CN103788650A - Colorless and transparent polyimide film and preparation method thereof - Google Patents
Colorless and transparent polyimide film and preparation method thereof Download PDFInfo
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- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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Abstract
The invention discloses a colorless and transparent polyimide film, the molecular structural formula as shown in a formula I. A preparation method of the polyimide film comprises the following steps: polymerizing a fluorine-containing diamine monomer and a dianhydride monomer which have same moles in a polar aprotic solvent to produce a colorless and transparent poly(amicacid) solution, carrying out dehydration and ring closing on the colorless and transparent poly(amicacid) solution by using a hot imidization method or a chemical imidization method to produce the colorless and transparent polyimide film, wherein the dianhydride monomer is one or two of compounds selected from bicyclic (3,3,0)octane-2,4,6,7-tetracid dihydride or bicyclic (4,3,0)nonane-3,4,7,9-tetracid dihydride, the fluorine-containing diamine monomer is one or a combination of two of compounds selected from 4,4'-di(4-amino-2-trifluoromethylphenoxy)diphenyl ether, 4,4'-di(4-amino-2- trifluoromethylphenoxy) biphenyl and 2,2'-di(4-(4-amino-2- trifluoromethylphenoxy) phenyl) hexafluoropropane. The colorless and transparent polyimide film produced by using the alicyclic type dianhydride monomer has excellent performances such as good heat resistance, good solubility and high light transmittance.
Description
Technical field
The invention belongs to polymeric material field, relate to a kind of transparent polyimide film and preparation method thereof.
Background technology
Transparent polyimide film has the excellent properties such as the low and light transmission rate of good heat resistance, thermal expansivity is high, can replace glass, as the transparent substrate of flexible display and thin-film solar cells.And other transparent polymer materials, such as the thermotolerance of polyethylene terephthalate, polycarbonate, polyacrylic ester, polyethersulfone etc. does not all reach processing requirement.
Traditional fragrant Kapton has very high aromatic nucleus density, easily forms charge transfer complex (CTC), makes it present tawny, has limited its application in photoelectric field.And, due to traditional large and strong molecular interaction of fragrant polyimide molecule chain rigidity, it being shown and do not dissolve, infusible feature, brings very large difficulty to forming process.In order to improve the light transmission rate of Kapton, can, by introducing containing fluoro substituents, introduce meta-substituent or unsymmetrical structure in molecular structure, the method such as content that reduces aromatic ring structure in molecule realizes film transparence.And in order to improve Drawing abillity, conventionally to improve its solvability through changing its molecular structure, main method has introduces flexible structure unit in molecular backbone chain, introduce large side group or side chain, introduce the nonplanar structure of distortion, by repetition regularity and the symmetry of copolymerization saboteur chain.With ester ring type dianhydride monomer synthesis of polyimides, not only can reduce the content of aromatic ring structure in molecule, improve light transmission rate, can also reduce the overlapping of π-π-electron cloud between molecular linkage, improve solubleness.
Exercise question is the " preparation of fluorine-containing half alicyclic ring transparent polyimide film and performance (investigation of materials journal, 2008, 22 (6): 615-618) in document ", author is respectively by alicyclic dianhydride monomer 1, 2, 3, 4-tetramethylene tetracarboxylic dianhydride (CBDA), 1, 2, 4, 5-pentamethylene tetracarboxylic dianhydride (CPDA) and 1, 2, 4, 5-hexanaphthene tetracarboxylic dianhydride (CHDA) and aromatic series fluorinated diamine 1, two (4-amido-2-4-trifluoromethylphenopendant) benzene (6FAPB) and 4 of 4-, two serial fluorine-containing half alicyclic polyimides of 4 '-bis-(4-amido-2-4-trifluoromethylphenopendant) biphenyl (6FBAB) reaction preparation, in these PI film visible-ranges, (400-700nm) has good transmitance, the transmitance at 450nm place exceedes 88%, ultraviolet cut-on wavelength is at 295nm～319nm, in nitrogen, initial heat decomposition temperature exceedes 450 ℃, 250～277 ℃ of second-order transition temperatures.Show to introduce in PI molecular structure and can significantly reduce its absorption in ultraviolet-visible light region by alicyclic structure with containing fluoro substituents, and there is good heat-resistant stability.But glass transition temperature is lower, limit its range of application.
In the Chinese patent that exercise question is " a kind of Kapton and preparation method thereof (publication number is CN102993750A) ", author is with 1,2,3,4-hexanaphthene tetracarboxylic dianhydride (1,2,3,4-CHDA) with 4,4 '-diamino-dicyclohexyl methane (DCHM) or the reaction of two (4-amino-3-methylcyclohexyl) methane (MMCA) make half alicyclic polyimides film.It is 270～300nm that the UV-light of this PI film sees through cutoff wavelength, be a kind of transparent thin-film material of excellence, but second-order transition temperature is 250～265 ℃, and this has just limited range of application.
In the Chinese patent that exercise question is " soluble fluorine-containing aromatic half alicyclic ring polyimide film material and preparation method thereof (publication number is CN102898644A) ", author uses alicyclic dianhydride monomer like 1, 2, 3, 4-tetramethylene tetracarboxylic dianhydride, 1, 2, 4, 5-pentamethylene tetracarboxylic dianhydride, 1, 2, 4, 5-hexanaphthene tetracarboxylic dianhydride, carry out condensation reaction with the diamine monomer that contains trifluoromethyl and ehter bond, the PI film making is keeping under the prerequisite of higher glass transition temperature (283～288 ℃), (transmitance at 450nm place exceedes 91%～95% to have increased the optical transmittance of material, ultraviolet cut-on wavelength is at 280nm～306nm), and dissolve in DMAc, in the non-proton strong polar solvent such as NMP.
Known by above summary, in polyimide molecule structure, introduce ester ring type two anhydride groups and can greatly improve optical transmittance and the solvability of film, but for traditional fragrant polyimide, its resistance toheat decreases.
Summary of the invention
The object of the invention is to adopt two novel ester ring type dianhydride monomers higher with the diamine monomer preparation transparency that contains trifluoromethyl and ehter bond, have good solubility in solvent, polyimide film material that thermotolerance is higher;
Another object of the present invention is to provide a kind of above-mentioned polyimide film material preparation method.
The technical scheme that realizes the object of the invention is:
A kind of transparent polyimide film, the molecular structural formula of described Kapton is suc as formula shown in I:
In formula I, R
1for dianhydride residue, for one of following formula a or formula b:
R
2for diamines residue, be one or more the combination with in following formula c, formula d or formula e, be preferably formula c or formula e:
In formula I, n is the polymerization degree, is more than 20 integers.
The weight-average molecular weight of described transparent polyimide film is between 10000～200000.
The present invention also provides the preparation method of described transparent polyimide film, and described method is:
By waiting fluorinated diamine monomer and dianhydride monomer polymerization in polar aprotic solvent of amount of substance, make water white polyamic acid solution, then by hot imidization method or chemical imidization method dehydration closed-loop, make transparent polyimide film; Described dianhydride monomer is dicyclo [3,3,0] octane-2,4,6,7-tetracarboxylic dianhydride (being called for short 330BODA) or dicyclo [4,3,0] nonane-3, one or both in 4,7,9-tetracarboxylic dianhydride (being called for short BNDA), preferred described dianhydride monomer is dicyclo [3,3,0] octane-2,4,6,7-tetracarboxylic dianhydride (being called for short 330BODA) or dicyclo [4,3,0] nonane-3,4,7,9-tetracarboxylic dianhydride; Described fluorinated diamine monomer is 4,4 '-bis-(4-amino-2-4-trifluoromethylphenopendant) phenyl ether, 4,4 '-bis-(4-amino-2-4-trifluoromethylphenopendant) biphenyl, 2, the combination of one or more in 2 '-bis-[4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] HFC-236fa, preferably 4,4 '-bis-(4-amino-2-4-trifluoromethylphenopendant) phenyl ether or 2,2 '-bis-[4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] HFC-236fa.
Further, transparent polyimide film can be by any one preparation in following two kinds of methods:
Method one:
(1) fluorinated diamine monomer is dissolved in polar aprotic solvent completely, adds dianhydride monomer, under nitrogen protection, under mechanical stirring room temperature, react 1～24 hour, make polyamic acid solution colourless, transparent, thickness; Described fluorinated diamine monomer is 1:1 with the ratio of the amount of substance of dianhydride monomer; Described dianhydride monomer is dicyclo [3,3,0] octane-2,4,6,7-tetracarboxylic dianhydride (being called for short 330BODA) or dicyclo [4,3,0] nonane-3, one or both in 4,7,9-tetracarboxylic dianhydride (being called for short BNDA); Described fluorinated diamine monomer is 4,4 '-bis-(4-amino-2-4-trifluoromethylphenopendant) phenyl ether, 4,4 '-bis-(4-amino-2-4-trifluoromethylphenopendant) biphenyl, 2, the combination of one or more in 2 '-bis-[4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] HFC-236fa, preferably 4,4 '-bis-(4-amino-2-4-trifluoromethylphenopendant) phenyl ether or 2,2 '-bis-[4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] HFC-236fa;
(2) polyamic acid solution step (1) being made under vacuum condition degassed 1～4 hour, eliminate wherein bubble, then film on the smooth sheet glass of any surface finish, sheet glass after film is first dried 1～4 hour at 50～90 ℃, rise to 210～310 ℃ with the heat-up rate of 5 ℃ of per minutes again, constant temperature 1～3 hour, then natural cooling down is to room temperature, sheet glass after cooling is positioned over demoulding in deionized water, obtains transparent polyimide film.
Described under vacuum condition degassed 1～4 hour of room temperature under the degassed condition that is preferably 0.08～0.1MPa at relative vacuum degree.
Method two:
(1) fluorinated diamine monomer is dissolved in polar aprotic solvent completely, adds dianhydride monomer, under nitrogen protection, under mechanical stirring room temperature, react 1～24 hour, make polyamic acid solution colourless, transparent, thickness; Described fluorinated diamine monomer is 1:1 with the ratio of the amount of substance of dianhydride monomer; Described dianhydride monomer is dicyclo [3,3,0] octane-2,4,6,7-tetracarboxylic dianhydride (being called for short 330BODA) or dicyclo [4,3,0] nonane-3, one or both in 4,7,9-tetracarboxylic dianhydride (being called for short BNDA); Described fluorinated diamine monomer is 4,4 '-bis-(4-amino-2-4-trifluoromethylphenopendant) phenyl ether, 4,4 '-bis-(4-amino-2-4-trifluoromethylphenopendant) biphenyl, 2, the combination of one or more in 2 '-bis-[4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] HFC-236fa, preferably 4,4 '-bis-(4-amino-2-4-trifluoromethylphenopendant) phenyl ether or 2,2 '-bis-[4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] HFC-236fa;
(2) catalyzer and dewatering agent are added in the polyamic acid solution that step (1) makes, under nitrogen protection, be uniformly mixed, be warming up at 80～200 ℃ of temperature and carry out imidization 1～24 hour, gained reaction solution is poured in methyl alcohol or ethanol, separate out throw out, collecting precipitation thing washing, dry, make polyimide resin; The volumetric usage of described methyl alcohol or ethanol is 1～10 times of reaction solution volume;
(3) polyimide resin step (2) being made is dissolved in organic solvent, obtain polyimide solution, then film on the smooth sheet glass of any surface finish, sheet glass after film is first dried 1～4 hour at 50～90 ℃, rise to 210～310 ℃ with the heat-up rate of 5 ℃ of per minutes again, constant temperature 1～3 hour, then natural cooling down is to room temperature, sheet glass after cooling is positioned over demoulding in deionized water, obtains transparent polyimide film.
In the step (1) of described method one or method two, described polar aprotic solvent is N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), DMF or N,N-dimethylacetamide, preferably N,N-dimethylacetamide (DMAc).The add-on of described polar aprotic solvent is that to make the solid content of polyamic acid solution be 10～30%, preferably 15%.
In the step (2) of described method two, described catalyzer is pyridine, beta-picoline, quinoline, the mixing of one or more in quinoline, imidazoles, triethylamine, tripropyl amine, tributylamine, thanomin, preferably pyridine; Described dewatering agent is one or more the mixing in diacetyl oxide, toluene, dimethylbenzene, preferably diacetyl oxide.
The ratio of the amount of substance of described dianhydride monomer, catalyzer is 1:0～5, and 0 representative is wherein infinitely close to 0 but be not 0, and preferably the ratio of the amount of substance of dianhydride monomer, catalyzer is 1:1～3, more preferably 1:2.1.
The ratio of the amount of substance of described dianhydride monomer, dewatering agent is 1:0～5, and 0 representative is wherein infinitely close to 0 but be not 0; Preferably the ratio of the amount of substance of dianhydride monomer, dewatering agent is 1:1～2, more preferably 1:1.1.
In the step (3) of described method two, described organic solvent is N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), N, dinethylformamide, N, the mixing of one or more in N-N,N-DIMETHYLACETAMIDE, trichloromethane, methylene dichloride, tetrahydrofuran (THF) or acetone, preferably N,N-dimethylacetamide (DMAc).The add-on of organic solvent is that to make the solid content of polyimide solution be 10～30%, preferably 15%.
Dianhydride monomer is dicyclo [3,3,0] octane-2,4,6,7-tetracarboxylic dianhydride (being called for short 330BODA) or dicyclo [4,3,0] nonane-3, and 4,7,9-tetracarboxylic dianhydride (being called for short BNDA), is published compound, can make according to the preparation method of disclosed document.
The thickness of the transparent polyimide film that described method one or method two make is generally 10～500 μ m, preferably 10～100 μ m, this is the industrial usual thickness that Kapton is prepared in this area, can be by coating process control thickness, this is known technology, and the present invention repeats no more.
Beneficial effect of the present invention is: ester ring type dianhydride monomer molecular rigidity used is larger, and there is part trapezoidal shape structure, the polyimide material of being prepared by them shows higher second-order transition temperature and heat decomposition temperature, and ester ring type structure is difficult for forming charge transfer complex, reduce the overlapping equimolecular interphase interaction of π-π-electron cloud simultaneously, made polyimide there is the features such as the high and solvability of transparency is good.The trifluoromethyl of being introduced by diamine monomer and ehter bond, can further improve polyimide transparency and thermotolerance.The Kapton second-order transition temperature that the present invention makes is 280～310 ℃, and ultraviolet cut-on wavelength is 300～360nm, and the light transmission rate at 450nm place is 85～95%, dissolves in multiple organic solvent.
Embodiment
With specific embodiment, the present invention program is further described below, but protection scope of the present invention is not limited to this.
Embodiment 1
At room temperature, by 4.1634g(8mmol) 4,4 '-bis-(4-amino-2-4-trifluoromethylphenopendant) phenyl ether joins in 37.30ml DMAc; nitrogen protection, mechanical stirring, treats that it dissolves completely and adds 2.0016g(8mmol) dicyclo [3; 3; 0] octane-2,4,6; 7-tetracarboxylic dianhydride; continue to stir, under nitrogen protection, react 24 hours, the polyamic acid solution (PAA) that to obtain colourless, transparent, thickness, solid content be 15%.The PAA solution obtaining is placed in to normal temperature in the vacuum drying oven that relative vacuum degree is 0.08MPa and removes bubble 2 hours, treat that bubble removes totally, on the smooth sheet glass of any surface finish, use coating machine film, sheet glass after film is dried 2 hours prior to 70 ℃, be raised to 300 ℃ with the temperature rise rate of 5 ℃/min, and keep 1 hour, then naturally cool to room temperature, cooled sheet glass is put into deionized water demoulding, obtain water white Kapton, it is 4.1 × 10 that sampling detects weight-average molecular weight by gel permeation chromatography (GPC)
4.The salient features of this film as shown in Table 1 and Table 2.
Embodiment 2
At room temperature, by 5.2356g(8mmol) 2,2 '-bis-[4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] HFC-236fa joins in 43.79ml DMAc; nitrogen protection, mechanical stirring, treats that it dissolves completely and adds 2.0016g(8mmol) dicyclo [3; 3; 0] octane-2,4,6; 7-tetracarboxylic dianhydride; continue to stir, under nitrogen protection, react 24 hours, the polyamic acid solution (PAA) that to obtain colourless, transparent, thickness, solid content be 15%.In the PAA solution obtaining, add 0.90g diacetyl oxide and 1.33g pyridine; under nitrogen protection, stir after 30 minutes; temperature of reaction is brought up to 120 ℃; under nitrogen protection, continue reaction 24 hours, gained reaction solution is poured in the ethanol of 5 times of volumes, separates out throw out; filter; collecting precipitation thing, dry after washing with alcohol, obtain polyimide resin (PI resin).Taking 2g polyimide resin is dissolved in 12.10mlDMAc to obtain solid content is 15% PI solution, on the smooth sheet glass of any surface finish, use coating machine film, sheet glass after film is dried 2 hours prior to 70 ℃, be raised to 300 ℃ with the temperature rise rate of 5 ℃/min, and keep 1 hour, then naturally cool to room temperature, cooled sheet glass is put into deionized water demoulding, obtain water white Kapton, it is 4.5 × 10 that sampling detects weight-average molecular weight by gel permeation chromatography (GPC)
4.The salient features of this film as shown in Table 1 and Table 2.
Embodiment 3
At room temperature, by 4.1634g(8mmol) 4, 4 '-bis-(4-amino-2-4-trifluoromethylphenopendant) phenyl ether joins in 37.98ml DMAc, nitrogen protection, mechanical stirring, treating that it dissolves completely adds 2.1138g(8mmol) dicyclo [4, 3, 0] nonane-3, 4, 7, 9-tetracarboxylic dianhydride, continue to stir, under nitrogen protection, react 24 hours, obtain colourless, transparent, thickness, solid content is 15% polyamic acid solution (PAA), the follow-up same operation through embodiment 1 obtains water white Kapton, it is 3.5 × 10 that sampling gel permeation chromatography (GPC) detects weight-average molecular weight
4.The salient features of this film as shown in Table 1 and Table 2.
Embodiment 4
At room temperature, by 5.2356g(8mmol) 2,2 '-bis-[4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] HFC-236fa joins in 44.47ml DMAc; nitrogen protection, mechanical stirring, treats that it dissolves completely and adds 2.1138g(8mmol) dicyclo [3; 3; 0] octane-2,4,6; 7-tetracarboxylic dianhydride; continue to stir, under nitrogen protection, react 24 hours, the polyamic acid solution (PAA) that to obtain colourless, transparent, thickness, solid content be 15%.In the PAA solution obtaining, add 0.90g diacetyl oxide and 1.33g pyridine; under nitrogen protection, stir after 30 minutes; temperature of reaction is brought up to 120 ℃; under nitrogen protection, continue reaction 24 hours, gained reaction solution is poured in the ethanol of 5 times of volumes, separate out throw out; filter; collecting precipitation thing, dry after washing with alcohol, obtain polyimide resin.Taking 2g polyimide resin is dissolved in 12.10mlDMAc to obtain solid content is 15% PI solution, obtain water white Kapton through the same operation of embodiment 2 again, it is 4.0 × 10 that sampling detects weight-average molecular weight by gel permeation chromatography (GPC)
4.The salient features of this film as shown in Table 1 and Table 2.
Comparative example 1
At room temperature, by 5.2356g(8mmol) 2, 2 '-bis-[4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] HFC-236fa joins in 41.17ml DMAc, nitrogen protection, mechanical stirring, treating that it dissolves completely adds 1.5689g(8mmol) 1, 2, 3, 4-tetramethylene tetracarboxylic dianhydride, continue to stir, under nitrogen protection, react 24 hours, obtain colourless, transparent, thickness, solid content is 15% polyamic acid solution (PAA), obtain Kapton through the same operation of embodiment 1 again, it is 4.5 × 10 that sampling detects weight-average molecular weight by gel permeation chromatography (GPC)
4.The salient features of this film as shown in Table 1 and Table 2.
Comparative example 2
At room temperature; by 4.1634g(8mmol) 4; 4 '-bis-(4-amino-2-4-trifluoromethylphenopendant) phenyl ether joins in 36.04ml DMAc; nitrogen protection; mechanical stirring; treating that it dissolves completely adds 1.7934g(8mmol) 1; 2; 4,5-hexanaphthene tetracarboxylic dianhydride, continues to stir; under nitrogen protection, react 24 hours; the polyamic acid solution (PAA) that to obtain colourless, transparent, thickness, solid content be 15%, then obtain Kapton through the same operation of embodiment 1, sampling is 3.8 × 10 by gel permeation chromatography (GPC) detection weight-average molecular weight
4.The salient features of this film as shown in Table 1 and Table 2.
The salient features of table 1 Kapton
* the thermal characteristics of film is measured by dynamic mechanical analyzer and thermal gravimetric analyzer, T
gand T
dbe respectively second-order transition temperature and the temperature of initial decomposition of film;
The mechanical analysis of * film is measured by universal testing machine, T
sand T
mbe respectively tensile strength and the tensile modulus of film;
The optical property of * * film is measured by ultraviolet-visible absorption spectroscopy instrument, λ
0and T
450be respectively the ultraviolet cut-on wavelength of film and the transmitance at 450nm place.
The solubility property of table 2 Kapton
* DMAc, NMP, DMSO and THF represent respectively N,N-dimethylacetamide, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO) and tetrahydrofuran (THF);
* ++ ,+,+-and-represent respectively this solvent to the dissolution degree of film for easily molten, solvable, swelling and insoluble.
Can see that by above-mentioned performance table transparent polyimide film material of the present invention has not only kept excellent optical property, also improve the solvability in resistance toheat and organic solvent, compared with comparative example, the second-order transition temperature of transparent polyimide film of the present invention significantly improves, and easily molten in more kinds of solvents, expand the scope of application of thin-film material.Transparent polyimide film of the present invention is applicable to the transparent substrate material of flexible display and thin-film solar cells.
Claims (10)
1. a transparent polyimide film, is characterized in that the molecular structural formula of described Kapton is suc as formula shown in I:
In formula I, R
1for dianhydride residue, for one of following formula a or formula b:
R
2for diamines residue, it is one or more the combination with in following formula c, formula d or formula e
In formula I, n is the polymerization degree, is more than 20 integers.
2. transparent polyimide film as claimed in claim 1, is characterized in that described R2 is formula c or formula e.
3. the preparation method of transparent polyimide film as claimed in claim 1, it is characterized in that described method is: fluorinated diamine monomer and dianhydride monomer polymerization in polar aprotic solvent of amount of substance will be waited, make polyamic acid solution, by hot imidization method or chemical imidization method dehydration closed-loop, make transparent polyimide film again; Described dianhydride monomer is dicyclo [3,3,0] octane-2,4,6,7-tetracarboxylic dianhydride or dicyclo [4,3,0] nonane-3, one or both in 4,7,9-tetracarboxylic dianhydride; Described fluorinated diamine monomer is 4,4 '-bis-(4-amino-2-4-trifluoromethylphenopendant) phenyl ether, 4,4 '-bis-(4-amino-2-4-trifluoromethylphenopendant) biphenyl, 2, the combination of one or more in 2 '-bis-[4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] HFC-236fa.
4. method as claimed in claim 3, is characterized in that described polar aprotic solvent is N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), DMF or N,N-dimethylacetamide.
5. method as claimed in claim 4, is characterized in that said method comprising the steps of:
(1) fluorinated diamine monomer is dissolved in polar aprotic solvent completely, adds dianhydride monomer, under nitrogen protection, under mechanical stirring room temperature, react 1～24 hour, make polyamic acid solution; Described fluorinated diamine monomer is 1:1 with the ratio of the amount of substance of dianhydride monomer; Described dianhydride monomer is dicyclo [3,3,0] octane-2,4,6,7-tetracarboxylic dianhydride or dicyclo [4,3,0] nonane-3, one or both in 4,7,9-tetracarboxylic dianhydride; Described fluorinated diamine monomer is 4,4 '-bis-(4-amino-2-4-trifluoromethylphenopendant) phenyl ether, 4,4 '-bis-(4-amino-2-4-trifluoromethylphenopendant) biphenyl, 2, the combination of one or more in 2 '-bis-[4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] HFC-236fa;
(2) polyamic acid solution step (1) being made under vacuum condition degassed 1～4 hour, then film on the smooth sheet glass of any surface finish, sheet glass after film is first dried 1～4 hour at 50～90 ℃, rise to 210～310 ℃ with the heat-up rate of 5 ℃ of per minutes again, constant temperature 1～3 hour, then natural cooling down is to room temperature, and the sheet glass after cooling is positioned over demoulding in deionized water, obtains transparent polyimide film.
6. method as claimed in claim 4, is characterized in that said method comprising the steps of:
(1) fluorinated diamine monomer is dissolved in polar aprotic solvent completely, adds dianhydride monomer, under nitrogen protection, under mechanical stirring room temperature, react 1～24 hour, make polyamic acid solution; Described fluorinated diamine monomer is 1:1 with the ratio of the amount of substance of dianhydride monomer; Described dianhydride monomer is dicyclo [3,3,0] octane-2,4,6,7-tetracarboxylic dianhydride or dicyclo [4,3,0] nonane-3, one or both in 4,7,9-tetracarboxylic dianhydride; Described fluorinated diamine monomer is 4,4 '-bis-(4-amino-2-4-trifluoromethylphenopendant) phenyl ether, 4,4 '-bis-(4-amino-2-4-trifluoromethylphenopendant) biphenyl, 2, the combination of one or more in 2 '-bis-[4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] HFC-236fa;
(2) catalyzer and dewatering agent are added in the polyamic acid solution that step (1) makes, under nitrogen protection, be uniformly mixed, be warming up at 80～200 ℃ of temperature and carry out imidization 1～24 hour, gained reaction solution is poured in methyl alcohol or ethanol, separate out throw out, collecting precipitation thing washing, dry, make polyimide resin;
(3) polyimide resin step (2) being made is dissolved in organic solvent, obtain polyimide solution, then film on the smooth sheet glass of any surface finish, sheet glass after film is first dried 1～4 hour at 50～90 ℃, rise to 210～310 ℃ with the heat-up rate of 5 ℃ of per minutes again, constant temperature 1～3 hour, then natural cooling down is to room temperature, sheet glass after cooling is positioned over demoulding in deionized water, obtains transparent polyimide film.
7. method as claimed in claim 6, it is characterized in that in described step (3), described organic solvent is N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), N, the mixing of one or more of dinethylformamide, N,N-dimethylacetamide, trichloromethane, methylene dichloride, tetrahydrofuran (THF), acetone.
8. method as claimed in claim 6, is characterized in that in described step (2), and described catalyzer is pyridine, beta-picoline, quinoline, the mixing of one or more in quinoline, imidazoles, triethylamine, tripropyl amine, tributylamine, thanomin; The ratio of the amount of substance of described dianhydride monomer, catalyzer is 1:0～5, and 0 representative is wherein infinitely close to 0 but be not 0.
9. method as claimed in claim 6, is characterized in that in described step (2), and described dewatering agent is one or more the mixing in diacetyl oxide, toluene, dimethylbenzene; The ratio of the amount of substance of described dianhydride monomer, dewatering agent is 1:0～5, and 0 representative is wherein infinitely close to 0 but be not 0.
10. the method as described in claim 5 or 6, the add-on that it is characterized in that described polar aprotic solvent is that to make the solid content of polyamic acid solution be 10～30%.
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