CN112175184A - Modified high-transparency polyimide flexible film and preparation method thereof - Google Patents
Modified high-transparency polyimide flexible film and preparation method thereof Download PDFInfo
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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
- C08G73/1075—Partially aromatic polyimides
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- 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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- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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- 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
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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
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
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- 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
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Abstract
The invention relates to a modified high-transparency polyimide flexible film and a preparation method thereof, the film is prepared from copolymerized polyamic acid added with ionic liquid by a thermal imidization method, the mass number of the ionic liquid in the copolymerized polyamic acid accounts for more than five percent of the total mass number of the copolymerized polyamic acid, and the copolymerized polyimide acid diamine comprises less than or equal to 20-60 percent of aliphatic diamine and more than or equal to 80-40 percent of aromatic diamine. The transparent polyimide composite film has high transparency, low chroma and good thermal property, and has good application prospect in the fields of transparent flexible device base materials and the like.
Description
Technical Field
The invention relates to the field of films, in particular to a modified high-transparency polyimide flexible film and a preparation method thereof.
Background
Polyimide (PI) refers to a high-performance polymer having an imide ring in the main chain. The unique aromatic ring structure of polyimide enables the polyimide material to have the advantages of high temperature resistance, solvent resistance, dimensional stability, good electrical insulation, excellent mechanical property and the like, and can be widely applied to the high-tech fields of mechanical engineering, microelectronic devices, petrochemical industry, aerospace and the like in the forms of films, fibers, separation membranes, adhesives and the like. However, the polyimide material has poor solubility and is difficult to process due to the highly rigid and conjugated aromatic heterocyclic structure in the polyimide molecular chain. In addition, the easy formation of Charge Transfer Complex (CTC) in the polyimide molecule causes the color of the polyimide material to show a characteristic yellow or dark brown color, which severely limits the application of polyimide in the fields of transparent flexible device substrates and the like.
At present, there are many common methods for preparing transparent polyimide, such as introducing fluorine-containing groups, introducing fats (especially alicyclic structure units), introducing asymmetric structures, adding ionic liquids, etc., to inhibit charge transfer interaction. Among them, fluorine atoms have high electronegativity, large free volume and low polarizability of carbon-fluorine bonds, and are introduced into the polyimide main chain or branched chain, so that the optical transparency of the polyimide is improved. On the other hand, the introduction of aliphatic monomers can also make the polyimide have excellent transparency, mainly because of the low molecular density and low polarity, the charge transfer interaction can be effectively inhibited. The polyimide added with the ionic liquid can also improve the transparency of the film, and mainly due to the introduction of ions in the ionic liquid, anions or cations in the ionic liquid are combined with functional groups in the polyimide through hydrogen bonds, the conjugated electron cloud density is reduced by the ions, the electron cloud conjugation is cut off, and the charge transfer interaction is effectively inhibited.
Chinese patent CN108735349B provides a transparent conductive film containing silver nanowires in ionic solution. The silver nanowire is modified by the ionic liquid, so that the silver nanowire transparent conductive film with excellent conductivity, low cost, high light transmittance and low sheet resistance is prepared. However, this transparent conductive film does not use aliphatic diamine and discusses whether it has low chroma and low thermal expansion coefficient.
Disclosure of Invention
The invention combines the comprehensive advantages of ionic liquid and aliphatic polyimide, provides a flexible polyimide film with high transparency, low chroma and good thermal property and a preparation method thereof, and the flexible polyimide film is prepared from a copolymerized polyamic acid solution containing semi-aromatic polyimide acid modified by the ionic liquid and a flexible polyimide transparent film prepared from the copolymerized polyamic acid solution.
The invention realizes the aim through the following technical scheme: a modified high-transparency flexible polyimide film is prepared from copolymerized polyamic acid added with ionic liquid through a thermal imidization method, wherein the mass number of the ionic liquid in the copolymerized polyamic acid accounts for more than five percent of the total mass number of the copolymerized polyamic acid, and the copolymerized polyimide acid diamine contains aliphatic diamine with the molar ratio of less than or equal to 20-60 percent and aromatic diamine with the molar ratio of more than or equal to 80-40 percent.
A preparation method of a modified high-transparency polyimide flexible film comprises the following steps:
(1) adding aliphatic diamine and aromatic diamine into a polar aprotic solvent protected by inert gas, completely dissolving the aliphatic diamine and the aromatic diamine at a set temperature, and adding aromatic anhydride, wherein the molar ratio of the diamine to the aromatic anhydride is controlled to be 1: 1-1.05, reacting for 4-8 hours to obtain a copolymer polyamic acid solution;
(2) adding ionic liquid into the copolymerized polyamic acid solution obtained in the step (1) and continuously stirring, and continuously stirring for 1-3 hours under the protection of inert gas to obtain a transparent copolymerized polyamic acid solution;
(3) and (3) uniformly coating the transparent copolymerized polyamide acid solution obtained in the step (2) on a clean glass substrate in a set thickness, then placing the glass substrate in an oven for programmed heating for thermal imidization, and taking out the glass substrate after the temperature of the oven is reduced to the room temperature to obtain the transparent polyimide composite film.
Further, the temperature programming in the step (3) is sequentially 150 ℃, 40 minutes, 240 ℃, 40 minutes, 310 ℃, 40 minutes, 350 ℃ and 40 minutes.
Further, the temperature set in step (1) was 10 ℃.
Still further, the ionic liquid is selected from one or more of 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-allyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt, and 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt.
Still further, the polar aprotic solvent is selected from one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and tetrahydrofuran.
Still further, the aromatic acid anhydride is aromatic dianhydride selected from one or more of 1,2,4, 5-pyromellitic dianhydride, 3,3',4,4' -benzophenonetetracarboxylic dianhydride, 4,4' -diphenyl ether dianhydride, 3,3',4,4' -biphenyl dianhydride, 4, 4-hexafluoroisopropyl phthalic anhydride, 4,4' - (trifluoromethylphenylisopropyl) phthalic anhydride, and 4,4' - (trifluoromethyl-m, m-bistrifluoromethylphenyl-isopropyl) phthalic anhydride.
Still further, the aliphatic diamine is selected from one or more of 4-cyclohexanediamine, 4,4' -diaminodicyclohexylmethane, L-arginine, 1, 2-cyclohexanediamine, 1, 4-cyclohexanediamine, and 1, 3-cyclohexanediamine.
Still further, the aromatic diamine is selected from one or more of 2,2 '-bistrifluoromethyl-4, 4' -diaminobiphenyl, 1, 4-bis (4-aminophenoxy) benzene, 9-bis (4-aminophenyl) fluorene, 3 '-bistrifluoromethyl-5, 5' -diaminobiphenyl, 2-bis (4-aminophenoxy benzene) hexafluoropropane, 3-trifluoromethyl m-phenylenediamine, tetrafluorop-phenylenediamine, 2-bis (4-aminophenyl) hexafluoropropane, tetrafluoro-m-phenylenediamine, 4,4 '-octafluorobiphenyldiamine, or 4,4' -diaminooctafluorobiphenyl ether.
The invention has the beneficial effects that: the transparent polyimide composite film has high transparency, low chroma and good thermal property, and has good application prospect in the fields of transparent flexible device base materials and the like.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. 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.
The invention relates to a high-transparency polyimide flexible film modified by adding ionic liquid, which is prepared from copolymerized polyamic acid added with ionic liquid by a thermal imidization method, wherein the copolymerized polyamic acid contains semi-aromatic polyamic acid, the mass number of the ionic liquid in the copolymerized polyamic acid accounts for more than five percent of the total mass number of the copolymerized polyamic acid, the light transmittance of the transparent polyimide film is more than 87 percent, the CTE (coefficient of thermal expansion) is less than 30 ppm/DEG C, the chroma b is less than 3, and the transparent polyimide flexible film has good flexibility and good application prospect in the fields of transparent flexible device substrates and the like.
Specifically, the modified high-transparency polyimide flexible film is prepared from copolymerized polyamic acid added with ionic liquid through a thermal imidization method, wherein the mass number of the ionic liquid in the copolymerized polyamic acid accounts for more than five percent of the total mass number of the copolymerized polyamic acid. The preparation method of the modified high-transparency polyimide flexible film comprises the following steps:
(1) adding aliphatic diamine and aromatic diamine into a polar aprotic solvent protected by nitrogen or other inert gases, completely dissolving the diamine (aliphatic diamine and aromatic diamine) at a set temperature (10 ℃), adding aromatic acid anhydride, and controlling the molar ratio of the diamine (aliphatic diamine and aromatic diamine) to the acid anhydride (aromatic acid anhydride) to be 1: 1-1.05, reacting for 4-8 hours to obtain (copolymerization) polyamic acid solution;
(2) adding the ionic liquid into the (co) polyamic acid solution obtained in the step (1), continuously stirring, and continuously stirring for 1-3 hours under the protection of nitrogen or other inert gases to obtain a transparent (co) polyamic acid solution;
(3) and (3) uniformly coating the transparent (co) polyamic acid solution obtained in the step (2) on a clean glass substrate with a set thickness, then placing the glass substrate in an oven for temperature programming and thermal imidization, and taking out the glass substrate after a period of time to obtain the transparent polyimide (composite film).
Further, the ionic liquid is selected from one or more of 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-allyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt and 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt.
Further, the polar aprotic solvent (also called aprotic polar solvent) is selected from N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, tetrahydrofuran, and the like.
Further, the (co) polyamic acid solution contains a semi-aromatic polyimide acid produced by a reaction between an aromatic acid anhydride and an aliphatic diamine.
The preparation method is characterized in that the aromatic dianhydride is aromatic dianhydride, and the aromatic dianhydride is selected from one or more of 1,2,4, 5-pyromellitic dianhydride, 3,3',4,4' -benzophenonetetracarboxylic dianhydride, 4,4' -diphenyl ether dianhydride, 3,3',4,4' -biphenyl dianhydride, 4, 4-hexafluoroisopropyl phthalic anhydride, 4,4' - (trifluoromethylphenylisopropyl) phthalic anhydride and 4,4' - (trifluoromethyl-m, m-bistrifluoromethylphenyl-isopropyl) phthalic anhydride.
The aliphatic diamine is selected from one or more of 4-cyclohexanediamine, 4,4' -diaminodicyclohexylmethane, L-arginine, 1, 2-cyclohexanediamine, 1, 4-cyclohexanediamine and 1, 3-cyclohexanediamine.
In the preparation method, the aromatic diamine is selected from one or more of 2,2 '-bis-trifluoromethyl-4, 4' -diaminobiphenyl, 1, 4-bis (4-aminophenoxy) benzene, 9-bis (4-aminophenyl) fluorene, 3 '-bis-trifluoromethyl-5, 5' -diaminobiphenyl, 2-bis (4-aminophenoxy benzene) hexafluoropropane, 3-trifluoromethyl m-phenylenediamine, tetrafluoro-p-phenylenediamine, 2-bis (4-aminophenyl) hexafluoropropane, tetrafluoro-m-phenylenediamine, 4,4 '-octafluoro-biphenyl diamine and 4,4' -diamino-octafluoro-biphenyl ether.
And (3) when the thickness of the polyimide (composite film) obtained in the step (3) is 50um, the elongation is more than 20%. The polyimide film has a light transmittance of greater than 87%, a color b of less than 3, and a CTE of less than 30 ppm/DEG C.
The polyimide with high transparency, flexibility and low chroma is prepared from (copolymerization) polyimide acid which is added with ionic liquid and consists of wholly aromatic (copolymerization) polyimide acid and semi-aromatic (copolymerization) polyimide acid, wherein the copolymerization polyimide acid diamine contains aliphatic diamine with a molar ratio of not more than 20-60% and aromatic diamine with a molar ratio of not less than 80-40%. Wherein the ratio of the mass of the ionic liquid to the mass of the copolymerized polyimide acid is not less than 5.
Compared with the prior art, the thickness range of the high-transparency polyimide film prepared by the invention is about 50 μm, the ultraviolet average transmittance of the high-transparency polyimide film at 350-800nm is up to 87%, the CTE (coefficient of thermal expansion) is less than 30 ppm/DEG C, the chroma b is less than 3, and the high-transparency polyimide film has good flexibility.
< example 1>
Into a 500ml three-necked flask equipped with nitrogen blanket and mechanical stirring was charged 210ml of N, N-dimethylacetamide, followed by 0.09mol of a diamine mixture of L-arginine and 1, 4-bis (4-aminophenoxy) benzene (molar ratio 4: 6). The mixture was dissolved by stirring at 10 ℃. Then 0.0945mol of 4,4' - (trifluoromethylphenylisopropyl) diphenyl anhydride was added to react with diamine, and stirred at 10 ℃ for 8 hours to obtain a copolyamide acid solution.
17.5g of 1-ethyl-3-methylimidazolium tetrafluoroborate was added to the transparent (co) polyamic acid solution and mechanically stirred for 3 hours to uniformly disperse the same in the transparent (co) polyamic acid solution, thereby finally forming a colorless and transparent homogeneous mixed solution.
The preparation method of the transparent (polyimide) film comprises the following specific steps: first, the colorless transparent (co) polyamic acid solution was defoamed for one hour, cast onto a clean and dust-free glass plate, then coated to a predetermined thickness with a doctor blade, and the glass plate with the film (raw material) was placed in an oven to perform thermal imidization at 150 ℃, 40 minutes, 240 ℃, 40 minutes, 310 ℃, 40 minutes, 350 ℃, and 40 minutes according to the following process. And after a period of time, cooling the temperature of the oven to room temperature, and taking out the glass substrate to obtain the transparent polyimide composite film.
< example 2>
Into a 500ml three-necked flask equipped with nitrogen blanket and mechanical stirring was charged 210ml of N, N-dimethylacetamide, followed by 0.09mol of a diamine mixture of L-arginine and 1, 4-bis (4-aminophenoxy) benzene (molar ratio 4: 6). The mixture was dissolved by stirring at 10 ℃. Then 0.0945mol of 4,4' - (trifluoromethylphenylisopropyl) diphenyl anhydride was added to react with diamine, and stirred at 10 ℃ for 8 hours to obtain a copolyamide acid solution.
17.5g of 1-butyl-3-methylimidazolium tetrafluoroborate was added to the transparent (co) polyamic acid solution and mechanically stirred for 3 hours to uniformly disperse the same in the transparent (co) polyamic acid solution, thereby finally forming a colorless and transparent homogeneous mixed solution. A polyimide (composite) film will be subsequently formed in the same manner as in example 1.
< example 3>
Into a 500ml three-necked flask equipped with nitrogen blanket and mechanical stirring was charged 210ml of N, N-dimethylacetamide, followed by 0.09mol of a diamine mixture of L-arginine and 1, 4-bis (4-aminophenoxy) benzene (molar ratio 4: 6). The mixture was dissolved by stirring at 10 ℃. Then 0.0945mol of 4,4' - (trifluoromethylphenylisopropyl) diphenyl anhydride was added to react with diamine, and stirred at 10 ℃ for 8 hours to obtain a copolyamide acid solution.
17.5g of 1-butyl-3-methylimidazolium hexafluorophosphate was added to the transparent (co) polyamic acid solution, and the mixture was mechanically stirred for 3 hours to be uniformly dispersed in the transparent (co) polyamic acid solution, thereby finally forming a colorless and transparent homogeneous mixed solution. A polyimide (composite) film will be subsequently formed in the same manner as in example 1.
< example 4>
Into a 500ml three-necked flask equipped with nitrogen blanket and mechanical stirring was charged 210ml of N, N-dimethylacetamide, followed by 0.09mol of a diamine mixture of L-arginine and 1, 4-bis (4-aminophenoxy) benzene (molar ratio 4: 6). The mixture was dissolved by stirring at 10 ℃. Then 0.0945mol of 4,4' - (trifluoromethylphenylisopropyl) diphenyl anhydride was added to react with diamine, and stirred at 10 ℃ for 8 hours to obtain a copolyamide acid solution.
17.5g of 1-allyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt was added to the above transparent (co) polyamic acid solution and mechanically stirred for 3 hours to uniformly disperse it in the transparent (co) polyamic acid solution, and finally a colorless transparent homogeneous mixed solution was formed. A polyimide (composite) film will be subsequently formed in the same manner as in example 1.
< example 5>
Into a 500ml three-necked flask equipped with nitrogen blanket and mechanical stirring was charged 210ml of N, N-dimethylacetamide, followed by 0.09mol of a diamine mixture of L-arginine and 1, 4-bis (4-aminophenoxy) benzene (molar ratio 4: 6). The mixture was dissolved by stirring at 10 ℃. Then 0.0945mol of 4,4' - (trifluoromethylphenylisopropyl) diphenyl anhydride was added to react with diamine, and stirred at 10 ℃ for 8 hours to obtain a copolyamide acid solution.
17.5g of 1-butyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide salt was added to the above-mentioned transparent (co) polyamic acid solution, and mechanically stirred for 3 hours to be uniformly dispersed in the transparent (co) polyamic acid solution, thereby finally forming a colorless and transparent homogeneous mixed solution. A polyimide (composite) film will be subsequently formed in the same manner as in example 1.
The results of the product performance tests obtained in the above examples are shown in the following table,
Claims (9)
1. A modified high-transparency flexible polyimide film is characterized in that the film is prepared from copolymerized polyamic acid added with ionic liquid through a thermal imidization method, the mass number of the ionic liquid in the copolymerized polyamic acid accounts for more than five percent of the total mass number of the copolymerized polyamic acid, and the copolymerized polyimide acid diamine comprises less than or equal to 20-60 percent of aliphatic diamine and more than or equal to 80-40 percent of aromatic diamine.
2. A preparation method of a modified high-transparency polyimide flexible film is characterized by comprising the following steps:
(1) adding aliphatic diamine and aromatic diamine into a polar aprotic solvent protected by inert gas, completely dissolving the aliphatic diamine and the aromatic diamine at a set temperature, and adding aromatic anhydride, wherein the molar ratio of the diamine to the aromatic anhydride is controlled to be 1: 1-1.05, reacting for 4-8 hours to obtain a copolymer polyamic acid solution;
(2) adding ionic liquid into the copolymerized polyamic acid solution obtained in the step (1) and continuously stirring, and continuously stirring for 1-3 hours under the protection of inert gas to obtain a transparent copolymerized polyamic acid solution;
(3) and (3) uniformly coating the transparent copolymerized polyamide acid solution obtained in the step (2) on a clean glass substrate in a set thickness, then placing the glass substrate in an oven for programmed heating for thermal imidization, and taking out the glass substrate after the temperature of the oven is reduced to the room temperature to obtain the transparent polyimide composite film.
3. The method for preparing a modified highly transparent polyimide flexible film according to claim 2, wherein the temperature programming in step (3) is sequentially 150 ℃, 40 minutes, 240 ℃, 40 minutes, 310 ℃, 40 minutes, 350 ℃, 40 minutes.
4. The method for preparing a modified highly transparent polyimide flexible film according to claim 2, wherein the temperature set in the step (1) is 10 ℃.
5. The method of claim 2, 3 or 4, wherein the ionic liquid is selected from one or more of 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-allyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt, and 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt.
6. The method for preparing a modified highly transparent polyimide flexible film according to claim 2, 3 or 4, wherein the polar aprotic solvent is selected from one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide and tetrahydrofuran.
7. The method of claim 2, 3 or 4, wherein the aromatic dianhydride is one or more selected from the group consisting of 1,2,4, 5-pyromellitic dianhydride, 3,3',4,4' -benzophenone tetracarboxylic dianhydride, 4,4' -diphenyl ether dianhydride, 3,3',4,4' -biphenyl dianhydride, 4, 4-hexafluoroisopropylphthalic anhydride, 4,4' - (trifluoromethylphenyl isopropyl) phthalic anhydride, and 4,4' - (trifluoromethyl-m, m-bistrifluoromethylphenyl-isopropyl) phthalic anhydride.
8. The method of claim 2, 3 or 4, wherein the aliphatic diamine is selected from one or more of 4-cyclohexanediamine, 4,4' -diaminodicyclohexylmethane, L-arginine, 1, 2-cyclohexanediamine, 1, 4-cyclohexanedimethylamine, and 1, 3-cyclohexanediamine.
9. The method for preparing a modified highly transparent polyimide flexible film according to claim 2 or 3 or 4, the aromatic diamine is characterized in that the aromatic diamine is one or more selected from 2,2 '-bis (trifluoromethyl) -4, 4' -diaminobiphenyl, 1, 4-bis (4-aminophenoxy) benzene, 9-bis (4-aminophenyl) fluorene, 3 '-bis (trifluoromethyl) -5, 5' -diaminobiphenyl, 2-bis (4-aminophenoxy) benzene hexafluoropropane, 3-trifluoromethyl m-phenylenediamine, tetrafluoro-p-phenylenediamine, 2-bis (4-aminophenyl) hexafluoropropane, tetrafluoro-m-phenylenediamine, 4,4 '-octafluoro-biphenyl diamine or 4,4' -diamino-octafluoro-biphenyl ether.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114085378A (en) * | 2021-11-16 | 2022-02-25 | 吉林奥来德光电材料股份有限公司 | Polyamide acid solution and preparation method thereof, polyimide film and preparation method and application thereof |
| CN114106324A (en) * | 2021-10-25 | 2022-03-01 | 吉林奥来德光电材料股份有限公司 | Polyamide acid solution and preparation method and application thereof |
| CN114621439A (en) * | 2022-04-19 | 2022-06-14 | 宝珠特种材料科技(江苏)有限公司 | Preparation method of polyimide film |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114106324A (en) * | 2021-10-25 | 2022-03-01 | 吉林奥来德光电材料股份有限公司 | Polyamide acid solution and preparation method and application thereof |
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| CN114085378B (en) * | 2021-11-16 | 2023-08-18 | 吉林奥来德光电材料股份有限公司 | Polyamide acid solution and preparation method thereof, polyimide film and preparation method and application thereof |
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| CN114621439A (en) * | 2022-04-19 | 2022-06-14 | 宝珠特种材料科技(江苏)有限公司 | Preparation method of polyimide film |
| CN115181305A (en) * | 2022-07-25 | 2022-10-14 | 河北金力新能源科技股份有限公司 | Modified polyimide proton exchange membrane and preparation method thereof |
| CN115181305B (en) * | 2022-07-25 | 2023-11-03 | 河北金力新能源科技股份有限公司 | Modified polyimide proton exchange membrane and preparation method thereof |
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