CN-116084057-B - Self-early-warning self-repairing agent material and preparation method and application thereof

CN116084057BCN 116084057 BCN116084057 BCN 116084057BCN-116084057-B

Abstract

The invention belongs to the technical field of corrosion monitoring and intelligent self-repairing coating, and particularly relates to a self-early-warning self-repairing electrostatic spinning core-shell fiber coating material with aggregation-induced emission response and a preparation method and application thereof. The material is in a shell-core form formed by a fiber shell material and a fiber core material, wherein the fiber core material contains an aggregation-induced emission self-early warning agent and a water environment self-repairing material, and the fiber shell material contains a non-Newtonian fluid polymer material. The intelligent fiber coating provided by the invention has the advantages of simple preparation process, high load rate and repair efficiency, self-early warning and self-repair integrated function and high practical value for the electrostatic spinning technology in the field of marine anti-corrosion nano coatings.

Inventors

JI XIAOHONG
DUAN JIZHOU
WANG WEI
JI WENHUI
HOU BAORONG

Assignees

中国科学院海洋研究所

Dates

Publication Date: 20260512
Application Date: 20230105

Claims (5)

1. A self-early-warning and self-repairing agent material is characterized in that the material is formed into a shell-core form by a fiber shell material and a fiber core material, wherein the fiber core material contains an aggregation-induced emission self-early-warning agent and a water environment self-repairing material, and the fiber shell material contains a non-Newtonian fluid polymer material; The non-Newtonian fluid polymer material is one or more of polyacrylonitrile, cellulose acetate, PCL, PS and the like, and the shell material solvent is one or more of acetone, N, N-dimethylformamide, N, N-dimethylacetamide and dimethyl sulfoxide; The self-repairing material for water environment is a film forming material capable of reacting when meeting water or water vapor or an underwater solidified epoxy resin; The fiber core material contains an aggregation-induced emission self-early warning agent and a water environment self-repairing material which are mixed according to the mass ratio of 0.05-1:5-10; The fiber shell material is prepared by mixing a non-Newtonian fluid polymer material and a shell material solvent according to the mass ratio of 1:8-20; And a surfactant is also added into the fiber shell material, and the mass ratio of the surfactant to the fiber shell material is 0.01-1:1.
2. A preparation method of a self-warning-self-repairing material according to claim 1 is characterized in that the fiber shell material and the fiber core material are subjected to core shell coaxial spinning by utilizing electrostatic spinning equipment, and the self-warning-self-repairing material is obtained.
3. The method for preparing the self-warning-self-repairing agent material according to claim 2, which is characterized in that: 1) The preparation of the fiber shell material comprises the steps of adding a non-Newtonian fluid polymer material into a shell material solvent according to the proportion under the stirring condition, and stirring at the temperature of 40-65 ℃ at the rotating speed of 1000-5000 rmp for 1-2 h until the non-Newtonian fluid polymer material is dissolved, so as to obtain the fiber shell material; or, after the non-Newtonian fluid polymer material is dissolved, adding a surfactant, and continuously stirring for 3-6 h, wherein the total mass ratio of the surfactant to the non-Newtonian fluid polymer material to the shell material solvent is 0.01-1:1; 2) The preparation of the fiber core material comprises the steps of mixing an aggregation-induced emission self-early warning agent with a water environment self-repairing material, and magnetically stirring for 3-6 h at normal temperature; 3) The preparation of the electrostatic spinning core-shell fiber comprises the steps of adjusting an electrostatic spinning machine, assembling and fixing a coaxial needle injector, simultaneously injecting a fiber shell material and a fiber core material, and coaxially spinning at room temperature to obtain the self-warning-self-repairing agent material, and the self-warning-self-repairing agent material is applied to metal corrosion prevention.
4. The method of using the self-warning-self-repairing material of claim 1, wherein the self-warning-self-repairing material is used as an aggregation-induced emission response water environment.
5. A water environment self-early-warning self-repairing coating with aggregation-induced emission response is characterized in that the coating contains the self-early-warning self-repairing agent material as set forth in claim 1.

Description

Self-early-warning self-repairing agent material and preparation method and application thereof Technical Field The invention belongs to the technical field of corrosion monitoring and intelligent self-repairing coating, and particularly relates to a self-early-warning self-repairing electrostatic spinning core-shell fiber coating material with aggregation-induced emission response and a preparation method and application thereof. Background The corrosion hazard severely restricts the sustainable development of national economy, which is not only a safety and economic problem, but also a national life problem. In order to reduce corrosion hazards, organic coatings have been used to date most effectively, economically and most commonly. However, the coating may fail over time due to mechanical damage and aging effects. Even on the micro-nano scale, coating damage inevitably damages the integrity of the polymer matrix, resulting in initiation of subcontracting corrosion. If not found and repaired in time, corrosion expansion can ultimately lead to catastrophic failure of the structure with serious economic and safety consequences. Meanwhile, defects such as pores, micro-nano cracks and the like are easy to appear in the organic coating in the application or curing process, so that the service life of the coating is seriously shortened, and long-term corrosion protection cannot be provided. Therefore, the method has important significance in monitoring early warning and micro-crack damage repair in early corrosion occurrence. The self-repairing coating is a coating material capable of repairing damage and recovering performance under the condition of little or no external interference, and a coating based on a graphene nano container, a self-repairing coating and a preparation method and application thereof are disclosed in Chinese patent CN 201810934463.3. In the Chinese patent CN20201177355. X, a self-repairing aqueous acrylic coating based on quinoline nano metal-organic frame material is provided, the self-repairing coating is prepared by loading zinc phosphate into the organic frame material, zinc phosphate molecules can be gradually released, and damaged areas of the coating are repaired in time to achieve the aim of prolonging the corrosion resistance of steel. The two coatings only have self-repairing performance, corrosion and repairing processes of the early warning coating cannot be monitored in time, and the existing nano container in the published self-warning-self-repairing coating is complex in preparation, low in early warning and repairing efficiency and incapable of effectively early warning and monitoring micro-nano cracks of the coating in water environment. The aggregation-induced emission (AIE) response early warning material is a material which has the advantages that material molecules hardly emit light in a solution, and the luminescence of the material is greatly enhanced in an aggregation state or a solid film, the material has strong luminescence property in a solid state, has strong stability to ultraviolet excitation light, has the advantages of strong emissivity, quick response, high sensitivity and the like, can realize the luminescence regulation and control of different wave bands through flexible chemical modification, is applied to a coating, detects crack damage through a nondestructive visual signal, and is beneficial to preventing final structural failure and prolonging the service life of the coating. However, AIE research is in the initiation phase in the field of corrosion protection, and the research of applying AIE to self-repairing coatings is more than that of the Phoenix's horn. Disclosure of Invention The invention aims to provide a self-early-warning self-repairing agent material for aggregation-induced emission response, and a preparation method and application thereof. In order to achieve the above purpose, the invention adopts the technical scheme that: A self-early-warning and self-repairing agent material is formed by a fiber shell material and a fiber core material, wherein the fiber core material contains an aggregation-induced emission self-early-warning agent and a water environment self-repairing material, and the fiber shell material contains a non-Newtonian fluid polymer material. The fiber core material contains an aggregation-induced emission self-early warning agent and a water environment self-repairing material which are mixed according to the mass ratio of 0.05-1:5-10; the fiber shell material is prepared by mixing a non-Newtonian fluid polymer material and a shell material solvent according to the mass ratio of 1:8-20. The fiber shell material is also added with a surfactant, such as a nonionic surfactant Tween 20 (Tween 20) or a cationic surfactant Cetyl Trimethyl Ammonium Bromide (CTAB), wherein the mass ratio of the surfactant to the fiber shell material is 0.01-1:1, so that the conductivity of the fiber spinning shell solution is increased