CN115417989A - Preparation of degradable high-heat-resistance polyimide material - Google Patents
Preparation of degradable high-heat-resistance polyimide material Download PDFInfo
- Publication number
- CN115417989A CN115417989A CN202210961340.5A CN202210961340A CN115417989A CN 115417989 A CN115417989 A CN 115417989A CN 202210961340 A CN202210961340 A CN 202210961340A CN 115417989 A CN115417989 A CN 115417989A
- Authority
- CN
- China
- Prior art keywords
- dianhydride
- bis
- diamine
- heat resistance
- polyimide film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The invention provides a preparation method of a degradable polyimide film with high heat resistance. The method mainly synthesizes novel diamine 3,9-di [4- (5-amino-2-pyridyloxy) pyridyl ] -2,4,8,10-heteroxy-spiro (5,5) undecane containing acetal and pyridine structures, and utilizes the diamine to modify the performance of polyimide. By introducing an acetal structure, the internal structure of the polyimide is improved, the limitation that hydrolysis can be carried out only under high temperature and strong alkali is broken, and the material can be degraded under an acidic condition. Meanwhile, the introduction of the acetal structure can destroy the regularity of the polyimide structure, so that the heat resistance of the polyimide structure is greatly reduced, and the defect can be avoided by introducing the pyridine structure.
Description
Technical Field
The invention relates to the field of modification of polyimide materials, in particular to preparation of a degradable high-heat-resistance polyimide material.
Background
Polyimide materials have had a very long time to develop and have been synthesized in 1908. Polyimide has a large number of benzene rings and imide rings in a molecular structure, so that the polyimide has excellent comprehensive performance, is an indispensable polymer material, and is widely applied to the fields of aerospace, biomedicine, automobile manufacturing and the like. However, the traditional polyimide material still has certain disadvantages, and the requirement of the development of times can be met through modification.
The excellent performance of the polyimide enables the polyimide to have wide application prospect and use value. The polyimide material has excellent chemical stability, and can be hydrolyzed only under the dual actions of high temperature of 150 ℃ and strong alkali, so that the diamine and the dianhydride with high recovery rate are obtained. In the current society, environmental protection becomes mainstream, and harsh degradation conditions are contrary to the idea, which greatly limits the application of polyimide materials. Therefore, modification of the material is urgently needed, so that the material is degraded in a mild environment and becomes an environment-friendly material. By introducing an acetal structure, the internal structure of the polyimide is improved, the limitation that hydrolysis can be carried out only under high temperature and strong alkali is avoided, the material can be degraded under an acidic condition, and the requirement of times development is met. However, the introduction of acetal structure can damage the regularity of polyimide structure, and thus the heat resistance is greatly reduced. The pyridine structure is introduced to improve the heat resistance of the material, so that the disadvantage is greatly avoided, and the pyridine structure can be used in the fields with higher requirements on heat resistance, such as aerospace, automobile manufacturing and the like. Therefore, it is important to develop a polyimide material having degradability and high heat resistance.
Disclosure of Invention
Aiming at the requirements of the current environmental protection and aerospace materials and the like on polyimide, the invention provides a preparation method of a polyimide material with degradability and high heat resistance.
Researchers in this project found that to achieve the objectives of the present invention, the following preparation method can be used: the novel diamine monomer 3,9-di [4- (5-amino-2-pyridyloxy) pyridyl ] -2,4,8,10-heteroxy-spiro (5,5) undecane containing acetal and pyridine structures is synthesized by using pentaerythritol, 2-formyl-5-hydroxypyridine and other raw materials, and is dried to remove moisture. The dried 3,9-bis [4- (5-amino-2-pyridyloxy) pyridyl ] -2,4,8,10-hetero-oxy-spiro (5,5) undecane and other diamine monomers were dissolved in a polar aprotic solution at normal temperature. When the dianhydride monomer is completely dissolved, controlling the temperature of the system to be 4-10 ℃ by utilizing an ice water bath, and adding the dianhydride monomer five times according to a one-half feeding method. And (3) after the last dosing is finished, continuously stirring for 10 hours to obtain the polyamide acid solution with certain viscosity. The polyamic acid solution obtained was defoamed under vacuum for 0.5 hour, then coated on a glass plate or a steel plate to a thickness of about 35 μm, the solvent was removed at 80 to 150 ℃ and imidization was carried out at 180 to 300 ℃. After imidization is finished, cooling to room temperature, putting in a 80 ℃ constant-temperature water bath kettle, and boiling in water for demolding to obtain the polyimide film with degradability and high heat resistance.
In the preparation process, the novel acetal and pyridine structure-containing diamine monomer 3,9-bis [4- (5-amino-2-pyridyloxy) pyridyl ] -2,4,8,10-heteroxy-spiro (5,5) undecane as claimed in claim 1, wherein the amount thereof is 50% to 100% of the total moles of diamine monomer, and the ratio of the total moles of dianhydride to the total moles of diamine is 1.02: about 1 and a solid content (the total mass of all monomers of dianhydride and diamine accounts for the total mass of the polyamic acid) of 20 percent. The polar aprotic solvent used is one of N, N-dimethylformamide, N-dimethylacetamide or N-methylpyrrolidone. Other diamine monomers are one or more of 4,4- (hexafluoroisopropyl) bis (p-phenoxy) diphenylamine, p-phenylenediamine, 4,4 '-diaminophenyl ether, 3,3' -diaminodiphenyl sulfone, 4,4 '-diaminobiphenyl, 2,2' -bis (trifluoromethyl) -4,4 '-diaminobiphenyl, 2,2' -bis (trifluoromethyl) -4,4 '-diaminophenyl ether, 4,4' -diaminodiphenylmethane, 2,2-bis [4- (3-aminophenoxy) phenyl ] propane. The dianhydride monomer is one or more of 2,3,3', 4-biphenyl tetracarboxylic dianhydride, 3,3',4,4 '-benzophenone tetracarboxylic dianhydride, pyromellitic dianhydride, 4,4' -hexafluoroisopropylphthalic anhydride and 3,3',4,4' -biphenyl tetracarboxylic dianhydride.
The invention has the beneficial effects that:
because an acetal structure exists in the synthesized novel diamine monomer, the novel diamine monomer can be hydrolyzed under a mild acidic condition, so that the obtained polyimide material can be degraded under the acidic condition and recovered to obtain diamine and dianhydride raw materials, and the method is extremely environment-friendly. Meanwhile, the synthesized diamine monomer has a pyridine structure, so that the influence of acetal on the heat resistance of the polyimide material is improved, and the requirement of the fields of automobile manufacturing, aerospace and the like on the high heat resistance of the material can be met.
Detailed Description
In order to make the technical means, the characteristics, the objectives and the functions of the present invention easy to understand, the present invention will be further described with reference to the following embodiments.
Example 1
The dried 3,9-bis [4- (5-amino-2-pyridyloxy) pyridyl ] -2,4,8,10-hetero-oxy-spiro (5,5) undecane was dissolved in N, N-dimethylacetamide at room temperature and stirred at room temperature for about 0.5 hour. After the mixture is completely dissolved, the temperature of the system is adjusted to 4-10 ℃ through an ice-water bath, pyromellitic dianhydride and 2,3,3', 4-biphenyl tetracarboxylic dianhydride are added for five times according to a half-feeding method, and the molar ratio is 5:5. and after the last dosing is finished, continuously stirring for 10 hours, and controlling the solid content to be 20% through the solvent to obtain the polyamide acid solution with certain viscosity. The polyamic acid solution obtained was defoamed in vacuo for 0.5 hour, then applied to a glass plate, adjusted to a wet film thickness of about 35 μm, heat-treated at 80 deg.C, 120 deg.C and 150 deg.C, respectively, for 1 hour to remove the solvent, and imidized at 180 deg.C, 210 deg.C, 240 deg.C, 270 deg.C and 300 deg.C, respectively, for 1 hour. And cooling to room temperature after imidization is complete, and boiling in water to remove the film, thus obtaining the polyimide film with degradability and high heat resistance, wherein the thickness of a dry film is 25 micrometers.
Example 2
Dried 3,9-bis [4- (5-amino-2-pyridyloxy) pyridyl ] -2,4,8,10-heterooxo-spiro (5,5) undecane and 4,4' -diaminophenyl ether were dissolved in N, N-dimethylacetamide at room temperature in a molar ratio of 7: 3, stirring and dissolving for about 0.5 hour at room temperature. After the mixture is completely dissolved, the temperature of the system is adjusted to 4-10 ℃ through an ice-water bath, pyromellitic dianhydride and 2,3,3', 4-biphenyl tetracarboxylic dianhydride are added for five times according to a half-feeding method, and the molar ratio is 5:5. and after the last dosing is finished, continuously stirring for 10 hours, and controlling the solid content to be 20% through the solvent to obtain the polyamide acid solution with certain viscosity. The polyamic acid solution obtained was defoamed in vacuum for 0.5 hour, then applied to a glass plate, the wet film thickness was adjusted to about 35 μm, the solvent was removed by heat treatment at 80 deg.C, 120 deg.C and 150 deg.C for 1 hour, respectively, and imidized at 180 deg.C, 210 deg.C, 240 deg.C, 270 deg.C and 300 deg.C for 1 hour, respectively. And cooling to room temperature after imidization is complete, and boiling in water to remove the film, thus obtaining the polyimide film with degradability and high heat resistance, wherein the thickness of a dry film is 25 micrometers.
Example 3
Dried 3,9-bis [4- (5-amino-2-pyridyloxy) pyridyl ] -2,4,8,10-heterooxo-spiro (5,5) undecane and 4,4' -diaminophenyl ether were dissolved in N, N-dimethylacetamide at room temperature in a molar ratio of 5: and 5, stirring and dissolving for about 0.5 hour at room temperature. After the mixture is completely dissolved, the temperature of the system is adjusted to 4-10 ℃ through an ice-water bath, pyromellitic dianhydride and 2,3,3', 4-biphenyl tetracarboxylic dianhydride are added for five times according to a half-feeding method, and the molar ratio is 5:5. and after the last dosing is finished, continuously stirring for 10 hours, and controlling the solid content to be 20% through the solvent to obtain the polyamide acid solution with certain viscosity. The polyamic acid solution obtained was defoamed in vacuum for 0.5 hour, then applied to a glass plate, the wet film thickness was adjusted to about 35 μm, the solvent was removed by heat treatment at 80 deg.C, 120 deg.C and 150 deg.C for 1 hour, respectively, and imidized at 180 deg.C, 210 deg.C, 240 deg.C, 270 deg.C and 300 deg.C for 1 hour, respectively. And cooling to room temperature after imidization is complete, and boiling in water to remove the film, thus obtaining the polyimide film with degradability and high heat resistance, wherein the thickness of a dry film is 25 micrometers.
Comparative example 1
The dried 4,4' -diaminophenyl ether was dissolved in N, N-dimethylacetamide at room temperature, and the solution was stirred at room temperature for about 0.5 hour. After the mixture is completely dissolved, the temperature of the system is adjusted to 4-10 ℃ through an ice-water bath, pyromellitic dianhydride and 2,3,3', 4-biphenyl tetracarboxylic dianhydride are added for five times according to a half-feeding method, and the molar ratio is 5:5. and after the last dosing is finished, continuously stirring for 10 hours, and controlling the solid content to be 20% through the solvent to obtain the polyamide acid solution with certain viscosity. The polyamic acid solution obtained was defoamed in vacuum for 0.5 hour, then applied to a glass plate, the wet film thickness was adjusted to about 35 μm, the solvent was removed by heat treatment at 80 deg.C, 120 deg.C and 150 deg.C for 1 hour, respectively, and imidized at 180 deg.C, 210 deg.C, 240 deg.C, 270 deg.C and 300 deg.C for 1 hour, respectively. And cooling to room temperature after imidization is complete, and boiling in water to remove the film to obtain the polyimide film, wherein the thickness of the dry film is 25 microns.
Comparative example 2
The dried 4,4- (hexafluoroisopropyl) bis (p-phenoxy) diphenylamine was dissolved in N, N-dimethylacetamide at room temperature and dissolved with stirring at room temperature for about 0.5 hour. After the mixture is completely dissolved, the temperature of the system is adjusted to 4-10 ℃ through an ice-water bath, pyromellitic dianhydride and 2,3,3', 4-biphenyl tetracarboxylic dianhydride are added for five times according to a half-feeding method, and the molar ratio is 5:5. and after the last dosing is finished, continuously stirring for 10 hours, and controlling the solid content to be 20% through the solvent to obtain the polyamide acid solution with certain viscosity. The resulting polyamic acid solution was defoamed under vacuum for 0.5 hour, then applied to a glass plate, the wet film thickness was adjusted to about 35 μm, the solvent was removed by heat treatment at 80 deg.C, 120 deg.C and 150 deg.C for 1 hour, respectively, and imidized at 180 deg.C, 210 deg.C, 240 deg.C, 270 deg.C and 300 deg.C for 1 hour, respectively. And cooling to room temperature after imidization is complete, and boiling in water to remove the film to obtain the polyimide film, wherein the thickness of the dry film is 25 microns.
Comparative example 3
The dried 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl was dissolved in N, N-dimethylacetamide at room temperature, and dissolved with stirring at room temperature for about 0.5 hour. After the mixture is completely dissolved, the temperature of the system is adjusted to 4-10 ℃ through an ice-water bath, pyromellitic dianhydride and 2,3,3', 4-biphenyl tetracarboxylic dianhydride are added for five times according to a half-feeding method, and the molar ratio is 5:5. and after the last dosing is finished, continuously stirring for 10 hours, and controlling the solid content to be 20% through the solvent to obtain the polyamide acid solution with certain viscosity. The resulting polyamic acid solution was defoamed under vacuum for 0.5 hour, then applied to a glass plate, the wet film thickness was adjusted to about 35 μm, the solvent was removed by heat treatment at 80 deg.C, 120 deg.C and 150 deg.C for 1 hour, respectively, and imidized at 180 deg.C, 210 deg.C, 240 deg.C, 270 deg.C and 300 deg.C for 1 hour, respectively. And cooling to room temperature after imidization is complete, and boiling in water to remove the film to obtain the polyimide film, wherein the thickness of the dry film is 25 microns.
The properties of the materials tested in this example and comparative example are shown in the following table:
Claims (7)
1. a preparation method of a degradable polyimide film with high heat resistance is characterized by comprising the following steps: the novel diamine monomer 3,9-di [4- (5-amino-2-pyridyloxy) pyridyl ] -2,4,8,10-heteroxy-spiro (5,5) undecane containing acetal and pyridine structures is synthesized by using pentaerythritol, 2-formyl-5-hydroxypyridine and other raw materials, and the water is removed by drying treatment. The dried 3,9-bis [4- (5-amino-2-pyridyloxy) pyridinyl ] -2,4,8,10-heterooxo-spiro (5,5) undecane and other diamine monomers were dissolved in a polar aprotic solution at room temperature. When the dianhydride monomer is completely dissolved, controlling the temperature of the system to be 4-10 ℃ by utilizing an ice water bath, and adding the dianhydride monomer five times according to a one-half feeding method. And after the last dosing is finished, continuously stirring for 10 hours to obtain the polyamide acid solution with certain viscosity. The polyamic acid solution obtained was defoamed under vacuum for 0.5 hour, then coated on a glass plate or a steel plate to a thickness of about 35 μm, the solvent was removed at 80 to 150 ℃ and imidization was carried out at 180 to 300 ℃. After imidization is finished, cooling to room temperature, putting the polyimide film in a constant-temperature water bath kettle at the temperature of 80 ℃ for water boiling and demoulding, and obtaining the polyimide film with degradability and high heat resistance.
2. The method for preparing the degradable polyimide film with high heat resistance according to claim 1, wherein the novel diamine monomer containing acetal and pyridine structure 3,9-bis [4- (5-amino-2-pyridyloxy) pyridyl ] -2,4,8,10-heteroxy-spiro (5,5) undecane is synthesized by the following steps: pentaerythritol (5.45g, 40.0mmol) and 2-formyl-5-hydroxypyridine (9.84g, 80.0mmol) are weighed into a 500mL three-necked bottle, 300mL of toluene and a proper amount of N, N-dimethylformamide are added, the temperature is slowly increased to 60 ℃, the mixture is stirred to be dissolved, p-toluenesulfonic acid (PTSA) (0.41g, 2.4 mmol) is added after the solution is completely dissolved and is cooled to the normal temperature, the temperature is slowly increased to 110 ℃, reaction is carried out for 6 hours, white solid precipitation can be observed, the toluene is distilled out and water is added to precipitate to obtain a crude product, and recrystallization and suction filtration are carried out on the crude product by using the toluene and the ultra-dry N, N-dimethylformamide to obtain the diphenol intermediate A (10.65g, 30.8mmol) of the white solid, wherein the yield is 77%.
To a 250mL three-necked flask under nitrogen protection, the diphenol intermediate A (3.46g, 10.0 mmol) and 2-fluoro-5-nitropyridine (2.84g, 20.0 mmol) were added dissolved in N, N-dimethylformamide (50.0 mL). Anhydrous potassium carbonate (3.04g, 10.0 mmol) was added, and the mixture was stirred at room temperature for 15 minutes to dissolve it, and then heated to 80 ℃ to react for 12 hours. Standing to room temperature, pouring into water, precipitating white solid crude product, vacuum filtering to obtain product, and recrystallizing with N, N-dimethylformamide and water to obtain dinitro intermediate B (3.95g, 6.7 mmol) as light yellow solid with yield of 67%.
Tetrahydrofuran was added to a 100mL three-necked flask containing dinitro intermediate B (3.54g, 6.0 mmol) under nitrogen, heated to 50 ℃ and stirred for 30 minutes to dissolve it, 5% Pd/C (0.30 g) and 12mL hydrazine hydrate were added to the flask cooled to room temperature, stirred under reflux for 12 hours, filtered to remove Pd/C, and recrystallized from ethanol and N, N-dimethylformamide to give a white solid of specialty diamine C (2.45g, 4.6 mmol), i.e., 3,9-bis [4- (5-amino-2-pyridyloxy) pyridyl ] -2,4,8,10-hetero-oxo-spiro (5,5) undecane, in 77% yield.
3. The method for preparing a polyimide film with high thermal resistance and degradability according to claim 1, wherein the diamine monomer containing acetal and pyridine structure 3,9-bis [4- (5-amino-2-pyridyloxy) pyridyl ] -2,4,8,10-heteroxy-spiro (5,5) undecane is used in an amount of 50% -100% of the total mole number of the diamine monomer.
4. The method of claim 1, wherein the polar aprotic solvent is one of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
5. The method of claim 1, wherein the other diamine monomer is one or more selected from 4,4- (hexafluoroisopropyl) bis (p-phenoxy) diphenylamine, p-phenylenediamine, 4,4 '-diaminophenyl ether, 3,3' -diaminodiphenyl sulfone, 4,4 '-diaminodiphenyl, 2,2' -bis (trifluoromethyl) -4,4 '-diaminobiphenyl, 2,2' -bis (trifluoromethyl) -4,4 '-diaminophenyl ether, 4,4' -diaminodiphenylmethane, 2,2-bis [4- (3-aminophenoxy) phenyl ] propane.
6. The method for preparing a polyimide film which is degradable and has high heat resistance according to claim 1, wherein the dianhydride monomer is one or more of 2,3,3', 4-biphenyltetracarboxylic dianhydride, 3,3',4,4 '-benzophenonetetracarboxylic dianhydride, pyromellitic dianhydride, 4,4' -hexafluoroisopropylphthalic anhydride, 3,3',4,4' -biphenyltetracarboxylic dianhydride.
7. The method for preparing a polyimide film degradable while having high heat resistance according to claim 1, wherein the polyamic acid solution has a ratio of total moles of dianhydride to total moles of diamine of 1.02: about 1 and a solid content (the total mass of all monomers of dianhydride and diamine accounts for the total mass of the polyamic acid) of 20 percent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210961340.5A CN115417989A (en) | 2022-08-11 | 2022-08-11 | Preparation of degradable high-heat-resistance polyimide material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210961340.5A CN115417989A (en) | 2022-08-11 | 2022-08-11 | Preparation of degradable high-heat-resistance polyimide material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115417989A true CN115417989A (en) | 2022-12-02 |
Family
ID=84198987
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210961340.5A Pending CN115417989A (en) | 2022-08-11 | 2022-08-11 | Preparation of degradable high-heat-resistance polyimide material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115417989A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105061302A (en) * | 2015-08-27 | 2015-11-18 | 哈尔滨工程大学 | Pyridine-ring-containing diamine, polyimide prepared from pyridine-ring-containing diamine and preparation method of polyimide |
| CN110229333A (en) * | 2019-06-25 | 2019-09-13 | 湘潭大学 | A kind of synthetic method of new type polyimide |
-
2022
- 2022-08-11 CN CN202210961340.5A patent/CN115417989A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105061302A (en) * | 2015-08-27 | 2015-11-18 | 哈尔滨工程大学 | Pyridine-ring-containing diamine, polyimide prepared from pyridine-ring-containing diamine and preparation method of polyimide |
| CN110229333A (en) * | 2019-06-25 | 2019-09-13 | 湘潭大学 | A kind of synthetic method of new type polyimide |
Non-Patent Citations (1)
| Title |
|---|
| 何福兰: "基于缩醛结构、三氟甲基结构、吡啶环结构的新型可降解聚酰亚胺的合成及性能研究", 中国优秀硕士学位论文全文数据库（电子期刊），工程科技I辑, no. 2020, pages 016 - 182 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101385279B1 (en) | Asymmetric diamine compounds containing two functional groups, and polymers therefrom | |
| KR100494631B1 (en) | Polyamic acid, polyimide, process for producing these, and film of the polyimide | |
| US6013760A (en) | Soluble polyimide resin for liquid crystal alignment layer and process of preparation of the same | |
| KR20110010009A (en) | Manufacturing method of polyimide, polyimide manufactured by thereof and film manufactured using said polyimide | |
| CN113511980A (en) | Aromatic polyimide with main chain containing benzonorbornene structure and preparation method thereof | |
| KR20010049649A (en) | Novel polyimide compositions and novel acid dianhydrides to be used therein | |
| Liu et al. | Synthesis and characterization of new polybenzimidazopyrrolones derived from pyridine‐bridged aromatic tetraamines and dianhydrides | |
| US6054554A (en) | Soluble polyimide resin comprising polyalicyclic structure | |
| KR100205962B1 (en) | Novel soluble polyimide resin | |
| Wang et al. | High solubility, low‐dielectric constant, and optical transparency of novel polyimides derived from 3, 3′, 5, 5′‐tetramethyl‐4, 4′‐diaminodiphenyl‐4 ″‐isopropyltoluene | |
| Wang et al. | Synthesis and properties of new fluorinated polyimides derived from an unsymmetrical and noncoplanar diamine | |
| TWI602853B (en) | Polyadimide containing adamantane imine preparation | |
| Hsiao et al. | Synthesis and characterization of new polyimides based on 3, 6-bis (4-aminophenoxy) benzonorbornane | |
| JP2003183387A (en) | Fluorine-containing alicylic diamine and polymer using the same | |
| US6046303A (en) | Soluble polyimide resin having alkoxy substituents and the preparation method thereof | |
| JP2537188B2 (en) | Polyimide | |
| CN115417989A (en) | Preparation of degradable high-heat-resistance polyimide material | |
| KR102439488B1 (en) | Method for producing polyimide film with excellent transparency and flexibility | |
| KR100600449B1 (en) | Unsymmetric Diamine Monomer Having Trifluoromethyl and Soluble Aromatic Polyimides Prepared by Using the Same | |
| JP3988007B2 (en) | Soluble polyimide and method for producing the same | |
| US7317110B2 (en) | Low dielectric constant organo-soluble polyimides | |
| WO2023203897A1 (en) | Novel diamine, method for producing same, and polyamic acid and polyimide produced from said diamine | |
| KR100483710B1 (en) | New aromatic diamine monomers and polyimide derivatives therefrom | |
| KR100193384B1 (en) | New soluble polyimide resins and preparation method thereof | |
| WO2020158523A1 (en) | Novel diamine, novel polyimide derived therefrom, and molded body thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |