CN112574409A - High-barrier polyimide film material and preparation method thereof - Google Patents
High-barrier polyimide film material and preparation method thereof Download PDFInfo
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- CN112574409A CN112574409A CN202011278580.2A CN202011278580A CN112574409A CN 112574409 A CN112574409 A CN 112574409A CN 202011278580 A CN202011278580 A CN 202011278580A CN 112574409 A CN112574409 A CN 112574409A
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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
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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
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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
- C08G73/1075—Partially aromatic polyimides
- C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- 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 high-barrier polyimide film material and a preparation method thereof, and the polyimide film material has good gas barrier property and flexibility and is expected to be widely applied to the field of flexible displays.
Description
Technical Field
The invention relates to the technical field of flexible display materials, in particular to a high-barrier polyimide film material and a preparation method thereof.
Background
With the development of flexible display technology, flexible display products closer to the traditional display mode will quickly come to the home of common people. The flexible display brings a lot of unique user experiences due to the characteristic of flexibility of the flexible display.
According to the processing and application requirements of the flexible display device, the substrate material used as the flexible display device needs to have specific requirements on oxygen and water vapor barrier properties so as to prevent the display medium from being degraded when exposed to water vapor and oxygen environments.
In order to solve the above problems, in the prior art, water and oxygen barrier layers such as silicon oxide, aluminum oxide layers, etc. are usually constructed on the surface of a polymer flexible material, however, the water and oxygen barrier layers are not resistant to bending and insufficient in flexibility, which destroys the basic flexibility requirement of the flexible display material, and the barrier layers are easy to break and fall off, and cannot realize the improvement of water and oxygen barrier properties for a long time. Therefore, how to obtain a flexible substrate material with high flexibility, good water and oxygen barrier performance and excellent performance becomes a problem to be solved urgently in the industry.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a high-barrier polyimide film material and a preparation method thereof.
The invention provides a high-barrier polyimide film material, which is prepared by carrying out polycondensation reaction on a diamine monomer containing amido bond and a tetracarboxylic dianhydride monomer to obtain polyamic acid, reacting the polyamic acid with isocyanatopropyl triethoxysilane, adding tetraethoxysilane for reaction, and then coating a film.
Preferably, the diamine monomer containing an amide bond is 4, 4' -diaminobenzanilide.
Preferably, the tetracarboxylic dianhydride monomer is 3, 3', 4, 4' -biphenyltetracarboxylic dianhydride
4, 4' -oxydiphthalic anhydride
3, 3', 4, 4' -benzophenone tetracarboxylic dianhydride
4, 4' - (Hexafluoroisopropylene) diphthalic anhydride
1, 2, 3, 4-cyclobutanetetracarboxylic dianhydride
At least one of (1).
Preferably, the preparation method of the high-barrier polyimide film material comprises the following steps:
s1, dissolving a diamine monomer containing an amido bond in an organic solvent, and then adding a tetracarboxylic dianhydride monomer to carry out polycondensation reaction to obtain a polyamic acid solution;
and S2, adding isocyanatopropyl triethoxysilane into the polyamic acid solution for reaction, adding tetraethoxysilane for reaction, then coating, and heating for thermal imidization reaction to obtain the polyimide film material.
Preferably, the molar ratio of the diamine monomer containing the amide bond to the tetracarboxylic dianhydride monomer is 1.05-1.15: 1.
Preferably, in step S1, the polycondensation reaction is carried out at a temperature of 10-30 ℃ for 5-8 hours.
Preferably, the amount of the isocyanatopropyltriethoxysilane is 50-80% of the molar amount of the tetracarboxylic dianhydride monomer, and the amount of the tetraethoxysilane is 60-150% of the molar amount of the tetracarboxylic dianhydride monomer.
Preferably, in step S2, adding isocyanatopropyltriethoxysilane for reaction at 50-60 ℃ for 1-3 h; adding tetraethoxysilane for reaction at 20-30 ℃ for 15-20 h.
Preferably, in step S2, the thermal imidization is performed by heating at 80-350 ℃ for 3-8 h.
The invention also provides an application of the high-barrier polyimide film material in a flexible display.
According to the invention, by adopting the diamine monomer containing amido bond and the tetracarboxylic dianhydride monomer to carry out polycondensation, in the main chain structure of the obtained polyimide, the main chain structure contains an amide group structure, and can be bonded with isocyanatopropyltriethoxysilane to generate carbamido, so that silicon dioxide is uniformly and firmly dispersed on the surface of the polyimide, and the polyimide has good water-oxygen barrier property; and the carbamido generated by the method generates hydrogen bonds among molecular chains, so that the regular arrangement and the close packing of polymer chains are realized, and the obtained polyimide film material has excellent mechanical property.
Detailed Description
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 preparation method of a high-barrier polyimide film material comprises the following steps:
s1, under the protection of nitrogen, adding 11mmol of 4, 4' -diaminobenzanilide serving as a diamine monomer raw material and 50mL of N, N-dimethylacetamide solvent into a 100mL three-neck flask, stirring until the materials are completely dissolved, adding 10mmol of 3, 3', 4, 4' -biphenyltetracarboxylic dianhydride serving as a tetracarboxylic dianhydride monomer raw material, continuing stirring until the materials are completely dissolved, and stirring at room temperature for reacting for 8 hours to obtain a transparent polyamic acid solution;
s2, adding 6mmol of isocyanatopropyltriethoxysilane into the polyamic acid solution, heating to 50 ℃, stirring for reaction for 1h, adding 10mmol of tetraethoxysilane, stirring for 20h at room temperature, performing vacuum defoaming treatment on the obtained solution, pouring the solution onto a clean glass plate, controlling the thickness of a coating film to be 50 microns by using a coating machine, placing the glass plate in a drying box at 80 ℃ for 1h, heating to 150 ℃, drying for 1h, heating to 200 ℃, drying for 1h, heating to 250 ℃, drying for 1h, continuing heating to 350 ℃, drying for 1h, naturally cooling to room temperature, taking out the glass plate, soaking the glass plate in hot water for demoulding, and then placing the film in a drying box at 100 ℃ for drying to remove water to obtain the polyimide film material.
The reaction process is as follows:
the relevant performance test results of the polyimide film material are shown in table 1.
Example 2
A high-barrier polyimide film material was prepared in the same manner as in example 1, except that 10mmol of 4, 4' -oxydiphthalic anhydride was used as a starting material for the tetracarboxylic dianhydride monomer in the preparation of the polyamic acid solution, and the results of the performance test on the polyimide film thus obtained were also shown in Table 1.
Example 3
A high barrier polyimide film material, which was prepared in the same manner as in example 1, except that 10mmol of 3, 3', 4, 4' -benzophenone tetracarboxylic dianhydride was used as the starting material for the tetracarboxylic dianhydride monomer in the preparation of the polyamic acid solution, and the results of the performance test on the polyimide film thus obtained were also shown in table 1.
Example 4
A high barrier polyimide film material was prepared in the same manner as in example 1, except that 10mmol of 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride was used as the starting material of the tetracarboxylic dianhydride monomer in the preparation of the polyamic acid solution, and the results of the performance test on the polyimide film thus obtained are also shown in Table 1.
Example 5
A high barrier polyimide film material, which was prepared in the same manner as in example 1, except that 10mmol of 1, 2, 3, 4-cyclobutanetetracarboxylic dianhydride was used as a raw material for the tetracarboxylic dianhydride monomer in the preparation of the polyamic acid solution, and the results of the performance test on the polyimide film thus obtained were also shown in Table 1.
Comparative example 1
A polyimide film material is prepared by the following steps:
s1, under the protection of nitrogen, adding 11mmol of 4, 4' -diaminobenzanilide serving as a diamine monomer raw material and 50mL of N, N-dimethylacetamide solvent into a 100mL three-neck flask, stirring until the materials are completely dissolved, adding 10mmol of 3, 3', 4, 4' -biphenyltetracarboxylic dianhydride serving as a tetracarboxylic dianhydride monomer raw material, continuing stirring until the materials are completely dissolved, and stirring at room temperature for reacting for 8 hours to obtain a transparent polyamic acid solution;
s2, adding 10mmol of tetraethoxysilane into the polyamic acid solution, stirring for 20 hours at room temperature, performing vacuum defoaming treatment on the obtained solution, pouring the solution onto a clean glass plate, controlling the thickness of a coating film to be 50 micrometers by using a coating machine, placing the glass plate in a drying oven at 80 ℃ for 1 hour, heating to 150 ℃, drying for 1 hour, heating to 200 ℃, drying for 1 hour, heating to 250 ℃, drying for 1 hour, continuously heating to 350 ℃, drying for 1 hour, naturally cooling to room temperature, taking out the glass plate, soaking the glass plate in hot water for demoulding, and then placing the film in a drying oven at 100 ℃ for drying and removing water to obtain the polyimide film material, wherein the relevant performance test results of the polyimide film material are shown in Table 1.
The polyimide film materials obtained in examples 1 to 5 and comparative example 1 were subjected to the performance tests shown in the following methods, and the results are shown in Table 1.
Water vapor transmission rate: water Vapor Transmission Rate (WVTR) was determined using a measuring instrument (e.g., PERMATRAN-W, MOCON) at 40 ℃ and 90% relative humidity.
Oxygen transmission rate: the Oxygen Transmission Rate (OTR) is measured using an oxygen permeameter (e.g., ox-TRAN, MOCON) at 25 ℃ and a relative humidity of 60%.
Thermal properties: the measurement was carried out using a differential scanning calorimetry analyzer at a temperature rise rate of 10 ℃/min under a nitrogen atmosphere.
Mechanical properties: measured by a universal material tester according to GB/T1040.3-2006.
Table 1 test results of polyimide films obtained in examples 1 to 5 and comparative example 1
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 (10)
1. A high-barrier polyimide film material is characterized in that a diamine monomer containing amido bond and a tetracarboxylic dianhydride monomer are subjected to polycondensation reaction to obtain polyamic acid, the polyamic acid is reacted with isocyanatopropyl triethoxysilane, tetraethoxysilane is added for reaction, and then coating is carried out to obtain the polyimide film material.
2. The high-barrier polyimide film material according to claim 1, wherein the diamine monomer containing the amide bond is 4, 4' -diaminobenzanilide.
3. The high-barrier polyimide film material according to claim 1 or 2, wherein the tetracarboxylic dianhydride monomer is at least one of 3, 3', 4, 4' -biphenyltetracarboxylic dianhydride, 4, 4 '-oxydiphthalic anhydride, 3', 4, 4 '-benzophenonetetracarboxylic dianhydride, 4, 4' - (hexafluoroisopropylene) diphthalic anhydride, and 1, 2, 3, 4-cyclobutanetetracarboxylic dianhydride.
4. A method for preparing the high-barrier polyimide film material according to any one of claims 1 to 3, which comprises the following steps:
s1, dissolving a diamine monomer containing an amido bond in an organic solvent, and then adding a tetracarboxylic dianhydride monomer to carry out polycondensation reaction to obtain a polyamic acid solution;
and S2, adding isocyanatopropyl triethoxysilane into the polyamic acid solution for reaction, adding tetraethoxysilane for reaction, then coating, and heating for thermal imidization reaction to obtain the polyimide film material.
5. The preparation method of the high-barrier polyimide film material as claimed in any one of claims 1 to 4, wherein the molar ratio of the diamine monomer containing the amide bond to the tetracarboxylic dianhydride monomer is 1.05-1.15: 1.
6. The method for preparing a high-barrier polyimide film material according to any one of claims 1 to 5, wherein in the step S1, the polycondensation reaction is carried out at a temperature of 10 to 30 ℃ for 5 to 8 hours.
7. The preparation method of the high-barrier polyimide film material as claimed in any one of claims 1 to 6, wherein the amount of the isocyanatopropyltriethoxysilane is 50-80% of the molar amount of the tetracarboxylic dianhydride monomer, and the amount of the tetraethoxysilane is 60-150% of the molar amount of the tetracarboxylic dianhydride monomer.
8. The method for preparing a high-barrier polyimide film material according to any one of claims 1 to 7, wherein in step S2, the temperature for adding the isocyanatopropyltriethoxysilane is 50-60 ℃ for 1-3 h; adding tetraethoxysilane for reaction at 20-30 ℃ for 15-20 h.
9. The method for preparing a high-barrier polyimide film material according to any one of claims 1 to 8, wherein in step S2, the heating is carried out at a temperature of 80 to 350 ℃ for 3 to 8 hours.
10. Use of a high barrier polyimide film material according to any one of claims 1 to 3 in a flexible display.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113493608A (en) * | 2021-06-21 | 2021-10-12 | 浙江中科玖源新材料有限公司 | Water-oxygen barrier polyimide film |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104262655A (en) * | 2014-09-24 | 2015-01-07 | 哈尔滨理工大学 | Method for preparing unified-size and uniformly-dispersed PI/SiO2 nanocomposite film in novel coupling way |
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2020
- 2020-11-16 CN CN202011278580.2A patent/CN112574409B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104262655A (en) * | 2014-09-24 | 2015-01-07 | 哈尔滨理工大学 | Method for preparing unified-size and uniformly-dispersed PI/SiO2 nanocomposite film in novel coupling way |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113493608A (en) * | 2021-06-21 | 2021-10-12 | 浙江中科玖源新材料有限公司 | Water-oxygen barrier polyimide film |
| CN113493608B (en) * | 2021-06-21 | 2023-09-19 | 浙江中科玖源新材料有限公司 | Water-oxygen barrier polyimide film |
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