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CN-121991348-A - Polyimide material, colored polyamide acid precursor composition and application thereof in preparation of copolymerized phthalocyanine colored polyimide film

CN121991348ACN 121991348 ACN121991348 ACN 121991348ACN-121991348-A

Abstract

The invention provides a polyimide material, a coloring polyamide acid precursor composition thereof and application thereof in preparing a copolymerization type phthalocyanine coloring polyimide film. The polyimide is formed by copolymerizing hexafluorodianhydride and biphenyl tetracarboxylic dianhydride according to a specific proportion. The corresponding polyamic acid precursor composition is soluble in conventional polar aprotic solvents, and has excellent solution stability and film forming property. After thermal imidization treatment, the obtained film shows high transparency, low chromaticity deviation and uniform and controllable light color appearance while keeping the 5% thermal weight loss temperature higher than 500 ℃, and meets the application requirements of colorless or light-color high-performance polyimide. The material remarkably improves the serious yellowing problem of the traditional aromatic polyimide caused by strong intramolecular charge transfer, combines the processing convenience and the thermo-mechanical performance, and is particularly suitable for the high-end technical fields of flexible OLED display substrates, optoelectronic device packaging, transparent high-temperature-resistant coatings and the like.

Inventors

  • PENG XIAOJUN
  • Lian Zihan
  • CHEN PENGZHONG
  • WANG DONGPING
  • FAN JIANGLI
  • DU JIANJUN

Assignees

  • 大连理工大学

Dates

Publication Date
20260508
Application Date
20260213

Claims (10)

  1. 1. A polyimide material is characterized in that the polyimide material is prepared by polymerization and imidization of a reaction system comprising the following monomers: (i) A first dianhydride monomer; (ii) A second dianhydride monomer; (iii) An aromatic diamine monomer; Wherein the first dianhydride monomer is fluorine-containing dianhydride, and the second dianhydride monomer is fluorine-free rigid dianhydride, and the molar ratio of the first dianhydride monomer to the second dianhydride monomer is 1:4-1:1; the ratio of the total molar quantity of the first dianhydride monomer to the second dianhydride monomer to the molar quantity of the aromatic diamine monomer is 0.95-1.05:1.
  2. 2. The polyimide material according to claim 1, characterized in that: the structural formula of the first dianhydride is one of the following: , , , ; the structural formula of the second dianhydride is one of the following: , , , ; the aromatic diamine monomer is selected from one of the following structural formulas: , , , , , , , 。
  3. 3. The polyimide material according to claim 1 or 2, wherein the aromatic diamine monomer is one selected from the group consisting of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl (TFMB), 2, 5-bis (trifluoromethyl) -1, 4-phenylenediamine, 2- (trifluoromethyl) -1, 4-phenylenediamine, 2, 5-dimethyl-1, 4-phenylenediamine, and p-phenylenediamine (PPD).
  4. 4. A colored polyamic acid precursor composition is characterized in that the composition comprises: (a) A polyamic acid copolymerized from the following monomers used in claim 1: (i) A first dianhydride monomer; (ii) A second dianhydride monomer; (iii) An aromatic diamine monomer; Wherein the first dianhydride monomer is fluorine-containing dianhydride, the second dianhydride monomer is fluorine-free rigid dianhydride, and the molar ratio of the first dianhydride monomer to the second dianhydride monomer is 1 (1-4); The ratio of the total molar quantity of the first dianhydride monomer to the second dianhydride monomer to the molar quantity of the aromatic diamine monomer is 0.95-1.05:1; (b) A metal phthalocyanine compound having the structural formula shown in the following formula I: I Wherein the substituent R 1 、R 2 、R 3 、R 4 contains 2 to 4-NH 2 , when the number of amino groups is less than 4, the rest substituents are independently selected from one of-H, -C 1 -C 12 alkyl, -C 1 -C 12 alkoxy, -OH, -COOH, -SO 3 H and halogen, and M is one of Co, cu, al, fe, zn, ti or Mo; (c) A polar aprotic organic solvent selected from at least one of N, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP) or sulfolane, m-cresol and HMPT; wherein the molar amount of the metal phthalocyanine compound is 0.5-10% of the molar amount of the aromatic diamine monomer.
  5. 5. The colored polyamic acid precursor composition according to claim 4, wherein the solid content of the precursor composition is 10 to 40 wt%.
  6. 6. A phthalocyanine-based high-performance colored polyimide film, which is obtained by imidizing and film-forming the colored polyamic acid precursor composition according to claim 5.
  7. 7. The colored polyimide film of claim 6, wherein the film chromaticity coordinates lie in the blue region of less than or equal to 55, less than or equal to 10, less than or equal to a, less than or equal to-15, and less than or equal to a.
  8. 8. The method for producing a phthalocyanine-based high-performance colored polyimide film according to claim 6, comprising the steps of: S1, adding an aromatic diamine monomer and a metal phthalocyanine compound into an organic solvent I under a protective atmosphere, and stirring to dissolve or uniformly disperse the aromatic diamine monomer and the metal phthalocyanine compound to obtain a mixed solution, wherein the organic solvent I is at least one selected from N, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP) or sulfolane, m-cresol and HMPT; S2, sequentially adding the first dianhydride monomer and the second dianhydride monomer used in the method of claim 1 into the mixed solution at the temperature of-20-0 ℃ and stirring and reacting for 12-24 hours to obtain a colored polyamic acid precursor solution; polyimide films were prepared from the colored polyamic acid precursor solution using one of two imidization modes: Chemical imidization, comprising the following steps: S3-1, adding a catalyst and a dehydrating agent into the polyamic acid precursor solution for chemical imidization, and obtaining a polyimide solution after reaction; S3-2, dissolving the prepared polyimide in an organic solvent II, defoaming, filtering to obtain uniform casting solution, coating the casting solution on a glass substrate by a tape casting method, and then placing the glass substrate in a program temperature control device; the second mode is thermal imidization, which comprises the following steps: S3-1', regulating the solid content of the polyamic acid precursor solution to be 10-40%, defoaming, filtering, and casting and coating on a glass substrate; s3-2'. Under inert atmosphere, carrying out thermal imidization by a gradient heating program, namely heating to 80-120 ℃ at 1-5 ℃ per min, keeping the temperature for 0.5-2 hours, heating to 250-350 ℃ at 1-3 ℃ per min, and keeping the temperature for 0.5-2 hours to obtain the polyimide film; The catalyst used for chemical imidization is at least one selected from pyridine, triethylamine and imidazole, the dehydrating agent is at least one selected from acetic anhydride and propionic anhydride, the volume ratio of the catalyst to the dehydrating agent is 1 (2-5), the chemical imidization reaction temperature is 20-50 ℃, the reaction time is 10-24 hours, the types of the organic solvent II and the organic solvent I used by S1 are consistent, and the poor solvent is at least one selected from methanol, ethanol and deionized water.
  9. 9. Use of a polyimide material according to any of claims 1 to 3 for the preparation of a high temperature resistant, solution processable functional optical element.
  10. 10. Use according to claim 9, comprising the use of a polyimide material for the preparation of flexible display substrates, blue optical filters or thermal control coatings for spacecraft.

Description

Polyimide material, colored polyamide acid precursor composition and application thereof in preparation of copolymerized phthalocyanine colored polyimide film Technical Field The invention belongs to the technical field of high-performance high polymer materials, and particularly relates to a polyimide material, a coloring polyamide acid precursor composition thereof and application thereof in preparation of a copolymerization type phthalocyanine coloring polyimide film Background Polyimide is used as a high-performance polymer, and plays an indisputable role in the fields of flexible electronic display, aerospace insulation, microelectronic packaging and the like due to its excellent thermal stability, mechanical strength and chemical resistance. In many practical applications, not only are materials required to possess these basic properties, but often specific colors are imparted to them to meet the requirements of optical masking, visual identification, or functional filtering. Therefore, development of polyimide films having both excellent comprehensive properties and stable and uniform coloring ability has been a technical subject of continued attention in the art. To achieve the coloration of polyimides to meet the labeling, decoration or functional light filtering requirements, especially to achieve high saturation and high stability of color patterning of red, blue, green, etc. in flexible displays, wearable electronics, the prior art has relied primarily on physical blending methods to introduce chromophores. Patent CN114164688a discloses a method for preparing color PI films by blending inorganic pigments. The method has simple process, but inorganic pigment is easy to agglomerate and settle, so that color is uneven, high-energy consumption equipment is needed for achieving basic dispersity, and the production cost is increased. Patent CN116120605A discloses a color polyimide film prepared by mixing dye molecules with soluble yellow polyimide, but in the long-term use process of the device, organic dye molecules are easy to undergo thermal migration, volatilization or aggregation, which leads to color fading and poor stability, thereby affecting the performance or service life of the device. Metal phthalocyanine compounds are considered to be ideal choices for achieving stable coloration at high temperatures due to their extremely high thermal decomposition temperatures and vivid colors. The core challenge in introducing it into PI systems is compatibility and dispersibility. The prior art has attempted to chemically modify phthalocyanines to improve their binding to polymers, such as the surface grafting of phthalocyanines by aminosilanes, as described in patent CN107587871 a. However, such methods are complex in process and may alter the optical properties of the chromophore, a passive adaptation in nature, and do not address compatibility issues from the source of PI backbone design. Therefore, developing a method for preparing a colored polyimide film, which can realize perfect matching with a specific high-performance chromophore by precisely and quantitatively regulating and controlling the main chain structure of a polymer from the source of molecular design, so as to obtain excellent processability, high thermal stability and excellent color performance at one time is a technical blank to be broken through in the field. Disclosure of Invention Aiming at the inherent contradiction and performance bottleneck existing between the processability, heat resistance and long-term color stability of the traditional colored polyimide material, the high-performance colored polyimide film and the preparation method thereof are provided. The method starts from molecular main chain engineering, and actively constructs a polymer microenvironment highly compatible with the metal phthalocyanine chromophore by quantitatively designing the proportion of the monomers, thereby realizing the synergistic optimization and breakthrough balance of the dissolution processability, high temperature tolerance, color uniformity and fastness, and providing a coloring substrate solution with excellent comprehensive performance for high-end photoelectric devices. Firstly, the invention protects a polyimide material, which is prepared by polymerization and imidization of a reaction system comprising the following monomers: (i) A first dianhydride monomer; (ii) A second dianhydride monomer; (iii) An aromatic diamine monomer; Wherein the first dianhydride monomer is fluorine-containing dianhydride and the second dianhydride monomer is fluorine-free rigid dianhydride, and the molar ratio of the first dianhydride monomer to the second dianhydride monomer is 1:4 to 1:1, preferably 1:3 to 1:1, more preferably 3:7 to 1:1, and most preferably 3:7; Wherein the ratio of the total molar amount of the first dianhydride monomer to the second dianhydride monomer to the molar amount of the aromatic diamine monomer is 0.95-1.05:1, prefera