CN114716677A - Polyimide resin for OLED flexible substrate and preparation method thereof - Google Patents
Polyimide resin for OLED flexible substrate and preparation method thereof Download PDFInfo
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- CN114716677A CN114716677A CN202210528531.2A CN202210528531A CN114716677A CN 114716677 A CN114716677 A CN 114716677A CN 202210528531 A CN202210528531 A CN 202210528531A CN 114716677 A CN114716677 A CN 114716677A
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- polyimide resin
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- dianhydride
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 39
- 239000009719 polyimide resin Substances 0.000 title claims abstract description 39
- 239000000758 substrate Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000000178 monomer Substances 0.000 claims abstract description 65
- -1 diphenyl ether diamine Chemical class 0.000 claims abstract description 28
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 24
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims abstract description 14
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims abstract description 14
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000004985 diamines Chemical class 0.000 claims abstract description 8
- 235000010290 biphenyl Nutrition 0.000 claims abstract description 7
- 239000004305 biphenyl Substances 0.000 claims abstract description 7
- 229920003026 Acene Polymers 0.000 claims abstract description 6
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 229920005575 poly(amic acid) Polymers 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical group C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 claims description 9
- QIKYZXDTTPVVAC-UHFFFAOYSA-N 4-Aminobenzamide Chemical compound NC(=O)C1=CC=C(N)C=C1 QIKYZXDTTPVVAC-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 6
- YTVNOVQHSGMMOV-UHFFFAOYSA-N naphthalenetetracarboxylic dianhydride Chemical group C1=CC(C(=O)OC2=O)=C3C2=CC=C2C(=O)OC(=O)C1=C32 YTVNOVQHSGMMOV-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 238000006068 polycondensation reaction Methods 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 125000006160 pyromellitic dianhydride group Chemical group 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 230000009477 glass transition Effects 0.000 abstract description 5
- 239000011521 glass Substances 0.000 description 12
- 238000001035 drying Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- FYYYKXFEKMGYLZ-UHFFFAOYSA-N 4-(1,3-dioxo-2-benzofuran-5-yl)-2-benzofuran-1,3-dione Chemical group C=1C=C2C(=O)OC(=O)C2=CC=1C1=CC=CC2=C1C(=O)OC2=O FYYYKXFEKMGYLZ-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 229920001621 AMOLED Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses polyimide resin for an OLED flexible substrate and a preparation method thereof, wherein the polyimide resin is prepared by reacting dianhydride monomers and diamine monomers in a molar ratio of 1:1, wherein: the dianhydride monomers are one or two of pyromellitic dianhydride, biphenyl and acene dianhydride monomers; the diamine monomer is diphenyl ether diamine monomer and biphenyl amide diamine monomer, and the molar ratio of the diphenyl ether diamine monomer to the biphenyl amide diamine monomer is (1-2): 1. The prepared polyimide resin has good high temperature resistance and small thermal expansion coefficient, the glass transition temperature is not less than 420 ℃, and the linear thermal expansion coefficient is not more than 10 ppm/K.
Description
Technical Field
The invention belongs to the technical field of optical materials, and particularly relates to polyimide resin for an OLED flexible substrate and a preparation method thereof.
Background
Flexible-active-matrix organic light emitting diode (AMOLED) display technology has attracted attention because of its characteristics of fast response, wide viewing angle, wide color gamut, and ultra-portability. The polyimide resin is one of the best high-temperature resistant materials in the existing polymers, has excellent chemical stability and mechanical properties, is considered to be a flexible substrate material with great application potential, and initially shows excellent properties in the manufacturing of OLED flexible substrates.
The OLED flexible substrate requires that the polyimide resin has good high-temperature resistance, strong dimensional stability and high modulus, and the thermal expansion coefficient is less than or equal to that of the inorganic quartz glass material. However, the existing polyimide resin film is difficult to achieve the effect of having both higher glass transition temperature and lower linear expansion coefficient, and the application of the polyimide resin film in an OLED flexible substrate is limited.
Disclosure of Invention
The invention aims to provide polyimide resin for an OLED flexible substrate and a preparation method thereof, and the prepared polyimide resin has good high-temperature resistance and small thermal expansion coefficient, the glass transition temperature of the polyimide resin is not less than 420 ℃, and the linear thermal expansion coefficient of the polyimide resin is not more than 10 ppm/K.
The invention adopts the following technical scheme: the polyimide resin for the OLED flexible substrate is prepared by reacting a dianhydride monomer and a diamine monomer in a molar ratio of 1:1, wherein:
the dianhydride monomer is one or two of monomer of symbenzene, biphenyl and acene dianhydride;
the diamine monomer is diphenyl ether diamine monomer and biphenyl amide diamine monomer, and the molar ratio of the diphenyl ether diamine monomer to the biphenyl amide diamine monomer is (1-2): 1.
Further, the monomer of the pyromellitic dianhydride is pyromellitic dianhydride with the structural formula
Further, the biphenyl dianhydride monomer is 2, 3, 3, 4-biphenyl tetracarboxylic dianhydride, and the structural formula is as follows:
further, the acene dianhydride monomer is 1, 4, 5, 8-naphthalene tetracarboxylic dianhydride with the structural formula
Further, the diphenyl ether diamine monomer is 3, 4' -diaminodiphenyl ether, and the structural formula is shown in the specification
Further, the benzidine diamine monomer is N, N '- [1, 1, -biphenyl-4, 4' -bis (4-aminobenzamide) ], and the structural formula is
The invention also discloses a preparation method of the polyimide resin for the OLED flexible substrate, which comprises the following steps:
dissolving diphenyl ether diamine monomers and benzidine diamine monomers in an organic solvent, and adding dianhydride monomers under the protection of nitrogen and stirring for polycondensation reaction to obtain polyamide acid solution;
the organic solvent is N-methyl pyrrolidone, N-dimethylformamide or N, N-dimethylacetamide; the reaction temperature is 0-35 ℃, and the reaction time is 8-12 h;
and step two, coating the polyamic acid solution obtained in the step one, and then carrying out imidization reaction to obtain the polyimide resin film.
Further, in the second step, the imidization procedure is: 80 ℃/5min → 120 ℃/5min → 150 ℃/5min → 180 ℃/5min → 200 ℃/5min → 250 ℃/5min → 300 ℃/4min → 350 ℃/4min → 400 ℃/3 min.
The invention has the beneficial effects that: the prepared polyimide resin for the OLED flexible substrate has good high temperature resistance and small thermal expansion coefficient, the glass transition temperature is not less than 420 ℃, the linear thermal expansion coefficient is not more than 10ppm/K,
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
The invention discloses polyimide resin for an OLED flexible substrate, which is prepared by the following steps of: the dianhydride monomer is prepared by reacting a dianhydride monomer and a diamine monomer in a molar ratio of 1:1, wherein the dianhydride monomer is one or more of a pyromellitic dianhydride monomer, a biphenyl dianhydride monomer and an acene dianhydride monomer, the diamine monomer is a diphenyl ether diamine monomer and a benzidine diamine monomer, and the molar ratio of the diphenyl ether diamine monomer to the benzidine diamine monomer is (1-2: 1);
the pyromellitic dianhydride monomer is pyromellitic dianhydride, and the structure of the monomer is as follows:
the biphenyl dianhydride monomer is 2, 3, 3 ', 4' -biphenyl tetracarboxylic dianhydride, and the structural formula is shown as follows:
the acene dianhydride monomer is 1, 4, 5, 8-naphthalene tetracarboxylic dianhydride, and the structural formula is shown as follows:
the diphenyl ether diamine monomer is 3, 4' -diaminodiphenyl ether, and the structural formula is shown as follows:
the benzidine diamine monomer is N, N ' - [1, 1 ' -biphenyl-4, 4 ' -bis (4-aminobenzamide) ], and the structural formula is shown as follows:
the preparation method of the polyimide resin for the OLED flexible substrate comprises the following steps:
dissolving diphenyl ether diamine monomers and benzidine diamine monomers in an organic solvent, adding dianhydride monomers under stirring, and performing polycondensation reaction to obtain polyamide acid solution;
the polycondensation reaction is carried out under the protection of nitrogen, the reaction temperature is 0-35 ℃, the reaction time is 8-12h, and the organic solvent is one or the combination of more of N-methylpyrrolidone, N-dimethylformamide or N, N-dimethylacetamide; and adding the dianhydride monomer for 2-4 times.
And step two, coating the polyamic acid solution obtained in the step one, and then carrying out imidization reaction to obtain the polyimide resin film. The imidization procedure is as follows: 80 ℃/5min → 120 ℃/5min → 150 ℃/5min → 180 ℃/5min → 200 ℃/5min → 250 ℃/5min → 300 ℃/4min → 350 ℃/4min → 400 ℃/3 min.
Example 1
Under the protection of nitrogen and stirring, adding 30mmol of pyromellitic dianhydride into an N, N-dimethylacetamide solution in which 15mmol of 3, 4 '-diaminodiphenyl ether and 15mmol of N, N' - [1, 1 '-biphenyl-4, 4' -bis (4-aminobenzamide) ] are dissolved for 2-4 times, and reacting for 8 hours at 0-35 ℃ to obtain a polyamic acid solution with the solid content of 15 wt%;
the obtained polyamic acid solution was coated on a glass plate, and the glass plate was placed in an explosion-proof drying oven and heated to imidize. The imidization process is as follows: 80 ℃/5min → 120 ℃/5min → 150 ℃/5min → 180 ℃/5min → 200 ℃/5min → 250 ℃/5min → 300 ℃/4min → 350 ℃/4min → 400 ℃/3 min. Thereafter, the film was cooled and released to obtain a polyimide resin film M1 having a thickness of 25 μ M.
Example 2
Under the protection of nitrogen and stirring, adding 30mmol of 2, 3, 3 ', 4 ' -biphenyl tetracarboxylic dianhydride into an N, N-dimethylacetamide solution in which 15mmol of 3, 4 ' -diaminodiphenyl ether and 15mmol of N, N ' - [1, 1, -biphenyl-4, 4 ' -bis (4-aminobenzamide) ] are dissolved for 2-4 times, and reacting at 0-35 ℃ for 10 hours to obtain a polyamic acid solution with the solid content of 15 wt%;
the obtained polyamic acid solution was coated on a glass plate, and the glass plate was placed in an explosion-proof drying oven and heated to imidize. Wherein the imidization process is as follows: 80 ℃/5min → 120 ℃/5min → 150 ℃/5min → 180 ℃/5min → 200 ℃/5min → 250 ℃/5min → 300 ℃/4min → 350 ℃/4min → 400 ℃/3 min. Thereafter, the film was cooled and released to obtain a polyimide resin film M2 having a thickness of 25 μ M.
Example 3
Under the protection of nitrogen and stirring, adding 30mmol of 1, 4, 5, 8-naphthalene tetracarboxylic dianhydride into an N, N-dimethylformamide solution dissolved with 15mmol of 3, 4 '-diaminodiphenyl ether and 15mmol of N, N' - [1, 1 '-biphenyl-4, 4' -bis (4-aminobenzamide) ] for 2-4 times, and reacting at 0-35 ℃ for 12 hours to obtain a polyamic acid solution with the solid content of 15 wt%;
the obtained polyamic acid solution was coated on a glass plate, and the glass plate was placed in an explosion-proof drying oven and heated to imidize. Wherein the imidization process is as follows: 80 ℃/5min → 120 ℃/5min → 150 ℃/5min → 180 ℃/5min → 200 ℃/5min → 250 ℃/5min → 300 ℃/4min → 350 ℃/4min → 400 ℃/3 min. Thereafter, the film was cooled and released to obtain a polyimide resin film M3 having a thickness of 25 μ M.
Example 4
Under the protection of nitrogen and stirring, adding 15mmol of pyromellitic dianhydride and 15mmol of 2, 3, 3 ', 4 ' -biphenyl tetracarboxylic dianhydride into an N, N-dimethylformamide solution dissolved with 20mmol of 3, 4 ' -diaminodiphenyl ether and 10mmol of N, N ' - [1, 1, -biphenyl-4, 4 ' -bis (4-aminobenzamide) ] for 2-4 times, and reacting at 0-35 ℃ for 8 hours to obtain a polyamic acid solution with the solid content of 15 wt%;
the obtained polyamic acid solution was coated on a glass plate, and the glass plate was placed in an explosion-proof drying oven and heated to imidize. Wherein the imidization process is as follows: 80 ℃/5min → 120 ℃/5min → 150 ℃/5min → 180 ℃/5min → 200 ℃/5min → 250 ℃/5min → 300 ℃/4min → 350 ℃/4min → 400 ℃/3 min. Thereafter, the film was cooled and released to obtain a polyimide resin film M4 having a thickness of 25 μ M.
Example 5
Under the protection of nitrogen and stirring, pouring 15mmol of 1, 4, 5, 8-naphthalene tetracarboxylic dianhydride and 15mmol of 2, 3, 3 ', 4' -biphenyl tetracarboxylic dianhydride into an N-methyl pyrrolidone solution dissolved with 20mmol of 3, 4 '-diaminodiphenyl ether and 10mmol of N, N, - [1, 1, -biphenyl-4, 4' -bis (4-aminobenzamide) ] for 2-4 times, and reacting for 10 hours at 0-35 ℃ to obtain a polyamic acid solution with the solid content of 15 wt%;
the obtained polyamic acid solution was coated on a glass plate, and the glass plate was placed in an explosion-proof drying oven and heated to imidize. Wherein the imidization process is as follows: 80 ℃/5min → 120 ℃/5min → 150 ℃/5min → 180 ℃/5min → 200 ℃/5min → 250 ℃/5min → 300 ℃/4min → 350 ℃/4min → 400 ℃/3 min. Thereafter, the film was cooled and released to obtain a polyimide resin film M5 having a thickness of 25 μ M.
Example 6
Under the protection of nitrogen and stirring, adding 15mmol of pyromellitic dianhydride and 15mmol of 1, 4, 5, 8-naphthalene tetracarboxylic dianhydride into an N-methylpyrrolidone solution dissolved with 20mmol of 3, 4 '-diaminodiphenyl ether and 10mmol of N, N, - [1, 1, -biphenyl-4, 4' -bis (4-aminobenzamide) ] for 2-4 times, and reacting for 12 hours at 0-35 ℃ to obtain a polyamic acid solution with the solid content of 15 wt%;
the obtained polyamic acid solution was coated on a glass plate, and the glass plate was placed in an explosion-proof drying oven and heated to imidize. Wherein the imidization process is as follows: 80 ℃/5min → 120 ℃/5min → 150 ℃/5min → 180 ℃/5min → 200 ℃/5min → 250 ℃/5min → 300 ℃/4min → 350 ℃/4min → 400 ℃/3 min. Then, the film was cooled and released to obtain a polyimide resin film M6 having a thickness of 25 μ M.
The properties of the polyimide resin films M1, M2, M3, M4, M5 and M6 prepared in the above examples were measured, and the measurement methods and data are shown in table 1:
table 1 performance test data
As can be seen from the data in Table 1, the polyimide resin for the OLED flexible substrate prepared by the method of the invention has good high temperature resistance and small thermal expansion coefficient, the glass transition temperature of the polyimide resin is not less than 420 ℃, and the linear thermal expansion coefficient of the polyimide resin is not more than 10 ppm/K. It has high tensile strength and high elastic modulus.
Claims (8)
1. The polyimide resin for the OLED flexible substrate is characterized by being prepared by reacting dianhydride monomers and diamine monomers in a molar ratio of 1:1, wherein:
the dianhydride monomers are one or two of pyromellitic dianhydride, biphenyl and acene dianhydride monomers;
the diamine monomer is a diphenyl ether diamine monomer and a benzidine diamine monomer, and the molar ratio of the diphenyl ether diamine monomer to the benzidine diamine monomer is (1-2): 1.
2. The polyimide resin for an OLED flexible substrate according to claim 1, wherein the pyromellitic dianhydride monomer is pyromellitic dianhydride and has a structural formula of
3. The polyimide resin for an OLED flexible substrate according to claim 1, wherein the biphenyl dianhydride monomer is 2, 3, 3, 4, -biphenyl tetracarboxylic dianhydride, and has a structural formula:
4. the polyimide resin for the OLED flexible substrate according to claim 1, wherein the monomer of the pyromellitic dianhydride is 1, 4, 5, 8-naphthalene tetracarboxylic dianhydride, and has the structural formula
5. The polyimide resin for the OLED flexible substrate according to claim 1, 2, 3 or 4, wherein the diphenyl ether diamine monomer is 3, 4' -diaminodiphenyl ether and has a structural formula of
6. The polyimide resin for the OLED flexible substrate according to claim 5, wherein the benzidine diamine monomer is N, N '- [1, 1, -biphenyl-4, 4' -bis (4-aminobenzamide) ], and has a structural formula of
7. The method for preparing the polyimide resin for the OLED flexible substrate according to any one of claims 1 to 6, wherein the method comprises the following steps:
dissolving diphenyl ether diamine monomers and benzidine diamine monomers in an organic solvent, and adding dianhydride monomers under the protection of nitrogen and stirring for polycondensation reaction to obtain polyamide acid solution;
the organic solvent is N-methyl pyrrolidone, N-dimethylformamide or N, N-dimethylacetamide; the reaction temperature is 0-35 ℃, and the reaction time is 8-12 h;
and step two, coating the polyamic acid solution obtained in the step one, and then carrying out imidization reaction to obtain the polyimide resin film.
8. The method of claim 7, wherein in the second step, the imidization procedure is as follows: 80 ℃/5min → 120 ℃/5min → 150 ℃/5min → 180 ℃/5min → 200 ℃/5min → 250 ℃/5min → 300 ℃/4min → 350 ℃/4min → 400 ℃/3 min.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07292103A (en) * | 1994-04-25 | 1995-11-07 | Shin Etsu Chem Co Ltd | Polyimide copolymer and method for producing the same |
| CN108659533A (en) * | 2018-06-12 | 2018-10-16 | 中国科学院化学研究所 | A kind of high heat-resisting super-low expansion Kapton and the preparation method and application thereof |
| CN108864426A (en) * | 2018-06-12 | 2018-11-23 | 中国科学院化学研究所 | A kind of super-low expansion fluorinated polyimide film and the preparation method and application thereof |
| CN112708134A (en) * | 2020-12-28 | 2021-04-27 | 深圳瑞华泰薄膜科技股份有限公司 | Colorless transparent copolyamide-imide film and preparation method thereof |
-
2022
- 2022-05-16 CN CN202210528531.2A patent/CN114716677A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07292103A (en) * | 1994-04-25 | 1995-11-07 | Shin Etsu Chem Co Ltd | Polyimide copolymer and method for producing the same |
| CN108659533A (en) * | 2018-06-12 | 2018-10-16 | 中国科学院化学研究所 | A kind of high heat-resisting super-low expansion Kapton and the preparation method and application thereof |
| CN108864426A (en) * | 2018-06-12 | 2018-11-23 | 中国科学院化学研究所 | A kind of super-low expansion fluorinated polyimide film and the preparation method and application thereof |
| CN112708134A (en) * | 2020-12-28 | 2021-04-27 | 深圳瑞华泰薄膜科技股份有限公司 | Colorless transparent copolyamide-imide film and preparation method thereof |
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