CN101787129A - Soluble and high-temperature resistant aromatic polyimide and preparation method thereof - Google Patents
Soluble and high-temperature resistant aromatic polyimide and preparation method thereof Download PDFInfo
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- CN101787129A CN101787129A CN 201010117153 CN201010117153A CN101787129A CN 101787129 A CN101787129 A CN 101787129A CN 201010117153 CN201010117153 CN 201010117153 CN 201010117153 A CN201010117153 A CN 201010117153A CN 101787129 A CN101787129 A CN 101787129A
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Abstract
The invention discloses soluble and high-temperature resistant aromatic polyimide and a preparation method thereof. The preparation method comprises the following steps: stirring a 2,2'-R,R-4,4'-diaminodiphenyl compound and a 2,2'-R,R-4,4',5,5'-diphenyltetracarboxylic dianhydride compound in molar ratio of 1 to 1 in a strongly polar non-proton organic solvent at the room temperature to obtain homogeneous-phase, transparent and viscous polyimide solution; and dehydrating the polyimide solution to obtain the soluble and high-temperature resistant aromatic polyimide. The soluble and high-temperature resistant aromatic polyimide has the polyimide of the repetitive unit of a general formula [1] that number average molecular weight Mn is equal to 8,000 to 20,000; molecular weight distribution Mw/Mn is equal to 1.2 to 1.7; and R is a group in the 2,2'-R,R-4,4'-diaminodiphenyl compound, and R' is a group in the 2,2'-R,R-4,4',5,5'-diphenyltetracarboxylic dianhydride compound. The aromatic polyimide is soluble in the high-temperature or chemical dehydration full ring closure of weakly polar solvents.
Description
Technical field
The invention belongs to the aromatic polyimide synthetic technology, particularly a kind of solubility high-temperature resistant aromatic polyimide and preparation method thereof.
Background technology
Polyimide is the very excellent polymkeric substance of a class over-all properties, has very good thermotolerance, lower temperature resistance, self lubricity, radiation resistance and characteristic such as fire-retardant, has excellent mechanical property and dielectric properties simultaneously.Therefore, it is widely used in the high temperature resistant radiative material of spaceship, satellite, space craft etc.; The advanced configuration matrix material of aspects such as aerospace, automobile, electromechanics, insulating material, high temperature resistant gluing agent, high temperature sealing material etc.; Can be used for the body material of FPC or PCB, interlayer dielectic, great scale integrated circuit passivating coating and the alpha-particle blocking layer coating material etc. of IC at microelectronic.
Common polyimide both infusibility melt also insoluble characteristics make they be difficult to processing and moulding, thereby have a strong impact on its using value.The secondary processing of being made film, coating and other members by insoluble aromatic polyimide needs complicated technology usually.For example film can be made by the soluble polyimide acid precursor of insoluble polyimide.This film makes this precursor film change into Kapton through heat dehydration or chemical dehydration after removing excessive solvent.Remain some problems in addition, for example in the middle of the process of cure stage, cause the formation of pin hole owing to the water volatilization of by product.
Though people do not understand fully as yet fully to the structure of polyimide and the relation of solubility property at present, but a large amount of studies show that, polyimide have higher softening-melt temperature and the insoluble in organic solvent, all result from characteristics such as reactive force between molecule chain rigidity and the stronger molecular chain and crystallinity.Because the interaction between the strong molecular chain that electronics polarity and crystallinity produce causes the polyimide molecule chain closely to be piled up, thereby has improved the melt temperature and the solvent resistance of polyimide.It is generally acknowledged, the factor of impact polymer solubility property mainly comprises the reactive force between the polymer molecule, as the crystallizing power of Van der Waals force, hydrogen bond and polymkeric substance (influenced by the crystallizing power etc. of symmetry, regularity, snappiness and the multipolymer of polymer chain).
Polyimide adhesive is also used to some extent in the FPC of microelectronic system, but often has phenomenons such as bonding strength is on the low side, solidification value is higher, is unfavorable for industrialization and the following process of FPC.
U.S. Pat 7026436 discloses a kind of preparation method of polyimide adhesive, with bonding Copper Foil and Kapton, be primarily characterized in that: aromatic series dianhydride and diamines (wherein diamines is made up of aliphatie diamine and the 10mol%～50mol% aromatic diamine of 50mol%～90mol%) obtain polyimide adhesive by condensation reaction, are used for the bonding of FPC or PCB or hard and soft printed circuit board.
The shortcoming of this method is: owing to used a large amount of aliphatic diamines, cause the thermotolerance of adhesive composition to descend greatly, its glass transition temperature is at 150～200 ℃, thereby limited the use of printed circuit board in hot environment.
Japanese Patent JP62-278687 discloses a kind of preparation method of polyimide adhesive, with bonding Copper Foil and Kapton, be primarily characterized in that: the siloxanes segment is introduced in the polyimide skeleton structure, to improve the cohesive strength between Copper Foil and Kapton base material, yet its defective is also apparent: the second-order transition temperature of polyimide adhesive system descends greatly during the introducing of siloxanes segment, the phenomenon of phase separation that adhesive composition also can occur simultaneously.Therefore, be difficult to make the polyimide adhesive system of homogeneous phase transparent.
U.S. Pat 520074 discloses a kind of preparation method of polyimide adhesive, with bonding Copper Foil and polyimide, is primarily characterized in that: bismaleimides and polyamic acid through modification are formed the polyimide adhesive system.Its main drawback is: need carry out long term high temperature and solidify under 350 ℃ hot conditions.This not only expends the energy, equipment has been proposed higher technical requirements, and makes Copper Foil generation oxidizing reaction again easily.
Summary of the invention
The object of the present invention is to provide a kind of dissolving in than the high temperature of weak polar solvent or aromatic polyimide of chemical dehydration loopfulization and preparation method thereof.
The technical solution that realizes the object of the invention is:
A kind of solubility high-temperature resistant aromatic polyimide has the polyimide of general formula [1] repeating unit:
Number-average molecular weight Mn=8000-20000; Molecular weight distribution mw/mn=1.2-1.7; R is 2,2 '-R, R-4,4 '-the benzidine compound in group; R ' is 2,2 '-R ', R '-4,4 ', 5,5 '-the BPDA compound in group.
A kind of solubility high-temperature resistant aromatic polyimide preparation method, mol ratio be 1: 12,2 '-R, R-4,4 '-benzidine compound and 2,2 '-R ', R '-4,4 ', 5,5 '-the BPDA compound in strong polar non-proton organic solvent, under room temperature, stir, obtain homogeneous phase, transparent, heavy-gravity polyamic acid solution, and polyamic acid solution dewatered obtain the solubility high-temperature resistant aromatic polyimide.
The present invention compared with prior art, its remarkable advantage:
(1) polyimide contains big fragrant side group group, the introducing of these groups can destroy monomeric regularity, making polymkeric substance carry out non-copline arranges, solved material because main chain phenyl ring rigidity and the little problem of solvability, big free volume can reduce the specific inductivity of polymkeric substance and improve photopermeability simultaneously.
(2) polyimide has excellent thermostability, and glass transition temperature and decomposition temperature all up to more than 500 ℃, can be used as resistant to elevated temperatures sizing agent.
(3) the fluorine-containing monomer of some of them, the diamine monomer of different fluorine contents and fluoric-containing acid anhydride monomer gather with, but the fluorine content of telomerized polymer is further regulated the specific refractory power of material and is improved translucidus, and this just promptly can be applicable to optical waveguide material for material provides a kind of new application.
Below in conjunction with accompanying drawing the present invention is described in further detail.
Embodiment
Solubility high-temperature resistant aromatic polyimide of the present invention has the polyimide of general formula [1] repeating unit:
Number-average molecular weight Mn=8000-20000; Molecular weight distribution mw/mn=1.2-1.7; R is 2,2 '-R, R-4,4 '-the benzidine compound in group; R ' is 2,2 '-R ', R '-4,4 ', 5,5 '-the BPDA compound in group.
The synthetic above-mentioned resistant to elevated temperatures polyimide of solubilized with general formula [1], comprise the steps: (1) mol ratio be 1: 12,2 '-R, R-4,4 '-benzidine compound and 2,2 '-R ', R '-4,4 ', 5,5 '-the BPDA compound is in strong polar non-proton organic solvent, after stirred for several under the room temperature hour, obtain homogeneous phase, transparent, heavy-gravity polyamic acid solution.(2) dewatering: 1. in the nitrogen atmosphere, add dewatering agent, reflux dehydration imidization 1～6 hour is cooled to pour into after the room temperature and obtains the polyimide precipitation in the methyl alcohol, and filtration drying promptly obtains the polyimide solid; Perhaps 2. polyamic acid solution is coated on the substrate material, is heated to the high temperature cyclodehydration, promptly gets Kapton.Described stirring at room is to stir 4h～48h down at 20 ℃～30 ℃.The chemical dehydration reflux temperature is 100 ℃～160 ℃.Chemical dehydrator is pyridine/diacetyl oxide, triethylamine/diacetyl oxide and sodium acetate/diacetyl oxide.The temperature of high temperature cyclodehydration is 200 ℃～300 ℃.
Above-mentioned strong polar non-proton organic solvent is N, dinethylformamide (DMF), N, N-N,N-DIMETHYLACETAMIDE (DMAc), N-Methyl pyrrolidone (NMP), 1,3-dimethyl-2-imidazolidone (DMI), tetrahydrofuran (THF) (THF), 1,4-dioxane (OD), dimethyl sulfoxide (DMSO) (DMSO), dimethyl sulfone (MSM), the mixture of one or more in the tetramethylene sulfone.
Chemical equation of the present invention is as follows:
Below in conjunction with specific embodiment, further set forth the present invention.
Embodiment 1
Under nitrogen protection, add 0.5965g (1mmol) 2,2 '-two (4 " (3 ' " in the there-necked flask; 4 ' ", 5 ' " trifluorophenyl)) phenyl-4,4 '-benzidine and 5mL N; dinethylformamide; be stirred to solid under the room temperature and all dissolve, add 0.2942g (1mmol) 3,3 '; 4; 4 '-BPDA, continue stirring at room 4h, obtain thickness, homogeneous phase, faint yellow transparent polyamic acid solution.Add 5mL N again, dinethylformamide dilutes system, adds the mixture of equimolar diacetyl oxide/pyridine then, is warming up to 100 ℃, continues to stir 4h.Body obtains the reddish-brown polyimide adhesive after being cooled to room temperature.Get half solution and pour in the 20mL methyl alcohol, a large amount of yellow mercury oxides are separated out, and filter, and wash washing successively with methyl alcohol.100 ℃ of dryings of vacuum obtain the faint yellow solid powder.Infrared data (KBr compressing tablet, cm
-1): 1777cm
-1(the C=O symmetry is flexible), 1723cm
-1(C=O asymmetric stretch), 1363cm
-1(C-N stretching vibration), 1043cm
-1(C-F stretching vibration), 831cm
-1(1,4-substituted benzene ring C-H out-of-plane deformation vibration).Collosol and gel chromatogram (CPG) determining molecular weight, Mn=13008, Mw/Mn=1.54.Ultimate analysis: theoretical value: C, 73.07%; H, 2.83%; N, 3.28%.Measured value: C, 72.67%; H, 3.11%; N, 3.24%.Under nitrogen atmosphere, TGA thermogravimetric analysis: T
d=538 ℃, T
10%=599 ℃, the remaining rate 69.54% in the time of 800 ℃.Dsc analysis, temperature are higher than 400 ℃ and do not observe glass transition temperature yet.
This polyimide can be dissolved in toluene, acetone, methylene dichloride, chloroform, N-Methyl pyrrolidone, N,N-DIMETHYLACETAMIDE, dimethyl formamide, tetrahydrofuran (THF), dioxane and the meta-cresol greater than 20% solids content (based on polymkeric substance).Polyimide is in the N,N-dimethylacetamide solution of 0.5g/dL, and the limiting viscosity in the time of 30 ℃ is 0.65dL/g.
After being coated on the polyimide adhesive of not pouring methyl alcohol on the Kapton base material that surface corona handles, with the compound hot pressing moulding of Copper Foil, curing process is: room temperature → 60 ℃/1h+100 ℃/1h+140 ℃/1h+180 ℃/1h+220 ℃/1h.The stripping strength of gained Kapton base material and Copper Foil is 1.24N/mm.
Embodiment 2
Under nitrogen protection, add 0.5965g (1mmol) 2,2 '-two (4 " (3 ' " in the there-necked flask; 4 ' ", 5 ' " trifluorophenyl)) phenyl-4,4 '-benzidine and 5mL N; be stirred to solid under the N-N,N-DIMETHYLACETAMIDE, room temperature and all dissolve, add 0.4464g (1mmol) 2; 2 '-phenylbenzene-4; 4 ', 5,5 '-BPDA; continue stirring at room 10h, obtain thickness, homogeneous phase, faint yellow transparent polyamic acid solution.Add the 5mL N,N-dimethylacetamide again system is diluted, add the mixture of equimolar diacetyl oxide/pyridine then, be warming up to 120 ℃, continue to stir 4h.Be cooled to room temperature and obtain polyimide adhesive.Get half solution and pour in the 20mL methyl alcohol, a large amount of yellow mercury oxides are separated out, and filter, and wash washing successively with methyl alcohol.100 ℃ of dryings of vacuum obtain the faint yellow solid powder.Infrared data (KBr compressing tablet, cm
-1): 1778cm
-1(the C=O symmetry is flexible), 1724cm
-1(C=O asymmetric stretch), 1364cm
-1(C-N stretching vibration), 1043cm
-1(C-F stretching vibration), 831cm
-1(1,4-substituted benzene ring C-H out-of-plane deformation vibration).768,699cm
-1(single-substituted ring C-H out-of-plane deformation vibration).Collosol and gel chromatogram (CPG) determining molecular weight, Mn=8543, Mw/Mn=1.65.Ultimate analysis: theoretical value: C, 76.34%; H, 3.20%; N, 2.78%.Measured value: C, 76.53%; H, 3.47%; N, 2.69%.Under nitrogen atmosphere, TGA thermogravimetric analysis: T
d=556 ℃, T
10%=593 ℃, the remaining rate 69.95% in the time of 800 ℃.Dsc analysis is examined glass transition temperature T
g=542 ℃.
This polyimide can be dissolved in toluene, acetone, methylene dichloride, chloroform, N-Methyl pyrrolidone, N,N-DIMETHYLACETAMIDE, dimethyl formamide, tetrahydrofuran (THF), dioxane and the meta-cresol greater than 20% solids content (based on polymkeric substance).In the N,N-dimethylacetamide solution of 0.5g/dL, the limiting viscosity in the time of 30 ℃ is 0.54dL/g.
After being coated on the polyimide adhesive of not pouring methyl alcohol on the Kapton base material that surface corona handles, with the compound hot pressing moulding of Copper Foil, curing process is: room temperature → 60 ℃/1h+100 ℃/1h+140 ℃/1h+180 ℃/1h+240 ℃/1h.The stripping strength of gained Kapton base material and Copper Foil is 1.29N/mm.
Embodiment 3
Under nitrogen protection, add 0.5965g (1mmol) 2,2 '-two (4 " (3 ' " in the there-necked flask; 4 ' ", 5 ' " trifluorophenyl)) phenyl-4,4 '-benzidine and 5mL N; be stirred to solid under the N-N,N-DIMETHYLACETAMIDE, room temperature and all dissolve, add 0.5986g (1mmol) 2; 2 '-two (4 " phenyl) phenyl-4; 4 ', 5,5 '-BPDA; continue stirring at room 14h, obtain thickness, homogeneous phase, faint yellow transparent polyamic acid solution.Add 5mLN again, the N-N,N-DIMETHYLACETAMIDE dilutes system, adds the mixture of equimolar diacetyl oxide/pyridine then, is warming up to 130 ℃, continues to stir 4h.Be cooled to room temperature and obtain polyimide adhesive.Get half solution and pour in the 20mL methyl alcohol, a large amount of yellow mercury oxides are separated out, and filter, and wash washing successively with methyl alcohol.100 ℃ of dryings of vacuum obtain the faint yellow solid powder.Infrared data (KBr compressing tablet, cm
-1): 1778cm
-1(the C=O symmetry is flexible), 1724cm
-1(C=O asymmetric stretch), 1364cm
-1(C-N stretching vibration), 1044cm
-1(C-F stretching vibration), 832cm
-1(1,4-substituted benzene ring C-H out-of-plane deformation vibration).768,698cm
-1(single-substituted ring C-H out-of-plane deformation vibration).Collosol and gel chromatogram (CPG) determining molecular weight, Mn=8681, Mw/Mn=1.41 ultimate analysis: theoretical value: C, 78.75%; H, 3.48%; N, 2.42%.Measured value: C, 78.50%; H, 3.72%; N, 2.30%.Under nitrogen atmosphere, TGA thermogravimetric analysis: T
d=525 ℃, T
10%=576 ℃, the remaining rate 70.00% in the time of 800 ℃.Dsc analysis, glass transition temperature T
g=528 ℃.
This polyimide can be dissolved in toluene, acetone, methylene dichloride, chloroform, N-Methyl pyrrolidone, N,N-DIMETHYLACETAMIDE, dimethyl formamide, tetrahydrofuran (THF) and the meta-cresol greater than 20% solids content (based on polymkeric substance).In the N,N-dimethylacetamide solution of 0.5g/dL, the limiting viscosity in the time of 30 ℃ is 0.68dL/g.
After being coated on the polyimide adhesive of not pouring methyl alcohol on the Kapton base material that surface corona handles, with the compound hot pressing moulding of Copper Foil, curing process is: room temperature → 60 ℃/1h+100 ℃/1h+140 ℃/1h+180 ℃/1h+260 ℃/1h.The stripping strength of gained Kapton base material and Copper Foil is 1.34N/mm.
Embodiment 4
Under nitrogen protection; add 0.5965g (1mmol) 2 in the there-necked flask; 2 '-two (4 " (3 ' "; 4 ' "; 5 ' " trifluorophenyl)) phenyl-4; 4 '-benzidine and 5mL1; the mixture of 3-dimethyl-2-imidazolidone and tetrahydrofuran (THF) (v: v=1: 1), be stirred to solid under the room temperature and all dissolve, add 0.6987g (1mmol) 2; 2 '-two (4 " naphthyl) phenyl-4; 4 ', 5,5 '-BPDA; continue stirring at room 18h, obtain thickness, homogeneous phase, faint yellow transparent polyamic acid solution.Add 5mL1 again, the mixture of 3-dimethyl-2-imidazolidone and tetrahydrofuran (THF) (v: v=1: 1) with the system dilution, add the mixture of equimolar diacetyl oxide/pyridine then, be warming up to 140 ℃, continue to stir 4h.Be cooled to room temperature and obtain polyimide adhesive.Get half solution and pour in the 20mL methyl alcohol, a large amount of yellow mercury oxides are separated out, and filter, and wash washing successively with methyl alcohol.100 ℃ of dryings of vacuum obtain the faint yellow solid powder.Infrared data (KBr compressing tablet, cm
-1): 1777cm
-1(the C=O symmetry is flexible), 1724cm
-1(C=O asymmetric stretch), 1363cm
-1(C-N stretching vibration), 1044cm
-1(C-F stretching vibration), 831cm
-1(1,4-substituted benzene ring C-H out-of-plane deformation vibration).778,801cm
-1(single naphthalene nucleus C-H out-of-plane deformation vibration that replaces).Collosol and gel chromatogram (CPG) determining molecular weight, Mn=11718, Mw/Mn=1.56.Ultimate analysis: theoretical value: C, 80.12%; H, 3.52%; N, 2.22%.Measured value: C, 79.82%; H, 3.52%; N, 2.26%.Under nitrogen atmosphere, TGA thermogravimetric analysis: T
d=481 ℃, T
10%=573 ℃, the remaining rate 72.00% in the time of 800 ℃.Dsc analysis, temperature are higher than 450 ℃ and do not observe glass transition temperature yet.
This polyimide can be dissolved in toluene, acetone, methylene dichloride, chloroform, N-Methyl pyrrolidone, N,N-DIMETHYLACETAMIDE, dimethyl formamide, tetrahydrofuran (THF), dioxane and the meta-cresol greater than 20% solids content (based on polymkeric substance).In the N,N-dimethylacetamide solution of 0.5g/dL, the limiting viscosity in the time of 30 ℃ is 0.73dL/g.
After being coated on the polyimide adhesive of not pouring methyl alcohol on the Kapton base material that surface corona handles, with the compound hot pressing moulding of Copper Foil, curing process is: room temperature → 60 ℃/1h+100 ℃/1h+140 ℃/1h+180 ℃/1h+280 ℃/1h.The stripping strength of gained Kapton base material and Copper Foil is 1.39N/mm.
Embodiment 5
Under nitrogen protection; add 0.5965g (1mmol) 2 in the there-necked flask; 2 '-two (4 " (3 ' "; 4 ' "; 5 ' " trifluorophenyl)) phenyl-4,4 '-benzidine and 5mL 1, the 4-dioxane; the mixture of dimethyl sulfoxide (DMSO) and dimethyl sulfone (v: v: v=1: 1: 1); being stirred to solid under the room temperature all dissolves; adding 0.7065g (1mmol) 2,2 '-two (4 " (3 ' ", 4 ' "; 5 ' " trifluorophenyl)) phenyl-4; 4 ', 5,5 '-BPDA; continue stirring at room 20h, obtain thickness; homogeneous phase; faint yellow transparent polyamic acid solution.Add 5mL 1 again, the mixture of 4-dioxane, dimethyl sulfoxide (DMSO) and dimethyl sulfone (v: v: v=1: 1: 1) adds the mixture of equimolar diacetyl oxide/pyridine then with the system dilution, is warming up to 140 ℃, continues to stir 4h.Be cooled to room temperature and obtain polyimide adhesive.Get half solution and pour in the 50mL water, a large amount of yellow mercury oxides are separated out, and filter hot water wash.100 ℃ of dryings of vacuum obtain the yellow solid powder.Infrared data (KBr compressing tablet, cm
-1): 1779cm
-1(the C=O symmetry is flexible), 1726cm
-1(C=O asymmetric stretch), 1365cm
-1(C-N stretching vibration), 1044cm
-1(C-F stretching vibration), 832cm
-1(1,4-substituted benzene ring C-H out-of-plane deformation vibration).Collosol and gel chromatogram (CPG) determining molecular weight, Mn=19008, Mw/Mn=1.54.Ultimate analysis: theoretical value: C, 71.98%; H, 2.78%; N, 2.21%.Measured value: C, 71.89%; H, 2.67%; N, 2.34%.Under nitrogen atmosphere, TGA thermogravimetric analysis: T
d=548 ℃, T
10%=599 ℃, the remaining rate 69.22% in the time of 800 ℃.Dsc analysis, temperature are higher than 450 ℃ and do not observe glass transition temperature yet.
This polyimide can be dissolved in toluene, acetone, methylene dichloride, chloroform, N-Methyl pyrrolidone, N,N-DIMETHYLACETAMIDE, dimethyl formamide, tetrahydrofuran (THF), dioxane and the meta-cresol greater than 20% solids content (based on polymkeric substance).In the N,N-dimethylacetamide solution of 0.5g/dL, the limiting viscosity in the time of 30 ℃ is 0.86dL/g.
After being coated on the polyimide adhesive of not pouring methyl alcohol on the Kapton base material that surface corona handles, with the compound hot pressing moulding of Copper Foil, curing process is: room temperature → 60 ℃/1h+100 ℃/1h+140 ℃/1h+280 ℃/1h+320 ℃/1h.The stripping strength of gained Kapton base material and Copper Foil is 1.42N/mm.
Embodiment 6
Under nitrogen protection, add 0.4886g (1mmol) 2,2 '-two (4 " phenyl) phenyl-4 in the there-necked flask; 4 '-benzidine and 5mL1; the mixture of 4-dioxane, dimethyl sulfoxide (DMSO) and tetramethylene sulfone (v: v: v=1: 1: 1), be stirred to solid under the room temperature and all dissolve, add 0.5986g (1mmol) 2; 2 '-two (4 " phenyl) phenyl-4; 4 ', 5,5 '-BPDA; continue stirring at room 24h, obtain thickness, homogeneous phase, faint yellow transparent polyamic acid solution.Add 1 again, the mixture of 4-dioxane, dimethyl sulfoxide (DMSO) and tetramethylene sulfone (v: v: v=1: 1: 1) adds the mixture of equimolar diacetyl oxide/pyridine then with the system dilution, is warming up to 160 ℃, continues to stir 4h.Be cooled to room temperature and obtain polyimide adhesive.Get half solution and pour in the 50mL water, a large amount of yellow mercury oxides are separated out, and filter hot water wash.100 ℃ of dryings of vacuum obtain the yellow solid powder.Infrared data (KBr compressing tablet, cm
-1): 1779cm
-1(the C=O symmetry is flexible), 1723cm
-1(C=O asymmetric stretch), 1364cm
-1(C-N stretching vibration), 840cm
-1(1,4-substituted benzene ring C-H out-of-plane deformation vibration), 769cm
-1, 697cm
-1(single) for phenyl ring C-H out-of-plane deformation vibration.Collosol and gel chromatogram (CPG) determining molecular weight, Mn=13670, Mw/Mn=1.34.Ultimate analysis: theoretical value: C, 86.67%; H, 4.41%; N, 2.66%.Measured value: C, 86.67%; H, 4.54%; N, 2.61%.Under nitrogen atmosphere, TGA thermogravimetric analysis: T
d=535 ℃, T
10%=587 ℃, the remaining rate 67.25% in the time of 800 ℃.Dsc analysis, temperature are higher than 450 ℃ and do not observe glass transition temperature yet.
This polyimide can be dissolved in toluene, acetone, methylene dichloride, chloroform, N-Methyl pyrrolidone, N,N-DIMETHYLACETAMIDE, dimethyl formamide, tetrahydrofuran (THF), dioxane and the meta-cresol greater than 20% solids content (based on polymkeric substance).In the N,N-dimethylacetamide solution of 0.5g/dL, the limiting viscosity in the time of 30 ℃ is 0.56dL/g.
After being coated on the polyimide adhesive of not pouring methyl alcohol on the Kapton base material that surface corona handles, with the compound hot pressing moulding of Copper Foil, curing process is: room temperature → 60 ℃/1h+100 ℃/1h+140 ℃/1h+280 ℃/1h+320 ℃/1h.The stripping strength of gained Kapton base material and Copper Foil is 1.46N/mm.
Embodiment 7
Under nitrogen protection, add 0.4886g (1mmol) 2,2 '-two (4 " phenyl) phenyl-4 in the there-necked flask; 4 '-benzidine and 5mLN, N-N,N-DIMETHYLACETAMIDE and N, the mixture of dinethylformamide (v: v=1: 1); be stirred to solid under the room temperature and all dissolve; add 0.4464g (1mmol) 2,2 '-phenylbenzene-4,4 '; 5; 5 '-BPDA, continue stirring at room 24h, obtain thickness, homogeneous phase, faint yellow transparent polyamic acid solution.Add 5mL N,N-dimethylacetamide and N again, the mixture of dinethylformamide (v: v=1: 1) with the system dilution, add the mixture of equimolar diacetyl oxide/triethylamine then, be warming up to 100 ℃, continue to stir 4h.Be cooled to room temperature and obtain polyimide adhesive.Get half solution and pour in the 50mL water, a large amount of yellow mercury oxides are separated out, and filter hot water wash.100 ℃ of dryings of vacuum obtain the yellow solid powder.Infrared data (KBr compressing tablet, cm
-1): 1778cm
-1(the C=O symmetry is flexible), 1723cm
-1(C=O asymmetric stretch), 1363cm
-1(C-N stretching vibration), 839cm
-1(1,4-substituted benzene ring C-H out-of-plane deformation vibration), 741cm
-1, 697cm
-1(single) for phenyl ring C-H out-of-plane deformation vibration.Collosol and gel chromatogram (CPG) determining molecular weight, Mn=15421, Mw/Mn=1.25.Ultimate analysis: theoretical value: C, 85.50%; H, 4.26%; N, 3.12%.Measured value: C, 85.23%; H, 4.44%; N, 3.25%.Under nitrogen atmosphere, TGA thermogravimetric analysis: T
d=524 ℃, T
10%=597 ℃, the remaining rate 68.75% in the time of 800 ℃.Dsc analysis, temperature are higher than 450 ℃ and do not observe glass transition temperature yet.
This polyimide can be dissolved in toluene, acetone, methylene dichloride, chloroform, N-Methyl pyrrolidone, N,N-DIMETHYLACETAMIDE, dimethyl formamide, tetrahydrofuran (THF), dioxane and the meta-cresol greater than 20% solids content (based on polymkeric substance).In the N,N-dimethylacetamide solution of 0.5g/dL, the limiting viscosity in the time of 30 ℃ is 0.63dL/g.
After being coated on the polyimide adhesive of not pouring methyl alcohol on the Kapton base material that surface corona handles, with the compound hot pressing moulding of Copper Foil, curing process is: room temperature → 60 ℃/1h+100 ℃/1h+140 ℃/1h+180 ℃/1h+270 ℃/1h.The stripping strength of gained Kapton base material and Copper Foil is 1.21N/mm.
Embodiment 8
Under nitrogen protection; add in the there-necked flask 0.4886g (1mmol) 2,2 '-two (4 " phenyl) phenyl-4,4 '-benzidine and 5mL methyl-sulphoxide; be stirred to solid under the room temperature and all dissolve; add 0.6987g (1mmol) 2,2 '-two (4 " (Alpha-Naphthyl)) phenyl-4,4 '; 5; 5 '-BPDA, continue stirring at room 30h, obtain thickness, homogeneous phase, faint yellow transparent polyamic acid solution.Add the 5mL methyl-sulphoxide again system is diluted, add the mixture of equimolar sodium acetate/diacetyl oxide then, be warming up to 160 ℃, continue to stir 4h.Be cooled to room temperature and obtain polyimide adhesive.Get half solution and pour in the 50mL water, a large amount of yellow mercury oxides are separated out, and filter hot water wash.100 ℃ of dryings of vacuum obtain the yellow solid powder.Infrared data (KBr compressing tablet, cm
-1): 1778cm
-1(the C=O symmetry is flexible), 1723cm
-1(C=O asymmetric stretch), 1364cm
-1(C-N stretching vibration), 842cm
-1(1,4-substituted benzene ring C-H out-of-plane deformation vibration), 777cm
-1, 743cm
-1, 697cm
-1(naphthalene nucleus C-H out-of-plane deformation vibration).Collosol and gel chromatogram (CPG) determining molecular weight, Mn=14573, Mw/Mn=1.39.Ultimate analysis: theoretical value: C, 87.63%; H, 4.38%; N, 2.43%.Measured value: C, 87.87%; H, 4.43%; N, 2.37%.Under nitrogen atmosphere, TGA thermogravimetric analysis: T
d=548 ℃, T
10%=604 ℃, the remaining rate 69.75% in the time of 800 ℃.Dsc analysis, temperature are higher than 450 ℃ and do not observe glass transition temperature yet.
This polyimide can be dissolved in toluene, acetone, methylene dichloride, chloroform, N-Methyl pyrrolidone, N,N-DIMETHYLACETAMIDE, dimethyl formamide, tetrahydrofuran (THF), dioxane and the meta-cresol greater than 20% solids content (based on polymkeric substance).In the N,N-dimethylacetamide solution of 0.5g/dL, the limiting viscosity in the time of 30 ℃ is 0.73dL/g.
After being coated on the polyimide adhesive of not pouring methyl alcohol on the Kapton base material that surface corona handles, with the compound hot pressing moulding of Copper Foil, curing process is: room temperature → 60 ℃/1h+100 ℃/1h+140 ℃/1h+240 ℃/1h+300 ℃/1h.The stripping strength of gained Kapton base material and Copper Foil is 1.32N/mm.
Embodiment 9
Under nitrogen protection, add 0.4886g (1mmol) 2,2 '-two (4 " phenyl) phenyl-4 in the there-necked flask; 4 '-benzidine and 5mL tetramethylene sulfone, be stirred to solid under the room temperature and all dissolve, add 0.7065g (1mmol) 2; 2 '-two (4 " (3 ' "; 4 ' ", 5 ' " trifluorophenyl)) phenyl-4,4 '; 5; 5 '-BPDA, continue stirring at room 48h, obtain thickness, homogeneous phase, faint yellow transparent polyamic acid solution.Add the 5mL tetramethylene sulfone again system is diluted, add the mixture of equimolar diacetyl oxide/pyridine then, be warming up to 100 ℃, continue to stir 4h.Be cooled to room temperature and obtain polyimide adhesive.Get half solution and pour in the 50mL water, a large amount of yellow mercury oxides are separated out, and filter hot water wash.100 ℃ of dryings of vacuum obtain the yellow solid powder.Infrared data (KBr compressing tablet, cm
-1): 1778cm
-1(the C=O symmetry is flexible), 1724cm
-1(C=O asymmetric stretch), 1366cm
-1(C-N stretching vibration), 1046cm
-1(C-F stretching vibration), 833cm
-1(1,4-substituted benzene ring C-H out-of-plane deformation vibration), 769cm
-1, 742cm
-1(single C-H out-of-plane deformation vibration that replaces).Collosol and gel chromatogram (CPG) determining molecular weight, Mn=16878, Mw/Mn=1.50.Ultimate analysis: theoretical value: C, 78.75%; H, 3.48%; N, 2.42%.Measured value: C, 78.61%; H, 3.63%; N, 2.35%.Under nitrogen atmosphere, TGA thermogravimetric analysis: T
d=557 ℃, T
10%=587 ℃, the remaining rate 67.95% in the time of 800 ℃.Dsc analysis, temperature are higher than 450 ℃ and do not observe glass transition temperature yet.
This polyimide can be dissolved in toluene, acetone, methylene dichloride, chloroform, N-Methyl pyrrolidone, N,N-DIMETHYLACETAMIDE, dimethyl formamide, tetrahydrofuran (THF), dioxane and the meta-cresol greater than 20% solids content (based on polymkeric substance).In the N,N-dimethylacetamide solution of 0.5g/dL, the limiting viscosity in the time of 30 ℃ is 0.45dL/g.
After being coated on the polyimide adhesive of not pouring methyl alcohol on the Kapton base material that surface corona handles, with the compound hot pressing moulding of Copper Foil, curing process is: room temperature → 60 ℃/1h+100 ℃/1h+140 ℃/1h+180 ℃/1h+220 ℃/1h.The stripping strength of gained Kapton base material and Copper Foil is 1.53N/mm.
Embodiment 10
Under nitrogen protection, add 0.3364g (1mmol) 2,2 '-phenylbenzene-4 in the there-necked flask; 4 '-benzidine and 5mL N, dinethylformamide is stirred to solid under the room temperature and all dissolves; adding 0.7065g (1mmol) 2,2 '-two (4 " (3 ' ", 4 ' "; 5 ' " trifluorophenyl)) phenyl-4; 4 ', 5,5 '-BPDA; continue stirring at room 48h, obtain thickness, homogeneous phase, faint yellow transparent polyamic acid solution.Add 5mL N again, dinethylformamide dilutes system, adds the mixture of equimolar diacetyl oxide/pyridine then, is warming up to 100 ℃, continues to stir 4h.Be cooled to room temperature and obtain polyimide adhesive.Get half solution and pour in the 50mL water, a large amount of yellow mercury oxides are separated out, and filter hot water wash.100 ℃ of dryings of vacuum obtain the yellow solid powder.Infrared data (KBr compressing tablet, cm
-1): 1780cm
-1(the C=O symmetry is flexible), 1724cm
-1(C=O asymmetric stretch), 1366cm
-1(C-N stretching vibration), 1046cm
-1(C-F stretching vibration), 833cm
-1(1,4-substituted benzene ring C-H out-of-plane deformation vibration), 771cm
-1, 699cm
-1(single C-H out-of-plane deformation vibration that replaces).Collosol and gel chromatogram (CPG) determining molecular weight, Mn=18586, Mw/Mn=1.32.Ultimate analysis: theoretical value: C, 76.34%; H, 3.20%; N, 2.78%.Measured value: C, 76.18%; H, 3.41%; N, 2.65%.Under nitrogen atmosphere, TGA thermogravimetric analysis: T
d=560 ℃, T
10%=594 ℃, the remaining rate 70.95% in the time of 800 ℃.Dsc analysis, temperature are higher than 450 ℃ and do not observe glass transition temperature yet.
This polyimide can be dissolved in toluene, acetone, methylene dichloride, chloroform, N-Methyl pyrrolidone, N,N-DIMETHYLACETAMIDE, dimethyl formamide, tetrahydrofuran (THF), dioxane and the meta-cresol greater than 20% solids content (based on polymkeric substance).In the N,N-dimethylacetamide solution of 0.5g/dL, the limiting viscosity in the time of 30 ℃ is 0.59dL/g.
After being coated on the polyimide adhesive of not pouring methyl alcohol on the Kapton base material that surface corona handles, with the compound hot pressing moulding of Copper Foil, curing process is: room temperature → 60 ℃/1h+100 ℃/1h+140 ℃/1h+180 ℃/1h+220 ℃/1h.The stripping strength of gained Kapton base material and Copper Foil is 1.27N/mm.
The present invention relates to 4,4 '-benzidine, 2,2 '-two (Alpha-Naphthyl)-4,4 '-benzidine, 2,2 '-two (betanaphthyl)-4,4 '-benzidine, 2,2 '-two (3 "; 4 " trifluorophenyl)-4,45 " '-benzidine, 2; 2 '-two (4 " (4 ' "-fluorophenyl) phenyl)-4; 4 '-benzidine, 2,2 '-two (4 " (3 ' "; 4 ' " difluorophenyl) phenyl)-4,4 '-benzidine, 2,2 '-two (4 " (3 ' ", 5 ' " difluorophenyl) phenyl)-4; 4 '-benzidine, 2,2 '-two (4 " (4 ' "-phenyl) phenyl) phenyl-4; 4 '-benzidine; 2,2 '-two (3 " (betanaphthyl)) phenyl-4,4 '-benzidine, 2,2 '-two (α-(and 4 " phenyl) naphthyl)-4,4 '-benzidine, 2; 2 '-two (β-(and 6 " phenyl) naphthyl)-4,4 '-benzidine, 2,2 '-two (β-(and 7 " phenyl) naphthyl)-4; 4 '-benzidine; 2,2 '-two (α-(4 " (Alpha-Naphthyl)) naphthyl)-4,4 '-benzidine, 2,2 '-two (α-(4 " (betanaphthyl)) naphthyl)-4,4 '-benzidine, 2; 2 '-two (β-(4 " (Alpha-Naphthyl)) naphthyl)-4,4 '-benzidine, 2,2 '-two (β-(4 " (betanaphthyl)) naphthyl)-4; 4 '-benzidine; 2,2 '-two (9H-carbazyls)-4,4 '-benzidine; 2; 2 '-two (4 " (9H-carbazyl) phenyl)-4,4 '-benzidine, 2,2 '-two (4 " (4 ' "-(9H-carbazyl) phenyl) phenyl-4,4 '-benzidine, 2,2 '-two (4 " (N; N-hexichol amido) phenyl-4; 4 '-the benzidine phenyl, 2,2 '-two (4 " (4 ' "-(N; N-hexichol amido) phenyl) phenyl)-4; 4 '-benzidine, 2,2 '-two (3 ", 5 " phenyl phenylbenzene))-4; 4 '-benzidine, 2,2 '-two (4 " (3 ' "; 5 ' " phenylbenzene) phenyl) phenyl-4,4 '-benzidine; 2,2 '-two (Alpha-Naphthyl)-4,4 ', 5,5 '-BPDA, 2,2 '-two (betanaphthyl)-4,4 ', 5,5 '-BPDA, 2,2 '-two (3 "; 4 ", 5 " and trifluorophenyl)-4,4 '; 5,5 '-BPDA, 2; 2 '-two (4 " phenyl) phenyl-4,4 ', 5,5 '-BPDA, 2,2 '-two (4 " (4 ' "-fluorophenyl) phenyl)-4,4 ', 5,5 '-BPDA, 2,2 '-two (4 " (3 ' ", 4 ' " difluorophenyl) phenyl)-4; 4 ', 5,5 '-BPDA; 2,2 '-two (4 " (3 ' ", 5 ' " difluorophenyl) phenyl)-4,4 ', 5,5 '-BPDA, 2,2 '-two (4 " (4 ' "-phenyl) phenyl) phenyl-4,4 ', 5,5 '-BPDA, 2,2 '-two (4 " (betanaphthyl)) phenyl-4,4 ', 5; 5 '-BPDA, 2,2 '-two (3 " (betanaphthyl)) phenyl-4,4 ', 5,5 '-BPDA, 2,2 '-two (α-(and 4 " phenyl) naphthyl)-4,4 ', 5; 5 '-BPDA; 2,2 '-two (β-(and 6 " phenyl) naphthyl)-4,4 ', 5,5 '-BPDA, 2,2 '-two (β-(and 7 " phenyl) naphthyl)-4; 4 '; 5,5 '-BPDA, 2; 2 '-two (α-(4 " (Alpha-Naphthyl)) naphthyl)-4,4 ', 5,5 '-BPDA, 2,2 '-two (α-(4 " (betanaphthyl)) naphthyl)-4,4 ', 5; 5 '-BPDA; 2,2 '-two (β-(4 " (Alpha-Naphthyl)) naphthyl)-4,4 ', 5,5 '-BPDA, 2,2 '-two (β-(4 " (betanaphthyl)) naphthyl)-4; 4 '; 5,5 '-BPDA, 2; 2 '-two (9H-carbazyls)-4; 4 ', 5,5 '-BPDA; 2,2 '-two (4 " (9H-carbazyl) phenyl)-4,4 ', 5; 5 '-BPDA; 2,2 '-two (4 " (4 ' "-(9H-carbazyl) phenyl) phenyl-4,4 '; 5; 5 '-BPDA, 2,2 '-two (4 " (N, N-hexichol amido) phenyl)-4,4 ', 5,5 '-BPDA, 2,2 '-two (4 " (4 ' "-(N, N-hexichol amido) phenyl) phenyl)-4,4 ', 5,5 '-BPDA, 2,2 '-two (4 " (3 ", 5 " phenyl phenylbenzene))-4; 4 ', 5,5 '-BPDA; 2; 2 '-two (4 " (3 ' ", 5 ' " phenylbenzene) phenyl) phenyl-4,4 ', 5,5 '-BPDA also can prepare polyimide according to the foregoing description.
Claims (10)
1. solubility high-temperature resistant aromatic polyimide, the polyimide of [1] repeating unit that it is characterized in that having general formula:
Number-average molecular weight Mn=8000-20000; Molecular weight distribution mw/mn=1.2-1.7; R is 2,2 '-R, R-4,4 '-the benzidine compound in group; R ' is 2,2 '-R ', R '-4,4 ', 5,5 '-the BPDA compound in group.
2. solubility high-temperature resistant aromatic polyimide preparation method is characterized in that: mol ratio be 1: 12,2 '-R, R-4,4 '-benzidine compound and 2,2 '-R ', R '-4,4 ', 5,5 '-the BPDA compound in strong polar non-proton organic solvent, under room temperature, stir, obtain homogeneous phase, transparent, heavy-gravity polyamic acid solution, and polyamic acid solution dewatered obtain the solubility high-temperature resistant aromatic polyimide.
3. solubility high-temperature resistant aromatic polyimide preparation method according to claim 2, it is characterized in that the process of dewatering is: in the nitrogen atmosphere, add dewatering agent, reflux dehydration imidization, be cooled to pour into after the room temperature and obtain the polyimide precipitation in the methyl alcohol, filtration drying promptly obtains the polyimide solid.
4. solubility high-temperature resistant aromatic polyimide preparation method according to claim 3 is characterized in that the chemical dehydration reflux temperature is 100 ℃～160 ℃.
5. solubility high-temperature resistant aromatic polyimide preparation method according to claim 3 is characterized in that chemical dehydrator is pyridine/diacetyl oxide, triethylamine/diacetyl oxide or sodium acetate/diacetyl oxide.
6. solubility high-temperature resistant aromatic polyimide preparation method according to claim 2, it is characterized in that the process of dewatering is: polyamic acid solution is coated on the substrate material, is heated to the high temperature cyclodehydration, promptly gets Kapton.
7. solubility high-temperature resistant aromatic polyimide preparation method according to claim 2, it is characterized in that 2,2 '-R, R-4,4 '-the benzidine compound is 2,2 '-phenylbenzene-4,4 '-benzidine, 2,2 '-two (Alpha-Naphthyl)-4,4 '-benzidine, 2,2 '-two (betanaphthyl)-4,4 '-benzidine, 2,2 '-two (3 ", 4 ", 5 " trifluorophenyl)-4; 4 '-benzidine, 2,2 '-two (4 " phenyl) phenyl-4,4 '-benzidine, 2,2 '-two (4 " (4 " '-fluorophenyl) phenyl)-4,4 '-benzidine, 2,2 '-two (4 " (3 " ', 4 " '-difluorophenyl) phenyl)-4,4 '-benzidine; 2; 2 '-two (4 " (3 " ', 5 " '-difluorophenyl) phenyl)-4,4 '-benzidine, 2,2 '-two (4 " (3 " ', 4 " ', 5 " '-trifluorophenyl) phenyl)-4,4 '-benzidine, 2,2 '-two (4 " (Alpha-Naphthyl)) phenyl-4,4 '-benzidine; 2; 2 '-two (4 " (4 " '-phenyl) phenyl) phenyl-4,4 '-benzidine, 2; 2 '-two (3 " (betanaphthyl)) phenyl-4,4 '-benzidine, 2,2 '-two (α-(and 4 " phenyl) naphthyl)-4; 4 '-benzidine; 2,2 '-two (β-(and 6 " phenyl) naphthyl)-4,4 '-benzidine, 2,2 '-two (β-(and 7 " phenyl) naphthyl)-4,4 '-benzidine, 2; 2 '-two (α-(4 " (Alpha-Naphthyl)) naphthyl)-4,4 '-benzidine, 2,2 '-two (α-(4 " (betanaphthyl)) naphthyl)-4; 4 '-benzidine; 2,2 '-two (β-(4 " (Alpha-Naphthyl)) naphthyl)-4,4 '-benzidine, 2,2 '-two (β-(4 " (betanaphthyl)) naphthyl)-4,4 '-benzidine, 2; 2 '-two (9H-carbazyls)-4; 4 '-benzidine, 2,2 '-two (4 " (9H-carbazyl) phenyl)-4,4 '-benzidine, 2,2 '-two (4 " (4 " '-(9H-carbazyl) phenyl) phenyl-4,4 '-benzidine, 2,2 '-two (4 " (N, N-hexichol amido) phenyl-4,4 '-the benzidine phenyl; 2; 2 '-two (4 " (4 ' "-(N, N-hexichol amido) phenyl) phenyl)-4,4 '-benzidine; 2; 2 '-two (3 ", 5 " phenylbenzene) phenyl)-4,4 '-benzidine; 2,2 '-two (4 " (3 " ', 5 " '-phenylbenzene) phenyl) phenyl-4,4 '-a kind of in the benzidine.
8. solubility high-temperature resistant aromatic polyimide preparation method according to claim 2, it is characterized in that 2,2 '-R ', R '-4,4 ', 5,5 '-the BPDA compound is 3,3 ', 4,4 '-BPDA, 2,2 '-phenylbenzene-4,4 ', 5,5 '-BPDA, 2,2 '-two (Alpha-Naphthyl)-4,4 ', 5,5 '-BPDA, 2,2 '-two (betanaphthyl)-4,4 ', 5,5 '-BPDA, 2,2 '-two (3 "; 4 ", 5 " and trifluorophenyl)-4,4 '; 5,5 '-BPDA, 2; 2 '-two (4 " phenyl) phenyl-4,4 ', 5,5 '-BPDA, 2,2 '-two (4 " (4 " '-fluorophenyl) phenyl)-4,4 ', 5,5 '-BPDA, 2,2 '-two (4 " (3 " ', 4 " '-difluorophenyl) phenyl)-4; 4 '; 5,5 '-BPDA, 2; 2 '-two (4 " (3 " '; 5 " phenyl)-4,4 '-difluorophenyl) ', 5,5 '-BPDA, 2,2 '-two (4 " (3 " ', 4 " '; 5 " '-trifluorophenyl) phenyl)-4,4 ', 5,5 '-BPDA, 2,2 '-two (4 " (Alpha-Naphthyl)) phenyl-4,4 ', 5; 5 '-BPDA; 2,2 '-two (4 " (4 " '-phenyl) phenyl) phenyl-4,4 '; 5; 5 '-BPDA, 2,2 '-two (4 " (betanaphthyl)) phenyl-4,4 ', 5,5 '-BPDA, 2,2 '-two (3 " (betanaphthyl)) phenyl-4; 4 ', 5,5 '-BPDA; 2; 2 '-two (α-(and 4 " phenyl) naphthyl)-4,4 ', 5,5 '-BPDA,, 2 '-two (β-(and 6 " phenyl) naphthyl)-4,4 '; 5; 5 '-BPDA, 2,2 '-two (β-(and 7 " phenyl) naphthyl)-4,4 ', 5,5 '-BPDA, 2,2 '-two (α-(4 " (Alpha-Naphthyl)) naphthyl)-4; 4 ', 5,5 '-BPDA; 2; 2 '-two (α-(4 " (betanaphthyl)) naphthyl)-4,4 ', 5,5 '-BPDA, 2,2 '-two (β-(4 " (Alpha-Naphthyl)) naphthyl)-4,4 '; 5; 5 '-BPDA, 2,2 '-two (β-(4 " (betanaphthyl)) naphthyl)-4,4 ', 5,5 '-BPDA, 2,2 '-two (9H-carbazyls)-4,4 ', 5,5 '-BPDA, 2,2 '-two two (4 " (9H-carbazyl) phenyl)-4,4 ', 5; 5 '-BPDA; 2,2 '-two (4 " (4 " '-(9H-carbazyl) phenyl) phenyl-4,4 '; 5; 5 '-BPDA, 2,2 '-two (4 " (N, N-hexichol amido) phenyl)-4,4 ', 5,5 '-BPDA, 2,2 '-two (4 " (4 " '-(N, N-hexichol amido) phenyl) phenyl)-4,4 ', 5,5 '-BPDA, 2,2 '-two (4 " (3 ", 5 " phenyl phenylbenzene))-4; 4 ', 5,5 '-BPDA; 2; 2 '-two (4 " (3 " ', 5 " '-phenylbenzene) phenyl) phenyl-4,4 ', 5,5 '-a kind of in the BPDA.
9. solubility high-temperature resistant aromatic polyimide preparation method according to claim 2 is characterized in that strong polar non-proton organic solvent is N, dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone, 1,3-dimethyl-2-imidazolidone, tetrahydrofuran (THF), 1, the 4-dioxane, dimethyl sulfoxide (DMSO), dimethyl sulfone, the mixture of one or more in the tetramethylene sulfone.
10. solubility high-temperature resistant aromatic polyimide preparation method according to claim 2 is characterized in that stirring at room is to stir 4h～48h down at 20 ℃～30 ℃.
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