CN116178763A - Imide covalent organic framework film material with crystallinity and preparation method thereof - Google Patents
Imide covalent organic framework film material with crystallinity and preparation method thereof Download PDFInfo
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- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 55
- 239000000463 material Substances 0.000 title claims abstract description 47
- 150000003949 imides Chemical class 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000002834 transmittance Methods 0.000 claims abstract description 11
- 230000006750 UV protection Effects 0.000 claims abstract description 5
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 20
- 239000003708 ampul Substances 0.000 claims description 15
- 239000012046 mixed solvent Substances 0.000 claims description 15
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 10
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 10
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 150000008064 anhydrides Chemical class 0.000 claims description 8
- 238000004729 solvothermal method Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 5
- QHQSCKLPDVSEBJ-UHFFFAOYSA-N 1,3,5-tri(4-aminophenyl)benzene Chemical compound C1=CC(N)=CC=C1C1=CC(C=2C=CC(N)=CC=2)=CC(C=2C=CC(N)=CC=2)=C1 QHQSCKLPDVSEBJ-UHFFFAOYSA-N 0.000 claims description 4
- WHSQATVVMVBGNS-UHFFFAOYSA-N 4-[4,6-bis(4-aminophenyl)-1,3,5-triazin-2-yl]aniline Chemical compound C1=CC(N)=CC=C1C1=NC(C=2C=CC(N)=CC=2)=NC(C=2C=CC(N)=CC=2)=N1 WHSQATVVMVBGNS-UHFFFAOYSA-N 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 125000006160 pyromellitic dianhydride group Chemical group 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 229920006254 polymer film Polymers 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- 238000010521 absorption reaction Methods 0.000 description 6
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- -1 amine compounds Chemical class 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000005501 phase interface Effects 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
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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
-
- 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
- C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
- C08G73/1032—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous characterised by the solvent(s) used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1085—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
- 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 belongs to the field of polymer film preparation, and discloses an imide covalent organic framework film material with crystallinity and a preparation method thereof. The COFs polymer film prepared by the method has good light transmittance in a long wavelength (700 nm) range, strong stability and good potential application prospect, such as application to ultraviolet protection.
Description
Technical Field
The invention belongs to the field of polymer film preparation, and particularly relates to a preparation method of an imide COFs film material.
Background
COFs are porous crystalline polymer materials, have the characteristics of adjustable structure function, large specific surface area, ordered pore structure and the like, and have application prospects in the fields of gas storage, energy storage, photocatalysis, analytical chemistry and the like. In the field of material synthesis, preparation of film materials has been attracting attention, and before COFs film materials are synthesized by adopting a phase interface synthesis method or an in-situ diffusion growth method. However, the method using phase interface synthesis generally requires two solvents, and requires a high reaction speed or good reaction reversibility. The in-situ diffusion film growth method needs to be realized under high vacuum condition and requires that one monomer has certain volatilizing capability, and is not suitable for synthesizing the monomer which is difficult to volatilize or the monomer which cannot volatilize. There are few cases in which film synthesis is currently achieved for imide-based COFs materials.
In the invention, a simple synthesis method is provided, and the synthesis of the crystalline imide COFs film material can be realized only by controlling the proportion and the amount of the solvent. Compared with the interfacial synthesis, the method has the advantages that the synthesis process is simpler, the film material can be prepared only in a single liquid phase, the imine material is generally adopted for the diffusion method to synthesize the film material, the reaction speed is higher, and the COFs film material with opaque powder particles doped on the surface is easy to form; compared with the synthesis method of in-situ diffusion growth, the imide COFs film synthesized by the solvothermal method does not need a high-vacuum diffusion furnace, and the synthesis equipment is simple. The film material synthesized by the method has a certain light transmittance, and the potential application potential of the film material is improved. The method is simple and feasible in synthesis and has good practical significance.
Disclosure of Invention
The invention discloses a preparation method of an imide COFs film which is light-permeable and has crystallinity, and the preparation method has innovative significance and potential application prospect.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
the preparation of the imide COFs film is synthesized by utilizing anhydride and amine compounds through dehydration condensation reaction under the solvothermal condition.
The preparation method of the PI-COF comprises the following steps:
respectively weighing two monomers according to a certain stoichiometric ratio: and (3) placing amine compounds such as pyromellitic dianhydride and 1,3, 5-tris (4-aminophenyl) benzene in an ampoule bottle, adding a mixed solvent such as mesitylene, N-methylpyrrolidone, isoquinoline and the like, cooling in a liquid nitrogen bath, vacuumizing, sealing by flame, placing in an oven for solvothermal reaction, heating the oven program to 120-250 ℃, preserving the heat for 1-5 days, and obtaining the crude product of the imide COFs film by a solvothermal method. The reaction product was washed, soxhlet with THF, collected and dried overnight in a vacuum oven to give a clear imide COFs film material.
The preferred solvent volume ratio is mesitylene: n-methylpyrrolidone: isoquinoline = 0.4:0.4:0.2.
the preferred reaction temperature is 150 ℃.
Application: the imide COFs film material is applied to the field of ultraviolet protection.
The invention has the beneficial effects that:
1) The invention synthesizes a transparent crystalline imide COFs film material by using pyromellitic dianhydride and amine monomers through solvothermal reaction, realizes the synthesis of the large-area imide COFs film material, and has the characteristics of low reaction cost and safe and reliable production process.
2) The equipment and chemical reagents used in the invention are easy to obtain, the synthesis process is simple and convenient to operate, the synthesis process condition is simple, the practicability is strong, and the popularization and the application are easy. The synthesized COF film material can absorb ultraviolet light with the wavelength smaller than 420nm, has the transmittance of more than 70% for visible light with the wavelength larger than 650nm, and can be used as an ultraviolet protection material. The imide COFs film material synthesized by the solvothermal method has good chemical stability and has the innovative significance of imide film synthesis.
Drawings
FIG. 1 is a schematic diagram of the synthesis of imide covalent organic framework film materials PMDA-TAPB and PMDA-TATTA in accordance with the present invention;
FIG. 2 is an X-ray diffraction pattern of the imide COFs film material of the present invention;
FIG. 3 is an infrared absorption diagram of an imide COFs film material of the present invention;
FIG. 4 is a graph showing the transmittance of light in the 400-1000nm wavelength band of the imide COFs film material of the present invention;
FIG. 5 is a thermogravimetric test of imide COFs film materials of the present invention;
FIG. 6 is an X-ray diffraction chart of a film material obtained after immersing the film material in a chemical solution, showing the results of stability test of the imide COFs film of the present invention;
FIG. 7 is a schematic diagram of the imide COFs film material PMDA-TATTA of the present invention under a microscope.
Detailed Description
The present invention will be further described in detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more clearly understood. It is to be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In the solvothermal synthesis condition, the preparation method of the imide covalent organic framework film material with crystallinity synthesizes a mesoporous imide COFs film material with the aperture of 2-4nm, and the transmittance of the imide COFs film material at the wavelength of more than 600nm is more than 60%; the light transmittance is more than 70% at wavelengths greater than 650 nm.
Further, the preparation method specifically comprises the following steps:
1) The mole ratio of anhydride to amine monomer is 3:2, mixing and placing the mixture in an ampoule bottle, and adding a mixed solvent;
2) Carrying out ultrasonic treatment on the mixture obtained in the step 1) for 3-10min to uniformly mix the system;
3) Sealing the ampoule bottle by using a flame gun under a vacuum condition;
4) Placing the sealed ampoule bottle into a baking oven or a muffle furnace to react for 1-5 days at 120-250 ℃;
5) Washing the product obtained in the step 4) with acetone and THF, and drying to obtain the imide-based COFs film material with crystallinity.
Further, the anhydride is pyromellitic dianhydride.
Further, the amine monomer is any one of 1,3, 5-tris (4-aminophenyl) benzene (CAS 118727-34-7) or 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine.
Further, the mixed solvent consists of mesitylene, N-methylpyrrolidone and isoquinoline.
Further, the volume ratio of mesitylene, N-methylpyrrolidone and isoquinoline in the mixed solvent is 1-x-y: x: y, wherein x is more than or equal to 0.5,0.02 and less than or equal to y is less than or equal to 0.5, and satisfies 1-x-y >0.
Further, the volume ratio of mesitylene, N-methylpyrrolidone and isoquinoline in the mixed solvent is 4:4:2. Further, the volume of the ampoule bottle, the volume of the added mixed solvent and the quantity of reactant anhydride are in a mutually restricted relation, wherein the ratio of the volume of the ampoule bottle to the volume of the mixed solvent is 500-50; the ratio of the volume of the mixed solvent/0.1 mL and the mass of the acid anhydride/1 mg is 1-5.
Example 1 preparation of imide COF film PMDA-TAPB:
pyromellitic dianhydride (3.3 mg,0.015 mmol) and 1,3,5- (p-aminophenyl) benzene (3.5 mg,0.01 mmol) were placed in a 10mL ampoule and mesitylene (0.15 mL), N-methylpyrrolidone (0.15 mL) and isoquinoline (0.03 mL) were added. The ampoule is sonicated for 3min and then flame sealed under vacuum (-10 mbar) and subsequently placed in an oven at 150 ℃ for 5 days. The crude product was washed 3 times with acetone, THF, the product was collected and dried overnight in vacuo to give a clear pale yellow film PMDA-TAPB.
Example 2 preparation of imide COF film PMDA-TATTA:
pyromellitic dianhydride (3.3 mg,0.015 mmol) and 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine (3.5 mg,0.01 mmol) were placed in a 10mL ampoule and mesitylene (0.15 mL), N-methylpyrrolidone (0.15 mL) and isoquinoline (0.03 mL) were added. The ampoule is sonicated for 3min and then flame sealed under vacuum (-10 mbar) and subsequently placed in an oven at 150 ℃ for 5 days. The crude product was washed 3 times with acetone, THF, the product was collected and dried overnight in vacuo to give a clear pale yellow film PMDA-TATTA.
FIG. 2 is an X-ray diffraction pattern of imide COFs film, showing significant peaks near 2.8℃in the pattern as characteristic diffraction peaks of PI-COF, demonstrating successful synthesis of PI-COF.
FIG. 3 is an infrared absorption diagram of an imide COFs film material, in which it can be seen that the imide ring synthesized from pyromellitic dianhydride is at 1780cm -1 And 1720cm -1 Characteristic absorption peaks at.
FIG. 4 is an ultraviolet absorption diagram of an imide COFs film material measured at 400-1000nm, and it can be seen that the two COFs film materials have less absorption in the long-wave visible light range and have a visible light transmittance of more than 70% at a wavelength of more than 650 nm; in the short wavelength, violet region, absorption is strong, and the transmittance is basically 0 at the wavelength of light wave less than 420 nm. Therefore, the COFs film material can be applied to ultraviolet protection equipment, such as glasses equipment with certain requirements on light transmittance, such as snow glasses.
FIG. 5 shows the thermal weight test of the synthesized imide COFs film, wherein the COFs film material still keeps more than 90% of the weight at 500 ℃, which shows that the thermal stability of the material is good.
FIG. 6 is a chemical stability test of a synthetic imide COFs film, in which a COF film material was immersed in 1mol/L hydrochloric acid, 1mol/L NaOH solution, and 1mol/L NaCl solution, respectively, for 24 hours, and then removed, and surface residues were washed off. After testing the crystallinity of the COFs film, it can be seen that the PMDA-TAPB and PMDA-TATTA remained well crystalline after 24 hours of soaking, demonstrating good chemical stability.
FIG. 7 is a photograph of a synthetic imide COFs film under a microscope, wherein (a), (b), and (c) are partial views of the COF film, and it can be seen that the film surface is flat and smooth, and the overall light transmission is uniform; (d) The writing written on the background paper was visible through the COF film, indicating that the film had good light transmission.
While the present invention has been described in detail through the foregoing description of the preferred embodiment, it should be understood that the foregoing description should not be deemed a limitation of the invention. Many modifications and alternatives to the present invention will be apparent to those of skill in the art upon reading the foregoing description. Accordingly, the scope of the invention should be limited only by the attached claims.
Claims (10)
1. A preparation method of an imide covalent organic framework film material with crystallinity is characterized by comprising the following steps: under the solvothermal synthesis condition, synthesizing a mesoporous imide type COFs film material with the aperture of 2-4nm, wherein the transmittance of the imide type COFs film material at the position with the wavelength of more than 600nm is more than 60%; the light transmittance is greater than 70% at wavelengths greater than 650 nm.
2. The method of manufacturing according to claim 1, characterized in that: the method comprises the following steps:
1) The mole ratio of anhydride to amine monomer is 3:2, mixing and placing the mixture in an ampoule bottle, and adding a mixed solvent;
2) Carrying out ultrasonic treatment on the mixture obtained in the step 1) for 3-10min to uniformly mix the system;
3) Sealing the ampoule bottle by using a flame gun under a vacuum condition;
4) Placing the sealed ampoule bottle into an oven or a muffle furnace, and reacting for 1-5 days at 120-250 ℃;
5) Washing the product obtained in the step 4) with acetone and THF, and drying to obtain the imide-based COFs film material with crystallinity.
3. The preparation method according to claim 2, characterized in that: the anhydride is pyromellitic dianhydride.
4. The preparation method according to claim 2, characterized in that: the amine monomer is any one of 1,3, 5-tri (4-aminophenyl) benzene or 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine.
5. The preparation method according to claim 2, characterized in that: the mixed solvent consists of mesitylene, N-methyl pyrrolidone and isoquinoline.
6. The preparation method according to claim 5, characterized in that: the volume ratio of mesitylene, N-methyl pyrrolidone and isoquinoline in the mixed solvent is 1-x-y: x: y, wherein x is more than or equal to 0.5, y is more than or equal to 0.02 and less than or equal to 0.5, and 1-x-y >0 is satisfied.
7. The preparation method according to claim 6, characterized in that: the volume ratio of mesitylene, N-methyl pyrrolidone and isoquinoline in the mixed solvent is 4:4:2.
8. The preparation method according to claim 2, characterized in that: the volume of the ampoule bottle, the volume of the added mixed solvent and the amount of reactant anhydride are in a mutually restricted relation, wherein the ratio of the volume of the ampoule bottle to the volume of the mixed solvent is 500-50; the ratio between the volume of the mixed solvent/0.1. 0.1mL and the mass of the anhydride/1. 1mg is 1-5.
9. An imide COFs film material prepared by the preparation method according to any one of claims 1 to 8.
10. The application of the imide COFs film material according to claim 9 in the field of ultraviolet protection.
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| CN109776814A (en) * | 2019-03-18 | 2019-05-21 | 福州大学 | A kind of acid imide covalent organic frame material and its preparation method and application |
| CN110218317A (en) * | 2019-06-06 | 2019-09-10 | 南京邮电大学 | A kind of polyimide type covalent organic frame material and the preparation method and application thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104118167A (en) * | 2010-02-10 | 2014-10-29 | 宇部兴产株式会社 | Polyimide film, polyimide laminate comprising same, and polyimide/metal laminate comprising same |
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