CN104961893A - High-dielectric-constant polyimide and preparation method thereof - Google Patents
High-dielectric-constant polyimide and preparation method thereof Download PDFInfo
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Abstract
The invention discloses high-dielectric-constant polyimide and a preparation method thereof. Polyimide can be applied to energy storage elements and the structure thereof is shown by the following general formula as shown in the accompanying drawing, wherein Ar<1> and Ar<2 > are tetravalent organic groups with one or a plurality of aromatic rings; B is a divalent organic group with one or a plurality of aromatic rings; R<1>-R<8> are one of H, C1-C6 alkyl, OH and C1-C6 alkoxy. The molecular backbone of the polyimide is provided with a certain proportion of amide functional groups, and the aromatic rings are provided with groups such as alkyl or alkoxy. The polyimide disclosed by the invention has the advantages of high dielectric constant, high temperature resistance, high strength and high dimensional stability, is suitable for being used as dielectric layers of energy storage elements and can be widely applied to electronic, electromechanical and microelectronic industries, especially the field of large-scale integrated circuits.
Description
Technical field
The present invention relates to one and can be applicable to the high-k of energy-storage travelling wave tube (as high power capacitor, miniature buried capacitors), the polyimide of high temperature resistant, high strength, high-dimensional stability, and the preparation method of this polyimide film material.Specifically, relate to by introduce in molecular backbone chain from molecular backbone chain with the structural unit of diamine monomer amide functional group, aromatic nucleus with alkyl, alkoxyl group, obtain having the polyimide of high-k, high temperature resistant, high strength, high-dimensional stability.
Background technology
Polyimide, in the molecular structure containing imide ring, be a class high strength, high temperature resistant, stability is high, have the macromolecular material of excellent flexibility, can be used as the dielectric insulation layer in electron device and base film, be particularly widely used in large-scale integrated circuit field at microelectronic industry.At present, along with electronic circuit and electron device are to the future development such as miniaturization, less energy-consumption, at capacitor area, the demand of the high power capacitor lightweight, volume is little, energy storage density is high increases, and also increases the demand of the polyimide film material of high-k, low-dielectric loss; In printed circuit board field, use embedded high capacitance film capacitor to realize the integrated circuit memory that integrated level increases, the density of data storage increases, it also day by day increases the demand of the polyimide type copper-clad plate of high-k.There is the polyimide film material of high-k, low-dielectric loss, become the key that these fields are fast-developing further.
The relative permittivity of common aromatic polyimide is 2.5-4, is generally no more than 5, can not meet the application requiring of the energy-storage travelling wave tube such as high power capacitor, miniature buried capacitors.The Lee of du pont company etc. (US 6150456) adopt BaTiO
3fill thermoplastic polyimide or Thermocurable polyimide Deng high-k filler, obtain the polyimide material of high-k, its specific inductivity can arrive 4-60.But the tensile strength of these Kaptons lower (about 100Mpa), elongation at break is lower (being less than 10%) also; BaTiO
3the mechanical property of Kapton can be reduced Deng mineral filler, affect the stability of electronic product.The Zhu Baoku of Zhejiang University etc. (CN 1763134 A) are by titanium doped for lithium nickel oxide, zirconium barium titanate or be evenly dispersed in polyimide matrix by powdered ceramic such as the titanium doped nickel oxide of the lithium of active group modification, zirconium barium titanates, prepare the polyimide/ceramic complex film of high-k.The Zhang Xiangyu of Shengyi Science and Technology Co., Ltd, Guangdong etc. (CN 101934619 A) fill high-k filler in thermoset polyimide resin and thermoplastic polyimide resin, be prepared into the polyimide composite film that specific inductivity is greater than 10, bury capacitive circuit double side flexible copper coated board further across preparation after composite coating, solidification.But all along with following subject matter in these achievements: (1) poor compatibility between mineral filler and polyimide resin, the dispersed texture homogeneity of mineral filler is unstable; (2) be subject to the impact of high-content mineral filler, the tensile strength of polyimide film material and elongation at break reduce, and it applies and is restricted in the electronic product of high performance requirements; (3) thickness, the planarization of the wayward composite membrane of the forming method of this kind of polyimide film material, the binding property between composite membrane and substrate or electrode is difficult to improve.
To the adjustment of polyimide molecule structure, and the introducing of end-capping reagent, also can the specific inductivity of corresponding raising polyimide resin.What equality (CN 103724624 A) of Huicheng Electrical Co. Ltd., Shenzhen City adopts organic solvent soluble polyaniline as end-capping reagent, carry out polycondensation with dianhydride and diamine monomer, form the block copolymerized polyimide film of A-B-A type with high-k, low-dielectric loss.The Kapton of this polyaniline end-blocking, its second-order transition temperature is between 220-300 DEG C, and more common polyimide is low, and the dimensional stability under its thermotolerance and high temperature is difficult to ensure.Marquis's lofty sentiments of Jiangxi Normal University etc. (CN 103102488 A) adopt the diamines raw material containing connection pyrimidine structure, prepare the polyimide resin of specific inductivity at 6.0-10.0; The introducing of connection pyrimidine structure group, while not reducing the thermostability of polyimide, mechanical property, can improve its specific inductivity.But the diamines raw material containing connection pyrimidine structure is difficult to synthesis and obtains, and cost intensive, limits the practical application of this polyimide resin.
In order to solve above-mentioned high dielectric constant polyimide material Problems existing, the present inventor is through further investigation, be there is by screening dianhydride, the diamine monomer raw material of different functional groups, and adjust the synthetic method of polyimide resin, search out a kind of polyimide material that can be applicable to the high-k of energy-storage travelling wave tube.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of high dielectric constant polyimide is provided, there is the performance of high-k, high temperature resistant, high strength, high-dimensional stability, can be applicable in the energy-storage travelling wave tube such as high power capacitor, miniature buried capacitors.
Another object of the present invention is to provide the preparation method of described high dielectric constant polyimide.
The object of the invention is to be realized by following technical scheme: a kind of high dielectric constant polyimide, has following structural formula:
In formula, R
1-R
8be H, C
1-C
6alkyl, OH, C
1-C
6alkoxyl group in one, x, y are the molar fractions of each integral part in polyimide structures formula, and wherein x is 0.1-1, y is 0-0.9, and meets x+y=1, Ar
1, Ar
2all be selected from the residue of pyromellitic acid anhydride, 3,3', 4, the residue, 2,3,3' of 4'-bibenzene tetracarboxylic dianhydride, the residue, 3,3' of 4'-bibenzene tetracarboxylic dianhydride, 4, the residue, 3,3' of 4'-diphenyl ether tetraformic dianhydride, 4, the residue, 3 of 4'-benzophenone dianhydride, the residue of 3', 4,4'-p-terphenyl tetracarboxylic acid dianhydride, the residue of Bisphenol A Type Diether Dianhydride, B is the residue being selected from Ursol D, the residue of mphenylenediamine, 4, the residue of 4'-diaminodiphenyl oxide, 3, the residue of 4'-diaminodiphenyl oxide, 4, the residue of 4'-diaminobenzophenone, 4, the residue of 4'-diaminodiphenyl-methane, 4, the residue of 4'-diaminobenzene sulfone, the residue of two (3-amino-4-hydroxylphenyl) sulfone, the residue of two (3-amino-benzene oxygen) benzene of 1.3-, the residue of two (4-amino-benzene oxygen) benzene of 1.3-, 4, the residue of two (4-amino-benzene oxygen) biphenyl of 4'-, 4, the residue of two (3-amino-benzene oxygen) biphenyl of 4'-, 2, the residue of two [4-(4-amino-benzene oxygen) phenyl] propane of 2-, the residue of two [4-(3-amino-benzene oxygen) phenyl] sulfone, 4, 4'-diamino-2, the residue of 2'-dimethyl diphenyl, the residue of 2-(4-aminophenyl)-5-aminobenzimidazole, the residue of 2-(4-aminophenyl)-6-An base benzoxazole.
Further, the specific inductivity of described several polyimide is 5-25, Young's modulus at 100 DEG C is 2-10GPa, tensile strength reaches 100-200MPa, second-order transition temperature is greater than 320 DEG C, 5 quality % weightless temperatures are more than 450 DEG C, and rate of moisture absorption is less than or equal to 3 quality %, and the thermal expansivity between 100-200 DEG C is 0-40ppm/K.
A preparation method for high dielectric constant polyimide thin-film material, comprises the following steps:
(1) polyimide precursor solution preparation: in strong polar organic solvent, add appropriate aromatic diamine compounds, make the mass percent of aromatic diamine compounds be 8%-12%; Then divide and add one or more aromatic tetracarboxylic two compound anhydrides for three times according to any mixture than composition, the mol ratio of tetracarboxylic acid dianhydride compounds and diamine compounds is (0.95-1.05): 1; Wherein, the part by weight that tetracarboxylic acid dianhydride compounds adds at every turn is respectively 60%, 30%, 10%; Stirring at room temperature in a nitrogen atmosphere, polymerization obtains polyimide precursor solution;
Wherein, aromatic tetracarboxylic two compound anhydride has the structural formula described in following general formula (1), aromatic diamine compounds is mixed by the aromatic diamines shown in the aromatic diamines shown in x part (molar fraction) general formula (2) and y part (molar fraction) general formula (3), x is 0.1-1, y is 0-0.9, and meets x+y=1;
NH
2-B-NH
2(3)
In general formula (1), Ar is the 4 valency organic groups with one or more aromatic nucleus, is selected from the residue of pyromellitic acid anhydride, 3, the residue, 2 of 3', 4,4'-bibenzene tetracarboxylic dianhydride, the residue, 3 of 3,3', 4'-bibenzene tetracarboxylic dianhydride, the residue, 3 of 3', 4,4'-diphenyl ether tetraformic dianhydride, the residue, 3 of 3', 4,4'-benzophenone dianhydride, the residue of 3', 4,4'-p-terphenyl tetracarboxylic acid dianhydride, the residue of Bisphenol A Type Diether Dianhydride;
R in general formula (2)
1-R
8h, C
1-C
6alkyl, OH, C
1-C
6alkoxyl group in one;
In general formula (3), B is the divalent organic group with one or more aromatic nucleus, is selected from the residue of Ursol D, the residue of mphenylenediamine, the residue of 4,4'-diaminodiphenyl oxide, the residue of 3,4'-diaminodiphenyl oxide, the residue of 4,4'-diaminobenzophenone, the residue of 4,4'-diaminodiphenyl-methane, the residue of 4,4'-diaminobenzene sulfone, the residue of two (3-amino-4-hydroxylphenyl) sulfone, the residue of two (3-amino-benzene oxygen) benzene of 1.3-, the residue of two (4-amino-benzene oxygen) benzene of 1.3-, the residue of two (4-amino-benzene oxygen) biphenyl of 4,4'-, the residue of two (3-amino-benzene oxygen) biphenyl of 4,4'-, the residue of two [4-(4-amino-benzene oxygen) phenyl] propane of 2,2-, the residue of two [4-(3-amino-benzene oxygen) phenyl] sulfone, the residue of 4,4'-diamino-2,2'-dimethyl diphenyl, the residue of 2-(4-aminophenyl)-5-aminobenzimidazole, the residue of the aromatic diamines such as 2-(4-aminophenyl)-6-An base benzoxazole,
Wherein, described strong polar organic solvent is made up of according to any proportioning one or more in N,N-dimethylacetamide (DMAc), DMF (DMF), N-Methyl pyrrolidone (NMP);
(2) film forming and solvent evaporates is applied: polyimide precursor solution prepared by step (1) applied on a glass, then volatilize 5-120min at 80-150 DEG C, make solvent between 15-40 quality %, obtain polyimide precursor dry film;
(3) high temperature imidization: the sheet glass being coated with polyimide precursor dry film is carried out imidization 10-60min at the temperature of 280-350 DEG C, forms polyimide film material; After cooling, the sheet glass being coated with polyimide film material is boiled in water, afterwards Kapton is peeled off, namely obtain required polyimide film material.
Further, in step (1), the aromatic diamine representated by general formula (2), is selected from 4,4'-diaminobenzene anilide, 2,2'-dimethoxy-4 's, 4'-diaminobenzene anilide.
The invention has the beneficial effects as follows: on polyimide molecule main chain, introduce amide functional group, and alkyl, alkoxyl group is introduced on the aromatic nucleus of aromatic diamine residue, while not affecting the mechanical property of polyimide, resistance toheat, improve the specific inductivity of polyimide.Kapton prepared by described polyimide, specific inductivity is 5-25, Young's modulus at 100 DEG C is 2-10GPa, tensile strength reaches 100-200MPa, second-order transition temperature is greater than 320 DEG C, and 5 quality % weightless temperatures are more than 450 DEG C, and rate of moisture absorption is less than or equal to 3 quality %, thermal expansivity between 100-200 DEG C is 0-40ppm/K, makes on its dielectric materials that can be applied in high power capacitor, the contour energy-storage travelling wave tube of micro embedded electrical condenser.
Accompanying drawing explanation
Fig. 1 is the Dynamic Viscoelastic linearity curve of the polyimide C that embodiment prepares, and its glass transition temperature Tg is 383 DEG C, and the store elastic modulus (E') of 100 DEG C is 6.08Gpa.
Fig. 2 is the length variations amount of the polyimide C that embodiment prepares and the relation curve of temperature, and its thermal linear expansion coefficient CTE is 16.4ppm/K.
Fig. 3 is the thermogravimetric weight-loss curve of the polyimide C that embodiment prepares, and the temperature Td 5% when its weight reduces 5% is 489 DEG C.
Fig. 4 is the infrared spectrogram of the polyimide C that embodiment prepares.
Embodiment
Representational embodiment specifically describes content of the present invention below, but these embodiments are not used in scope of invention belonging to restriction herein.
The dummy suffix notation used in embodiment is expressed as follows.
DMAc:N, N-N,N-DIMETHYLACETAMIDE;
PMDA: pyromellitic acid anhydride;
3,3', 4,4'-BPDA:3,3', 4,4'-bibenzene tetracarboxylic dianhydride;
3,3', 4,4'-ODPA:3,3', 4,4'-diphenyl ether tetraformic dianhydride;
BPADA: Bisphenol A Type Diether Dianhydride;
4,4'-DABA:4,4'-diaminobenzene anilide;
MODABA:2,2'-dimethoxy-4 ', 4'-diaminobenzene anilide;
P-PDA: Ursol D;
M-Tolidine:4,4'-diamino-2,2'-dimethyl diphenyl;
4,4'-ODA:4,4'-diaminodiphenyl oxide;
4,4'-MDA:4,4'-diaminodiphenyl-methane;
4,4'-DABPO:4,4'-diaminobenzophenone;
Two (3-amino-benzene oxygen) biphenyl of 43 BAPOBP:4,4'-.
[embodiment 1-14]
[polyimide A-N] prepares according to the raw material input amount in table 1 and following experimental procedure:
In a nitrogen atmosphere, in the there-necked flask of 100mL, while stirring the amount of aromatic race diamine compounds shown in table 1 is dissolved in 40g intensive polar solvent DMAc, makes the mass percent of aromatic diamine compounds be 8%-12%.Divide aromatic tetracarboxylic two compound anhydride added for three times shown in table 1 afterwards, each add-on be respectively account for gross weight be followed successively by 60%, 30%, 10%, and the mol ratio of tetracarboxylic acid dianhydride compounds and diamine compounds is (0.95-1.05): 1.Then, solution is at room temperature continued stir about 24h, obtained corresponding polyimide precursor---polyamic acid solution.
Use coating machine, by polyimide precursor solution coating on a glass, and make the thickness of dry rear polyimide be about 20um.Volatilize 5-120min at 80-150 DEG C, makes solvent between 15-40 quality %, obtain polyimide precursor dry film.The sheet glass being coated with polyimide precursor dry film is carried out imidization 10-60min at the temperature of 280-350 DEG C, forms polyimide film material; After cooling, the sheet glass being coated with polyimide film material is boiled in water, afterwards Kapton is peeled off, namely obtain required polyimide film material.
[comparative example 15-17]
[polyimide O-Q] is as a comparison polymerized according to the raw material input amount in table 1, and its detailed process prepared is consistent with the preparation process of above-mentioned [polyimide A-N].The composition of [polyimide O] in [comparative example 15] forms consistent with the Kapton type PI of Dupont, in order to the advantage of polyimide of the present invention in specific inductivity to be described.
Physical property sign is carried out to the high dielectric constant polyimide material prepared in the present invention, its measuring method and condition as follows:
1. specific inductivity: the specific inductivity K testing the obtained Kapton (diameter 50.8mm) of each embodiment with LCR precision digital electric bridge (HP 4276 A type).At sample two sided coatings silver slurry, abundant dry post-treatment diameter is the disk figure of 25.4mm, afterwards 23 DEG C, leave standstill at least 40 hours under the condition of 50RH%.Test frequency: 1MHz.Use special test presss from both sides, and test obtains the capacitance of sample, and asks the specific inductivity calculating sample.
2. tensile strength: the tensile strength of testing the obtained Kapton (10mm*150mm) of each embodiment with universal testing machine.Rate of extension: 50.8mm/min; Every sample repeats 5 times.Force value suffered when fracture per sample, and the width of sample, thickness data, ask the tensile strength calculating Kapton sample.
3. second-order transition temperature (Tg), store elastic modulus (E'): Tg, E' of measuring the obtained Kapton (5mm*30mm) of each embodiment with dynamic thermomechanical analysis apparatus (DMA).Temperature rise rate: 5 DEG C/min; Temperature range: 20 DEG C-400 DEG C.According to the Dynamic Viscoelastic linearity curve obtained, obtain the store elastic modulus (E') of second-order transition temperature (tan maximum value) and 100 DEG C.
4. thermal linear expansion coefficient (CTE): the CTE measuring the obtained Kapton (5mm*20mm) of each embodiment with static heat mechanical analyzer (TMA).Sample load: 0.05N; Temperature rise rate: 5 DEG C/min; Temperature range: 30 DEG C-260 DEG C.According to the length variations amount of acquisition and the relation curve of temperature, obtain CTE.
5. heat decomposition temperature (Td 5%): use thermogravimetric analyzer (TGA) to measure the Td 5% of the obtained Kapton (8-15mg) of each embodiment.Temperature rise rate: 10 DEG C/min; Temperature range: 30 DEG C-650 DEG C.According to thermogravimetric weight-loss curve, obtain the temperature (Td 5%) when weight reduces 5%.
6. rate of moisture absorption: by the Kapton (each three) of 10cm*10cm at 150 DEG C after dry 2 hours, 23 DEG C, leave standstill in the constant temperature and humidity machine of 50RH% and be more than or equal to 24 hours.Obtained by following formula by the changes in weight of standing front and back:
Rate of moisture absorption (%)=[before (after moisture absorption before weight-moisture absorption weight)/moisture absorption weight] * 100%.
The polyimide prepared in the present invention, has higher specific inductivity, and has excellent mechanical property, thermotolerance, dimensional stability, and its specific inductivity can arrive in the scope of 5-25, and tensile strength is more than 150MPa.Especially use the Kapton prepared containing the diamines with alkoxy base on amide group backbone structure, aromatic nucleus, its specific inductivity to more than 20, can have good mechanical property, thermotolerance concurrently, less thermal linear expansion coefficient simultaneously.Utilize these characteristics, polyimide of the present invention can be applied in microelectronic industry particularly large-scale integrated circuit field, is particularly suitable for the application of the energy-storage travelling wave tube such as high power capacitor, miniature buried capacitors.
Above-described embodiment is only the preferred embodiments of the present invention, can not limit protection scope of the present invention with this.The change of any unsubstantiality that those skilled in the art does on basis of the present invention and replacement all belong to the scope of protection of the presently claimed invention.
Claims (4)
1. a high dielectric constant polyimide, is characterized in that, has following structural formula:
In formula, R
1-R
8be H, C
1-C
6alkyl, OH, C
1-C
6alkoxyl group in one, x, y are the molar fractions of each integral part in polyimide structures formula, and wherein x is 0.1-1, y is 0-0.9, and meets x+y=1, Ar
1, Ar
2all be selected from the residue of pyromellitic acid anhydride, 3,3', 4, the residue, 2,3,3' of 4'-bibenzene tetracarboxylic dianhydride, the residue, 3,3' of 4'-bibenzene tetracarboxylic dianhydride, 4, the residue, 3,3' of 4'-diphenyl ether tetraformic dianhydride, 4, the residue, 3 of 4'-benzophenone dianhydride, the residue of 3', 4,4'-p-terphenyl tetracarboxylic acid dianhydride, the residue of Bisphenol A Type Diether Dianhydride, B is the residue being selected from Ursol D, the residue of mphenylenediamine, 4, the residue of 4'-diaminodiphenyl oxide, 3, the residue of 4'-diaminodiphenyl oxide, 4, the residue of 4'-diaminobenzophenone, 4, the residue of 4'-diaminodiphenyl-methane, 4, the residue of 4'-diaminobenzene sulfone, the residue of two (3-amino-4-hydroxylphenyl) sulfone, the residue of two (3-amino-benzene oxygen) benzene of 1.3-, the residue of two (4-amino-benzene oxygen) benzene of 1.3-, 4, the residue of two (4-amino-benzene oxygen) biphenyl of 4'-, 4, the residue of two (3-amino-benzene oxygen) biphenyl of 4'-, 2, the residue of two [4-(4-amino-benzene oxygen) phenyl] propane of 2-, the residue of two [4-(3-amino-benzene oxygen) phenyl] sulfone, 4, 4'-diamino-2, the residue of 2'-dimethyl diphenyl, the residue of 2-(4-aminophenyl)-5-aminobenzimidazole, the residue of 2-(4-aminophenyl)-6-An base benzoxazole.
2. high dielectric constant polyimide according to claim 1, it is characterized in that, the specific inductivity of described several polyimide is 5-25, Young's modulus at 100 DEG C is 2-10GPa, tensile strength reaches 100-200MPa, and second-order transition temperature is greater than 320 DEG C, and 5 quality % weightless temperatures are more than 450 DEG C, rate of moisture absorption is less than or equal to 3 quality %, and the thermal expansivity between 100-200 DEG C is 0-40ppm/K.
3. a preparation method for high dielectric constant polyimide thin-film material, is characterized in that, comprises the following steps:
(1) polyimide precursor solution preparation: in strong polar organic solvent, add appropriate aromatic diamine compounds, make the mass percent of aromatic diamine compounds be 8%-12%; Then divide and add one or more aromatic tetracarboxylic two compound anhydrides for three times according to any mixture than composition, the mol ratio of tetracarboxylic acid dianhydride compounds and diamine compounds is (0.95-1.05): 1; Wherein, the part by weight that tetracarboxylic acid dianhydride compounds adds at every turn is respectively 60%, 30%, 10%; Stirring at room temperature in a nitrogen atmosphere, polymerization obtains polyimide precursor solution;
Wherein, aromatic tetracarboxylic two compound anhydride has the structural formula described in following general formula (1), aromatic diamine compounds is mixed by the aromatic diamines shown in the aromatic diamines shown in x part (molar fraction) general formula (2) and y part (molar fraction) general formula (3), x is 0.1-1, y is 0-0.9, and meets x+y=1;
In general formula (1), Ar is the 4 valency organic groups with one or more aromatic nucleus, is selected from the residue of pyromellitic acid anhydride, 3, the residue, 2 of 3', 4,4'-bibenzene tetracarboxylic dianhydride, the residue, 3 of 3,3', 4'-bibenzene tetracarboxylic dianhydride, the residue, 3 of 3', 4,4'-diphenyl ether tetraformic dianhydride, the residue, 3 of 3', 4,4'-benzophenone dianhydride, the residue of 3', 4,4'-p-terphenyl tetracarboxylic acid dianhydride, the residue of Bisphenol A Type Diether Dianhydride;
R in general formula (2)
1-R
8h, C
1-C
6alkyl, OH, C
1-C
6alkoxyl group in one;
In general formula (3), B is the divalent organic group with one or more aromatic nucleus, is selected from the residue of Ursol D, the residue of mphenylenediamine, the residue of 4,4'-diaminodiphenyl oxide, the residue of 3,4'-diaminodiphenyl oxide, the residue of 4,4'-diaminobenzophenone, the residue of 4,4'-diaminodiphenyl-methane, the residue of 4,4'-diaminobenzene sulfone, the residue of two (3-amino-4-hydroxylphenyl) sulfone, the residue of two (3-amino-benzene oxygen) benzene of 1.3-, the residue of two (4-amino-benzene oxygen) benzene of 1.3-, the residue of two (4-amino-benzene oxygen) biphenyl of 4,4'-, the residue of two (3-amino-benzene oxygen) biphenyl of 4,4'-, the residue of two [4-(4-amino-benzene oxygen) phenyl] propane of 2,2-, the residue of two [4-(3-amino-benzene oxygen) phenyl] sulfone, the residue of 4,4'-diamino-2,2'-dimethyl diphenyl, the residue of 2-(4-aminophenyl)-5-aminobenzimidazole, the residue of the aromatic diamines such as 2-(4-aminophenyl)-6-An base benzoxazole,
Wherein, described strong polar organic solvent is made up of according to any proportioning one or more in N,N-dimethylacetamide (DMAc), DMF (DMF), N-Methyl pyrrolidone (NMP);
(2) film forming and solvent evaporates is applied: polyimide precursor solution prepared by step (1) applied on a glass, then volatilize 5-120min at 80-150 DEG C, make solvent between 15-40 quality %, obtain polyimide precursor dry film;
(3) high temperature imidization: the sheet glass being coated with polyimide precursor dry film is carried out imidization 10-60min at the temperature of 280-350 DEG C, forms polyimide film material; After cooling, the sheet glass being coated with polyimide film material is boiled in water, afterwards Kapton is peeled off, namely obtain required polyimide film material.
4. preparation method according to claim 3, is characterized in that, in step (1), the aromatic diamine representated by general formula (2), is selected from 4,4'-diaminobenzene anilide, 2,2'-dimethoxy-4 's, 4'-diaminobenzene anilide.
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