CN102807675A - Flexible transparent polyimide film material and preparation method thereof - Google Patents
Flexible transparent polyimide film material and preparation method thereof Download PDFInfo
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- CN102807675A CN102807675A CN2012102959343A CN201210295934A CN102807675A CN 102807675 A CN102807675 A CN 102807675A CN 2012102959343 A CN2012102959343 A CN 2012102959343A CN 201210295934 A CN201210295934 A CN 201210295934A CN 102807675 A CN102807675 A CN 102807675A
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Abstract
The invention discloses a flexible transparent polyimide film material. The flexible transparent polyimide film material contains a novel diamine monomer. The adopted monoether bond bridged diamine monomer is high in reaction activity and moderate for polymerization condition, the adopted alicyclic dianhydride breaks off the conjugation and is high in rigidity, and the obtained polyimide film is high in transparency and excellent in thermal performance. The ultraviolet transmission cutoff wavelength of the polyimide film is 280-402 nm; and the glass-transition temperature is 284.36-336 DEG C.
Description
Technical field:
The invention belongs to the technical field of macromolecular material, relate to a kind of flexible transparent polyimide film material and preparation method thereof, described polyimide film material contains the new diamine monomer.
Technical background:
Polyimide is a kind of high performance material, is used widely in high-tech sectors such as space flight and aviation, electric and electronic, photoelectrons.Last century the mid-1960s, E.I.Du Pont Company has applied for a series of patents, at first with Kapton (Kapton) and varnish (Pyre ML) commercialization, the epoch of a polyimide develop rapidly that Open from This Side.In flexible display technologies and field of thin film solar cells, adopt the clear polyimides film as flexible base, board, not only realize the flexibility of device own, and alleviated the weight of device largely.
Tradition Kapton band look, light transmission rate is not high, is owing to there is stronger intermolecular and intramolecular interaction in the molecular chain structure, between electron donor(ED) diamines and electron acceptor(EA) dianhydride, is prone to form charge transfer complex.The thinking that improves the transparency of Kapton mainly contains blocking-up polyimide molecule chain conjugation, reduces conjugated degree, reduces diamines electron donation and dianhydride electron-withdrawing power, increases the molecular chain torsion resistance, reduces intramolecularly and piles up degree or the like.The employing means have main even the introducing to contain fluoro substituents or side group, adopt to have the alicyclic ring substituted benzene ring, introduce non-coplanar structure, introduce bridged linkages such as sulfuryl.
In present research, the diamine monomer that extensively adopts is 2,2'-two (trifluoromethyl) benzidine (TFDB), and this diamine monomer contains biphenyl structural, contains the trifluoromethyl electron-withdrawing group.The biphenyl structural rigidity is big, can improve polyimide glass transition temperature, but can cause its decreased solubility.Can suppress generation intermolecular or intramolecularly transfer transport complex compound about the strong electrophilic of trifluoromethyl, reduce the polymerization activity of diamine monomer simultaneously.Therefore, in the diamines molecular structure, introduce the polymerization activity that the ehter bond bridging improves diamine monomer, improve the polyimide solvability.
Be in the document of " Highly Organosoluble and Flexible Polyimides with Color Lightness and Transparency Based on2; 2-Bis [4-(2-trifluoromethyl-4-aminophenoxy)-3; 5-dimeth-ylphenyl] propane " at exercise question; Author designed the novel ether diamine monomer 2 that contains, 2-two [4-(2-trifluoromethyl-4-amino-benzene oxygen-3,5-3,5-dimethylphenyl] propane.This kind diamines and 4, the cutoff wavelength of the Kapton that the polymerization of 4'-(the different propylene of hexafluoro) two anhydride phthalic acids (6FDA) obtains is 356nm, and second-order transition temperature is 264 ℃, and heat decomposition temperature is 462 ℃ in air.Owing to introduce the bis ether key, molecular chain is flexible to be increased, and second-order transition temperature descends.In two amine molecules, introduce four methyl structural, also reduced heat decomposition temperature.
Be in the document of " Synthesis and Properties of Fluorinated Polyimides. 1.Derived from Novel 4; 4-Bis (aminophenoxy)-3; 3-trifluoromethyl Terphenyl " at exercise question; The author has synthesized new diamine monomer 4, two (amino-benzene oxygen)-3, the 3-trifluoromethyl-biphenyls of 4-.The cutoff wavelength of the Kapton that this diamines and hexafluorodianhydride polymerization obtain is 372nm, and second-order transition temperature is 278 ℃, and heat decomposition temperature is 519 ℃ in air.The author obtains two amine molecules through the suziki linked reaction in document, and the synthetic route of being developed is comparatively expensive, is not suitable for industrial production.
So, in order to improve the solvability of molecular chain, improve the diamine monomer polymerization activity, guarantee high glass transition simultaneously, we have developed new diamine monomer 2,2'-two (trifluoromethyl) diamino-phenyl ether.This diamines introduces monoether key bridging and a position replaces the trifluoromethyl structure.In order to improve the transparency of Kapton, we have also adopted alicyclic ring dianhydride and new diamine polymerization, interrupt the conjugation of molecular chain, improve the molecule chain rigidity.
Summary of the invention
Main purpose of the present invention provides a kind of flexible transparent polyimide film material.
Another object of the present invention is to provide a kind of preparation method of flexible transparent polyimide film material.
The object of the invention is realized through following technical scheme:
A kind of flexible transparent polyimide film material; It is that described polyimide film material has following structural unit:
, R represents the dianhydride residue in the formula.
The weight-average molecular weight of above-mentioned polyimide film material is 2000 ~ 500000; Be preferably: 8000 ~ 200000.
The dianhydride residue of R representative is selected from:
(1) full aromatic dianhydride
(2) fatty dianhydride
(3) bridging aromatic dianhydride
Wherein one or more;
Be preferably:
Among
one or more.
Above-mentioned flexible transparent polyimide film material, it is to adopt any one preparation in following two kinds of methods:
Method one:
The first step: with strong polar non-proton organic solvent diamine monomer is dissolved in the polyreaction bottle fully, dianhydride monomer is added in batches, reaction is 1-48 hour under the mechanical stirring, obtains transparent, thick polyamic acid solution;
Second step: with the polyamic acid solution of gained leave standstill treated that wherein bubble was eliminated in 1-48 hour after; On clean base plate, filming, dried 1 ~ 3 hour down at 70 ~ 90 ℃ earlier, is a ladder with 20 ~ 50 ℃ again; Be warmed up to 200 ~ 300 ℃; Each ladder was kept 1-120 minute, naturally cooling then, and demoulding obtains Kapton;
Method two:
The first step: diamine monomer and dianhydride monomer are dissolved in the high boiling solvent, add catalyzer, under protection of inert gas heating reflux reaction 1-48 hour, to pour into after the cooling and separate out polyimide resin in the alcohol, pure washing and drying obtains polyimide resin;
Second step: polyimide resin is dissolved in the organic solvent, on substrate, films, dried 1 ~ 3 hour down at 70 ~ 90 ℃ earlier; Be a ladder with 20 ~ 50 ℃ again, be warmed up to 200-300 ℃, each ladder was kept 1-120 minute; Naturally cooling then, demoulding obtains Kapton.
The present invention provides two kinds of methods that prepare flexible transparent polyimide film material.
First kind of preparation method may further comprise the steps:
The first step: with strong polar non-proton organic solvent diamine monomer is dissolved in the polyreaction bottle fully, dianhydride monomer is added in batches, reaction is 1-48 hour under the mechanical stirring, obtains transparent, thick polyamic acid solution;
Second step: with the polyamic acid solution of gained leave standstill treated that wherein bubble was eliminated in 1-48 hour after; On clean base plate, filming, dried 1 ~ 3 hour down at 70 ~ 90 ℃ earlier, is a ladder with 20 ~ 50 ℃ again; Be warmed up to 200-300 ℃; Each ladder was kept 1-120 minute, naturally cooling then, and demoulding obtains Kapton.
Among first kind of preparation method: used strong polar non-proton organic solvent is N, dinethylformamide, DMAC N,N, DMSO 99.8MIN. or N-Methyl pyrrolidone.
Among first kind of preparation method: by the quality percentage composition, the solid content of controlling said polyamic acid solution is 10 ~ 70%.
Second kind of preparation method may further comprise the steps:
The first step: diamine monomer and dianhydride monomer are dissolved in the high boiling solvent, add catalyzer, under protection of inert gas heating reflux reaction 1-48 hour, to pour into after the cooling and separate out polyimide resin in the alcohol, pure washing and drying obtains polyimide resin;
Second step: polyimide resin is dissolved in the organic solvent, on substrate, films, dried 1 ~ 3 hour down at 70 ~ 90 ℃ earlier; Be a ladder with 20 ~ 50 ℃ again, be warmed up to 200-300 ℃, each ladder was kept 1-120 minute; Naturally cooling then, demoulding obtains Kapton.
Among second kind of preparation method: used high boiling solvent is N, dinethylformamide, DMAC N,N, DMSO 99.8MIN., N-Methyl pyrrolidone, meta-cresol, para-chlorophenol or phenylformic acid; The used organic solvent of filming is N, dinethylformamide, DMAC N,N, DMSO 99.8MIN., N-Methyl pyrrolidone, meta-cresol or THF; Used catalyzer is isoquinoline 99.9, quinoline, phenylformic acid, diacetyl oxide or pyridine; Described alcohol is ethanol or methyl alcohol.
Among first kind of preparation method and the second kind of preparation method: the molar ratio of said diamine monomer and dianhydride monomer is 0.9:1 ~ 1:1.1; The structural formula of said diamine monomer is:
。
Room temperature described in the application documents of the present invention is 20 ~ 30 ℃.
Beneficial effect of the present invention:
The diamine monomer of the monoether key bridging that the present invention adopts, reactive behavior is high, and polymerizing condition is gentle, and the alicyclic ring dianhydride of employing is break-in conjugated, and rigidity is big, and the Kapton transparency that obtains is high, and thermal property is excellent.It is 280nm-402nm that this type of Kapton UV-light sees through cutoff wavelength; Second-order transition temperature is between 284.36 ℃-336 ℃.
Description of drawings
Fig. 1 is the ir spectra of TFODA/CHDA-PI Kapton.
Fig. 2 is the ir spectra of TFODA/6FDA-PI Kapton.
Fig. 3 is the TGA curve of TFODA/PMDA-PI Kapton.
Fig. 4 is the TGA curve of TFODA/CHDA-PI Kapton.
Fig. 5 is the TGA curve of TFODA/6FDA-PI Kapton.
Fig. 6 is the DSC curve of TFODA/PMDA-PI Kapton.
Fig. 7 is the DSC curve of TFODA/CHDA-PI Kapton.
Fig. 8 is the DSC curve of TFODA/6FDA-PI Kapton.
Embodiment:
Embodiment 1
At room temperature, with 1.3450 gram (0.004 moles) 2,2 '-bis trifluoromethyl-4; 4 '-diaminodiphenyl oxide (TFODA) is dissolved in 8.87 gram N; In the N-N,N-DIMETHYLACETAMIDE, mechanical stirring adds 0.8725 gram (0.004 mole) pyromellitic acid dianhydride (PMDA) fully in batches after the dissolving; Continue stirring reaction 12 hours, and obtained solid content and be 20% transparent, thick polyamic acid solution.
Second step: with the polyamic acid solution of gained leave standstill treated that wherein bubble was eliminated in 24 hours after, on glass the filming of cleaning, put into high temperature oven.80 ℃ of down bakings 2 hours, ladder-elevating temperature to 110 ℃, 140 ℃, 170 ℃, 200 ℃, 240 ℃, 270 ℃ was respectively kept 30 minutes, to 300 ℃ of bakings 1 hour, naturally cooled to room temperature then again, and sheet glass is put into the water demoulding, obtained Kapton.
The molecular structure of clear polyimides film is following in the present embodiment:
The UV, visible light light transmission cutoff wavelength of measuring film is 402nm.Second-order transition temperature is 342.89 ℃.Polymkeric substance weight-average molecular weight M
wBe 131,000.
Embodiment 2
At room temperature, with 1.3450 gram (0.004 moles) 2,2 '-bis trifluoromethyl-4; 4 '-diaminodiphenyl oxide (TFODA) is dissolved in 12.49 gram N; In the dinethylformamide, mechanical stirring adds 1.7770 gram (0.004 mole) hexafluorodianhydrides (6FDA) fully in batches after the dissolving; Continue stirring reaction 12 hours, and obtained solid content and be 30% transparent, thick polyamic acid solution.
Second step: with the polyamic acid solution of gained leave standstill treated that wherein bubble was eliminated in 24 hours after, on glass the filming of cleaning, put into high temperature oven.70 ℃ of down bakings 2 hours, ladder-elevating temperature to 100 ℃, 140 ℃, 180 ℃, 220 ℃, 260 ℃ was respectively kept 30 minutes, naturally cooled to room temperature then in 1 hour to 280 ℃ of bakings again, and sheet glass is put into the water demoulding, obtained Kapton.
The molecular structure of clear polyimides film is following in the present embodiment:
The UV, visible light light transmission cutoff wavelength of measuring film is 334nm, and transmitance is 81% at the 400nm place.Second-order transition temperature is 284.36 ℃.Polymkeric substance weight-average molecular weight M
wBe 89,580.
Embodiment 3
At room temperature, with 1.3450 gram (0.004 moles) 2,2 '-bis trifluoromethyl-4; 4 '-diaminodiphenyl oxide (TFODA) is dissolved in the 8.97 gram N-Methyl pyrrolidone, and mechanical stirring adds 1.1769 gram (0.004 moles) 3 fully in batches after the dissolving; 3', 4,4'-biphenyl tetracarboxylic dianhydride (BPDA); Continue stirring reaction 12 hours, and obtained solid content and be 40% transparent, thick polyamic acid solution.
With the polyamic acid solution of gained leave standstill treated that wherein bubble was eliminated in 24 hours after, on glass the filming of cleaning, put into high temperature oven.80 ℃ of down bakings 2 hours, ladder-elevating temperature to 110 ℃, 140 ℃, 170 ℃, 200 ℃, 240 ℃, 270 ℃ was respectively kept 30 minutes, to 300 ℃ of bakings 1 hour, naturally cooled to room temperature then again, and sheet glass is put into the water demoulding, obtained Kapton.
The molecular structure of clear polyimides film is following in the present embodiment:
The UV, visible light light transmission cutoff wavelength of measuring film is 372nm, and transmitance is 68% at the 400nm place.Second-order transition temperature is 320 ℃.Polymkeric substance weight-average molecular weight M
wBe 115,450.
Embodiment 4
At room temperature, take by weighing 1.3450 gram (0.004 moles) 2,2 '-bis trifluoromethyl-4; 4 '-diaminodiphenyl oxide (TFODA) and 0.8967 gram (0.004 mole) 1,2,4; 5-hexanaphthene tetracarboxylic dianhydride (CHDA) joins reaction flask, and nitrogen protection adds the 15g meta-cresol down, after stirring; Add 4 isoquinoline 99.9, be warming up to 190 ℃, reacted 12 hours.Pour reaction solution into ethanol after the cooling and separate out, ethanol boils to be washed, and filtering drying obtains polyimide powder.
Take by weighing the 1g polyimide powder, use 10gN, obtain polyimide solution after the dissolving of N-N,N-DIMETHYLACETAMIDE, on sheet glass, film, put into high temperature oven.80 ℃ of down bakings 2 hours, ladder-elevating temperature to 110 ℃, 140 ℃, 170 ℃ was respectively kept 30 minutes, to 200 ℃ of bakings 1 hour, put into the water demoulding again, obtained Kapton.
The molecular structure of clear polyimides film is following in the present embodiment:
The UV, visible light light transmission cutoff wavelength of measuring film is 298nm, and transmitance is 89% at the 400nm place.Second-order transition temperature is 308 ℃.Polymkeric substance weight-average molecular weight M
wBe 26,200.
Embodiment 5
At room temperature; With 1.3450 gram (0.004 moles) 2,2 '-bis trifluoromethyl-4,4 '-diaminodiphenyl oxide (TFODA) are dissolved in the 8.52 gram methyl-sulphoxides; Mechanical stirring; Add 0.7844 gram (0.004 mole) tetramethylene tetracarboxylic dianhydride (CBDA) fully after the dissolving in batches, continued stirring reaction 12 hours, obtain solid content and be 20% transparent, thick polyamic acid solution.
With the polyamic acid solution of gained leave standstill treated that wherein bubble was eliminated in 24 hours after, on glass the filming of cleaning, put into high temperature oven.80 ℃ of down bakings 2 hours, ladder-elevating temperature to 110 ℃, 140 ℃, 170 ℃, 200 ℃, 240 ℃, 270 ℃ was respectively kept 30 minutes, naturally cooled to room temperature then in 1 hour to 300 ℃ of bakings again, and sheet glass is put into the water demoulding, obtained Kapton.
The molecular structure of clear polyimides film is following in the present embodiment:
The UV, visible light light transmission cutoff wavelength of measuring film is 280nm, and transmitance is 91% at the 400nm place.Second-order transition temperature is 317 ℃.Polymkeric substance weight-average molecular weight M
wBe 14,600.
Embodiment 6
At room temperature, with 1.3450 gram (0.004 moles) 2,2 '-bis trifluoromethyl-4; 4 '-diaminodiphenyl oxide (TFODA) is dissolved in the 8.74 gram DMAC N,Ns, mechanical stirring; Add 0.8406 gram (0.004 mole) 1,2,3 fully after the dissolving in batches; 4-pentamethylene tetracarboxylic dianhydride (CPDA) continued stirring reaction 12 hours, obtained solid content and be 20% transparent, thick polyamic acid solution.
With the polyamic acid solution of gained leave standstill treated that wherein bubble was eliminated in 24 hours after, on glass the filming of cleaning, put into high temperature oven.80 ℃ of down bakings 2 hours, ladder-elevating temperature to 110 ℃, 140 ℃, 170 ℃, 200 ℃, 240 ℃, 270 ℃ was respectively kept 30 minutes, to 300 ℃ of bakings 1 hour, naturally cooled to room temperature then again, and sheet glass is put into the water demoulding, obtained Kapton.
The molecular structure of clear polyimides film is following in the present embodiment:
The UV, visible light light transmission cutoff wavelength of measuring film is 285nm, and transmitance is 86% at the 400nm place.Second-order transition temperature is 312 ℃.Polymkeric substance weight-average molecular weight M
wBe 19,700.
Embodiment 7
At room temperature, take by weighing 1.3450 gram (0.004 moles) 2,2 '-bis trifluoromethyl-4; 4 '-diaminodiphenyl oxide (TFODA) and 09447 gram (0.004 mole) 4,5,6; 7-dicyclo [2.2.1] heptane tetracarboxylic dianhydride (BHDA) joins reaction flask, and nitrogen protection adds the 15g para-chlorophenol down, after stirring; Add the 1g phenylformic acid, be warming up to 205 ℃, reacted 12 hours.Pour reaction solution into ethanol after the cooling and separate out, ethanol boils to be washed, and filtering drying obtains polyimide powder.
Take by weighing the 1g polyimide powder, use 10gN, obtain polyimide solution after the dissolving of N-N,N-DIMETHYLACETAMIDE, on sheet glass, film, put into high temperature oven.80 ℃ of down bakings 2 hours, ladder-elevating temperature to 100 ℃, 120 ℃, 140 ℃, 180 ℃ was respectively kept 30 minutes, to 200 ℃ of bakings 1 hour, put into the water demoulding after the cooling again, obtained Kapton.
The molecular structure of clear polyimides film is following in the present embodiment:
The UV, visible light light transmission cutoff wavelength of measuring film is 294nm, and transmitance is 90% at the 400nm place.Second-order transition temperature is 320 ℃.Polymkeric substance weight-average molecular weight M
wBe 38,500.
Embodiment 8
At room temperature, take by weighing 1.3450 gram (0.004 moles) 2,2 '-bis trifluoromethyl-4; 4 '-diaminodiphenyl oxide (TFODA) and 0.9928 gram (0.004 mole) 5,6,7; 8-dicyclo [2.2.2]-2-heptene tetracarboxylic dianhydride (BCDA) joins reaction flask, and nitrogen protection adds the 15g meta-cresol down, after stirring; Add 4 isoquinoline 99.9, be warming up to 190 ℃, reacted 12 hours.Pour reaction solution into ethanol after the cooling and separate out, ethanol boils to be washed, and filtering drying obtains polyimide powder.
Take by weighing the 1g polyimide powder, use 10gN, obtain polyimide solution after the dinethylformamide dissolving, on sheet glass, film, put into high temperature oven.80 ℃ of down bakings 2 hours, ladder-elevating temperature to 100 ℃, 120 ℃, 140 ℃, 160 ℃, 180 ℃ was respectively kept 30 minutes, and to 200 ℃ of bakings 1 hour, the water demoulding was put in cooling, obtains Kapton again.
The molecular structure of clear polyimides film is following in the present embodiment:
The UV, visible light light transmission cutoff wavelength of measuring film is 302nm, and transmitance is 85% at the 400nm place.Second-order transition temperature is 336 ℃.Polymkeric substance weight-average molecular weight M
wBe 57,500.
Measure UV, visible light light transmission rate, thermal property and the mechanical property of embodiment 1-8 flexible transparent polyimide film.
Test result: it is 280nm-402nm that this type of Kapton UV-light sees through cutoff wavelength; Second-order transition temperature is between 284.36 ℃-342.89 ℃.
Claims (10)
1. flexible transparent polyimide film material is characterized in that described polyimide film material has following structural unit:
R represents the dianhydride residue in the formula.
2. flexible transparent polyimide film material according to claim 1, the weight-average molecular weight that it is characterized in that said polyimide film material is 2000 ~ 500000; Be preferably: 8000 ~ 200000.
3. flexible transparent polyimide film material according to claim 1 is characterized in that the dianhydride residue of R representative is selected from:
(1) full aromatic dianhydride
(2) fatty dianhydride
(3) bridging aromatic dianhydride
Wherein one or more;
Be preferably:
4. flexible transparent polyimide film material according to claim 1 is characterized in that adopting any one preparation in following two kinds of methods:
Method one:
The first step: with strong polar non-proton organic solvent diamine monomer is dissolved in the polyreaction bottle fully, dianhydride monomer is added in batches, reaction is 1-48 hour under the mechanical stirring, obtains transparent, thick polyamic acid solution;
Second step: with the polyamic acid solution of gained leave standstill treated that wherein bubble was eliminated in 1-48 hour after; On clean base plate, filming, dried 1 ~ 3 hour down at 70 ~ 90 ℃ earlier, is a ladder with 20 ~ 50 ℃ again; Be warmed up to 200 ~ 300 ℃; Each ladder was kept 1-120 minute, naturally cooling then, and demoulding obtains Kapton;
Method two:
The first step: diamine monomer and dianhydride monomer are dissolved in the high boiling solvent, add catalyzer, under protection of inert gas heating reflux reaction 1-48 hour, to pour into after the cooling and separate out polyimide resin in the alcohol, pure washing and drying obtains polyimide resin;
Second step: polyimide resin is dissolved in the organic solvent, on substrate, films, dried 1 ~ 3 hour down at 70 ~ 90 ℃ earlier; Be a ladder with 20 ~ 50 ℃ again, be warmed up to 200-300 ℃, each ladder was kept 1-120 minute; Naturally cooling then, demoulding obtains Kapton.
5. the preparation method of the described flexible transparent polyimide film of claim 1 is characterized in that comprising the steps:
The first step: with strong polar non-proton organic solvent diamine monomer is dissolved in the polyreaction bottle fully, dianhydride monomer is added in batches, reaction is 1-48 hour under the mechanical stirring, obtains transparent, thick polyamic acid solution;
Second step: with the polyamic acid solution of gained leave standstill treated that wherein bubble was eliminated in 1-48 hour after; On clean base plate, filming, dried 1 ~ 3 hour down at 70 ~ 90 ℃ earlier, is a ladder with 20 ~ 50 ℃ again; Be warmed up to 200-300 ℃; Each ladder was kept 1-120 minute, naturally cooling then, and demoulding obtains Kapton.
6. the preparation method of flexible transparent polyimide film according to claim 3 is characterized in that: used strong polar non-proton organic solvent is N, dinethylformamide, DMAC N,N, DMSO 99.8MIN. or N-Methyl pyrrolidone.
7. the preparation method of flexible transparent polyimide film according to claim 3 is characterized in that: the solid content of controlling said polyamic acid solution is 10 ~ 70%.
8. the preparation method of the described flexible transparent polyimide film of claim 1 is characterized in that comprising the steps:
The first step: diamine monomer and dianhydride monomer are dissolved in the high boiling solvent, add catalyzer, under protection of inert gas heating reflux reaction 1-48 hour, to pour into after the cooling and separate out polyimide resin in the alcohol, pure washing and drying obtains polyimide resin;
Second step: polyimide resin is dissolved in the organic solvent, on substrate, films, dried 1 ~ 3 hour down at 70 ~ 90 ℃ earlier; Be a ladder with 20 ~ 50 ℃ again, be warmed up to 200-300 ℃, each ladder was kept 1-120 minute; Naturally cooling then, demoulding obtains Kapton.
9. the preparation method of flexible transparent polyimide film according to claim 6; It is characterized in that: used high boiling solvent is N; Dinethylformamide, DMAC N,N, DMSO 99.8MIN., N-Methyl pyrrolidone, meta-cresol, para-chlorophenol or phenylformic acid; The used organic solvent of filming is N, dinethylformamide, DMAC N,N, DMSO 99.8MIN., N-Methyl pyrrolidone, meta-cresol or THF; Used catalyzer is isoquinoline 99.9, quinoline, phenylformic acid, diacetyl oxide or pyridine; Described alcohol is ethanol or methyl alcohol.
10. according to the preparation method of claim 4 or 7 described flexible transparent polyimide film materials, it is characterized in that the molar ratio of said diamine monomer and dianhydride monomer is 0.9:1 ~ 1:1.1; The structural formula of said diamine monomer is:
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