CN113501958B - Colorless transparent heat-resistant polyimide film and preparation method thereof - Google Patents
Colorless transparent heat-resistant polyimide film and preparation method thereof Download PDFInfo
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- CN113501958B CN113501958B CN202110664547.1A CN202110664547A CN113501958B CN 113501958 B CN113501958 B CN 113501958B CN 202110664547 A CN202110664547 A CN 202110664547A CN 113501958 B CN113501958 B CN 113501958B
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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
- C08G73/14—Polyamide-imides
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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
Abstract
The invention provides a colorless transparent heat-resistant polyimide film and a preparation method thereof. The polyimide film has excellent light transmittance and heat resistance, and has potential application possibility as an optical film in the advanced microelectronics field.
Description
Technical Field
The invention relates to the technical field of optical materials, in particular to a colorless transparent heat-resistant polyimide film and a preparation method thereof.
Background
In recent years, with the rapid development of microelectronics and photoelectric engineering technologies, the demand for high light transmittance, high integration, high reliability and high signal transmission speed of photoelectric devices is increasing, and research on novel optical films having high light transmittance and high heat resistance is also receiving increasing attention. Polyimide (PI) films have been widely used in engineering fields as a film having excellent thermal stability, chemical resistance, mechanical properties, and low dielectric properties. Among them, the colorless transparent polyimide film (CPI) has many advantages such as high light transmittance, high heat resistance, etc., and is one of the best materials for preparing novel optical films at present.
However, the conventional PI film cannot be applied to optoelectronic devices because the dianhydride and diamine generate electron transfer complexes during polymerization, so that the optical properties of the film become poor. With the advent of CPI films, this area of gap can be exactly filled. This is mainly because CPI films possess a relatively high optical transmittance and excellent combination of properties of PI itself, and can be widely used in optical films required for optoelectronic devices.
Currently, researchers have incorporated strong electron-withdrawing groups in synthetic monomers CF 3 The color of PI is changed either by the use of cycloaliphatic diamines or dianhydrides, but the resulting CPI optical clarity is still less satisfactory. And increasing the optical clarity of CPI materials is often accompanied by a sacrifice in other properties, such as high temperature stability, etc., such that CPI related applications are greatly limited.Therefore, it is important to develop a CPI material with high optical transparency and excellent thermal properties.
Disclosure of Invention
Based on the technical problems in the background technology, the invention provides a colorless transparent heat-resistant polyimide film and a preparation method thereof, wherein the polyimide film has excellent light transmittance and heat resistance, and has potential application possibility as an optical film in the advanced microelectronics field.
The invention provides a colorless transparent heat-resistant polyimide film, which comprises alicyclic dianhydride, terephthaloyl chloride and polyimide obtained by polycondensation of isophthaloyl chloride and aromatic diamine.
Preferably, the cycloaliphatic dianhydride has the following structural formula:
preferably, the aromatic diamine has at least one of the following structural formulas:
preferably, the molar usage ratio of terephthaloyl chloride to isophthaloyl chloride is 1:1-3.
Preferably, the total molar amount of terephthaloyl chloride to isophthaloyl chloride is 20 to 40 mole% of the aromatic diamine.
Preferably, the polyimide film has a light transmittance of 88% or more at 550nm, a yellowness index of 2.5 or less, and a glass transition temperature of 375 ℃ or more.
The invention also provides a preparation method of the colorless transparent heat-resistant polyimide film, which comprises the following steps:
(1) Performing polymerization reaction on alicyclic dianhydride, terephthaloyl chloride and isophthaloyl chloride and aromatic diamine in an organic solvent to obtain polyamide acid;
(2) Imidizing the polyamide acid under the conditions of a catalyst and a dehydrating agent to obtain polyimide;
(3) And (3) dissolving the polyimide, and then coating the polyimide film to form a film to obtain the polyimide film.
Preferably, in the step (1), the organic solvent is at least one of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide or dimethylsulfoxide.
Preferably, in the step (2), the catalyst is at least one of pyridine, quinoline or pyrroline, and the dehydrating agent is at least one of acetic anhydride, trifluoroacetic anhydride or propionic anhydride.
The invention provides an optical film, which comprises the polyimide film or the polyimide film prepared by the preparation method.
The invention provides a colorless transparent heat-resistant polyimide film, which comprises alicyclic dianhydride, terephthaloyl chloride and polyimide obtained by polycondensation of isophthaloyl chloride and aromatic diamine. The polyimide film formed by compounding the specific monomers has excellent comprehensive performance in both optical and thermal aspects, shows light transmittance of more than 90% at 550nm and ultralow yellow index of less than 2, and has glass transition temperature of more than 380 ℃, so that the defect that the optical transparency and high-temperature stability of the traditional CPI material cannot be considered is well overcome.
Detailed Description
The invention provides a colorless transparent heat-resistant polyimide film, which comprises alicyclic dianhydride, terephthaloyl chloride and polyimide obtained by polycondensation of isophthaloyl chloride and aromatic diamine.
In the polyimide film, the alicyclic dianhydride, the terephthaloyl chloride and the isophthaloyl chloride are compounded to serve as carboxylic acid monomers, and the carboxylic acid monomers and the diamine monomers of the aromatic diamine are subjected to polycondensation, so that on one hand, the structure of an amide bond and an imide bond is introduced into the polyimide composition of the obtained film, the light transmittance of the obtained polyimide film is obviously improved, and the yellow index is effectively reduced; on the other hand, other dianhydrides are omitted as carboxylic acid monomers, so that not only the defect of increasing the color of polyimide generally accompanied by other dianhydrides is restrained, but also the heat-resistant stability of the obtained polyimide film can be improved.
Meanwhile, as the terephthaloyl chloride and the isophthaloyl chloride are simultaneously selected as the compound monomers, the larger space occupation of the isophthaloyl chloride relative to the terephthaloyl chloride is utilized, so that the inter-molecular chain gap of the obtained polyimide is relatively increased, the defect that the solubility of the obtained polyimide is poor when the terephthaloyl chloride is singly used as the monomer is overcome, and the good film forming performance is finally obtained, and the excellent comprehensive performance is presented.
In the present invention, the alicyclic dianhydride is specifically selected from the dianhydrides represented by the following structural formulas:
the specific selection of the alicyclic dianhydride leads the polyimide composition of the obtained film to be introduced with a bridged ring hydrocarbon structure, and the bridged ring hydrocarbon structure is compounded with the structure of the imide bond introduced by the terephthaloyl chloride and the isophthaloyl chloride, thereby further improving the light transmittance of the obtained polyimide film, further reducing the yellow index and obviously improving the heat stability.
In the invention, the molar ratio of terephthaloyl chloride to isophthaloyl chloride is 1:1-3, and the total amount of terephthaloyl chloride and isophthaloyl chloride is 30-60mol% of aromatic diamine.
The specific limitation of the content regulates and controls the polymerization degree of the polyimide film synthesized by terephthaloyl chloride, isophthaloyl chloride, alicyclic dianhydride and aromatic diamine, and obviously improves the heat-resistant stability while realizing excellent optical performance.
In the invention, when the polyimide film is prepared, the prior known method is used for carrying out polycondensation on alicyclic dianhydride, terephthaloyl chloride, isophthaloyl chloride and aromatic diamine to obtain polyamide acid; then adding a dehydrating agent and a catalyst into the obtained polyamide acid for imidization, and then adding the polyamide acid into a poor solvent for precipitation to obtain polyimide; and finally preparing the obtained polyimide into a solution by using an organic solvent, and forming a film on a substrate to obtain the polyimide film.
In the above-mentioned process, the aromatic diamine is first dissolved in an organic solvent, and then alicyclic dianhydride, terephthaloyl chloride and isophthaloyl chloride are added thereto, and the polymerization reaction is carried out at a suitable reaction temperature to obtain the polyamic acid. The organic solvent may be N-methylpyrrolidone, dimethyl sulfoxide, N-dimethylformamide or N, N-dimethylacetamide.
The dehydrating agent used in the preparation of the polyimide can be trifluoroacetic anhydride, acetic anhydride, propionic anhydride, aromatic monocarboxylic acid anhydride or acetyl chloride, and the catalyst used can be pyridine, p-pyrroline, lutidine, collidine, quinoline, isoquinoline, triethylamine or N, N-dimethylethanolamine; the poor solvent may be methanol, ethanol, isopropanol (2-propanol), ethylene glycol, triethylene glycol or 2-butanol.
The organic solvent used in the above-mentioned process for producing the polyimide film may be dimethylformamide, dimethylacetamide or N-methylpyrrolidone.
The technical scheme of the present invention will be described in detail by means of specific examples, which should be explicitly set forth for illustration, but should not be construed as limiting the scope of the present invention.
Example 1
A colorless transparent heat-resistant polyimide film, its preparation method includes:
3.2023g (10 mmol) of 2,2' -bis (trifluoromethyl) diaminobiphenyl (TFDB) is dissolved in 50mL of N, N-dimethylacetamide, the solution is stirred and dissolved completely after nitrogen is introduced, 2.6888g (7 mmol) of norbornane-2-spirolactone-alpha-cyclopentanone-alpha ' -spirolactone-2 ' -norbornane-5, 5 ', 6 ' -tetracarboxylic dianhydride (CpODA), 0.2030g (1 mmol) of terephthaloyl chloride (TPC) and 0.4060g (2 mmol) of isophthaloyl chloride (IPC) are slowly added, and the solution is stirred and reacted for 10 hours at room temperature to obtain a transparent polyamic acid solution;
adding 3.56g of pyridine as a catalyst into the polyamic acid solution, stirring and dispersing at room temperature completely, adding 2.37g of acetic anhydride as a dehydrating agent, stirring and reacting at room temperature overnight, transferring the reaction liquid into a dropping funnel, dripping the reaction liquid into a beaker with a large amount of methanol at a speed of 2 drops/second, gradually separating out precipitate, filtering and washing the precipitate with a large amount of methanol after the precipitation is completed, crushing the obtained precipitate solid, and vacuum drying at 100 ℃ to obtain polyimide powder;
and adding the polyimide powder into N-methyl pyrrolidone, dissolving completely to obtain polyimide solution with the solid content of 20%, coating the polyimide solution on a glass substrate, heating to 60 ℃ in an oven, drying for 0.5h, continuously heating to 150 ℃, drying for 1h, heating to 220 ℃ again, drying for 1h, heating to 260 ℃, drying for 0.5h, cooling to room temperature, taking out a glass plate from the oven, stripping a film from the glass plate to obtain the polyimide film, and controlling the thickness of the polyimide film to be about 50 mu m.
The results of the performance test on the polyimide film are shown in the following table.
Example 2
A colorless transparent heat-resistant polyimide film, its preparation method includes:
1.8423g (10 mmol) of 4,4' -diaminobiphenyl (MSDS) is dissolved in 50mL of N, N-dimethylacetamide in an ice water bath, nitrogen is introduced, stirring is carried out completely, 2.6888g (7 mmol) of norbornane-2-spirolactone-alpha-cyclopentanone-alpha ' -spirolactone-2 ' -norbornane-5, 5 ', 6 ' -tetracarboxylic dianhydride (CpODA), 0.2030g (1 mmol) of terephthaloyl chloride (TPC) and 0.4060g (2 mmol) of isophthaloyl chloride (IPC) are slowly added, and stirring is carried out at room temperature for 10 hours to obtain a transparent polyamic acid solution;
adding 3.56g of pyridine as a catalyst into the polyamic acid solution, stirring and dispersing at room temperature completely, adding 2.37g of acetic anhydride as a dehydrating agent, stirring and reacting at room temperature overnight, transferring the reaction liquid into a dropping funnel, dripping the reaction liquid into a beaker with a large amount of methanol at a speed of 2 drops/second, gradually separating out precipitate, filtering and washing the precipitate with a large amount of methanol after the precipitation is completed, crushing the obtained precipitate solid, and vacuum drying at 100 ℃ to obtain polyimide powder;
and adding the polyimide powder into N-methyl pyrrolidone, dissolving completely to obtain polyimide solution with the solid content of 20%, coating the polyimide solution on a glass substrate, heating to 60 ℃ in an oven, drying for 0.5h, continuously heating to 150 ℃, drying for 1h, heating to 220 ℃ again, drying for 1h, heating to 260 ℃, drying for 0.5h, cooling to room temperature, taking out a glass plate from the oven, stripping a film from the glass plate to obtain the polyimide film, and controlling the thickness of the polyimide film to be about 50 mu m.
The results of the performance test on the polyimide film are shown in the following table.
Example 3
A colorless transparent heat-resistant polyimide film, its preparation method includes:
2.0024g (10 mmol) of 4,4' -diaminodiphenyl ether (ODA) is dissolved in 50mL of N, N-dimethylacetamide, after nitrogen is introduced, stirring and dissolving are completed, 2.6888g (7 mmol) of norbornane-2-spirolactone-alpha-cyclopentanone-alpha ' -spirolactone-2 ' -norbornane-5, 5 ', 6 ' -tetracarboxylic dianhydride (CpODA), 0.2030g (1 mmol) of terephthaloyl chloride (TPC) and 0.4060g (2 mmol) of isophthaloyl chloride (IPC) are slowly added, and stirring and reacting are carried out at room temperature for 10 hours to obtain a transparent polyamic acid solution;
adding 3.56g of pyridine as a catalyst into the polyamic acid solution, stirring and dispersing at room temperature completely, adding 2.37g of acetic anhydride as a dehydrating agent, stirring and reacting at room temperature overnight, transferring the reaction liquid into a dropping funnel, dripping the reaction liquid into a beaker with a large amount of methanol at a speed of 2 drops/second, gradually separating out precipitate, filtering and washing the precipitate with a large amount of methanol after the precipitation is completed, crushing the obtained precipitate solid, and vacuum drying at 100 ℃ to obtain polyimide powder;
and adding the polyimide powder into N-methyl pyrrolidone, dissolving completely to obtain polyimide solution with the solid content of 20%, coating the polyimide solution on a glass substrate, heating to 60 ℃ in an oven, drying for 0.5h, continuously heating to 150 ℃, drying for 1h, heating to 220 ℃ again, drying for 1h, heating to 260 ℃, drying for 0.5h, cooling to room temperature, taking out a glass plate from the oven, stripping a film from the glass plate to obtain the polyimide film, and controlling the thickness of the polyimide film to be about 50 mu m.
The results of the performance test on the polyimide film are shown in the following table.
Example 4
A colorless transparent heat-resistant polyimide film, its preparation method includes:
3.2023g (10 mmol) of 2,2' -bis (trifluoromethyl) diaminobiphenyl (TFDB) is dissolved in 50mL of N, N-dimethylacetamide in an ice water bath, the mixture is stirred and dissolved completely after nitrogen is introduced, 1.3728g (7 mmol) of cyclobutane tetracarboxylic dianhydride (CBDA), 0.2030g (1 mmol) of terephthaloyl chloride (TPC) and 0.4060g (2 mmol) of isophthaloyl chloride (IPC) are slowly added, and the mixture is stirred and reacted for 10 hours at room temperature to obtain a transparent polyamic acid solution;
adding 3.56g of pyridine as a catalyst into the polyamic acid solution, stirring and dispersing at room temperature completely, adding 2.37g of acetic anhydride as a dehydrating agent, stirring and reacting at room temperature overnight, transferring the reaction liquid into a dropping funnel, dripping the reaction liquid into a beaker with a large amount of methanol at a speed of 2 drops/second, gradually separating out precipitate, filtering and washing the precipitate with a large amount of methanol after the precipitation is completed, crushing the obtained precipitate solid, and vacuum drying at 100 ℃ to obtain polyimide powder;
and adding the polyimide powder into N-methyl pyrrolidone, dissolving completely to obtain polyimide solution with the solid content of 20%, coating the polyimide solution on a glass substrate, heating to 60 ℃ in an oven, drying for 0.5h, continuously heating to 150 ℃, drying for 1h, heating to 220 ℃ again, drying for 1h, heating to 260 ℃, drying for 0.5h, cooling to room temperature, taking out a glass plate from the oven, stripping a film from the glass plate to obtain the polyimide film, and controlling the thickness of the polyimide film to be about 50 mu m.
The results of the performance test on the polyimide film are shown in the following table.
Example 5
A colorless transparent heat-resistant polyimide film, its preparation method includes:
3.2023g (10 mmol) of 2,2' -bis (trifluoromethyl) diaminobiphenyl (TFDB) is dissolved in 50mL of N, N-dimethylacetamide, the solution is stirred and dissolved completely after nitrogen is introduced, 2.3047g (6 mmol) of norbornane-2-spirolactone-alpha-cyclopentanone-alpha ' -spirolactone-2 ' -norbornane-5, 5 ', 6 ' -tetracarboxylic dianhydride (CpODA), 0.2030g (1 mmol) of terephthaloyl chloride (TPC) and 0.6091g (3 mmol) of isophthaloyl chloride (IPC) are slowly added, and the solution is stirred and reacted for 10 hours at room temperature to obtain a transparent polyamic acid solution;
adding 3.56g of pyridine as a catalyst into the polyamic acid solution, stirring and dispersing at room temperature completely, adding 2.37g of acetic anhydride as a dehydrating agent, stirring and reacting at room temperature overnight, transferring the reaction liquid into a dropping funnel, dripping the reaction liquid into a beaker with a large amount of methanol at a speed of 2 drops/second, gradually separating out precipitate, filtering and washing the precipitate with a large amount of methanol after the precipitation is completed, crushing the obtained precipitate solid, and vacuum drying at 100 ℃ to obtain polyimide powder;
and adding the polyimide powder into N-methyl pyrrolidone, dissolving completely to obtain polyimide solution with the solid content of 20%, coating the polyimide solution on a glass substrate, heating to 60 ℃ in an oven, drying for 0.5h, continuously heating to 150 ℃, drying for 1h, heating to 220 ℃ again, drying for 1h, heating to 260 ℃, drying for 0.5h, cooling to room temperature, taking out a glass plate from the oven, stripping a film from the glass plate to obtain the polyimide film, and controlling the thickness of the polyimide film to be about 50 mu m.
The results of the performance test on the polyimide film are shown in the following table.
Example 6
A colorless transparent heat-resistant polyimide film, its preparation method includes:
3.2023g (10 mmol) of 2,2' -bis (trifluoromethyl) diaminobiphenyl (TFDB) is dissolved in 50mL of N, N-dimethylacetamide, the solution is stirred and dissolved completely after nitrogen is introduced, 3.0729g (8 mmol) of norbornane-2-spirolactone-alpha-cyclopentanone-alpha ' -spirolactone-2 ' -norbornane-5, 5 ', 6 ' -tetracarboxylic dianhydride (CpODA), 0.2030g (1 mmol) of terephthaloyl chloride (TPC) and 0.2030g (1 mmol) of isophthaloyl chloride (IPC) are slowly added, and the solution is stirred and reacted for 10 hours at room temperature to obtain a transparent polyamic acid solution;
adding 3.56g of pyridine as a catalyst into the polyamic acid solution, stirring and dispersing at room temperature completely, adding 2.37g of acetic anhydride as a dehydrating agent, stirring and reacting at room temperature overnight, transferring the reaction liquid into a dropping funnel, dripping the reaction liquid into a beaker with a large amount of methanol at a speed of 2 drops/second, gradually separating out precipitate, filtering and washing the precipitate with a large amount of methanol after the precipitation is completed, crushing the obtained precipitate solid, and vacuum drying at 100 ℃ to obtain polyimide powder;
and adding the polyimide powder into N-methyl pyrrolidone, dissolving completely to obtain polyimide solution with the solid content of 20%, coating the polyimide solution on a glass substrate, heating to 60 ℃ in an oven, drying for 0.5h, continuously heating to 150 ℃, drying for 1h, heating to 220 ℃ again, drying for 1h, heating to 260 ℃, drying for 0.5h, cooling to room temperature, taking out a glass plate from the oven, stripping a film from the glass plate to obtain the polyimide film, and controlling the thickness of the polyimide film to be about 50 mu m.
The results of the performance test on the polyimide film are shown in the following table.
Comparative example 1
A colorless transparent heat-resistant polyimide film, its preparation method includes:
3.2023g (10 mmol) of 2,2' -bis (trifluoromethyl) diaminobiphenyl (TFDB) is dissolved in 50mL of N, N-dimethylacetamide, the mixture is stirred and dissolved completely after nitrogen is introduced, 2.6888g (7 mmol) of norbornane-2-spirolactone-alpha-cyclopentanone-alpha ' -spirolactone-2 ' -norbornane-5, 5 ', 6 ' -tetracarboxylic dianhydride (CpODA) and 0.6091g (3 mmol) of terephthaloyl chloride (TPC) are slowly added, and the mixture is stirred and reacted at room temperature for 10 hours to obtain a transparent polyamic acid solution;
adding 3.56g of pyridine as a catalyst into the polyamic acid solution, stirring and dispersing at room temperature completely, adding 2.37g of acetic anhydride as a dehydrating agent, stirring and reacting at room temperature overnight, transferring the reaction liquid into a dropping funnel, dripping the reaction liquid into a beaker with a large amount of methanol at a speed of 2 drops/second, gradually separating out precipitate, filtering and washing the precipitate with a large amount of methanol after the precipitation is completed, crushing the obtained precipitate solid, and vacuum drying at 100 ℃ to obtain polyimide powder;
and adding the polyimide powder into N-methyl pyrrolidone, dissolving completely to obtain polyimide solution with the solid content of 20%, coating the polyimide solution on a glass substrate, heating to 60 ℃ in an oven, drying for 0.5h, continuously heating to 150 ℃, drying for 1h, heating to 220 ℃ again, drying for 1h, heating to 260 ℃, drying for 0.5h, cooling to room temperature, taking out a glass plate from the oven, stripping a film from the glass plate to obtain the polyimide film, and controlling the thickness of the polyimide film to be about 50 mu m.
The results of the performance test on the polyimide film are shown in the following table.
Comparative example 2
A colorless transparent heat-resistant polyimide film, its preparation method includes:
3.2023g (10 mmol) of 2,2' -bis (trifluoromethyl) diaminobiphenyl (TFDB) is dissolved in 50mL of N, N-dimethylacetamide, the mixture is stirred and dissolved completely after nitrogen is introduced, 2.6888g (7 mmol) of norbornane-2-spirolactone-alpha-cyclopentanone-alpha ' -spirolactone-2 ' -norbornane-5, 5 ', 6 ' -tetracarboxylic dianhydride (CpODA) and 0.6091g (3 mmol) of isophthaloyl chloride (IPC) are slowly added, and the mixture is stirred and reacted at room temperature for 10 hours to obtain a transparent polyamic acid solution;
adding 3.56g of pyridine as a catalyst into the polyamic acid solution, stirring and dispersing at room temperature completely, adding 2.37g of acetic anhydride as a dehydrating agent, stirring and reacting at room temperature overnight, transferring the reaction liquid into a dropping funnel, dripping the reaction liquid into a beaker with a large amount of methanol at a speed of 2 drops/second, gradually separating out precipitate, filtering and washing the precipitate with a large amount of methanol after the precipitation is completed, crushing the obtained precipitate solid, and vacuum drying at 100 ℃ to obtain polyimide powder;
and adding the polyimide powder into N-methyl pyrrolidone, dissolving completely to obtain polyimide solution with the solid content of 20%, coating the polyimide solution on a glass substrate, heating to 60 ℃ in an oven, drying for 0.5h, continuously heating to 150 ℃, drying for 1h, heating to 220 ℃ again, drying for 1h, heating to 260 ℃, drying for 0.5h, cooling to room temperature, taking out a glass plate from the oven, stripping a film from the glass plate to obtain the polyimide film, and controlling the thickness of the polyimide film to be about 50 mu m.
The results of the performance test on the polyimide film are shown in the following table.
Comparative example 3
A colorless transparent heat-resistant polyimide film, its preparation method includes:
3.2023g (10 mmol) of 2,2 '-bis (trifluoromethyl) diaminobiphenyl (TFDB) is dissolved in 50mL of N, N-dimethylacetamide in an ice water bath, the solution is stirred and dissolved completely after nitrogen is introduced, 3.1098g (7 mmol) of 4,4' - (hexafluoroisopropenyl) diphthalic anhydride (6 FDA) and 0.2030g (1 mmol) of terephthaloyl chloride (TPC) and 0.4060g (2 mmol) of isophthaloyl chloride (IPC) are slowly added, and the solution is stirred and reacted for 10 hours at room temperature to obtain a transparent polyamic acid solution;
adding 3.56g of pyridine as a catalyst into the polyamic acid solution, stirring and dispersing at room temperature completely, adding 2.37g of acetic anhydride as a dehydrating agent, stirring and reacting at room temperature overnight, transferring the reaction liquid into a dropping funnel, dripping the reaction liquid into a beaker with a large amount of methanol at a speed of 2 drops/second, gradually separating out precipitate, filtering and washing the precipitate with a large amount of methanol after the precipitation is completed, crushing the obtained precipitate solid, and vacuum drying at 100 ℃ to obtain polyimide powder;
and adding the polyimide powder into N-methyl pyrrolidone, dissolving completely to obtain polyimide solution with the solid content of 20%, coating the polyimide solution on a glass substrate, heating to 60 ℃ in an oven, drying for 0.5h, continuously heating to 150 ℃, drying for 1h, heating to 220 ℃ again, drying for 1h, heating to 260 ℃, drying for 0.5h, cooling to room temperature, taking out a glass plate from the oven, stripping a film from the glass plate to obtain the polyimide film, and controlling the thickness of the polyimide film to be about 50 mu m.
The results of the performance test on the polyimide film are shown in the following table.
Comparative example 4
A colorless transparent heat-resistant polyimide film, its preparation method includes:
3.2023g (10 mmol) of 2,2' -bis (trifluoromethyl) diaminobiphenyl (TFDB) is dissolved in 50mL of N, N-dimethylacetamide, the solution is stirred and dissolved completely after nitrogen is introduced, 2.6888g (7 mmol) of norbornane-2-spirolactone-alpha-cyclopentanone-alpha ' -spirolactone-2 ' -norbornane-5, 5 ', 6 ' -tetracarboxylic dianhydride (CpODA), 0.4060g (2 mmol) of terephthaloyl chloride (TPC) and 0.2030g (1 mmol) of isophthaloyl chloride (IPC) are slowly added, and the solution is stirred and reacted for 10 hours at room temperature to obtain a transparent polyamic acid solution;
adding 3.56g of pyridine as a catalyst into the polyamic acid solution, stirring and dispersing at room temperature completely, adding 2.37g of acetic anhydride as a dehydrating agent, stirring and reacting at room temperature overnight, transferring the reaction liquid into a dropping funnel, dripping the reaction liquid into a beaker with a large amount of methanol at a speed of 2 drops/second, gradually separating out precipitate, filtering and washing the precipitate with a large amount of methanol after the precipitation is completed, crushing the obtained precipitate solid, and vacuum drying at 100 ℃ to obtain polyimide powder;
and adding the polyimide powder into N-methyl pyrrolidone, dissolving completely to obtain polyimide solution with the solid content of 20%, coating the polyimide solution on a glass substrate, heating to 60 ℃ in an oven, drying for 0.5h, continuously heating to 150 ℃, drying for 1h, heating to 220 ℃ again, drying for 1h, heating to 260 ℃, drying for 0.5h, cooling to room temperature, taking out a glass plate from the oven, stripping a film from the glass plate to obtain the polyimide film, and controlling the thickness of the polyimide film to be about 50 mu m.
The results of the performance test on the polyimide film are shown in the following table.
Comparative example 5
A colorless transparent heat-resistant polyimide film, its preparation method includes:
3.2023g (10 mmol) of 2,2' -bis (trifluoromethyl) diaminobiphenyl (TFDB) is dissolved in 50mL of N, N-dimethylacetamide, the solution is stirred and dissolved completely after nitrogen is introduced, 1.9206g (5 mmol) of norbornane-2-spirolactone-alpha-cyclopentanone-alpha ' -spirolactone-2 ' -norbornane-5, 5 ', 6 ' -tetracarboxylic dianhydride (CpODA), 0.4060g (2 mmol) of terephthaloyl chloride (TPC) and 0.6091g (3 mmol) of isophthaloyl chloride (IPC) are slowly added, and the solution is stirred and reacted for 10 hours at room temperature to obtain a transparent polyamic acid solution;
adding 3.56g of pyridine as a catalyst into the polyamic acid solution, stirring and dispersing at room temperature completely, adding 2.37g of acetic anhydride as a dehydrating agent, stirring and reacting at room temperature overnight, transferring the reaction liquid into a dropping funnel, dripping the reaction liquid into a beaker with a large amount of methanol at a speed of 2 drops/second, gradually separating out precipitate, filtering and washing the precipitate with a large amount of methanol after the precipitation is completed, crushing the obtained precipitate solid, and vacuum drying at 100 ℃ to obtain polyimide powder;
and adding the polyimide powder into N-methyl pyrrolidone, dissolving completely to obtain polyimide solution with the solid content of 20%, coating the polyimide solution on a glass substrate, heating to 60 ℃ in an oven, drying for 0.5h, continuously heating to 150 ℃, drying for 1h, heating to 220 ℃ again, drying for 1h, heating to 260 ℃, drying for 0.5h, cooling to room temperature, taking out a glass plate from the oven, stripping a film from the glass plate to obtain the polyimide film, and controlling the thickness of the polyimide film to be about 50 mu m.
The results of the performance test on the polyimide film are shown in the following table.
The polyimide films obtained in examples and comparative examples were subjected to performance tests as shown in the following methods, and the results are shown in table 1.
Glass transition temperature: using a differential scanning calorimeter device, performing DSC measurement at a temperature rising speed of 10 ℃/min in a temperature range of 50-450 ℃ under the nitrogen atmosphere, and obtaining a glass transition temperature;
thermal decomposition temperature: performing TGA measurement at a temperature range of 50-700 ℃ at a heating rate of 10 ℃/min under nitrogen atmosphere by using a thermogravimetric analyzer, wherein the thermal weight loss temperature of 5% is taken as the thermal decomposition temperature;
light transmittance at wavelength 550 nm: the transmittance was measured at 550nm using an ultraviolet spectrophotometer;
yellowness index YI: the yellowness index was determined according to ASTM E313 standard using an ultraviolet spectrophotometer.
Table 1 polyimide film test results obtained in examples and comparative examples
The polyimide obtained in example 1 and comparative examples 1 to 2 was subjected to a solution processability test, and the results are shown in table 2.
Solution processability: adding 99 times of solvent into polyimide, stirring for 5min with a test tube stirrer, and visually observing the dissolution state; wherein the solvents are acetone, tetrahydrofuran, ethyl acetate, cyclohexanone, N-dimethylacetamide, N-methyl-pyrrolidone and dimethyl sulfoxide.
If it is dissolved at normal temperature, it is evaluated as "++"; if it is soluble under heat and remains homogeneous after cooling to room temperature, it is rated "+"; if swelling occurs or only a part of the solution is dissolved, the evaluation is "±"; if insoluble, evaluate as "-"; wherein, when acetone, tetrahydrofuran, ethyl acetate and cyclohexanone are used as solvents, the heating temperature is 50 ℃, and when N, N-dimethylacetamide, N-methyl-pyrrolidone and dimethyl sulfoxide are used as solvents, the heating temperature is 150 ℃.
TABLE 2 solution processibility of the polyimide obtained in example 1 and comparative examples 1-2
++: soluble at normal temperature; +: soluble under heating; and (3) the following steps: partially soluble; -: insoluble in water
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (6)
1. A colorless transparent heat-resistant polyimide film is characterized in that the polyimide film comprises polyimide which is formed by polycondensation of alicyclic dianhydride, terephthaloyl chloride and isophthaloyl chloride and aromatic diamine;
the alicyclic dianhydride has the following structural formula:
the aromatic diamine has at least one of the following structural formulas:
the molar dosage ratio of terephthaloyl chloride to isophthaloyl chloride is 1:1-3;
the total molar amount of terephthaloyl chloride and isophthaloyl chloride is 20 to 40mol% based on the aromatic diamine.
2. The colorless transparent heat-resistant polyimide film according to claim 1, wherein the polyimide film has a light transmittance of 88% or more at 550nm, a yellowness index of 2.5 or less, and a glass transition temperature of 375 ℃ or more.
3. A method for producing the colorless transparent heat-resistant polyimide film as claimed in claim 1 or 2, comprising:
(1) Performing polymerization reaction on alicyclic dianhydride, terephthaloyl chloride and isophthaloyl chloride and aromatic diamine in an organic solvent to obtain polyamide acid;
(2) Imidizing the polyamide acid under the conditions of a catalyst and a dehydrating agent to obtain polyimide;
(3) And (3) dissolving the polyimide, and then coating the polyimide film to form a film to obtain the polyimide film.
4. The method for producing a colorless and transparent heat-resistant polyimide film according to claim 3, wherein in the step (1), the organic solvent is at least one of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide or dimethylsulfoxide.
5. The method for producing a colorless transparent heat-resistant polyimide film according to claim 3 or 4, wherein in the step (2), the catalyst is at least one of pyridine, quinoline or pyrroline, and the dehydrating agent is at least one of acetic anhydride, trifluoroacetic anhydride or propionic anhydride.
6. An optical film comprising the polyimide film of claim 1 or 2 or the polyimide film produced by the production method of any one of claims 3 to 5.
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| WO2015099478A1 (en) * | 2013-12-26 | 2015-07-02 | 코오롱인더스트리 주식회사 | Transparent polyamide-imide resin and film using same |
| JP2018172669A (en) * | 2017-03-30 | 2018-11-08 | Ｊｘｔｇエネルギー株式会社 | Polyamide imide, resin solution and film |
| CN111363150A (en) * | 2020-04-22 | 2020-07-03 | 中国地质大学（北京） | Flame-retardant transparent polyimide film and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2015099478A1 (en) * | 2013-12-26 | 2015-07-02 | 코오롱인더스트리 주식회사 | Transparent polyamide-imide resin and film using same |
| JP2018172669A (en) * | 2017-03-30 | 2018-11-08 | Ｊｘｔｇエネルギー株式会社 | Polyamide imide, resin solution and film |
| CN111363150A (en) * | 2020-04-22 | 2020-07-03 | 中国地质大学（北京） | Flame-retardant transparent polyimide film and preparation method and application thereof |
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