阅读说明：本技术 低温快速制备二维共价有机框架材料的方法及二维共价有机框架材料 (Method for rapidly preparing two-dimensional covalent organic framework material at low temperature and two-dimensional covalent organic framework material ) 是由 孙兵 冯甜甜 于 2020-08-03 设计创作，主要内容包括：本发明涉及有机材料制备技术领域,尤其是一种低温快速制备二维共价有机框架材料的方法及二维共价有机框架材料。该材料由芳香胺与芳香醛在0℃-室温下反应得到；其中,所述芳香胺为1,4-苯二胺、1,4-联苯二胺、4,4’,4”-(1,3,5-三嗪-2,4,6-三基)三苯胺、1,3,5-三(4-氨苯基)苯、三(4-氨基苯基)胺、四(4-氨基苯基)卟啉、四(4-氨基苯基)甲烷和四(4-氨基苯基)乙烯中的一种或多种；所述芳香醛为含有吡啶、吩嗪结构的芳香醛,3,3’-联吡啶-6,6’-二甲醛、2,2’-联吡啶-5,5’-二甲醛,5,5’,5”-(苯基-1,3,5-三基)三吡啶醛,6,6’,6”-(苯基-1,3,5-三基)三吡啶醛,2,5-二甲酰基吩嗪中的一种或多种；所述芳香胺与所述芳香醛的摩尔比为(0.1–10):1。(The invention relates to the technical field of organic material preparation, in particular to a method for quickly preparing a two-dimensional covalent organic framework material at a low temperature and the two-dimensional covalent organic framework material. The material is obtained by the reaction of aromatic amine and aromatic aldehyde at 0-room temperature; wherein the aromatic amine is one or more of 1, 4-phenylenediamine, 1, 4-biphenyldiamine, 4' - (1,3,5-triazine-2,4,6-triyl) triphenylamine, 1,3,5-tris (4-aminophenyl) benzene, tris (4-aminophenyl) amine, tetrakis (4-aminophenyl) porphyrin, tetrakis (4-aminophenyl) methane and tetrakis (4-aminophenyl) ethylene; the aromatic aldehyde is one or more of aromatic aldehyde containing pyridine and phenazine structures, 3,3 '-bipyridine-6, 6' -dicarboxaldehyde, 2 '-bipyridine-5, 5' -dicarboxaldehyde, 5,5'- (phenyl-1, 3, 5-triyl) tripyridal aldehyde, 6,6' - (phenyl-1, 3, 5-triyl) tripyridal aldehyde and 2, 5-diformylphenoyl phenazine; the molar ratio of the aromatic amine to the aromatic aldehyde is (0.1-10): 1.)

1. A two-dimensional covalent organic framework material is characterized in that the material is obtained by the reaction of aromatic amine and aromatic aldehyde at 0-room temperature; wherein the content of the first and second substances,

the aromatic amine is one or more of the following compounds:

1, 4-phenylenediamine, 1, 4-biphenyldiamine, 4',4 "- (1,3,5-triazine-2,4,6-triyl) triphenylamine, 1,3,5-tris (4-aminophenyl) benzene, tris (4-aminophenyl) amine, tetrakis (4-aminophenyl) porphyrin, tetrakis (4-aminophenyl) methane, and tetrakis (4-aminophenyl) ethylene;

the aromatic aldehyde is one or more of the following compounds:

aromatic aldehyde containing pyridine and phenazine structures, 3,3 '-bipyridine-6, 6' -dicarboxaldehyde, 2 '-bipyridine-5, 5' -dicarboxaldehyde, 5,5'- (phenyl-1, 3, 5-triyl) tripyridinal, 6,6' - (phenyl-1, 3, 5-triyl) tripyridinal, and 2, 5-diformylphenoyl phenazine;

the molar ratio of the aromatic amine to the aromatic aldehyde is (0.1-10): 1.

2. The two-dimensional covalent organic framework material of claim 1, wherein the two-dimensional covalent organic framework material comprises a structure according to formula i:

3. the two-dimensional covalent organic framework material of claim 1, wherein the two-dimensional covalent organic framework material comprises a structure according to formula ii:

4. the two-dimensional covalent organic framework material of claim 1, comprising a structure according to formula iii:

5. a method of preparing a two-dimensional covalent organic framework material according to any of the claims 1 to 4, comprising the steps of:

(1) sequentially adding aromatic amine, aromatic aldehyde and an acid catalyst into a reaction solvent to obtain a mixed reaction solution; wherein the molar ratio of the aromatic amine to the aromatic aldehyde is (0.1-10) to 1; the aromatic amine is one or more of 1, 4-phenylenediamine, 1, 4-biphenyldiamine, 4' - (1,3,5-triazine-2,4,6-triyl) triphenylamine, 1,3,5-tris (4-aminophenyl) benzene, tris (4-aminophenyl) amine, tetrakis (4-aminophenyl) porphyrin, tetrakis (4-aminophenyl) methane and tetrakis (4-aminophenyl) ethylene; the aromatic aldehyde is one or more of aromatic aldehyde containing pyridine and phenazine structures, 3,3 '-bipyridine-6, 6' -dicarboxaldehyde, 2 '-bipyridine-5, 5' -dicarboxaldehyde, 5,5'- (phenyl-1, 3, 5-triyl) tripyridal aldehyde, 6,6' - (phenyl-1, 3, 5-triyl) tripyridal aldehyde and 2, 5-diformylphenoyl phenazine; the reaction solvent is a mixed solution of dioxane and mesitylene;

(2) sealing the reaction container in which the mixed reaction liquid is located; wherein the sealing is performed at normal temperature and normal pressure, or the sealing is performed in vacuum after the liquid nitrogen is frozen;

(3) and placing the sealed mixed reaction solution in an environment of 0-room temperature for reacting for 1-60 minutes to prepare the two-dimensional covalent organic framework material.

6. The method according to claim 5, wherein the volume ratio of dioxane to mesitylene in the reaction solvent is (1-9): 1.

7. The process according to claim 5, characterized in that the acidic catalyst consists of acetic acid and a Lewis acid; wherein the content of the first and second substances,

in the mixed reaction liquid, the volume ratio of the acetic acid solution with the concentration of 6mol/L to the reaction solvent is (0.01-1.5): 1;

in the mixed reaction liquid, the molar ratio of the Lewis acid catalyst to the aromatic amine is (0.1-10): 1.

8. The method according to claim 7, wherein the volume ratio of the acetic acid solution having a concentration of 6mol/L to the reaction solvent in the mixed reaction solution is (0.2-0.8): 1;

in the mixed reaction liquid, the molar ratio of the Lewis acid catalyst to the aromatic amine is (0.2-5) to 1;

in the mixed reaction liquid, the molar ratio of the aromatic amine to the aromatic aldehyde is (0.5-5): 1.

9. The process according to claim 8, wherein the volume ratio of dioxane to mesitylene in the reaction solvent is 4: 1;

in the mixed reaction liquid, the molar ratio of aromatic amine to aromatic aldehyde is 2: 3;

the aromatic amine is 4,4' - (1,3,5-triazine-2,4,6-triyl) triphenylamine, and the aromatic aldehyde is 3,3' -bipyridyl-6, 6' -dicarboxaldehyde; or the aromatic amine is 1,3,5-tri (4-aminophenyl) benzene, and the aromatic aldehyde is 3,3 '-bipyridyl-6, 6' -dicarboxaldehyde; or the aromatic amine is 4,4' - (1,3,5-triazine-2,4,6-triyl) triphenylamine, and the aromatic aldehyde is 2, 5-diformylphenoxazine.

10. The method of claim 7, wherein the Lewis acid is one or more of copper triflate, cuprous triflate, ferrous triflate, zinc triflate, calcium triflate, ferrous tetrafluoroborate, and zinc tetrafluoroborate.

Technical Field

The invention relates to the technical field of organic material preparation, in particular to a method for quickly preparing a two-dimensional covalent organic framework material at a low temperature and the two-dimensional covalent organic framework material.

Background

Two-dimensional Covalent Organic Framework (COF) materials are a class of materials formed by linking organic monomer molecules in the form of covalent bonds, and have a certain topology and high crystallinity. Due to the diversity and designability of the organic molecular structure, the design and selection of organic monomer molecules can realize the regulation and synthesis of the two-dimensional covalent organic framework material with rich topological structure, adjustable pore structure, modifiable pore channel and diversified functionality. Compared with a molecular assembly system, the two-dimensional covalent organic framework material connected by the covalent bond has good chemical stability and thermal stability. Compared with inorganic porous materials or metal organic frameworks and other materials, the two-dimensional covalent organic framework material has the characteristics of light weight, small density, high specific surface area and the like. Compared with polymer materials, the two-dimensional covalent organic framework material has higher crystallinity and an ordered long-range stacking structure. In addition, the two-dimensional covalent organic framework material constructed based on the conjugated organic molecules or the conjugated connecting units can also show higher carrier mobility, excellent photoelectrochemistry and optoelectronics performances and quick electron or ion transmission property. Therefore, the two-dimensional covalent organic framework material has wide application prospects in the fields of gas adsorption and separation, pollutant treatment, fluorescence detection, drug loading and transportation, ion transmission, photoelectrocatalysis, heterogeneous catalysis, energy storage, photoelectronic devices and the like.

The most common preparation method for the two-dimensional covalent organic framework material at present is a solvothermal method, and in addition, a microwave-assisted synthesis method, a thermal reflux synthesis method, an ionothermal synthesis method, an interface-assisted synthesis method, a mechanical synthesis method and the like are also available. These processes generally require relatively high reaction temperatures (. gtoreq.90 ℃), relatively long reaction times (varying from hours to days) or complicated operating procedures. Therefore, a method for preparing a two-dimensional covalent organic framework material with mild reaction conditions and high preparation efficiency is needed.

Disclosure of Invention

The embodiment of the invention provides a method for quickly preparing a two-dimensional covalent organic framework material at a low temperature and the two-dimensional covalent organic framework material. The method has the characteristics of simple operation, mild reaction conditions, high synthesis speed and high preparation efficiency.

In a first aspect, the embodiments of the present invention provide a two-dimensional covalent organic framework material, which is obtained by reacting aromatic amine with aromatic aldehyde at 0 ℃ to room temperature; wherein the content of the first and second substances,

the aromatic amine is one or more of the following compounds:

1, 4-phenylenediamine, 1, 4-biphenyldiamine, 4',4 "- (1,3,5-triazine-2,4,6-triyl) triphenylamine, 1,3,5-tris (4-aminophenyl) benzene, tris (4-aminophenyl) amine, tetrakis (4-aminophenyl) porphyrin, tetrakis (4-aminophenyl) methane, and tetrakis (4-aminophenyl) ethylene;

the aromatic aldehyde is one or more of the following compounds:

aromatic aldehyde containing pyridine and phenazine structures, 3,3 '-bipyridine-6, 6' -dicarboxaldehyde, 2 '-bipyridine-5, 5' -dicarboxaldehyde, 5,5'- (phenyl-1, 3, 5-triyl) tripyridinal, 6,6' - (phenyl-1, 3, 5-triyl) tripyridinal, and 2, 5-diformylphenoyl phenazine;

the molar ratio of the aromatic amine to the aromatic aldehyde is (0.1-10): 1.

In one embodiment, the two-dimensional covalent organic framework material comprises a structure according to formula i:

in one embodiment, the two-dimensional covalent organic framework material comprises a structure according to formula ii:

in one embodiment, the two-dimensional covalent organic framework material comprises a structure according to formula iii:

in a second aspect, embodiments of the present invention provide a method for preparing the two-dimensional covalent organic framework material of the first aspect, comprising the steps of:

(1) sequentially adding aromatic amine, aromatic aldehyde and an acid catalyst into a reaction solvent to obtain a mixed reaction solution; wherein the molar ratio of the aromatic amine to the aromatic aldehyde is (0.1-10) to 1; the aromatic amine is one or more of 1, 4-phenylenediamine, 1, 4-biphenyldiamine, 4' - (1,3,5-triazine-2,4,6-triyl) triphenylamine, 1,3,5-tris (4-aminophenyl) benzene, tris (4-aminophenyl) amine, tetrakis (4-aminophenyl) porphyrin, tetrakis (4-aminophenyl) methane and tetrakis (4-aminophenyl) ethylene; the aromatic aldehyde is one or more of aromatic aldehyde containing pyridine and phenazine structures, 3,3 '-bipyridine-6, 6' -dicarboxaldehyde, 2 '-bipyridine-5, 5' -dicarboxaldehyde, 5,5'- (phenyl-1, 3, 5-triyl) tripyridal aldehyde, 6,6' - (phenyl-1, 3, 5-triyl) tripyridal aldehyde and 2, 5-diformylphenoyl phenazine; the reaction solvent is a mixed solution of dioxane and mesitylene;

(2) sealing the reaction container in which the mixed reaction liquid is located; wherein the sealing is performed at normal temperature and normal pressure, or the sealing is performed in vacuum after the liquid nitrogen is frozen;

(3) and placing the sealed mixed reaction solution in an environment of 0-room temperature for reacting for 1-60 minutes to prepare the two-dimensional covalent organic framework material.

In one embodiment, the volume ratio of dioxane to mesitylene in the reaction solvent is (1-9): 1.

In one embodiment, the acidic catalyst consists of acetic acid and a lewis acid; wherein the content of the first and second substances,

in the mixed reaction liquid, the volume ratio of the acetic acid solution with the concentration of 6mol/L to the reaction solvent is (0.01-1.5): 1;

in the mixed reaction liquid, the molar ratio of the Lewis acid catalyst to the aromatic amine is (0.1-10): 1.

In one embodiment, the volume ratio of the acetic acid solution with the concentration of 6mol/L to the reaction solvent in the mixed reaction liquid is (0.2-0.8): 1;

in the mixed reaction liquid, the molar ratio of the Lewis acid catalyst to the aromatic amine is (0.2-5) to 1;

in the mixed reaction liquid, the molar ratio of the aromatic amine to the aromatic aldehyde is (0.5-5): 1.

In one embodiment, the volume ratio of dioxane to mesitylene in the reaction solvent is 4: 1;

in the mixed reaction liquid, the molar ratio of aromatic amine to aromatic aldehyde is 2: 3;

the aromatic amine is 4,4' - (1,3,5-triazine-2,4,6-triyl) triphenylamine, and the aromatic aldehyde is 3,3' -bipyridyl-6, 6' -dicarboxaldehyde; or the aromatic amine is 1,3,5-tri (4-aminophenyl) benzene, and the aromatic aldehyde is 3,3 '-bipyridyl-6, 6' -dicarboxaldehyde; or the aromatic amine is 4,4' - (1,3,5-triazine-2,4,6-triyl) triphenylamine, and the aromatic aldehyde is 2, 5-diformylphenoxazine.

In one embodiment, the lewis acid is one or more of copper triflate, cuprous triflate, ferrous triflate, zinc triflate, calcium triflate, ferrous tetrafluoroborate, zinc tetrafluoroborate.

The scheme of the embodiment of the invention at least has the following beneficial effects:

1, a high-crystallinity two-dimensional covalent organic framework material can be rapidly prepared at room temperature and lower temperature;

2, the method is simple to operate, mild in reaction condition, high in synthesis speed and high in preparation efficiency, and the two-dimensional covalent organic framework material can be rapidly prepared within minutes.

Drawings

FIG. 1a is a powder X-ray diffraction pattern of a two-dimensional covalent organic framework material prepared in example 1 of the present invention;

FIG. 1b is a Fourier transform infrared spectrum of a two-dimensional covalent organic framework material prepared in example 1 of the present invention;

FIG. 2a is a powder X-ray diffraction pattern of a two-dimensional covalent organic framework material prepared in example 2 of the present invention;

FIG. 2b is a Fourier transform infrared spectrum of a two-dimensional covalent organic framework material prepared in example 2 of the present invention;

FIG. 3a is a powder X-ray diffraction pattern of a two-dimensional covalent organic framework material prepared in example 3 of the present invention;

FIG. 3b is a Fourier transform infrared spectrum of a two-dimensional covalent organic framework material prepared in example 3 of the present invention.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present 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.