CN-117511532-B - Photochromic material introduced with HOFs framework material and preparation method and application thereof

Abstract

The invention discloses a photochromic material introduced with HOFs framework materials, a preparation method and application thereof, belonging to the technical field of organic solid photochromic materials, wherein a host-guest eutectic method is utilized to load a HOFs framework material with photochromic molecules. The invention also discloses the photochromic material prepared by the preparation method, and simultaneously discloses the application of the photochromic material in the field of information storage encryption and the application of the photochromic material in the field of anti-counterfeiting. The invention realizes photochromic, has faster light response rate compared with physical adsorption method, has better photochromic performance, has better development prospect in the anti-counterfeiting field, and has excellent information storage encryption function.

Inventors

• YANG YUHUI
• GAO YANGYANG
• WEI YOUHAO
• Wu Conghao
• CAI HAITAO

Assignees

• 浙江理工大学

Dates

Publication Date

20260505

Application Date

20231129

Claims (8)

1. 1. A preparation method of a photochromic material introduced into HOFs framework materials is characterized in that a host-guest eutectic method is utilized to load HOFs framework materials with photochromic molecules, and the preparation method specifically comprises the following steps: uniformly mixing a ligand of HOFs framework material and photochromic molecules through a liquid auxiliary grinding method to obtain eutectic powder, dissolving the eutectic powder into an organic solvent, and standing for one week under a dark condition to obtain the photochromic material; The ligand comprises 2,4, 6-tris (4-carboxyphenyl) -1,3, 5-triazine or biphenyl-3, 3', 5' -tetrakis- (phenyl-4-carboxylic acid).
2. 2. A method of preparing a photochromic material incorporating a HOFs framework material according to claim 1 wherein the molar ratio of ligand to photochromic molecule is 1:1.
3. 3. A method of preparing a photochromic material comprising a HOFs framework material according to claim 1 wherein the photochromic molecules comprise methyl spiropyran, carboxyl spiropyran and hydroxyl spiropyran.
4. 4. The method for preparing a photochromic material comprising HOFs framework materials according to claim 1, wherein the organic solvent is a mixed solution of dichloromethane and ethanol; The volume ratio of the dichloromethane to the methanol is (20-40) to (3-6).
5. 5. The method of claim 1, wherein the mass to volume ratio of the eutectic powder to the organic solvent is 20-40 mg/23-46 mL.
6. 6. A photochromic material prepared by a process for preparing a photochromic material incorporating HOFs framework material as set out in any one of claims 1 to 5.
7. 7. Use of a photochromic material incorporating HOFs framework material as set forth in claim 6 in the field of information storage encryption.
8. 8. Use of a photochromic material incorporating HOFs framework material as claimed in claim 6 in the field of security.

Description

Photochromic material introduced with HOFs framework material and preparation method and application thereof Technical Field The invention belongs to the technical field of organic solid photochromic materials, and particularly relates to a photochromic material with HOFs framework materials introduced, a preparation method and application thereof. Background The hydrogen bond organic framework (HOFs) is a novel porous crystalline material and is assembled by organic or metal organic building units through intermolecular hydrogen bonding. It is used in gas adsorption and separation, proton conduction, heterogeneous catalysis, fluorescence and sensing, biological application, enantiomer resolution, aromatic compound separation, environment pollutant elimination and organic structure measurement. The spiropyran compound is a photochromic molecule, and the current research shows that the spiropyran molecule in solid state is difficult to generate photochromism, and the main reason is that in solid state, spiropyran is closely piled, and has insufficient space volume to cause the spiropyran to generate the process of ring opening-ring closing isomerization, so that the spiropyran compound has poor color changing performance under the irradiation of ultraviolet light, and the application prospect in the fields of information storage and anti-counterfeiting is greatly limited. Therefore, how to provide a method for combining HOFs framework material and spiropyran compound and applying the same to photochromic material is an important technical problem to be solved by researchers in the field in anti-counterfeiting and information storage encryption. Disclosure of Invention In order to solve the technical problems, the invention provides a photochromic material with HOFs frame materials, and a preparation method and application thereof. In order to achieve the above purpose, the present invention provides the following technical solutions: A preparation method of a photochromic material introduced HOFs framework material uses a host-guest eutectic method to load a HOFs framework material with photochromic molecules. Preferably, the method specifically comprises the following steps: and uniformly mixing the ligand of HOFs framework material and the photochromic molecules through a liquid auxiliary grinding method to obtain eutectic powder, dissolving the eutectic powder into an organic solvent, and standing for one week under the dark condition to obtain the photochromic material. Preferably, the molar mass ratio of the ligand to the photochromic molecule is 1:1. Preferably, the ligand comprises 2,4, 6-tris (4-carboxyphenyl) -1,3, 5-triazine (H 3 TATB) or biphenyl-3, 3', 5' -tetrakis- (phenyl-4-carboxylic acid) (H 4 TCBP). Preferably, the photochromic molecules include methyl spiropyran (SP-CH 3), carboxyl spiropyran (SP-COOH) and hydroxyl spiropyran (SP-OH). More preferably, the photochromic molecule is methyl spiropyran (SP-CH 3). Preferably, the milling time is 15 minutes. Preferably, the organic solvent is a mixed solution of dichloromethane and ethanol; The volume ratio of the dichloromethane to the methanol is 20-40mL:3-6mL. Preferably, the mass volume ratio of the eutectic powder to the organic solvent is 20-40 mg/23-46 mL. A photochromic material prepared by a preparation method of a photochromic material introduced HOFs framework material. Use of a photochromic material incorporating HOFs framework material in the field of information storage encryption. Use of a photochromic material incorporating HOFs framework material in the field of security. Compared with the prior art, the invention has the following advantages and technical effects: According to the invention, the main guest eutectic crystal is grown in the mixed solution of dichloromethane and methanol by a simple liquid auxiliary grinding method through the two ligands and the photochromic molecules, so that the obtained photochromic material has the advantages of good crystal form, high crystallinity, simple operation, low cost and high repeatability. And secondly, the photochromic molecules are loaded into the pores of HOFs framework materials in the ligand self-assembly process by a solvent volatilization method, so that the densely packed spiropyran molecules are dispersed, the free volume of the spiropyran molecules is increased, and meanwhile, the spiropyran molecules have enough space freedom degree in a solid state to carry out ring opening-ring closing reaction, so that the photochromic effect of the spiropyran is more obvious, and the solid state photochromic performance of the spiropyran molecules is remarkably improved. The solid powder of the photochromic material prepared by the invention has obvious change of the physical color and the fluorescent color of the solid powder within 10 seconds under the irradiation of ultraviolet light with the wavelength of 365nm, the physical color is changed from white to purple, and the fluorescen