CN111117241A - High-transparency low-expansion polyimide film and preparation method thereof - Google Patents
High-transparency low-expansion polyimide film and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of polyimide films, and particularly relates to a high-transparency low-expansion polyimide film material and a preparation method thereof. The high-transparency low-expansion polyimide film is obtained by polycondensation of diamine monomer and dianhydride monomer, wherein the diamine monomer comprises nitrogen-containing aromatic diamine R1The dianhydride monomer comprises 3,3' -amido bis-o-cyclohexyl tetracarboxylic dianhydride Ar1(ii) a The 3,3' -amido bis-o-cyclohexyl tetracarboxylic dianhydride Ar1Is prepared by introducing amide group into 2,2',3,3' -biphenyl tetracarboxylic dianhydride and then hydrogenating. The high-transparency low-expansion polyimide film provided by the invention has good light transmittance, low expansion coefficient and excellent heat resistance, and is suitable for a flexible display cover plate; the invention also provides a preparation method of the composition.
Description
Technical Field
The invention belongs to the technical field of polyimide films, and particularly relates to a high-transparency low-expansion polyimide film material and a preparation method thereof.
Background
At present, the market of flat panel display equipment is continuously expanded, a leap demand appears on high-transparency Polyimide (PI) for a flexible display cover plate, the demand of the high-transparency polyimide in 2019 is 4.5 ten thousand square meters, and the demand is estimated to reach 45 ten thousand square meters in 2022. However, the light transmittance of the conventional aromatic polyimide in the visible light region is characteristic yellow, which cannot meet the requirement of high transparency of the photoelectric display substrate material to the film, and the common polyimide has a Coefficient of Thermal Expansion (CTE) of about 35 to 80 ppm/DEG C, which cannot meet the requirement of less than 15 ppm/DEG C in the high temperature process. Therefore, special structural monomers and polyimides need to be designed to meet the requirements of high transparency and low expansion properties.
The method for realizing the high transparency of the polyimide mainly introduces a bulky substituent, a fluorine-containing group, a flexible group, an asymmetric structure, an alicyclic structure, a non-coplanar structure and the like into a molecular chain. The low-expansion polyimide is prepared mainly by adopting a molecular structure design method (introducing a rigid rod-shaped structural unit), a multi-copolymerization method and a nano particle adding method. Researchers have done a lot of research work using the above method: the Chinese patent with publication number CN102911359A reports that 1, 4-bis (3, 4-dicarboxylic phenoxy) cyclohexane dianhydride and diamine primary amine monomer are subjected to polycondensation reaction to prepare polyimide, cyclohexane is introduced into a molecular structure to improve the light transmittance of the polyimide (the light transmittance at 450nm is 70-90%), and the linear expansion coefficient is not mentioned. The Chinese patent publication No. CN109824894A introduces an alicyclic structure into a polyimide molecular chain, the light transmittance at 400nm is higher than 85%, the CTE is less than 30 ppm/DEG C, and the glass transition temperature is higher than 280 ℃. The invention patent of the patent No. CN101796105B discloses a polyimide film, the light transmittance of the polyimide film obtained by the invention is 85% in the range of 380-780 nm, the thermal expansion coefficient is 35.0 ppm/DEG C, but the thermal expansion coefficient is still higher.
Therefore, in order to solve the technical problems that high light transmittance, low expansion, and high heat resistance are difficult to combine at the same time, it is necessary to develop a novel polyimide film that can be applied to a flexible cover film.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a high-transparency low-expansion polyimide film which has good light transmittance, lower expansion coefficient and excellent heat resistance and is suitable for a flexible display cover plate; the invention also provides a preparation method of the composition.
The high-transparency low-expansion polyimide film is obtained by polycondensation of diamine monomer and dianhydride monomer, wherein the diamine monomer comprises nitrogen-containing aromatic diamine R1The dianhydride monomer comprises 3,3' -amido bis-o-cyclohexyl tetracarboxylic dianhydride Ar1；
The 3,3' -amido bis-o-cyclohexyl tetracarboxylic dianhydride Ar1The polyimide is obtained by introducing an amide group into 2,2',3,3' -biphenyl tetracarboxylic dianhydride and then hydrogenating the amide group, and the structural formula of the polyimide is as follows:
specifically, the 3,3' -amido bis-o-cyclohexyl tetracarboxylic dianhydride Ar13,3 '-amido biphenyl tetracid is prepared by using 3-chloro-phthalic anhydride as a raw material, and then the 3,3' -amido biphenyl tetracid is obtained by hydrogenation and dehydration. The 3,3' -acylamino bis-o-cyclohexyl tetracarboxylic dianhydride monomer is a novel dianhydride monomer, contains an alicyclic structure and a non-coplanar structure, can effectively inhibit the formation of intermolecular and intramolecular charge transfer complexes, greatly improves the transparency of a polymer, and simultaneously can reduce the thermal expansion coefficient of polyimide due to acylamino contained in the dianhydride monomer and a nitrogen-containing rigid structure contained in a diamine monomer.
Preferably, the diamine monomer is a nitrogen-containing aromatic diamine R1Or a nitrogen-containing aromatic diamine R1With aromatic diamines R2Of a nitrogen-containing aromatic diamine R1Aromatic diamine R2Have different molecular structures;
the dianhydride monomer is 3,3' -amido bis-o-cyclohexyl tetracarboxylic dianhydride Ar1Or 3,3' -amido bis (o-cyclohexyl) tetracarboxylic dianhydride Ar1With fluorine-containing dianhydride Ar2A mixture of (a).
Fluorine-containing dianhydride Ar2Is one of the following dianhydrides:
aromatic diamine R containing nitrogen1Any one of the following diamines:
the preparation method of the high-transparency low-expansion polyimide film is characterized by comprising the following steps of: the method comprises the following steps:
(1) nitrogen-containing aromatic diamine R1Aromatic diamine R2Adding into organic solvent for dissolving, adding 3,3' -acylamino bis-o-cyclohexyl tetracarboxylic dianhydride Ar into the obtained solution in batches1And fluorine-containing dianhydride Ar2Obtaining a polyamic acid (PAA) solution through a polycondensation reaction;
(2) adding a catalyst and a dehydrating agent into the polyamic acid solution, and carrying out chemical imidization to obtain a polyimide solution;
(3) and (3) casting the polyimide solution on super-flat glass, and then placing the super-flat glass in an oven to dry and remove the solvent to obtain the high-transparency low-expansion polyimide film.
In the step (1), the organic solvent is one or more of N, N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP) and N, N-Dimethylformamide (DMF), and the solid content of PAA (the solid content of PAA formed by condensation polymerization and dehydration of diamine monomers and dianhydride monomers) is 10-30 wt%.
In the step (1), the nitrogen-containing aromatic diamine R1And aromatic diamine R2The molar ratio of (A) to (B) is 1: 9-10: 0.
In the step (1), 3,3' -amido bis (o-cyclohexyl) tetracarboxylic dianhydride Ar1And fluorine-containing dianhydride Ar2The molar ratio of (A) to (B) is 1: 9-10: 0.
In the step (1), the molar ratio of the dianhydride monomer to the diamine monomer is 1-1.2: 1.
In the step (1), the polycondensation reaction temperature is 10-50 ℃.
In the step (2), the catalyst is a tertiary amine catalyst, the dehydrating agent is acid anhydride, the molar ratio of the catalyst to the polyamic acid is 2-5: 1, and the molar ratio of the dehydrating agent to the polyamic acid is 2-5: 1.
Preferably, the tertiary amine catalyst is pyridine or triethylamine, and the dehydrating agent is acetic anhydride or propionic anhydride.
In the step (2), the chemical imidization temperature of the polyamic acid is 25-60 ℃;
in the step (3), the casting film forming temperature is 70-150 ℃, and preferably 100 ℃; the time is 10-48 h, preferably 24 h.
The high-transparency low-expansion polyimide film prepared by the invention has the light transmittance of more than 88% at 380-780 nm and more than 90% at 450nm, the thermal expansion coefficient is reduced to below 16 ppm/DEG C, and the glass transition temperature is between 300 and 400 ℃.
The polyimide is prepared by polycondensation and copolymerization of 3,3' -amido bis-o-cyclohexyl tetracarboxylic dianhydride with a new structure, fluorine-containing dianhydride and a nitrogen-containing aromatic diamine monomer, and a fluorine-containing group, an alicyclic structure, a non-coplanar structure and an amide group are introduced into a polyimide molecular chain, so that the polyimide is high-transparency low-expansion polyimide with a new structure. The introduction of fluorine-containing groups, alicyclic structures and non-coplanar structures can destroy the conjugated structure on the molecular main chain, inhibit the formation of a Charge Transfer Complex (CTC), improve the light transmission of the polymer, widen the light transmission range and solve the problem of narrow wavelength range of high light transmission of the existing material. Meanwhile, the amide group and the nitrogen-containing heterocycle in the molecular chain can reduce the thermal expansion coefficient of the polyimide. In addition, the rigid nitrogen-containing heterocyclic aniline structure enables the polyimide to still keep higher thermal stability, the glass transition temperature is 300-400 ℃, and the requirement of a high-temperature manufacturing process of a flexible display device is met.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, nitrogen-containing aromatic diamine, 3' -acylamino bis-o-cyclohexyl tetracarboxylic dianhydride and fluorine-containing dianhydride are used as raw materials, and a fluorine-containing group, an alicyclic structure, a non-coplanar structure and an amide group are introduced into a polyimide molecular chain to prepare polyimide with a new structure, which has the characteristics of high transparency, low expansion and excellent thermal stability, and solves the problem that the existing polyimide film is difficult to have the excellent performances at the same time;
(2) the high-transparency low-expansion polyimide film prepared by the invention has the advantages that the light transmittance is more than 88% at 380-780 nm and more than 90% at 450nm, the thermal expansion coefficient is reduced to be less than 16 ppm/DEG C, and the glass transition temperature is between 300 and 400 ℃;
(3) the polyimide film prepared by the invention can be applied to flexible display cover plate films, promotes the domestic development of the flexible display cover plate films, and provides a flexible cover plate material with reliable quality and up-to-standard performance for the development of the flexible display device industry in China.
Detailed Description
The present invention is further illustrated below with reference to examples. It should be noted that the following examples are only for illustrating the present invention and not for limiting the technical solutions described in the present invention, and therefore all technical solutions and modifications thereof without departing from the spirit and scope of the present invention are included in the claims of the present invention.
Example 1
The high-transparency low-expansion polyimide film is prepared according to the following method:
(1) 2.253g of 2- (4-amino-phenyl) -benzooxazol-5-aminediamine monomer was added to a four-necked flask containing 23.2g of DMAc and dissolved with stirring under a nitrogen atmosphere; weighing 3.528g of 3,3' -acylamino bis-o-cyclohexyl tetracarboxylic dianhydride monomer, adding the monomer into the solution in batches under the stirring condition, stirring for 4 hours at 40 ℃, and carrying out polycondensation reaction to obtain a polyamic acid solution;
(2) adding 3.036g of catalyst triethylamine and 3.063g of dehydrating agent acetic anhydride into the polyamic acid solution to perform chemical imidization, and stirring for 8 hours at 40 ℃ to obtain a polyimide solution;
(3) and casting the obtained polyimide solution on ultra-flat glass, and then placing the ultra-flat glass in an oven at 100 ℃ for drying for 24 hours to obtain the high-transparency low-expansion polyimide film.
The obtained polyimide film is subjected to performance characterization, the light transmittance at 380 nm-780 nm is 88%, the light transmittance at 450nm is 90%, the thermal expansion coefficient is 15 ppm/DEG C, and the glass transition temperature is 315.7 ℃.
Example 2
The high-transparency low-expansion polyimide film is prepared according to the following method:
(1) 2.253g of 2- (4-amino-phenyl) -benzooxazol-5-aminediamine monomer was added to a four-necked flask containing 25.04g of DMAc and dissolved with stirring under a nitrogen atmosphere; weighing 1.764g of 3,3 '-acylamino bis-o-cyclohexyltetracarboxylic dianhydride and 2.243g of 6FDA (the molar ratio of 3,3' -acylamino bis-o-cyclohexyltetracarboxylic dianhydride to 6FDA is 1:1), adding the weighed materials into the solution in batches under the stirring condition, stirring the solution for 4 hours at the temperature of 40 ℃, and obtaining polyamic acid solution through polycondensation reaction;
(2) adding 3.036g of catalyst triethylamine and 3.063g of dehydrating agent acetic anhydride into the polyamic acid solution to perform chemical imidization, and stirring for 8 hours at 40 ℃ to obtain a polyimide solution;
(3) and casting the obtained polyimide solution on ultra-flat glass, and then placing the ultra-flat glass in an oven at 100 ℃ for drying for 24 hours to obtain the high-transparency low-expansion polyimide film.
The obtained polyimide film is subjected to performance characterization, the light transmittance of the polyimide film is 88% at 380 nm-780 nm, the light transmittance of the polyimide film is 92% at 450nm, the thermal expansion coefficient is 16 ppm/DEG C, and the glass transition temperature is 333.5 ℃.
Example 3
The high-transparency low-expansion polyimide film is prepared according to the following method:
(1) 2.253g of 2- (4-amino-phenyl) -benzooxazol-5-aminediamine monomer was added to a four-necked flask containing 24.28g of DMAc and dissolved with stirring under nitrogen; weighing 3,3 '-acylamino bis-o-cyclohexyltetracarboxylic dianhydride and 1.346g6FDA (the molar ratio of 3,3' -acylamino bis-o-cyclohexyltetracarboxylic dianhydride to 6FDA is 7:3), adding the mixture into the solution in batches under the stirring condition, stirring the mixture for 4 hours at 40 ℃, and carrying out polycondensation reaction to obtain a polyamic acid solution;
(2) adding 3.036g of catalyst triethylamine and 3.063g of dehydrating agent acetic anhydride into the polyamic acid solution to perform chemical imidization, and stirring for 8 hours at 40 ℃ to obtain a polyimide solution;
(3) and casting the obtained polyimide solution on ultra-flat glass, and then placing the ultra-flat glass in an oven at 100 ℃ for drying for 24 hours to obtain the high-transparency low-expansion polyimide film.
The obtained polyimide film is subjected to performance characterization, the light transmittance of the polyimide film is 88% at 380 nm-780 nm, the light transmittance of the polyimide film is 91% at 450nm, the thermal expansion coefficient is 13 ppm/DEG C, and the glass transition temperature is 325.5 ℃.
Example 4
The high-transparency low-expansion polyimide film is prepared according to the following method:
(1) 2.253g of 2- (4-amino-phenyl) -benzooxazol-5-aminediamine and 0.961g of TFMB diamine monomer (2- (4-amino-phenyl) -benzooxazol-5-aminediamine and TFMB in a 7:3 molar ratio) were added to a four-necked flask containing 25.4g of DMAc and dissolved with stirring under nitrogen; weighing 3,3 '-acylamino bis-o-cyclohexyltetracarboxylic dianhydride and 1.346g6FDA (the molar ratio of 3,3' -acylamino bis-o-cyclohexyltetracarboxylic dianhydride to 6FDA is 7:3) under the stirring condition, adding the mixture into the solution in batches, stirring the mixture for 4 hours at 40 ℃, and carrying out polycondensation reaction to obtain a polyamic acid solution;
(2) adding 3.036g of catalyst triethylamine and 3.063g of dehydrating agent acetic anhydride into the polyamic acid solution, performing chemical imidization, and stirring for 8 hours at 40 ℃ to obtain a polyimide solution;
(3) and casting the obtained polyimide solution on ultra-flat glass, and then placing the ultra-flat glass in an oven at 100 ℃ for drying for 24 hours to obtain the high-transparency low-expansion polyimide film.
The obtained polyimide film is subjected to performance characterization, the light transmittance of the polyimide film is 89% at 380 nm-780 nm, the light transmittance of the polyimide film is 92% at 450nm, the thermal expansion coefficient is 16 ppm/DEG C, and the glass transition temperature is 319.7 ℃.
Example 5
The high-transparency low-expansion polyimide film is prepared according to the following method:
(1) 2.273g of 4,4' -diaminobenzanilide diamine monomer was added to a four-necked flask containing 23.204g of DMAc, and the mixture was stirred under nitrogen to dissolve the monomer; weighing 3.528g of 3,3' -acylamino bis-o-cyclohexyl tetracarboxylic dianhydride monomer, adding the monomer into the solution in batches under the stirring condition, stirring for 4 hours at 40 ℃, and carrying out polycondensation reaction to obtain a polyamic acid solution;
(2) adding 3.036g of catalyst triethylamine and 3.063g of dehydrating agent acetic anhydride into the polyamic acid solution to perform chemical imidization, and stirring for 8 hours at 40 ℃ to obtain a polyimide solution;
(3) and casting the obtained polyimide solution on ultra-flat glass, and then placing the ultra-flat glass in an oven at 100 ℃ for drying for 24 hours to obtain the high-transparency low-expansion polyimide film.
The obtained polyimide film is subjected to performance characterization, the light transmittance of the polyimide film is 88% at 380 nm-780 nm, the light transmittance of the polyimide film is 90% at 450nm, the thermal expansion coefficient is 16 ppm/DEG C, and the glass transition temperature is 306.7 ℃.
Example 6
The high-transparency low-expansion polyimide film is prepared according to the following method:
(1) 2.273g of 4,4' -diaminobenzanilide diamine monomer was added to a four-necked flask containing 25.12g of DMAc, and the mixture was stirred under nitrogen to dissolve the monomer; weighing 1.764g of 3,3 '-acylamino bis-o-cyclohexyltetracarboxylic dianhydride and 2.243g of 6FDA (the molar ratio of 3,3' -acylamino bis-o-cyclohexyltetracarboxylic dianhydride to 6FDA is 1:1), adding the weighed materials into the solution in batches under the stirring condition, stirring the solution for 4 hours at the temperature of 40 ℃, and obtaining polyamic acid solution through polycondensation reaction;
(2) adding 3.036g of catalyst triethylamine and 3.063g of dehydrating agent acetic anhydride into the polyamic acid solution to perform chemical imidization, and stirring for 8 hours at 40 ℃ to obtain a polyimide solution;
(3) and casting the obtained polyimide solution on ultra-flat glass, and then placing the ultra-flat glass in an oven at 100 ℃ for drying for 24 hours to obtain the high-transparency low-expansion polyimide film.
The obtained polyimide film is subjected to performance characterization, the light transmittance of the polyimide film is 88% at 380 nm-780 nm, the light transmittance of the polyimide film is 92% at 450nm, the thermal expansion coefficient is 16 ppm/DEG C, and the glass transition temperature is 316.5 ℃.
Example 7
The high-transparency low-expansion polyimide film is prepared according to the following method:
(1) 2.273g of 4,4' -diaminobenzanilide diamine monomer was added to a four-necked flask containing 24.36g of DMAc and the mixture was stirred under nitrogen to dissolve the monomer; weighing 3,3 '-acylamino bis-o-cyclohexyltetracarboxylic dianhydride and 1.346g6FDA (the molar ratio of 3,3' -acylamino bis-o-cyclohexyltetracarboxylic dianhydride to 6FDA is 7:3), adding the mixture into the solution in batches under the stirring condition, stirring the mixture for 4 hours at 40 ℃, and carrying out polycondensation reaction to obtain a polyamic acid solution;
(2) adding 3.036g of catalyst triethylamine and 3.063g of dehydrating agent acetic anhydride into the polyamic acid solution to perform chemical imidization, and stirring for 8 hours at 40 ℃ to obtain a polyimide solution;
(3) and casting the obtained polyimide solution on ultra-flat glass, and then placing the ultra-flat glass in an oven at 100 ℃ for drying for 24 hours to obtain the high-transparency low-expansion polyimide film.
The obtained polyimide film is subjected to performance characterization, the light transmittance of the polyimide film is 88% at 380 nm-780 nm, the light transmittance of the polyimide film is 90% at 450nm, the thermal expansion coefficient is 15 ppm/DEG C, and the glass transition temperature is 311.4 ℃.
Example 8
The high-transparency low-expansion polyimide film is prepared according to the following method:
(1) 1.591g of 4,4 '-diaminobenzanilide diamine and 0.961g of TFMB monomer (molar ratio of 4,4' -diaminobenzanilide diamine to TFMB: 7:3) were added to a four-necked flask containing 23.204g of DMAc, and the mixture was stirred and dissolved under nitrogen atmosphere; weighing 3,3 '-acylamino bis-o-cyclohexyltetracarboxylic dianhydride and 1.346g6FDA (the molar ratio of 3,3' -acylamino bis-o-cyclohexyltetracarboxylic dianhydride to 6FDA is 7:3) under the stirring condition, adding the mixture into the solution in batches, stirring the mixture for 4 hours at 40 ℃, and carrying out polycondensation reaction to obtain a polyamic acid solution;
(2) adding 3.036g of catalyst triethylamine and 3.063g of dehydrating agent acetic anhydride into the polyamic acid solution to perform chemical imidization, and stirring for 8 hours at 40 ℃ to obtain a polyimide solution;
(3) and casting the obtained polyimide solution on ultra-flat glass, and then placing the ultra-flat glass in an oven at 100 ℃ for drying for 24 hours to obtain the high-transparency low-expansion polyimide film.
The obtained polyimide film is subjected to performance characterization, the light transmittance of the polyimide film is 88% at 380 nm-780 nm, the light transmittance of the polyimide film is 92% at 450nm, the thermal expansion coefficient is 16 ppm/DEG C, and the glass transition temperature is 310.7 ℃.
Comparative example 1
The polyimide film was prepared as follows:
(1) adding 2.253g of 2- (4-amino-phenyl) -benzoxazol-5-amine monomer into a four-neck flask containing 20.900g of DMAc solution, stirring under the protection of nitrogen until the monomer is completely dissolved, weighing 2.972g of 2,2',3,3' -biphenyltetracarboxylic acid (2,2',3,3' -BPDA), adding the mixture into the solution in batches under the stirring condition, and stirring at 40 ℃ for 4 hours to obtain a polyamic acid solution;
(2) adding 3.036g of catalyst triethylamine and 3.063g of dehydrating agent acetic anhydride into the polyamic acid solution to perform chemical imidization, and stirring for 8 hours at 40 ℃ to obtain a polyimide solution;
(3) and casting the obtained polyimide solution on ultra-flat glass, and then placing the ultra-flat glass in an oven at 100 ℃ for drying for 24 hours to obtain the high-transparency low-expansion polyimide film.
The obtained polyimide film is subjected to performance characterization, the light transmittance of the polyimide film is 40% at 380 nm-780 nm, the light transmittance of the polyimide film is 61% at 450nm, the thermal expansion coefficient is 15 ppm/DEG C, and the glass transition temperature is 339.2 ℃.
Comparative example 2
The polyimide film was prepared as follows:
(1) adding 2.253g of 2- (4-amino-phenyl) -benzoxazol-5-amine monomer into a four-neck flask containing 21.39g of DMAc solution, stirring under the protection of nitrogen until the monomer is completely dissolved, weighing 3.094g of dicyclohexyl-2, 2',3,3' -tetracarboxylic dianhydride (3,3-HBPDA), adding into the solution in batches under the stirring condition, and stirring at 40 ℃ for 4 hours to obtain a polyamic acid solution;
(2) adding 3.036g of catalyst triethylamine and 3.063g of dehydrating agent acetic anhydride into the polyamic acid solution to perform chemical imidization, and stirring for 8 hours at 40 ℃ to obtain a polyimide solution;
(3) and casting the obtained polyimide solution on ultra-flat glass, and then placing the ultra-flat glass in an oven at 100 ℃ for drying for 24 hours to obtain the high-transparency low-expansion polyimide film.
The obtained polyimide film is subjected to performance characterization, the light transmittance of the polyimide film is 88% at 380 nm-780 nm, the light transmittance of the polyimide film is 91% at 450nm, the thermal expansion coefficient is 56 ppm/DEG C, and the glass transition temperature is 301.5 ℃.
Comparative example 3
The polyimide film was prepared as follows:
(1) adding 2.253g of 2- (4-amino-phenyl) -benzoxazol-5-amine monomer into a four-neck flask containing 26.96g of DMAc solution, stirring under the protection of nitrogen until the monomer is completely dissolved, weighing 4.487g of 6FDA, adding the weighed solution into the solution in batches under the stirring condition, and stirring at 40 ℃ for 4 hours to obtain polyamic acid solution;
(2) adding 3.036g of catalyst triethylamine and 3.063g of dehydrating agent acetic anhydride into the polyamic acid solution to perform chemical imidization, and stirring for 8 hours at 40 ℃ to obtain a polyimide solution;
(3) and casting the obtained polyimide solution on ultra-flat glass, and then placing the ultra-flat glass in an oven at 100 ℃ for drying for 24 hours to obtain the high-transparency low-expansion polyimide film.
The obtained polyimide film is subjected to performance characterization, the light transmittance of the polyimide film is 70% at 380 nm-780 nm, the light transmittance of the polyimide film is 85% at 450nm, the thermal expansion coefficient is 41 ppm/DEG C, and the glass transition temperature is 341.6 ℃.
Comparative example 4
The high-transparency low-expansion polyimide film is prepared according to the following method:
(1) 3.202g of TFMB diamine monomer was added to a four-necked flask containing 28.07g of DMAc, and the mixture was stirred and dissolved under nitrogen; weighing 3,3 '-acylamino bis-o-cyclohexyltetracarboxylic dianhydride and 1.346g6FDA (the molar ratio of 3,3' -acylamino bis-o-cyclohexyltetracarboxylic dianhydride to 6FDA is 7:3), adding the mixture into the solution in batches under the stirring condition, stirring the mixture for 4 hours at 40 ℃, and carrying out polycondensation reaction to obtain a polyamic acid solution;
(2) adding 3.036g of catalyst triethylamine and 3.063g of dehydrating agent acetic anhydride into the polyamic acid solution to perform chemical imidization, and stirring for 8 hours at 40 ℃ to obtain a polyimide solution;
(3) and casting the obtained polyimide solution on ultra-flat glass, and then placing the ultra-flat glass in an oven at 100 ℃ for drying for 24 hours to obtain the high-transparency low-expansion polyimide film.
The obtained polyimide film is subjected to performance characterization, the light transmittance of the polyimide film is 89% at 380 nm-780 nm, the light transmittance of the polyimide film is 92% at 450nm, the thermal expansion coefficient is 49 ppm/DEG C, and the glass transition temperature is 313.3 ℃.
The performance test results of the polyimide films prepared in examples 1 to 8 and comparative examples 1 to 4 are shown in Table 1.
TABLE 1 polyimide film prepared in examples 1 to 8 and comparative examples 1 to 4. results of property test
Claims (10)
1. A high-transparency low-expansion polyimide film is characterized in that: obtained by polycondensation of diamine monomer and dianhydride monomer, wherein the diamine monomer comprises nitrogen-containing aromatic diamine R1The dianhydride monomer comprises 3,3' -amido bis-o-cyclohexyl tetracarboxylic dianhydride Ar1；
The 3,3' -amido bis-o-cyclohexyl tetracarboxylic dianhydride Ar1The polyimide is obtained by introducing an amide group into 2,2',3,3' -biphenyl tetracarboxylic dianhydride and then hydrogenating the amide group, and the structural formula of the polyimide is as follows:
2. the high-transparency low-expansion polyimide film according to claim 1, wherein: the diamine monomer is nitrogen-containing aromatic diamine R1Or a nitrogen-containing aromatic diamine R1With aromatic diamines R2Of a nitrogen-containing aromatic diamine R1Aromatic diamine R2Have different molecular structures;
the dianhydride monomer is 3,3' -amido bis-o-cyclohexyl tetracarboxylic dianhydride Ar1Or 3,3' -amido bis (o-cyclohexyl) tetracarboxylic dianhydride Ar1With fluorine-containing dianhydride Ar2A mixture of (a).
3. The high-transparency low-expansion polyimide film according to claim 2, wherein: fluorine-containing dianhydride Ar2Is one of the following dianhydrides:
4. the high-transparency low-expansion polyimide film according to claim 2, wherein: aromatic diamine R containing nitrogen1Any one of the following diamines:
5. the high-transparency low-expansion polyimide film according to claim 2, wherein: aromatic diamine R2Any one of the following diamines:
6. a method for preparing a high-transparency low-expansion polyimide film according to any one of claims 1 to 5, wherein: the method comprises the following steps:
(1) nitrogen-containing aromatic diamine R1Aromatic diamine R2Adding into organic solvent for dissolving to obtain solutionAdding 3,3' -amido bis-o-cyclohexyl tetracarboxylic dianhydride Ar in batches1And fluorine-containing dianhydride Ar2Obtaining polyamic acid solution through polycondensation reaction;
(2) adding a catalyst and a dehydrating agent into the polyamic acid solution, and carrying out chemical imidization to obtain a polyimide solution;
(3) and (3) casting the polyimide solution on super-flat glass, and then placing the super-flat glass in an oven to dry and remove the solvent to obtain the high-transparency low-expansion polyimide film.
7. The method for preparing a highly transparent and low-expansion polyimide film according to claim 6, wherein: in the step (1), the organic solvent is one or more of N, N-dimethylacetamide, N-methylpyrrolidone and N, N-dimethylformamide, and the solid content of PAA is 10-30 wt%.
8. The method for preparing a highly transparent and low-expansion polyimide film according to claim 6, wherein: in the step (1), the nitrogen-containing aromatic diamine R1And aromatic diamine R2The molar ratio of (A) to (B) is 1: 9-10: 0.
3,3' -amido bis (o-cyclohexyl) tetracarboxylic acid dianhydride Ar1And fluorine-containing dianhydride Ar2The molar ratio of (A) to (B) is 1: 9-10: 0.
9. The method for preparing a highly transparent and low-expansion polyimide film according to claim 6, wherein: in the step (1), the molar ratio of the dianhydride monomer to the diamine monomer is 1-1.2: 1, and the polycondensation reaction temperature is 10-50 ℃.
10. The method for preparing a highly transparent and low-expansion polyimide film according to claim 6, wherein: in the step (2), the catalyst is a tertiary amine catalyst, the dehydrating agent is acid anhydride, the molar ratio of the catalyst to the polyamic acid is 2-5: 1, the molar ratio of the dehydrating agent to the polyamic acid is 2-5: 1, and the chemical imidization temperature of the polyamic acid is 25-60 ℃;
in the step (3), the casting film forming temperature is 70-150 ℃, and the time is 10-48 h.
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