WO2023098424A1 - 聚酰亚胺树脂、聚酰亚胺薄膜及制备方法、柔性设备 - Google Patents

聚酰亚胺树脂、聚酰亚胺薄膜及制备方法、柔性设备 Download PDF

Info

Publication number
WO2023098424A1
WO2023098424A1 PCT/CN2022/130717 CN2022130717W WO2023098424A1 WO 2023098424 A1 WO2023098424 A1 WO 2023098424A1 CN 2022130717 W CN2022130717 W CN 2022130717W WO 2023098424 A1 WO2023098424 A1 WO 2023098424A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyimide
dianhydride
polyimide resin
film
aromatic
Prior art date
Application number
PCT/CN2022/130717
Other languages
English (en)
French (fr)
Inventor
路庆华
夏雪健
秦圆
孙难见
洪起一
马戎
吕旺春
Original Assignee
华为技术有限公司
同济大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 华为技术有限公司, 同济大学 filed Critical 华为技术有限公司
Publication of WO2023098424A1 publication Critical patent/WO2023098424A1/zh

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the application relates to a polyimide resin, a polyimide film, a preparation method, and a flexible device containing the polyimide film.
  • PET polyethylene terephthalate
  • PET polyethylene naphthalate
  • PC polycarbonate Esters
  • PES polyethersulfone
  • Polyimide can be widely used in microelectronics and optoelectronic industries due to its good heat resistance stability, excellent transparency, and excellent insulation.
  • CTC charge transfer complex
  • the molecular chains are tightly packed, which makes PI have strong absorption in the visible light range, making PI appear yellow or brown.
  • CTC charge transfer complex
  • the design concept of colorless and transparent polyimide (CPI) is to reduce the accumulation between PI molecular chains or use the alicyclic structure to weaken the CTC effect, and these methods inevitably cause the loss of PI mechanical properties.
  • the first aspect of the embodiment of the present application provides a polyimide resin, which is obtained by complexing aromatic diamine with crown ether, and then copolymerizing with alicyclic dianhydride and aromatic dianhydride, wherein the aromatic Diamines include aromatic diamines containing amide bonds;
  • the Young's modulus of the polyimide resin is more than 8Gpa, the elongation at break is more than 15%, and the tensile strength is more than 200Mpa.
  • the crown ether is added to the main chain of polyimide through self-assembly, which is equivalent to "knotting" on the molecular chain to limit the sliding between molecular chains, so as to improve the polyimide
  • the mechanical strength of the imide resin the polyimide resin has high modulus, high elongation at break, high tensile strength, low haze, high transparency.
  • the aromatic diamines used in this application contain amide bonds.
  • the crown ether can be fixed by complexation to prevent sliding between bonds.
  • the amide bonds are hydrogen bond donors and polyimide chains.
  • the ketone carbonyl groups form hydrogen bonds, which strengthen the interaction between molecular chains.
  • the addition of cycloaliphatic dianhydride is beneficial to increase the transparency, increase the tensile strength, and also increase the glass transition temperature.
  • the content of the crown ether is 2%-15% by weight.
  • the optical transmittance of the polyimide resin at 550 nm is ⁇ 88% as measured by an ultraviolet-visible photometer.
  • the yellowness of the polyimide resin is ⁇ 3.0, and the haze is ⁇ 1.0.
  • the polyimide resin has high transparency.
  • the chemical structural formula of the polyimide resin is:
  • R1 and R2 are independently selected from a hydrogen atom, a halogen atom, a halogenated alkyl group with 1 to 4 carbon atoms, or an alkyl group with 1 to 5 carbon atoms;
  • X1 is a benzene or biphenyl group containing a substituent
  • X2 is an aliphatic group or an aromatic group
  • n and m are natural numbers >1, respectively.
  • R1 and R2 are independently selected from a hydrogen atom, a halogen atom, a haloalkyl group with 1 to 4 carbon atoms, or an alkyl group with 1 to 5 carbon atoms;
  • X 1 is a substituted benzene or biphenyl group.
  • the crown ether is selected from 12-crown ether-4, 15-crown ether-5, 18-crown ether-6, dicyclohexane-18-crown ether-6, benzo-18 - at least one of crown 6-ether, dibenzo-18-crown-6, and dibenzo-24-crown-8.
  • the aromatic dianhydride is selected from 1,2,4,5-pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 4,4 - Hexafluoroisopropyl phthalic anhydride, 3,3,4,4-diphenylsulfone tetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, bisphenol A diether di At least one of anhydrides;
  • the aliphatic dianhydride is selected from 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2, 3,4-Cyclopentanetetracarboxylic dianhydride, 3,3,6,6-tetramethyltetrahydrocyclobutyrate-1,3,4,6-tetraketone, 3,6-dimethyltetrahydro At least one of cycl
  • the molar ratio of the aromatic diamine containing an amide bond relative to the aromatic diamine is more than 10%; the alicyclic dianhydride relative to the alicyclic dianhydride and aromatic
  • the ratio of the total molar weight of the two family dianhydrides is more than 10%.
  • the second aspect of the embodiment of the present application provides a film, including the polyimide resin described in the first aspect of the embodiment of the present application.
  • the third aspect of the embodiment of the present application provides a flexible device, including the film described in the second aspect of the embodiment of the present application.
  • the flexible device is a flexible display, a flexible sensor, a flexible antenna, a flexible solar cell, or a flexible circuit.
  • the flexible device is a flexible display
  • the flexible device includes a display screen
  • the thin film is used as a cover film to cover the display screen.
  • the flexible device is a flexible organic light-emitting semiconductor display, and the flexible device includes a substrate, a thin film transistor array layer, and a light-emitting layer stacked in sequence, and the substrate is the thin film.
  • the fourth aspect of the embodiment of the present application provides a method for preparing a polyimide film, including:
  • step S1 the molar ratio of the crown ether to the aromatic diamine is (0.2-2.4): 1; in step S2, the alicyclic dianhydride and the aromatic diamine The molar ratio of the total amount of anhydride to the aromatic diamine is (1 ⁇ 1.15):1.
  • step S3 includes: adding a chemical imidization reagent to the polyamic acid glue for reaction to obtain the polyimide glue, and the reagent includes a mixture of an organic acid anhydride and an organic amine and then pour the polyimide glue solution into an organic solvent with a boiling point of ⁇ 80°C or a mixed solvent of an organic solvent with a boiling point of ⁇ 80°C and water to obtain the polyimide fiber by precipitation.
  • a chemical imidization reagent to the polyamic acid glue for reaction to obtain the polyimide glue
  • the reagent includes a mixture of an organic acid anhydride and an organic amine and then pour the polyimide glue solution into an organic solvent with a boiling point of ⁇ 80°C or a mixed solvent of an organic solvent with a boiling point of ⁇ 80°C and water to obtain the polyimide fiber by precipitation.
  • the amount of the organic amine is 0.1 to 1 times the number of moles of the organic anhydride, and the organic anhydride is selected from at least one of acetic anhydride, metaphthalic anhydride, and maleic anhydride. species; the organic amine is selected from at least one of triethylamine, pyridine, and N,N-dimethylaniline.
  • the organic solvent used in step S1 and the anhydrous solvent used in step S4 are all selected from N,N-dimethylacetamide, N,N-dimethylformamide, dimethylmethylene At least one of sulfone, m-cresol, N-methyl-2-pyrrolidone, and ⁇ -butyrolactone.
  • step S5 the temperature is raised so that the temperature for complete imidization is 180°C-250°C.
  • Another advantage of chemical imidization is that it avoids the high temperature treatment process above 300 °C, and only needs to remove the solvent at 250 °C or lower temperature, and the terminal amino group is blocked by acetic anhydride, which avoids the oxidation of the terminal group.
  • the resulting polyimide film usually has better transparency and lighter color; chemical imidization also avoids molecular chain breaks caused by high-temperature cyclodehydration, so it is more conducive to high-strength polyimide Amine Preparation.
  • the molar ratio of the aromatic diamine containing an amide bond relative to the aromatic diamine is more than 10%; the alicyclic dianhydride relative to the alicyclic dianhydride and aromatic
  • the ratio of the total molar weight of the two family dianhydrides is more than 10%.
  • the polyimide fiber obtained in step S3 needs to be dried, and the drying method is to vacuum dry the obtained polyimide fiber at 100°C-150°C for 24h-48h.
  • Drying the polyimide fiber in the air will result in a higher yellowness value of the obtained polyimide resin, and vacuum drying can ensure that the obtained polyimide resin has a lower yellowness value.
  • Fig. 1A and Fig. 1B are the infrared spectrograms of embodiment 1 and comparative example 1.
  • Fig. 2 is the thermogravimetric analysis spectrogram of embodiment 1 and comparative example 1.
  • Fig. 3 is the proton nuclear magnetic spectrogram of embodiment 1 and comparative example 1.
  • the CPI hardened film used for the mobile phone cover requires that the average transmittance of the CPI film in the visible light region is 88%, the yellowness is less than or equal to 3.0, and the modulus is greater than or equal to 6GPa.
  • the mechanical properties of existing transparent PI cannot meet this requirement.
  • the application provides a colorless and transparent polyimide resin and a film of the polyimide resin, which have high modulus and high elongation at break rate, high tensile strength, low haze, high glass transition temperature (Tg) and ultra-high transparency.
  • the polyimide resin is obtained by first complexing aromatic diamine with crown ether, and then copolymerizing with alicyclic dianhydride and aromatic dianhydride.
  • the aromatic diamine includes an amide bond-containing aromatic diamine.
  • the molar ratio of the aromatic diamine containing an amide bond to the aromatic diamine is more than 10%; in other embodiments, the aromatic diamine containing an amide bond is The molar ratio of the aromatic diamine is 50% or more; in some embodiments, the molar ratio of the aromatic diamine containing amide bonds to the aromatic diamine is 90% or more.
  • the crown ether is added to the main chain of polyimide by self-assembly, which is equivalent to "knotting" on the molecular chain to limit the sliding between molecular chains, so as to improve the polyimide resin. mechanical strength.
  • the Young's modulus of the polyimide resin is more than 8Gpa, the elongation at break is more than 15%, and the tensile strength is more than 200Mpa.
  • the optical transmittance of the polyimide resin at 550 nm is ⁇ 88% as measured by an ultraviolet-visible photometer.
  • the yellowness of the polyimide resin is less than or equal to 3.0, and the haze is less than or equal to 1.0.
  • the weight percentage of the crown ether is 2%-15%.
  • the corresponding weight percentage in the polyimide resin is 60% to 65%, and the two monomers of the alicyclic dianhydride and the aromatic dianhydride are polymerized The latter corresponds to 30%-34% by weight in the polyimide resin.
  • the ratio of the alicyclic dianhydride to the total molar weight of the alicyclic dianhydride and the aromatic dianhydride is more than 10%. In some other embodiments, the ratio of the alicyclic dianhydride to the total molar weight of the alicyclic dianhydride and the aromatic dianhydride is 30%.
  • the chemical structural formula of the polyimide resin is:
  • R1 and R2 are independently selected from a hydrogen atom, a halogen atom, a haloalkyl group with 1 to 4 carbon atoms, or an alkyl group with 1 to 5 carbon atoms;
  • crown ether with 12-24 elements, and the crown ether is set on the main chain of polyimide to form a collar-like supramolecular structure;
  • X1 is a benzene or biphenyl group containing a substituent
  • X2 is an aliphatic group or an aromatic group
  • n and m are natural numbers >1, respectively.
  • the crown ether molecules are set on the main chain of polyimide, so that the polyimide molecular chain expands from two-dimensional to three-dimensional, the flexibility of the molecular chain is reduced, and the rigidity is improved; in addition, the polarity of crown ether is lower than that of polyimide , has a certain shielding effect on the force between polyimide molecular chains, so the interaction force between polyimide molecular chains is reduced, the slip is easier, and the elongation at break of the film is increased.
  • the chemical formula of the aromatic diamine (AB-TFMB) containing an amide bond is:
  • R 1 and R 2 are independently selected from a hydrogen atom, a halogen atom, a halogenated alkyl group with 1 to 4 carbon atoms, or an alkyl group with 1 to 5 carbon atoms;
  • X 1 is benzene containing substituents or Biphenyl group.
  • the aromatic dianhydride is 1,2,4,5-pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 4,4-hexafluoroisopropyl o
  • phthalic anhydride 3,3,4,4-diphenylsulfone tetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, bisphenol A diether dianhydride kind.
  • the specific chemical structural formulas of the listed aromatic dianhydrides are as follows:
  • the aliphatic dianhydride is 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentadicarboxylic Acid dianhydride, 3,3,6,6-tetramethyltetrahydrocyclobutyrate-1,3,4,6-tetraketone, 3,6-dimethyltetrahydrocyclobutyrate-1,3 , one or more of 4,6-tetraketones.
  • the specific chemical structural formulas of the listed aliphatic dianhydrides are as follows:
  • the alicyclic dianhydride accounts for at least 10% of the total molar weight of the alicyclic dianhydride and the aromatic dianhydride, and in some embodiments, the alicyclic dianhydride accounts for at least 10% of the total molar weight of the alicyclic dianhydride and the aromatic dianhydride. 30% of the total molar weight.
  • the crown ether is 12-crown ether-4, 15-crown ether-5, 18-crown ether-6, dicyclohexyl-18-crown ether-6, benzo-18-crown 6-ether, two One or more of benzo-18-crown-6 and dibenzo-24-crown-8.
  • the specific chemical structural formulas of the listed crown ethers are as follows:
  • the aromatic diamines used in this application contain amide bonds.
  • the crown ether can be fixed by complexation, which plays a role in preventing slippage between bonds in the molecular chain.
  • the amide bond is a hydrogen bond donor and another polyimide
  • the ketone carbonyl on the amine chain forms a hydrogen bond, which strengthens the interaction between the molecular chains.
  • the addition of cycloaliphatic dianhydride is beneficial to increase the transparency, increase the tensile strength, and also increase the glass transition temperature.
  • the polyimide resin of the present application can be used in various application scenarios in the form of thin films, such as flexible displays, flexible sensors, flexible antennas, flexible batteries, flexible circuits, and the like.
  • the present application also provides a polyimide resin film, including the polyimide resin.
  • Polyimide resin film can be used as a transparent, high-mechanical-strength film layer in flexible displays, flexible sensors, flexible antennas, flexible solar cells, flexible circuits, and the like.
  • the flexible display includes a display screen and the polyimide resin film attached to the display screen.
  • the polyimide resin film is not used as a protective film, but as a transparent cover window that is indispensable for a display.
  • the flexible device may also be a flexible organic light-emitting semiconductor (Organic Light-Emitting Diode, OLED) display, and the flexible device includes a sequentially stacked substrate, a thin film transistor array layer, and a light-emitting layer, and the polyimide resin film serves as the substrate.
  • OLED Organic Light-Emitting Diode
  • the present application also provides a method for preparing a polyimide resin film, which includes the following steps.
  • Step S1 mixing and reacting aromatic diamines and crown ethers in an organic solvent to obtain a solution of an assembly of diamines and crown ethers, where the aromatic diamines include aromatic diamines containing amide bonds.
  • Step S1 can be performed under the protection of protective gas (such as nitrogen).
  • protective gas such as nitrogen
  • the molar ratio of the crown ether to the aromatic diamine is (0.2-2.4):1.
  • the organic solvent used in this step can be N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, m-cresol, N-methyl-2-pyrrolidone, ⁇ -butyl One or more of lactones.
  • Step S2 adding the solution of the assembly of diamine and crown ether into alicyclic dianhydride and aromatic dianhydride to obtain polyamic acid glue.
  • Step S2 can be performed under the protection of protective gas (such as nitrogen).
  • protective gas such as nitrogen
  • the molar ratio of the total amount of the alicyclic dianhydride and the aromatic dianhydride added in step S2 to the aromatic diamine is (1 ⁇ 1.15):1. Stirring is kept during the process of step S2. In addition, the state of the glue solution needs to be observed, and an organic solvent is added as needed to maintain the viscosity of the system at an appropriate level. After stirring and reacting, a transparent and viscous polyamic acid glue was obtained.
  • Step S3 using the polyamic acid glue to prepare a polyimide glue by chemical imidization, and then precipitating the polyimide glue to obtain polyimide fibers.
  • the reagents used in the chemical imidization include a mixture of organic acid anhydride and organic amine, and the amount of the organic amine is 0.1-1 times the number of moles of the organic acid anhydride.
  • Types of organic acid anhydrides include but not limited to acetic anhydride, metaphenylic anhydride, maleic anhydride, etc.; types of organic amines include but not limited to triethylamine, pyridine, N,N-dimethylaniline, etc.
  • step S3 the reagent used for chemical imidization is gradually dropped into the polyamic acid glue, and kept at room temperature for stirring and reacting to obtain a transparent and viscous polyimide glue. During the reaction process, observe the viscosity of the system at all times and add an organic solvent to prevent gelation. Then pour the polyimide glue solution into an organic solvent with a boiling point of ⁇ 80°C (such as methanol) or a mixed solvent of an organic solvent with a boiling point of ⁇ 80°C and water to obtain a filamentous precipitate (polyimide fiber).
  • a mixed solvent of methanol and water is used to precipitate the polymer from the solvent, and generally the volume ratio of methanol and water is 1:1.
  • the filamentous precipitate (polyimide fiber) obtained in this step can be washed three times with a mixed solvent of methanol and water, and then the polyimide fiber is dried.
  • the drying method of the polyimide fiber is as follows: put the obtained polyimide fiber into a vacuum oven, and vacuum dry at 100° C. to 150° C. for 24h to 48h to obtain a dried polyimide fiber. Drying the polyimide fiber in the air will result in a higher yellowness value of the obtained polyimide resin, and vacuum drying can ensure that the obtained polyimide resin has a lower yellowness value.
  • Step S4 dissolving the polyimide fiber in an anhydrous solvent to obtain a transparent glue solution, and coating the transparent glue solution on a carrier to prepare a wet film.
  • the dried polyimide fiber obtained in step S3 is redissolved in an anhydrous solvent to prepare a transparent glue solution with a suitable viscosity with a solid content of 10wt%-13wt%.
  • the anhydrous solvent can be N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), dimethylsulfoxide, m-cresol, N-methyl-2-pyrrolidone , one or more of ⁇ -butyrolactone.
  • the polyimide film can be prepared by solution casting method, but not limited thereto. Put a clean carrier (such as a glass plate) on the film coating machine, then pour the polyimide glue solution on the glass plate, and adjust the height of the stainless steel scraper to coat the film.
  • a clean carrier such as a glass plate
  • the chemical imidization is directly through the polyimide coating film, it avoids the generation of small molecule water in the imidization process, and at the same time, it also avoids the degradation caused by the instability of polyacrylic acid (PAA), which can obtain higher quality film.
  • PAA polyacrylic acid
  • Another advantage of chemical imidization is that it avoids the high temperature treatment process above 300 °C, and only needs to remove the solvent at 250 °C or lower temperature, and the terminal amino group is blocked by acetic anhydride, which avoids the oxidation of the terminal group.
  • the resulting polyimide film usually has better transparency and lighter color; chemical imidization also avoids molecular chain breaks caused by high-temperature cyclodehydration, so it is more conducive to high-strength polyimide Amine Preparation.
  • Step S5 vacuum drying the wet film to remove the solvent, and raising the temperature to complete imidization to obtain a polyimide film.
  • the coated glass plate is transferred to a vacuum oven for vacuum drying, and pre-baked at 60°C to 100°C for 1 to 2 hours to remove most of the solvent in the wet film; then transferred to a high temperature oven at 180°C to Further imidization and solvent removal were carried out at a temperature of 250 °C.
  • a polyimide resin film adhered to a glass plate was obtained.
  • the average thickness of the obtained polyimide film film can be 50 ⁇ m, but not limited thereto, and the thickness can be set as required.
  • aromatic diamine AB-TFMB (8.3772g, 15.0mmol) containing amide bonds, 18 crown 6 ether (5.2863g, 20.0mmol) and a certain volume of anhydrous N-methylpyrrolidone (NMP, as organic solvent), stirred at room temperature.
  • NMP N-methylpyrrolidone
  • Hexafluorodianhydride (6FDA, 1.9991g, 4.5mmol) and cyclobutanecarboxylic dianhydride (CBDA, 2.0592g, 10.5mmol) were added, and NMP was added to adjust the solid content of the system to 20%.
  • CBDA cyclobutanecarboxylic dianhydride
  • the dried filamentary polyimide precipitate is re-dissolved in anhydrous DMF to prepare a transparent glue with a solid content of 10 wt%-13 wt% and a suitable viscosity.
  • Polyimide film was prepared by solution casting method. Put the clean glass plate on the film coating machine, then pour the polyimide glue solution on the plate, adjust the height of the stainless steel scraper, and coat the film at a speed of 5mm/s. It was transferred into a vacuum oven and pre-baked at 80 °C for 1 hour to remove most of the solvent. Afterwards, it was transferred to a high-temperature oven for further imidization and solvent removal at 250 °C for 2 h. After cooling, place the glass plate with the polyimide film in hot water, peel it off to obtain a self-supporting film with a certain strength, and then dry it in a blast oven at 100°C for 2 hours to obtain the final film.
  • the dried filamentary polyimide precipitate is re-dissolved in anhydrous DMF to prepare a transparent glue with a solid content of 10 wt%-13 wt% and a suitable viscosity.
  • Polyimide film was prepared by solution casting method. Put the clean glass plate on the film coating machine, then pour the polyimide glue solution on the plate, adjust the height of the stainless steel scraper, and coat the film at a speed of 5mm/s. It was transferred into a vacuum oven and pre-baked at 80 °C for 1 hour to remove most of the solvent. Afterwards, it was transferred to a high-temperature oven for further imidization and solvent removal at 250 °C for 2 h. After cooling, place the glass plate with the polyimide film in hot water, peel it off to obtain a self-supporting film with a certain strength, and then dry it in a blast oven at 100°C for 2 hours to obtain the final film.
  • the dried filamentous polyimide precipitate is re-dissolved in anhydrous NMP to prepare a transparent glue solution with a solid content of 10wt%-13wt% and a suitable viscosity.
  • Polyimide film was prepared by solution casting method. Put the clean glass plate on the film coating machine, then pour the polyimide glue solution on the plate, adjust the height of the stainless steel scraper, and coat the film at a speed of 5mm/s. It was transferred into a vacuum oven and pre-baked at 80 °C for 1 hour to remove most of the solvent. Afterwards, it was transferred to a high-temperature oven for further imidization and solvent removal at 250 °C for 2 h. After cooling, place the glass plate with the polyimide film in hot water, peel it off to obtain a self-supporting film with a certain strength, and then dry it in a blast oven at 100°C for 2 hours to obtain the final film.
  • the dried filamentous polyimide precipitate is re-dissolved in anhydrous NMP to prepare a transparent glue solution with a solid content of 10wt%-13wt% and a suitable viscosity.
  • Polyimide film was prepared by solution casting method. Put the clean glass plate on the film coating machine, then pour the polyimide glue solution on the plate, adjust the height of the stainless steel scraper, and coat the film at a speed of 5mm/s. It was transferred into a vacuum oven and pre-baked at 80 °C for 1 hour to remove most of the solvent. Afterwards, it was transferred to a high-temperature oven for further imidization and solvent removal at 250 °C for 2 h. After cooling, place the glass plate with the polyimide film in hot water, peel it off to obtain a self-supporting film with a certain strength, and then dry it in a blast oven at 100°C for 2 hours to obtain the final film.
  • the dried filamentous polyimide precipitate is re-dissolved in anhydrous NMP to prepare a transparent glue solution with a solid content of 10wt%-13wt% and a suitable viscosity.
  • Polyimide film was prepared by solution casting method. Put a clean glass plate on a film coating machine at 70°C, then pour the polyimide glue solution on the plate, adjust the height of the stainless steel scraper, and coat the film at a speed of 5mm/s. It was transferred into a vacuum oven and pre-baked at 80 °C for 1 hour to remove most of the solvent. Afterwards, it was transferred to a high-temperature oven for further imidization and solvent removal at 250 °C for 2 h. After cooling, place the glass plate with the polyimide film in hot water, peel it off to obtain a self-supporting film with a certain strength, and then dry it in a blast oven at 100°C for 2 hours to obtain the final film.
  • Comparative Example 1 is the infrared spectrogram of pure PI, and there is no stretching vibration of methylene on the crown ether near 2850cm -1 peak, while Example 1 is a crown ether complex PI, and the stretching vibration peak of the methylene group on the crown ether can be seen near 2850cm -1 .
  • Comparative Example 1 is pure PI, which has no obvious thermal weight loss before 500°C. The decomposition of crown ether produces weight loss.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

本申请提供一种聚酰亚胺树脂，由芳香族二胺先与冠醚络合后，再与脂环族二酐和芳香族二酐共聚得到，其中所述芳香族二胺包括含酰胺键的芳香族二胺。所述聚酰亚胺树脂的杨氏模量≥8Gpa,断裂伸长率≥15％，拉伸强度≥200Mpa。本申请还提供一种包括该聚酰亚胺树脂的薄膜、该聚酰亚胺树脂薄膜的制备方法、含有该薄膜的柔性设备。本申请的聚酰亚胺树脂，冠醚通过自组装的方式添加到聚酰亚胺的主链上，以提高聚酰亚胺树脂的机械强度，所述聚酰亚胺树脂具有高模量、高断裂伸长率、高拉伸强度、低雾度、高透明度。

Description

聚酰亚胺树脂、聚酰亚胺薄膜及制备方法、柔性设备
相关申请的交叉引用
本申请要求在2021年11月30日提交中国专利局、申请号为202111447257.8、申请名称为“聚酰亚胺树脂、聚酰亚胺薄膜及制备方法、柔性设备”的中国专利的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请涉及一种聚酰亚胺树脂、聚酰亚胺薄膜及制备方法、含有该聚酰亚胺薄膜的柔性设备。
背景技术
近年来，随着光电器件的发展，传统透明玻璃基板已经无法满足柔性器件的要求，无色透明聚合物由于具有透明、质轻、耐冲击等优点，在图案化显示设备、液晶取向层、光学薄膜、有机光伏太阳能电池板、柔性印刷电路板和触摸平板等领域受到越来越多的重视。光电行业要求柔性聚合物不仅要有良好的光学透光率同时还要拥有很高的玻璃化转变为温度(Tg)(>300℃)以及良好的机械性能。但是市售的无色透明超级工程塑料如聚对苯二甲酸乙二醇酯(PET)(Tg≈78℃)、聚萘二甲酸乙二醇酯(PET)(Tg≈120℃)、聚碳酸酯(PC)(Tg≈120℃)和聚醚砜(PES)(Tg≈225℃)无法满足加工时的高温要求。
聚酰亚胺(PI)由于具有良好的耐热稳定性、优良的透明性、极优的绝缘性，可广泛应用于微电子及光电产业。然而PI由于分子链内或分子链间具有强烈的电荷转移络合物(CTC)作用造成分子链紧密的堆积，使PI在可见光范围内具有强烈的吸收，使PI显黄色或棕色。一般无色透明聚酰亚胺(CPI)的设计理念是降低PI分子链之间的堆积或使用脂环结构减弱CTC作用，而这些方法不可避免地造成PI机械性能的损失。
发明内容
本申请实施例第一方面提供了一种聚酰亚胺树脂，由芳香族二胺先与冠醚络合后，再与脂环族二酐和芳香族二酐共聚得到，其中所述芳香族二胺包括含酰胺键的芳香族二胺；
所述聚酰亚胺树脂的杨氏模量≥8Gpa,断裂伸长率≥15％，拉伸强度≥200Mpa。
本申请的聚酰亚胺树脂，冠醚通过自组装的方式添加到聚酰亚胺的主链上，相当于分子链上进行了“打结”限制了分子链间的滑动，以提高聚酰亚胺树脂的机械强度，所述聚酰亚胺树脂具有高模量、高断裂伸长率，高拉伸强度，低雾度、高透明度。本申请中使用的芳香族二胺含酰胺键，一方面能通过络合固定冠醚，起到防止键间滑动的作用，另一方面酰胺键是氢键供体和另外聚酰亚胺链上的酮羰基形成氢键，强化分子链之间相互作用。添加脂环族二酐有利于增加透明度，提高拉升强度，同时也可以提高玻璃化转变温度。
本申请实施方式中，所述聚酰亚胺树脂中，所述冠醚的重量百分含量为2％～15％。
本申请实施方式中，所述聚酰亚胺树脂采用紫外可见光光度计测得在550nm处的光学透过率≥88％。
本申请实施方式中，所述聚酰亚胺树脂的黄度≤3.0，雾度<1.0。
所述聚酰亚胺树脂透明度高。
本申请实施方式中，所述聚酰亚胺树脂的化学结构式为：
Figure PCTCN2022130717-appb-000001
其中，R 1和R 2分别独立地选自氢原子、卤素原子、碳原子数为1～4的卤代烷基、或碳原子数为1～5的烷基；
Figure PCTCN2022130717-appb-000002
为元素数为12～24的冠醚；
X 1为含有取代基的苯或者联苯基团；X 2为脂肪族基团或者芳香族基团；
n和m分别为>1的自然数。
本申请实施方式中，所述含酰胺键的芳香族二胺的化学式为：
Figure PCTCN2022130717-appb-000003
其中，R 1和R 2分别独立地选自氢原子、卤素原子、碳原子数为1～4的卤代烷基、或者碳原子数为1～5的烷基；
X 1为含有取代基的苯或者联苯基团。
本申请实施方式中，所述冠醚选自12-冠醚-4、15-冠醚-5、18-冠醚-6、二环己烷并-18-冠醚-6、苯并-18-冠6-醚、二苯并-18-冠醚-6、二苯并-24-冠醚-8中的至少一种。
本申请实施方式中，所述芳香族二酐选自1,2,4,5-均苯四甲酸二酐、3,3',4,4'-联苯四羧酸二酐、4,4-六氟异丙基邻苯二甲酸酐、3,3,4,4-二苯基砜四羧酸二酸酐、4,4'-氧双邻苯二甲酸酐、双酚A型二醚二酐中的至少一种；所述脂肪族二酐选自1,2,4,5-环己烷四甲酸二酐、1,2,3,4-环丁四羧二酐、1,2,3,4-环戊四羧酸二酐、3,3,6,6-四甲基四氢环丁酸酯-1,3,4,6-四酮、3,6-二甲基四氢环丁酸酯-1,3,4,6-四酮中的至少一种。
本申请实施方式中，所述含酰胺键的芳香族二胺相对所述芳香族二胺的摩尔量占比为10％以上；所述脂环族二酐相对所述脂环族二酐和芳香族二酐的二者总摩尔量的占比为10％以上。
本申请实施例第二方面提供了一种薄膜，包括本申请实施例第一方面所述的聚酰亚胺树脂。
本申请实施例第三方面提供了一种柔性设备，包括本申请实施例第二方面所述的薄膜。
本申请实施方式中，所述柔性设备为柔性显示器、柔性传感器、柔性天线、柔性太阳能电池、或者柔性电路。
本申请实施方式中，所述柔性设备为柔性显示器，所述柔性设备包括显示屏，所述薄膜作为盖板膜覆盖在所述显示屏上。
本申请实施方式中，所述柔性设备为柔性有机发光半导体显示器，所述柔性设备包括依次层叠的基材、薄膜晶体管阵列层、发光层，所述基材为所述薄膜。
本申请实施例第四方面提供了一种聚酰亚胺薄膜的制备方法，包括：
S1：将芳香族二胺与冠醚在有机溶剂中混合反应，得到二胺与冠醚的组装体的溶液，所述芳香族二胺包括含酰胺键的芳香族二胺；
S2：将所述二胺与冠醚的组装体的溶液加入脂环族二酐和芳香族二酐，得到聚酰胺酸胶液；
S3：将所述聚酰胺酸胶液使用化学亚胺化的方法制备聚酰亚胺胶液，然后将所述聚酰亚胺胶液进行沉淀得到聚酰亚胺纤维；
S4：将所述聚酰亚胺纤维溶解于无水溶剂中得到透明胶液，将所述透明胶液涂布在载体上制备得到湿薄膜；
S5：将所述湿薄膜进行真空干燥以除去溶剂，并升温使得亚胺化完全，得到聚酰亚胺薄膜。
本申请实施方式中，步骤S1中，所述冠醚与所述芳香族二胺的摩尔比为(0.2～2.4)：1；步骤S2中，所述脂环族二酐和所述芳香族二酐的总量与所述芳香族二胺的摩尔比为(1～1.15)：1。
本申请实施方式中，步骤S3包括：向所述聚酰胺酸胶液中添加化学亚胺化的试剂反应后，得到所述聚酰亚胺胶液，所述试剂包括有机酸酐和有机胺的混合物；然后将所述聚酰亚胺胶液倒入沸点<80℃的有机溶剂或沸点<80℃的有机溶剂与水的混合溶剂中，以沉淀得到所述聚酰亚胺纤维。
本申请实施方式中，步骤S3中，所述有机胺的量为所述有机酸酐的0.1～1倍摩尔数，所述有机酸酐选自包括乙酸酐、偏苯酸酐、马来酸酐中的至少一种；所述有机胺选自三乙胺、吡啶、N,N-二甲基苯胺中的至少一种。
本申请实施方式中，步骤S1采用的所述有机溶剂和步骤S4采用的所述无水溶剂均选自N,N-二甲基乙酰胺、N,N-二甲基甲酰胺、二甲亚砜、间甲酚、N-甲基-2-吡咯烷酮、γ-丁内酯中的至少一种。
本申请实施方式中，步骤S5中，所述升温使得亚胺化完全的温度为180℃～250℃。
化学亚胺化的另一个优点是避免了300℃以上的高温处理过程，只需在250℃或更低温度下去除溶剂即可，再加上端氨基被乙酸酐封端，避免了端基氧化变黄，因而得到的聚酰亚胺薄膜通常具有更优异的透明性和更浅的颜色；采用化学亚胺化还避免了高温环化脱水引起的分子链断裂，因此更有利于高强度聚酰亚胺的制备。
本申请实施方式中，所述含酰胺键的芳香族二胺相对所述芳香族二胺的摩尔量占比为10％以上；所述脂环族二酐相对所述脂环族二酐和芳香族二酐的二者总摩尔量的占比为10％以上。
本申请实施方式中，步骤S3中得到的聚酰亚胺纤维需进行干燥，干燥方法为将所得到的聚酰亚胺纤维在100℃～150℃下真空干燥24h～48h。
空气中干燥聚酰亚胺纤维会导致得到的聚酰亚胺树脂的黄度值偏高，真空干燥能够保证得到的聚酰亚胺树脂的黄度值较低。
附图说明
图1A和图1B为实施例1和对照例1的红外谱图。
图2为实施例1和对照例1的热重分析谱图。
图3为实施例1和对照例1的核磁氢谱谱图。
具体实施方式
下面结合本申请实施例中的附图对本申请实施例进行描述。本申请中涉及的数据范围如无特别说明均应包括端值。
手机盖板用的CPI硬化膜要求CPI膜在可见光区域的平均透过率为88％,黄度小于等于3.0，模量大于等于6GPa。然而，现有的透明PI的机械性能无法达到此要求。
为了满足市场对高强度无色透明聚酰亚胺的需求，本申请提供了一种无色透明的聚酰亚胺树脂以及该聚酰亚胺树脂的薄膜，具有高模量、高断裂伸长率、高拉伸强度、低雾度、高玻璃化转变温度(Tg)且超高透明度。
所述聚酰亚胺树脂由芳香族二胺先与冠醚络合后，再与脂环族二酐和芳香族二酐共聚得到。所述芳香族二胺包括含酰胺键的芳香族二胺。一些实施例中，所述含酰胺键的芳香族二胺相对所述芳香族二胺的摩尔量占比为10％以上；另一些实施例中，所述含酰胺键的芳香族二胺相对所述芳香族二胺的摩尔量占比为50％及以上；再一些实施例中，所述含酰胺键的芳香族二胺相对所述芳香族二胺的摩尔量占比为90％及以上。本申请中，所述冠醚通过自组装的方式添加到聚酰亚胺的主链上，相当于分子链上进行了“打结”限制了分子链间的滑动，以提高聚酰亚胺树脂的机械强度。
所述聚酰亚胺树脂的杨氏模量≥8Gpa,断裂伸长率≥15％，拉伸强度≥200Mpa。采用紫外可见光光度计测得所述聚酰亚胺树脂在550nm处的光学透过率≥88％。所述聚酰亚胺树脂的黄度≤3.0，雾度<1.0。
所述聚酰亚胺树脂中，所述冠醚的重量百分含量为2％～15％。所述芳香族二胺单体聚合后对应在所述聚酰亚胺树脂中的重量百分含量为60％～65％，所述脂环族二酐和芳香族二酐的两种单体聚合后对应在所述聚酰亚胺树脂中的重量百分含量为30％～34％。一些实施例中，所述脂环族二酐相对所述脂环族二酐和芳香族二酐的二者总摩尔量的占比为10％以上。另一些实施例中，所述脂环族二酐相对所述脂环族二酐和芳香族二酐的二者总摩尔量的占比为30％。
一些实施例中，所述聚酰亚胺树脂的化学结构式为：
Figure PCTCN2022130717-appb-000004
其中，R 1和R 2分别独立地选自氢原子、卤素原子、碳原子数为1～4的卤代烷基、或者碳原子数为1～5的烷基；
Figure PCTCN2022130717-appb-000005
为元素数为12～24的冠醚，所述冠醚套在聚酰亚胺的主链上形成项圈式超分子结构；
X 1为含有取代基的苯或者联苯基团；X 2为脂肪族基团或者芳香族基团；
n和m分别为>1的自然数。
冠醚分子套在聚酰亚胺的主链上，使聚酰亚胺分子链由二维扩展为三维，分子链柔顺性降低，刚性得到提升；另外冠醚的极性较聚酰亚胺低，对聚酰亚胺分子链间的作用力有一定的屏蔽作用，因此聚酰亚胺分子链间相互作用力降低，滑移较容易，使薄膜的断裂伸长率增加。
一些实施例中，所述含酰胺键的芳香族二胺(AB-TFMB)的化学式为：
Figure PCTCN2022130717-appb-000006
其中，R 1和R 2分别独立地选自氢原子、卤素原子、碳原子数为1～4的卤代烷基、或者碳原子数为1～5的烷基；X 1为含有取代基的苯或者联苯基团。
所述芳香族二酐为1,2,4,5-均苯四甲酸二酐、3,3',4,4'-联苯四羧酸二酐、4,4-六氟异丙基邻苯二甲酸酐、3,3,4,4-二苯基砜四羧酸二酸酐、4,4'-氧双邻苯二甲酸酐、双酚A型二醚二酐中的一种或多种。所列的芳香族二酐具体的化学结构式如下：
Figure PCTCN2022130717-appb-000007
所述脂肪族二酐为1,2,4,5-环己烷四甲酸二酐、1,2,3,4-环丁四羧二酐、1,2,3,4-环戊四羧酸二酐、3,3,6,6-四甲基四氢环丁酸酯-1,3,4,6-四酮、3,6-二甲基四氢环丁酸酯-1,3,4,6-四酮中的一种或多种。所列的脂肪族二酐具体的化学结构式如下：
Figure PCTCN2022130717-appb-000008
其中脂环族二酐至少占脂环族二酐和芳香族二酐二者总摩尔量的10％，一些实施例中，脂环族二酐至少占脂环族二酐和芳香族二酐二者总摩尔量的30％。
所述冠醚为12-冠醚-4、15-冠醚-5、18-冠醚-6、二环己烷并-18-冠醚-6、苯并-18-冠6-醚、二苯并-18-冠醚-6、二苯并-24-冠醚-8中的一种或多种。所列的冠醚具体的化学结构式如下：
Figure PCTCN2022130717-appb-000009
本申请中使用的芳香族二胺含酰胺键，一方面能通过络合固定冠醚，起到分子链中防止键间滑动的作用，另一方面酰胺键是氢键供体和另外聚酰亚胺链上的酮羰基形成氢键，强化分子链之间相互作用。添加脂环族二酐有利于增加透明度，提高拉升强度，同时也可以提高玻璃化转变温度。
本申请的聚酰亚胺树脂，可以薄膜的形式应用于多种应用场景，例如柔性显示器、柔性传感器、柔性天线、柔性电池、柔性电路等。
本申请还提供一种聚酰亚胺树脂薄膜，包括所述聚酰亚胺树脂。聚酰亚胺树脂薄膜可作为一个透明、机械强度高的膜层应用于柔性显示器、柔性传感器、柔性天线、柔性太阳能电池、柔性电路等中。以柔性显示器为例，所述柔性显示器包括显示屏以及附着在所述显示屏上的所述聚酰亚胺树脂薄膜。所述聚酰亚胺树脂薄膜并非作为保护膜，而是显示器必不可少的透明的盖板膜(cover window)。
所述柔性设备也可为柔性有机发光半导体(Organic Light-Emitting Diode，OLED)显示器，所述柔性设备包括依次层叠的基材、薄膜晶体管阵列层、发光层，所述聚酰亚胺树脂薄膜作为所述基材。本申请还提供一种聚酰亚胺树脂薄膜的制备方法，包括如下步骤。
步骤S1：将芳香族二胺与冠醚在有机溶剂中混合反应，得到二胺与冠醚的组装体的溶液，所述芳香族二胺包括含酰胺键的芳香族二胺。
步骤S1可在保护气体(例如氮气)的保护下进行。所述冠醚与所述芳香族二胺的摩尔比为(0.2～2.4)：1。该步骤所采用的有机溶剂可为N,N-二甲基乙酰胺、N,N-二甲基甲酰胺、二甲亚砜、间甲酚、N-甲基-2-吡咯烷酮、γ-丁内酯中的一种或多种。
步骤S2：将所述二胺与冠醚的组装体的溶液加入脂环族二酐和芳香族二酐，得到聚酰胺酸胶液。
步骤S2可在保护气体(例如氮气)的保护下进行。步骤S2中添加的所述脂环族二酐和所述芳香族二酐的总量与所述芳香族二胺的摩尔比为(1～1.15)：1。步骤S2的过程中保持搅拌，此外需观察胶液的状态，根据需要补加有机溶剂，使体系粘度维持在合适的水平。搅拌反应后，得到透明粘稠的聚酰胺酸胶液。
步骤S3：将所述聚酰胺酸胶液使用化学亚胺化的方法制备聚酰亚胺胶液，然后将所述聚酰亚胺胶液进行沉淀得到聚酰亚胺纤维。
化学亚胺化采用的试剂包括有机酸酐和有机胺的混合物，有机胺的量为有机酸酐的0.1～1倍摩尔数。有机酸酐的类别包括但不限于乙酸酐、偏苯酸酐、马来酸酐等；有机胺的类别包括但不限于三乙胺、吡啶、N,N-二甲基苯胺等。
步骤S3中，向所述聚酰胺酸胶液中逐渐滴入化学亚胺化采用的试剂，并保持在室温条件下搅拌反应，得到透明粘稠的聚酰亚胺胶液。反应过程中时刻观察体系粘度补加有机溶剂，防止出现凝胶化现象。然后将聚酰亚胺胶液倒入沸点<80℃的有机溶剂(例如甲醇)或沸点<80℃的有机溶剂和水的混合溶剂中得到丝状沉淀(聚酰亚胺纤维)。一实施例中，采用甲醇和水的混合溶剂用以将聚合物从溶剂中沉淀出来，且一般甲醇和水的体积比例为1：1。此步骤得到的丝状沉淀(聚酰亚胺纤维)可用甲醇和水的混合溶剂洗涤三遍，然后将聚酰亚胺纤维进行干燥。所述聚酰亚胺纤维的干燥方法为将所得到的聚酰亚胺纤维放入真空烘箱中，在100℃～150℃下真空干燥24h～48h得到干燥的聚酰亚胺纤维。空气中干燥聚酰亚胺纤维会导致得到的聚酰亚胺树脂的黄度值偏高，真空干燥能够保证得到的聚酰亚胺树脂的黄度值较低。步骤S4：将所述聚酰亚胺纤维溶解于无水溶剂中得到透明胶液，将所述透明胶液涂附在载体上制备湿薄膜。
将步骤S3中得到的干燥后的聚酰亚胺纤维重新溶解于无水溶剂中，配制为固含量10wt％～13wt％的适宜粘度的透明胶液。所述无水溶剂可为N,N-二甲基乙酰胺(DMAc)、N,N-二甲基甲酰胺(DMF)、二甲亚砜、间甲酚、N-甲基-2-吡咯烷酮、γ-丁内酯中的一种或多种。
聚酰亚胺薄膜可采用溶液流延法进行制备，但不以此为限。将洁净的载体(例如玻璃板)置于薄膜涂布机上，然后将聚酰亚胺胶液倾倒于玻璃板上，调整不锈钢刮刀的高度进行涂膜。
化学亚胺化由于是直接通过聚酰亚胺涂膜，避免了亚胺化过程中小分子水的产生，同时，也避免了聚丙烯酸(PAA)不稳定带来的降解，其能得到质量更高的薄膜。化学亚胺化的另一个优点是避免了300℃以上的高温处理过程，只需在250℃或更低温度下去除溶剂即可，再加上端氨基被乙酸酐封端，避免了端基氧化变黄，因而得到的聚酰亚胺薄膜通常具有更优异的透明性和更浅的颜色；采用化学亚胺化还避免了高温环化脱水引起的分子链断裂，因此更有利于高强度聚酰亚胺的制备。
步骤S5：将所述湿薄膜进行真空干燥以除去溶剂，并升温使得亚胺化完全，得到聚酰亚胺薄膜。
涂膜后的玻璃板转移至真空烘箱中进行真空干燥，在60℃～100℃预烘1～2小时，以除去所述湿薄膜中的大部分溶剂；然后转移至高温烘箱中，180℃～250℃的温度下进一步亚胺化和溶剂脱除。如此得到附着在玻璃板上的聚酰亚胺树脂薄膜。
冷却后，将带有聚酰亚胺薄膜的玻璃板置于热水中，剥离得到具有一定强度的自支撑薄膜，再在鼓风烘箱中干燥得到最终的薄膜。所得的聚酰亚胺薄膜薄膜平均厚度可为50μm，但 不以此为限，厚度可根据需要进行设定。
下面通过具体实施例对本申请实施例进行进一步的说明。
实施例1
在接有氮气出入口和机械搅拌的250mL三口烧瓶中，加入含酰胺键芳香族二胺AB-TFMB(8.3772g，15.0mmol)、18冠6醚(5.2863g，20.0mmol)和一定体积的无水N-甲基吡咯烷酮(NMP，作为有机溶剂)，室温下搅拌。再加入六氟二酐(6FDA，1.9991g，4.5mmol)和环丁烷甲酸二酐(CBDA，2.0592g，10.5mmol)，补加NMP调整体系的固含量为20％。随时观察胶液状态，补加NMP溶剂，使体系粘度维持在合适的水平。反应24h后，得到透明粘稠的聚酰胺酸胶液。
然后缓慢向体系中滴入乙酸酐(7.1mL)和三乙胺(2.2mL)的混合溶液，并时刻观察体系粘度补加NMP，防止出现凝胶化现象。室温搅拌24h后，得到透明粘稠的聚酰亚胺胶液。将胶液倒入到2000mL甲醇和水的混合溶剂中得到丝状沉淀，并用甲醇和水的混合溶剂洗涤三遍。最后，将所得到的丝状物放入真空烘箱中，在150℃下真空干燥24h得到干燥的聚酰亚胺纤维。
将干燥后的丝状聚酰亚胺沉淀重新溶解于无水DMF中，配制固含量为10wt％～13wt％的适宜粘度的透明胶液。聚酰亚胺薄膜采用溶液流延法进行制备。将洁净的玻璃板置于薄膜涂布机上，然后将聚酰亚胺胶液倾倒于板上，调整不锈钢刮刀的高度，以5mm/s的速度涂膜。将其转移进真空烘箱中，并在80℃下预烘1小时，以除去大部分溶剂。之后将其转移至高温烘箱中，250℃ 2h的程序进行进一步亚胺化和溶剂脱除。冷却后，将带有聚酰亚胺薄膜的玻璃板置于热水中，剥离得到具有一定强度的自支撑薄膜，再在鼓风烘箱中100℃烘干2h得到最终的薄膜。
实施例2
在接有氮气出入口和机械搅拌的250mL三口烧瓶中，加入含酰胺键芳香族二胺AB-TFMB(8.3772g，15.0mmol)、18冠6醚(1.7621g，10.0mmol)和一定体积的无水N-甲基吡咯烷酮(NMP，作为有机溶剂)，室温下搅拌。再加入六氟二酐(6FDA，1.9991g，4.5mmol)和环丁烷甲酸二酐(CBDA，2.0592g，10.5mmol)，补加无水NMP调整体系的固含量为20％。随时观察胶液状态，补加NMP溶剂，使体系粘度维持在合适的水平。反应24h后，得到透明粘稠的聚酰胺酸胶液。
然后缓慢向体系中滴入乙酸酐(7.1mL)和三乙胺(2.2mL)的混合溶液，并时刻观察体系粘度补加NMP，防止出现凝胶化现象。室温搅拌24h后，得到透明粘稠的聚酰亚胺胶液。将胶液倒入到2000mL甲醇和水的混合溶剂中得到丝状沉淀，并用甲醇和水的混合溶剂洗涤三遍。最后，将所得到的丝状物放入真空烘箱中，在150℃下真空干燥24h得到干燥的聚酰亚胺纤维。
将干燥后的丝状聚酰亚胺沉淀重新溶解于无水DMF中，配制固含量为10wt％～13wt％的适宜粘度的透明胶液。聚酰亚胺薄膜采用溶液流延法进行制备。将洁净的玻璃板置于薄膜涂布机上，然后将聚酰亚胺胶液倾倒于板上，调整不锈钢刮刀的高度，以5mm/s的速度涂膜。将其转移进真空烘箱中，并在80℃下预烘1小时，以除去大部分溶剂。之后将其转移至高温烘箱中，250℃ 2h的程序进行进一步亚胺化和溶剂脱除。冷却后，将带有聚酰亚胺薄膜的玻璃板置于热水中，剥离得到具有一定强度的自支撑薄膜，再在鼓风烘箱中100℃烘干2h得到最终的薄膜。
实施例3
在接有氮气出入口和机械搅拌的250mL三口烧瓶中，加入AB-TFMB(6.7018g，12.0mmol)、18冠6醚(3.806g，14.4mmol)和一定体积的无水二甲基乙酰胺(DMAc)，室温下搅拌。再加入6FDA(2.1324g，4.8mmol)和CBDA(1.4120g，7.2mmol)，补加无水DMAc调整体系的固含量为30％。随时观察胶液状态，补加DMAc溶剂，使体系粘度维持在合适的水平。反应24h后，得到透明粘稠的聚酰胺酸胶液。
然后缓慢向体系中滴入乙酸酐(7.1mL)和三乙胺(2.2mL)的混合溶液，并时刻观察体系粘度补加DMAc，防止出现凝胶化现象。室温搅拌24h后，得到透明粘稠的聚酰亚胺胶液。将胶液倒入到2000mL甲醇和水的混合溶剂中得到丝状沉淀，并用甲醇和水的混合溶剂洗涤三遍。最后，将所得到的丝状物放入真空烘箱中，在150℃下真空干燥24h得到干燥的聚酰亚胺纤维。
将干燥后的丝状聚酰亚胺沉淀重新溶解于无水NMP中，配制固含量为10wt％～13wt％的适宜粘度的透明胶液。聚酰亚胺薄膜采用溶液流延法进行制备。将洁净的玻璃板置于薄膜涂布机上，然后将聚酰亚胺胶液倾倒于板上，调整不锈钢刮刀的高度，以5mm/s的速度涂膜。将其转移进真空烘箱中，并在80℃下预烘1小时，以除去大部分溶剂。之后将其转移至高温烘箱中，250℃ 2h的程序进行进一步亚胺化和溶剂脱除。冷却后，将带有聚酰亚胺薄膜的玻璃板置于热水中，剥离得到具有一定强度的自支撑薄膜，再在鼓风烘箱中100℃烘干2h得到最终的薄膜。
对照例1
在接有氮气出入口和机械搅拌的250mL三口烧瓶中，加入AB-TFMB(8.3772g，15.0mmol)和一定体积的无水NMP，搅拌后，加入6FDA(2.1324g，4.8mmol)和CBDA(1.4120g，7.2mmol)，补加无水NMP调整体系的固含量为30％。随时观察胶液状态，补加NMP溶剂，使体系粘度维持在合适的水平。反应24h后，得到透明粘稠的聚酰胺酸胶液。
然后缓慢向体系中滴入乙酸酐(7.1mL)和三乙胺(2.2mL)的混合溶液，并时刻观察体系粘度补加NMP，防止出现凝胶化现象。室温搅拌24h后，得到透明粘稠的聚酰亚胺胶液。将胶液倒入到2000mL甲醇和水的混合溶剂中得到丝状沉淀，并用甲醇和水的混合溶剂洗涤三遍。最后，将所得到的丝状物放入真空烘箱中，在150℃下真空干燥24h得到干燥的聚酰亚胺纤维。
将干燥后的丝状聚酰亚胺沉淀重新溶解于无水NMP中，配制固含量为10wt％～13wt％的适宜粘度的透明胶液。聚酰亚胺薄膜采用溶液流延法进行制备。将洁净的玻璃板置于薄膜涂布机上，然后将聚酰亚胺胶液倾倒于板上，调整不锈钢刮刀的高度，以5mm/s的速度涂膜。将其转移进真空烘箱中，并在80℃下预烘1小时，以除去大部分溶剂。之后将其转移至高温烘箱中，250℃ 2h的程序进行进一步亚胺化和溶剂脱除。冷却后，将带有聚酰亚胺薄膜的玻璃板置于热水中，剥离得到具有一定强度的自支撑薄膜，再在鼓风烘箱中100℃烘干2h得到最终的薄膜。
对照例2
在接有氮气出入口和机械搅拌的250mL三口烧瓶中，加入TFMB(4.8035g，15.0mmol)和一定体积的无水NMP，搅拌溶解后，加入6FDA(1.9991g，4.5mmol)和CBDA(2.0592g，10.5mmol)，补加无水NMP调整体系的固含量为30％。随时观察胶液状态，补加DMAc溶剂，使体系粘度维持在合适的水平。反应24h后，得到透明粘稠的聚酰胺酸胶液。
然后缓慢向体系中滴入乙酸酐(7.1mL)和三乙胺(2.2mL)的混合溶液，并时刻观察体系粘度补加NMP，防止出现凝胶化现象。室温搅拌24h后，得到透明粘稠的聚酰亚胺胶液。将胶液倒入到2000mL甲醇和水的混合溶剂中得到丝状沉淀，并用甲醇和水的混合溶剂洗涤三遍。最后，将所得到的丝状物放入真空烘箱中，在150℃下真空干燥24h得到干燥的聚酰亚胺纤维。
将干燥后的丝状聚酰亚胺沉淀重新溶解于无水NMP中，配制固含量为10wt％～13wt％的适宜粘度的透明胶液。聚酰亚胺薄膜采用溶液流延法进行制备。将洁净的玻璃板置于70℃的薄膜涂布机上，然后将聚酰亚胺胶液倾倒于板上，调整不锈钢刮刀的高度，以5mm/s的速度涂膜。将其转移进真空烘箱中，并在80℃下预烘1小时，以除去大部分溶剂。之后将其转移至高温烘箱中，250℃ 2h的程序进行进一步亚胺化和溶剂脱除。冷却后，将带有聚酰亚胺薄膜的玻璃板置于热水中，剥离得到具有一定强度的自支撑薄膜，再在鼓风烘箱中100℃烘干2h得到最终的薄膜。
实施例1至3和对照例1和2的薄膜的性能测试结果如下表所示。根据表中的测试结果可知：与对照例1和2相比，实施例1至3的薄膜在保证透明度的情况下且具有更好的机械性能。
Figure PCTCN2022130717-appb-000010
请参阅图1A和图1B，实施例1和对照例1的薄膜的红外光谱图，可知：对照例1为纯PI的红外光谱图，在2850cm -1附近无冠醚上亚甲基的伸缩振动峰，而实施例1为冠醚复合PI，2850cm -1附近可见冠醚上亚甲基的伸缩振动峰。
请参阅图2，实施例1和对照例1的薄膜的热重分析谱图，对照例1为纯PI，500℃前无明显热失重，实施例为冠醚复合PI，500℃前主链上冠醚分解产生失重。
请参阅图3，实施例1和对照例1的薄膜的核磁氢谱谱图，对照例1为不含冠醚的纯PI，3.6ppm处无冠醚的质子信号，实施例1为冠醚复合PI，3.6ppm处有冠醚的质子信号。
需要说明的是，以上仅为本申请的具体实施方式，但本申请的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本申请揭露的技术范围内，可轻易想到变化或替换，都应涵盖在本申请的保护范围之内；在不冲突的情况下，本申请的实施方式及实施方式中的特征可以相互组合。因此，本申请的保护范围应以权利要求的保护范围为准。

Claims (22)

  1. 一种聚酰亚胺树脂，其特征在于，所述聚酰亚胺树脂由芳香族二胺先与冠醚络合后，再与脂环族二酐和芳香族二酐共聚得到，其中所述芳香族二胺包括含酰胺键的芳香族二胺；
    所述聚酰亚胺树脂的杨氏模量≥8Gpa,断裂伸长率≥15％，拉伸强度≥200Mpa。
  2. 根据权利要求1所述的聚酰亚胺树脂，其特征在于，所述聚酰亚胺树脂中，所述冠醚的重量百分含量为2％～15％。
  3. 根据权利要求1或2所述的聚酰亚胺树脂，其特征在于，所述聚酰亚胺树脂采用紫外可见光光度计测得在550nm处的光学透过率≥88％。
  4. 根据权利要求1至3中任一项所述的聚酰亚胺树脂，其特征在于，所述聚酰亚胺树脂的黄度≤3.0，雾度<1.0。
  5. 根据权利要求1至4中任一项所述的聚酰亚胺树脂，其特征在于，所述聚酰亚胺树脂的化学结构式为：
    Figure PCTCN2022130717-appb-100001
    其中，R 1和R 2分别独立地选自氢原子、卤素原子、碳原子数为1～4的卤代烷基、或碳原子数为1～5的烷基；
    Figure PCTCN2022130717-appb-100002
    为元素数为12～24的冠醚；
    X 1为含有取代基的苯或者联苯基团；X 2为脂肪族基团或者芳香族基团；
    n和m分别为>1的自然数。
  6. 根据权利要求1至5中任一项所述的聚酰亚胺树脂，其特征在于，所述含酰胺键的芳香族二胺的化学式为：
    Figure PCTCN2022130717-appb-100003
    其中，R 1和R 2分别独立地选自氢原子、卤素原子、碳原子数为1～4的卤代烷基、或碳原子数为1～5的烷基；
    X 1为含有取代基的苯或者联苯基团。
  7. 根据权利要求1至6中任一项所述的聚酰亚胺树脂，其特征在于，所述冠醚选自12- 冠醚-4、15-冠醚-5、18-冠醚-6、二环己烷并-18-冠醚-6、苯并-18-冠6-醚、二苯并-18-冠醚-6、二苯并-24-冠醚-8中的至少一种。
  8. 根据权利要求1至7中任一项所述的聚酰亚胺树脂，其特征在于，所述芳香族二酐选自1,2,4,5-均苯四甲酸二酐、3,3',4,4'-联苯四羧酸二酐、4,4-六氟异丙基邻苯二甲酸酐、3,3,4,4-二苯基砜四羧酸二酸酐、4,4'-氧双邻苯二甲酸酐、双酚A型二醚二酐中的至少一种；所述脂肪族二酐选自1,2,4,5-环己烷四甲酸二酐、1,2,3,4-环丁四羧二酐、1,2,3,4-环戊四羧酸二酐、3,3,6,6-四甲基四氢环丁酸酯-1,3,4,6-四酮、3,6-二甲基四氢环丁酸酯-1,3,4,6-四酮中的至少一种。
  9. 根据权利要求1至8中任一项所述的聚酰亚胺树脂，其特征在于，所述含酰胺键的芳香族二胺相对所述芳香族二胺的摩尔量占比为10％以上；所述脂环族二酐相对所述脂环族二酐和芳香族二酐的二者总摩尔量的占比为10％以上。
  10. 一种薄膜，其特征在于，包括权利要求1至9中任一项所述的聚酰亚胺树脂。
  11. 一种柔性设备，其特征在于，包括权利要求10所述的薄膜。
  12. 根据权利要求11所述的柔性设备，其特征在于，所述柔性设备为柔性显示器、柔性传感器、柔性天线、柔性太阳能电池、或者柔性电路。
  13. 根据权利要求12所述的柔性设备，其特征在于，所述柔性设备为柔性显示器，所述柔性设备包括显示屏，所述薄膜作为盖板膜覆盖在所述显示屏上。
  14. 根据权利要求12所述的柔性设备，其特征在于，所述柔性设备为柔性有机发光半导体显示器，所述柔性设备包括依次层叠的基材、薄膜晶体管阵列层、发光层，所述基材为所述薄膜。
  15. 一种聚酰亚胺薄膜的制备方法，其特征在于，包括：
    S1：将芳香族二胺与冠醚在有机溶剂中混合反应，得到二胺与冠醚的组装体的溶液，所述芳香族二胺包括含酰胺键的芳香族二胺；
    S2：将所述二胺与冠醚的组装体的溶液加入脂环族二酐和芳香族二酐，得到聚酰胺酸胶液；
    S3：将所述聚酰胺酸胶液使用化学亚胺化的方法制备聚酰亚胺胶液，然后将所述聚酰亚胺胶液进行沉淀得到聚酰亚胺纤维；
    S4：将所述聚酰亚胺纤维溶解于无水溶剂中得到透明胶液，将所述透明胶液涂布在载体上制备得到湿薄膜；
    S5：将所述湿薄膜进行真空干燥以除去溶剂，并升温使得亚胺化完全，得到聚酰亚胺薄膜。
  16. 根据权利要求15所述的聚酰亚胺薄膜的制备方法，其特征在于，步骤S1中，所述冠醚与所述芳香族二胺的摩尔比为(0.2～2.4)：1；步骤S2中，所述脂环族二酐和所述芳香族二酐的总量与所述芳香族二胺的摩尔比为(1～1.15)：1。
  17. 根据权利要求15或16所述的聚酰亚胺薄膜的制备方法，其特征在于，步骤S3包括：向所述聚酰胺酸胶液中添加化学亚胺化的试剂反应后，得到所述聚酰亚胺胶液，所述试剂包括有机酸酐和有机胺的混合物；然后将所述聚酰亚胺胶液倒入沸点<80℃的有机溶剂或沸点<80℃的有机溶剂与水的混合溶剂中，以沉淀得到所述聚酰亚胺纤维。
  18. 根据权利要求17所述的聚酰亚胺薄膜的制备方法，其特征在于，步骤S3中，所述有机胺的量为所述有机酸酐的0.1～1倍摩尔数，所述有机酸酐选自包括乙酸酐、偏苯酸酐、 马来酸酐中的至少一种；所述有机胺选自三乙胺、吡啶、N,N-二甲基苯胺中的至少一种。
  19. 根据权利要求15至18中任一项所述的聚酰亚胺薄膜的制备方法，其特征在于，步骤S1采用的所述有机溶剂和步骤S4采用的所述无水溶剂均选自N,N-二甲基乙酰胺、N,N-二甲基甲酰胺、二甲亚砜、间甲酚、N-甲基-2-吡咯烷酮、γ-丁内酯中的至少一种。
  20. 根据权利要求15至19中任一项所述的聚酰亚胺薄膜的制备方法，其特征在于，步骤S5中，所述升温使得亚胺化完全的温度为180℃～250℃。
  21. 根据权利要求15至19中任一项所述的聚酰亚胺薄膜的制备方法，其特征在于，所述含酰胺键的芳香族二胺相对所述芳香族二胺的摩尔量占比为10％以上；所述脂环族二酐相对所述脂环族二酐和芳香族二酐的二者总摩尔量的占比为10％以上。
  22. 根据权利要求15至21中任一项所述的聚酰亚胺薄膜的制备方法，其特征在于，步骤S3中得到的聚酰亚胺纤维需进行干燥，干燥方法为将所得到的聚酰亚胺纤维在100℃～150℃下真空干燥24h～48h。
PCT/CN2022/130717 2021-11-30 2022-11-08 聚酰亚胺树脂、聚酰亚胺薄膜及制备方法、柔性设备 WO2023098424A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202111447257.8A CN116199883A (zh) 2021-11-30 2021-11-30 聚酰亚胺树脂、聚酰亚胺薄膜及制备方法、柔性设备
CN202111447257.8 2021-11-30

Publications (1)

Publication Number Publication Date
WO2023098424A1 true WO2023098424A1 (zh) 2023-06-08

Family

ID=86516081

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2022/130717 WO2023098424A1 (zh) 2021-11-30 2022-11-08 聚酰亚胺树脂、聚酰亚胺薄膜及制备方法、柔性设备

Country Status (2)

Country Link
CN (1) CN116199883A (zh)
WO (1) WO2023098424A1 (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117106303A (zh) * 2023-08-21 2023-11-24 中山大学 一种聚酰胺-聚酰亚胺复合物及其制备方法和应用
CN118373981A (zh) * 2024-04-15 2024-07-23 深圳大学 一种低介电聚酰亚胺、低介电聚酰亚胺薄膜及其柔性软板的制备方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116640305B (zh) * 2023-07-26 2023-10-27 北京建工环境修复股份有限公司 一种聚酰亚胺亚磺酸盐及其制备方法和用途

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012012493A (ja) * 2010-06-30 2012-01-19 Nissan Chem Ind Ltd 液晶配向剤及びそれを用いた液晶表示素子
CN104356647A (zh) * 2014-10-31 2015-02-18 华南理工大学 一种冠醚改性聚酰亚胺杂化膜及其制备方法
CN110643374A (zh) * 2019-09-27 2020-01-03 江苏三月光电科技有限公司 一种液晶取向剂、液晶取向膜以及液晶显示元件
CN112877079A (zh) * 2020-12-03 2021-06-01 深圳清荷科技有限公司 一种液晶取向剂、液晶取向膜以及液晶显示元件

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012012493A (ja) * 2010-06-30 2012-01-19 Nissan Chem Ind Ltd 液晶配向剤及びそれを用いた液晶表示素子
CN104356647A (zh) * 2014-10-31 2015-02-18 华南理工大学 一种冠醚改性聚酰亚胺杂化膜及其制备方法
CN110643374A (zh) * 2019-09-27 2020-01-03 江苏三月光电科技有限公司 一种液晶取向剂、液晶取向膜以及液晶显示元件
CN112877079A (zh) * 2020-12-03 2021-06-01 深圳清荷科技有限公司 一种液晶取向剂、液晶取向膜以及液晶显示元件

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117106303A (zh) * 2023-08-21 2023-11-24 中山大学 一种聚酰胺-聚酰亚胺复合物及其制备方法和应用
CN118373981A (zh) * 2024-04-15 2024-07-23 深圳大学 一种低介电聚酰亚胺、低介电聚酰亚胺薄膜及其柔性软板的制备方法

Also Published As

Publication number Publication date
CN116199883A (zh) 2023-06-02

Similar Documents

Publication Publication Date Title
WO2023098424A1 (zh) 聚酰亚胺树脂、聚酰亚胺薄膜及制备方法、柔性设备
TWI638843B (zh) 聚醯胺醯亞胺及其製備方法、聚醯胺醯亞胺膜以及顯示器用覆蓋基板
CN110684195B (zh) 聚酰亚胺膜、聚酰亚胺前体和聚酰亚胺
TWI637981B (zh) 聚醯胺醯亞胺及其製備製程及包含其的聚醯胺醯亞胺膜
KR101984171B1 (ko) 고강도 투명 폴리아미드이미드 및 이의 제조방법
CN111892818B (zh) 聚酰亚胺无色透明薄膜及其制备方法和应用
US20230145854A1 (en) High modulus colorless polyimide film and method of preparation
TWI759335B (zh) 聚醯亞胺、聚醯亞胺前驅物樹脂、該等之溶液、聚醯亞胺之製造方法及使用聚醯亞胺之薄膜
TW201525026A (zh) 聚醯亞胺前驅體組成物、聚醯亞胺之製造方法、聚醯亞胺、聚醯亞胺膜及基板
KR20070017001A (ko) 광학 타입 분야에 유용한 저색상 폴리이미드 조성물 및이와 관련된 방법 및 조성물
KR102054545B1 (ko) 폴리이미드 전구체 용액 및 이를 이용한 폴리이미드 필름의 제조방법
CN112708134A (zh) 一种无色透明共聚酰胺-酰亚胺膜及其制备方法
CN112646183A (zh) 聚酰亚胺材料及其制备方法和应用
WO2022133722A1 (zh) 聚酰亚胺材料及其制备方法和应用
CN112375241B (zh) 一种无色透明聚酰亚胺薄膜及其制备方法
JP2022172466A (ja) 新規なジアミン化合物、それを用いたポリイミド前駆体およびポリイミドフィルム、並びにその用途
KR20220092774A (ko) 폴리아미드이미드 공중합체 및 그를 포함하는 필름
WO2017111134A1 (ja) ポリイミド共重合体及びそれを用いた成形体
JP2010037401A (ja) ポリイミド、その製造方法、及びポリイミドフィルムの製造方法
JP6765093B2 (ja) ポリイミド
TWI758034B (zh) 聚醯亞胺及其所形成之膜
KR20020055837A (ko) 폴리아믹산 수지 조성물
KR20150137700A (ko) 폴리이미드 공중합체를 포함하는 위상차 필름 및 이를 포함하는 디스플레이 장치
JP2004339363A (ja) ポリイミド前駆体液組成物及びポリイミド被膜
JP7095115B2 (ja) ポリイミド溶液、及び、ポリイミド

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22900229

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE