CN111690135A - Diamine monomer containing adamantane structure, polyimide film, preparation method and application thereof - Google Patents

Diamine monomer containing adamantane structure, polyimide film, preparation method and application thereof Download PDF

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CN111690135A
CN111690135A CN202010706499.3A CN202010706499A CN111690135A CN 111690135 A CN111690135 A CN 111690135A CN 202010706499 A CN202010706499 A CN 202010706499A CN 111690135 A CN111690135 A CN 111690135A
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diamine monomer
polyimide
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CN111690135B (en
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王献伟
苗杰
阎敬灵
王震
孟祥胜
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Ningbo Institute of Material Technology and Engineering of CAS
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    • 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
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Abstract

The invention discloses a diamine monomer containing a adamantane structure, which has a structure shown in any one of the following formulas:
Figure DDA0002594958630000011
the invention also provides a preparation method of the diamine monomer containing the adamantane structure, which comprises the following steps: carrying out Friedel-crafts alkylation reaction on 1-adamantanol, acetanilide derivatives and a catalyst at the temperature of 20-35 ℃ for 2-10 h to prepare a bisamide compound; then dissolving the bisamide compound, the inorganic base and the solvent in 80-130%And reacting at the temperature of 6-24 hours to obtain the diamine monomer containing the adamantane structure. The invention also discloses a polyimide film and a preparation method thereof. The colorless polyimide film prepared by the invention has better heat resistance, solubility, mechanical property and excellent optical property, and has optical transmittance at 400nm>85 percent, and can reach 91 percent at most, and the preparation method has good application prospect in the fields of flexible display, thin-film solar cells, photoelectron engineering and the like.

Description

Diamine monomer containing adamantane structure, polyimide film, preparation method and application thereof
Technical Field
The invention belongs to the technical field of chemical synthesis technology and organic high polymer materials, and particularly relates to a diammine monomer containing a adamantane structure, a polyimide film, a preparation method and an application thereof, in particular to a diammine monomer containing a adamantane structure, a preparation method and an application thereof, and a colorless transparent polyimide film containing a adamantane structure, a preparation method and an application thereof.
Background
The development of photoelectric devices gradually shows the trend of light weight, ultra-thin and flexibility, the glass serving as the traditional transparent substrate material cannot meet the development requirement of the future flexible packaging technology, and the high-transparency polymer material has the advantages of transparency, flexibility, light weight, high impact resistance and the like, so that the high-transparency polymer material becomes the first choice of the future flexible photoelectric packaging substrate material. Conventional high transparency polymer films such as polyethylene terephthalate (PET, T)g78.8 ℃ C.), polycarbonate (PC, T)g145 ℃ C.), polymethyl methacrylate (PMMA, T)gAbout 105 ℃ C., etc., but the heat resistance is insufficient, and the requirements of high temperature treatment in the process of processing a photovoltaic device cannot be satisfied. The Polyimide (PI) film has excellent heat-resistant stability, and can meet the requirements of high-temperature processes such as electrode film deposition, annealing treatment and the like in the processing process of photoelectric devices, so that the development of high-transparency PI materials becomes a key point of research. The traditional wholly aromatic PI film is brownish yellow, the light transmittance of visible light (with the wavelength of 400-800 nm) is low, the light transmittance at the 400nm position is almost 100 percent absorbed, and the application requirements of optical waveguide materials, photoelectric materials, orientation film materials and the like in the photoelectric field such as the optical communication field and the liquid crystal display field cannot be met. Semi-aromatic or full-aliphatic PI film materials are light in color or nearly colorless, but such PI film materials are limited by structural factors, and generally have heat resistanceThe energy is poor. Introduction of a rigid and highly conjugated structure into a molecular chain can improve heat resistance of the film, but can result in a decrease in light transmittance, and vice versa. In practical applications, the light transmittance and heat resistance of the film need to be considered comprehensively, so that the development of a PI film with high heat resistance and high light transmittance is the goal of many researchers.
Adamantane (adamantane) is highly symmetrical and very stable cage-shaped hydrocarbon, and can be used as a raw material to synthesize various mono-substituted and poly-substituted adamantane derivatives, and the di-substituted derivative with bifunctional groups can be easily synthesized into various different high-molecular materials, and the materials have good transparency, high hardness, excellent shock resistance and thermal stability, and have wide application prospects in the field of new organic materials, particularly in the field of optical communication. However, a systematic study on the optical properties of polyimide film materials containing adamantane structures is still lacking.
Disclosure of Invention
The invention mainly aims to provide a diamine monomer containing a adamantane structure, a polyimide film, a preparation method and an application thereof, so as to overcome the defects of the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a diamine monomer containing a adamantane structure, which has a structure shown in any one of the following formulas:
Figure BDA0002594958610000021
the embodiment of the invention also provides a preparation method of the diamine monomer containing the adamantane structure, which comprises the following steps:
carrying out Friedel-crafts alkylation reaction on a first uniformly mixed reaction system containing 1-adamantanol, acetanilide and/or acetanilide derivatives and a catalyst at the temperature of 20-35 ℃ for 2-10 h to prepare a bisamide compound;
and reacting the second uniformly mixed reaction system containing the bisamide compound, the inorganic base and the solvent at the temperature of 80-130 ℃ for 6-24 hours to obtain the diamine monomer containing the adamantane structure.
The embodiment of the invention also provides application of the diamine monomer containing the adamantane structure in preparing a polyimide compound or a polyimide film.
Embodiments of the present invention also provide a polyimide compound having a structure represented by the following formula:
Figure BDA0002594958610000022
wherein R is1、R2、R3Are all independently selected from H, CH3、F、CF3A has a structure represented by any one of the following formulae:
Figure BDA0002594958610000023
the embodiment of the invention also provides a preparation method of the polyimide film, which comprises the following steps:
reacting a third uniformly mixed reaction system containing the diamine monomer containing the adamantane structure, the dianhydride monomer and the polar organic solvent at the temperature of 20-30 ℃ for 12-24 hours in a protective atmosphere to obtain a polyamic acid solution;
spreading a polyamide acid solution on a substrate by adopting a tape casting method, drying at 60-80 ℃ for 12-24 h, and performing step heating treatment to obtain a polyimide film (namely the colorless polyimide film); the dianhydride monomer has a structure represented by any one of the following formulas:
Figure BDA0002594958610000031
the embodiment of the invention also provides a preparation method of the polyimide film, which comprises the following steps:
reacting a fourth uniformly mixed reaction system containing the diamine monomer containing the adamantane structure, the dianhydride monomer, the polar organic solvent and the catalyst at 60-100 ℃ for 1-4 h in a protective atmosphere, heating the fourth uniformly mixed reaction system to 160-200 ℃, and continuously reacting for 10-20 h to obtain polyimide;
dissolving the polyimide in an organic solvent to form a polyimide solution, then spreading the polyimide solution on a substrate by adopting a tape casting method, drying at 60-80 ℃ for 12-24 h, and performing step heating treatment to obtain a polyimide film (namely a colorless polyimide film); the dianhydride monomer has a structure represented by any one of the following formulas:
Figure BDA0002594958610000032
embodiments of the present invention also provide polyimide films (i.e., colorless polyimide films) prepared by the foregoing methods.
The embodiment of the invention also provides application of the polyimide film in the fields of flexible display, thin-film solar cells or optoelectronic engineering.
Compared with the prior art, the invention has the beneficial effects that:
(1) the colorless polyimide film prepared by the invention has better heat resistance, the glass transition temperature of the colorless polyimide film can reach 440 ℃ at most, the prepared colorless polyimide has good solubility in various organic solvents such as N, N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), m-cresol, chloroform and the like, the prepared colorless polyimide film has good mechanical property and excellent optical property, the cutoff wavelength is 275-288 nm, and the optical transmittance of the prepared colorless polyimide film at 400nm is more than 85 percent and can reach 91 percent at most; the prepared polyimide film has a L value of more than 94, a value close to zero, and b value between 1.07-3.93;
(2) the diamine monomer containing the adamantane structure is applied to the preparation of the colorless polyimide film for the first time, the preparation method of the diamine monomer containing the adamantane structure has the advantages of easily available raw materials, low cost and high yield (more than 60%), and the colorless transparent polyimide and the film thereof containing the adamantane structure on the main chain have the advantages of good solubility, excellent thermal property and mechanical property, excellent optical property and the like, and have good application prospects in the fields of flexible display, thin-film solar cells, optoelectronic engineering and the like.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a nuclear magnetic hydrogen spectrum of 1, 3-bis (4-acetamidophenyl) adamantane prepared in example 1 of the present invention;
FIG. 2 is a nuclear magnetic hydrogen spectrum of a diamine monomer containing an adamantane structure, i.e., 1, 3-bis (4-aminophenyl) adamantane (ADMDA), prepared in example 1 of the invention;
FIG. 3 is a nuclear magnetic hydrogen spectrum of 1, 3-bis (3, 5-dimethyl-4-acetamidophenyl) adamantane prepared in example 2 of the present invention;
FIG. 4 is a nuclear magnetic hydrogen spectrum of a diammine monomer containing a adamantane structure, i.e., 1, 3-bis (3, 5-dimethyl-4-aminophenyl) adamantane (DMADMDA), prepared in example 2 of the present invention;
FIG. 5 is a nuclear magnetic hydrogen spectrum of 1, 3-bis (3-fluoro-4-acetamidophenyl) adamantane prepared in example 3 of the present invention;
FIG. 6 is a nuclear magnetic hydrogen spectrum of a diammine monomer containing a adamantane structure, i.e., 1, 3-bis (3-fluoro-4-aminophenyl) adamantane (FAMDA), prepared in example 3 of the invention;
FIG. 7 is a nuclear magnetic hydrogen spectrum of a diamine monomer containing an adamantane structure, i.e., 1, 3-bis (3, 5-difluoro-4-aminophenyl) adamantane (DFADMDA), prepared in example 5 of the present invention;
FIG. 8 is a DMA graph of colorless polyimide films prepared in examples 1-3 of the present invention;
FIG. 9 is a TGA profile of colorless polyimide films prepared in examples 1-3 of the present invention;
FIG. 10 is a graph of the UV-Vis spectra of colorless polyimide films prepared in examples 1-3 of the present invention;
Detailed Description
In view of the defects of the prior art, the inventor of the present invention provides a technical scheme of the present invention through long-term research and a great deal of practice, wherein 1-adamantane alcohol and acetanilide and/or acetanilide derivatives are mainly used as initial raw materials, a bisacetanilide unit containing an adamantane structure is prepared through a friedel-crafts alkylation reaction under a strong acid condition, and then a diamine monomer containing an adamantane structure is prepared through a hydrolysis reaction; the prepared diamine monomer containing the adamantane structure and a part of commercialized dianhydride monomer are used as raw materials, a colorless transparent polyimide film containing the adamantane structure and a semi-alicyclic structure is prepared through condensation polymerization reaction and subsequent treatment steps, and analysis and test data show that the colorless polyimide film prepared by the technical scheme of the invention has excellent heat resistance and optical performance.
The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It is to be noted that the definitions of the terms mentioned in the description of the present invention are known to those skilled in the art. For example, some of the terms are defined as follows:
l, a, b are colorimetric values representing the color of the film, and can be detected by a color difference meter. The numerical values range from-100 to + 100. L represents the lightness, the closer the value is to 100, the whiter or brighter the sample is, and the darker the sample is; a represents red-green degree, positive values represent red bias, and negative values represent green bias; b represents yellow-blue degree, positive values represent yellow bias, and negative values represent blue bias.
One aspect of embodiments of the present invention provides a diamine monomer containing a adamantane structure, having a structure represented by any one of the following formulas:
Figure BDA0002594958610000051
another aspect of the embodiments of the present invention provides a method for preparing a diamine monomer containing a adamantane structure, including:
carrying out Friedel-crafts alkylation reaction on a first uniformly mixed reaction system containing 1-adamantanol, acetanilide and/or acetanilide derivatives and a catalyst at the temperature of 20-35 ℃ for 2-10 h to prepare a bisamide compound;
and reacting the second uniformly mixed reaction system containing the bisamide compound, the inorganic base and the solvent at the temperature of 80-130 ℃ for 6-24 hours to obtain the diamine monomer containing the adamantane structure.
In some more specific embodiments, the catalyst comprises concentrated sulfuric acid, and is not limited thereto.
Further, the concentration of the concentrated sulfuric acid is 98 wt%.
Further, the molar ratio of the 1-adamantanol to the acetanilide and/or the acetanilide derivative is 1: 2-1: 2.3.
Further, the molar ratio of the 1-adamantanol to concentrated sulfuric acid is 1: 20-40;
further, the acetanilide derivative is prepared by acylation reaction of an aniline derivative and any one of acyl chloride, acid anhydride and glacial acetic acid, and is preferably acid anhydride or glacial acetic acid.
Further, the preparation method comprises the following steps: adding a proper amount of zinc powder into the reaction system of the acylation reaction to protect aniline compounds from being oxidized, such as:
Figure BDA0002594958610000061
and/or the acetanilide derivative has a structure represented by any one of the following formulae:
Figure BDA0002594958610000062
in some more specific embodiments, the preparation method comprises: and uniformly mixing the bisamide compound, the inorganic alkali solution and the solvent to form the second uniformly mixed reaction system.
Further, the preparation method further comprises the following steps: after the reaction is completed, the obtained mixture is subjected to precipitation, washing, filtration and recrystallization.
Further, the inorganic base includes any one of sodium hydroxide and potassium hydroxide or a combination of both, and is not limited thereto.
Further, the solvent includes any one of absolute ethyl alcohol, ethylene glycol, or a combination of both, and is not limited thereto.
Furthermore, the molar ratio of the bisamide compound to the inorganic base to the solvent is 1 (30-100) to 6-16.
Another aspect of the embodiments of the present invention provides a use of the foregoing diamine monomer containing an adamantane structure for preparing a polyimide compound or a polyimide film.
Another aspect of embodiments of the present invention provides a polyimide compound having a structure represented by the following formula:
Figure BDA0002594958610000063
wherein R is1、R2、R3Are all independently selected from H, CH3、F、CF3A has a structure represented by any one of the following formulae:
Figure BDA0002594958610000071
in some more specific embodiments, the polyimide compound is prepared by the polycondensation reaction of the diamine monomer and the dianhydride monomer.
Further, the dianhydride monomer has a structure represented by any one of the following formulae:
Figure BDA0002594958610000072
another aspect of an embodiment of the present invention provides a method for preparing a polyimide film, including:
reacting a third uniformly mixed reaction system containing the diamine monomer containing the adamantane structure, the dianhydride monomer and the polar organic solvent at the temperature of 20-30 ℃ for 12-24 hours in a protective atmosphere to obtain a polyamic acid solution;
spreading a polyamide acid solution on a substrate by adopting a tape casting method, drying at 60-80 ℃ for 12-24 h, and performing step heating treatment to obtain a polyimide film (namely the colorless polyimide film); the dianhydride monomer has a structure represented by any one of the following formulas:
Figure BDA0002594958610000073
in some more specific embodiments, the preparation method comprises: under the conditions of protective atmosphere and ice bath with the environmental humidity lower than 40%, dissolving the diamine monomer containing the adamantane structure in a polar organic solvent to form a diamine monomer solution, and then adding the dianhydride monomer to form the third uniform mixed reaction system.
Further, the solid content of the diamine monomer solution is 15-30 wt%.
Further, the molar ratio of the diamine monomer to the diamine monomer is 1: 1.
Further, the polar organic solvent includes any one or a combination of two or more of N-methylpyrrolidone, N-dimethylformamide, and N, N-dimethylacetamide, but is not limited thereto.
Further, the protective atmosphere includes a nitrogen atmosphere or an inert gas atmosphere.
In some more specific embodiments, the preparation method further comprises: and adding a polar organic solvent into the polyamic acid solution, and controlling the solid content in the polyamic acid solution to be 5-15 wt%.
Further, the step heating heat treatment comprises 5 heat preservation stages, wherein the temperature of each heat preservation stage is 100-300 ℃, and the heat preservation time is 1-5 hours.
Further, the preparation method further comprises the following steps: and carrying out water boiling treatment on the matrix subjected to the step heating heat treatment in distilled water.
Further, the substrate includes a glass plate or a teflon plate, and is not limited thereto.
Another aspect of an embodiment of the present invention provides a method for preparing a polyimide film, including:
reacting a fourth uniformly mixed reaction system containing the diamine monomer containing the adamantane structure, the dianhydride monomer, the polar organic solvent and the catalyst at 60-100 ℃ for 1-4 h in a protective atmosphere, heating the fourth uniformly mixed reaction system to 160-200 ℃, and continuously reacting for 10-20 h to obtain polyimide;
dissolving the polyimide in an organic solvent to form a polyimide solution, then spreading the polyimide solution on a substrate by adopting a tape casting method, drying at 60-80 ℃ for 12-24 h, and performing step heating treatment to obtain a polyimide film (colorless polyimide film); the dianhydride monomer has a structure represented by any one of the following formulas:
Figure BDA0002594958610000081
in some more specific embodiments, the preparation method comprises: under a protective atmosphere, dissolving the diamine monomer containing the adamantane structure and the dianhydride monomer in a polar organic solvent to form a mixed solution, and then adding a catalyst to form the fourth uniform mixed reaction system.
Further, the solid content of the mixed solution is 15-30 wt%.
Further, the polar organic solvent includes m-cresol, and is not limited thereto.
Further, the catalyst includes benzoic acid or isoquinoline, and is not limited thereto.
In some more specific embodiments, the preparation method further comprises: and after the fourth uniformly mixed reaction system finishes the reaction, purifying the obtained mixture.
Further, the purification treatment comprises: extracting for 12-24 h with methanol in a Soxhlet extractor.
In some more specific embodiments, the polyimide solution has a solid content of 3 to 10 wt%.
Further, the step heating heat treatment comprises 5 heat preservation stages, wherein the temperature of each heat preservation stage is 100-300 ℃, and the heat preservation time is 1-5 hours.
Further, the preparation method further comprises the following steps: and carrying out water boiling treatment on the matrix subjected to the step heating heat treatment in distilled water.
Further, the organic solvent includes any one or a combination of two or more of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, m-cresol, and chloroform, and is not limited thereto.
Further, the substrate includes a glass plate or a teflon plate, and is not limited thereto.
In some more specific embodiments, the method for preparing the colorless transparent polyimide film comprises:
dissolving a diamine monomer in a polar organic solvent under the environment of ice bath and nitrogen with the ambient humidity lower than 40%, keeping the solid content at 15-30 wt%, completely dissolving diamine through mechanical stirring, adding the equimolar dianhydride monomer in batches, continuously stirring for 12-24 h at 20-30 ℃ to obtain a viscous polyamide acid solution, adding a proper amount of the polar organic solvent to dilute the solid content of the polyamide acid solution to 5-15 wt%, then spreading a film on a dry and clean horizontal glass plate by using a tape casting method, placing the glass plate in a thermostat at 60-80 ℃ for 12-24 h, and treating the glass plate in a vacuum oven according to a step heating condition, wherein the temperature range is as follows: and (3) preserving heat for 1-5 h at 100-300 ℃ in each stage, and boiling the glass plate with distilled water after cooling to obtain the colorless polyimide film.
In some more specific embodiments, the method for preparing the colorless transparent polyimide film comprises:
(1) in a nitrogen environment, dissolving diamine monomers and dianhydride monomers with equal molar mass in a polar organic solvent, keeping the solid content of a mixed system at 15-30 wt%, keeping mechanical stirring, adding benzoic acid and isoquinoline with catalyst amount, heating the reaction system to 60-100 ℃, keeping the temperature for 1-4 h, and heating to 160-200 ℃ and keeping the temperature for 10-20 h. And cooling to room temperature, pouring the obtained polymer solution into a certain amount of methanol, filtering, extracting for 12-24 h in a Soxhlet extractor by using methanol, and then drying in vacuum to obtain the polyimide fibrous solid.
(2) Dissolving the obtained polyimide solid in an organic solvent, keeping the solid content at 3-10 wt%, pouring the solution on a dry and clean horizontal glass plate after filtering, paving a film by a tape casting method, placing the film in a thermostat at 60-80 ℃ for 12-24 h, and treating the film in a vacuum oven according to a step heating condition, wherein the temperature range is as follows: and (3) preserving heat for 1-5 h at 100-300 ℃ in each stage, and boiling the glass plate with distilled water after cooling to obtain the colorless polyimide film.
Another aspect of an embodiment of the present invention provides a polyimide film prepared by the foregoing method.
Further, the thickness of the polyimide film is 20-50 μm.
Furthermore, the optical transmittance of the polyimide film at 400nm is more than 85%, the L value is more than 94, the a value is close to zero, and the b value is between 1.07 and 3.93.
Another aspect of the embodiments of the present invention provides a use of the foregoing polyimide film in the fields of flexible display, thin film solar cell, or optoelectronic engineering.
The technical solutions of the present invention are further described in detail below with reference to several preferred embodiments and the accompanying drawings, which are implemented on the premise of the technical solutions of the present invention, and a detailed implementation manner and a specific operation process are provided, but the scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples used below were all available from conventional biochemical reagents companies, unless otherwise specified.
Example 1
(1) Adding 1-adamantanol (3.75g) and acetanilide (7.8g) into a 100mL three-mouth round-bottom flask provided with a mechanical stirring and condensing tube, then adding 37.5mL concentrated sulfuric acid (98 wt%), stirring the mixed system at 20 ℃ for reaction for 10h, after the reaction is finished, slowly pouring the reaction mixed system into 100mL deionized water, stirring to separate out a white precipitate, carrying out vacuum filtration, washing with water to obtain a crude product, recrystallizing the white crude product with ethanol/water (1/3, volume ratio), and carrying out vacuum drying (100 ℃/10h) to obtain a bisamide compound, namely 1, 3-bis (4-acetamidophenyl) adamantane (6.32g, yield 63.2%), wherein the melting point: 274-275 deg.C (nuclear magnetic hydrogen spectrum is shown in figure 1);
(2) adding absolute ethanol (30mL) and 1, 3-bis (4-acetamidophenyl) adamantane (3.0g) obtained in the step (1) into a 100mL single-neck round-bottom flask, stirring and dissolving, then adding 10mL sodium hydroxide solution (10 wt%), heating a mixed system to 130 ℃, stirring and reacting for 6h, cooling to room temperature, adding the mixed system into 150mL deionized water, stirring and precipitating a light yellow precipitate, carrying out vacuum filtration and washing with water to obtain a crude product, recrystallizing the crude product with ethanol, and carrying out vacuum drying to obtain a white solid diamine monomer (1.95g, yield 83%) containing an adamantane structure, namely 1, 3-bis (4-aminophenyl) adamantane (ADMDA), wherein the melting point: 193- & ltSUB & gt-194 ℃ (nuclear magnetic hydrogen spectrogram is shown in figure 2);
in this example, the synthetic route of the diamine monomer ADMDA containing adamantane structure prepared is as follows:
Figure BDA0002594958610000111
(3) under the environment of 35% of ambient humidity, ice bath and nitrogen, dissolving diamine monomer ADMDA (1mmol) containing an adamantane structure obtained in the step (2) in anhydrous N, N-dimethylacetamide (DMAc), wherein the initial solid content is 30 wt%, completely dissolving the diamine monomer by mechanical stirring, adding 4,4' - (hexafluoroisopropyl) phthalic anhydride (6FDA) or hydrogenated pyromellitic dianhydride (HPMDA) or hydrogenated biphenyl tetracarboxylic dianhydride (HBPDA) in batches in equal molar amount, continuously stirring for 24h at 20 ℃ to prepare viscous polyamic acid solution, and continuously adding a proper amount of DMAc to dilute the solid content of the polyamic acid solution to 5 wt%; the polyamic acid solution was poured onto a dry, clean, horizontal glass plate, kept in a thermostat at 60 ℃ for 24h, and then treated in a vacuum oven according to the following conditions: 100 ℃ (5h), 150 ℃ (4h), 200 ℃ (3h), 250 ℃ (2h) and 300 ℃ (1h), cooling, and boiling the glass plate with distilled water to obtain colorless polyimide film;
the DMA curves of the colorless polyimide films prepared in this example, i.e., the colorless PI-ADMDA-6FDA film, the colorless PI-ADMDA-HPMDA film and the colorless PI-ADMDA-HBPDA, are shown in FIG. 8; the TGA curve is shown in FIG. 9; the optical transmission properties in the visible region of the film are shown in fig. 10; the optical properties and heat resistance data of the colorless film are shown in Table 1.
Example 2
(1) Adding 1-adamantanol (3.75g) and 2, 6-dimethylacetanilide (8.8g) into a 100mL three-neck round-bottom flask provided with a mechanical stirring and condensing tube, then adding 37.5mL concentrated sulfuric acid (98 wt%), stirring the mixed system at 35 ℃ for 2h, after the reaction is finished, slowly pouring the reacted mixed system into 100mL deionized water, stirring to separate out a white precipitate, carrying out vacuum filtration and washing to obtain a crude product, recrystallizing the crude product with ethanol/water (1/3, volume ratio), and carrying out vacuum drying (100 ℃/10h) to obtain a bisamide compound, namely 1, 3-bis (3, 5-dimethyl-4-acetamidophenyl) adamantane (6.4g, yield 69%), and melting point: 215 ℃ (nuclear magnetic hydrogen spectrum figure 3);
(2) adding ethylene glycol (25mL) and 1, 3-bis (3, 5-dimethyl-4-acetamidophenyl) adamantane (2.5g) obtained in the step (1) into a 100mL single-neck round-bottom flask, stirring and dissolving, then adding 10mL sodium hydroxide solution (50 wt%), heating the mixed system to 80 ℃, stirring and reacting for 24 hours, cooling to room temperature, adding the mixed system into 100mL deionized water, stirring to separate out light yellow precipitate, carrying out vacuum filtration, washing with water to obtain a crude product, recrystallizing the crude product with ethanol, and carrying out vacuum drying to obtain a white solid diamine monomer (1.8g, yield 90%) containing an adamantane structure, namely 1, 3-bis (3, 5-dimethyl-4-aminophenyl) adamantane (DMADMDA), wherein the melting point: 206 ℃ and 207 ℃ (the nuclear magnetic hydrogen spectrogram is shown in figure 4);
in this example, a gold-containing steel was preparedThe synthesis route of diamine monomer DMADMDA with alkane structure is shown as follows:
Figure BDA0002594958610000121
(3) under nitrogen atmosphere, adding diamine monomer (DMADMDA) (1mmol) containing an adamantane structure and dianhydride monomer 4,4' - (hexafluoroisopropyl) phthalic anhydride (6FDA) or hydrogenated pyromellitic dianhydride (HPMDA) or hydrogenated biphenyltetracarboxylic dianhydride (HBPDA) (1mmol) obtained in the step (2) into a polymerization bottle with mechanical stirring, adding anhydrous m-cresol to enable the solid content of the mixed system to be 15 wt%, keeping mechanical stirring, adding catalytic amount of benzoic acid and isoquinoline, heating the reaction system to 80 ℃ for 2h to enable the reaction system to be uniformly transparent, heating to 180 ℃ for 15h, cooling to room temperature, pouring the obtained viscous polymer solution into stirred methanol (400mL), precipitating white fibrous solid, filtering and collecting, extracting with methanol in a Soxhlet extractor for 24h, and then drying in vacuum (150 ℃/20h), obtaining polyimide PI-DMADMDA-6FDA or PI-DMADMDA-HPMDA or PI-DMADMDA-HBPDA, dissolving the obtained polyimide solid in N-methylpyrrolidone (NMP), keeping the solid content at 5 wt%, pouring the solution after filtration, paving a film on a dry and clean horizontal glass plate by a tape casting method, placing the glass plate in a thermostat at 80 ℃ for 12 hours, and treating the glass plate in a vacuum oven according to the following conditions: 100 ℃ (5h), 150 ℃ (4h), 200 ℃ (3h), 250 ℃ (2h) and 300 ℃ (1h), cooling, and boiling the glass plate with distilled water to obtain colorless polyimide film, i.e. colorless PI-DMADMDA-6FDA film, colorless PI-DMADMDA-HPMDA film or PI-DMADMDA-HBPDA film;
the DMA curves of the colorless polyimide films prepared in this example, i.e., the colorless PI-DMADMDA-6FDA film, the PI-DMADMDA-HPMDA film, or the PI-DMADMDA-HBPDA film, are shown in FIG. 8; the TGA profile of the film is shown in FIG. 9; the optical transmission properties in the visible region of the film are shown in fig. 10; the optical properties and heat resistance of the film are shown in Table 1.
Example 3
(1) Adding 1-adamantanol (1.52g) and 2-fluoroacetanilide (3.06g) into a 100mL three-neck round-bottom flask provided with a mechanical stirring and condensing tube, then adding 15mL concentrated sulfuric acid (98 wt%), stirring the mixed system at 25 ℃ for 6h, after the reaction is finished, slowly pouring the reaction mixed system into 100mL deionized water, stirring to separate out a white precipitate, washing the mixture for 4 times by using the deionized water, carrying out vacuum filtration to obtain a crude product, recrystallizing the crude product by using ethanol/water (1/3, volume ratio), and carrying out vacuum drying (100 ℃/10h) to obtain a bisamide compound, namely 1, 3-bis (3-fluoro-4-acetamidophenyl) adamantane (2.9g, yield 69%), and melting point: 190 ℃ to 192 ℃ (the nuclear magnetic hydrogen spectrogram is shown in figure 5);
(2) adding ethylene glycol (25mL) and 1, 3-bis (3-fluoro-4-acetamidophenyl) adamantane (2.5g) obtained in the step (1) into a 100mL single-neck round-bottom flask, stirring and dissolving, then adding 10mL of sodium hydroxide solution (50 wt%), heating a mixed system to 100 ℃, stirring and reacting for 10 hours, cooling to room temperature, adding the mixed system into 100mL deionized water, stirring to separate out a light yellow precipitate, carrying out vacuum filtration, washing to obtain a crude product, recrystallizing the crude product with ethanol, and carrying out vacuum drying to obtain a white solid, namely 1, 3-bis (3-fluoro-4-aminophenyl) adamantane (FAMDA) (1.8g, the yield is 90%), wherein the melting point is 103 ℃ (the nuclear magnetic hydrogen spectrum diagram is shown in figure 6);
in this example, the synthetic route of the diamine monomer famda containing adamantane structure prepared is as follows:
Figure BDA0002594958610000131
(3) under the nitrogen environment, adding diamine monomer (FAMDA) (1mmol) containing an adamantane structure obtained in the step (2) and dianhydride monomer hydrogenated pyromellitic dianhydride (HPMDA) (1mmol) into a polymerization bottle with mechanical stirring, adding anhydrous m-cresol to enable the solid content of a mixed system to be 15 wt%, keeping mechanical stirring, adding catalytic amount of benzoic acid or isoquinoline, heating the reaction system to 60 ℃ for 4h, enabling the reaction system to be uniform and transparent, heating to 160 ℃ for 20h, cooling to room temperature, pouring the obtained viscous polymer solution into stirred methanol (300mL), separating out white fibrous solid, filtering and collecting, extracting with methanol in a Soxhlet extractor for 24h, then drying in vacuum (150 ℃/20h) to obtain polyimide PI-FAMDA-HPMDA, dissolving the obtained polyimide solid in N-methylpyrrolidone (NMP), keeping the solid content at 5 wt%, pouring the solution on a dry and clean horizontal glass plate after filtering, spreading the film by a tape casting method, placing the glass plate in a thermostat at 60 ℃ for 24 hours, and then treating the glass plate in a vacuum oven according to the following conditions: 100 ℃ (5h), 150 ℃ (4h), 200 ℃ (3h), 250 ℃ (2h) and 300 ℃ (1h), cooling, and boiling the glass plate with distilled water to obtain colorless polyimide film, namely colorless PI-FAMDA-HPMDA film;
the DMA curve of the colorless polyimide film prepared in this example, i.e., the colorless PI-FAMDA-HPDA film, is shown in FIG. 8; the TGA curve of the colorless PI-FAMDA-HPMDA film is shown in FIG. 9; the optical transmission performance of the colorless PI-FAMDA-HPMDA film in the visible light region is shown in FIG. 10; the optical properties and heat resistance of the colorless PI-FAMDA-HPMDA film are shown in Table 1.
TABLE 1 data of optical properties and Heat resistance of the colorless polyimide films of examples 1-3
Figure BDA0002594958610000132
Figure BDA0002594958610000141
As can be seen from Table 1, the colorless polyimide film prepared by the present invention has good mechanical properties, thermal stability and excellent optical properties.
Example 4
(1) Adding 1-adamantanol (1.52g) and 2-fluoroacetanilide (3.06g) into a 100mL three-neck round-bottom flask provided with a mechanical stirring and condensing tube, then adding 15mL concentrated sulfuric acid (98 wt%), stirring the mixed system at 25 ℃ for reacting for 6h, after the reaction is finished, slowly pouring the reaction mixed system into 100mL deionized water, stirring to separate out a white precipitate, washing the mixture for 4 times by using the deionized water, carrying out vacuum filtration to obtain a crude product, recrystallizing the crude product by using ethanol/water (1/3, volume ratio), and carrying out vacuum drying (100 ℃/10h) to obtain a bisamide compound, namely 1, 3-bis (3-fluoro-4-acetamidophenyl) adamantane;
(2) adding ethylene glycol (25mL) and 1, 3-bis (3-fluoro-4-acetamidophenyl) adamantane (2.5g) obtained in the step (1) into a 100mL single-neck round-bottom flask, stirring and dissolving, then adding 10mL of sodium hydroxide solution (50 wt%), heating a mixed system to 100 ℃, stirring and reacting for 10 hours, cooling to room temperature, adding the mixed system into 100mL deionized water, stirring to separate out a light yellow precipitate, carrying out vacuum filtration, washing with water to obtain a crude product, recrystallizing the crude product with ethanol, and carrying out vacuum drying to obtain a white solid, namely 1, 3-bis (3, 5-dimethyl-4-aminophenyl) adamantane (FAMDA);
(3) under the nitrogen environment, adding diamine monomer (FAMDA) (1mmol) containing an adamantane structure obtained in the step (2) and dianhydride monomer hydrogenated pyromellitic dianhydride (HPMDA) (1mmol) into a polymerization bottle with mechanical stirring, adding anhydrous m-cresol to enable the solid content of a mixed system to be 15 wt%, keeping mechanical stirring, adding catalytic amount of benzoic acid or isoquinoline, heating the reaction system to 100 ℃ for 1h, enabling the reaction system to be uniform and transparent, heating to 200 ℃ for 10h, cooling to room temperature, pouring the obtained viscous polymer solution into stirred methanol (300mL), separating out white fibrous solid, filtering and collecting, extracting with methanol in a Soxhlet extractor for 24h, then drying in vacuum (150 ℃/20h) to obtain polyimide PI-FAMDA-HPMDA, dissolving the obtained polyimide solid in N-methylpyrrolidone (NMP), keeping the solid content at 5 wt%, pouring the solution on a dry and clean horizontal glass plate after filtering, spreading the film by a tape casting method, placing the glass plate in a thermostat at 70 ℃ for 16h, and then treating the glass plate in a vacuum oven according to the following conditions: 100 ℃ (5h), 150 ℃ (4h), 200 ℃ (3h), 250 ℃ (2h) and 300 ℃ (1h), cooling, and boiling the glass plate with distilled water to obtain colorless polyimide film, namely colorless PI-FAMDA-HPMDA film;
example 5
(1) Adding 1-adamantanol (3.75g) and 2, 6-difluoroacetanilide (8.8g) into a 100mL three-neck round-bottom flask provided with a mechanical stirring and condensing tube, then adding 37.5mL of concentrated sulfuric acid (98 wt%), stirring the mixed system at 30 ℃ for reaction for 2h, after the reaction is finished, slowly pouring the reacted mixed system into 100mL of deionized water, stirring to separate out a white precipitate, carrying out vacuum suction filtration and washing to obtain a crude product, recrystallizing the crude product with ethanol/water (1/3, volume ratio), and carrying out vacuum drying (100 ℃/10h) to obtain a bisamide compound, namely 1, 3-bis (3, 5-difluoro-4-acetamidophenyl) adamantane;
(2) adding ethylene glycol (25mL) and 1, 3-bis (3, 5-difluoro-4-acetamidophenyl) adamantane (2.5g) obtained in the step (1) into a 100mL single-neck round-bottom flask, stirring and dissolving, then adding 10mL of sodium hydroxide solution (50 wt%), heating the mixed system to 120 ℃, stirring and reacting for 24 hours, cooling to room temperature, adding the mixed system into 200mL of deionized water, stirring to separate out light yellow precipitate, carrying out vacuum filtration, washing with water to obtain a crude product, recrystallizing the crude product with ethanol, and carrying out vacuum drying to obtain a white solid diamine monomer containing an adamantane structure, namely 1, 3-bis (3, 5-difluoro-4-aminophenyl) adamantane (a nuclear magnetic hydrogen spectrum diagram is shown in figure 7);
(3) under the environment of 35% of ambient humidity, ice bath and nitrogen, dissolving the diamine monomer containing the adamantane structure obtained in the step (2) in anhydrous N, N-dimethylacetamide (DMAc), wherein the initial solid content is 30 wt%, completely dissolving the diamine monomer by mechanical stirring, adding equimolar hydrogenated pyromellitic dianhydride (HPMDA) in batches, continuously stirring at 30 ℃ for 12 hours to obtain viscous polyamic acid solution, and continuously adding a proper amount of DMAc to dilute the solid content of the polyamic acid solution to 5 wt%; the polyamic acid solution was poured onto a dry, clean, horizontal glass plate, kept at 80 ℃ for 12h in a thermostat and then treated in a vacuum oven according to the following conditions: 100 ℃ (5h), 150 ℃ (4h), 200 ℃ (3h), 250 ℃ (2h) and 300 ℃ (1h), cooling, and boiling the glass plate with distilled water to obtain colorless polyimide film;
example 6
(1) Adding 1-adamantanol (3.75g) and 2, 5-bis (trifluoromethyl) acetanilide (8.8g) into a 100mL three-neck round-bottom flask provided with a mechanical stirring and condensing tube, then adding 37.5mL of concentrated sulfuric acid (98 wt%), stirring the mixed system at 30 ℃ for 2h, after the reaction is finished, slowly pouring the reacted mixed system into 100mL of deionized water, stirring to separate out a white precipitate, carrying out vacuum filtration and washing to obtain a crude product, recrystallizing the crude product with ethanol/water (1/3, volume ratio), and carrying out vacuum drying (100 ℃/10h) to obtain a bisamide compound, namely 1, 3-bis (2, 5-bis (trifluoromethyl) -4-acetamidophenyl) adamantane;
(2) adding ethylene glycol (25mL) and 1, 3-bis (2, 5-bis (trifluoromethyl) -4-acetamidophenyl) adamantane (2.5g) obtained in the step (1) into a 100mL single-neck round-bottom flask, stirring and dissolving, then adding 10mL sodium hydroxide solution (50 wt%), heating the mixed system to 80 ℃, stirring and reacting for 24 hours, cooling to room temperature, adding the mixed system into 100mL deionized water, stirring to separate out light yellow precipitate, carrying out vacuum filtration, washing with water to obtain a crude product, recrystallizing the crude product with ethanol, and carrying out vacuum drying to obtain a white solid diamine monomer containing an adamantane structure, namely 1, 3-bis (2, 5-bis (trifluoromethyl) -4-aminophenyl) adamantane;
(3) under the environment of 35% of ambient humidity, ice bath and nitrogen, dissolving the diamine monomer containing the adamantane structure obtained in the step (2) in anhydrous N, N-dimethylacetamide (DMAc), wherein the initial solid content is 30 wt%, completely dissolving the diamine monomer by mechanical stirring, adding equimolar hydrogenated pyromellitic dianhydride (HPMDA) in batches, continuously stirring for 16 hours at 25 ℃ to obtain viscous polyamic acid solution, and continuously adding a proper amount of DMAc to dilute the solid content of the polyamic acid solution to 5 wt%; the polyamic acid solution was poured onto a dry, clean, horizontal glass plate, kept at 70 ℃ for 20h in a thermostat, and then treated in a vacuum oven according to the following conditions: 100 ℃ (5h), 150 ℃ (4h), 200 ℃ (3h), 250 ℃ (2h), 300 ℃ (1h), cooling, and boiling the glass plate with distilled water to obtain colorless polyimide film.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.
Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.
It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.

Claims (10)

1. A diamine monomer containing a adamantane structure, characterized in that it has a structure represented by any one of the formulae (I) to (IV):
Figure FDA0002594958600000011
2. a preparation method of diamine monomer containing adamantane structure is characterized by comprising the following steps:
carrying out Friedel-crafts alkylation reaction on a first uniformly mixed reaction system containing 1-adamantanol, acetanilide derivatives and a catalyst at the temperature of 20-35 ℃ for 2-10 h to prepare a bisamide compound;
and reacting the second uniformly mixed reaction system containing the bisamide compound, the inorganic base and the solvent at the temperature of 80-130 ℃ for 6-24 hours to obtain the diamine monomer containing the adamantane structure.
3. The method of claim 2, wherein: the catalyst comprises concentrated sulfuric acid; preferably, the concentration of the concentrated sulfuric acid is 98 wt%;
and/or the molar ratio of the 1-adamantanol to the acetanilide derivative is 1: 2-1: 2.3;
and/or the molar ratio of the 1-adamantanol to concentrated sulfuric acid is 1: 20-40;
and/or the acetanilide derivative is prepared by acylation reaction of an aniline derivative and any one of acyl chloride, acid anhydride and glacial acetic acid, preferably the acid anhydride and/or the glacial acetic acid; preferably, the preparation method comprises the following steps: adding zinc into the reaction system of the acylation reaction;
and/or the acetanilide derivative has a structure represented by any one of the following formulae:
Figure FDA0002594958600000012
and/or, the preparation method comprises the following steps: uniformly mixing the bisamide compound, the inorganic alkali solution and the solvent to form a second uniformly mixed reaction system;
and/or, the preparation method further comprises the following steps: after the reaction is finished, carrying out precipitation, washing, filtering and recrystallization treatment on the obtained mixture;
and/or, the inorganic base comprises sodium hydroxide and/or potassium hydroxide;
and/or, the solvent comprises absolute ethanol and/or ethylene glycol;
and/or the molar ratio of the bisamide compound to the inorganic base to the solvent is 1 (30-100) to (6-16).
4. A polyimide compound characterized by having a structure represented by the formula (VI):
Figure FDA0002594958600000021
wherein R is1、R2、R3Are all independently selected from H, CH3、F、CF3A has a structure represented by any one of the following formulae:
Figure FDA0002594958600000022
preferably, the polyimide compound is prepared by the polycondensation reaction of the diamine monomer and the dianhydride monomer as described in claim 1; preferably, the dianhydride monomer has a structure represented by any one of the following formulae:
Figure FDA0002594958600000023
5. a method for preparing a polyimide film is characterized by comprising the following steps:
reacting a third uniformly mixed reaction system containing diamine monomer containing an adamantane structure, dianhydride monomer and a polar organic solvent in claim 1 at 20-30 ℃ for 12-24 hours under a protective atmosphere to obtain a polyamic acid solution;
spreading a film on the matrix by adopting a tape casting method, drying at 60-80 ℃ for 12-24 h, and performing step heating heat treatment to obtain a polyimide film; the dianhydride monomer has a structure represented by any one of the following formulas:
Figure FDA0002594958600000031
6. the production method according to claim 5, characterized by comprising: under the conditions of protective atmosphere and ice bath with the environmental humidity lower than 40%, dissolving the diamine monomer containing the adamantane structure in a polar organic solvent to form a diamine monomer solution, and then adding the dianhydride monomer to form the third uniform mixed reaction system; preferably, the solid content in the diamine monomer solution is 15-30 wt%; preferably, the molar ratio of the diamine monomer to the diamine monomer is 1: 1; preferably, the polar organic solvent comprises any one or a combination of more than two of N-methyl pyrrolidone, N-dimethylformamide and N, N-dimethylacetamide;
and/or, the preparation method further comprises the following steps: adding a polar organic solvent into the polyamic acid solution, and controlling the solid content in the polyamic acid solution to be 5-15 wt%;
and/or the step heating heat treatment comprises 5 heat preservation stages, wherein the temperature of each heat preservation stage is 100-300 ℃, and the heat preservation time is 1-5 h;
and/or, the preparation method further comprises the following steps: boiling the matrix subjected to the step heating heat treatment in water;
and/or the substrate comprises a glass plate and/or a polytetrafluoroethylene plate.
7. A method for preparing a polyimide film is characterized by comprising the following steps:
reacting a fourth uniformly mixed reaction system containing diamine monomer containing an adamantane structure, dianhydride monomer, polar organic solvent and catalyst in claim 1 at 60-100 ℃ for 1-4 h in a protective atmosphere, heating the fourth uniformly mixed reaction system to 160-200 ℃, and continuously reacting for 10-20 h to obtain polyimide;
dissolving the polyimide in an organic solvent to form a polyimide solution, then spreading the polyimide solution on a substrate by adopting a tape casting method, drying at 60-80 ℃ for 12-24 h, and then carrying out step heating treatment to obtain a polyimide film; the dianhydride monomer has a structure represented by any one of the following formulas:
Figure FDA0002594958600000041
8. the production method according to claim 7, characterized by comprising: under a protective atmosphere, dissolving the diamine monomer and the dianhydride monomer containing the adamantane structure in a polar organic solvent to form a mixed solution, and then adding a catalyst to form a fourth uniform mixed reaction system; preferably, the solid content in the mixed solution is 15-30 wt%; preferably, the polar organic solvent comprises m-cresol; preferably, the catalyst comprises benzoic acid and/or isoquinoline;
and/or, the preparation method further comprises the following steps: after the reaction is completed, purifying the obtained mixture; preferably, the purification treatment comprises: extracting for 12-24 h by using methanol in a Soxhlet extractor;
and/or the solid content in the polyimide solution is 3-10 wt%;
and/or the step heating heat treatment comprises 5 heat preservation stages, wherein the temperature of each heat preservation stage is 100-300 ℃, and the heat preservation time is 1-5 h;
and/or, the preparation method further comprises the following steps: boiling the matrix subjected to the step heating heat treatment in distilled water;
and/or the organic solvent comprises any one or the combination of more than two of N-methyl pyrrolidone, N-dimethylformamide, N-dimethylacetamide, m-cresol and chloroform;
and/or the substrate comprises a glass plate and/or a polytetrafluoroethylene plate.
9. A polyimide film prepared by the method of any one of claims 5-8; preferably, the thickness of the polyimide film is 20-50 μm;
preferably, the polyimide film has an optical transmittance of > 85% at 400nm, a value of L > 94, a value of a close to zero, and b value of 1.07-3.93.
10. Use of the polyimide film according to claim 9 in the fields of flexible displays, thin film solar cells, or opto-electronic engineering.
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CN115557848B (en) * 2022-11-04 2024-05-31 河北科技大学 Diamine monomer, low CTE, high permeability polyimide and preparation method thereof

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