CN112521641A - Polyimide film and graphite film with high crystal orientation - Google Patents
Polyimide film and graphite film with high crystal orientation Download PDFInfo
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- CN112521641A CN112521641A CN202011351068.6A CN202011351068A CN112521641A CN 112521641 A CN112521641 A CN 112521641A CN 202011351068 A CN202011351068 A CN 202011351068A CN 112521641 A CN112521641 A CN 112521641A
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- Prior art keywords
- polyimide film
- diamine
- film
- monomer
- dianhydride
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 103
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 67
- 239000010439 graphite Substances 0.000 title claims abstract description 67
- 239000013078 crystal Substances 0.000 title claims abstract description 12
- 150000004985 diamines Chemical class 0.000 claims abstract description 37
- 239000000178 monomer Substances 0.000 claims abstract description 32
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 22
- 125000000355 1,3-benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 claims abstract description 15
- 125000003118 aryl group Chemical group 0.000 claims abstract description 9
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims abstract description 9
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 29
- 229920005575 poly(amic acid) Polymers 0.000 claims description 28
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 17
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 16
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical group C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 15
- 239000010954 inorganic particle Substances 0.000 claims description 12
- 238000005087 graphitization Methods 0.000 claims description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 10
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052791 calcium Inorganic materials 0.000 claims description 10
- 239000011575 calcium Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- 239000000945 filler Substances 0.000 claims description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 6
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 238000003763 carbonization Methods 0.000 claims description 5
- 238000005266 casting Methods 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- JUNWLZAGQLJVLR-UHFFFAOYSA-J calcium diphosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])(=O)OP([O-])([O-])=O JUNWLZAGQLJVLR-UHFFFAOYSA-J 0.000 claims description 3
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 claims description 3
- 229940064002 calcium hypophosphite Drugs 0.000 claims description 3
- 229910001382 calcium hypophosphite Inorganic materials 0.000 claims description 3
- ROPDWRCJTIRLTR-UHFFFAOYSA-L calcium metaphosphate Chemical compound [Ca+2].[O-]P(=O)=O.[O-]P(=O)=O ROPDWRCJTIRLTR-UHFFFAOYSA-L 0.000 claims description 3
- 239000001506 calcium phosphate Substances 0.000 claims description 3
- 229940043256 calcium pyrophosphate Drugs 0.000 claims description 3
- 235000019821 dicalcium diphosphate Nutrition 0.000 claims description 3
- 235000019700 dicalcium phosphate Nutrition 0.000 claims description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 3
- CNALVHVMBXLLIY-IUCAKERBSA-N tert-butyl n-[(3s,5s)-5-methylpiperidin-3-yl]carbamate Chemical compound C[C@@H]1CNC[C@@H](NC(=O)OC(C)(C)C)C1 CNALVHVMBXLLIY-IUCAKERBSA-N 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 3
- 235000019731 tricalcium phosphate Nutrition 0.000 claims description 3
- 229940078499 tricalcium phosphate Drugs 0.000 claims description 3
- 229910000391 tricalcium phosphate Inorganic materials 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000009792 diffusion process Methods 0.000 abstract description 4
- 239000010408 film Substances 0.000 description 70
- 238000002360 preparation method Methods 0.000 description 13
- 239000004642 Polyimide Substances 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 238000010304 firing Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 8
- UMGYJGHIMRFYSP-UHFFFAOYSA-N 2-(4-aminophenyl)-1,3-benzoxazol-5-amine Chemical compound C1=CC(N)=CC=C1C1=NC2=CC(N)=CC=C2O1 UMGYJGHIMRFYSP-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000007906 compression Methods 0.000 description 5
- 108010025899 gelatin film Proteins 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- GHJFGINJLSLYHD-UHFFFAOYSA-N 4-[5-[2-(4-aminophenyl)-1,3-benzoxazol-5-yl]-1,3-benzoxazol-2-yl]aniline Chemical compound C1=CC(N)=CC=C1C1=NC2=CC(C=3C=C4N=C(OC4=CC=3)C=3C=CC(N)=CC=3)=CC=C2O1 GHJFGINJLSLYHD-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000011268 mixed slurry Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IAWQUHCVFXQBMC-UHFFFAOYSA-N 1,3-benzoxazol-5-amine Chemical compound NC1=CC=C2OC=NC2=C1 IAWQUHCVFXQBMC-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000003490 calendering Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 230000017525 heat dissipation Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- XAFOTXWPFVZQAZ-UHFFFAOYSA-N 2-(4-aminophenyl)-3h-benzimidazol-5-amine Chemical compound C1=CC(N)=CC=C1C1=NC2=CC=C(N)C=C2N1 XAFOTXWPFVZQAZ-UHFFFAOYSA-N 0.000 description 1
- DIXHWJYQQGNWTI-UHFFFAOYSA-N 2-[4-(5-amino-1,3-benzoxazol-2-yl)phenyl]-1,3-benzoxazol-5-amine Chemical compound NC1=CC=C2OC(C3=CC=C(C=C3)C=3OC4=CC=C(C=C4N=3)N)=NC2=C1 DIXHWJYQQGNWTI-UHFFFAOYSA-N 0.000 description 1
- NXDMHKQJWIMEEE-UHFFFAOYSA-N 4-(4-aminophenoxy)aniline;furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1.C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O NXDMHKQJWIMEEE-UHFFFAOYSA-N 0.000 description 1
- 206010019909 Hernia Diseases 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000009759 San-Chi Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- -1 and the like Chemical compound 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000012938 design process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
Classifications
-
- 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
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
- 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
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- 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
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2272—Ferric oxide (Fe2O3)
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/325—Calcium, strontium or barium phosphate
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Geology (AREA)
- Physics & Mathematics (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a polyimide film with high crystal orientation and a graphite film, wherein the polyimide film comprises a polycondensation reaction raw material of a diamine monomer and a dianhydride monomer, the diamine monomer comprises diamine containing benzoxazole groups, and the dianhydride monomer comprises tetracarboxylic dianhydride containing aromatic ring groups. The polyimide film disclosed by the invention is excellent in molecular orientation, and a graphite film prepared by using the polyimide film has excellent mechanical property and thermal diffusion efficiency.
Description
Technical Field
The invention relates to the technical field of graphite films, in particular to a polyimide film with high crystal orientation and a graphite film.
Background
Nowadays, electronic products are developing towards the field of high power and high operation, and along with the thinning development of electronic equipment, heat dissipation increasingly becomes a difficult problem to be solved urgently. After research, researchers have provided a brand-new heat-dissipating electronic product, namely a high-thermal-conductivity graphite film. The graphite film has the characteristics of high heat dissipation efficiency, small occupied space, light weight, uniform heat conduction along two directions and the like, and can uniformly distribute heat on a two-dimensional plane so as to effectively transfer the heat.
Currently, firing through polyimide films is the primary method for preparing graphite films. The core technology of the high-thermal-conductivity graphite film lies in the molecular structure design and preparation process selection of the polyimide film. Along with the increase of the application range, the demand for the graphite film on the market is diversified, and the urgent demand of the graphite film product is developed towards the direction of wider thickness range and higher heat conduction efficiency.
At present, researchers can conveniently research the change of the thermal conductivity of different polyimide graphite films by graphitizing polyimide films with different structures, and the PPT type polyimide film is most easy to prepare a graphite film with high orientation and high carbon layer orientation degree through comparison and has the best performance. Therefore, how to regulate the molecular structure and the preparation process of polyimide makes it easiest to prepare a graphite film with high orientation and high carbon layer orientation degree, which is obviously an important research direction for preparing a graphite film with higher heat conduction efficiency.
Disclosure of Invention
Based on the technical problems in the prior art, the invention provides a polyimide film with high crystal orientation and a graphite film, wherein the polyimide film has excellent molecular orientation, and the graphite film prepared by using the polyimide film has excellent mechanical property and thermal diffusion efficiency.
The polyimide film with high crystal orientation provided by the invention comprises a polycondensation reaction raw material of a diamine monomer and a dianhydride monomer, wherein the diamine monomer comprises diamine containing benzoxazole groups, and the dianhydride monomer comprises tetracarboxylic dianhydride containing aromatic ring groups.
Preferably, the benzoxazole group-containing diamine is at least one of the monomer structures shown as follows:
preferably, the benzoxazole group-containing diamine accounts for 1 to 20 mol% of the total amount of diamine monomers.
Preferably, the tetracarboxylic dianhydride containing an aromatic ring group is pyromellitic dianhydride.
Preferably, the diamine monomer further comprises a diamine containing an aromatic ring group;
preferably, the aromatic ring group-containing diamine is 4, 4' -diaminodiphenyl ether.
Preferably, the polyimide film further comprises a filler of inorganic particles;
preferably, the inorganic particles comprise 0.01 to 1 wt% of the total amount of diamine and dianhydride monomers;
further preferably, the inorganic particles have an average particle diameter of 0.1 to 5 μm.
Preferably, the inorganic particles are at least one of calcium-containing compounds or transition metal oxides;
preferably, the calcium-containing compound is at least one of calcium hydrogen phosphate, tricalcium phosphate, calcium hypophosphite, calcium pyrophosphate, calcium metaphosphate or calcium carbonate;
further preferably, the transition metal oxide is at least one of iron oxide, ferroferric oxide, vanadium pentoxide or titanium dioxide.
Preferably, the polyimide film is prepared by the following method:
(1) dispersing inorganic particles in an organic solvent uniformly to obtain a filler dispersion liquid; performing polycondensation reaction on a diamine monomer and a dianhydride monomer in an organic solvent to obtain a polyamic acid solution;
(2) and adding the filler dispersion into the polyamic acid solution, uniformly mixing, casting to form a film, stretching in two directions, and carrying out thermal imidization reaction to obtain the polyimide film.
Preferably, the organic solvent is at least one of N-methylpyrrolidone, dimethylsulfoxide, N-dimethylformamide or N, N-dimethylacetamide.
The invention also provides a graphite film which is obtained by sequentially carrying out high-temperature carbonization and high-temperature graphitization on the polyimide film.
Preferably, the temperature of the high-temperature carbonization is above 800 ℃, and the temperature of the high-temperature graphitization is above 2000 ℃.
The polyimide film of the invention adopts diamine containing benzoxazole group as a polycondensation reaction raw material, so that a benzoxazole liquid crystal group is introduced into the molecular structure of the polyimide film: on one hand, the polyimide prepared in the way has high crystal orientation degree, and a highly oriented graphite film is easy to prepare; on the other hand, the benzoxazole group can catalyze the closing of the polyamic acid ring, improve the imidization degree of the polyimide film in the casting stage and further improve the crystal orientation degree of the polyimide film. By the two actions, the orientation degree of the obtained graphite film carbon layer is further improved, and the thermal diffusivity and the mechanical property of the graphite film carbon layer are effectively improved.
Compared with the graphite film obtained by the conventional polyimide film, the graphite film has higher thermal diffusivity and more excellent mechanical property.
Detailed Description
In the present invention, the polyimide film proposed comprises a raw material for polycondensation reaction of dianhydride and diamine, specifically 4, 4' -diaminodiphenyl ether (ODA), pyromellitic dianhydride (PMDA), and diamine containing a benzoxazole group.
The content of the benzoxazolyl group-containing diamine is preferably not too high or too low, and is preferably in the range of 1 to 20 mol% based on the total amount of dianhydride. Too high or too low may not serve to adjust the properties of the polyimide film and the corresponding graphite film. The benzoxazole group-containing diamine may be selected from one or more of the following structures: 2- (4-aminophenyl) -5-aminobenzoxazole
1, 4-phenylene-bis- (5-aminobenzoxazole)
1, 4-bis (5 '-aminobenzoxazole-2' -) benzene
2, 2 '-bis (4-aminophenyl) -5, 5' -bibenzoxazole
The benzoxazole group introduced by the invention can improve the crystal orientation degree of the polyimide film, so that the birefringence of the polyimide film is improved, and the benzoxazole group can play a role in catalyzing imidization reaction, so that the birefringence of the polyimide film is further improved, and the performance of the graphite film prepared by the method is also better.
It has been shown that generally, the higher the birefringence of polyimide films, the better the performance of the graphite films produced. The birefringence index is a difference between a refractive index in an arbitrary direction in the film plane and a refractive index in the thickness direction. Birefringence is mainly represented by the ability of crystal orientation, and the orientation of common PMDA-ODA polyimide is limited, so that the introduction of diamine containing benzoxazole groups into the system can improve the birefringence of the polyimide film. The other important influence factor of the double refraction is that besides the influence of the molecular structure, the other is that the imidization degree is increased before the biaxial stretching, and the introduced benzoxazole group can catalyze the closing of the polyamic acid and improve the imidization degree of the polyamic acid in the casting stage so as to ensure that the crystal orientation is better, the double refraction rate of the prepared polyimide film is higher, and the performance of the graphite film obtained by roasting is better.
In addition to the diamine and dianhydride, the polyimide film of the present invention also has two fillers of inorganic particles added during the polyimide synthesis prior to firing the graphite film. A filler of inorganic particles is used as foaming agent, and is decomposed in the process of graphitizing polyimide film to generate gas to promote the foaming of graphite film. Whether the graphite film can be foamed or not is also an important quality measurement index, and a calcium-containing compound is often selected as a foaming agent. Alternative calcium-containing compounds are calcium hydrogen phosphate, tricalcium phosphate, calcium hypophosphite, calcium pyrophosphate, calcium metaphosphate or calcium carbonate, etc. The other inorganic filler is a graphitization promoter which is used for promoting the graphitization of the polyimide film and reducing the graphitization temperature, and a transition metal oxide is often selected as the graphitization promoter. Common transition metal oxides include iron oxide, ferroferric oxide, vanadium pentoxide, titanium dioxide, or the like.
In the present invention, when preparing a polyimide film by firing a graphite film, it is necessary to prepare a polyamic acid, and here, the polyamic acid can be obtained by a conventionally known method, and then imidization can be performed by a method selected from known imidization methods, for example, an imidization method including thermal imidization, chemical imidization, or a combination of thermal imidization and chemical imidization. The chemical imidization method and the thermal imidization method are advantageous, and the thermal imidization method is preferred in the present invention.
The specific process for preparing the polyamic acid can be specifically described below, for example, when the polyamic acid is obtained from a tetracarboxylic dianhydride monomer and a diamine monomer, the addition sequence or the addition method of the tetracarboxylic dianhydride and the diamine monomer is not particularly limited, and the process can be performed under a condition known in the art. For example, the diamine-based monomer may be dissolved in an organic solvent, and a tetracarboxylic dianhydride-based monomer may be added thereto to perform a polymerization reaction at an appropriate reaction temperature, thereby obtaining a polyamic acid solution; wherein the amount of the diamine-based monomer added is usually 0.8mol or more and 1.2mol or less based on 1mol of the tetracarboxylic dianhydride; the reaction temperature is not particularly limited as long as it is a temperature at which the reaction can proceed, and is usually 0 ℃ or higher, preferably 5 ℃; the reaction time is usually 5 hours or more, preferably 10 hours; the reaction environment may be under air, preferably under an inert gas atmosphere; the organic solvent for the reaction is not particularly limited as long as it can dissolve the polyamic acid, and amide solvents such as N, N-dimethylformamide, N-dimethylacetamide, and N-methyl-2-pyrrolidone are preferable.
The polymerization reaction can be controlled by adding a small amount of an end-capping agent to the diamine before the polymerization reaction, and the end-capping agent is not particularly limited, and a known end-capping agent can be used. Vacuum degassing in polymerization reaction is an effective method for producing an organic solvent solution of high-quality polyamic acid.
In addition, when the polyamic acid is cured to prepare polyimide, the curing (i.e., thermal imidization) of the polyamic acid solution obtained as described above can be performed.
Generally, the method for producing the polyimide film of the present invention is as follows: the polyamide acid resin is cast on an annular steel belt through a slit die head, a gel film is obtained after partial solvent is removed through heating, the gel film is subjected to biaxial stretching (longitudinal stretching and transverse stretching), the stretching ratio in the longitudinal direction and the transverse direction is controlled to be 0.9-1.3, and the polyimide film of the artificial graphite film with excellent mechanical property is obtained through high-temperature imidization during transverse stretching.
The properties of graphite thin films made from polyimide films are related to the thickness of the polyimide film. If the thickness of the polyimide film is too large, it is difficult to achieve uniform heat treatment in the thickness direction, and if it is too thin, surface defects are easily generated in the heat treatment, and the proportion of defects is high. Therefore, the thickness of the polyimide film is controlled within a certain range, and the thickness of the polyimide film used in the present invention is not particularly limited, but is preferably in the range of 5 μm to 200 μm, and more preferably in the range of 10 μm to 150 μm.
In the present invention, the graphite film of the present invention can be obtained by firing and graphitizing the polyimide film of the present invention.
In general, the temperature for the graphitization treatment needs to be in an appropriate range, and is usually 2000 ℃ or higher, preferably 2200 ℃ or higher, more preferably 2600 ℃ or higher, and further preferably 3000 ℃ or higher. If the baking temperature is higher than 3500 ℃, the baking furnace is required to have excellent heat resistance. At maximum firing temperatures below 2000 c, the resulting graphite film tends to be excessively hard and brittle. The rate of temperature rise during firing is not particularly limited, and may be about 1 to 10 ℃/min. Known heating equipment may be used in the firing. The baking time is not particularly limited.
The high-temperature calcination is usually carried out in an inert atmosphere, and usually an inert gas may be introduced into the calcination apparatus, and the inert gas to be introduced is not particularly limited, and examples thereof include helium, argon, nitrogen, and the like, and argon is preferably used. In addition, the pressure during roasting is only normal pressure.
The compression step is required for the graphite film after high-temperature firing. By the compression process, the thickness unevenness caused by the expansion of the graphite film after firing can be reduced. Further, the compression step treatment can increase the density of the graphite film after firing and improve the thermal conductivity. In the compression step, a method of compressing the sheet-like material into a sheet-like shape, a method of rolling the sheet-like material with a metal roll, or the like may be used. The compression step may be performed at room temperature or may be performed in the graphitization step.
Generally, before high-temperature baking and graphitization, the polyimide film needs to be carbonized at a temperature of 1600 ℃ or higher at room temperature. The highest temperature of the heat treatment of the carbonization treatment should be at least 800 ℃, preferably 900 ℃ or higher, and particularly preferably 1000 ℃ or higher.
Hereinafter, the technical solution of the present invention will be described in detail by specific examples, but these examples should be explicitly proposed for illustration, but should not be construed as limiting the scope of the present invention.
Example 1
Preparation of polyimide film:
(1) adding calcium hydrophosphate (with the average particle size of 3 mu m) into N, N-dimethylacetamide, and uniformly stirring and dispersing at a high speed to obtain calcium hydrophosphate slurry with the solid content of 10%; adding ferric oxide (with average particle size of 3 μm) into N, N-dimethylacetamide, stirring at high speed, and dispersing uniformly to obtain ferric oxide slurry with solid content of 10%;
(2) adding 4, 4' -diaminodiphenyl ether, pyromellitic dianhydride and 2- (4-aminophenyl) -5-aminobenzoxazole into N, N-dimethylacetamide according to a molar ratio of 90:100:10 in a nitrogen atmosphere, and stirring and reacting at 40 ℃ for 6 hours to obtain a polyamic acid solution with a solid content of 20%;
(3) adding the calcium hydrophosphate slurry and the ferric oxide slurry into the polyamic acid solution, controlling the dosage of calcium hydrophosphate to be 0.5 percent of the total weight of monomers (4, 4 '-diaminodiphenyl ether, pyromellitic dianhydride and 2- (4-aminophenyl) -5-aminobenzoxazole), controlling the mass of ferric oxide to be 0.06 percent of the total weight of the monomers (4, 4' -diaminodiphenyl ether, pyromellitic dianhydride and 2- (4-aminophenyl) -5-aminobenzoxazole), fully stirring uniformly to obtain mixed slurry, filtering the mixed slurry, defoaming, conveying the defoamed mixed slurry to a die head through a pipeline, casting on a steel belt, and removing a solvent at 160 ℃ to obtain a self-supporting polyimide gel film;
(4) and longitudinally stretching the polyimide gel film, transversely stretching the polyimide gel film, controlling the stretching ratio to be 1.20, and then completing high-temperature imidization at 160 ℃ for 30s, 350 ℃ for 30s and 450 ℃ for 30s to obtain the polyimide film with the thickness of 50 microns.
Preparing a graphite film:
cutting the polyimide film into a size of 300 x 300mm, vertically putting the film surface into a cylindrical closed holding container made of graphite, heating the film surface to 1000 ℃ at a heating rate of 3 ℃/min in argon gas and holding the film for 1h, heating the film surface to 2700 ℃ at a heating rate of 3 ℃/min and holding the film for 1h so as to bake the polyimide carbonized film, graphitizing the polyimide carbonized film, and calendering the obtained graphite sheet by using a calendering roller to obtain the graphite film with the thickness of 24 mu m.
Example 2
Preparation of polyimide film:
a polyimide film was prepared as described with reference to example 1, except that 4, 4' -diaminodiphenyl ether, pyromellitic dianhydride, and 1, 4-phenylene-2- (5-aminobenzoxazole) were added to N, N-dimethylacetamide in a molar ratio of 90:100:10 in the synthesis of a polyamic acid solution.
Preparing a graphite film:
the polyimide film described above was prepared to give a graphite film by the method described in example 1.
Example 3
Preparation of polyimide film:
a polyimide film was prepared as described in reference example 1, except that 4, 4 ' -diaminodiphenyl ether, pyromellitic dianhydride, and 1, 4-bis (5' -aminobenzoxazole-2 ' -) benzene were added to N, N-dimethylacetamide in a molar ratio of 90:100:10 in the polyamic acid solution synthesis.
Preparing a graphite film:
the polyimide film described above was prepared to give a graphite film by the method described in example 1.
Example 4
Preparation of polyimide film:
a polyimide film was prepared as described in reference to example 1, except that 4, 4 ' -diaminodiphenyl ether, pyromellitic dianhydride, and 2, 2' -bis (4-aminophenyl) -5, 5' -bibenzoxazole were added to N, N-dimethylacetamide in a molar ratio of 90:100:10 in the synthesis of a polyamic acid solution.
Preparing a graphite film:
the polyimide film described above was prepared to give a graphite film by the method described in example 1.
Example 5
Preparation of polyimide film:
a polyimide film was prepared as described with reference to example 1, except that 4, 4' -diaminodiphenyl ether, pyromellitic dianhydride, and 2- (4-aminophenyl) -5-aminobenzoxazole were added to N, N-dimethylacetamide in a molar ratio of 80:100:20 in the synthesis of a polyamic acid solution.
Preparing a graphite film:
the polyimide film described above was prepared to give a graphite film by the method described in example 1.
Example 6
Preparation of polyimide film:
a polyimide film was prepared as described with reference to example 1, except that 4, 4' -diaminodiphenyl ether, pyromellitic dianhydride, and 1, 4-phenylene-2- (5-aminobenzoxazole) were added to N, N-dimethylacetamide in a molar ratio of 80:100:20 in the polyamic acid solution synthesis.
Preparing a graphite film:
the polyimide film described above was prepared to give a graphite film by the method described in example 1.
Example 7
Preparation of polyimide film:
a polyimide film was prepared as described in reference example 1, except that in the polyamic acid solution synthesis, 4 ' -diaminodiphenyl ether, pyromellitic dianhydride, and 1, 4-bis (5' -aminobenzoxazole-2 ' -) benzene were added to N, N-dimethylacetamide in a molar ratio of 80:100:20, and the reaction was stirred at 40 ℃ for 6 hours.
Preparing a graphite film:
the polyimide film described above was prepared to give a graphite film by the method described in example 1.
Example 8
Preparation of polyimide film:
a polyimide film was prepared as described in reference to example 1, except that 4, 4 ' -diaminodiphenyl ether, pyromellitic dianhydride, and 2, 2' -bis (4-aminophenyl) -5, 5' -bibenzoxazole were added to N, N-dimethylacetamide in a molar ratio of 80:100:20 in the polyamic acid solution synthesis.
Preparing a graphite film:
the polyimide film described above was prepared to give a graphite film by the method described in example 1.
Comparative example 1
Preparation of polyimide film:
a polyimide film was prepared as described in reference example 1, except that 4, 4' -diaminodiphenyl ether, pyromellitic dianhydride, and 2- (4-aminophenyl) -5-aminobenzimidazole were used in the synthesis of the polyamic acid solution
Adding the mixture into N, N-dimethylacetamide according to a molar ratio of 90:100: 10.
Preparing a graphite film:
the polyimide film described above was prepared to give a graphite film by the method described in example 1.
Comparative example 2
Preparation of polyimide film:
a polyimide film was prepared as described with reference to example 1, except that 4, 4' -diaminodiphenyl ether, pyromellitic dianhydride, and p-phenylenediamine were added to N, N-dimethylacetamide in a molar ratio of 90:100:10 in the synthesis of a polyamic acid solution.
Preparing a graphite film:
the polyimide film described above was prepared to give a graphite film by the method described in example 1.
Comparative example 3
Preparation of polyimide film:
a polyimide film was prepared as described with reference to example 1, except that 4, 4' -diaminodiphenyl ether, pyromellitic dianhydride, and 2- (4-aminophenyl) -5-aminobenzoxazole were added to N, N-dimethylacetamide in a molar ratio of 60:100:40 in the synthesis of a polyamic acid solution.
Preparing a graphite film:
the polyimide film described above was prepared to give a graphite film by the method described in example 1.
The polyimide films and graphite films obtained in the above examples and comparative examples were subjected to the performance tests shown in the following methods, and the results thereof are shown in the following table 1:
coefficient of linear thermal expansion
A thermal mechanical analyzer was used to apply a 50mN load under a nitrogen atmosphere, and the temperature was measured at a temperature rise rate of 10 ℃/min to obtain an average value.
Double refractive index
The birefringence of the polyimide film was measured using a refractive index and film thickness measuring system (model number: 2010Prism coupler) manufactured by Metricon (in the measurement, the refractive index was measured in TE mode and TM mode using a light source having a wavelength of 594nm in an environment of 23 ℃, and the measured "(value of refractive index in TE mode) - (value of refractive index in TM mode)" was used as the birefringence).
Mechanical Properties
The tensile strength and elongation at break of the graphite film were measured by the method specified in astm d882 using an universal tensile machine.
Coefficient of thermal diffusion
Using a diffusion method thermal conductivity meter LFA467 manufactured by sanchi corporation, the measurement method was: hernia flash method, test temperature: room temperature, mode: In-Plane, light spot: 14 mm; protective gas: the measurement was performed under nitrogen.
Table 1 test results of polyimide films and graphite films obtained in accordance with examples 1 to 8 and comparative examples 1 to 3
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. A polyimide film with high crystal orientation comprises a raw material of polycondensation reaction of a diamine monomer and a dianhydride monomer, and is characterized in that the diamine monomer comprises diamine containing benzoxazole groups, and the dianhydride monomer comprises tetracarboxylic dianhydride containing aromatic ring groups.
2. The highly crystal-oriented polyimide film according to claim 1, wherein the benzoxazole group-containing diamine is at least one of monomer structures shown as follows:
preferably, the benzoxazole group-containing diamine accounts for 1 to 20 mol% of the total amount of diamine monomers.
3. The highly crystal-oriented polyimide film according to claim 1 or 2, wherein the tetracarboxylic dianhydride containing an aromatic ring group is pyromellitic dianhydride.
4. The highly crystalline oriented polyimide film of any of claims 1-3, wherein the diamine monomer further comprises an aromatic ring group-containing diamine;
preferably, the aromatic ring group-containing diamine is 4, 4' -diaminodiphenyl ether.
5. The high crystalline orientation polyimide film of any of claims 1-4, further comprising a filler of inorganic particles;
preferably, the inorganic particles comprise 0.01 to 1 wt% of the total amount of diamine and dianhydride monomers;
further preferably, the inorganic particles have an average particle diameter of 0.1 to 5 μm.
6. The highly crystalline oriented polyimide film of claim 5, wherein said inorganic particles are at least one of calcium-containing compounds or transition metal oxides;
preferably, the calcium-containing compound is at least one of calcium hydrogen phosphate, tricalcium phosphate, calcium hypophosphite, calcium pyrophosphate, calcium metaphosphate or calcium carbonate;
further preferably, the transition metal oxide is at least one of iron oxide, ferroferric oxide, vanadium pentoxide or titanium dioxide.
7. The highly crystal-oriented polyimide film according to claim 5 or 6, wherein the polyimide film is produced by a method comprising:
(1) dispersing inorganic particles in an organic solvent uniformly to obtain a filler dispersion liquid; performing polycondensation reaction on a diamine monomer and a dianhydride monomer in an organic solvent to obtain a polyamic acid solution;
(2) and adding the filler dispersion into the polyamic acid solution, uniformly mixing, casting to form a film, stretching in two directions, and carrying out thermal imidization reaction to obtain the polyimide film.
8. The highly crystalline oriented polyimide film of claim 7, wherein said organic solvent is at least one of N-methylpyrrolidone, dimethylsulfoxide, N-dimethylformamide, or N, N-dimethylacetamide.
9. A graphite film obtained by subjecting the polyimide film according to any one of claims 1 to 8 to high-temperature carbonization and high-temperature graphitization in this order.
10. The graphite film according to claim 9, wherein the temperature of the high-temperature carbonization is 800 ℃ or more, and the temperature of the high-temperature graphitization is 2000 ℃ or more.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114736019A (en) * | 2022-06-10 | 2022-07-12 | 宁波长阳科技股份有限公司 | Artificial graphite sheet with high vertical heat conduction and radiating fin comprising artificial graphite sheet |
| CN115011315A (en) * | 2022-06-14 | 2022-09-06 | 华南理工大学 | Preparation and application of flexible electronic biomass/polyimide-based heat-dissipation material film |
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| CN106832923A (en) * | 2016-12-16 | 2017-06-13 | 深圳瑞华泰薄膜科技有限公司 | A kind of Kapton for preparing electrographite film and preparation method thereof |
| CN109734908A (en) * | 2018-12-20 | 2019-05-10 | 武汉柔显科技股份有限公司 | The preparation method of polyamic acid and preparation method, polyimides and Kapton |
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| CN101274992A (en) * | 2007-03-31 | 2008-10-01 | 宇部兴产株式会社 | Process for producing polyimide film, and polyimide film |
| CN106832923A (en) * | 2016-12-16 | 2017-06-13 | 深圳瑞华泰薄膜科技有限公司 | A kind of Kapton for preparing electrographite film and preparation method thereof |
| CN109734908A (en) * | 2018-12-20 | 2019-05-10 | 武汉柔显科技股份有限公司 | The preparation method of polyamic acid and preparation method, polyimides and Kapton |
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| CN114736019A (en) * | 2022-06-10 | 2022-07-12 | 宁波长阳科技股份有限公司 | Artificial graphite sheet with high vertical heat conduction and radiating fin comprising artificial graphite sheet |
| CN115011315A (en) * | 2022-06-14 | 2022-09-06 | 华南理工大学 | Preparation and application of flexible electronic biomass/polyimide-based heat-dissipation material film |
| CN115011315B (en) * | 2022-06-14 | 2023-09-26 | 华南理工大学 | Preparation and application of flexible electronic biomass/polyimide-based heat dissipation material film |
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