CN113429601B - Preparation method of high-barrier polyimide film - Google Patents
Preparation method of high-barrier polyimide film Download PDFInfo
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- CN113429601B CN113429601B CN202110683889.8A CN202110683889A CN113429601B CN 113429601 B CN113429601 B CN 113429601B CN 202110683889 A CN202110683889 A CN 202110683889A CN 113429601 B CN113429601 B CN 113429601B
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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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- 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
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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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
Abstract
The invention provides a preparation method of a high-barrier polyimide film, which comprises the following steps: adding nano silicon dioxide and polyimide powder into polyamic acid, and performing thermal imidization to obtain a high-barrier polyimide film; the polyamic acid is obtained by polymerizing dianhydride and diamine; the diamine comprises diamine containing amido bond. The method is simple, and the obtained polyimide film has ideal barrier property.
Description
Technical Field
The invention belongs to the technical field of flexible film preparation, and particularly relates to a preparation method of a high-barrier polyimide film.
Background
Generally, O is an international chemical bond 2 Transmittance of less than 3.8cm 3 The high polymer material for every square meter/d is called high-barrier high polymer material. The high-barrier polymer material has wide application in the fields of food packaging, military, microelectronics and the like. Polyimide (PI) has the characteristics of outstanding thermal stability and dimensional stability, good molecular structure designability and the like, and is considered to be a high-molecular flexible material with great potential, but the traditional PI has relatively poor barrier performance and is difficult to meet the requirements of special fields on water and oxygen barrier performance.
At present, methods such as alternate plating, molecular layer deposition, atomic layer deposition, magnetron sputtering and the like are mainly adopted to improve the barrier property of PI. However, the alternate plating method is complicated in process; the molecular layer deposition and the atomic layer deposition can deposit to obtain a compact and uniform coating, but the deposition efficiency is low, and the inorganic barrier layer is easy to crack; the magnetron sputtering technology has the advantages of high deposition efficiency and the like, but the target material needs to be refined and the utilization rate is low. Therefore, it is highly desirable to develop a simple and efficient method for improving PI barrier performance.
Disclosure of Invention
Based on the problems, the invention provides a preparation method of a high-barrier polyimide film, which is relatively simple, and the obtained polyimide film has relatively ideal barrier property.
The specific scheme of the invention is as follows:
a preparation method of a high-barrier polyimide film comprises the following steps: adding nano silicon dioxide and polyimide powder into polyamic acid, and performing thermal imidization to obtain a high-barrier polyimide film; the polyamic acid is obtained by polymerizing dianhydride and diamine; the diamine comprises diamine containing amido bond.
The dianhydride for synthesizing polyamic acid according to the present invention is not particularly limited, and includes, but is not limited to: pyromellitic dianhydride (PMDA), benzophenone Tetracarboxylic Dianhydride (BTDA), biphenyl tetracarboxylic dianhydride (BPDA), 2, 3',4' -diphenyl ether tetracarboxylic dianhydride (a-ODPA), and the like.
The particle size of the nano silicon dioxide is not particularly limited and can be selected according to the requirement. Such as particle size of 10-100nm; preferably 10-40nm.
Preferably, the weight ratio of the nano silica to the polyamic acid is 1-5.
Preferably, the weight ratio of the nano silica to the polyimide powder is 5-15.
Preferably, the preparation method of the polyimide powder comprises the following steps: adding a polar organic solvent into the polyamic acid to dilute the polyamic acid to the concentration of 5-10%, heating the diluted polyamic acid at 180-190 ℃ and keeping the temperature for 2-3h, removing the solvent, washing, drying in vacuum, and grinding to obtain polyimide powder.
Preferably, the polar organic solvent is selected from one or more of N, N-dimethylformamide, N-diethylformamide, N-diethylacetamide, N-methyl-2-pyrrolidone in combination.
Preferably, the temperature of the vacuum drying is 280-320 ℃, and the vacuum drying time is 0.5-1h.
Preferably, the thermal imidization specifically comprises the steps of: casting polyamic acid mixed with nano silicon dioxide and polyimide powder on glass to form a film, drying at 90-100 ℃ for 0.5-1h, heating to 150-200 ℃, and preserving heat for 0.5-1h; keeping the temperature at 250-300 ℃ for 0.5-1h.
Preferably, the temperature is raised to 150-200 ℃ at a rate of 0.5-0.8 ℃/min during thermal imidization.
Preferably, the diamine contains amide bond and accounts for not less than 20% of the total molar amount of the diamine.
The diamine for synthesizing polyamic acid according to the present invention is not particularly limited to other diamines, other than the diamine having an amide bond, and includes, but is not limited to: diaminodiphenyl ether (ODA), p-phenylenediamine (pPDA), 2,4, 6-trimethyl-1, 3-phenylenediamine, 2,3,5, 6-tetramethyl-1, 4-phenylenediamine, 3', 5' -tetramethylbenzidine, and the like.
Has the advantages that:
according to the invention, through the synergistic effect of the polyamic acid with a specific structure, the nano silicon dioxide and the polyimide powder, the polyimide film obtained through thermal imidization has high barrier property.
According to the invention, a small amount of nano silicon dioxide is added into polyamide acid synthesized by taking diamine containing amido bond as a monomer, the nano silicon dioxide can be connected with amido bond in a polyamide acid molecular chain in a hydrogen bond mode, the dispersibility and compatibility of the nano silicon dioxide and a polyimide matrix are improved, the water and oxygen blocking performance of the nano silicon dioxide is facilitated, and the formation of the hydrogen bond is also beneficial to the close packing of a polymer chain; the added polyimide powder has a semi-crystalline structure, so that the formation of a regular ordered structure is facilitated in the polyamide acid thermal imidization process, and the barrier property is promoted.
In the preferred scheme, the proportion of the nano silicon dioxide, the polyimide powder and the polyamic acid is controlled within a specific range, so that the dispersibility and the barrier property of the nano silicon dioxide in the polyimide can be ensured, and the obstruction of the nano silicon dioxide to the formation of an ordered regular structure during thermal imidization is avoided, thereby ensuring that the effects of the two substances can be well balanced.
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 comprises the following steps:
s1, preparing polyimide powder: 4,4' -diaminobenzanilide is used as a diamine monomer, pyromellitic dianhydride is used as a dianhydride monomer, and polymerization is carried out to obtain polyamic acid; specifically, 4' -diaminobenzanilide is added into N, N-dimethylformamide and stirred until the diaminobenzanilide is completely dissolved, pyromellitic dianhydride is added into the solution, and stirring reaction is carried out for 10 hours at room temperature to obtain polyamic acid;
adding N, N-dimethylformamide into the polyamic acid to dilute the polyamic acid to a concentration of 8%, heating the diluted polyamic acid at 185 ℃ and keeping the temperature for 2h, removing the solvent, washing with an alcohol solvent, vacuum-drying at 280 ℃ for 0.5h, and grinding to obtain polyimide powder;
s2, polyimide film: preparing the same polyamic acid according to the method S1, adding nano silicon dioxide into the polyamic acid, stirring for 0.5h, then adding the polyimide powder, and stirring for 2h; casting a mixed solution mixed with nano silicon dioxide and polyimide powder on clean glass to form a film, removing a solvent by hot air at 160 ℃, and cooling to room temperature; then placing the mixture in a vacuum oven with controllable heating rate, and heating according to the program: drying at 100 deg.C for 0.5h; heating to 200 ℃ at the heating rate of 0.8 ℃/min, and drying for 1h; continuously heating to 280 ℃, drying for 0.5h, naturally cooling, and peeling in water after the temperature of the oven is reduced to room temperature to obtain a polyimide film with the thickness of about 30 mu m;
the weight ratio of the nano silicon dioxide to the polyamic acid is 1.5; the weight ratio of the nano silicon dioxide to the polyimide powder is 10.
Example 2
A preparation method of a high-barrier polyimide film comprises the following steps:
s1, preparing polyimide powder: 4,4' -diaminobenzanilide and diaminodiphenyl ether are used as diamine monomers, pyromellitic dianhydride is used as dianhydride monomer, and polymerization is carried out to obtain polyamic acid; adding 4,4' -diaminobenzanilide and diaminodiphenyl ether into N-methyl-2-pyrrolidone, stirring until the mixture is completely dissolved, then adding pyromellitic dianhydride into the solution, and stirring and reacting for 8 hours at room temperature to obtain polyamic acid; wherein 4,4' -diaminobenzanilide accounts for 35% of the total molar weight of diamine monomers.
Adding N-methyl-2-pyrrolidone into the polyamic acid to dilute the polyamic acid to a concentration of 10%, heating the diluted polyamic acid at 180 ℃ and keeping the temperature for 3h, removing the solvent, washing with an alcohol solvent, drying in vacuum at 300 ℃ for 1h, and grinding to obtain polyimide powder;
s2, polyimide film: preparing polyamic acid according to the method S1, adding nano silicon dioxide into polyamic acid, stirring for 1h, then adding the polyimide powder, and stirring for 2.5h; casting the mixed solution mixed with the nano silicon dioxide and the polyimide powder on clean glass to form a film, removing the solvent by hot air at 165 ℃, and cooling to room temperature; then placing the mixture in a vacuum oven with controllable heating rate, and heating according to the program: drying at 90 deg.C for 1h; heating to 180 ℃, and drying for 1h; continuously heating to 300 ℃, drying for 0.5h, naturally cooling, and peeling in water after the temperature of the oven is reduced to room temperature to obtain a polyimide film with the thickness of about 30 mu m;
the weight ratio of the nano silicon dioxide to the polyamic acid is 3; the weight ratio of the nano silicon dioxide to the polyimide powder is 5.
Example 3
In the same manner as in example 1, only in S1, the diamine was replaced with "4,4 '-diaminobenzanilide and 2,4, 6-trimethyl-1, 3-phenylenediamine, wherein 4,4' -diaminobenzanilide accounts for 60% of the total molar amount of the diamine monomers"; the dianhydride was replaced with pyromellitic dianhydride and 2,3,3',4' -diphenylether tetracarboxylic dianhydride, wherein pyromellitic dianhydride accounted for 50% of the total molar amount of dianhydride. The rest is the same as example 1.
Comparative example 1
A preparation method of a polyimide film comprises the following steps:
s1, polyamic acid: polymerizing 4,4' -diaminobenzanilide as a diamine monomer and pyromellitic dianhydride as a dianhydride monomer to obtain polyamic acid; specifically, 4' -diaminobenzanilide is added into N, N-dimethylformamide and stirred until the diaminobenzanilide is completely dissolved, pyromellitic dianhydride is added into the solution, and stirring reaction is carried out for 10 hours at room temperature to obtain polyamic acid;
s2, polyimide film: adding nano silicon dioxide into polyamic acid, and stirring for 0.5h; casting the mixed solution mixed with the nano silicon dioxide on clean glass to form a film, removing the solvent by hot air at 160 ℃, and cooling to room temperature; then placing the mixture in a vacuum oven with controllable heating rate, and heating according to the program: drying at 100 deg.C for 0.5h; heating to 200 ℃ at the heating rate of 0.8 ℃/min, and drying for 1h; continuously heating to 280 ℃, drying for 0.5h, naturally cooling, and peeling in water after the temperature of the oven is reduced to room temperature to obtain a polyimide film with the thickness of about 30 microns; the weight ratio of the nano silicon dioxide to the polyamic acid is 1.5.
Comparative example 2
Like example 1, only the weight ratio of nanosilica to polyimide powder was replaced with "20.
The polyimide films obtained in examples 1 to 3 and comparative examples 1 to 2 were subjected to a performance test in the following manner:
(1) Water vapor transmission rate: with reference to standard astm f1249, the test conditions are, relative humidity 90%;
(2) Oxygen transmission rate, according to standard astm d3985, under test conditions of 0% relative humidity;
test results of Table 1, examples 1-3 and comparative examples 1-2
| Water vapor transmission rate (g/m) 2 /d) | Oxygen transmission rate (cm) 3 /m 2 /d) | |
| Example 1 | 0.0016 | 0.0028 |
| Example 2 | 0.0047 | 0.0053 |
| Example 3 | 0.0022 | 0.0031 |
| Comparative example 1 | 0.0285 | 0.0216 |
| Comparative example 2 | 0.0098 | 0.0075 |
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 (7)
1. A preparation method of a high-barrier polyimide film is characterized by comprising the following steps: adding nano silicon dioxide and polyimide powder into polyamic acid, and performing thermal imidization to obtain a high-barrier polyimide film; the polyamic acid is obtained by polymerizing dianhydride and diamine; the diamine comprises diamine containing amido bond;
the weight ratio of the nano silicon dioxide to the polyamic acid is 1-5; the weight ratio of the nano silicon dioxide to the polyimide powder is 5-15.
2. The method for preparing the high-barrier polyimide film according to claim 1, wherein the method for preparing the polyimide powder comprises the following steps: adding a polar organic solvent into the polyamic acid to dilute the polyamic acid to the concentration of 5-10%, heating the diluted polyamic acid at 180-190 ℃ and keeping the temperature for 2-3h, removing the solvent, washing, drying in vacuum, and grinding to obtain polyimide powder.
3. The method for preparing a high-barrier polyimide film according to claim 2, wherein the polar organic solvent is one or more selected from the group consisting of N, N-dimethylformamide, N-diethylformamide, N-diethylacetamide, and N-methyl-2-pyrrolidone.
4. The method for preparing a high-barrier polyimide film according to claim 2 or 3, wherein the temperature of the vacuum drying is 280-320 ℃, and the time of the vacuum drying is 0.5-1h.
5. The method for preparing a high-barrier polyimide film according to claim 1, wherein the thermal imidization specifically comprises the steps of: casting polyamic acid mixed with nano silicon dioxide and polyimide powder on glass to form a film, drying at 90-100 ℃ for 0.5-1h, heating to 150-200 ℃, and preserving heat for 0.5-1h; keeping the temperature at 250-300 ℃ for 0.5-1h.
6. The method for preparing a high-barrier polyimide film according to claim 5, wherein the temperature is raised to 150-200 ℃ at a rate of 0.5-0.8 ℃/min during thermal imidization.
7. The method for preparing a high-barrier polyimide film according to claim 5, wherein the diamine comprises amide bonds in the diamine in an amount of not less than 20% based on the total molar amount of the diamine.
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| CN101597380A (en) * | 2009-06-30 | 2009-12-09 | 西安航天三沃化学有限公司 | The chemical imidization preparation method of nano rectorite |
| CN102108124A (en) * | 2010-12-30 | 2011-06-29 | 上海市合成树脂研究所 | Preparation method of meltable polyimide moulding compound |
| CN105440286B (en) * | 2016-01-12 | 2018-03-09 | 湖南工业大学 | A kind of polyimides containing fluorenes or Fluorenone structure and its preparation method and application |
| CN105820368B (en) * | 2016-05-25 | 2018-11-27 | 中国科学院长春应用化学研究所 | A kind of polyimide nano foam and preparation method thereof |
| CN111647159B (en) * | 2020-05-29 | 2022-12-02 | 浙江中科玖源新材料有限公司 | Polyimide film and preparation method thereof |
| CN112194791A (en) * | 2020-06-16 | 2021-01-08 | 中国科学院长春应用化学研究所 | Transparent polyimide film and preparation method thereof |
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