared covalent triazine-based material is dispersed in a solvent after being washed, and a nanosheet dispersion liquid of the covalent triazine-based material can be obtained through centrifugation.
Description
Technical Field
The invention relates to a preparation method of a covalent triazine-based material, in particular to a preparation method of a covalent triazine-based material with a controllable and adjustable structure.
Background
Covalent triazine-based materials have received much attention in recent years due to their unique characteristics of good chemical and thermal stability, high porosity and high specific surface area. Due to its unique properties, covalent triazine-based materials are useful in gas adsorption and separation, energy storage, photocatalysis, and electricity Has wide application prospect in the aspects of catalysis and the like. However, to date, there are four methods of synthesizing covalent triazine-based materials: (1) cyano high-temperature ionothermal trimerization strategy, (2) superacid (trifluoromethanesulfonic acid, CH)3SO3H) Catalytic cyano strategy, (3) amidino polycondensation process, (4) phosphorus pentoxide (P)2O5) Catalytic formamide process. Thomas et al 2008 for the first time use zinc chloride (ZnCl)2) And aromatic nitriles as reactants, using method (1) to synthesize crystalline products, which has monomer scalability. However, zinc chloride (ZnCl) is used2) As a catalyst, trace metal zinc is remained in the product, which affects the application performance and is not friendly to the environment. Although the proposal of the method (2) solves the problem of metal residue, CH3SO3The strong corrosiveness and expensive price of H limit its industrial application. Method (3) involves a complicated monomer synthesis process, a long reaction time (60h) and a large solvent consumption. Method (4) uses phosphorus pentoxide (P)2O5) As a catalyst for catalyzing the direct synthesis crystallization of aromatic amide and has the highest surface area (2034.1 m)2g-1) The covalent triazine-based material of (a). The covalent triazine-based materials synthesized by the above 4 methods have a general disadvantage that the morphologies of the products are random blocks, which greatly limits the further processing and utilization of the materials, and it is our motivation to develop new synthetic routes to solve the defects of the above methods.
Disclosure of Invention
The method expands the synthetic method of the covalent triazine-based material, and has the characteristics of simple synthetic process, cheap and easily obtained raw materials and controllable material structure and appearance; the prepared covalent triazine-based material is dispersed in a solvent after being washed, and can be centrifuged to obtain a nanosheet dispersion liquid of the covalent triazine-based material (the system can directly generate the two-dimensional covalent triazine-based material in one step)
The technical scheme of the invention comprises the following implementation steps:
a preparation method of a covalent triazine-based material with a controllable and adjustable structure comprises the following steps:
the method comprises the following specific steps:
1) weighing a certain amount of monomer and a certain amount of catalyst, uniformly mixing, adding into a quartz tube, and sealing the tube opening;
2) heating a quartz tube to a proper temperature by a program, preserving the temperature for a period of time, and then automatically cooling to obtain a primary reactant;
3) then sequentially grinding, washing and vacuum drying the primary product to obtain a covalent triazine-based material;
4) after washing, the prepared covalent triazine-based material is directly ultrasonically dispersed in a solvent, and a nanosheet dispersion liquid of the covalent triazine-based material is obtained under a centrifugal condition.
The invention relates to a novel method for synthesizing covalent triazine-based materials, which utilizes different catalysts to obtain covalent triazine-based products with different morphologies, has controllable and adjustable structure and can be used in different fields.
In the step 1), the mass ratio of the monomer to the catalyst is 50-300 mg: 50-150 mg.
In the step 1), the monomer is one or more of 1, 4-terephthalaldehyde dioxime (BDO), 4-biphenyldicarboxaldehyde dioxime or 1,3, 5-trimesylaldehyde trioxime, or other aldoxime monomers converted from aldehyde micromolecules; the catalyst is one or more of anhydrous aluminum chloride, anhydrous zinc chloride, phosphorus pentoxide, trifluoromethanesulfonic acid, ferric chloride, copper chloride, chromium chloride, manganese chloride and magnesium chloride.
In the step 2), the temperature after temperature rise is 150-400 ℃, and the heat preservation time is 8-40 h.
In the step 3), the washing solvent is one or more of dilute hydrochloric acid, absolute ethyl alcohol, N-dimethylformamide and dichloromethane.
In the step 3), in the washing process, dilute hydrochloric acid, N-dimethylformamide and ethanol are respectively and sequentially washed, or a mixed solution of N, N-dimethylformamide and dilute hydrochloric acid and a mixed solution of ethanol and dilute hydrochloric acid are sequentially washed for multiple times and then replaced by absolute ethyl alcohol.
In the step 3), the drying temperature in the vacuum drying process is 50-150 ℃.
In the step 4), the dispersed solvent is one or more of polar solvents such as water, ethanol, N-dimethylformamide, tetrahydrofuran and the like.
In the step 4), the centrifugal rotating speed is 1000-12000rap/min, the centrifugal time is 10-60min, the transverse size is 50-5000nm, and the thickness is 0.8-100 nm. And under different centrifugal conditions, covalent triazine-based nanosheet material dispersions of different sizes and different thicknesses can be obtained.
In a glove box protected by inert gas, uniformly mixing a monomer and a catalyst, adding the mixture into a quartz tube, melting and sealing the quartz tube outside the glove box in a vacuum pumping state, placing the sealed quartz tube in a muffle furnace for heating and reacting, opening the tube after the reaction is finished, collecting a product, and then sequentially grinding, washing and vacuum-drying the product to obtain the covalent triazine-based material powder.
The invention has the beneficial effects that:
the method expands the synthetic method of the covalent triazine-based material, and has the characteristics of simple synthetic process, cheap and easily obtained raw materials and controllable material structure and appearance; the prepared covalent triazine-based material is dispersed in a solvent after being washed, and a nanosheet dispersion liquid of the covalent triazine-based material is obtained through centrifugation (nanosheets with different qualities are obtained under different centrifugation conditions, and the system can be directly used for generating the two-dimensional covalent triazine-based material in one step). The invention has the technical characteristics that:
(1) And (3) economy: the material cost is low, and the synthesis cost is low;
(2) safety: the material is non-toxic, pollution-free, sanitary, safe, green and low-carbon;
(3) low energy consumption: the two-dimensional nanosheet product can be directly obtained in one reaction in the catalysis of aluminum chloride;
(4) the structure is adjustable: the structure of the polymer can be adjusted, and different use requirements can be met.
(5) The product has the following appearance diversity: the morphology can be optimized and controlled by the type and content of the catalyst.
(6) Film forming property: the prepared covalent triazine-based nanosheet can be uniformly covered on a substrate to form a film, and the film thickness is controllable.
Drawings
FIG. 1 shows Fourier transform infrared spectra of materials obtained by trimerization of 1, 4-diphenyl dioxime to covalent triazine group catalyzed by different catalysts in examples 1, 2, 3 and 4;
FIG. 2 shows X-ray powder polycrystalline diffraction, N, of the covalently triazine-based material of example 12Adsorption curve graph and pore size distribution curve graph;
FIG. 3 shows the solid NMR spectrum of the covalently triazine-based material of example 5.
Detailed Description
The present invention is further described below in conjunction with the following embodiments and the accompanying drawings, it being understood that the description of the figures and the following embodiments are only illustrative of the present invention and are not limiting.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available or synthesized by themselves, unless otherwise specified.
The method expands the synthetic method of the covalent triazine-based material, and has the characteristics of simple synthetic process, cheap and easily available raw materials and controllable structure; the product obtained by catalysis of part of the catalyst is dispersed in a solvent after being washed, nanosheets with different qualities can be obtained under different centrifugal conditions (the system can directly generate the two-dimensional covalent triazine-based material in one step), and the nanosheets can be applied to the fields of membrane separation and filtration, battery metal protection and the like. The embodiments of the invention are as follows:
example 1
First, 1, 4-diphenyldioxime (50mg) as a monomer and anhydrous aluminum chloride (60mg) as a catalyst were charged into a 10mL quartz heat-resistant tube, vacuum-melted and sealed, and then transferred to a muffle furnace to be heated at 400 ℃ for 20 hours. And after the reaction is finished, cooling the sealed tube to normal temperature, opening the sealed tube, washing the sealed tube with a mixed solution of N, N-dimethylformamide and dilute hydrochloric acid and a mixed solution of ethanol and dilute hydrochloric acid for multiple times in sequence, finally replacing the washed tube with absolute ethanol, and performing vacuum drying at 80 ℃ for 12 hours to obtain the covalent triazine-based product.
The material was subjected to powder X-ray diffraction measurement as shown in FIG. 2 (a). Simultaneously Fourier transform infrared spectroscopy is carried out on the material The test results are shown in figure 1. Next, the specific surface area and porosity of the covalent triazine-based material were measured, and as shown in FIG. 2(b), the specific surface area of the covalent triazine-based material was 735m2The pore size distribution of the material is mainly about 1.1nm as shown in the attached figure 2 (c).
Example 2
Firstly, monomer 1, 4-diphenyl dioxime (50mg) and catalyst anhydrous zinc chloride (50mg) are mixed and added into a 10mL quartz heat-resistant tube, the tube is sealed by vacuum melting, and the tube is transferred to a muffle furnace after being sealed and heated for 20h at 350 ℃. After the reaction is finished, cooling the sealed tube to normal temperature, opening the sealed tube, washing the sealed tube with dilute hydrochloric acid, N, N-dimethylformamide and ethanol for multiple times respectively, and performing vacuum drying at 80 ℃ for 12 hours to obtain the covalent triazine-based product.
The product was characterized by infrared, as shown in FIG. 1, 3000cm-1The nearby hydroxyl group stretching vibration peak disappears at 1512cm-1、1352cm-1The peaks appearing nearby can be attributed to the stretching vibration of-C-N-and-C-N-indicating that anhydrous zinc chloride can promote the successful occurrence of the trimerization reaction of 1, 4-diphenyldioxime.
Example 3
Firstly, monomer 1, 4-diphenyl dioxime (200mg) and catalyst trifluoromethanesulfonic acid (120mg) were added into a 10mL quartz heat-resistant tube, vacuum-melted and sealed, frozen with liquid nitrogen for 10min before sealing, sealed and transferred to a muffle furnace, and heated at 220 ℃ for 12 h. After the reaction is finished, cooling the sealed tube to normal temperature, opening the sealed tube, washing the sealed tube with dilute hydrochloric acid, N, N-dimethylformamide and ethanol for multiple times respectively, and performing vacuum drying at 80 ℃ for 12 hours to obtain the covalent triazine-based product.
The product was characterized by infrared, as shown in FIG. 1, 3000cm-1The nearby hydroxyl group stretching vibration peak disappears, 1512cm-1、1352cm-1The peaks appearing nearby can be attributed to the stretching vibration of-C ═ N-and-C-N ═ indicating that trifluoromethanesulfonic acid can promote the successful occurrence of 1, 4-diphenyldioxime trimerization.
Example 4
First, a monomer, 1, 4-diphenyldioxime (50mg), and a catalyst, phosphorus pentoxide (50mg), were mixed and charged into a 10mL quartz heat-resistant tube, and the tube was sealed by vacuum fusion, and then transferred to a muffle furnace and heated at 400 ℃ for 20 hours. After the reaction is finished, cooling the sealed tube to normal temperature, opening the sealed tube, washing the sealed tube with dilute hydrochloric acid, N, N-dimethylformamide and ethanol for multiple times respectively, and performing vacuum drying at 80 ℃ for 12 hours to obtain the covalent triazine-based product.
The product was characterized by infrared, as shown in FIG. 1, 3000cm-1The nearby hydroxyl group stretching vibration peak disappears, 1512cm-1、1352cm-1The peaks appearing nearby can be attributed to stretching vibration of-C-N-and-C-N-indicating that phosphorus pentoxide can promote the successful occurrence of 1, 4-diphenyldioxime trimerization reaction.
Example 5
First, a monomer, 4-biphenyldicarboxaldehyde dioxime (50mg) and a catalyst, anhydrous aluminum chloride (50mg), were mixed and charged into a 10mL quartz heat-resistant tube, vacuum-sealed by melting, sealed and transferred to a muffle furnace, and heated at 380 ℃ for 20 hours. After the reaction is finished, cooling the sealed tube to normal temperature, opening the sealed tube, washing the sealed tube with dilute hydrochloric acid, N, N-dimethylformamide and ethanol for multiple times respectively, and performing vacuum drying at 80 ℃ for 12 hours to obtain the covalent triazine-based product.
The product was subjected to solid nuclear magnetic characterization, and as shown in fig. 3, the peak at 170ppm was attributed to nitrogen atoms on the triazine ring, indicating that aluminum chloride can catalyze the trimerization of 4, 4-biphenyldicarboxaldehyde dioxime to occur successfully.
Claims (9)
1. A method for preparing a covalent triazine-based material with controllable and adjustable structure is characterized in that:
the method comprises the following specific steps:
1) weighing a certain amount of monomer and a certain amount of catalyst, uniformly mixing, adding into a quartz tube, and sealing the tube opening;
2) heating the quartz tube to a proper temperature, preserving the temperature for a period of time, and then automatically cooling to obtain a primary reactant;
3) then sequentially grinding, washing and vacuum drying the primary product to obtain a covalent triazine-based material;
4) after washing, the prepared covalent triazine-based material is directly ultrasonically dispersed in a solvent, and a nanosheet dispersion liquid of the covalent triazine-based material is obtained under a centrifugal condition.
2. The preparation method of the covalent triazine-based material with the controllable and adjustable structure, which is characterized by comprising the following steps: in the step 1), the mass ratio of the monomer to the catalyst is 50-300 mg: 50-150 mg.
3. The preparation method of the covalent triazine-based material with the controllable and adjustable structure, which is characterized by comprising the following steps: in the step 1), the monomer is one or more of 1, 4-terephthalaldehyde dioxime (BDO), 4-biphenyldicarboxaldehyde dioxime or 1,3, 5-trimesylaldehyde trioxime; the catalyst is one or more of anhydrous aluminum chloride, anhydrous zinc chloride, phosphorus pentoxide, trifluoromethanesulfonic acid, ferric chloride, copper chloride, chromium chloride, manganese chloride and magnesium chloride.
4. The method for preparing the structure-controllable and adjustable covalent triazine-based material according to claim 1, characterized in that: in the step 2), the temperature after temperature rise is 150-400 ℃, and the heat preservation time is 8-40 h.
5. The method for preparing the structure-controllable and adjustable covalent triazine-based material according to claim 1, characterized in that: in the step 3), the washing solvent is one or more of dilute hydrochloric acid, absolute ethyl alcohol, N-dimethylformamide and dichloromethane.
6. The method for preparing the structure-controllable and adjustable covalent triazine-based material according to claim 1, characterized in that: in the step 3), the drying temperature in the vacuum drying process is 50-150 ℃.
7. The method for preparing the structure-controllable and adjustable covalent triazine-based material according to claim 1, characterized in that: in the step 4), the dispersed solvent is one or more of polar solvents such as water, ethanol, N-dimethylformamide, tetrahydrofuran and the like.
8. The preparation method of the covalent triazine-based material with the controllable and adjustable structure, which is characterized by comprising the following steps: in the step 4), the centrifugal rotation speed is 1000-12000rap/min, the centrifugal time is 10-60min, the transverse size is 50-5000nm, and the thickness is 0.8-100 nm.
9. A covalent triazine-based material characterized by: the covalent triazine-based material prepared by the method of any one of claims 1 to 8.
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| CN102153186A (en) * | 2011-05-11 | 2011-08-17 | 南京大学 | Application of porous covalent triazine polymer for removing aromatic compound from water |
| CN102976436A (en) * | 2012-12-14 | 2013-03-20 | 南京大学 | Method for removing disinfection by-product chloroacetic acid in water by adsorption of covalent triazine porous polymer material |
| CN105017529A (en) * | 2014-04-24 | 2015-11-04 | 中国科学院大连化学物理研究所 | Preparing method of multi-stage hole structure covalent triazine framework microporous polymers |
| CN110003468A (en) * | 2019-03-29 | 2019-07-12 | 华中科技大学 | A kind of covalent triazine framework polymer, preparation method and application |
| CN110628038A (en) * | 2019-09-19 | 2019-12-31 | 中国科学院上海高等研究院 | Covalent triazine organic framework, limited-area metal catalyst, preparation method and application |
| CN113663728A (en) * | 2021-08-11 | 2021-11-19 | 西湖大学 | Preparation method and application of covalent triazine-based nanosheet with wide visible light response |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153186A (en) * | 2011-05-11 | 2011-08-17 | 南京大学 | Application of porous covalent triazine polymer for removing aromatic compound from water |
| CN102976436A (en) * | 2012-12-14 | 2013-03-20 | 南京大学 | Method for removing disinfection by-product chloroacetic acid in water by adsorption of covalent triazine porous polymer material |
| CN105017529A (en) * | 2014-04-24 | 2015-11-04 | 中国科学院大连化学物理研究所 | Preparing method of multi-stage hole structure covalent triazine framework microporous polymers |
| CN110003468A (en) * | 2019-03-29 | 2019-07-12 | 华中科技大学 | A kind of covalent triazine framework polymer, preparation method and application |
| CN110628038A (en) * | 2019-09-19 | 2019-12-31 | 中国科学院上海高等研究院 | Covalent triazine organic framework, limited-area metal catalyst, preparation method and application |
| CN113663728A (en) * | 2021-08-11 | 2021-11-19 | 西湖大学 | Preparation method and application of covalent triazine-based nanosheet with wide visible light response |
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