CN112625238B - High molecular weight polyimide precursor solution with stable storage and flexible substrate - Google Patents
High molecular weight polyimide precursor solution with stable storage and flexible substrate Download PDFInfo
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- CN112625238B CN112625238B CN202011372346.6A CN202011372346A CN112625238B CN 112625238 B CN112625238 B CN 112625238B CN 202011372346 A CN202011372346 A CN 202011372346A CN 112625238 B CN112625238 B CN 112625238B
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 75
- 239000004642 Polyimide Substances 0.000 title claims abstract description 70
- 239000002243 precursor Substances 0.000 title claims abstract description 63
- 239000000758 substrate Substances 0.000 title claims abstract description 57
- 238000003860 storage Methods 0.000 title claims abstract description 18
- 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 31
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims abstract description 23
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000001624 naphthyl group Chemical group 0.000 claims abstract description 13
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 10
- CQMIJLIXKMKFQW-UHFFFAOYSA-N 4-phenylbenzene-1,2,3,5-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C1C1=CC=CC=C1 CQMIJLIXKMKFQW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 26
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 claims description 17
- 239000011521 glass Substances 0.000 claims description 14
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 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 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- 238000001723 curing Methods 0.000 claims description 3
- 238000005266 casting Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000001029 thermal curing Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 description 20
- 239000010408 film Substances 0.000 description 18
- 239000000178 monomer Substances 0.000 description 18
- 229920005575 poly(amic acid) Polymers 0.000 description 18
- 238000001035 drying Methods 0.000 description 17
- 238000011056 performance test Methods 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000012456 homogeneous solution Substances 0.000 description 7
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000004985 diamines Chemical class 0.000 description 5
- -1 perylene anhydride Chemical class 0.000 description 5
- 238000010345 tape casting Methods 0.000 description 5
- 238000007865 diluting Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N binaphthyl group Chemical group C1(=CC=CC2=CC=CC=C12)C1=CC=CC2=CC=CC=C12 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920002457 flexible plastic Polymers 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0346—Organic insulating material consisting of one material containing N
-
- 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
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Abstract
The invention provides a high molecular weight polyimide precursor solution with stable storage and a flexible substrate, wherein the polyimide precursor solution comprises tetracarboxylic dianhydride containing naphthalene ring, 3 ', 4, 4' -biphenyl tetracarboxylic dianhydride and p-phenylenediamine which are subjected to polycondensation reaction at 50-80 ℃. The invention provides a high molecular weight polyimide precursor solution with storage stability and a flexible substrate.
Description
Technical Field
The invention relates to the technical field of polyimide, in particular to a high molecular weight polyimide precursor solution with stable storage and a flexible substrate.
Background
In recent years, Polyimide (PI) resins have been widely used as materials for integration in semiconductors such as LCDs, PDPs, etc., particularly, PI is used for flexible plastic display panels having light and flexible characteristics, because of advantages such as easy synthesis, capability of being formed into thin films, and no need for a crosslinking agent for curing.
In general, when PI is used for a flexible substrate, a polyimide flexible substrate excellent in optical, mechanical and thermal characteristics is prepared by coating a polyimide precursor solution (polyamic acid solution) on a support carrier, followed by imidization in the form of a thin film from the carrier, and peeling. It is known that if the molecular weight of the polyimide precursor solution (polyamic acid solution) is below a certain level (i.e., the molecular weight is too small), a polyimide film having good physical properties cannot be obtained after imidization. However, if the molecular weight of the obtained polyamic acid is too high, the viscosity thereof is too large to deteriorate the workability, and the polyimide precursor solution having too high a molecular weight generates a great internal stress due to the interaction between the molecules thereof, easily resulting in a decrease in storage stability at room temperature.
Disclosure of Invention
Based on the technical problems of the background art, the present invention provides a high molecular weight polyimide precursor solution with storage stability and a flexible substrate, wherein the polyimide precursor solution has the advantages of high molecular weight and storage stability at room temperature, so that the flexible substrate prepared from the polyimide precursor solution can have excellent heat resistance and mechanical strength.
The invention provides a high molecular weight polyimide precursor solution with stable storage, which is obtained by carrying out polycondensation reaction on tetracarboxylic dianhydride containing naphthalene ring, 3 ', 4, 4' -biphenyl tetracarboxylic dianhydride and p-phenylenediamine at 50-80 ℃.
Preferably, the tetracarboxylic dianhydride containing a naphthalene ring is at least one of the structures shown as follows:
preferably, the naphthalene ring-containing tetracarboxylic dianhydride is used in an amount of 5 to 20 mol% based on the 3, 3 ', 4, 4' -biphenyltetracarboxylic dianhydride.
Preferably, the molar total amount of the tetracarboxylic dianhydride containing a naphthalene ring and the 3, 3 ', 4, 4' -biphenyltetracarboxylic dianhydride is 0.995 to 1.005 times that of p-phenylenediamine.
Preferably, the time of the polycondensation reaction is 8 to 15 hours.
Preferably, the solvent of the polycondensation reaction is at least one of N-methylpyrrolidone, dimethylsulfoxide, N-dimethylformamide or N, N-dimethylacetamide.
The present invention provides a flexible substrate obtained by applying the polyimide precursor solution to a film, and then heating and curing the film.
Preferably, the method for coating and film forming is a casting method, and the support for coating and film forming is a glass plate.
Preferably, the heat curing comprises: heating to 70-80 ℃ for 1-2h, cooling to room temperature, heating to 150-.
According to the polyimide precursor solution, the tetracarboxylic dianhydride containing naphthalene ring, the 3, 3 ', 4, 4' -biphenyltetracarboxylic dianhydride and the p-phenylenediamine are used as raw materials for polycondensation reaction, naphthalene ring groups can be introduced into the molecular structure of the polyimide, so that the prepared polyimide precursor solution has excellent storage stability at room temperature, the naphthalene ring reaction activity is low, the molecular weight can be improved while the storage stability is improved by raising the polymerization reaction temperature, and finally the flexible substrate prepared from the polyimide precursor solution can have excellent mechanical properties and heat resistance.
Detailed Description
The polyimide precursor solution provided by the invention is prepared by performing polycondensation reaction on tetracarboxylic dianhydride containing naphthalene ring, 3 ', 4, 4' -biphenyl tetracarboxylic dianhydride and p-phenylenediamine at 50-80 ℃.
The polyimide precursor solution is obtained by dissolving the diamine monomer in an organic solvent, adding a dianhydride monomer, and carrying out polymerization reaction at a proper reaction temperature. The reaction temperature is required to be much higher than the temperature for the polycondensation reaction of general polyamic acid, and is preferably 50 ℃ or higher and 80 ℃ or lower; the reaction time is preferably 8 hours or more and 15 hours or less; as for the reaction environment, it is preferably an inert gas environment; as the organic solvent used for the reaction, N-methylpyrrolidone, dimethyl sulfoxide, N-dimethylformamide or N, N-dimethylacetamide is preferable.
The flexible substrate of the present invention is formed by coating a polyimide precursor solution on a support and imidizing the solution to form a film. The imidization process is preferably to dilute the polyamic acid solution by using an organic solvent and then coat the polyamic acid solution on a clean and smooth glass plate by a tape casting method to form a film, then place the glass plate in a blast drying box at 70-80 ℃ for 1-2h, place the glass plate in a tubular furnace after the temperature is reduced to room temperature, heat the glass plate to 150-.
Hereinafter, the technical solution of the present invention will be described in detail by specific examples, but these examples should be explicitly proposed for illustration, but should not be construed as limiting the scope of the present invention.
Example 1
A high molecular weight polyimide precursor solution with stable storage and a flexible substrate are prepared by the following steps:
s1, dissolving 20mmol of p-phenylenediamine as a diamine monomer raw material in 60mL of NMP under a nitrogen atmosphere, stirring until the p-phenylenediamine is completely dissolved, and adding 19mmol of 3, 3 ', 4, 4' -biphenyl tetracarboxylic dianhydride and 1mmol of binaphthyl dianhydride
Continuously stirring the raw materials serving as tetracarboxylic dianhydride monomer until the raw materials are completely dissolved to obtain homogeneous solution, and reacting the homogeneous solution at the temperature of 60 ℃ for 10 hours to obtain polyamic acid solution, namely the polyimide precursor solution;
s2, diluting the polyamic acid solution obtained in the step S1 with NMP to obtain a solution with a solid content of 10 wt%, uniformly coating the solution on a glass substrate by using a tape casting method to obtain the glass substrate with the surface coated with the polyamic acid solution, drying the substrate in a blast drying oven at 70 ℃ for 2h, cooling to 25 ℃, taking out, placing in a tube furnace, heating from room temperature to 150 ℃, treating at 150 ℃ for 60min, heating to 220 ℃, treating at 220 ℃ for 30min, heating to 310 ℃, treating at 310 ℃ for 30min, heating to 360 ℃, treating at 360 ℃ for 30min, heating to 400 ℃, treating at 400 ℃ for 30min, cooling to 25 ℃, taking out, placing in water to remove a film to obtain the film, and drying and dewatering the film in a drying oven at 100 ℃ to obtain the polyimide film with the thickness of 50 microns, namely the flexible substrate.
The results of the performance test on the polyimide precursor solution and the flexible substrate are shown in tables 1 and 2.
Example 2
A storage-stable high molecular weight polyimide precursor solution and a flexible substrate were prepared in the same manner as in example 1, except that 19mmol of 3, 3 ', 4, 4' -biphenyltetracarboxylic dianhydride and 1mmol of perylene anhydride were added to the polyimide precursor solution in the preparation
As a raw material of the tetracarboxylic dianhydride monomer.
The results of the performance test on the polyimide precursor solution and the flexible substrate thus obtained are shown in tables 1 and 2.
Example 3
A storage-stable high molecular weight polyimide precursor solution and a flexible substrate were prepared in the same manner as in example 1, except that 19mmol of 3, 3 ', 4, 4' -biphenyltetracarboxylic dianhydride and 1mmol of naphthalene dianhydride were added to the polyimide precursor solution in the preparation
As a raw material of the tetracarboxylic dianhydride monomer.
The results of the performance test on the polyimide precursor solution and the flexible substrate thus obtained are shown in tables 1 and 2.
Example 4
A storage-stable high molecular weight polyimide precursor solution and a flexible substrate were prepared in the same manner as in example 1, except that 18mmol of 3, 3 ', 4, 4' -biphenyltetracarboxylic dianhydride and 2mmol of binaphthyl dianhydride were added to the polyimide precursor solution in the preparation
As a raw material of the tetracarboxylic dianhydride monomer.
The results of the performance test on the polyimide precursor solution and the flexible substrate thus obtained are shown in tables 1 and 2.
Example 5
A storage-stable high molecular weight polyimide precursor solution and a flexible substrate were prepared in the same manner as in example 1, except that 18mmol of 3, 3 ', 4, 4' -biphenyltetracarboxylic dianhydride and 2mmol of perylene anhydride were added to the polyimide precursor solution in the preparation
As a raw material of the tetracarboxylic dianhydride monomer.
The results of the performance test on the polyimide precursor solution and the flexible substrate thus obtained are shown in tables 1 and 2.
Example 6
A storage-stable high molecular weight polyimide precursor solution and a flexible substrate were prepared in the same manner as in example 1, except that 18mmol of 3, 3 ', 4, 4' -biphenyltetracarboxylic dianhydride and 2mmol of naphthalene dianhydride were added to the polyimide precursor solution in the preparation
As a raw material of the tetracarboxylic dianhydride monomer.
The results of the performance test on the polyimide precursor solution and the flexible substrate thus obtained are shown in tables 1 and 2.
Example 7
A storage-stable high molecular weight polyimide precursor solution and a flexible substrate were prepared in the same manner as in example 1, except that 17mmol of 3, 3 ', 4, 4' -biphenyltetracarboxylic dianhydride and 3mmol of binaphthyl dianhydride were added to the polyimide precursor solution in the preparation
As a raw material of the tetracarboxylic dianhydride monomer.
The results of the performance test on the polyimide precursor solution and the flexible substrate thus obtained are shown in tables 1 and 2.
Example 8
A storage-stable high molecular weight polyimide precursor solution and a flexible substrate were prepared in the same manner as in example 1,except that in the preparation of the polyimide precursor solution, 17mmol of 3, 3 ', 4, 4' -biphenyltetracarboxylic dianhydride and 3mmol of perylene anhydride were added
As a raw material of the tetracarboxylic dianhydride monomer.
The results of the performance test on the polyimide precursor solution and the flexible substrate thus obtained are shown in tables 1 and 2.
Example 9
A storage-stable high molecular weight polyimide precursor solution and a flexible substrate were prepared in the same manner as in example 1, except that 17mmol of 3, 3 ', 4, 4' -biphenyltetracarboxylic dianhydride and 3mmol of naphthalene dianhydride were added to the polyimide precursor solution in the preparation
As a raw material of the tetracarboxylic dianhydride monomer.
The results of the performance test on the polyimide precursor solution and the flexible substrate thus obtained are shown in tables 1 and 2.
Comparative example 1
A polyimide precursor solution and a flexible substrate are prepared by the following steps:
s1, under the nitrogen atmosphere, dissolving 20mmol of p-phenylenediamine serving as a diamine monomer raw material in 60mL of NMP, stirring until the p-phenylenediamine is completely dissolved, adding 20mmol of 3, 3 ', 4, 4' -biphenyl tetracarboxylic dianhydride serving as a tetracarboxylic dianhydride monomer raw material, continuously stirring until the p-phenylenediamine is completely dissolved to obtain a homogeneous solution, and reacting at 60 ℃ for 10 hours to obtain a polyamic acid solution, namely the polyimide precursor solution;
s2, diluting the polyamic acid solution obtained in the step S1 with NMP to obtain a solution with a solid content of 10 wt%, uniformly coating the solution on a glass substrate by using a tape casting method to obtain the glass substrate with the surface coated with the polyamic acid solution, drying the substrate in a blast drying oven at 70 ℃ for 2h, cooling to 25 ℃, taking out, placing in a tube furnace, heating from room temperature to 150 ℃, treating at 150 ℃ for 60min, heating to 220 ℃, treating at 220 ℃ for 30min, heating to 310 ℃, treating at 310 ℃ for 30min, heating to 360 ℃, treating at 360 ℃ for 30min, heating to 400 ℃, treating at 400 ℃ for 30min, cooling to 25 ℃, taking out, placing in water to remove a film to obtain the film, and drying and dewatering the film in a drying oven at 100 ℃ to obtain the polyimide film with the thickness of 50 microns, namely the flexible substrate.
The results of the performance test on the polyimide precursor solution and the flexible substrate are shown in tables 1 and 2.
Comparative example 2
A polyimide precursor solution and a flexible substrate are prepared by the following steps:
s1, dissolving 20mmol of p-phenylenediamine as a diamine monomer raw material in 60mL of NMP under a nitrogen atmosphere, stirring until the p-phenylenediamine is completely dissolved, and adding 19mmol of 3, 3 ', 4, 4' -biphenyl tetracarboxylic dianhydride and 1mmol of binaphthyl dianhydride
Continuously stirring the raw materials serving as tetracarboxylic dianhydride monomer until the raw materials are completely dissolved to obtain homogeneous solution, and reacting the homogeneous solution at the temperature of 25 ℃ for 10 hours to obtain polyamic acid solution, namely the polyimide precursor solution;
s2, diluting the polyamic acid solution obtained in the step S1 with NMP to obtain a solution with a solid content of 10 wt%, uniformly coating the solution on a glass substrate by using a tape casting method to obtain the glass substrate with the surface coated with the polyamic acid solution, drying the substrate in a blast drying oven at 70 ℃ for 2h, cooling to 25 ℃, taking out, placing in a tube furnace, heating from room temperature to 150 ℃, treating at 150 ℃ for 60min, heating to 220 ℃, treating at 220 ℃ for 30min, heating to 310 ℃, treating at 310 ℃ for 30min, heating to 360 ℃, treating at 360 ℃ for 30min, heating to 400 ℃, treating at 400 ℃ for 30min, cooling to 25 ℃, taking out, placing in water to remove a film to obtain the film, and drying and dewatering the film in a drying oven at 100 ℃ to obtain the polyimide film with the thickness of 50 microns, namely the flexible substrate.
The results of the performance test on the polyimide precursor solution and the flexible substrate are shown in tables 1 and 2.
Comparative example 3
A polyimide precursor solution and a flexible substrate are prepared by the following steps:
s1, dissolving 20mmol of p-phenylenediamine as a diamine monomer raw material in 60mL of NMP under a nitrogen atmosphere, stirring until the p-phenylenediamine is completely dissolved, and adding 16mmol of 3, 3 ', 4, 4' -biphenyl tetracarboxylic dianhydride and 4mmol of binaphthyl dianhydride
Continuously stirring the raw materials serving as tetracarboxylic dianhydride monomer until the raw materials are completely dissolved to obtain homogeneous solution, and reacting the homogeneous solution at the temperature of 60 ℃ for 10 hours to obtain polyamic acid solution, namely the polyimide precursor solution;
s2, diluting the polyamic acid solution obtained in the step S1 with NMP to obtain a solution with a solid content of 10 wt%, uniformly coating the solution on a glass substrate by using a tape casting method to obtain the glass substrate with the surface coated with the polyamic acid solution, drying the substrate in a blast drying oven at 70 ℃ for 2h, cooling to 25 ℃, taking out, placing in a tube furnace, heating from room temperature to 150 ℃, treating at 150 ℃ for 60min, heating to 220 ℃, treating at 220 ℃ for 30min, heating to 310 ℃, treating at 310 ℃ for 30min, heating to 360 ℃, treating at 360 ℃ for 30min, heating to 400 ℃, treating at 400 ℃ for 30min, cooling to 25 ℃, taking out, placing in water to remove a film to obtain the film, and drying and dewatering the film in a drying oven at 100 ℃ to obtain the polyimide film with the thickness of 50 microns, namely the flexible substrate.
The results of the performance test on the polyimide precursor solution and the flexible substrate are shown in tables 1 and 2.
The polyimide precursor solutions and the flexible substrates obtained in the above examples and comparative examples were subjected to the performance tests shown in the following methods, and the results are shown in the following tables 1 and 2:
weight average molecular weight
Gel Permeation Chromatography (GPC) measurement was carried out, and the weight average molecular weight was measured in terms of polystyrene.
Storage stability
The polyimide precursor solution is unstable at normal temperature and its viscosity decreases with an excessively long storage time, and the storage stability is judged by measuring the change in viscosity of the polyimide precursor solution after storage at 25 ℃ for 14 days with a viscometer.
Glass transition temperature
DSC measurement was performed under a nitrogen atmosphere at a temperature rise rate of 10 ℃/min using a differential scanning calorimeter apparatus.
Coefficient of linear thermal expansion
A thermal mechanical analyzer was used to apply a 50mN load under a nitrogen atmosphere, and the temperature was measured at a temperature rise rate of 10 ℃/min to obtain an average value.
Mechanical Properties
The tensile strength and the elongation at break were measured by the method specified in astm d882 using an universal tensile machine.
TABLE 1 test results of polyimide precursor solutions obtained in examples 1 to 9 and comparative examples 1 to 3
Table 2 test results of flexible substrates obtained in correspondence with examples 1 to 9 and comparative examples 1 to 3
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (5)
1. A high molecular weight polyimide precursor solution with stable storage is characterized in that tetracarboxylic dianhydride containing naphthalene ring, 3 ', 4, 4' -biphenyl tetracarboxylic dianhydride and p-phenylenediamine are subjected to polycondensation reaction at 50-80 ℃;
the tetracarboxylic dianhydride containing naphthalene ring is at least one of the following structures:
the consumption of the tetracarboxylic dianhydride containing naphthalene ring is 5-20 mol% of 3, 3 ', 4, 4' -biphenyl tetracarboxylic dianhydride;
the total mole amount of the tetracarboxylic dianhydride containing naphthalene ring and the 3, 3 ', 4, 4' -biphenyl tetracarboxylic dianhydride is 0.995-1.005 times of that of the p-phenylenediamine;
the time of the polycondensation reaction is 8-15 h.
2. The storage stable, high molecular weight polyimide precursor solution of claim 1 wherein the solvent of the polycondensation reaction is at least one of N-methylpyrrolidone, dimethylsulfoxide, N-dimethylformamide, or N, N-dimethylacetamide.
3. A flexible substrate obtained by applying the polyimide precursor solution according to any one of claims 1 to 2 to a film, and then heating and curing the film.
4. The flexible substrate of claim 3, wherein the coating film is formed by a casting method, and the support is a glass plate.
5. The flexible substrate of claim 3 or 4, wherein the thermal curing comprises: heating to 70-80 ℃ for 1-2h, cooling to room temperature, heating to 150-.
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Denomination of invention: A Stable High Molecular Weight Polyimide Precursor Solution and Flexible Substrate for Storage Effective date of registration: 20231114 Granted publication date: 20220520 Pledgee: China Merchants Bank Co.,Ltd. Jinhua Branch Pledgor: Zhejiang Zhongke Jiuyuan New Material Co.,Ltd. Registration number: Y2023980065179 |