CN111116913A - Polyamide acid solution, polyimide film and application thereof - Google Patents

Polyamide acid solution, polyimide film and application thereof Download PDF

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CN111116913A
CN111116913A CN201911425339.5A CN201911425339A CN111116913A CN 111116913 A CN111116913 A CN 111116913A CN 201911425339 A CN201911425339 A CN 201911425339A CN 111116913 A CN111116913 A CN 111116913A
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polyamic acid
acid solution
tetracarboxylic dianhydride
aromatic
polyimide film
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吴京玮
王雪岚
李琳
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Beijing Sineva Technology Co ltd
Beijing Xinyihua Material Technology Co ltd
Fuyang Sineva Material Technology Co Ltd
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Fuyang Sineva Material Technology Co Ltd
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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
    • 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
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • G09F9/301—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements flexible foldable or roll-able electronic displays, e.g. thin LCD, OLED
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica

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Abstract

The invention provides a polyamic acid solution, a polyimide film and application thereof. The preparation raw materials of the polyamic acid solution comprise: aromatic tetracarboxylic dianhydride monomer, aromatic diamine monomer, compound containing tetracarboxyl structure and solvent; the structural formula of the compound containing the tetracarboxyl structure is shown as a formula C. The polyamic acid solution prepared by the invention has the characteristics of high solid content and low viscosity, has excellent tape casting film forming performance and is particularly suitable for the solution printing process. The polyimide film formed by the polyamic acid solution prepared by the invention has high heat resistance, low thermal expansion coefficient and good mechanical property, and is suitable for being used as a flexible substrate in a display panel.

Description

Polyamide acid solution, polyimide film and application thereof
Technical Field
The invention belongs to the technical field of flexible display, and particularly relates to a polyamic acid solution, a polyimide film and application thereof.
Background
With the rapid development of smart display terminals towards the directions of lightness, thinness, high definition, flexibility, curling and folding, flexible display gradually becomes an important mainstream display technology of the smart display terminals, and the smart display terminals are widely applied to the display fields of smart phones, wearable equipment, large-size televisions and the like. In a flexible display device, a flexible base material is a key material for realizing flexible display, and the flexible base material is adopted to replace a traditional rigid glass substrate to realize display forms such as bending, folding and curling of a display terminal. Among various flexible display substrate materials, polyimide has the characteristics of good heat resistance, low linear thermal expansion coefficient, excellent mechanical property and the like, and is an important display substrate material.
The flexible display device is complex in process, strict in condition requirements, and generally adopts a top-emission LTPS process in a flexible AMOLED (active matrix organic light emitting diode) display process, wherein a polyimide prepolymer polyamic acid solution is coated on the surface of a glass substrate, then a polyimide substrate is formed after high-temperature curing, then an LTPS process, an evaporation process and a packaging process are sequentially performed on the substrate, and finally a flexible display element is formed by peeling the polyimide flexible substrate from the glass substrate by using laser. The coating equipment in the panel production line has higher requirements on the viscosity and solid content of the polyamic acid slurry, and the viscosity of the polyamic acid resin solution is required to be within the range of 2000-10000 centipoises, and the solid content cannot be lower than 10%. Meanwhile, the prepared polyimide flexible substrate material is required to have higher glass transition temperature (Tg >450 ℃), and can keep good heat-resistant stability and dimensional stability at high temperature.
Usually, the polyamic acid solution prepared by polymerization has a relatively high viscosity, which can reach several tens of thousands to hundreds of thousands of centipoises, and cannot meet the process coating requirements of a panel production line. In the prior art, the viscosity of a resin solution is mostly reduced by reducing the molecular weight or solid content of the polyamic acid resin, but the reduction of the molecular weight can cause obvious reduction of the glass transition temperature, the heat resistance, the dimensional stability and the mechanical property of the polyimide flexible substrate; reducing the solids content results in a decrease in the thickness of the slurry film, an increase in the film formation time, and an increase in the amount of organic solvent used.
CN110092908A discloses a polyimide film. The polyimide film is a low-thermal-expansion colorless transparent film, and is prepared by mixing a mixture of rigid aromatic diamine and fluorine-containing aromatic diamine, and a mixture of rigid aromatic tetracarboxylic dianhydride and fluorine-containing aromatic tetracarboxylic dianhydride as raw materials to obtain a resin solution, and then imidizing and post-treating the resin solution. The polyamic acid slurry prepared by the method has high solid content, causes high viscosity, cannot meet the process coating requirements of a panel production line, and is difficult to adjust the thickness of a film during the coating process.
Therefore, it is a major research in the art to develop a polyamic acid slurry with high solid content and low viscosity to solve the problem of unmatched viscosity and solid content of the slurry, and unmatched heat resistance, dimensional stability and mechanical properties of the film with the requirements of flexible display process equipment and process.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a polyamic acid solution, a polyimide film and application thereof. The polyamic acid solution has the advantages of high solid content and low viscosity, and the polyimide film prepared from the polyamic acid solution has excellent heat resistance, dimensional stability and good mechanical property.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a polyamic acid solution, which comprises the following raw materials: aromatic tetracarboxylic dianhydride monomer, aromatic diamine monomer, compound containing tetracarboxyl structure and solvent;
the structural formula of the compound containing the tetracarboxyl structure is shown as a formula C:
Figure BDA0002353439860000031
wherein R is1The group is aryl, n is a natural number from 0 to 4 (n can be 0, 1, 2,3, 4).
The compound containing the tetracarboxyl structure is added into the polyamic acid solution, the compound is an aromatic or aromatic heterocyclic compound containing a dicarboxylic acid or tetracarboxylic acid structure, the compound containing more than two carboxyl structures is introduced into the polyamic acid solution, and in the stage of curing and film-forming of the polyamic acid solution, carboxyl groups in the compound and amino groups at the tail ends of molecular chains undergo amidation or imidization reaction, so that the polyamic acid solution undergoes chain growth reaction in the process of film-forming and curing, free molecular chains undergo crosslinking, the intermolecular crosslinking reaction limits the movement of the molecular chains, molecular weight is increased, molecular structure stability is improved, heat resistance of resin materials is improved, thermal expansion coefficient of films is reduced, viscosity of the resin solution can be obviously reduced under the condition of ensuring that solid content is unchanged, and casting film-forming process performance of the resin is improved. The heat resistance, the dimensional stability and the mechanical property of the flexible substrate material are ensured, and the problems that the viscosity and the solid content of polyimide precursor polyamic acid slurry and the heat resistance stability, the thermal expansion property and the mechanical property of a polyimide film can not meet the conditions of a display process are solved.
Preferably, the molar mass ratio of the aromatic tetracarboxylic dianhydride monomer, the aromatic diamine monomer, and the compound having a tetracarboxylic structure is 1 (1.001-1.5) (0.001-0.5), and may be, for example, 1:1.001:0.001, 1:1.002:0.002, 1:1.004:0.004, 1:1.006:0.006, 1:1.008:0.008, 1:1.01:0.01, 1:1.02:0.02, 1:1.04:0.04, 1:1.06:0.06, 1:1.08:0.08, 1:1.1:0.1, 1:1.2:0.2, 1:1.3:0.3, 1:1.4:0.4, 1:1.5: 0.5.
Preferably, the aromatic tetracarboxylic dianhydride monomer is a rigid structure aromatic tetracarboxylic dianhydride monomer and/or a semi-rigid structure aromatic tetracarboxylic dianhydride monomer.
The molar percentage of the aromatic tetracarboxylic dianhydride monomer of the rigid structure is preferably 70 mol% or more, for example, 70 mol%, 75 mol%, 80 mol%, 85 mol%, 90 mol%, 95 mol%, 100 mol%, based on 100 mol% of the total molar mass of the aromatic tetracarboxylic dianhydride monomer.
Preferably, the aromatic tetracarboxylic dianhydride monomer of the rigid structure includes any one or a mixture of at least two of 3,3',4,4' -biphenyltetracarboxylic dianhydride, 2',3,3' -biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, 1,4,5, 8-naphthalene tetracarboxylic dianhydride, or 2,3,6, 7-naphthalene tetracarboxylic dianhydride.
Preferably, the 3,3',4,4' -biphenyltetracarboxylic dianhydride is contained in a molar percentage of 40 mol% or more, for example, 40 mol%, 45 mol%, 50 mol%, 55 mol%, 60 mol%, 65 mol%, 70 mol%, 75 mol%, 80 mol%, 85 mol%, 90 mol%, 95 mol%, 100 mol% based on 100 mol% of the total molar mass of the aromatic tetracarboxylic dianhydride monomers having a rigid structure.
Preferably, the semi-rigid structure aromatic tetracarboxylic dianhydride monomer comprises any one or a mixture of at least two of diphenyl ether tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, or hexafluoro dianhydride.
Preferably, the molar percentage content of the diphenyl ether tetracarboxylic dianhydride is 30 to 90 mol%, for example, 30 mol%, 35 mol%, 40 mol%, 45 mol%, 50 mol%, 55 mol%, 60 mol%, 65 mol%, 70 mol%, 75 mol%, 80 mol%, 85 mol%, 90 mol% based on 100 mol% of the total molar mass of the semi-rigid structure aromatic tetracarboxylic dianhydride monomer.
Preferably, the aromatic diamine monomer is an aromatic diamine of a rigid structure and/or an aromatic diamine of a semi-rigid structure.
The molar percentage of the aromatic diamine having a rigid structure is preferably 60 mol% or more, and may be, for example, 60 mol%, 65 mol%, 70 mol%, 75 mol%, 80 mol%, 85 mol%, 90 mol%, 95 mol%, 100 mol%, based on 100 mol% of the total molar mass of the aromatic diamine monomers.
In the aromatic diamine monomer of the present invention, if the content of the aromatic diamine monomer having a rigid structure is less than 60 mol%, the heat resistance of the polyimide resin material formed is reduced, and the thermal expansion coefficient is increased; if the aromatic diamine monomer with a semi-rigid structure is not added, the prepared polyimide film becomes brittle, and the mechanical property of the resin material is influenced.
Preferably, the aromatic diamine with a rigid structure comprises any one or a mixture of at least two of p-phenylenediamine, m-phenylenediamine, o-phenylenediamine or p-terphenylenediamine;
the molar percentage of the p-phenylenediamine is preferably 30 mol% or more, and may be, for example, 30 mol%, 35 mol%, 40 mol%, 45 mol%, 50 mol%, 55 mol%, 60 mol%, 65 mol%, 70 mol%, 75 mol%, 80 mol%, 85 mol%, 90 mol%, 95 mol%, 100 mol%, based on 100 mol% of the total molar mass of the aromatic diamines having a rigid structure.
Preferably, the semi-rigid structure aromatic diamine comprises any one of 4,4 '-diaminodiphenyl ether, 3,4' -diaminodiphenyl ether, 4 '-diaminodiphenyl sulfone, 2' -bis-trifluoromethyl-4, 4 '-diaminobiphenyl, 9-bis- (4-aminophenyl) fluorene or 4,4' -diaminobenzophenone or a mixture of at least two thereof.
Preferably, said R is1The radicals being selected from
Figure BDA0002353439860000051
Wherein the dotted line is the attachment position of the group.
Preferably, said R is1The radicals being selected from
Figure BDA0002353439860000052
Wherein the dotted line is the attachment position of the group.
Preferably, the compound containing the tetracarboxyl structure is selected from any one of the following compounds C1-C6:
Figure BDA0002353439860000053
Figure BDA0002353439860000061
preferably, the solvent is a polar aprotic solvent.
Preferably, the solvent comprises any one of N-methylpyrrolidone, N-dimethylformamide, dimethylsulfoxide or N, N-dimethylacetamide, or a mixture of at least two thereof.
Preferably, the raw materials for preparing the polyamic acid solution further include an inorganic nanoparticle filler. The addition of the inorganic nano-filler can significantly reduce the thermal expansion coefficient of the material.
Preferably, the inorganic nanoparticle filler is added in an amount of 0.01 to 20% by mass based on the total mass of the polyamic acid solid content, and may be, for example, 0.01%, 0.1%, 0.2%, 0.4%, 0.6%, 0.8%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%.
Preferably, the inorganic nanoparticle filler comprises any one or a mixture of at least two of silica, alumina or titania;
preferably, the inorganic nanoparticulate filler has a particle size of 10 to 100nm, and may be, for example, 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100 nm.
Preferably, the polyamic acid solution has a solid content of 10 to 20% by weight, and may be, for example, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20% by weight
Preferably, the viscosity of the polyamic acid solution is 2000-10000cP, and may be, for example, 2000cP, 3000cP, 4000cP, 5000cP, 6000cP, 7000cP, 8000cP, 9000cP, 10000 cP.
If the solid content of the polyamic acid solution is too low, a polyimide film with uniform thickness is difficult to obtain due to too fast volatilization of the solvent in the process of curing and film forming of the polyamic acid slurry; too high a solid content results in a high viscosity, making it difficult to adjust the film thickness during the coating process.
In a second aspect, the present invention provides a preparation method of the polyamic acid solution, the preparation method comprising: mixing an aromatic diamine monomer and a solvent, stirring for the first time, adding an aromatic tetracarboxylic dianhydride monomer, stirring for the second time, finally adding a compound containing a tetracarboxyl structure, stirring for the third time, and reacting to obtain the polyamic acid solution.
Preferably, the temperature of the primary stirring is-20 to 50 ℃, for example, -20 ℃, -15 ℃, -10 ℃, -50 ℃,5 ℃, 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃ and 50 ℃.
Preferably, the aromatic tetracarboxylic dianhydride monomer is added in 3 to 5 portions, for example, 3,4, 5 portions.
Preferably, the temperature of the reaction system during the addition of the aromatic tetracarboxylic dianhydride monomer is 5 to 15 ℃, for example, 5 ℃,6 ℃,7 ℃,8 ℃, 9 ℃, 10 ℃, 11 ℃, 12 ℃, 13 ℃, 14 ℃ and 15 ℃.
Preferably, the temperature of the secondary stirring is-20 to 50 ℃, for example, -20 ℃, -15 ℃, -10 ℃, -50 ℃,5 ℃, 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃ and 50 ℃; the secondary stirring time is 5-7h, for example, 5h, 5.5h, 6h, 6.5h, 7h
Preferably, the temperature of the third stirring is-20 to 50 ℃, for example, -20 ℃, -15 ℃, -10 ℃, -50 ℃,5 ℃, 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃; the secondary stirring time is 16-30h, for example, 16h, 18h, 20h, 22h, 24h, 26h, 28h, 30 h.
In a third aspect, the present invention provides a polyimide film, wherein a raw material of the polyimide film comprises the polyamic acid solution according to the first aspect.
The thickness of the polyimide film is preferably 5 to 20 μm, and may be, for example, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, or 20 μm.
In a fourth aspect, the present invention provides a method for preparing a polyimide film, including the following steps:
(1) degassing a polyamic acid solution, spin-coating the polyamic acid solution on the surface of a substrate, and pre-drying to obtain the substrate containing a wet film;
(2) and (2) thermally curing the substrate containing the wet film obtained in the step (1), and peeling to obtain the polyimide film.
Preferably, the degassing in step (1) is degassing under vacuum for 20-40min, such as 20min, 25min, 30min, 35min, 40 min.
Preferably, the substrate in step (1) is a glass substrate.
Preferably, the spin coating in the step (1) is performed by a spin coater.
Preferably, the pre-baking in the step (1) is specifically: the pre-drying is carried out for 20-40min (for example, 20min, 25min, 30min, 35min, 40min) on a hot plate at 75-85 deg.C (for example, 75 deg.C, 80 deg.C, 85 deg.C), and for 20-40min (for example, 20min, 25min, 30min, 35min, 40min) on a hot plate at 115-125 deg.C (for example, 115 deg.C, 120 deg.C, 125 deg.C).
Preferably, the thickness of the wet film in step (1) is 16 to 18 μm, and may be 16 μm, 16.5 μm, 17 μm, 17.5 μm, 18 μm, for example.
Preferably, the heat curing in step (2) is specifically: the substrate containing the wet film obtained in the step (1) is placed in a high temperature oven for thermal curing, and the temperature is raised by a programmed temperature raising method, wherein the temperature is raised at a rate of 5 ℃/min from room temperature, the temperature is raised to 155 ℃ for example, 145 ℃, 150 ℃, 155 ℃ and kept for 25-35min (for example, 25min, 27min, 30min, 32min, 35min), the temperature is raised to 175 ℃ for 185 ℃ (for example, 175 ℃, 180 ℃, 185 ℃ and 25-35min (for example, 25min, 27min, 30min, 32min, 35min), the temperature is raised to 235 ℃ for 245 ℃ (for example, 235 ℃, 240 ℃, 245 ℃ and kept for 25-35min (for example, 25min, 27min, 30min, 32min, 35min), and the temperature is raised to 295 ℃ for 305 ℃ for example, 295 ℃, 300 ℃, 305 ℃ and kept for 25-35min (for example, 25min, 30min, 35min, 2, 35min, and the like), 27min, 30min, 32min, 35min), heating to 345 ℃ and 355 ℃ for 25-35min (for example, 345 ℃, 350 ℃, 355 ℃) and keeping for 25-35min (for example, 25min, 27min, 30min, 32min, 35min), heating to 445 ℃ and 450 ℃ (for example, 445 ℃, 450 ℃, 455 ℃) and keeping for 25-35min (for example, 25min, 27min, 30min, 32min, 35 min).
Preferably, the stripping in the step (2) is specifically: and (3) boiling the substrate containing the wet film after the thermal curing in boiling water for 20-40min (for example, 20min, 25min, 30min, 35min and 40min), and peeling the film from the substrate to obtain the polyimide film.
Preferably, the thickness of the polyimide film is 9 to 11 μm, and may be, for example, 9 μm, 9.2 μm, 9.4 μm, 9.6 μm, 9.8 μm, 10 μm, 10.2 μm, 10.4 μm, 10.6 μm, 10.8 μm, 11 μm.
In a fifth aspect, the present invention provides a use of the polyimide film according to the third aspect in preparing a flexible substrate for a display panel.
Compared with the prior art, the invention has the following beneficial effects:
(1) the polyamic acid solution has the advantages of high solid content and low viscosity, and the polyimide film prepared from the polyamic acid solution has excellent heat resistance, dimensional stability and good mechanical property.
(2) The polyimide film prepared from the polyamic acid solution has the thermal decomposition temperature of over 550 ℃, the thermal expansion coefficient of less than 11ppm/K and the tensile strength of over 280 MPa.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Preparation example 1
Preparation of Compound C2
The synthetic route is as follows:
Figure BDA0002353439860000101
(1) preparation of intermediate compound D1
23.6g of m-dibromobenzene, 55.88g of pinacol diboron, 58.8g of potassium acetate and 400mL of DMSO are added in sequence to a four-necked flask, mechanical stirring is started, the system is replaced by nitrogen, and then 14.61g of [1,1' -bis (diphenylphosphino) ferrocene]Palladium dichloride (Pd (dppf) Cl2) The system was heated to 80 ℃ for reflux reaction, and the progress of the reaction was monitored by TLC. After the reaction, water was added for quenching, followed by extraction separation with toluene, the aqueous phase was extracted 2 times with toluene, the organic phases were combined, the organic phase was concentrated and purified with silica gel column, followed by concentration under reduced pressure to give compound 25g D1 with a yield of 76%.
(2) Preparation of Compound C2
Into a four-necked flask were charged 36.75g of 4-bromophthalic acid, 250mL of N, N-dimethylformamide, 24.42g of intermediate compound D1 and 0.53g of bis (di-t-butyl-4-dimethylaminophenylphosphine) palladium chloride (Pd-132), and the system was heated to 90 ℃ and stirred for 20 min. Then 72.45g of potassium carbonate is weighed and dissolved in 80mL of pure water, and slowly and dropwise added into the reaction solution, the reaction temperature is controlled not to exceed 95 ℃, and after the addition is finished, the system continues to react for 10 hours at 85-90 ℃. Naturally cooling to room temperature, adjusting the pH value of the system to 3 by using 2M hydrochloric acid aqueous solution, then adding toluene for extraction and separation, combining organic phases, concentrating, and performing flash column purification to obtain the compound C224.3g with the yield of 81%.
The obtained compound C2 was subjected to nuclear magnetic identification, and the analytical data of the nuclear magnetic spectrum were as follows:1H-NMR (400MHz, DMSO-d6), delta (ppm): 13.5(4H, s),8.8(2H, d),8.4(2H, d),8.1(2H, d),7.5-7.3(4H, m); mass Spectrometry data MS (m/e) 406.05.
The preparation example part of the invention also provides other 4 specific compounds (C3-C6), and the synthesis method of the compounds is the same as that of the preparation example 1 and can be realized by replacing the raw materials. Therefore, the results of the raw materials, the total yield, the structure identification hydrogen spectrum and the mass spectrum data of other 4 compounds containing the tetracarboxyl structure, namely compounds C3-C6, are given in Table 1.
TABLE 1
Figure BDA0002353439860000111
Figure BDA0002353439860000121
The abbreviations used in the examples and comparative examples provided below represent the following specific compounds:
a1 represents pyromellitic dianhydride, A2 represents 3,3',4,4' -biphenyltetracarboxylic dianhydride, A3 represents 2,3,6, 7-naphthalenetetracarboxylic dianhydride, A4 represents 3,3',4,4' -benzophenonetetracarboxylic dianhydride;
b1 represents p-phenylenediamine, B2 represents 4,4' -diaminodiphenyl ether, and B3 represents p-terphenylenediamine.
The following examples and comparative examples prepared polyamic acid solutions obtained by the following methods for viscosity measurement: the rotational viscosity of the polymer solution was measured using a Brookfield viscometer (LVDVC) viscometer, and the test sample solution was placed in a test cuvette and the viscosity of the polymer was measured at 25 ℃.
Example 1
Respectively adding a diamine compound B15.51g and 110g N-methyl pyrrolidone into a reaction bottle, starting mechanical stirring, using nitrogen to replace air in the flask, placing the system into an ice-water bath after all monomers are dissolved, adding A210.29g and A13.27g into the mixed solution for 3 times, controlling the reaction temperature to be not more than 15 ℃, naturally returning the system to the room temperature after the addition is finished, stirring for 6 hours, then adding a compound C10.33g, and continuing stirring for 18 hours at the room temperature to obtain a polyamic acid solution (PAA1) with the solid content of 15 wt%. The polyamic acid solution was tested to have a viscosity of 4350cP at 25 ℃.
Example 2
Diamine compounds B13.88g, B34.0g and 135g N-methyl pyrrolidone are respectively added into a reaction bottle, mechanical stirring is started, the air in the reaction bottle is replaced by nitrogen in the system, and after all monomers are dissolved, 1.3g of SiO is added2Inorganic nanoparticles (particle size 20nm), stirring for 30min, placing the system in an ice-water bath, adding A214.7g into the mixed solution in batches, controlling the reaction temperature to be not more than 15 ℃, naturally returning the system to room temperature after the addition is finished, stirring for 6h, then adding compound C20.51g, and continuing stirring for 18h at room temperature to obtain a polyamic acid solution (PAA2) with the solid content of 15 wt%. The polyamic acid solution was tested to have a viscosity of 6800cP at 25 ℃.
Example 3
Adding diamine compounds B15.51g and 123g N-methyl pyrrolidone into a reaction bottle respectively, starting mechanical stirring, replacing air in the reaction bottle with nitrogen, adding 1.1g of SiO after all monomers are dissolved2Inorganic nanoparticles (particle size of 20nm), stirring for 30min, placing the system in ice-water bath, adding A214.7g into the above mixed solution in batches, controlling reaction temperature not to exceed 15 deg.C, naturally recovering the system to room temperature after adding, stirring for 6h, adding compound C30.41g, and stirring at room temperature for 18h to obtain solid content of 15 wt%Polyamic acid solution (PAA 3). The polyamic acid solution was tested to have a viscosity of 5500cP at 25 ℃.
Example 4
Respectively adding 15.45g of diamine compound and 114g N-methyl pyrrolidone into a reaction bottle, starting mechanical stirring, replacing air in the flask by nitrogen gas in the system, placing the system in an ice-water bath after all monomers are dissolved, adding 211.76g and 32.68g of diamine compound into the mixed solution in batches, controlling the reaction temperature to be not more than 15 ℃, naturally returning the system to room temperature after the addition is finished, stirring for 6 hours, then adding 40.24g of compound, and continuing stirring for 18 hours at room temperature to obtain a polyamic acid solution (PAA4) with the solid content of 15 wt%. The polyamic acid solution was tested to have a viscosity of 8800cP at 25 ℃.
Example 5
Adding diamine compounds B14.96g, B21.02g and 119g N-methyl pyrrolidone into a reaction bottle respectively, starting mechanical stirring, replacing air in the flask by nitrogen gas, placing the system into an ice-water bath after all monomers are dissolved, adding A211.76 and A32.68g into the mixed solution in batches, controlling the reaction temperature to be not more than 15 ℃, naturally returning the system to the room temperature after the addition is finished, stirring for 6 hours, then adding compound C50.56g, and continuing stirring for 18 hours at the room temperature to obtain a polyamic acid solution (PAA5) with the solid content of 15 wt%. The polyamic acid solution was tested for viscosity of 5100cP at 25 ℃.
Example 6
Diamine compounds B15.51g and 126g N-methyl pyrrolidone are respectively added into a reaction bottle, mechanical stirring is started, the air in the reaction bottle is replaced by nitrogen in the system, and after all the monomers are dissolved, 1.1g of SiO is added2Inorganic nanoparticles (the particle diameter is 20nm), stirring for 30min, putting the system in an ice-water bath, adding A211.76g and A43.22g into the mixed solution in batches, controlling the reaction temperature to be not more than 15 ℃, naturally returning the system to the room temperature after the addition, stirring for 6h, then adding the compound C60.63g, and continuously stirring for 18h at the room temperature to obtain a polyamic acid solution (PAA6) with the solid content of 15 wt%. The polyamic acid solution was tested for viscosity of 5100cP at 25 ℃.
Example 7
Respectively adding diamine compounds B15.51g and 142g N-methyl pyrrolidone into a reaction bottle, starting mechanical stirring, using nitrogen to replace air in the flask, placing the system into an ice-water bath after all monomers are dissolved, adding A210.29g and A13.27g into the mixed solution for 3 times, controlling the reaction temperature to be not more than 15 ℃, naturally returning the system to the room temperature after the addition is finished, stirring for 6 hours, then adding compound C10.33g (1.0mmol), and continuing stirring for 18 hours at the room temperature to obtain a polyamic acid solution (PAA7) with the solid content of 12 wt%. The polyamic acid solution was tested to have a viscosity of 3850cP at 25 ℃.
Example 8
Respectively adding 15.61g (52mmol) of diamine compound B and 77g N-methyl pyrrolidone into a reaction bottle, starting mechanical stirring, replacing air in the flask by nitrogen gas in the system, placing the system into an ice-water bath after all monomers are dissolved, adding 210.29g (35.00mmol) and 13.27g (15.00mmol) of A into the mixed solution in 3 times, controlling the reaction temperature to be not more than 15 ℃, naturally returning the system to room temperature after the addition is finished, stirring for 6 hours, then adding 20.81g (2mmol) of compound C, and continuing stirring for 18 hours at room temperature to obtain a polyamide acid solution (PAA8) with the solid content of 20 wt%. The polyamic acid solution was tested to have a viscosity of 9500cP at 25 ℃.
Example 9
Respectively adding 15.51 g (51mmol) of diamine compound B and 195g N-methyl pyrrolidone into a reaction bottle, starting mechanical stirring, replacing air in the flask by nitrogen gas, adding 1.1g of SiO2 inorganic nanoparticles (the particle size is 20nm) after all monomers are dissolved, stirring for 30min, putting the system into an ice-water bath, adding A-214.7g (50.00mmol) into the mixed solution in batches, controlling the reaction temperature to be not more than 15 ℃, naturally returning the system to room temperature after the addition is finished, stirring for 6h, then adding 30.41 g (1mmol) of compound C, and continuously stirring for 18h at room temperature to obtain a polyamic acid solution (PAA-9) with the mass concentration of 10%. The polyamic acid solution was tested to have a viscosity of 3750cP at 25 ℃.
Comparative example 1
The diamine compound B15.51g (51.00mmol) and 118g N-methyl pyrrolidone were added to a reaction flask, mechanical stirring was turned on, the air in the flask was replaced with nitrogen, after the monomers were completely dissolved, the system was placed in an ice-water bath, and A214.7g (50mmol) were added to the above mixed solution in portions, with the reaction temperature being controlled not to exceed 15 ℃. After the addition was completed, the whole reaction was stirred at room temperature for 24 hours to obtain a polyamic acid solution having a solid content of 15 wt%. The polyamic acid solution was tested for viscosity of 5200cP at 25 ℃.
Comparative example 2
The diamine compounds B14.41g (40.80mmol), B22.04g (10.20mmol) and 122g N-methyl pyrrolidone were added to the reaction flask, the mechanical stirring was turned on, the air in the flask was replaced with nitrogen, and after the monomers were completely dissolved, 1.2g of SiO was added2Inorganic nanoparticles (particle diameter of 20nm), stirring for 30min, placing the system in an ice-water bath, adding A25.88g (40mmol) and A48.04g (10mmol) to the mixed solution in batches, and controlling the reaction temperature to be not more than 15 ℃. After the addition was completed, the whole reaction was stirred at room temperature for 24 hours to obtain a polyamic acid solution having a solid content of 15 wt%. The polyamic acid solution was tested to have a viscosity of 4950cP at 25 ℃.
Comparative example 3
The diamine compound B15.56g (51.50mmol) and 120g N-methyl pyrrolidone were added to a reaction flask, mechanical stirring was started, the air in the flask was replaced with nitrogen, and after the monomers were completely dissolved, 1.1g of SiO was added2Inorganic nanoparticles (the particle diameter is 20nm), stirring for 30min, placing the system in an ice-water bath, adding A211.76g (40.00mmol) and A43.22g (10.00mmol) to the mixed solution in batches, and controlling the reaction temperature to be not more than 15 ℃. After the addition was completed, the whole reaction was stirred at room temperature for 24 hours to obtain a polyamic acid solution having a solid content of 15 wt%. The polyamic acid solution was tested to have a viscosity of 4250 mPa-s at 25 ℃.
Performance testing of polyimide films
1. Preparing a polyimide film:
(1) the polyamic acid solutions prepared in examples 1 to 9 and comparative examples 1 to 3 were filtered through 0.45 μm biofilms, respectively, and then degassed under vacuum for 30min, spin-coated on the surface of a glass substrate using a spin coater, followed by pre-baking on hot plates at 80 ℃ and 120 ℃ for 30min, respectively, to obtain a glass substrate containing a wet film having a thickness of 17 μm.
(2) And (2) placing the glass substrate containing the wet film obtained in the step (1) into a high-temperature oven for thermosetting, heating up at room temperature at a speed of 5 ℃/min, respectively heating up to 150 ℃, keeping 30min at 180 ℃, 30min at 240 ℃, 30min at 300 ℃, 30min at 350 ℃ and 30min at 450 ℃, placing the substrate into boiling water for boiling for 30min, and peeling the polyimide film from the glass substrate to obtain the polyimide film, wherein the thickness of the polyimide film is 10 mu m.
2. Performance test method of polyimide film
(1) Test method of Heat resistance: the polyimide film obtained above was tested for thermal decomposition temperature using METER TGA1, each test sample polyimide film was cut into small pieces, 10mg was weighed in a dry pan, and N was measured at 30 ℃ at a rate of 10 ℃/min2Heating to 800 ℃ under the atmosphere, recording a thermal weight loss curve within the range of 50-800 ℃, and calculating the thermal decomposition temperature Td (1%) of 1% of the material;
the thermal expansion performance of the polyimide film obtained above was measured by using TMAQ400 type dynamic thermo-mechanical analyzer, the polyimide film obtained above was cut into a block sample having a length of 4cm and a width of 5mm, and the static holding force was set to 0.02N in a film stretching mode2Heating and cooling at the speed of 10 ℃/min under the atmosphere, heating for the first time to eliminate the internal stress of the film, recording the length data of the polyimide film in the range of 50-400 ℃ in the second heating process, and calculating the thermal expansion coefficient of the polyimide film according to the formula of CTE (△ L/(L △ T), wherein L is the initial length of the polyimide film before heating, △ L is the change value of the length of the polyimide film before and after heating, and △ T is the temperature change value.
(2) The mechanical property testing method comprises the following steps: the mechanical properties of the polyimide film obtained above were measured using an electronic tensile tester, the polyimide film obtained above was cut into a block sample having a length of 10cm and a width of 5mm, a tensile test was carried out at a speed of 50mm/min according to the method of ASTM-D882, and the tensile strength of the polyimide film was determined in parallel 5 times, and the average value was taken as the tensile strength.
The specific test results are shown in table 2:
TABLE 2
Figure BDA0002353439860000171
Figure BDA0002353439860000181
As can be seen from the above test results, the polyimide films prepared from the polyamic acid solutions provided in examples 1 to 9 have a thermal decomposition temperature of 557-573 ℃, a thermal expansion coefficient of 5-11ppm/K, and a tensile strength of 285-340 MPa. The polyamic acid solution has the advantages of high solid content and low viscosity, and the polyimide film prepared from the polyamic acid solution has excellent heat resistance, dimensional stability and good mechanical property. The addition of the compound containing the tetracarboxyl structure in the polyamic acid solution can cause the polyamic acid to generate chain growth reaction in the film forming and curing process, thereby improving the heat resistance of the polyimide film, reducing the thermal expansion coefficient of the polyimide film, obviously reducing the viscosity of the resin solution under the condition of ensuring the solid content to be unchanged, and improving the performance of the tape casting film forming process. In addition, the addition of inorganic nanofillers can significantly reduce the coefficient of thermal expansion of the material.
The applicant states that the present invention is illustrated by the above examples of the polyamic acid solution, the polyimide film and the application thereof, but the present invention is not limited to the above examples, that is, the present invention is not meant to be implemented by relying on the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (10)

1. A polyamic acid solution is characterized in that the preparation raw material of the polyamic acid solution comprises: aromatic tetracarboxylic dianhydride monomer, aromatic diamine monomer, compound containing tetracarboxyl structure and solvent;
the structural formula of the compound containing the tetracarboxyl structure is shown as a formula C:
Figure FDA0002353439850000011
wherein R is1The group is aryl, and n is a natural number of 0-4.
2. The polyamic acid solution according to claim 1, wherein the molar mass ratio of the aromatic tetracarboxylic dianhydride monomer, the aromatic diamine monomer and the compound having a tetracarboxylic acid structure is 1 (1.001-1.5) to 0.001-0.5.
3. The polyamic acid solution according to claim 1 or 2, wherein the aromatic tetracarboxylic dianhydride monomer is a rigid-structure aromatic tetracarboxylic dianhydride monomer and/or a semi-rigid-structure aromatic tetracarboxylic dianhydride monomer;
preferably, the molar percentage content of the aromatic tetracarboxylic dianhydride monomer with the rigid structure is more than 70mol percent based on 100mol percent of the total molar mass of the aromatic tetracarboxylic dianhydride monomer;
preferably, the aromatic tetracarboxylic dianhydride monomer of the rigid structure includes any one or a mixture of at least two of 3,3',4,4' -biphenyltetracarboxylic dianhydride, 2',3,3' -biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, 1,4,5, 8-naphthalene tetracarboxylic dianhydride, or 2,3,6, 7-naphthalene tetracarboxylic dianhydride;
preferably, the molar percentage of the 3,3',4,4' -biphenyl tetracarboxylic dianhydride is more than 40mol percent based on 100mol percent of the total molar mass of the aromatic tetracarboxylic dianhydride monomers with rigid structures;
preferably, the semi-rigid structure aromatic tetracarboxylic dianhydride monomer comprises any one or a mixture of at least two of diphenyl ether tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride or hexafluoro dianhydride;
preferably, the molar percentage content of the diphenyl ether tetracarboxylic dianhydride is 30-90 mol% based on 100 mol% of the total molar mass of the semi-rigid structure aromatic tetracarboxylic dianhydride monomer;
preferably, the aromatic diamine monomer is an aromatic diamine with a rigid structure and/or an aromatic diamine with a semi-rigid structure;
preferably, the molar percentage of the aromatic diamine with rigid structure is more than 60mol percent based on 100mol percent of the total molar mass of the aromatic diamine monomer;
preferably, the aromatic diamine with a rigid structure comprises any one or a mixture of at least two of p-phenylenediamine, m-phenylenediamine, o-phenylenediamine or p-terphenylenediamine;
preferably, the mole percentage of the p-phenylenediamine is more than 30 mole percent based on 100 mole percent of the total mole mass of the aromatic diamines with rigid structures;
preferably, the semi-rigid structure aromatic diamine comprises any one of 4,4 '-diaminodiphenyl ether, 3,4' -diaminodiphenyl ether, 4 '-diaminodiphenyl sulfone, 2' -bis-trifluoromethyl-4, 4 '-diaminobiphenyl, 9-bis- (4-aminophenyl) fluorene or 4,4' -diaminobenzophenone or a mixture of at least two thereof.
4. The polyamic acid solution according to any one of claims 1 to 3, wherein R is1The radicals being selected from
Figure FDA0002353439850000021
Wherein the dotted line is the attachment position of the group;
preferably, said R is1The radicals being selected from
Figure FDA0002353439850000022
Wherein the dotted line is the attachment position of the group;
preferably, the compound containing the tetracarboxyl structure is selected from any one of the following compounds C1-C6:
Figure FDA0002353439850000031
preferably, the solvent is a polar aprotic solvent;
preferably, the solvent comprises any one or a mixture of at least two of N-methylpyrrolidone, N-dimethylformamide, dimethyl sulfoxide or N, N-dimethylacetamide;
preferably, the raw materials for preparing the polyamic acid solution further comprise an inorganic nanoparticle filler;
preferably, the addition amount of the inorganic nano-particle filler accounts for 0.01 to 20 percent of the total mass of the solid components of the polyamic acid;
preferably, the inorganic nanoparticle filler comprises any one or a mixture of at least two of silica, alumina or titania;
preferably, the inorganic nanoparticle filler has a particle size of 10-100 nm;
preferably, the solid content of the polyamic acid solution is 10 to 20 wt%;
preferably, the viscosity of the polyamic acid solution is 2000-10000 cP.
5. The method for producing a polyamic acid solution according to any one of claims 1 to 4, characterized in that the production method is: mixing an aromatic diamine monomer and a solvent, stirring for the first time, adding an aromatic tetracarboxylic dianhydride monomer, stirring for the second time, finally adding a compound containing a tetracarboxyl structure, stirring for the third time, and reacting to obtain a polyamic acid solution;
preferably, the temperature of the primary stirring is-20 to 50 ℃;
preferably, the aromatic tetracarboxylic dianhydride monomer is added in 3 to 5 times;
preferably, the temperature of the reaction system is 5-15 ℃ during the process of adding the aromatic tetracarboxylic dianhydride monomer;
preferably, the temperature of the secondary stirring is-20-50 ℃, and the secondary stirring time is 5-7 h;
preferably, the temperature of the third stirring is-20-50 ℃, and the time of the second stirring is 16-30 h.
6. A polyimide film characterized in that a raw material for producing the polyimide film comprises the polyamic acid solution according to any one of claims 1 to 4.
7. The polyimide film according to claim 6, wherein the thickness of the polyimide film is 5 to 20 μm.
8. The method for producing a polyimide film according to claim 6 or 7, comprising the steps of:
(1) degassing a polyamic acid solution, spin-coating the polyamic acid solution on the surface of a substrate, and pre-drying to obtain the substrate containing a wet film;
(2) and (2) thermally curing the substrate containing the wet film obtained in the step (1), and peeling to obtain the polyimide film.
9. The method according to claim 8, wherein the degassing in the step (1) is degassing under vacuum for 20 to 40 min;
preferably, the substrate in step (1) is a glass substrate;
preferably, the spin coating in the step (1) is performed by a spin coater;
preferably, the pre-baking in the step (1) is specifically: pre-baking the mixture for 20 to 40 minutes on a hot plate at the temperature of between 75 and 85 ℃, and then pre-baking the mixture for 20 to 40 minutes on a hot plate at the temperature of between 115 and 125 ℃;
preferably, the thickness of the wet film in step (1) is 16 to 18 μm;
preferably, the heat curing in step (2) is specifically: placing the substrate containing the wet film obtained in the step (1) into a high-temperature oven for heat curing, heating up by adopting a temperature programming mode, starting heating up at the speed of 5 ℃/min from room temperature, keeping for 25-35min when heating up to 145-155 ℃, keeping for 25-35min when heating up to 175-185 ℃, keeping for 25-35min when heating up to 235-245 ℃, keeping for 25-35min when heating up to 295-305 ℃, keeping for 25-35min when heating up to 345-355 ℃, and keeping for 25-35min when heating up to 445-455 ℃;
preferably, the stripping in the step (2) is specifically: and (3) boiling the substrate containing the wet film after heat curing in boiling water for 20-40min, and peeling the film from the substrate to obtain the polyimide film.
10. Use of the polyimide film according to claim 6 or 7 for the preparation of a flexible substrate for a display panel.
CN201911425339.5A 2019-12-31 2019-12-31 Polyamide acid solution, polyimide film and application thereof Pending CN111116913A (en)

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CN112029099A (en) * 2020-09-04 2020-12-04 吉林奥来德光电材料股份有限公司 Preparation method of polyamide acid solution and polyimide film
WO2024019360A1 (en) * 2022-07-22 2024-01-25 피아이첨단소재 주식회사 Polyamic acid composition

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CN106589371A (en) * 2015-10-19 2017-04-26 中国石油化工股份有限公司 Polyamide acid composition and preparation method and application thereof
CN110092908A (en) * 2019-04-03 2019-08-06 中国科学院化学研究所 A kind of Kapton and its preparation method and application

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CN106589371A (en) * 2015-10-19 2017-04-26 中国石油化工股份有限公司 Polyamide acid composition and preparation method and application thereof
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CN112029099A (en) * 2020-09-04 2020-12-04 吉林奥来德光电材料股份有限公司 Preparation method of polyamide acid solution and polyimide film
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