CN108794743B

CN108794743B - Preparation method of large-aperture organic covalent framework material

Info

Publication number: CN108794743B
Application number: CN201810782775.7A
Authority: CN
Inventors: 苗中正
Original assignee: Yancheng Teachers University
Current assignee: Hubei Chibi Jiji Industrial Technology Research Institute Co ltd
Priority date: 2018-07-07
Filing date: 2018-07-07
Publication date: 2021-02-19
Anticipated expiration: 2038-07-07
Also published as: CN108794743A

Abstract

The invention provides a preparation method of a large-aperture organic covalent framework material. A cuprous chloride catalyst with a nano scale is prepared by a solvothermal method, 1, 3, 5-tri [ 4-amino (1, 1-biphenyl-4-yl) ] benzene and benzidine are selected as monomer molecules, and an amino coupling reaction is carried out under the catalysis of cuprous chloride nanocrystals to prepare the organic polymer. The method disclosed by the invention can be carried out at room temperature, the reaction condition is mild, the method has the characteristics of simple preparation, low cost and easiness in industrial batch production, and the prepared polymer has large pore diameter and higher chemical stability and thermal stability and can be applied to many fields of composite electrode materials, organic dyes, biomedicines and the like.

Description

Preparation method of large-aperture organic covalent framework material

Technical Field

The invention belongs to the field of preparation of organic covalent framework materials, and particularly relates to a preparation method of a large-aperture organic covalent framework material.

Background

The covalent organic framework material is a polymer with periodicity and crystallinity, is connected by light elements through covalent bonds, has lower density, high thermal stability and inherent porosity, and has the advantages of intrinsic flexibility, low cost, light weight and the like. The covalent organic framework material has important application value and wide market prospect in the research fields of gas adsorption, heterogeneous catalysis, energy storage and the like, and has attracted strong research interest in the scientific community.

Covalent organic framework materials have tailorable properties. However, the preparation of covalent organic framework materials so far has been limited to readily accessible chemical reactions, involving very limited types of reactions, limiting the development of new structures and new materials. With the development of two-dimensional organic polymer materials, more requirements are put forward on the types and functions of synthetic polymers, and the development of novel two-dimensional organic polymers is urgently needed to meet various actual requirements. The pore size has great influence on the gas adsorption, proton conduction, photoelectric property, reaction yield, uniformity and electrochemical performance of the related composite material, and the preparation of the covalent organic framework material with large pore size has important practical significance.

Disclosure of Invention

A process for preparing the macroreticular organic covalent frame material is disclosed. The invention adopts the following technical scheme:

a preparation method of a large-aperture organic covalent framework material comprises the following steps:

(1) putting copper chloride powder into a high-pressure reaction kettle, adding ethanol, mixing uniformly, reacting at a certain temperature for a period of time, cooling to room temperature, carrying out vacuum filtration under reduced pressure, and drying in vacuum to obtain a cuprous chloride catalyst with a nano scale;

(2) dispersing 1, 3, 5-tri [ 4-amino (1, 1-biphenyl-4-yl) ] benzene (TABPB), benzidine and cuprous chloride nanocrystals into solvents such as acetonitrile, selecting the reaction temperature as room temperature, stirring continuously in the reaction process, washing by ammonia water, and drying to obtain the ultra-large-aperture organic covalent framework material.

In the step (1), the reaction is carried out at a certain temperature for a certain time, wherein the temperature is preferably 160 ℃, and the time is preferably 24 hours.

The size of the cuprous chloride catalyst in the step (1) is 2-10 nm.

The mass ratio of the 1, 3, 5-tri [ 4-amino (1, 1-biphenyl-4-yl) ] benzene, the benzidine and the cuprous chloride nanocrystals in the step (2) is preferably 0.6: 0.2.

The duration of the reaction process in the step (2) is 6-48 h, and the preferable time is 10 h.

The solvent used in step (2) is an organic solvent such as acetonitrile, N-dimethylformamide and dimethyl sulfoxide, and the preferred solvent is acetonitrile.

The invention has the following advantages:

(1) the temperature required by the selected amino coupling reaction is room temperature, the reaction condition is mild, and the method has the characteristics of simple preparation, low cost and easy industrialized mass production.

(2) The polymer prepared by the invention has large pore diameter, higher chemical stability and thermal stability, and can be applied to a plurality of fields such as composite electrode materials, organic dyes, biological medicines and the like.

Drawings

FIG. 1 is a schematic diagram of the reaction process and structure of a large-aperture organic covalent framework material prepared by the method of the present invention.

FIG. 2 is a transmission electron micrograph of a large-aperture organic covalent framework material prepared by the method of the present invention.

Detailed Description

For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the purpose of facilitating understanding of the present invention and should not be construed as specifically limiting the present invention.

Example 1

(1) 0.8524g of copper chloride dihydrate are weighed and placed in a high-pressure reaction kettle with a volume of 50mL and a polytetrafluoroethylene lining, 25mL of ethanol is added, the mixture is uniformly mixed, and the kettle cover is tightly covered.

(2) The autoclave was placed in a muffle furnace and reacted at 160 ℃ for 24 h. Cooling to room temperature, vacuum filtering, and vacuum drying at 50 deg.c for 12 hr. And (3) storing in the shade under the nitrogen protection atmosphere to obtain the cuprous chloride nanocrystal with the particle size of 2-10 nm.

(3) 10mg of cuprous chloride crystal powder, 10mg of benzidine and 30mg of 1, 3, 5-tris [ 4-amino (1, 1-biphenyl-4-yl) ] benzene were dissolved in 5.0mL of acetonitrile and stirred at room temperature for 10 hours.

(4) The reaction mixture was taken out, washed with 25% ammonia, water and acetone, dried and stored.

FIG. 1 contains a schematic representation of the reaction process and structure of the large pore size organic covalent framework material prepared in this example.

FIG. 2 contains a transmission electron micrograph of the large pore size organic covalent framework material prepared in this example.

Example 2

(3) 20mg of cuprous chloride crystal powder, 10mg of benzidine and 30mg of 1, 3, 5-tris [ 4-amino (1, 1-biphenyl-4-yl) ] benzene were dissolved in 5.0mL of acetonitrile and stirred at room temperature for 10 hours.

Example 3

(3) 10mg of cuprous chloride crystal powder, 10mg of benzidine and 30mg of 1, 3, 5-tris [ 4-amino (1, 1-biphenyl-4-yl) ] benzene were dissolved in 5.0mL of acetonitrile and stirred at room temperature for 48 hours.

Example 4

(3) 10mg of cuprous chloride crystal powder, 15mg of benzidine and 30mg of 1, 3, 5-tris [ 4-amino (1, 1-biphenyl-4-yl) ] benzene were dissolved in 5.0mL of acetonitrile and stirred at room temperature for 10 hours.

The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims

1. A preparation method of a large-aperture organic covalent framework material comprises the following steps:

(1) putting copper chloride powder into a high-pressure reaction kettle, adding ethanol, uniformly mixing, heating, cooling to room temperature, carrying out vacuum filtration, and carrying out vacuum drying to obtain a cuprous chloride catalyst with a nanoscale, wherein the size of the cuprous chloride catalyst is 2-10 nm;

(2) dispersing 1, 3, 5-tri [ 4-amino (1, 1-biphenyl-4-yl) ] benzene, benzidine and cuprous chloride nanocrystals into an acetonitrile solvent, selecting the reaction temperature as room temperature, stirring continuously in the reaction process, washing with ammonia water, and drying to obtain the ultra-large-aperture organic covalent framework material.

2. The method according to claim 1, wherein the heating treatment in the step (1) is carried out at 160 ℃ for 24 hours.

3. The method according to claim 1, wherein the mass ratio of 1, 3, 5-tris [ 4-amino (1, 1-biphenyl-4-yl) ] benzene, benzidine and cuprous chloride nanocrystals in step (2) is 0.6: 0.2.

4. The method according to claim 1, wherein the duration of the reaction process in the step (2) is 6 to 48 hours.