CN102634022B - Colorless highly-transparent polyimide film as well as preparation method and application thereof - Google Patents

Colorless highly-transparent polyimide film as well as preparation method and application thereof Download PDF

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CN102634022B
CN102634022B CN201210103787.5A CN201210103787A CN102634022B CN 102634022 B CN102634022 B CN 102634022B CN 201210103787 A CN201210103787 A CN 201210103787A CN 102634022 B CN102634022 B CN 102634022B
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bis
amino
trifluoromethyl
sulfobenzide
benzene oxygen
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范琳
翟磊
杨士勇
莫松
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Institute of Chemistry CAS
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Abstract

The invention discloses a colorless highly-transparent polyimide film as well as a preparation method and an application thereof. The film is prepared from semi-aromatic polyimide resin of which the structural formula is shown as formula I, wherein Al is an alicyclic structure, R1 is an aromatic diamine structure containing fluorine and sulfone, R2 is another aromatic diamine structure, and n:m=(0-400):1. The film has excellent optical transparency, colorless transparency of the film with great thickness (greater than or equal to 100 mu m) can be realized, the initial light-transmitting wavelength is below 300nm, and the light transmittance in a visible region is greater than or equal to 90%; and meanwhile, the film shows excellent heat resistance and mechanical property, and has important application values in the manufacturing of the photoelectric devices such as a solar battery, a display, an electronic book, an electronic label, a photoelectric sensor and the like.

Description

Colourless high transparent polyimide film and preparation method thereof and application
Technical field
The present invention relates to a kind of colourless high transparent polyimide film and preparation method thereof and application.
Background technology
Along with the develop rapidly of photoelectricity subdomain neck, the photoelectric device such as solar cell, liquid-crystal display (LCD), display of organic electroluminescence (OLED), e-book, electronic tag, photo-sensor presents the trend of lighting, maximization, ultrathin and flexibility in recent years.In the photoelectric devices such as solar cell and indicating meter are manufactured, hard crisp characteristic as the glass of conventional transparent baseplate material due to self, when further maximization and slimming, exist the problem in processing and carrying to be difficult to solution, and the fragility of glass causes it cannot free bend, thereby cannot meet the demand for development of following flexible package technology.At present, the advantages such as high transparent polymer materials is transparent owing to having, pliable and tough, light weight, high-impact, have obtained paying close attention to more and more widely as flexible optoelectronic base plate for packaging material of new generation.And flexible transparent polymer substrate goes for spirally wound technique (Roll to roll) and carry out serialization scale production in device fabrication process, be conducive to the reduction of manufacturing cost.Therefore, transparent polymer substrate will be expected to replace the manufacture that glass substrate is realized flexible photoelectric device future.
At present, the high transparent polymer material of commercialization that can be used as flexible base, board mainly comprises that the polyethylene terephthalate (PET) of Di Ren film company of Du Pont exploitation and polycarbonate (PC) the film Lexan of PEN (PEN) film Melinex and the exploitation of Teonex ,GE company are, polyethersulfone (PES) the film Sumilite of Sumitomo Bakelite company release etc.These transparent polymeric films generally have excellent optical transparence, good mechanical property and chemical stability, but its second-order transition temperature (T g) being generally no more than 220 ℃, thermotolerance is not ideal enough, cannot bear the test of the multiple tracks high-temperature heat treatment such as the deposition of the electrode film up to 300-400 ℃ and anneal in photoelectric device manufacturing processed.
For the more excellent polymer-based carbon panel material of exploitation resistance toheat, polyimide (PI) material with outstanding heat-resistant stability receives much concern.But traditional aromaticity polyimide is due to the existence of aromatic ring structure on main chain, easily form in strong molecule and Intermolecular charge transfer complex, therefore, film prepared therefrom has stronger photoabsorption in visible region, the faint yellow or dark brown of the poor and expression characteristics of transmittance.For improving the optical transparence of Kapton, researchist has carried out a large amount of research work, and finds, introduces the optical property that fluoro-containing group can effectively improve Kapton in polymer molecular structure.The people such as Matsuura of Japan NTT company are to based on 4,4 '-(2,2-hexafluoroisopropyli,ene) diphthalic anhydrides (6FDA) and 2,2 '-bis-(trifluoromethyl)-4, the fluorinated polyimide of 4 '-benzidine (TFDB) is studied discovery, material not only has superior heat resistance performance and shows the good transparency simultaneously, the T of material gup to 335 ℃, the initial printing opacity wavelength (λ of the film of 20 μ m thickness 0) be 350nm, transmittance in visible region reaches 90% (T.Matsuura, Y.Hasuda, S.Nishi, N.Yamada, Polyimide derived from 2,2 '-bis (trifluoromethyl)-4,4 '-diaminobiphenyl.l.Synthesis andcharacterization of polyimides prepared with2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride or pyromellitic dianhydride.Macromolecules, 1991,24,5001-5005).
CN 101195682 B disclose a kind of preparation method of flexible transparent polyimide film material, film after preparing polyamic acid by the aromatic dianhydride of bridge crosslinking structure and aromatic diamines, after the thermal treatment up to 350 ℃, obtain Kapton.But the initial printing opacity wavelength (λ of film 0) wavelength is still up to 395-430nm, the light transmission of film does not significantly improve.
The people such as Tao have synthesized the aromatic diamines 12FDA of high fluorine content and fluorine-containing aromatic dianhydride 6FDA and have prepared fluorine content and surpass 30% polyimide, the initial printing opacity wavelength (λ of the film of 7 μ m thickness 0) can be reduced to 298nm, the transmittance at 450nm place reaches 97%.But they find simultaneously, although the fluorine-containing aromatic polyimide of preparation has very high fluorine content, but when film thickness increases, its optical transparence significantly reduces, the transmittance of 100 μ m thickness thin films at 450nm place is only 55%, and can be observed comparatively significantly yellow (L.M.Tao, H.X.Yang, J.G.Liu, L.Fan, S.Y.Yang.Synthesis and characterization of highly optical transparent and low dielectric constant fluorinated polyimides.Polymer, 2009, 50, 6009-6018).In addition, multinomial result of study proves, although the optical transparence of fluorinated polyimide is better than traditional aromatic polyimide, owing to still there being a large amount of aromatic ring structures, fail effectively to eliminate the formation of charge transfer complex, thereby cannot obtain real water white Kapton.
For preparation can meet the transparent Kapton that optoelectronic package requires, people are incorporated into the alicyclic structure of low electron density in polyimide main chain, prepare the polyimide of full-cream ring structure or half alicyclic ring (semiaromatic) structure.Introducing that alicyclic structure is found in research is due to the formation having suppressed in molecule with Intermolecular charge transfer complex, can significantly improve the transparency of Kapton, reduce the coloring degree (A.S.Mathews of film, I.Kim, C.S.Ha.Synthesis, characterization, and properties of fully aliphatic polyimides and their derivatives for microelectronics and optoelectronics applications.Macromol.Res., 2007,15,114-128).
CN 101160202 B disclose a kind of method of preparing transparent Kapton, based on hexanaphthene tetracarboxylic dianhydride (CHDA), there is good thermotolerance and mechanicalness characteristic with Kapton prepared by aliphatic diamine, alicyclic diamine and aromatic diamines respectively, and have good transparency and dimensional stability concurrently, second-order transition temperature is 200-320 ℃, tensile modulus is greater than 1.7GPa, the linear expansivity of film is no more than 50ppm/ ℃, and the transmittance in visible region when thickness is 100 μ m reaches 90%.
CN 102093558 A disclose a kind of preparation method who can be used as the polyimide film material of flexible transparent conducting film substrate.This material is carried out the hot-imide processing of 200-350 ℃ and is made by alicyclic dianhydride and fluorine-containing phenylate type aromatic diamines after Low-temperature Solution Polycondensation obtains polyamic acid, its second-order transition temperature is 250-300 ℃, initial printing opacity wavelength is at 280-330nm, the transmittance > 90% at 450nm place.CN 101831074 A disclose a kind of preparation method who adopts alicyclic dianhydride and aromatic diamines to carry out the fluorinated polyimide of three monomer condenses copolymerization, the second-order transition temperature of the Kapton obtaining is 200-350 ℃, initial printing opacity wavelength is at 270-340nm, the transmittance 88-98% at 450nm place.But contriver is to light transmission, test does not explain with the thickness of film.
The people such as Liu Jingang adopt Low-temperature Solution Polycondensation to obtain polyamic acid with the alicyclic dianhydride of different structure and fluorine-containing phenylate type aromatic diamines to have prepared serial fluorine-containing half alicyclic ring Kapton by 300 ℃ of hot imides, its second-order transition temperature is between 245-277 ℃, this film thickness shows the good transparency while being 10 μ m, initial printing opacity wavelength is at 295-319nm, transmittance at 450nm place surpasses 88% (Liu Jingang, Li Zhuo, Gao Zhiqi, Yang Haixia, Yang Shiyong, " preparation of fluorine-containing half alicyclic ring transparent polyimide film and performance ", investigation of materials journal, 2008, 22 (6), 615-618).But the film that we adopt same resin system and preparation method to obtain, when thickness is 50 μ m, the transmittance at 450nm place is only 78%.In addition,, owing to adopting polyamic acid solution to process film forming through 300 ℃ of hot-imides in film preparation, therefore in film high-temperature process, must carry out nitrogen protection, otherwise film is very easily because high temperature oxidation is painted.
Summary of the invention
The object of this invention is to provide a kind of colourless high transparent polyimide film and preparation method thereof and application.
Colourless high transparent polyimide film provided by the invention, also consist of the film that the semiaromatic polyimide resin shown in formula I general structure makes,
Figure BDA0000151805550000031
(formula I)
In described formula I general structure, Al is any one in following alicyclic structure,
Figure BDA0000151805550000032
In described formula I general structure, R 1shown in II general structure:
Figure BDA0000151805550000033
(formula II)
Wherein, in described formula II general structure, X is H, F, CH 3or CF 3; Y is selected from any one in following radicals:
And in X and Y, have one at least and contain fluorine atom or trifluoromethyl, p=0 or 1.
In described general structure I, R 2be selected from any one in following radicals:
Figure BDA0000151805550000042
M is 1～300 integer, the integer that n is 0～400, and n: m=0～400: 1, the number-average molecular weight (M of the polyimide resin of semiaromatic shown in formula I n) at 40000～160000g/mol.
Semiaromatic polyimide resin shown in above-mentioned formula I formula shown I also can be the resin product obtaining according to following method preparation provided by the invention.
The method of semiaromatic polyimide resin shown in preparation formula I provided by the invention, comprise the steps: under protection of inert gas, aromatic diamines I is dissolved in organic solvent, then add alicyclic dianhydride, being stirred to whole dissolvings obtains after homogeneous phase solution, add again catalyzer and dewatering agent to heat up and react, react the complete described dewatering agent of removing, pour precipitation agent after cooling into and precipitate and obtain semiaromatic polyimide resin shown in described formula I;
In aforesaid method, described aromatic diamines I is fluorine-containing containing sulfone aromatic diamines or the described fluorine-containing mixture containing at least one composition in sulfone aromatic diamines and following aromatic diamines II: 4, and 4 '-diaminodiphenyl oxide, 3,4 '-diaminodiphenyl oxide, DDS, 3,3 '-diaminodiphenylsulfone(DDS), 2,2 '-bis-(trifluoromethyl)-4,4 '-benzidine, α, α '-bis-(4-aminophenyl)-Isosorbide-5-Nitrae-diisopropyl benzene, 4,4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) benzene, 3,3 '-bis-(2-trifluoromethyl-4-aminophenoxyl) benzene, 4,4 '-bis-(2-methyl-4-amino-benzene oxygen) benzene, 3,3 '-bis-(2-methyl-4-amino-benzene oxygen) benzene, 4,4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) biphenyl, 4,4 '-bis-(2-methyl-4-amino-benzene oxygen) biphenyl, 2,2 '-bis-(4-amino-benzene oxygen phenyl) propane, 2,2 '-bis-(4-amino-benzene oxygen phenyl) HFC-236fa, 2,2 '-bis-(2-trifluoromethyl-4-aminophenoxyl phenyl) propane, 2,2 '-bis-(2-trifluoromethyl-4-aminophenoxyl phenyl) HFC-236fa, 4,4 '-bis-(4-amino-benzene oxygen) sulfobenzide and 4,4 '-bis-(2-methyl-4-amino-benzene oxygen) sulfobenzide,
Described fluorine-containing containing sulfone aromatic diamines, be at least one in following: 3,3 '-bis-(4-amino-benzene oxygens)-5,5 '-difluorodiphenyl sulfone, 3,3 '-bis-(3-amino-benzene oxygens)-5,5 '-difluorodiphenyl sulfone, 3,3 '-bis-(4-amino-benzene oxygen)-5,5 '-bis-(trifluoromethyl) sulfobenzide, 3,3 '-bis-(3-amino-benzene oxygen)-5,5 '-bis-(trifluoromethyl) sulfobenzide, 3,3 ', 5,5 '-tetrafluoro-4,4 '-bis-(4-amino-benzene oxygen) sulfobenzide, 3,3 ', 5,5 '-tetrafluoro-4,4 '-bis-(3-amino-benzene oxygen) sulfobenzide, 3,3 ', 5,5 '-tetra-(trifluoromethyl)-4,4 '-bis-(4-amino-benzene oxygen) sulfobenzide, 3,3 ', 5,5 '-tetra-(trifluoromethyl)-4,4 '-bis-(3-amino-benzene oxygen) sulfobenzide, 3,3 '-bis-(2-methyl 4-amino-benzene oxygens)-5,5 '-difluorodiphenyl sulfone, 3,3 '-bis-(3-methyl-5-amino-benzene oxygens)-5,5 '-difluorodiphenyl sulfone, 3,3 '-bis-(2-methyl-4-amino-benzene oxygen)-5,5 '-bis-(trifluoromethyl) sulfobenzide, 3,3 '-bis-(3-methyl-5-amino-benzene oxygen)-5,5 '-bis-(trifluoromethyl) sulfobenzide, 3,3 ', 5,5 '-tetrafluoro-4,4 '-bis-(2-methyl-4-amino-benzene oxygen) sulfobenzide, 3,3 ', 5,5 '-tetrafluoro-4,4 '-bis-(3-methyl-5-amino-benzene oxygen) sulfobenzide, 3,3 ', 5,5 '-tetra-(trifluoromethyl)-4,4 '-bis-(2-methyl-4-amino-benzene oxygen) sulfobenzide, 3,3 ', 5,5 '-tetra-(trifluoromethyl)-4,4 '-bis-(3-methyl-5-amino-benzene oxygen) sulfobenzide, 2,2 '-bis-fluoro-DDSs, 3,3 '-bis-is fluoro-5,5 '-diaminodiphenylsulfone(DDS), 3,3 '-bis-(the fluoro-4-amino-benzene oxygen of 2-) sulfobenzide, 3,3 '-bis-(the fluoro-5-amino-benzene oxygen of 3-) sulfobenzide, 3,3 '-bis-(fluoro-4-amino-benzene oxygens of 2-)-5,5 '-difluorodiphenyl sulfone, 3,3 '-bis-(fluoro-5-amino-benzene oxygens of 3-)-5,5 '-difluorodiphenyl sulfone, 3,3 '-bis-(fluoro-4-amino-benzene oxygens of 2-)-5,5 '-diphenylsulfone dimethyl, 3,3 '-bis-(fluoro-5-amino-benzene oxygens of 3-)-5,5 '-diphenylsulfone dimethyl, 3,3 '-bis-(the fluoro-4-amino-benzene oxygen of 2-)-5,5 '-bis-(trifluoromethyl) sulfobenzide, 3,3 '-bis-(the fluoro-5-amino-benzene oxygen of 3-)-5,5 '-bis-(trifluoromethyl) sulfobenzide, 4,4 '-bis-(the fluoro-4-amino-benzene oxygen of 2-) sulfobenzide, 4,4 '-bis-(the fluoro-5-amino-benzene oxygen of 3-) sulfobenzide, 3,3 ', 5,5 '-tetrafluoro-4,4 '-bis-(the fluoro-4-amino-benzene oxygen of 2-) sulfobenzide, 3,3 ', 5,5 '-tetrafluoro-4,4 '-bis-(the fluoro-5-amino-benzene oxygen of 3-) sulfobenzide, 3,3 ', 5,5 '-tetramethyl--4,4 '-bis-(the fluoro-4-amino-benzene oxygen of 2-) sulfobenzide, 3,3 ', 5,5 '-tetramethyl--4,4 '-bis-(the fluoro-5-amino-benzene oxygen of 3-) sulfobenzide, 3,3 ', 5,5 '-tetra-(trifluoromethyl)-4,4 '-bis-(the fluoro-4-amino-benzene oxygen of 2-) sulfobenzide, 3,3 ', 5,5 '-tetra-(trifluoromethyl)-4,4 '-bis-(the fluoro-5-amino-benzene oxygen of 3-) sulfobenzide, 2,2 '-bis-(trifluoromethyl)-DDSs, 3,3 '-bis-(trifluoromethyl)-5,5 '-diaminodiphenylsulfone(DDS), 3,3 '-bis-(2-trifluoromethyl-4-aminophenoxyl) sulfobenzide, 3,3 '-bis-(3-trifluoromethyl-5-amino-benzene oxygen) sulfobenzide, 3,3 '-bis-(2-trifluoromethyl-4-aminophenoxyls)-5,5 '-difluorodiphenyl sulfone, 3,3 '-bis-(3-trifluoromethyl-5-amino-benzene oxygens)-5,5 '-difluorodiphenyl sulfone, 3,3 '-bis-(2-trifluoromethyl-4-aminophenoxyls)-5,5 '-diphenylsulfone dimethyl, 3,3 '-bis-(3-trifluoromethyl-5-amino-benzene oxygens)-5,5 '-diphenylsulfone dimethyl, 3,3 '-bis-(2-trifluoromethyl-4-aminophenoxyl)-5,5 '-bis-(trifluoromethyl) sulfobenzide, 3,3 '-bis-(3-trifluoromethyl-5-amino-benzene oxygen)-5,5 '-bis-(trifluoromethyl) sulfobenzide, 4,4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) sulfobenzide, 4,4 '-bis-(3-trifluoromethyl-5-amino-benzene oxygen) sulfobenzide, 3,3 ', 5,5 '-tetrafluoro-4,4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) sulfobenzide, 3,3 ', 5,5 '-tetrafluoro-4,4 '-bis-(3-trifluoromethyl-5-amino-benzene oxygen) sulfobenzide, 3,3 ', 5,5 '-tetramethyl--4,4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) sulfobenzide, 3,3 ', 5,5 '-tetramethyl--4,4 '-bis-(3-trifluoromethyl-5-amino-benzene oxygen) sulfobenzide, 3,3 ', 5,5 '-tetra-(trifluoromethyl)-4,4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) sulfobenzide and 3,3 ', 5,5 '-tetra-(trifluoromethyl)-4,4 '-bis-(3-trifluoromethyl-5-amino-benzene oxygen) sulfobenzide,
Described alicyclic dianhydride is 1, 2, 3, 4-tetramethylene tetracarboxylic dianhydride (CBDA), 1, 2, 4, 5-pentamethylene tetracarboxylic dianhydride (CPDA), 2, 3, 5-tricarboxylic basic ring pentyl acetic acid dianhydride (TCPAH), 1, 2, 4, 5-hexanaphthene tetracarboxylic dianhydride (CHDA), dicyclo [2.2.1] heptan-2, 3, 5, 6-tetracarboxylic dianhydride (BHDA), 3, 4, 6-tri-carboxyl dicyclo [2.2.2] heptane guanidine-acetic acid dianhydrides (TCHAH), dicyclo [2.2.2] pungent-2, 3, 5, 6-tetracarboxylic dianhydride (BODA), dicyclo [2.2.2] is pungent-7-alkene-2, 3, 5, 6-tetracarboxylic dianhydride (BCDA), decahydro-1, 4, 5, 8-dimethylene naphthalene-2, 3, 6, 7-tetracarboxylic dianhydride (DNDA) or decahydro biphenyl-3, 3 ', 4, 4 '-tetracarboxylic dianhydride (HBPDA),
Described organic solvent is selected from N-Methyl pyrrolidone (NMP), gamma-butyrolactone, hexamethylphosphoramide (HMPA), dimethyl sulfoxide (DMSO) (DMSO), N, at least one in N-N,N-DIMETHYLACETAMIDE (DMAc) and DMF (DMF);
Described catalyzer is triethylamine, tripropyl amine, tributylamine, trolamine, pyridine, imidazoles, quinoline or isoquinoline 99.9, is specially triethylamine, pyridine, quinoline or isoquinoline 99.9;
Described dewatering agent is toluene or dimethylbenzene;
Described precipitation agent is selected from least one in water, methyl alcohol, ethanol, propyl alcohol, butanols, Virahol, Pentyl alcohol and primary isoamyl alcohol;
The molar ratio example of described aromatic diamines I and alicyclic dianhydride is 0.9～1.1: 1.0, is specially 0.95～1.05: 1.0; The solid content of described homogeneous phase solution is 10～50% (quality), is specially 15-35% (quality);
The molar ratio example of described catalyzer and described aromatic diamines is 0.01～1.0: 1.0, is specially 0.05-0.1: 1.0;
In described reactions steps, temperature is 140～180 ℃, and the time is 6～48 hours.
The film being prepared by semiaromatic polyimide resin shown in above-mentioned formula I, also belongs to protection scope of the present invention.The initial printing opacity wavelength of described film below 300nm, transmittance >=90% in visible region; The thickness of described film is 25～150 μ m, is specially 50-125 μ m.
The method of the colourless high transparent polyimide film of preparation provided by the invention, comprises the steps:
Shown in the formula I that aforesaid method is prepared, semiaromatic polyimide resin is dissolved in organic solvent, obtain described resin solution, more described resin solution is coated in substrate, after oven dry, immerse in deionized water and peel off, obtain described transparent polyimide film.
In above-mentioned method for manufacturing thin film, described organic solvent is selected from N-Methyl pyrrolidone (NMP), gamma-butyrolactone, dimethyl sulfoxide (DMSO) (DMSO), N, at least one in N-N,N-DIMETHYLACETAMIDE (DMAc) and DMF (DMF);
Described base material is sheet glass or stainless steel plate;
The solid content of the resin solution of described polyimide is 10～50% (quality), is specially 15-40% (quality);
In described baking step, temperature is 80～200 ℃, and the time is 1～6 hour;
The colourless high transparent polyimide film that the invention described above provides application in preparing photoelectric device as base material, and contain and using the photoelectric device of described film as base material, also belong to protection scope of the present invention, wherein, described photoelectric device is selected from least one in solar cell, indicating meter, e-book, electronic tag and photo-sensor; Described base material is selected from least one in flexible solar cell substrates, flexible display substrate and compliant conductive film base material.
The present invention adopts alicyclic dianhydride and fluorine-containing containing sulfone aromatic diamines and prepare semiaromatic polyimide with the mixture of other structure aromatic diamines, by dianhydride, alicyclic structure is incorporated in polyimide main chain on the one hand, with this, destroys main chain conjugation; In aromatic diamines, introduce on the other hand fluoro-containing group and the sulfuryl of strong electrophilic simultaneously, further destroy two amine moieties to electronics, in addition, the steric effect of the fluoro-containing group of large volume is conducive to increase molecular chain spacing, thereby with intermolecular charge transfer, obtain colourless high transparent Kapton in Inhibitory molecules.This special molecular structure, gives the very excellent solvability of polyimide and workability simultaneously, therefore can adopt high temperature single stage method reaction (at 140-180 ℃) directly to obtain the polyimide resin of high molecular.This thin film preparation process is simple, can directly with resin solution, film, and in air, 200 ℃ of following Temperature Treatment are removed the film that desolventizing can obtain satisfactory mechanical property, have avoided high temperature oxidation to bring the painted problem of film.Colourless high transparent polyimide film provided by the invention not only has excellent optical transparence, can realize film water white transparency of (>=100 μ m) under high thickness, initial printing opacity wavelength is below 300nm, at visible region transmittance >=90%, film shows superior heat resistance performance and mechanical property simultaneously.The colourless high transparent polyimide film of this class has important using value as flexible transparent substrate material in the manufacture of the photoelectric devices such as solar cell, indicating meter, e-book, electronic tag, photo-sensor.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of the Kapton of embodiment 1 preparation.
Fig. 2 is the infrared spectrum of the Kapton of embodiment 2 preparations.
Fig. 3 is the infrared spectrum of the Kapton of embodiment 3 preparations.
Fig. 4 is the infrared spectrum of the Kapton of embodiment 5 preparations.
Fig. 5 is the infrared spectrum of the Kapton of embodiment 8 preparations.
Fig. 6 is the infrared spectrum of the Kapton of embodiment 10 preparations.
Fig. 7 is the infrared spectrum of the Kapton of embodiment 12 preparations.
Fig. 8 is the infrared spectrum of the Kapton of embodiment 16 preparations.
Embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated to explanation, but the present invention is not limited to following examples, wherein, embodiment 1-7 and comparative example 1 are the preparation of homopolymerization type Kapton, the preparation that embodiment 8-16 is copolyimide films.In the present invention, degree and percentage concentration if no special instructions, are quality percentage composition and mass percentage concentration.
The preparation of embodiment 1, homopolymerization Kapton
In being furnished with the there-necked flask of mechanical stirring, water trap, nitrogen gangway and thermometer; add 56.85 grams of (0.1 moles) 4; in 4 '-bis-(3-trifluoromethyl-5-amino-benzene oxygen) sulfobenzides and 143 milliliters of N-Methyl pyrrolidone (NMP); under nitrogen protection, be stirred to after dissolving completely, add 22.42 grams of (0.1 moles) 1,2; 4; 5-hexanaphthene tetracarboxylic dianhydride (CHDA), is stirred to whole dissolvings, obtains the homogeneous phase solution that solid content is 35wt.%.0.65 gram of (0.005 mole) isoquinoline 99.9 and 24 milliliters of toluene are joined in above-mentioned homogeneous phase solution, and reaction system was warming up to 180 ℃ of reactions after 24 hours, steamed toluene, stopped heating.After reaction solution is cooled to 80-120 ℃, pour in ethanol and obtain fibrous crude product, collect the crude product of separating out, with filtering, pulverize, dry after second alcohol and water repetitive scrubbing, obtain semiaromatic polyimide resin, productive rate is 98%, number-average molecular weight (M n) be 1.3 * 10 5g/mol.
FT-IR(film，cm -1)：3081，2941，1786，1720，1621，1490，1439，1386，1320，1242，1187，1054。As shown in Figure 1.
Semiaromatic polyimide resin is dissolved in to N, in N-N,N-DIMETHYLACETAMIDE (DMAc), obtain the resin solution that solid content is 35wt.%, after filtration, after vacuum defoamation, be coated on ganoid sheet glass or stainless steel plate, under air atmosphere after 80 ℃/2 hours, 120 ℃/1 hour, 160 ℃/1 hour, 180 ℃/1 hour ladder-elevating temperature heat is dried, by making thin film automatic stripping in sheet glass or stainless steel plate immersion deionized water, after 120 ℃ of vacuum-drying, obtain certain thickness transparent polyimide film.The thickness of film can be controlled by the film model of roller of adjusting.The salient features of this Kapton is in Table 1.
By the dianhydride using in the present embodiment, be 1,2,4,5-hexanaphthene tetracarboxylic dianhydride (CHDA) replaces with 1,2,3,4-tetramethylene tetracarboxylic dianhydride (CBDA), adopts the preparation condition identical with the present embodiment can obtain the colourless high transparent polyimide film that thermal characteristics, mechanical property and optical property etc. are suitable.
The preparation of embodiment 2, homopolymerization type Kapton
In being furnished with the there-necked flask of mechanical stirring, water trap, nitrogen gangway and thermometer; add 56.85 grams of (0.1 moles) 4; 4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) sulfobenzides and 173 milliliters of N-Methyl pyrrolidone (NMP); under nitrogen protection, be stirred to after dissolving completely, add 19.61 grams of (0.1 moles) 1,2; 3; 4-tetramethylene tetracarboxylic dianhydride (CBDA), is stirred to whole dissolvings, obtains the homogeneous phase solution that solid content is 30wt.%.0.13 gram of (0.001 mole) isoquinoline 99.9 and 30 milliliters of toluene are joined in above-mentioned homogeneous phase solution, and reaction system was warming up to 180 ℃ of reactions after 12 hours, steamed toluene, stopped heating.After reaction solution is cooled to 80-120 ℃, pour in ethanol and obtain fibrous crude product, collect the crude product of separating out, with filtering, pulverize, dry after second alcohol and water repetitive scrubbing, obtain semiaromatic polyimide resin, productive rate is 98%, number-average molecular weight (M n) be 1.5 * 10 5g/mol.
FT-IR(film，cm -1)：3078，2940，1785，1721，1588，1494，1438，1384，1320，1251，1150，1055。As shown in Figure 2.
Semiaromatic polyimide resin is dissolved in to N, in N-N,N-DIMETHYLACETAMIDE (DMAc), obtain the resin solution that solid content is 30wt.%, after filtration, after vacuum defoamation, be coated on ganoid sheet glass or stainless steel plate, under air atmosphere after 80 ℃/2 hours, 120 ℃/1 hour, 160 ℃/1 hour, 180 ℃/1 hour ladder-elevating temperature heat is dried, by making thin film automatic stripping in sheet glass or stainless steel plate immersion deionized water, after 120 ℃ of vacuum-drying, obtain certain thickness transparent polyimide film.The thickness of film can be controlled by the film model of roller of adjusting.The salient features of this Kapton is in Table 1.
By the dianhydride using in the present embodiment, be 1,2,3,4-tetramethylene tetracarboxylic dianhydride (CBDA) replaces with 1,2,4,5-hexanaphthene tetracarboxylic dianhydride (CHDA), adopts the preparation condition identical with the present embodiment can obtain the colourless high transparent polyimide film that thermal characteristics, mechanical property and optical property etc. are suitable.
The preparation of embodiment 3, homopolymerization Kapton
In being furnished with the there-necked flask of mechanical stirring, water trap, nitrogen gangway and thermometer; add 40.35 grams of (0.105 moles) 2; in 2 '-bis-(trifluoromethyl)-DDSs and 228 milliliters of gamma-butyrolactones, under nitrogen protection, be stirred to after dissolving completely; add 23.62 grams of (0.1 mole) dicyclos [2.2.1] heptan-2; 3,5,6-tetracarboxylic dianhydride (BHDA); be stirred to whole dissolvings, obtain the homogeneous phase solution that solid content is 20wt.%.1.29 grams of (0.01 mole) quinoline works and 55 milliliters of toluene are joined in above-mentioned homogeneous phase solution, and reaction system was warming up to 180 ℃ of reactions after 12 hours, steamed toluene, stopped heating.After being cooled to 80-120 ℃, pours reaction solution propanol/water mixing solutions (propanol/water volume ratio=1: obtain fibrous crude product 2) into, the crude product that collection is separated out, after water repetitive scrubbing, filter, pulverize, dry, obtain semiaromatic polyimide resin, productive rate is 97%, number-average molecular weight (M n) be 1.5 * 10 5g/mol.
FT-IR(film，cm -1)：3080，2939，1781，1718，1588，1486，1444，1377，1321，1236，1191，1047。As shown in Figure 3.
Semiaromatic polyimide resin is dissolved in gamma-butyrolactone, obtain the resin solution that solid content is 25wt.%, after filtration, after vacuum defoamation, be coated on ganoid sheet glass or stainless steel plate, under air atmosphere after 80 ℃/2 hours, 120 ℃/1 hour, 160 ℃/1 hour, 180 ℃/1 hour, 200 ℃/1 hour ladder-elevating temperature heat is dried, by making thin film automatic stripping in sheet glass or stainless steel plate immersion deionized water, after 120 ℃ of vacuum-drying, obtain certain thickness transparent polyimide film.The thickness of film can be controlled by the film model of roller of adjusting.The salient features of this Kapton is in Table 1.
By the dianhydride using in the present embodiment, be dicyclo [2.2.1] heptan-2,3,5,6-tetracarboxylic dianhydride (BHDA) replaces with 3,4,6-tri-carboxyl dicyclo [2.2.2] heptane guanidine-acetic acid dianhydrides (TCHAH), adopt the preparation condition identical with the present embodiment can obtain the colourless high transparent polyimide film that thermal characteristics, mechanical property and optical property etc. are suitable.
The preparation of embodiment 4, homopolymerization type Kapton
In being furnished with the there-necked flask of mechanical stirring, water trap, nitrogen gangway and thermometer; add 42.27 grams of (0.11 moles) 3; 3 '-bis-(trifluoromethyl)-5,5 '-diaminodiphenylsulfone(DDS) and 117 milliliters of hexamethylphosphoramides (HMPA) are stirred to after dissolving completely under nitrogen protection; add 22.42 grams of (0.1 moles) 1; 2,4,5-hexanaphthene tetracarboxylic dianhydride (CHDA); be stirred to whole dissolvings, obtain the homogeneous phase solution that solid content is 35wt.%.1.29 grams of (0.01 mole) quinoline and 23 milliliters of dimethylbenzene are joined in above-mentioned homogeneous phase solution, and reaction system was warming up to 180 ℃ of reactions after 24 hours, steamed dimethylbenzene, stopped heating.After reaction solution is cooled to 80-120 ℃, pour in methyl alcohol and obtain fibrous crude product, collect the crude product of separating out, with filtering after methyl alcohol repetitive scrubbing, pulverize, drying, obtain semiaromatic polyimide resin, productive rate is 98%, number-average molecular weight (M n) be 1.6 * 10 5g/mol.
FT-IR(film，cm -1)：3078，2935，1780，1721，1592，1488，1447，1373，1320，1238，1190，1045。
Semiaromatic polyimide resin is dissolved in to N, dinethylformamide (DMF) and N, mixed solvent (DMF/DMAC volume ratio=1: 1) of N-N,N-DIMETHYLACETAMIDE (DMAc), obtain the resin solution that solid content is 35wt.%, after filtration, after vacuum defoamation, be coated on ganoid sheet glass or stainless steel plate, under air atmosphere through 80 ℃/2 hours, 120 ℃/1 hour, 160 ℃/1 hour, 180 ℃/1 hour, after within 200 ℃/1 hour, ladder-elevating temperature heat is dried, to in sheet glass or stainless steel plate immersion deionized water, make thin film automatic stripping, after 120 ℃ of vacuum-drying, obtain certain thickness transparent polyimide film.The thickness of film can be controlled by the film model of roller of adjusting.The salient features of this Kapton is in Table 1.
By the dianhydride using in the present embodiment, be 1,2,4,5-hexanaphthene tetracarboxylic dianhydride (CHDA) replaces with 1,2,3,4-tetramethylene tetracarboxylic dianhydride (CBDA), adopts the preparation condition identical with the present embodiment can obtain the colourless high transparent polyimide film that thermal characteristics, mechanical property and optical property etc. are suitable.
The preparation of embodiment 5, homopolymerization type Kapton
In being furnished with the there-necked flask of mechanical stirring, water trap, nitrogen gangway and thermometer; add 64.05 grams of (0.1 moles) 3; 3 '; 5; 5 '-tetrafluoro-4; 4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) sulfobenzides and 222 milliliters of N; N-N,N-DIMETHYLACETAMIDE (DMAc); after being stirred under nitrogen protection completely and dissolving, add 24.82 grams of (0.1 mole) dicyclos [2.2.2] pungent-7-alkene-2,3; 5; 6-tetracarboxylic dianhydride (BCDA), is stirred to whole dissolvings, obtains the homogeneous phase solution that solid content is 30wt.%.0.51 gram of (0.005 mole) triethylamine and 37 milliliters of toluene are joined in above-mentioned homogeneous phase solution, and reaction system was warming up to 160 ℃ of reactions after 48 hours, steamed toluene, stopped heating.After being cooled to 80-120 ℃, pours reaction solution ethanol/water mixing solutions (ethanol/water volume ratio=1: obtain fibrous crude product 1) into, the crude product that collection is separated out, with filtering after second alcohol and water repetitive scrubbing, pulverize, drying, obtain semiaromatic polyimide resin, productive rate is 98%, number-average molecular weight (M n) be 8.2 * 10 4g/mol.
FT-IR(film，cm -1)：3073，2971，1782，1722，1587，1491，1438，1382，1320，1249，1150，1054。As shown in Figure 4.
Semiaromatic polyimide resin is dissolved in to N, in N-N,N-DIMETHYLACETAMIDE (DMAc), obtain the resin solution that solid content is 30wt.%, after filtration, after vacuum defoamation, be coated on ganoid sheet glass or stainless steel plate, under air atmosphere after 80 ℃/2 hours, 120 ℃/1 hour, 160 ℃/1 hour, 180 ℃/1 hour ladder-elevating temperature heat is dried, by making thin film automatic stripping in sheet glass or stainless steel plate immersion deionized water, after 120 ℃ of vacuum-drying, obtain certain thickness transparent polyimide film.The thickness of film can be controlled by the film model of roller of adjusting.The salient features of this Kapton is in Table 1.
By the diamines using in the present embodiment, be 3,3 ', 5,5 '-tetrafluoro-4,4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) sulfobenzide replaces with 3,3 ', 5,5 '-tetramethyl--4,4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) sulfobenzide, adopts the preparation condition identical with the present embodiment can obtain the colourless high transparent polyimide film that thermal characteristics, mechanical property and optical property etc. are suitable.
The preparation of embodiment 6, homopolymerization type Kapton
In being furnished with the there-necked flask of mechanical stirring, water trap, nitrogen gangway and thermometer; add 73.97 grams of (0.105 moles) 3; 3 '; 5; 5 '-tetra-(trifluoromethyl)-4; 4 '-bis-(4-amino-benzene oxygen) sulfobenzides and 245 milliliters of N; dinethylformamide (DMF); under nitrogen protection, be stirred to after dissolving completely; add 25.02 grams of (0.1 moles) 3,4,6-tri-carboxyl dicyclo [2.2.2] heptane guanidine-acetic acid dianhydrides (TCHAH); be stirred to whole dissolvings, obtain the homogeneous phase solution that solid content is 30wt.%.0.51 gram of (0.005 mole) triethylamine and 40 milliliters of dimethylbenzene are joined in above-mentioned homogeneous phase solution, and reaction system was warming up to 150 ℃ of reactions after 24 hours, steamed dimethylbenzene, stopped heating.After being cooled to 80-120 ℃, pours reaction solution methanol/water mixing solutions (methanol/water volume ratio=1: obtain fibrous crude product 3) into, the crude product that collection is separated out, with filtering after first alcohol and water repetitive scrubbing, pulverize, drying, obtain semiaromatic polyimide resin, productive rate is 97%, number-average molecular weight (M n) be 4.8 * 10 4g/mol.
FT-IR(film，cm -1)：3082，2962，1782，1720，1587，1490，1425，1375，1313，1182，1136，1076。
Semiaromatic polyimide resin is dissolved in to N, in dinethylformamide (DMF), obtain the resin solution that solid content is 30wt.%, after filtration, after vacuum defoamation, be coated on ganoid sheet glass or stainless steel plate, under air atmosphere after 80 ℃/2 hours, 120 ℃/1 hour, 160 ℃/1 hour, 180 ℃/1 hour ladder-elevating temperature heat is dried, by making thin film automatic stripping in sheet glass or stainless steel plate immersion deionized water, after 120 ℃ of vacuum-drying, obtain certain thickness transparent polyimide film.The thickness of film can be controlled by the film model of roller of adjusting.The salient features of this Kapton is in Table 1.
By the dianhydride using in the present embodiment, be 3, 4, 6-tri-carboxyl dicyclo [2.2.2] heptane guanidine-acetic acid dianhydrides (TCHAH) replace with dicyclo [2.2.1] heptan-2, 3, 5, 6-tetracarboxylic dianhydride (BHDA), or be 3 by diamines, 3 ', 5, 5 '-tetra-(trifluoromethyl)-4, 4 '-bis-(4-amino-benzene oxygen) sulfobenzide replaces with 3, 3 ', 5, 5 '-tetra-(trifluoromethyl)-4, 4 '-bis-(2-fluorine 4-amino-benzene oxygen) sulfobenzide, adopt the preparation condition identical with the present embodiment can obtain thermal characteristics, the colourless high transparent polyimide film that mechanical property and optical property etc. are suitable.
The preparation of embodiment 7, homopolymerization type Kapton
In being furnished with the there-necked flask of mechanical stirring, water trap, nitrogen gangway and thermometer, add 62.46 grams of (0.1 moles) 3,3 ', 5,5 '-tetramethyl--4,4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) sulfobenzides and 76 milliliters of N-Methyl pyrrolidone (NMP), 53 milliliters of N, N-N,N-DIMETHYLACETAMIDE (DMAc), system adopts mixed solvent, and wherein the mass ratio of N-Methyl pyrrolidone and N,N-dimethylacetamide is 2: 1.Under nitrogen protection, be stirred to after dissolving completely, add 23.12 grams of (0.11 moles) 1,2,4,5-pentamethylene tetracarboxylic dianhydride (CPDA), is stirred to whole dissolvings, obtains the homogeneous phase solution that solid content is 40wt.%.4.0 grams of (0.05 mole) pyridines and 22 milliliters of dimethylbenzene are joined in above-mentioned homogeneous phase solution, and reaction system was warming up to 160-180 ℃ of reaction after 36 hours, steamed dimethylbenzene, stopped heating.After being cooled to 80-120 ℃, pours reaction solution isopropanol/water mixing solutions (isopropanol/water volume ratio=1: obtain fibrous crude product 3) into, the crude product that collection is separated out, with filtering after isopropyl alcohol and water repetitive scrubbing, pulverize, drying, obtain semiaromatic polyimide resin, productive rate is 96%, number-average molecular weight (M n) be 8.4 * 10 4g/mol.
FT-IR(film，cm -1)：2965，1778，1714，1626，1528，1486，1445，1373，1304，1191，1086，1048。
Semiaromatic polyimide resin is dissolved in N-Methyl pyrrolidone (NMP), obtain the resin solution that solid content is 40wt.%, after filtration, after vacuum defoamation, be coated on ganoid sheet glass or stainless steel plate, under air atmosphere after 80 ℃/2 hours, 120 ℃/1 hour, 160 ℃/1 hour, 180 ℃/1 hour, 200 ℃/1 hour ladder-elevating temperature heat is dried, by making thin film automatic stripping in sheet glass or stainless steel plate immersion deionized water, after 120 ℃ of vacuum-drying, obtain certain thickness transparent polyimide film.The thickness of film can be controlled by the film model of roller of adjusting.The salient features of this Kapton is in Table 1.
By the dianhydride using in the present embodiment, be 1,2,4,5-pentamethylene tetracarboxylic dianhydride (CPDA) replaces with 2,3,5-tricarboxylic basic ring pentyl acetic acid dianhydride (TCPAH), or be 3,3 ' by diamines, 5,5 '-tetramethyl--4,4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) sulfobenzide replaces with 3,3 ', 5,5 '-tetra-(trifluoromethyl)-4,4 '-bis-(2-methyl-4-amino-benzene oxygen) sulfobenzide, adopts the preparation condition identical with the present embodiment can obtain the colourless high transparent polyimide film that thermal characteristics, mechanical property and optical property etc. are suitable.
The preparation of comparative example 1, homopolymerization type Kapton
Reference example 1, diamines is replaced with to 1, two (2-trifluoromethyl-4-aminophenoxyl) benzene of 4-, dianhydride adopts 1,2,4,5-hexanaphthene tetracarboxylic dianhydride (CHDA), to wait mole proportioning to be dissolved in N-Methyl pyrrolidone (NMP), be stirred to whole dissolvings, obtain the homogeneous phase solution that solid content is 20wt.%.Adopt the polymerization process identical with embodiment 1, obtain semiaromatic polyimide resin, productive rate is 97%, number-average molecular weight (M n) be 9.1 * 10 4g/mol.
FT-IR(film，cm -1)：3096，2941，1788，1720，1622，1492，1439，1385，1321，1242，1184，1053。
Semiaromatic polyimide resin is dissolved in N-Methyl pyrrolidone (NMP), obtain the resin solution that solid content is 20wt.%, after filtration, after vacuum defoamation, be coated on ganoid sheet glass or stainless steel plate, under air atmosphere after 80 ℃/2 hours, 120 ℃/1 hour, 160 ℃/1 hour, 180 ℃/1 hour, 200 ℃/1 hour ladder-elevating temperature heat is dried, by making thin film automatic stripping in sheet glass or stainless steel plate immersion deionized water, after 120 ℃ of vacuum-drying, obtain certain thickness Kapton.The thickness of film can be controlled by the film model of roller of adjusting.The salient features of this Kapton is in Table 1.
By the dianhydride using in the present embodiment, be 1,2,4,5-hexanaphthene tetracarboxylic dianhydride (CHDA) replaces with 1,2,4,5-pentamethylene tetracarboxylic dianhydride (CPDA) or 1,2,3,4-tetramethylene tetracarboxylic dianhydride (CBDA), or be 1 by used diamines, two (2-trifluoromethyl-4-aminophenoxyl) benzene of 4-replaces with 4, and 4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) biphenyl, adopts the preparation condition identical with the present embodiment all can obtain the Kapton that thermal characteristics, mechanical property and optical property etc. are suitable.
The preparation of embodiment 8, copolyimide films
In being furnished with the there-necked flask of mechanical stirring, water trap, nitrogen gangway and thermometer; add 14.09 grams of (0.02 moles) 3; 3 '-bis-(2-trifluoromethyl-4-aminophenoxyls)-5; 5 '-bis-(trifluoromethyl) sulfobenzide, 16.02 grams of (0.08 moles) 4; 4 '-diaminodiphenyl oxide and 52 milliliters of N-Methyl pyrrolidone (NMP); under nitrogen protection, be stirred to after dissolving completely; add 22.42 grams of (0.1 moles) 1; 2; 4; 5-hexanaphthene tetracarboxylic dianhydride (CHDA), is stirred to whole dissolvings, obtains the homogeneous phase solution that solid content is 50wt.%.2.58 grams of (0.02 mole) isoquinoline 99.9 and 8 milliliters of toluene are joined in above-mentioned homogeneous phase solution, and reaction system was warming up to 180 ℃ of reactions after 8 hours, steamed toluene, stopped heating.After being cooled to 80-120 ℃, pours reaction solution methanol/water mixing solutions (methanol/water volume ratio=1: obtain fibrous crude product 2) into, the crude product that collection is separated out, with filtering after first alcohol and water repetitive scrubbing, pulverize, drying, obtain semiaromatic polyimide resin, productive rate is 97%, number-average molecular weight (M n) be 1.6 * 10 5g/mol.
FT-IR(film，cm -1)：3086，2941，1787，1722，1618，1492，1426，1378，1313，1258，1183，1076。As shown in Figure 5.
Semiaromatic polyimide resin is dissolved in N-Methyl pyrrolidone (NMP), obtain the resin solution that solid content is 50wt.%, after filtration, after vacuum defoamation, be coated on ganoid sheet glass or stainless steel plate, under air atmosphere after 80 ℃/2 hours, 120 ℃/1 hour, 160 ℃/1 hour, 180 ℃/1 hour, 200 ℃/1 hour ladder-elevating temperature heat is dried, by making thin film automatic stripping in sheet glass or stainless steel plate immersion deionized water, after 120 ℃ of vacuum-drying, obtain certain thickness transparent polyimide film.The thickness of film can be controlled by the film model of roller of adjusting.The salient features of this Kapton is in Table 1.
By the dianhydride using in the present embodiment, be 1,2,4,5-hexanaphthene tetracarboxylic dianhydride (CHDA) replaces with 1,2,3,4-tetramethylene tetracarboxylic dianhydride (CBDA), or by 4 in diamines, 4 '-diaminodiphenyl oxide replaces with 3,4 '-diaminodiphenyl oxide, adopts the preparation condition identical with the present embodiment can obtain the colourless high transparent polyimide film that thermal characteristics, mechanical property and optical property etc. are suitable.
The preparation of embodiment 9, copolyimide films
Is being furnished with mechanical stirring, water trap, in the there-necked flask of nitrogen gangway and thermometer, add 43.95 grams of (0.06 moles) 3, 3 ', 5, 5 '-tetra-(trifluoromethyl)-4, 4 '-bis-(2-methyl-4-amino-benzene oxygen) sulfobenzide, 9.93 grams of (0.04 moles) 4, 4 '-diaminodiphenylsulfone(DDS) and 153 milliliters of hexamethylphosphoramides (HMPA), under nitrogen protection, be stirred to after dissolving completely, add 30.23 grams of (0.1 mole) decahydro-1, 4, 5, 8-dimethylene naphthalene-2, 3, 6, 7-tetracarboxylic dianhydride (DNDA), be stirred to whole dissolvings, obtain the homogeneous phase solution that solid content is 35wt.%.2.58 grams of (0.02 mole) isoquinoline 99.9 and 25 milliliters of toluene are joined in above-mentioned homogeneous phase solution, and reaction system was warming up to 140-180 ℃ of reaction after 48 hours, steamed toluene, stopped heating.After reaction solution is cooled to 80-120 ℃, pour in ethanol and obtain fibrous crude product, collect the crude product of separating out, with filtering after ethanol repetitive scrubbing, pulverize, drying, obtain semiaromatic polyimide resin, productive rate is 98%, number-average molecular weight (M n) be 5.6 * 10 4g/mol.
FT-IR(film，cm -1)：3076，2940，1785，1721，1588，1494，1438，1384，1320，1267，1109，1054。
Semiaromatic polyimide resin is dissolved in N-Methyl pyrrolidone (NMP), obtain the resin solution that solid content is 30wt.%, after filtration, after vacuum defoamation, be coated on ganoid sheet glass or stainless steel plate, under air atmosphere after 80 ℃/2 hours, 120 ℃/1 hour, 160 ℃/1 hour, 180 ℃/1 hour, 200 ℃/1 hour ladder-elevating temperature heat is dried, by making thin film automatic stripping in sheet glass or stainless steel plate immersion deionized water, after 120 ℃ of vacuum-drying, obtain certain thickness transparent polyimide film.The thickness of film can be controlled by the film model of roller of adjusting.The salient features of this Kapton is in Table 1.
By the diamines using in the present embodiment, be 3,3 '-bis-(2-trifluoromethyl-4-aminophenoxyls)-5,5 '-bis-(trifluoromethyl) sulfobenzide replaces with 3,3 '-bis-(2-trifluoromethyl-4-aminophenoxyls)-5,5 '-diphenylsulfone dimethyl, or by another kind of diamines 4,4 '-diaminodiphenylsulfone(DDS) replaces with 3,3 '-diaminodiphenylsulfone(DDS), adopts the preparation condition identical with the present embodiment can obtain the colourless high transparent polyimide film that thermal characteristics, mechanical property and optical property etc. are suitable.
The preparation of embodiment 10, copolyimide films
In being furnished with the there-necked flask of mechanical stirring, water trap, nitrogen gangway and thermometer; add 5.68 grams of (0.01 moles) 4; 4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) sulfobenzide, 28.82 grams of (0.09 moles) 2; 2 '-bis-(trifluoromethyl)-4; 4 '-benzidine and 182 milliliters of N; N-N,N-DIMETHYLACETAMIDE (DMAc); under nitrogen protection, be stirred to after dissolving completely; add 22.42 grams of (0.1 moles) 1; 2,4,5-hexanaphthene tetracarboxylic dianhydride (CHDA); be stirred to whole dissolvings, obtain the homogeneous phase solution that solid content is 25wt.%.2.58 grams of (0.02 mole) isoquinoline 99.9 and 30 milliliters of toluene are joined in above-mentioned homogeneous phase solution, and reaction system was warming up to 160 ℃ of reactions after 18 hours, steamed toluene, stopped heating.After reaction solution is cooled to 80-120 ℃, pour in ethanol and obtain fibrous crude product, collect the crude product of separating out, with filtering, pulverize, dry after second alcohol and water repetitive scrubbing, obtain semiaromatic polyimide resin, productive rate is 98%, number-average molecular weight (M n) be 1.6 * 10 5g/mol.
FT-IR(film，cm -1)：3074，2937，1779，1722，1599，1504，1447，1388，1325，1246，1189，1016。As shown in Figure 6.
Semiaromatic polyimide resin is dissolved in to N, in N-N,N-DIMETHYLACETAMIDE (DMAc), obtain the resin solution that solid content is 30wt.%, after filtration, after vacuum defoamation, be coated on ganoid sheet glass or stainless steel plate, under air atmosphere after 80 ℃/2 hours, 120 ℃/1 hour, 160 ℃/1 hour, 180 ℃/1 hour ladder-elevating temperature heat is dried, by making thin film automatic stripping in sheet glass or stainless steel plate immersion deionized water, after 120 ℃ of vacuum-drying, obtain certain thickness transparent polyimide film.The thickness of film can be controlled by the film model of roller of adjusting.The salient features of this Kapton is in Table 1.
By the dianhydride using in the present embodiment, be 1,2,4,5-hexanaphthene tetracarboxylic dianhydride (CHDA) replaces with 1,2,3,4-tetramethylene tetracarboxylic dianhydride (CBDA), adopts the preparation condition identical with the present embodiment can obtain the colourless high transparent polyimide film that thermal characteristics, mechanical property and optical property etc. are suitable.
The preparation of embodiment 11, copolyimide films
In being furnished with the there-necked flask of mechanical stirring, water trap, nitrogen gangway and thermometer; add 37.28 grams of (0.07 moles) 3; 3 '; 5; 5 '-tetrafluoro-4; 4 '-bis-(3-methyl-5-amino-benzene oxygen) sulfobenzide, 10.33 grams of (0.03 mole) α; α '-bis-(4-aminophenyl)-Isosorbide-5-Nitrae-diisopropyl benzene and 148 milliliters of gamma-butyrolactones are stirred to after dissolving completely under nitrogen protection; add 23.62 grams of (0.1 mole) dicyclos [2.2.1] heptan-2; 3,5,6-tetracarboxylic dianhydride (BHDA); be stirred to whole dissolvings, obtain the homogeneous phase solution that solid content is 30wt.%.2.58 grams of (0.02 mole) isoquinoline 99.9 and 25 milliliters of toluene are joined in above-mentioned homogeneous phase solution, and reaction system was warming up to 140-180 ℃ of reaction after 24 hours, steamed toluene, stopped heating.After being cooled to 80-120 ℃, pours reaction solution methyl alcohol/butanols mixing solutions (methyl alcohol/butanols volume ratio=3: obtain fibrous crude product 1) into, the crude product that collection is separated out, with filtering after methyl alcohol repetitive scrubbing, pulverize, drying, obtain semiaromatic polyimide resin, productive rate is 96%, number-average molecular weight (M n) be 9.6 * 10 4g/mol.
FT-IR(film，cm -1)：3068，2933，1782，1720，1602，1514，1468，1388，1333，1280，1131，1096。
Semiaromatic polyimide resin is dissolved in gamma-butyrolactone, obtain the resin solution that solid content is 30wt.%, after filtration, after vacuum defoamation, be coated on ganoid sheet glass or stainless steel plate, under air atmosphere after 80 ℃/2 hours, 120 ℃/1 hour, 160 ℃/1 hour, 180 ℃/1 hour, 200 ℃/1 hour ladder-elevating temperature heat is dried, by making thin film automatic stripping in sheet glass or stainless steel plate immersion deionized water, after 120 ℃ of vacuum-drying, obtain certain thickness transparent polyimide film.The thickness of film can be controlled by the film model of roller of adjusting.The salient features of this Kapton is in Table 1.
By the dianhydride using in the present embodiment, be dicyclo [2.2.1] heptan-2,3,5,6-tetracarboxylic dianhydride (BHDA) replaces with 3,4,6-tri-carboxyl dicyclo [2.2.2] heptane guanidine-acetic acid dianhydrides (TCHAH), adopt the preparation condition identical with the present embodiment can obtain the colourless high transparent polyimide film that thermal characteristics, mechanical property and optical property etc. are suitable.
The preparation of embodiment 12, copolyimide films
In being furnished with the there-necked flask of mechanical stirring, water trap, nitrogen gangway and thermometer; add 23.42 grams of (0.05 moles) 4; 4 '-bis-(the fluoro-5-amino-benzene oxygen of 3-) sulfobenzide, 21.42 grams of (0.05 moles) 1; two (2-trifluoromethyl-4-aminophenoxyl) benzene of 4-and 96 milliliters of dimethyl sulfoxide (DMSO) (DMSO); under nitrogen protection, be stirred to after dissolving completely; add 24.82 grams of (0.1 mole) dicyclos [2.2.2] pungent-7-alkene-2; 3; 5; 6-tetracarboxylic dianhydride (BCDA); be stirred to whole dissolvings, obtain the homogeneous phase solution that solid content is 40wt.%.7.91g (0.1 mole) pyridine and 14 milliliters of toluene are joined in above-mentioned homogeneous phase solution, and reaction system was warming up to 170 ℃ of reactions after 24 hours, steamed toluene, stopped heating.After being cooled to 80-120 ℃, pours reaction solution Pentyl alcohol/water mixed solution (Pentyl alcohol/water volume ratio=1: obtain fibrous crude product 3) into, the crude product that collection is separated out, after water repetitive scrubbing, filter, pulverize, dry, obtain semiaromatic polyimide resin, productive rate is 98%, number-average molecular weight (M n) be 7.9 * 10 4g/mol.
FT-IR(film，cm -1)：3075，2936，1779，1717，1597，1495，1474，1388，1328，1243，1186，1044。As shown in Figure 7.
Semiaromatic polyimide resin is dissolved in dimethyl sulfoxide (DMSO) (DMSO), obtain the resin solution that solid content is 35wt.%, after filtration, after vacuum defoamation, be coated on ganoid sheet glass or stainless steel plate, under air atmosphere after 80 ℃/2 hours, 120 ℃/1 hour, 160 ℃/1 hour, 180 ℃/1 hour, 200 ℃/1 hour ladder-elevating temperature heat is dried, by making thin film automatic stripping in sheet glass or stainless steel plate immersion deionized water, after 120 ℃ of vacuum-drying, obtain certain thickness transparent polyimide film.The thickness of film can be controlled by the film model of roller of adjusting.The salient features of this Kapton is in Table 1.
By the diamines using in the present embodiment 1, two (2-trifluoromethyl-4-aminophenoxyl) benzene of 4-replaces with 4,4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) biphenyl, adopts the preparation condition identical with the present embodiment can obtain the colourless high transparent polyimide film that thermal characteristics, mechanical property and optical property etc. are suitable.
The preparation of embodiment 13, copolyimide films
Is being furnished with mechanical stirring, water trap, in the there-necked flask of nitrogen gangway and thermometer, add 3.20 grams of (0.005 moles) 3, 3 ', 5, 5 '-tetrafluoro-4, 4 '-bis-(3-trifluoromethyl-5-amino-benzene oxygen) sulfobenzide, 17.84 grams of (0.045 moles) 4, 4 '-bis-(2-methyl-4-amino-benzene oxygen) biphenyl and 316 milliliters of N, N-N,N-DIMETHYLACETAMIDE (DMAc), under nitrogen protection, be stirred to after dissolving completely, add 6.26 grams of (0.025 mole) dicyclos [2.2.2] pungent-2, 3, 5, 6-tetracarboxylic dianhydride (BODA) and 5.60 grams of (0.025 moles) 1, 2, 4, 5-hexanaphthene tetracarboxylic dianhydride (CHDA), be stirred to whole dissolvings, obtain the homogeneous phase solution that solid content is 10wt.%.3.96g (0.05 mole) pyridine and 40 milliliters of toluene are joined in above-mentioned homogeneous phase solution, and reaction system was warming up to 160 ℃ of reactions after 36 hours, steamed toluene, stopped heating.After reaction solution is cooled to 80-120 ℃, pour in ethanol and obtain fibrous crude product, collect the crude product of separating out, with filtering, pulverize, dry after second alcohol and water repetitive scrubbing, obtain semiaromatic polyimide resin, productive rate is 95%, number-average molecular weight (M n) be 1.0 * 10 5g/mol.
FT-IR(film，cm -1)：3042，2956，1785，1721，1600，1492，1439，1384，1321，1248，1167，1053。
Semiaromatic polyimide resin is dissolved in to N, in N-N,N-DIMETHYLACETAMIDE (DMAc), obtain the resin solution that solid content is 10wt.%, after filtration, after vacuum defoamation, be coated on ganoid sheet glass or stainless steel plate, under air atmosphere after 80 ℃/2 hours, 120 ℃/1 hour, 160 ℃/1 hour, 180 ℃/1 hour ladder-elevating temperature heat is dried, by making thin film automatic stripping in sheet glass or stainless steel plate immersion deionized water, after 120 ℃ of vacuum-drying, obtain certain thickness transparent polyimide film.The thickness of film can be controlled by the film model of roller of adjusting.The salient features of this Kapton is in Table 1.
By the dianhydride using in the present embodiment, it is dicyclo [2.2.2] pungent-2, 3, 5, 6-tetracarboxylic dianhydride (BODA) replaces with dicyclo [2.2.1] heptan-2, 3, 5, 6-tetracarboxylic dianhydride (BHDA), or by 1, 2, 4, 5-hexanaphthene tetracarboxylic dianhydride (CHDA) replaces with 1, 2, 3, 4-tetramethylene tetracarboxylic dianhydride (CBDA), the diamines that the present embodiment can be used is in addition 3, 3 ', 5, 5 '-tetrafluoro-4, 4 '-bis-(3-trifluoromethyl-5-amino-benzene oxygen) sulfobenzide replaces with 3, 3 ', 5, 5 '-tetra-(trifluoromethyl)-4, 4 '-bis-(the fluoro-5-amino-benzene oxygen of 3-) sulfobenzide, or by another kind of diamines 4, 4 '-bis-(2-methyl-4-amino-benzene oxygen) biphenyl replaces with 4, 4 '-bis-(2-methyl-4-amino-benzene oxygen) benzene, adopt the preparation condition identical with the present embodiment can obtain thermal characteristics, the colourless high transparent polyimide film that mechanical property and optical property etc. are suitable.
The preparation of embodiment 14, copolyimide films
Is being furnished with mechanical stirring, water trap, in the there-necked flask of nitrogen gangway and thermometer, add 52.84 grams of (0.075 moles) 3, 3 ', 5, 5 '-tetra-(trifluoromethyl)-4, 4 '-bis-(3-amino-benzene oxygen) sulfobenzide, 10.34 grams of (0.02 moles) 2, 2 '-bis-(4-amino-benzene oxygen phenyl) HFC-236fa and 180 milliliters of dimethyl sulfoxide (DMSO) (DMSO), under nitrogen protection, be stirred to after dissolving completely, add 11.21 grams of (0.05 moles) 1, 2, 4, 5-hexanaphthene tetracarboxylic dianhydride (CHDA) and 10.51 grams of (0.05 moles) 1, 2, 4, 5-pentamethylene tetracarboxylic dianhydride (CPDA), be stirred to whole dissolvings, obtain the homogeneous phase solution that solid content is 30wt.%.6.07 grams of (0.06 mole) triethylamines and 23 milliliters of toluene are joined in above-mentioned homogeneous phase solution, and reaction system was warming up to 175 ℃ of reactions after 32 hours, steamed toluene, stopped heating.After being cooled to 80-120 ℃, pours reaction solution ethanol/primary isoamyl alcohol mixing solutions (ethanol/primary isoamyl alcohol volume ratio=3: obtain fibrous crude product 1) into, the crude product that collection is separated out, with filtering after ethanol repetitive scrubbing, pulverize, drying, obtain semiaromatic polyimide resin, productive rate is 95%, number-average molecular weight (M n) be 4.0 * 10 4g/mol.
FT-IR(film，cm -1)：2940，1783，1718，1603，1544，1477，1432，1380，1315，1209，1103，1034。
Semiaromatic polyimide resin is dissolved in to N, in dinethylformamide (DMF), obtain the resin solution that solid content is 30wt.%, after filtration, after vacuum defoamation, be coated on ganoid sheet glass or stainless steel plate, under air atmosphere after 80 ℃/2 hours, 120 ℃/1 hour, 160 ℃/1 hour, 180 ℃/1 hour ladder-elevating temperature heat is dried, by making thin film automatic stripping in sheet glass or stainless steel plate immersion deionized water, after 120 ℃ of vacuum-drying, obtain certain thickness transparent polyimide film.The thickness of film can be controlled by the film model of roller of adjusting.The salient features of this Kapton is in Table 1.
By the dianhydride using in the present embodiment, be 1,2,4,5-hexanaphthene tetracarboxylic dianhydride (CHDA) replaces with decahydro biphenyl-3,3 ', 4,4 '-tetracarboxylic dianhydride (HBPDA), or by 2 in diamines, 2 '-bis-(4-amino-benzene oxygen phenyl) HFC-236fa replaces with 2,2 '-bis-(4-amino-benzene oxygen phenyl) propane, adopts the preparation condition identical with the present embodiment can obtain the colourless high transparent polyimide film that thermal characteristics, mechanical property and optical property etc. are suitable.
The preparation of embodiment 15, copolyimide films
Is being furnished with mechanical stirring, water trap, in the there-necked flask of nitrogen gangway and thermometer, add 17.90 grams of (0.03 moles) 3, 3 '-bis-(3-trifluoromethyl-5-amino-benzene oxygens)-5, 5 '-diphenylsulfone dimethyl, 38.26 grams of (0.07 moles) 2, 2 '-bis-(2-trifluoromethyl-4-aminophenoxyl phenyl) propane and 118 milliliters of N-Methyl pyrrolidone (NMP), under nitrogen protection, be stirred to after dissolving completely, add 9.81 grams of (0.05 moles) 1, 2, 3, 4-tetramethylene tetracarboxylic dianhydride (CBDA) and 15.32 grams of (0.05 mole) decahydro biphenyl-3, 3 ', 4, 4 '-tetracarboxylic dianhydride (HBPDA), be stirred to whole dissolvings, obtain the homogeneous phase solution that solid content is 40wt.%.6.07 grams of (0.06 mole) triethylamines and 14 milliliters of toluene are joined in above-mentioned homogeneous phase solution, and reaction system was warming up to 180 ℃ of reactions after 24 hours, steamed toluene, stopped heating.After reaction solution is cooled to 80-120 ℃, pour in ethanol and obtain fibrous crude product, collect the crude product of separating out, with filtering, pulverize, dry after second alcohol and water repetitive scrubbing, obtain semiaromatic polyimide resin, productive rate is 97%, number-average molecular weight (M n) be 9.3 * 10 4g/mol.
FT-IR(film，cm -1)：2927，1781，1721，1600，1528，1486，1445，1368，1320，1195，1087，1045。
Semiaromatic polyimide resin is dissolved in to N-Methyl pyrrolidone (NMP) and N, mixed solvent (NMP/DMAC volume ratio=1: 1) of N-N,N-DIMETHYLACETAMIDE (DMAc), obtain the resin solution that solid content is 45wt.%, after filtration, after vacuum defoamation, be coated on ganoid sheet glass or stainless steel plate, under air atmosphere through 80 ℃/2 hours, 120 ℃/1 hour, 160 ℃/1 hour, 180 ℃/1 hour, after within 200 ℃/1 hour, ladder-elevating temperature heat is dried, to in sheet glass or stainless steel plate immersion deionized water, make thin film automatic stripping, after 120 ℃ of vacuum-drying, obtain certain thickness transparent polyimide film.The thickness of film can be controlled by the film model of roller of adjusting.The salient features of this Kapton is in Table 1.
By the dianhydride using in the present embodiment, be 1, 2, 3, 4-tetramethylene tetracarboxylic dianhydride (CBDA) replaces with 1, 2, 4, 5-pentamethylene tetracarboxylic dianhydride (CPDA), or by decahydro biphenyl-3, 3 ', 4, 4 '-tetracarboxylic dianhydride (HBPDA) replaces with 1, 2, 4, 5-hexanaphthene tetracarboxylic dianhydride (CHDA), can be 3 by used diamines in addition, 3 '-bis-(3-trifluoromethyl-5-amino-benzene oxygens)-5, 5 '-diphenylsulfone dimethyl replaces with 3, 3 '-bis-(3-methyl-5-amino-benzene oxygens)-5, 5 '-bis-(trifluoromethyl) sulfobenzide, or by another kind of diamines 2, 2 '-bis-(2-trifluoromethyl-4-aminophenoxyl phenyl) propane replaces with 2, 2 '-bis-(2-trifluoromethyl-4-aminophenoxyl phenyl) HFC-236fa, adopt the preparation condition identical with the present embodiment can obtain thermal characteristics, the colourless high transparent polyimide film that mechanical property and optical property etc. are suitable.
The preparation of embodiment 16, copolyimide films
Is being furnished with mechanical stirring, water trap, in the there-necked flask of nitrogen gangway and thermometer, add 29.30 grams of (0.04 moles) 3, 3 ', 5, 5 '-tetra-(trifluoromethyl)-4, 4 '-bis-(3-methyl-5-amino-benzene oxygen) sulfobenzide, 25.95 grams of (0.06 moles) 4, 4 '-bis-(4-amino-benzene oxygen) sulfobenzides and 230 milliliters of N-Methyl pyrrolidone (NMP), under nitrogen protection, be stirred to after dissolving completely, add 11.21 grams of (0.05 moles) 1, 2, 4, 5-hexanaphthene tetracarboxylic dianhydride (CHDA) and 12.41 grams of (0.05 mole) dicyclos [2.2.2] are pungent-7-alkene-2, 3, 5, 6-tetracarboxylic dianhydride (BCDA), be stirred to whole dissolvings, obtain the homogeneous phase solution that solid content is 25wt.%.6.07 grams of (0.06 mole) triethylamines and 23 milliliters of toluene are joined in above-mentioned homogeneous phase solution, and reaction system was warming up to 180 ℃ of reactions after 24 hours, steamed toluene, stopped heating.After reaction solution is cooled to 80-120 ℃, pour in methyl alcohol and obtain fibrous crude product, collect the crude product of separating out, with filtering, pulverize, dry after first alcohol and water repetitive scrubbing, obtain semiaromatic polyimide resin, productive rate is 97%, number-average molecular weight (M n) be 5.7 * 10 4g/mol.
FT-IR(film，cm -1)：3072，2965，1782，1722，1588，1491，1437，1381，1320，1251，1150，1054。As shown in Figure 8.
Semiaromatic polyimide resin is dissolved in N-Methyl pyrrolidone (NMP), obtain the resin solution that solid content is 35wt.%, after filtration, after vacuum defoamation, be coated on ganoid sheet glass or stainless steel plate, under air atmosphere after 80 ℃/2 hours, 120 ℃/1 hour, 160 ℃/1 hour, 180 ℃/1 hour, 200 ℃/1 hour ladder-elevating temperature heat is dried, by making thin film automatic stripping in sheet glass or stainless steel plate immersion deionized water, after 120 ℃ of vacuum-drying, obtain certain thickness transparent polyimide film.The thickness of film can be controlled by the film model of roller of adjusting.The salient features of this Kapton is in Table 1.
By the dianhydride using in the present embodiment, be 1, 2, 4, 5-hexanaphthene tetracarboxylic dianhydride (CHDA) replaces with decahydro biphenyl-3, 3 ', 4, 4 '-tetracarboxylic dianhydride (HBPDA), or be 3 by used diamines, 3 ', 5, 5 '-tetra-(trifluoromethyl)-4, 4 '-bis-(3-methyl-5-amino-benzene oxygen) sulfobenzide replaces with 3, 3 ', 5, 5 '-tetramethyl--4, 4 '-bis-(3-trifluoromethyl-5-amino-benzene oxygen) hexichol, in addition can be by another kind of diamines 4, 4 '-bis-(4-amino-benzene oxygen) sulfobenzide replaces with 4, 4 '-bis-(2-methyl-4-amino-benzene oxygen) sulfobenzide, adopt the preparation condition identical with the present embodiment can obtain thermal characteristics, the colourless high transparent polyimide film that mechanical property and optical property etc. are suitable.
The salient features of table 1, Kapton
Figure BDA0000151805550000201
athe thermal characteristics of film adopts differential scanning calorimetric analysis and thermogravimetic analysis (TGA) to measure, wherein T gfor second-order transition temperature, T dfor initial heat decomposition temperature (nitrogen atmosphere);
bthe mechanical property of film adopts universal testing machine to measure according to GB/T 1040.3-2006, T sfor tensile strength, T mfor tensile modulus;
cthe optical property of film adopts ultraviolet-visible light (UV-vis) absorption spectrum and color difference meter to measure, and film sample thickness is 100 μ m, wherein λ 0for initial printing opacity wavelength, T 450for 500nm place transmittance, T 500for 500nm place transmittance.

Claims (10)

1. semiaromatic polyimide resin shown in formula I,
Figure FDA0000379773670000011
In described formula I general structure, A1 is any one in following alicyclic structure,
Figure FDA0000379773670000012
In described formula I general structure, R 1shown in II general structure:
Figure FDA0000379773670000013
Wherein, in described formula II general structure, X is H, F, CH 3or CF 3; Y is selected from any one in following radicals:
And in X and Y, have one at least and contain fluorine atom or trifluoromethyl; P=0 or 1;
In described general structure I, R 2be selected from any one in following radicals:
Figure FDA0000379773670000021
M is 1～300 integer, the integer that n is 0～400, and n:m=0～400:1,
The number-average molecular weight of semiaromatic polyimide resin shown in described formula I is 40000～160000g/mol.
2. prepare the method for semiaromatic polyimide resin shown in formula I described in claim 1 for one kind; comprise the steps: under protection of inert gas; aromatic diamines I is dissolved in organic solvent; then add alicyclic dianhydride; being stirred to whole dissolvings obtains after homogeneous phase solution; add again catalyzer and dewatering agent to mix to heat up and react, react the complete described dewatering agent of removing, pour precipitation agent after cooling into and precipitate and obtain semiaromatic polyimide resin shown in described formula I.
3. method according to claim 2, is characterized in that: described aromatic diamines I is fluorine-containing containing sulfone aromatic diamines or the described fluorine-containing mixture containing at least one composition in sulfone aromatic diamines and following aromatic diamines II: 4, and 4 '-diaminodiphenyl oxide, 3,4 '-diaminodiphenyl oxide, DDS, 3,3 '-diaminodiphenylsulfone(DDS), 2,2 '-bis-(trifluoromethyl)-4,4 '-benzidine, α, α '-bis-(4-aminophenyl)-Isosorbide-5-Nitrae-diisopropyl benzene, 4,4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) benzene, 3,3 '-bis-(2-trifluoromethyl-4-aminophenoxyl) benzene, 4,4 '-bis-(2-methyl-4-amino-benzene oxygen) benzene, 3,3 '-bis-(2-methyl-4-amino-benzene oxygen) benzene, 4,4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) biphenyl, 4,4 '-bis-(2-methyl-4-amino-benzene oxygen) biphenyl, 2,2 '-bis-(4-amino-benzene oxygen phenyl) propane, 2,2 '-bis-(4-amino-benzene oxygen phenyl) HFC-236fa, 2,2 '-bis-(2-trifluoromethyl-4-aminophenoxyl phenyl) propane, 2,2 '-bis-(2-trifluoromethyl-4-aminophenoxyl phenyl) HFC-236fa, 4,4 '-bis-(4-amino-benzene oxygen) sulfobenzide and 4,4 '-bis-(2-methyl-4-amino-benzene oxygen) sulfobenzide,
Described fluorine-containing containing sulfone aromatic diamines, be at least one in following: 3,3 '-bis-(4-amino-benzene oxygens)-5,5 '-difluorodiphenyl sulfone, 3,3 '-bis-(3-amino-benzene oxygens)-5,5 '-difluorodiphenyl sulfone, 3,3 '-bis-(4-amino-benzene oxygen)-5,5 '-bis-(trifluoromethyl) sulfobenzide, 3,3 '-bis-(3-amino-benzene oxygen)-5,5 '-bis-(trifluoromethyl) sulfobenzide, 3,3 ', 5,5 '-tetrafluoro-4,4 '-bis-(4-amino-benzene oxygen) sulfobenzide, 3,3 ', 5,5 '-tetrafluoro-4,4 '-bis-(3-amino-benzene oxygen) sulfobenzide, 3,3 ', 5,5 '-tetra-(trifluoromethyl)-4,4 '-bis-(4-amino-benzene oxygen) sulfobenzide, 3,3 ', 5,5 '-tetra-(trifluoromethyl)-4,4 '-bis-(3-amino-benzene oxygen) sulfobenzide, 3,3 '-bis-(2-methyl 4-amino-benzene oxygens)-5,5 '-difluorodiphenyl sulfone, 3,3 '-bis-(3-methyl-5-amino-benzene oxygens)-5,5 '-difluorodiphenyl sulfone, 3,3 '-bis-(2-methyl-4-amino-benzene oxygen)-5,5 '-bis-(trifluoromethyl) sulfobenzide, 3,3 '-bis-(3-methyl-5-amino-benzene oxygen)-5,5 '-bis-(trifluoromethyl) sulfobenzide, 3,3 ', 5,5 '-tetrafluoro-4,4 '-bis-(2-methyl-4-amino-benzene oxygen) sulfobenzide, 3,3 ', 5,5 '-tetrafluoro-4,4 '-bis-(3-methyl-5-amino-benzene oxygen) sulfobenzide, 3,3 ', 5,5 '-tetra-(trifluoromethyl)-4,4 '-bis-(2-methyl-4-amino-benzene oxygen) sulfobenzide, 3,3 ', 5,5 '-tetra-(trifluoromethyl)-4,4 '-bis-(3-methyl-5-amino-benzene oxygen) sulfobenzide, 2,2 '-bis-fluoro-DDSs, 3,3 '-bis-is fluoro-5,5 '-diaminodiphenylsulfone(DDS), 3,3 '-bis-(the fluoro-4-amino-benzene oxygen of 2-) sulfobenzide, 3,3 '-bis-(the fluoro-5-amino-benzene oxygen of 3-) sulfobenzide, 3,3 '-bis-(fluoro-4-amino-benzene oxygens of 2-)-5,5 '-difluorodiphenyl sulfone, 3,3 '-bis-(fluoro-5-amino-benzene oxygens of 3-)-5,5 '-difluorodiphenyl sulfone, 3,3 '-bis-(fluoro-4-amino-benzene oxygens of 2-)-5,5 '-diphenylsulfone dimethyl, 3,3 '-bis-(fluoro-5-amino-benzene oxygens of 3-)-5,5 '-diphenylsulfone dimethyl, 3,3 '-bis-(the fluoro-4-amino-benzene oxygen of 2-)-5,5 '-bis-(trifluoromethyl) sulfobenzide, 3,3 '-bis-(the fluoro-5-amino-benzene oxygen of 3-)-5,5 '-bis-(trifluoromethyl) sulfobenzide, 4,4 '-bis-(the fluoro-4-amino-benzene oxygen of 2-) sulfobenzide, 4,4 '-bis-(the fluoro-5-amino-benzene oxygen of 3-) sulfobenzide, 3,3 ', 5,5 '-tetrafluoro-4,4 '-bis-(the fluoro-4-amino-benzene oxygen of 2-) sulfobenzide, 3,3 ', 5,5 '-tetrafluoro-4,4 '-bis-(the fluoro-5-amino-benzene oxygen of 3-) sulfobenzide, 3,3 ', 5,5 '-tetramethyl--4,4 '-bis-(the fluoro-4-amino-benzene oxygen of 2-) sulfobenzide, 3,3 ', 5,5 '-tetramethyl--4,4 '-bis-(the fluoro-5-amino-benzene oxygen of 3-) sulfobenzide, 3,3 ', 5,5 '-tetra-(trifluoromethyl)-4,4 '-bis-(the fluoro-4-amino-benzene oxygen of 2-) sulfobenzide, 3,3 ', 5,5 '-tetra-(trifluoromethyl)-4,4 '-bis-(the fluoro-5-amino-benzene oxygen of 3-) sulfobenzide, 2,2 '-bis-(trifluoromethyl)-DDSs, 3,3 '-bis-(trifluoromethyl)-5,5 '-diaminodiphenylsulfone(DDS), 3,3 '-bis-(2-trifluoromethyl-4-aminophenoxyl) sulfobenzide, 3,3 '-bis-(3-trifluoromethyl-5-amino-benzene oxygen) sulfobenzide, 3,3 '-bis-(2-trifluoromethyl-4-aminophenoxyls)-5,5 '-difluorodiphenyl sulfone, 3,3 '-bis-(3-trifluoromethyl-5-amino-benzene oxygens)-5,5 '-difluorodiphenyl sulfone, 3,3 '-bis-(2-trifluoromethyl-4-aminophenoxyls)-5,5 '-diphenylsulfone dimethyl, 3,3 '-bis-(3-trifluoromethyl-5-amino-benzene oxygens)-5,5 '-diphenylsulfone dimethyl, 3,3 '-bis-(2-trifluoromethyl-4-aminophenoxyl)-5,5 '-bis-(trifluoromethyl) sulfobenzide, 3,3 '-bis-(3-trifluoromethyl-5-amino-benzene oxygen)-5,5 '-bis-(trifluoromethyl) sulfobenzide, 4,4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) sulfobenzide, 4,4 '-bis-(3-trifluoromethyl-5-amino-benzene oxygen) sulfobenzide, 3,3 ', 5,5 '-tetrafluoro-4,4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) sulfobenzide, 3,3 ', 5,5 '-tetrafluoro-4,4 '-bis-(3-trifluoromethyl-5-amino-benzene oxygen) sulfobenzide, 3,3 ', 5,5 '-tetramethyl--4,4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) sulfobenzide, 3,3 ', 5,5 '-tetramethyl--4,4 '-bis-(3-trifluoromethyl-5-amino-benzene oxygen) sulfobenzide, 3,3 ', 5,5 '-tetra-(trifluoromethyl)-4,4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) sulfobenzide and 3,3 ', 5,5 '-tetra-(trifluoromethyl)-4,4 '-bis-(3-trifluoromethyl-5-amino-benzene oxygen) sulfobenzide,
Described alicyclic dianhydride is 1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2,4,5-pentamethylene tetracarboxylic dianhydride, 2,3,5-tricarboxylic basic ring pentyl acetic acid dianhydride, 1,2,4,5-hexanaphthene tetracarboxylic dianhydride, dicyclo [2.2.1] heptan-2,3,5,6-tetracarboxylic dianhydride, 3,4,6-tri-carboxyl dicyclo [2.2.2] heptane guanidine-acetic acid dianhydrides, dicyclo [2.2.2] pungent-2,3,5,6-tetracarboxylic dianhydride, dicyclo [2.2.2] be pungent-7-alkene-2,3,5,6-tetracarboxylic dianhydride, decahydro-1,4,5,8-dimethylene naphthalene-2,3,6,7-tetracarboxylic dianhydride or decahydro biphenyl-3,3 ', 4,4 '-tetracarboxylic dianhydride;
Described organic solvent be selected from N-Methyl pyrrolidone, gamma-butyrolactone, hexamethylphosphoramide, dimethyl sulfoxide (DMSO), N,N-dimethylacetamide and DMF at least one;
Described catalyzer is triethylamine, tripropyl amine, tributylamine, trolamine, pyridine, imidazoles, quinoline or isoquinoline 99.9;
Described dewatering agent is toluene or dimethylbenzene;
Described precipitation agent is selected from least one in water, methyl alcohol, ethanol, propyl alcohol, butanols, Virahol, Pentyl alcohol and primary isoamyl alcohol.
4. it is characterized in that according to the method in claim 2 or 3: the molar ratio example of described aromatic diamines I and alicyclic dianhydride is 0.9～1.1: 1.0; The solid content quality percentage composition of described homogeneous phase solution is 10～50%;
The molar ratio example of described catalyzer and described aromatic diamines is 0.01～1.0: 1.0;
In described reactions steps, temperature is 140～180 ℃, and the time is 6～48 hours.
5. by Kapton that described in claim 1, shown in formula I, semiaromatic polyimide resin is made.
6. film according to claim 5, is characterized in that: the initial printing opacity wavelength of described film below 300nm, transmittance >=90% in visible region; The thickness of described film is 25～150 μ m.
7. a method of preparing film described in claim 5 or 6, comprise the steps: semiaromatic polyimide resin shown in formula I described in claim 1 to be dissolved in organic solvent, obtain being coated in substrate after resin solution, after oven dry, immerse in deionized water and peel off, obtain described Kapton.
8. method according to claim 7, is characterized in that: described organic solvent is selected from least one in N-Methyl pyrrolidone, gamma-butyrolactone, dimethyl sulfoxide (DMSO), N,N-dimethylacetamide and DMF;
The material that forms described substrate is sheet glass or stainless steel plate;
The solid content quality percentage composition of described resin solution is 10～50%;
In described baking step, temperature is 80～200 ℃, and the time is 1～6 hour.
9. the arbitrary described film of claim 5 or 6 application in preparing photoelectric device as base material:
Contain and using the photoelectric device of the arbitrary described film of claim 5 or 6 as base material.
10. application according to claim 9, is characterized in that: described photoelectric device is selected from least one in solar cell, indicating meter, e-book, electronic tag and photo-sensor;
Described base material is selected from least one in flexible solar cell substrates, flexible display substrate and compliant conductive film base material.
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