CN114516959A - Polyamide membrane, preparation method thereof and graphite membrane - Google Patents
Polyamide membrane, preparation method thereof and graphite membrane Download PDFInfo
- Publication number
- CN114516959A CN114516959A CN202210258655.3A CN202210258655A CN114516959A CN 114516959 A CN114516959 A CN 114516959A CN 202210258655 A CN202210258655 A CN 202210258655A CN 114516959 A CN114516959 A CN 114516959A
- Authority
- CN
- China
- Prior art keywords
- polyamide
- film
- monomer
- dicarboxylic acid
- membrane
- 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.)
- Granted
Links
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
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/205—Preparation
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Polyamides (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The present application provides a polyamide membrane comprising a polyamide polymer. The polyamide polymer includes a reaction product of a diamine monomer and a dicarboxylic acid monomer, the diamine monomer including N, N-bis (4-aminophenyl) -N, N-diphenyl-1, 4-phenylenediamine. The polyamide film can be used for preparing a graphite film with a relatively thick thickness. The application also provides a graphite film prepared by adopting the polyamide film and a preparation method of the polyamide film.
Description
Technical Field
The application relates to the field of heat dissipation materials, in particular to a polyamide film, a graphite film applying the polyamide film and a preparation method of the polyamide film.
Background
The artificial graphite film is a heat dissipation material commonly used in electronic products due to its high heat dissipation coefficient and low density. The artificial graphite film is generally prepared by carbonizing, graphitizing and calendering a polyamide film. The carbon content of the conventional polyamide film after graphitization is low, and the thickness is greatly reduced during calendering, so that the thickness of the prepared graphite film is low. The graphite film is matched with a heat conduction material to be used as a heat dissipation material of an electronic product. However, the graphite film and the heat conductive material easily cause problems such as thermal interface and the like, and reduce the heat dissipation effect. Therefore, it is required to produce a graphite film having a high thickness.
Disclosure of Invention
In view of the above, it is desirable to provide a polyamide film that can be applied to the production of a graphite film having a high thickness and a method for producing the same.
The present application provides a polyamide membrane comprising a polyamide polymer. The polyamide polymer includes a reaction product of a diamine monomer and a dicarboxylic acid monomer, the diamine monomer including N, N-bis (4-aminophenyl) -N, N-diphenyl-1, 4-phenylenediamine.
The application also provides a graphite film, wherein the graphite film is prepared by carbonizing and graphitizing the polyamide film.
The present application also provides a method of preparing a polyamide membrane, comprising:
dissolving a diamine monomer and a dicarboxylic acid monomer in an organic solvent to obtain a reaction solution;
adding 3-methylpyridine and triphenyl phosphite into the reaction solution, and stirring and reacting under a nitrogen environment to obtain a mixed solution;
pouring the mixed solution into methanol for precipitation to obtain polyamide composition solid;
dissolving the polyamide composition solid and a catalyst in an organic solvent to obtain a polyamide solution;
coating the polyamide solution on a support plate to obtain a polyamide coating film;
and baking and curing the polyamide coating film to obtain the polyamide film.
In the application, the N, N-bis (4-aminophenyl) -N, N-diphenyl-1, 4-phenylenediamine has a plurality of heat-resistant benzene ring structures, and the bonding among the benzene rings is nitrogen, so that the prepared polyamide polymer has high carbon residue rate (high heat resistance), and the prepared polyamide film has high carbon content after graphitizing, so that the thickness change of the graphitized polyamide film after rolling is small, and the graphite film with high thickness can be prepared. In addition, the N, N-bis (4-aminophenyl) -N, N-diphenyl-1, 4-phenylenediamine has a large side chain group with a multi-benzene ring structure, so that free radicals among molecules are increased, gas dissipation and solvent volatilization are facilitated, and the production efficiency is further improved; and during subsequent carbonization or graphitization, the graphite film can be foamed through the channels, so that the appearance of the graphite film is improved.
Detailed Description
The technical solutions in the embodiments of the present application will be described clearly and completely below, and it is obvious that the described embodiments are only some embodiments of the present application, not all embodiments. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments in the present application without any inventive step are within the scope of protection of the present application.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used in the description herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.
An embodiment of the present application provides a polyamide membrane comprising a polyamide polymer. The polyamide polymer includes a reaction product of a diamine monomer and a dicarboxylic acid monomer. The diamine monomer comprises N, N-bis (4-aminophenyl) -N, N-diphenyl-1, 4-phenylenediamine (ENP SDA). The structural formula of the N, N-bis (4-aminophenyl) -N, N-diphenyl-1, 4-phenylenediamine is shown in the specification
The dicarboxylic acid monomer may be any commercially available dicarboxylic acid monomer. In some embodiments, the dicarboxylic acid monomer is a dicarboxylic acid monomer having a multiple benzene ring structure, for example, the dicarboxylic acid monomer includes at least one of 2, 6-naphthalenedicarboxylic acid (NPDA), 4 '-diphenylether dicarboxylic acid (ODBA), biphenyldicarboxylic acid (BPCA), 1, 4-phthalic acid (PTA), 1, 3-phthalic acid (IPA), and 4,4' -sulfonyldibenzoic acid (SFDA).
As used herein, the term "reaction product" refers to a product formed from one or more synthetic steps. Generally, the reaction that may be used to form the polyamide polymer as the reaction product may comprise at least a polymerization reaction. In some embodiments, the reaction product may be formed by reacting a diamine monomer and a dicarboxylic acid monomer via polymerization.
In some embodiments, the molar ratio of the dicarboxylic acid monomer to the diamine monomer is 0.9 to 1.1.
The diamine monomer may also include any commercially available diamine monomer, with ENPSDA comprising greater than 90% of the total moles of diamine monomer. In some embodiments, the diamine monomer further comprises a commercially available diamine monomer having a polyphenolic ring structure, such as diaminodiphenyl ether (ODA).
An embodiment of the present application also provides a method for preparing the above polyamide film, which includes the steps of:
dissolving a diamine monomer and a dicarboxylic acid monomer in an organic solvent to obtain a reaction solution;
adding 3-methylpyridine and triphenyl phosphite into the reaction solution, and stirring and reacting under a nitrogen environment to obtain a mixed solution;
pouring the mixed solution into methanol for precipitation to obtain polyamide composition solid;
dissolving the polyamide composition solid and a catalyst in an organic solvent to obtain a polyamide solution;
coating the polyamide solution on a support plate to obtain a polyamide coating film;
and baking and curing the polyamide coating film to obtain the polyamide film.
The polyamide solution includes the polyamide polymer and the organic solvent in which the polyamide polymer is dissolved. In some embodiments, the organic solvent comprises 80 to 85% by weight of the polyamide solution, in other words, the polyamide solution has a solid content of 15 to 20%.
In some embodiments, the catalyst has a particle size of less than 1.5 μm and is present in an amount of 0.02 to 0.5% by weight of the polyamide polymer.
The catalyst can be any commercially available inorganic or organic catalyst. In some embodiments, the organic catalyst comprises at least one of graphene, carbon black, carbon nanotubes, and fullerenes, and the inorganic catalyst comprises at least one of calcium bicarbonate, calcium hydrogen phosphate, barium dihydrogen phosphate, potassium bicarbonate, potassium dihydrogen phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate, boron phosphate, calcium carbide, copper oxide, ferric oxide, ferroferric oxide, and aluminum oxide.
In some embodiments, the organic solvent comprises at least one of dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), and N, N-Dimethylformamide (DMF).
It is to be understood that after the reaction solution is poured into methanol for precipitation, filtration is further carried out to take out a solid, and the solid is purified with methanol to obtain a solid of the polyamide composition.
It is understood that the method further comprises the following steps after the polyamide coating film is baked: the cured polyamide coating film is peeled off from the support plate to obtain a self-supporting polyamide coating film, and then the self-supporting polyamide coating film is subjected to biaxial stretching and heat treatment to obtain the polyamide film.
In some embodiments, the baking curing temperature is 120-170 ℃, the baking curing time is 20-30 min, and the heat treatment temperature is 400-450 ℃. The solvent content of the self-supporting polyamide coating film is 25-30%. After the polyamide solution is coated, the polyamide solution can be dried at a lower temperature to obtain a self-supporting polyamide coating film, and high-temperature treatment is not needed, so that the limitation of production equipment (such as a machine table) can be reduced. The polyamide of the present application has intermolecular hydrogen bonds, and the self-supporting polyamide coating film has good toughness, so that the self-supporting polyamide coating film can be biaxially stretched. Through high-temperature heat treatment, the crystallization orthotropic property and the arrangement compactness of the polyamide film can be improved, the intermolecular defects are reduced, and the property of the graphite film is further improved.
An embodiment of the present application further provides a graphite film, which is prepared by carbonizing and graphitizing the polyamide film.
The polyamide film is carbonized to form a carbonized film, and the carbonized film is subjected to catalytic graphitization reaction by the catalyst to form the graphite film. The catalyst can reduce graphitization activity and promote graphitization reaction of the carbonized film to form a graphite film. The catalyst is added when the polyamide solution is formed, and the dispersion uniformity of the catalyst can be improved.
In the application, the ENPSDA has a plurality of heat-resistant benzene ring structures, and bonding among the benzene rings is nitrogen, so that the prepared polyamide polymer has high carbon residual rate (high heat resistance), and the prepared polyamide film has high carbon content after graphitizing, so that the thickness change of the graphitized polyamide film after rolling is small, and the graphite film with high thickness can be prepared. In addition, the prepared polyamide film has high carbon content (including nitrogen elements or benzene ring structures) after high-temperature carbonization, so that the defect amount after carbonization can be reduced, and the carbon element can be diffused during subsequent graphitization. In addition, nitrogen elements in the ENPSDA are uniformly distributed, and the catalyst is added into the polyamide film, so that the subsequent graphitization is uniformly performed, and the graphite film has a good appearance.
In addition, ENPSDA has a large side chain group with a multi-benzene ring structure, so that intermolecular free radicals are increased, gas dissipation and solvent volatilization are facilitated, and the production efficiency is further improved; and during subsequent carbonization or graphitization, the graphite film can be foamed through the channels, so that the appearance of the graphite film is improved.
The polyamide film of the present application will be described below with reference to specific examples.
Example 1
A500 ml reaction flask was charged with diamine ENPSDA (0.1mol, 44.22g), dicarboxylic acid NPDA (0.1mol, 21.62g) and solvent NMP (197.52g), and stirred under nitrogen atmosphere for 1 hour to dissolve the diamine ENPSDA, then 3-methylpyridine (1mol, 93.13g) and triphenyl phosphite (0.21mol, 65.16g) were added, the temperature was raised to 100 to 110 ℃, and the mixture was stirred under nitrogen atmosphere for 12 hours to obtain a mixed solution. The mixed solution was poured into methanol to precipitate, and then filtered to obtain a solid, which was then purified with methanol to obtain a polyamide composition solid.
Example 2
A500 ml reaction flask was charged with diamine ENPSDA (0.09mol, 39.8g), diamine ODA (0.01mol, 2.00g), dicarboxylic acid NPDA (0.1mol, 21.62g) and solvent NMP (190.26g), stirred under nitrogen atmosphere for 1 hour to dissolve, then charged with 3-methylpyridine (1mol, 93.13g) and triphenyl phosphite (0.21mol, 65.16g), heated to 100 to 110 ℃ and stirred under nitrogen atmosphere for 12 hours to obtain a mixed solution. The mixed solution was poured into methanol to precipitate, and then filtered to obtain a solid, which was then purified with methanol to obtain a polyamide composition solid.
Example 3
A500 ml reaction flask was charged with diamine ENPSDA (0.1mol, 44.2g), dicarboxylic acid ODBA (0.1mol, 25.82g) and solvent NMP (210.13g), stirred under nitrogen atmosphere for 1 hour to dissolve, then charged with 3-methylpyridine (1mol, 93.13g) and triphenyl phosphite (0.21mol, 65.16g), heated to 100 to 110 ℃ and stirred under nitrogen atmosphere for 12 hours to obtain a mixed solution. The mixed solution was poured into methanol to precipitate, and then filtered to obtain a solid, which was then purified with methanol to obtain a polyamide composition solid.
Example 4
A500 ml reaction flask was charged with diamine ENPSDA (0.09mol, 39.8g), diamine ODA (0.01mol, 2.00g), dicarboxylic acid ODBA (0.1mol, 25.82g) and solvent NMP (202.87g), stirred under nitrogen atmosphere for 1 hour to dissolve, then charged with 3-methylpyridine (1mol, 93.13g) and triphenyl phosphite (0.21mol, 65.16g), heated to 100-110 ℃ and stirred under nitrogen atmosphere for 12 hours to obtain a mixed solution. The mixed solution was poured into methanol to precipitate, and then filtered to obtain a solid, which was then purified with methanol to obtain a polyamide composition solid.
Example 5
A500 ml reaction flask was charged with diamine ENPSDA (0.1mol, 44.22g), dicarboxylic acid BPCA (0.1mol, 24.22g) and solvent NMP (205.33g), and stirred under nitrogen atmosphere for 1 hour to dissolve the diamine ENPSDA, then 3-methylpyridine (1mol, 93.13g) and triphenyl phosphite (0.21mol, 65.16g) were added, the temperature was raised to 100 to 110 ℃, and the mixture was stirred under nitrogen atmosphere for 12 hours to obtain a mixed solution. The mixed solution was poured into methanol to precipitate, and then filtered to obtain a solid, which was then purified with methanol to obtain a polyamide composition solid.
Example 6
A500 ml reaction flask was charged with diamine ENPSDA (0.09mol, 39.8g), diamine ODA (0.01mol, 2.00g), dicarboxylic acid BPCA (0.1mol, 24.22g) and solvent NMP (198.07g), stirred under nitrogen atmosphere for 1 hour to dissolve, then charged with 3-methylpyridine (1mol, 93.13g) and triphenyl phosphite (0.21mol, 65.16g), heated to 100-110 ℃ and stirred under nitrogen atmosphere for 12 hours to obtain a mixed solution. The mixed solution was poured into methanol to precipitate, and then filtered to obtain a solid, which was then purified with methanol to obtain a polyamide composition solid.
Example 7
A500 ml reaction vessel was charged with diamine ENPSDA (0.1mol, 44.22g), dicarboxylic acid IPA (0.1mol, 16.61g) and solvent NMP (182.50g), and stirred under nitrogen atmosphere for 1 hour to dissolve the compounds, and then 3-methylpyridine (1mol, 93.13g) and triphenyl phosphite (0.21mol, 65.16g) were added, the temperature was raised to 100 to 110 ℃ and stirred under nitrogen atmosphere for 12 hours to obtain a mixed solution. The mixed solution was poured into methanol to precipitate, and then filtered to obtain a solid, which was then purified with methanol to obtain a polyamide composition solid.
Example 8
A500 ml reaction flask was charged with diamine ENPSDA (0.09mol, 39.8g), diamine ODA (0.01mol, 2.00g), dicarboxylic acid IPA (0.1mol, 16.61g) and solvent NMP (175.24g), stirred under nitrogen atmosphere for 1 hour to dissolve, then charged with 3-methylpyridine (1mol, 93.13g) and triphenyl phosphite (0.21mol, 65.16g), heated to 100 to 110 ℃ and stirred under nitrogen atmosphere for 12 hours to obtain a mixed solution. The mixed solution was poured into methanol to precipitate, and then filtered to obtain a solid, which was then purified with methanol to obtain a polyamide composition solid.
Comparative example 1
A diamine ODA (0.1mol, 20.02g), a catalyst (0.0084g), dianhydride pyromellitic dianhydride (PMDA) (0.1mol, 21.81g) and a solvent NMP (167.34g) were added to a 500ml reaction flask to obtain a mixed solution having a solid content of 15 to 20%, and the mixed solution was stirred under a nitrogen atmosphere for 24 hours to obtain a polyamic acid solution.
Comparative example 2
A500 ml reaction flask was charged with diamine ENPSDA (0.085mol, 37.59g), diamine ODA (0.015mol, 3.00g), dicarboxylic acid NPDA (0.1mol, 21.62g), and solvent NMP (186.63g), stirred under nitrogen atmosphere for 1 hour to dissolve, then charged with 3-methylpyridine (1mol, 93.13g) and triphenyl phosphite (0.21mol, 65.16g), heated to 100-110 deg.C, and stirred under nitrogen atmosphere for 12 hours to obtain a mixed solution. The mixed solution was poured into methanol to precipitate, and then filtered to obtain a solid, which was then purified with methanol to obtain a polyamide composition solid.
Comparative example 3
A500 ml reaction flask was charged with diamine ENPSDA (0.085mol, 37.59g), diamine ODA (0.015mol, 3.00g), dicarboxylic acid ODBA (0.1mol, 25.82g) and solvent NMP (199.24g), stirred under nitrogen atmosphere for 1 hour to dissolve, then charged with 3-methylpyridine (1mol, 93.13g) and triphenyl phosphite (0.21mol, 65.16g), heated to 100-110 ℃ and stirred under nitrogen atmosphere for 12 hours to obtain a mixed solution. The mixed solution was poured into methanol to precipitate, and then filtered to obtain a solid, which was then purified with methanol to obtain a polyamide composition solid.
Comparative example 4
A500 ml reaction flask was charged with diamine ENPSDA (0.085mol, 37.59g), diamine ODA (0.015mol, 3.00g), dicarboxylic acid BPCA (0.1mol, 24.22g) and solvent NMP (194.44g), stirred under nitrogen atmosphere for 1 hour to dissolve, then charged with 3-methylpyridine (1mol, 93.13g) and triphenyl phosphite (0.21mol, 65.16g), heated to 100-110 ℃ and stirred under nitrogen atmosphere for 12 hours to obtain a mixed solution. The mixed solution was poured into methanol to precipitate, and then filtered to obtain a solid, which was then purified with methanol to obtain a polyamide composition solid.
Comparative example 5
A500 ml reaction flask was charged with diamine ENPSDA (0.085mol, 37.59g), diamine ODA (0.015mol, 3.00g), dicarboxylic acid IPA (0.1mol, 16.61g) and solvent NMP (171.61g), stirred under nitrogen atmosphere for 1 hour to dissolve, then charged with 3-methylpyridine (1mol, 93.13g) and triphenyl phosphite (0.21mol, 65.16g), heated to 100-110 ℃ and stirred under nitrogen atmosphere for 12 hours to obtain a mixed solution. The mixed solution was poured into methanol to precipitate, and then filtered to obtain a solid, which was then purified with methanol to obtain a polyamide composition solid.
In a 250ml reaction flask, the solid polyamide compositions (20g) obtained in examples 1 to 8 and comparative examples 2 to 5 and 0.004g of the catalyst were dissolved in NMP (80g) as a solvent by stirring in an air atmosphere at room temperature for 12 hours to obtain a polyamide solution having a solid content of 15 to 20%. The viscosity of the polyamide solution is 10-20 ten thousand cps. And coating the polyamide solution on a steel plate, and baking at the temperature of 120 ℃ for 20-30 min to obtain a film with the solvent content of 25-30%. And peeling the film from the steel plate, stretching the film at the temperature of 130 ℃ for 100-150%, keeping the temperature at the temperature of 150 ℃ for 30min to remove the solvent, heating to 400-450 ℃ at the speed of 2.5 ℃/min, keeping the temperature for 1 hour for annealing, and cooling to room temperature at the speed of 5-8 ℃/min to obtain the polyamide film.
And (3) coating the polyamic acid solution prepared in the comparative example 1 on a steel plate, and baking at the temperature of 120 ℃ for 20-30 min to obtain a film with the solvent content of 25-30%. And peeling the film from the steel plate, stretching the film at the temperature of 130 ℃ by 100-150%, heating to 300-370 ℃ at the speed of 2.5 ℃/min in a nitrogen environment, keeping the temperature for 1 hour for cyclization treatment, heating to 400-450 ℃ at the speed of 2.5 ℃/min, keeping the temperature for 1 hour for annealing treatment, and cooling to room temperature at the speed of 5-8 ℃/min to obtain the polyamide film.
The polyamide films prepared in the embodiments 1-8 and the comparative examples 1-5 are respectively placed between two graphite plates, the temperature is raised from room temperature to 950-1050 ℃ at the speed of 2-3 ℃/min in an inert gas (argon) environment, the temperature is kept for 60min, and then the temperature is lowered to room temperature at the speed of 15-20 ℃/min, so that the carbonized film is obtained.
Respectively placing the carbonized films prepared in the embodiments 1-8 and the comparative examples 1-5 between two graphite plates, heating from room temperature to 2800-2900 ℃ at the speed of 2-3 ℃/min under the inert gas (argon) environment, keeping the temperature for 40min, then cooling to room temperature at the speed of 15-20 ℃/min, and rolling (10MPa) the graphitized film to obtain the graphite film.
The contents of some components in examples 1 to 8 and comparative examples 1 to 5 are shown in Table 1.
The thicknesses of the polyamide films obtained in examples 1 to 8 and comparative examples 1 to 5 were measured, and thermogravimetric analysis (TGA) was performed. The thermogravimetric analysis conditions were: the temperature range of the nitrogen environment is 40-800 ℃, and the heating rate is 10 ℃/min. Wherein the temperature at which the weight is reduced to 5% is Td 5%, and the remaining weight at 800 ℃ is the coke residual rate. The thickness, density and thermal conductivity of the graphite films obtained in examples 1 to 8 and comparative examples 1 to 5 were measured. The test results are shown in table 2.
TABLE 1
TABLE 2
The polyamides of examples 1 to 8, which were prepared from diamine monomers including ENPSDA, produced polyamide solutions and produced polyamide films having high carbon contents (coke residue rate of more than 70%) compared to comparative example 1. The graphite films of examples 1-8 produced with polyamide films of the same thickness had good appearance and similar density (about 2.0 g/cm) compared to comparative example 13) (ii) a And the prepared polyamide film is thicker and higher in heat conductivity coefficient. This is because the polyamide film prepared from the diamine monomer including ENPSDA has a higher carbon content and a lower defect amount after graphitization. On the other hand, comparative example 1, which could not be prepared as a polyamide solution, was biaxially stretched in the state of a polyamide acid film, but when cyclized at a high temperature, the intramolecular structure was changed (condensation ring closure and decrease in molecular polarity) and gas was released (dehydration ring closure), so that thick intermolecular alignment was caused during biaxial stretchingThe structure is destroyed (the defect amount is increased), and the density of the graphite film is 2.0g/cm3But low thermal conductivity (< 1650W/m K).
As shown in examples 1 to 8 and comparative examples 2 to 5, the proportion of ENPSDA in the diamine monomer is required to be more than 90 mol% so that the obtained polyamide film has high carbon content (the coke residual rate is more than 70%); less than 90 mol%, the residual rate of coke in the polyamide film is less than 70%, and the prepared graphite has reduced thickness, increased defect amount and reduced thermal conductivity (less than 1650W/m K). It is presumed that the number of benzene rings of the ENPSDA unit monomer is 5 and nitrogen (N) is bonded between the benzene rings (the heat resistance is preferable), the number of benzene rings of the ODA unit monomer is 2 and oxygen (O) is bonded between the benzene rings (the heat resistance is poor, for example, oxygen (O) is used in the carbonization process 2) Will escape first). Compared with examples 2, 4, 6 and 8 (the ratio of ENPSDA in diamine monomer is 90%), comparative examples 2-5 (the ratio of ENPSDA in diamine monomer is 85%) have reduced number of benzene rings in diamine monomer, and the number of benzene rings with N bonds is reduced at the same time, so that the heat resistance of the polyimide film is reduced (the residual rate of coke is reduced) in the TGA test, and the thickness of the polyimide film is greatly reduced after carbonization, graphitization and over-pressing, although the density is about 2.0g/cm3However, the number of O bonds between benzene rings is relatively increased, thereby destroying the overall arrangement structure (the amount of defects is increased), and causing a decrease in thermal conductivity.
While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention.
Claims (10)
1. A polyamide membrane comprising a polyamide polymer, characterized in that the polyamide polymer comprises a reaction product of a diamine monomer and a dicarboxylic acid monomer, the diamine monomer comprising N, N-bis (4-aminophenyl) -N, N-diphenyl-1, 4-phenylenediamine.
2. The polyamide membrane of claim 1 wherein the molar ratio of the dicarboxylic acid monomer to the diamine monomer is 0.9 to 1.1.
3. The polyamide film of claim 1, wherein the dicarboxylic acid monomer comprises at least one of 2, 6-naphthalenedicarboxylic acid, 4 '-diphenylether dicarboxylic acid, diphenyldicarboxylic acid, 1, 4-benzenedicarboxylic acid, 1, 3-benzenedicarboxylic acid, and 4,4' -sulfonyldibenzoic acid.
4. The polyamide membrane of claim 1 wherein the diamine monomer further comprises diaminodiphenyl ether, and N, N-bis (4-aminophenyl) -N, N-diphenyl-1, 4-phenylenediamine comprises greater than 90% of the total moles of diamine monomer.
5. A graphite film obtained by carbonizing and graphitizing the polyamide film according to any one of claims 1 to 4.
6. The method of producing a polyamide membrane according to any one of claims 1 to 4, comprising:
dissolving a diamine monomer and a dicarboxylic acid monomer in an organic solvent to obtain a reaction solution;
adding 3-methylpyridine and triphenyl phosphite into the reaction solution, and stirring and reacting under a nitrogen environment to obtain a mixed solution;
pouring the mixed solution into methanol for precipitation to obtain polyamide composition solid;
dissolving the polyamide composition solid and a catalyst in an organic solvent to obtain a polyamide solution;
Coating the polyamide solution on a support plate to obtain a polyamide coating film;
and baking and curing the polyamide coating film to obtain the polyamide film.
7. The polyamide membrane of claim 6 wherein the catalyst comprises 0.02 to 0.5% by weight of the polyamide polymer.
8. The polyamide membrane of claim 6, wherein the catalyst comprises at least one of graphene, carbon black, carbon nanotubes, fullerenes, calcium bicarbonate, calcium hydrogen phosphate, barium dihydrogen phosphate, potassium bicarbonate, potassium dihydrogen phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate, boron phosphate, calcium carbide, copper oxide, ferric oxide, ferroferric oxide, aluminum oxide.
9. The method of producing a polyamide film as claimed in claim 6, wherein the polyamide solution has a solid content of 15 to 20%.
10. The method of producing a polyamide membrane according to claim 6, wherein the organic solvent includes at least one of dimethylacetamide, N-methylpyrrolidone, and N, N-dimethylformamide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210258655.3A CN114516959B (en) | 2022-03-16 | 2022-03-16 | Polyamide film, method for producing same, and graphite film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210258655.3A CN114516959B (en) | 2022-03-16 | 2022-03-16 | Polyamide film, method for producing same, and graphite film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114516959A true CN114516959A (en) | 2022-05-20 |
| CN114516959B CN114516959B (en) | 2023-07-14 |
Family
ID=81598300
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210258655.3A Active CN114516959B (en) | 2022-03-16 | 2022-03-16 | Polyamide film, method for producing same, and graphite film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114516959B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116443864A (en) * | 2023-06-20 | 2023-07-18 | 广东工业大学 | Method for preparing graphene tubes by massive catalysis without template |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104445174A (en) * | 2014-12-12 | 2015-03-25 | 碳元科技股份有限公司 | Ultrathin high-thermal-conductivity graphite film and preparation method thereof |
| CN105924361A (en) * | 2016-06-20 | 2016-09-07 | 吉林大学 | Diamine monomer containing 4-dimethylamine-substituted tetraphenyl-p-phenylenediamine structure and preparation method and application of diamine monomer containing 4-dimethylamine-substituted tetraphenyl-p-phenylenediamine structure |
| CN109843796A (en) * | 2016-10-14 | 2019-06-04 | 株式会社钟化 | The manufacturing method of graphite film |
-
2022
- 2022-03-16 CN CN202210258655.3A patent/CN114516959B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104445174A (en) * | 2014-12-12 | 2015-03-25 | 碳元科技股份有限公司 | Ultrathin high-thermal-conductivity graphite film and preparation method thereof |
| CN105924361A (en) * | 2016-06-20 | 2016-09-07 | 吉林大学 | Diamine monomer containing 4-dimethylamine-substituted tetraphenyl-p-phenylenediamine structure and preparation method and application of diamine monomer containing 4-dimethylamine-substituted tetraphenyl-p-phenylenediamine structure |
| CN108864423A (en) * | 2016-06-20 | 2018-11-23 | 吉林大学 | The application for tetraphenyl-p-phenylenediamine structure diamine monomer that dimethyl amine containing 4- replaces |
| CN109843796A (en) * | 2016-10-14 | 2019-06-04 | 株式会社钟化 | The manufacturing method of graphite film |
Non-Patent Citations (3)
| Title |
|---|
| HUNG-JU YEN: "Enhanced near-infrared electrochromism in triphenylamine-based aramids bearing phenothiazine redox centers" * |
| SHENG-HUEI HSIAO: "High Contrast Ratio and Rapid Switching Electrochromic Polymeric Films Based on 4-(Dimethylamino)triphenylamine-Functionalized Aromatic Polyamides" * |
| TZY-HSIANG SU: "Novel Family of Triphenylamine-Containing, HoleTransporting, Amorphous, Aromatic Polyamides with Stable Electrochromic Properties" * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116443864A (en) * | 2023-06-20 | 2023-07-18 | 广东工业大学 | Method for preparing graphene tubes by massive catalysis without template |
| CN116443864B (en) * | 2023-06-20 | 2023-08-29 | 广东工业大学 | Method for preparing graphene tubes by massive catalysis without template |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114516959B (en) | 2023-07-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108137835B (en) | Polyimide film and preparation method thereof | |
| KR101883434B1 (en) | Polyimide Film for Graphite Sheet, Graphite Sheet Prepared by Using the Same And Method for Preparing Graphite Sheet | |
| CN114437349B (en) | Polyimide film, method for producing the same, and graphite film | |
| JP6982694B2 (en) | A polyimide film for a graphite sheet containing a spherical PI-based filler, a manufacturing method thereof, and a graphite sheet manufactured using the same. | |
| KR102063215B1 (en) | Polyimide Film for Graphite Sheet with Improved Thermal Conductivity, Manufacturing Method thereof and Graphite Sheet Prepared by Using the Same | |
| CN106543720B (en) | A kind of Kapton of low thermal coefficient of expansion and preparation method thereof | |
| CN110272552B (en) | Preparation method of polyimide film for graphite sintering | |
| KR20190103638A (en) | Polyimide Film for Graphite Sheet Comprising Spherical PI-based Filler Containing Graphene, Manufacturing Method thereof and Graphite Sheet Prepared by Using the Same | |
| TWI775102B (en) | Polyimide film for graphite sheet and manufacturing method for the polyimide film | |
| CN114516959B (en) | Polyamide film, method for producing same, and graphite film | |
| JP2004299919A (en) | Graphite and method for producing the same | |
| TW202122466A (en) | Polyimide film for graphite sheet, preparation method thereof, and graphite sheet prepared therefrom | |
| KR20200066144A (en) | Graphite sheet manufactured from polyimide film having superior orientation and manufacturing method for the same | |
| CN111886285A (en) | Polyimide film including omni-directional polymer chain, method of manufacturing the same, and graphite sheet manufactured using the same | |
| CN111349255B (en) | Graphene-polyimide conductive film and preparation method thereof | |
| CN110644075B (en) | Method for preparing graphite fiber by doping polyimide with planar aromatic macromolecules | |
| CN114144390A (en) | Graphite sheet and electronic device comprising same | |
| CN114685786A (en) | Polyimide film and preparation method and application thereof | |
| TW202122467A (en) | Polyimide film for graphite sheet, preparation method thereof, and graphite sheet prepared therefrom | |
| JP3820767B2 (en) | NOVEL POLYIMIDE, ITS MANUFACTURING METHOD, AND LAMINATED SUBSTRATE | |
| CN114561007B (en) | High-strength low-linear expansion coefficient transparent polyimide film and preparation method thereof | |
| KR102450700B1 (en) | Polyimide film for graphite sheet and graphite sheet prepared thereform | |
| CN114685821B (en) | Preparation method and application of high-performance polyimide film | |
| CN115974067A (en) | High-thermal-conductivity graphite film of pyridine ring modified polyimide and preparation method thereof | |
| KR20220065395A (en) | Method for preparing polyimide film for graphite sheet and method for preparing graphite sheet |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |