CN-121991384-A - Repairable polyimide film based on multiple dynamic bond cooperation and preparation method thereof

CN121991384ACN 121991384 ACN121991384 ACN 121991384ACN-121991384-A

Abstract

The invention discloses a repairable polyimide film based on multiple dynamic bond cooperation and a preparation method thereof, belonging to the field of polyimide film production; the preparation method comprises the steps of stirring and mixing diamine and a solvent, adding dianhydride step by step to react to obtain polyamide acid resin, dispersing a chain extender into the solvent to obtain a dispersion liquid A, dispersing a coordination ion liquid into the solvent to obtain a dispersion liquid B, sequentially adding the dispersion liquid A and the dispersion liquid B into the polyamide acid resin, stirring for polymerization reaction to obtain composite polyamide acid resin, vacuum defoaming, casting the composite polyamide acid resin after vacuum defoaming to remove the solvent to obtain a self-supporting film, carrying out thermal imidization to remove the solvent, and carrying out longitudinal and transverse stretching to obtain the polyamide acid resin. The polyimide film has the characteristics of high mechanical property, good dimensional stability, self-repairing property and the like, and can be applied to the fields of high performance requirements such as 5G communication, AI models, flexible display, new energy automobiles, medical health and the like.

Inventors

PAN CHENG
SHI ENTAI
PANG CHONG
JIN HONGSHENG
LIU MINGYANG

Assignees

安徽国风新材料股份有限公司
安徽国风新材料技术有限公司

Dates

Publication Date: 20260508
Application Date: 20260119

Claims (10)

1. The preparation method of the repairable polyimide film based on the cooperation of multiple dynamic bonds is characterized by comprising the following steps of: stirring and mixing diamine and a solvent, and then adding dianhydride step by step to react to obtain polyamide acid resin; Dispersing a chain extender in a solvent to obtain a dispersion liquid A; Dispersing the coordination ion liquid in a solvent to obtain a dispersion liquid B; sequentially adding the dispersion liquid A and the dispersion liquid B into the polyamide acid resin, stirring for polymerization reaction to obtain composite polyamide acid resin, and carrying out vacuum defoaming; And carrying out thermal imidization, removing the solvent, and carrying out longitudinal and transverse stretching to obtain the self-supporting film.
2. The method for preparing the repairable polyimide film based on the cooperation of multiple dynamic bonds, which is characterized in that the molar ratio of diamine to dianhydride is 1:0.95-1.015.
3. The method for preparing a repairable polyimide film based on the cooperation of multiple dynamic bonds according to claim 1, wherein the viscosity of the polyamic acid resin is 80-200 Pa s.
4. The method for preparing a repairable polyimide film based on multiple dynamic bond synergism according to claim 1, wherein the diamine is one or more of 6,6' -diamino-3, 3' -methylenedibenzoic acid ((MBAA), 4' -diaminodiphenyl ether, 4' -diaminodiphenylmethane, 4' -diaminobenzil anilide (DABA), 2-bis [ (4-aminophenoxy) phenyl ] propane, 1, 3-bis (3-aminophenoxy) benzene, 1, 2-bis (4-aminophenoxy) ethane, 1, 4-bis (4-aminophenoxy) benzene; The dianhydride is one or more of pyromellitic dianhydride, 3', 4' -biphenyl tetracarboxylic dianhydride, 4 '-diaminobiphenyl-2, 2' -dicarboxylic acid, 1,4,5, 8-naphthalene tetracarboxylic dianhydride, 4 '-biphenyl ether tetracarboxylic dianhydride, bisphenol A type diether dianhydride, p-biphenylene-bisphenol trimellitate dianhydride and 4,4' -terephthaloyl diphthalic anhydride.
5. The preparation method of the repairable polyimide film based on the cooperation of multiple dynamic bonds, which is disclosed in claim 1, is characterized in that the chain extender is one or more of bio-based small molecule acid, diethylenetriamine and diacetylethylenediamine, and the bio-based small molecule acid is one or two of citric acid and sebacic acid.
6. The method for preparing the repairable polyimide film based on the cooperation of multiple dynamic bonds, which is characterized in that the coordination ionic liquid is one or two of acetate coordination liquids of Zn 2+ 、Fe 3+ 、Al 3+ 、Sn 4+ .
7. The preparation method of the repairable polyimide film based on the cooperation of multiple dynamic bonds, which is disclosed in claim 1, is characterized in that the addition amount of the chain extender is 5-30% of the molar amount of the polyamic acid resin, and the addition amount of the coordination ionic liquid is 1-10% of the solid content of the polyamic acid resin.
8. The method for preparing the repairable polyimide film based on the cooperation of multiple dynamic bonds, which is disclosed in claim 1, is characterized in that the thermal imidization condition is that 50 ℃ gradient heating treatment is carried out within 100-450 ℃.
9. A repairable polyimide film prepared by the method of any one of claims 1-8.
10. Use of the repairable polyimide film of claim 9 in the manufacture of a flexible display device.

Description

Repairable polyimide film based on multiple dynamic bond cooperation and preparation method thereof Technical Field The invention belongs to the field of polyimide film production, and particularly relates to a repairable polyimide film based on multiple dynamic bond cooperation and a preparation method thereof. Background With the advent of the AI age and the development of electronic packaging technology, electronic components and electronic devices have been increasingly high-performance, miniaturized and highly integrated, and the use environment tends to be complicated and diversified, so that the overall requirement on materials is also higher. The material is affected by stress concentration, uneven temperature distribution and the like in the service process under severe service conditions, various cracks and damages are formed inside and outside the material, and various performances and service life of the material are obviously reduced. Therefore, scientists are continuously devoted to research on intelligent materials, so that the materials have self-repairing function, and the comprehensive performance of the materials is improved, and the service life of the materials is prolonged. Self-healing materials can be broadly classified into two types, external-aid type self-healing and intrinsic type self-healing in mechanism. The self-healing material for external assistance is mainly self-healed by embedding microcapsules, hollow fibers or a network of micro-blood vessels, from which a polymerizable or cross-linking component is released, the healing capacity of which depends on the amount of the remaining healing agent, and once the healing agent is consumed, the ability to self-heal at the same location is permanently lost. The intrinsic self-repairing material does not need external addition, and utilizes dynamic reversible chemical bonds in the molecular internal structure of the material to complete reversible bonding reaction at the fracture and breakage position, thereby achieving the repairing purpose and recovering the original performance and characteristics of the material, wherein the common dynamic reversible chemical bonds comprise hydrogen bonds, coordination bonds, ionic bonds, pi-pi stacks and the like. In contrast, intrinsic self-healing materials are not affected by the content and distribution of external healing agents, but rather by utilizing specific and reversible interactions inside the matrix, they can repeatedly repair the same damaged area more times, more rapidly and effectively, and are one of the more effective means for developing self-healing materials. Polyimide (PI) is a polymer with an imide ring (-CO-N-CO-) on a main chain, has excellent heat resistance, mechanical property, electrical property and chemical stability, and has been widely applied to the technical fields of aerospace, rail transit, new energy automobiles, medical appliances, low-altitude flight, bionic robots and the like. Although polyimide has good mechanical property, electrical property and chemical corrosion resistance, most of traditional polyimide is made of disposable materials and does not have a self-repairing function, particularly as a film product, the surface of the polyimide is extremely easy to scratch and mechanically damage under complex stress and extreme environments, and the polyimide is irreversibly repaired, so that performance degradation and even failure are caused, and further the use stability in FCCL and flexible display screen is affected, so that devices are scrapped. Therefore, providing a polyimide material with excellent self-repairing capability and good thermodynamic properties is a technical problem to be solved in the art. Disclosure of Invention Aiming at the defects of the prior art, the invention aims to provide a repairable polyimide film based on the cooperation of multiple dynamic bonds and a preparation method thereof, and solves the problems in the prior art. The aim of the invention can be achieved by the following technical scheme: the preparation method of the repairable polyimide film based on the cooperation of multiple dynamic bonds comprises the following steps: stirring and mixing diamine and a solvent, and then adding dianhydride step by step to react to obtain polyamide acid resin; Dispersing a chain extender in a solvent to obtain a dispersion liquid A; Dispersing the coordination ion liquid in a solvent to obtain a dispersion liquid B; sequentially adding the dispersion liquid A and the dispersion liquid B into the polyamide acid resin, stirring for polymerization reaction to obtain composite polyamide acid resin, and carrying out vacuum defoaming; And carrying out thermal imidization, removing the solvent, and carrying out longitudinal and transverse stretching to obtain the self-supporting film. Further, the molar ratio of the diamine to the dianhydride is 1:0.95-1.015. Further, the viscosity of the polyamic acid resin is 80-200 Pa s. Fur