CN111138695A - Polyimide film and preparation method thereof - Google Patents
Polyimide film and preparation method thereof Download PDFInfo
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- CN111138695A CN111138695A CN202010025596.6A CN202010025596A CN111138695A CN 111138695 A CN111138695 A CN 111138695A CN 202010025596 A CN202010025596 A CN 202010025596A CN 111138695 A CN111138695 A CN 111138695A
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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
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
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- 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
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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
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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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
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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Abstract
The invention relates to a polyimide film and a preparation method thereof, and particularly discloses a polyimide film prepared by the following method: 1) polymerizing a fluorine-containing diamine monomer and a dianhydride monomer to obtain a polyamic acid precursor solution; 2) adding a catalyst into the polyamic acid precursor solution, carrying out chemical imidization, and then pouring into an alcohol solvent for precipitation to prepare polyimide resin containing a terminal anhydride functional group; 3) dissolving polyimide resin, and adding a bridging compound for reaction; 4) coating the film-forming solution by a spin coater to form a film, and performing thermal imidization treatment on the film to obtain a polyimide film; wherein the bridging compound is selected from N ((CH)2)nNH2)3The compound shown, n is 2-5. The film of the invention has high transparency, low dielectric constant and excellent mechanical property.
Description
Technical Field
The invention belongs to the technical field of polymer films, and particularly relates to a polyimide film which is transparent, has a low dielectric constant and excellent mechanical properties, and a preparation method thereof.
Background
Polyimide is an aromatic polymer engineering plastic researched and developed in nearly half century, and is widely applied to the fields of aerospace, rail transit, electronic packaging, chemical engineering and the like due to excellent thermal stability, mechanical strength, chemical corrosion resistance and insulating property. In general, polyimide is prepared by liquid-phase polymerization of an aromatic dianhydride and an aromatic diamine, followed by dehydration imidization under high-temperature conditions.
However, in the conventional polyimide material, a large amount of carbonyl groups and amino groups remain in a polyimide molecular chain, and the interaction of electrons between the carbonyl groups and the amino groups causes an electron complex to be formed in the molecular chain and between the molecular chains, so that the polyimide material presents light yellow or reddish brown, and has low light transmittance, which seriously restricts the further application of the polyimide material in emerging fields, such as flexible thin film solar cells, liquid crystal displays, flexible AMOLEDs and the like.
Therefore, it is necessary to rationally design a molecular structure and develop a polyimide resin having high transparency without sacrificing other properties. The most effective method for preparing the transparent polyimide film at present is to introduce a fluorine-containing group, and Chinese patent application CN108517035A discloses a fluorine-containing PI film with high transparency and mechanical property and application thereof, wherein a diamine compound containing a hexafluoronaphthalene structure is adopted to react with tetracarboxylic dianhydride to prepare the transparent PI film with the light transmittance of 91 percent at 450 nm. However, the introduction of the fluorine-containing group not only causes the thermal stability of the polyimide resin to be lowered, but also causes the mechanical properties to be lowered. The research shows that the tensile strength of the fluorine-containing group transparent polyimide film materials which are developed at present is below 130 MPa. Therefore, how to reasonably introduce fluorine-containing groups and design a molecular structure, improve the transparency of the polyimide material, reduce the dielectric constant of the polyimide material and make up for the deficiency of weakened mechanical strength becomes a difficult problem to be solved urgently.
Disclosure of Invention
In order to solve the problems of low transparency of the polyimide film and poor mechanical property of the transparent polyimide film, the invention develops and provides a preparation method of the polyimide film with low dielectric constant, which has good mechanical property and high transparency.
According to the invention, the polyimide film with enhanced mechanical properties, high transparency and low dielectric constant is finally prepared by a thermal imidization method after chemical imidization is carried out firstly, then re-dissolved and added with a bridging compound for reaction, and the defect of poor mechanical properties of the prior fluorine-containing transparent polyimide film is overcome.
One aspect of the present invention provides a method for preparing a polyimide film, comprising the steps of:
1) polymerizing a fluorine-containing diamine monomer and a dianhydride monomer to obtain a polyamic acid precursor solution;
2) adding a catalyst into the polyamic acid precursor solution, carrying out chemical imidization, and then pouring into an alcohol solvent for precipitation to prepare polyimide resin containing a terminal anhydride functional group;
3) dissolving polyimide resin, adding a bridging compound, and reacting to obtain a film forming solution;
4) coating the film-forming solution by a spin coater to form a film, and performing thermal imidization treatment on the film to obtain a polyimide film;
wherein the bridging compound is selected from N ((CH)2)nNH2)3In the compounds shown, n is 2 to 5, preferably 3,4 or 5.
In the technical scheme of the invention, the fluorine-containing diamine monomer is selected from 2,2' -bis (trifluoromethyl) diaminobiphenyl, 1, 4-bis (4-amino-2-trifluoromethylphenoxy) benzene, 1, 3-bis (4-amino-2-trifluoromethylphenoxy) benzene, 1, 2-bis (4-amino-2-trifluoromethylphenoxy) benzene, 1, 4-bis (4-amino-3-trifluoromethylphenoxy) benzene, 1, 3-bis (4-amino-3-trifluoromethylphenoxy) benzene, 1, 2-bis (4-amino-3-trifluoromethylphenoxy) benzene, 2, 5-bis (4-amino-2-trifluoromethylphenoxy) toluene, and, 2, 5-bis (4-amino-3-trifluoromethylphenoxy) toluene, 2, 5-bis (4-amino-2-trifluoromethylphenoxy) trifluorotoluene, 2, 5-bis (4-amino-3-trifluoromethylphenoxy) trifluorotoluene, 1, 4-bis (4-amino-2-trifluoromethylphenoxy) -2-tert-butylbenzene, 1, 4-bis (4-amino-3-trifluoromethylphenoxy) -2, 5-diterbutylbenzene, 1, 4-bis (4-amino-2-trifluoromethylphenoxy) -2, 5-di-tert-butylbenzene, 4 '-bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4' -bis (4-amino-3-trifluoromethylphenoxy) biphenyl, 4 '-bis (4-amino-2-trifluoromethylphenoxy) -3, 3', 5, 5 '-tetramethylbiphenyl, 4' -bis (4-amino-3-trifluoromethylphenoxy) -3, 3 ', 5, 5' -tetramethylbiphenyl, 4 '-bis (4-amino-2-trifluoromethylphenoxy) -3, 3', 5, 5 '-tetramethyldiphenylsulfone, 4' -bis (4-amino-3-trifluoromethylphenoxy) -3, 3 ', 5, 5' -tetramethyldiphenylsulfone, 4 '-bis (4-amino-2-trifluoromethylphenoxy) diphenylsulfone, 4' -bis (4-amino-3-trifluoromethylphenoxy) diphenylsulfone, 2-bis [4- (4-amino-3-trifluoromethylphenoxy) phenyl ] propane, 2-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl ] propane, 2-bis [4- (4-amino-3-trifluoromethylphenoxy) phenyl ] hexafluoropropane, 2-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl ] hexafluoropropane, 4 '-bis (4-amino-3-trifluoromethylphenoxy) diphenylmethane, 4' -bis (4-amino-3-trifluoromethylphenoxy) diphenylmethane, 4,4 '-bis (4-amino-2-trifluoromethylphenoxy) diphenylmethane, 4' -bis (4-amino-3-trifluoromethylphenoxy) diphenyl ether, 4 '-bis (4-amino-2-trifluoromethylphenoxy) diphenyl sulfide, 4' -bis (4-amino-3-trifluoromethylphenoxy) diphenyl sulfide, 2-bis [4- (4-amino-2-trifluoromethylphenoxy) -3, 5-dimethylphenyl ] propane, 2-bis [4- (4-amino-3-trifluoromethylphenoxy) -3, one or more of 5-dimethylphenyl ] propane, 2-bis [4- (4-amino-2-trifluoromethylphenoxy) -3, 5-dimethylphenyl ] hexafluoropropane, 2-bis [4- (4-amino-3-trifluoromethylphenoxy) -3, 5-dimethylphenyl ] hexafluoropropane, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 2-bis [4- (3-aminophenoxy) phenyl ] hexafluoropropane, 3 '-bis (trifluoromethyl) -4, 4' -diaminobiphenyl, and 2,2 '-bis (trifluoromethyl) -4, 4' -diaminobiphenyl.
In the technical scheme of the invention, the dianhydride monomer is selected from one or more of 4,4 '-diphenyl ether dianhydride, hexafluoro dianhydride and benzophenone tetracarboxylic dianhydride, and is preferably selected from the combination of 4,4' -diphenyl ether dianhydride and hexafluoro dianhydride.
In the technical scheme of the invention, the polymerization method in the step 1) is to add dianhydride monomer into fluorine-containing diamine monomer solution, uniformly mix and carry out polymerization reaction to obtain polyamic acid precursor solution.
In the technical scheme of the invention, the catalyst in the step 2) is selected from one or more of isoquinoline, quinoline, picoline, pyridine and acetic anhydride.
In the technical scheme of the invention, the molar ratio of the fluorine-containing diamine monomer to the dianhydride monomer is 1:1.1-1.3, preferably 1: 1.2.
In the technical scheme of the invention, the step 3) is carried out in a polar solvent, preferably one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran and dimethyl sulfoxide.
In the technical scheme of the invention, the amount of the bridging compound in the step 3) is that the molar ratio of the bridging compound to the fluorine-containing diamine monomer in the step 1) is 1:3-7, preferably 1:4-6, and more preferably 1: 5.
In the technical scheme of the invention, the thermal imidization treatment is heat preservation for 1-5h at 80-120 ℃ and 250-350 ℃.
In another aspect, the present invention provides a polyimide film obtained by the method of the present invention.
In the technical scheme of the invention, the thickness of the polyimide film is 15-30 μm.
In the technical scheme of the invention, the dielectric constant of the polyimide film at 1KHz is not higher than 3.0, and preferably 2.6-2.8.
In the technical scheme of the invention, the tensile strength of the polyimide film is 160MPa-210 MPa.
In the technical scheme of the invention, the ultraviolet visible light transmittance of the polyimide film is 90-95%.
Advantageous effects
On the basis of keeping high ultraviolet and visible light transmittance and low dielectric constant, the polyimide film realizes the enhancement of mechanical property through the design and introduction of a cross-linking structure, makes up the defect of insufficient mechanical strength of the prior fluorine-containing transparent polyimide film, and improves the practical application of the fluorine-containing transparent polyimide film. Meanwhile, the reaction of the polyimide containing end functional groups and the bridging compound is realized through the steps of secondary imidization (firstly preparing soluble polyimide resin through chemical imidization and then performing thermal imidization), and the mechanical property of the finally obtained polyimide film is greatly enhanced. The research has simple preparation method and obviously enhanced mechanical property.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, specific embodiments thereof are described in detail below, but the present invention is not to be construed as being limited to the implementable range thereof.
In a specific embodiment of the present invention, the light transmittance is characterized by an ultraviolet-visible spectrophotometer, the tensile strength of the film is measured by a dynamic thermomechanical analyzer, and the dielectric constant is measured by an alternating current impedance analyzer. The equipment types used are shown in the following table.
Laboratory apparatus
Instrument name model manufacturer
1200 ℃ double temperature zone slide rail furnace OTF-1200X-II-80 complex fertilizer crystal
UV-vis 3600 Shimadzu of ultraviolet visible spectrophotometer
Dynamic thermomechanical analyzer Q800 TA
AC impedance analyzer 4294A Agilent
KQ-700DA ultrasonic Instrument Co., Ltd., Kunshan City, ultrasonic cleaning machine
Microelectronic research institute of KW-4A Chinese academy of sciences of desk type spin coater
Desk centrifuge Allegra X-30 Beckman
The technical solution of the present invention will be further described with reference to specific embodiments.
EXAMPLE 1 preparation of transparent polyimide film
(1) 1.601g (0.005mol) of diamine monomer 2,2 '-bis (trifluoromethyl) diaminobiphenyl (TFMB) is dissolved in 21mL of N, N-dimethylformamide solution at room temperature, after ultrasonic stirring for 30min, 1.303g of 4,4' -diphenyl ether dianhydride (ODPA) (0.0042mol) is added into the solution, mechanical stirring is carried out for 8h under the protection of nitrogen, 0.800g of hexafluoro dianhydride (6FDA) (0.0018mol) is added into the solution to obtain a transparent polyamide acid solution with the solid content of 15 wt%, after ultrasonic stirring for 12h, a catalyst (the amount ratio of acetic anhydride to pyridine is 10: 1) is added into the solution to carry out chemical imidization, after stirring is continued for 12h, the solution is poured into ethanol to precipitate polyimide resin containing terminal anhydride functional groups, and then the polyimide resin is washed for multiple times.
(2) Dissolving polyimide resin in N, N-dimethylformamide solution, ultrasonic stirring for 1 hr, and adding 0.188g bridging compound
And (3-aminopropyl) amine, and reacting for 6 hours to prepare a film forming solution.
(3) And (3) placing the film-forming solution in an ultrasonic cleaning machine for ultrasonic treatment for 30min, and then placing the film-forming solution in a vacuum oven for defoaming treatment under the vacuum condition.
(4) The defoamed film-forming solution was dropped on a glass plate and rotated at 500rpm for 30 seconds to form a polyimide film having a uniform thickness.
(5) Putting the polyimide film into a tube furnace, providing nitrogen atmosphere, and then sequentially preserving heat at 100 ℃ and 300 ℃ for 1h respectively to obtain the polyimide film after thermal imidization treatment.
The thickness of the polyimide film prepared by the embodiment is 15-20 μm, the dielectric constant (1KHz) is 2.83, the tensile strength is 162MPa, the ultraviolet and visible light transmittance is 90.6%, the cut-off frequency is 330nm, and the transmittance at 400nm is 67%.
Example 2 preparation of a transparent polyimide film (1) 1.601g (0.005mol) of diamine monomer 2,2' -bis (trifluoromethyl) diaminobiphenyl (TFMB) was dissolved in 21mL of N, N-dimethylformamide solution at room temperature, after ultrasonic stirring for 30min, adding 1.303g of 4,4' -diphenyl ether dianhydride (ODPA) (0.0042mol), mechanically stirring for 8h under the protection of nitrogen, adding 0.800g of hexafluoro dianhydride (6FDA) (0.0018mol) to obtain a transparent polyamic acid solution with the solid content of 15 wt%, ultrasonically stirring for 12h, adding a catalyst (the amount ratio of acetic anhydride to pyridine is 10: 1) to perform chemical imidization reaction, continuously stirring for 12h, pouring into ethanol to precipitate polyimide resin containing terminal anhydride functional groups, and then washing the polyimide resin for multiple times.
(2) Dissolving polyimide resin in N, N-dimethylformamide solution, ultrasonic stirring for 1 hr, and adding 0.188g bridging compound
And (3-aminopropyl) amine, and reacting for 6 hours to prepare a film forming solution.
(3) And (3) placing the film-forming solution in an ultrasonic cleaning machine for ultrasonic treatment for 30min, and then placing the film-forming solution in a vacuum oven for defoaming treatment under the vacuum condition.
(4) Coating the defoamed film forming solution on a glass plate, setting the rotating speed of a spin coater to be 500rpm, and rotating for 30s to form a polyimide film with uniform thickness.
(5) Putting the polyimide film into a tube furnace, providing nitrogen atmosphere, and then sequentially preserving heat at 100 ℃ and 300 ℃ for 1h respectively to obtain the polyimide film after thermal imidization treatment.
The thickness of the polyimide film prepared by the embodiment is 20-23 μm, the dielectric constant (1KHz) is 2.78, the tensile strength is 203MPa, the ultraviolet and visible light transmittance is 92.1%, the cut-off frequency is 310nm, and the transmittance at 400nm is 78%.
EXAMPLE 3 preparation of transparent polyimide film
(1) 1.601g (0.005mol) of diamine monomer 2,2 '-bis (trifluoromethyl) diaminobiphenyl (TFMB) is dissolved in 22mL of N, N-dimethylformamide solvent at room temperature, after ultrasonic stirring for 30min, 0.558g of 4,4' -diphenyl ether dianhydride (ODPA) (0.0018mol) is added, mechanical stirring is carried out for 8h under the protection of nitrogen, 1.866g of hexafluoro dianhydride (6FDA) (0.0042mol) is added to obtain a transparent polyamic acid solution with the solid content of 15 wt%, after ultrasonic stirring for 12h, a catalyst (the ratio of the amount of acetic anhydride to the amount of pyridine is 10: 1) is added to carry out chemical imidization reaction, after stirring is continued for 12h, the polyimide resin containing the terminal anhydride functional group is precipitated by pouring into ethanol, and the polyimide resin is washed and dried for many times.
(2) Dissolving polyimide resin in N, N-dimethylformamide solvent, ultrasonically stirring for 1h, and adding 0.188g bridging compound
And (3-aminopropyl) amine, and continuously reacting for 6 hours to prepare the film forming solution.
(3) And (3) placing the film-forming solution in an ultrasonic cleaning machine for ultrasonic treatment for 30min, and then placing the film-forming solution in a vacuum oven for defoaming treatment under the vacuum condition.
(4) Coating the defoamed film forming solution on a glass plate, setting the rotating speed of a spin coater to be 500rpm, and rotating for 30s to form a polyimide film with uniform thickness.
(5) Putting the polyimide film into a tube furnace, providing nitrogen atmosphere, and then sequentially preserving heat at 100 ℃ and 300 ℃ for 1h respectively to obtain the polyimide film after thermal imidization treatment.
The thickness of the polyimide film prepared in the embodiment is 15-20 μm, the dielectric constant (1KHz) is 2.71, the tensile strength is 186MPa, and the ultraviolet and visible light transmittance is 94%. The cut-off frequency was 280nm, and the transmittance at 400nm was 86%.
EXAMPLE 4 preparation of transparent polyimide film
(1) 1.601g (0.005mol) of diamine monomer 2,2 '-bis (trifluoromethyl) diaminobiphenyl (TFMB) is dissolved in 22mL of DMF solvent at room temperature, after ultrasonic stirring is carried out for 30min, 0.558g of 4,4' -diphenyl ether dianhydride (ODPA) (0.0018mol) is added into the solution, mechanical stirring is carried out for 8h under the protection of nitrogen, 1.866g of hexafluoro dianhydride (6FDA) (0.0042mol) is added into the solution, so as to obtain a transparent polyamide acid solution with the solid content of 15 wt%, after ultrasonic stirring is carried out for 12h, a catalyst (the ratio of the amount of acetic anhydride to the amount of pyridine is 10: 1) is added into the solution to carry out chemical imidization, after stirring is carried out for 12h, the solution is poured into ethanol to precipitate polyimide resin containing terminal anhydride functional groups, and the polyimide resin is washed and dried for many times.
(2) Dissolving polyimide resin in N, N-dimethylformamide solvent, ultrasonically stirring for 1h, and adding 0.188g bridging compound
And (3-aminopropyl) amine, and reacting for 6 hours to prepare a film forming solution.
(3) And (3) placing the film-forming solution in an ultrasonic cleaning machine for ultrasonic treatment for 30min, and then placing the film-forming solution in a vacuum oven for defoaming treatment under the vacuum condition.
(4) Coating the defoamed film forming solution on a glass plate, setting the rotating speed of a spin coater to be 500rpm, and rotating for 30s to form a polyimide film with uniform thickness.
(5) Putting the polyimide film into a tube furnace, providing nitrogen atmosphere, and then sequentially preserving heat at 100 ℃ and 300 ℃ for 1h respectively to obtain the polyimide film after thermal imidization treatment.
The thickness of the polyimide film prepared by the embodiment is 20-23 μm, the dielectric constant (1KHz) is 2.62, the tensile strength is 208MPa, the ultraviolet and visible light transmittance is 93%, the cut-off frequency is 276nm, and the transmittance at 400nm is 88%.
Claims (10)
1. A preparation method of a polyimide film comprises the following steps:
1) polymerizing a fluorine-containing diamine monomer and a dianhydride monomer to obtain a polyamic acid precursor solution;
2) adding a catalyst into the polyamic acid precursor solution, carrying out chemical imidization, and then pouring into an alcohol solvent for precipitation to prepare polyimide resin containing a terminal anhydride functional group;
3) dissolving polyimide resin, and adding a bridging compound to react to obtain a film forming solution;
4) coating the film-forming solution by a spin coater to form a film, and performing thermal imidization treatment on the film to obtain a polyimide film;
wherein the bridging compound is selected from N ((CH)2)nNH2)3In the compounds shown, n is 2 to 5, preferably 3,4 or 5.
2. The process according to claim 1, wherein the fluorine-containing diamine monomer is selected from the group consisting of 2,2' -bis (trifluoromethyl) diaminobiphenyl, 1, 4-bis (4-amino-2-trifluoromethylphenoxy) benzene, 1, 3-bis (4-amino-2-trifluoromethylphenoxy) benzene, 1, 2-bis (4-amino-2-trifluoromethylphenoxy) benzene, 1, 4-bis (4-amino-3-trifluoromethylphenoxy) benzene, 1, 3-bis (4-amino-3-trifluoromethylphenoxy) benzene, 1, 2-bis (4-amino-3-trifluoromethylphenoxy) benzene, 2, 5-bis (4-amino-2-trifluoromethylphenoxy) toluene, and mixtures thereof, 2, 5-bis (4-amino-3-trifluoromethylphenoxy) toluene, 2, 5-bis (4-amino-2-trifluoromethylphenoxy) trifluorotoluene, 2, 5-bis (4-amino-3-trifluoromethylphenoxy) trifluorotoluene, 1, 4-bis (4-amino-2-trifluoromethylphenoxy) -2-tert-butylbenzene, 1, 4-bis (4-amino-3-trifluoromethylphenoxy) -2, 5-diterbutylbenzene, 1, 4-bis (4-amino-2-trifluoromethylphenoxy) -2, 5-di-tert-butylbenzene, 4 '-bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4' -bis (4-amino-3-trifluoromethylphenoxy) biphenyl, 4 '-bis (4-amino-2-trifluoromethylphenoxy) -3, 3', 5, 5 '-tetramethylbiphenyl, 4' -bis (4-amino-3-trifluoromethylphenoxy) -3, 3 ', 5, 5' -tetramethylbiphenyl, 4 '-bis (4-amino-2-trifluoromethylphenoxy) -3, 3', 5, 5 '-tetramethyldiphenylsulfone, 4' -bis (4-amino-3-trifluoromethylphenoxy) -3, 3 ', 5, 5' -tetramethyldiphenylsulfone, 4 '-bis (4-amino-2-trifluoromethylphenoxy) diphenylsulfone, 4' -bis (4-amino-3-trifluoromethylphenoxy) diphenylsulfone, 2-bis [4- (4-amino-3-trifluoromethylphenoxy) phenyl ] propane, 2-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl ] propane, 2-bis [4- (4-amino-3-trifluoromethylphenoxy) phenyl ] hexafluoropropane, 2-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl ] hexafluoropropane, 4 '-bis (4-amino-3-trifluoromethylphenoxy) diphenylmethane, 4' -bis (4-amino-3-trifluoromethylphenoxy) diphenylmethane, 4,4 '-bis (4-amino-2-trifluoromethylphenoxy) diphenylmethane, 4' -bis (4-amino-3-trifluoromethylphenoxy) diphenyl ether, 4 '-bis (4-amino-2-trifluoromethylphenoxy) diphenyl sulfide, 4' -bis (4-amino-3-trifluoromethylphenoxy) diphenyl sulfide, 2-bis [4- (4-amino-2-trifluoromethylphenoxy) -3, 5-dimethylphenyl ] propane, 2-bis [4- (4-amino-3-trifluoromethylphenoxy) -3, one or more of 5-dimethylphenyl ] propane, 2-bis [4- (4-amino-2-trifluoromethylphenoxy) -3, 5-dimethylphenyl ] hexafluoropropane, 2-bis [4- (4-amino-3-trifluoromethylphenoxy) -3, 5-dimethylphenyl ] hexafluoropropane, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 2-bis [4- (3-aminophenoxy) phenyl ] hexafluoropropane, 3 '-bis (trifluoromethyl) -4, 4' -diaminobiphenyl, and 2,2 '-bis (trifluoromethyl) -4, 4' -diaminobiphenyl.
3. The preparation method according to claim 1, wherein the dianhydride monomer is selected from one or more of 4,4 '-diphenyl ether dianhydride, hexafluoro dianhydride and benzophenone tetracarboxylic dianhydride, preferably from the combination of 4,4' -diphenyl ether dianhydride and hexafluoro dianhydride.
4. The preparation method according to claim 1, wherein the polymerization method in step 1) is to add dianhydride monomer into the fluorine-containing diamine monomer solution, mix them uniformly and perform polymerization reaction to obtain polyamic acid precursor solution.
5. The preparation method according to claim 1, wherein the catalyst in step 2) is selected from one or more of isoquinoline, quinoline, picoline, pyridine and acetic anhydride.
6. The preparation method according to claim 1, wherein the step 3) is carried out in a polar solvent, preferably one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran and dimethyl sulfoxide.
7. The method according to claim 1, wherein the molar ratio of the fluorine-containing diamine monomer to the dianhydride monomer is 1:1.1 to 1.3, preferably 1: 1.2.
8. The method according to claim 1, wherein the bridging compound is used in step 3) in a molar ratio of the bridging compound to the fluorine-containing diamine monomer in step 1) of 1:3 to 7, preferably 1:4 to 6, and more preferably 1: 5.
9. The method as defined in claim 1, wherein the thermal imidization treatment is carried out at 80-120 ℃ and 250-350 ℃ for 1-5 h.
10. The polyimide film obtained by the production method according to any one of claims 1 to 9, preferably, the polyimide film has a thickness of 15 to 30 μm.
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