Method for preparing and repairing covalent organic framework materials

Patent metadata

Field	Value
Publication number	US-12071503-B2
Application number	US-201817292485-A
Country	US
Kind code	B2
Filing date	Nov 19, 2018
Priority date	Nov 19, 2018
Publication date	Aug 27, 2024
Grant date	Aug 27, 2024

Abstract

The present invention relates to a method for preparing a covalent organic framework (COF) materials—a reversible polycondensation/termination method, the COF materials prepared by the method have high crystallinity, high specific surface area, regular and controllable morphology. The present invention also relates to a method for repairing defects of COF materials—reversible degradation-recombination, the method can eliminate defects of existing COF materials, thereby increasing the crystallinity and specific surface area of COF materials and improving their morphological characteristics.

First claim

The invention claimed is:

1. A method for preparing a covalent organic framework (COF) material by reversible polycondensation-termination (RPT) method, comprising the steps:
dissolving a monomer A in solvent 1, adding a control agent AP, and optionally adding a catalyst CA to obtain a solution A;
dissolving a monomer B in solvent 2, adding a control agent BP, and optionally adding a catalyst CB to obtain a solution B;
mixing the solution A and the solution B to obtain a mixed solution, and allowing the mixed solution to react; and
after the completion of the reaction, separating obtained precipitate and drying it to obtain a COF material;
wherein the control agent AP is selected from the group consisting of monoaldehydes and derivatives thereof, monoboric acids and derivatives thereof, catechol, and 2,3-dihydroxyl naphthalene;
the control BP is selected from the group consisting of monoamines and derivatives thereof, monohydrazides and derivatives thereof, and monoboronic acids and derivatives thereof.

2. The method according to claim 1 , wherein the monomer A is selected from the group consisting of aromatic amines and derivatives thereof, aromatic hydrazides and derivatives thereof, and aromatic boronic acids and derivatives thereof; the monomer B is selected from the group consisting of aromatic aldehydes and derivatives thereof, aromatic boronic acids and derivatives thereof, and phenols and derivatives thereof.

3. The method according to claim 1 , wherein the control agent AP is selected from the group consisting of benzaldehyde, 2-chlorobenzaldehyde, 3-chlorobenzaldehyde, 4-chlorobenzaldehyde, 2-nitrobenzaldehyde, 3-nitrobenzaldehyde, 4-nitrobenzaldehyde, 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenzaldehyde, 4-tert-butylbenzaldehyde, 4-fluorobenzaldehyde, 1-naphthaldehyde, 2-naphthaldehyde, formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, hexanal, heptaldehyde, caprylic aldehyde, phenylboronic acid, 4-tert-butylbenzeneboronic acid, n-propylboronic acid, cyclohexylboronic acid, catechol, 2,3-dihydroxyl naphthalene, and combinations thereof; the control agent BP is selected from the group consisting of aniline, 2-chloroaniline, 3-chloroaniline, 4-chloroaniline, 1,3-benzothiazole-5-amine, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-tert-butylaniline, 4-fluoroaniline, 1-naphthylamine, 2-naphthylamine, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, cyclohexylamine, phenylboronic acid, 4-tert-butylphenylboronic acid, n-propylboronic acid, cyclohexylboronic acid, benzoylhydrazide, 4-chlorobenzoyl hydrazide, nicotinohydrazide, formic acid hydrazide, acetic acid hydrazide, propionic acid hydrazide, cyclohexanoic hydrazide, and combinations thereof.

4. The method according to claim 3 , wherein the control agent AP is selected from the group consisting of benzaldehyde, 4-tert-butylbenzaldehyde, butyraldehyde, phenylboronic acid, catechol, and combinations thereof, the control agent BP is selected from the group consisting of aniline, 4-tert-butylaniline, butylamine, phenylboronic acid, benzoylhydrazide, and combinations thereof.

5. The method according to claim 1 , wherein the concentration of monomer A in the solution A and the concentration of monomer B in the solution B are 0.01-100 mM, respectively.

6. The method according to claim 1 , wherein the molar ratio of the control agent AP to the monomer A and the molar ratio of the control agent BP to the monomer B are 0.01-200:1, respectively; the molar ratio of monomer A to monomer B is 0.05-20:1.

7. The method according to claim 6 , wherein the molar ratio of the control agent AP to the monomer A and the molar ratio of the control agent BP to the monomer B are 0.1-100:1, respectively.

8. The method according to claim 7 , wherein the molar ratio of the control agent AP to the monomer A and the molar ratio of the control agent BP to the monomer B are 0.5-50:1, respectively.

Assignees

• Univ Zhejiang

Inventors

• Wang Wenjun
• Wang Song
• Liu Pingwei
• Li Bogeng

Classifications

• C08G12/30

  with substituted triazines · CPC title

• C08G12/08 Primary

  aromatic · CPC title

• C08G12/06 Primary

  Amines · CPC title