CN112608474A - Polyimide film and graphite film - Google Patents
Polyimide film and graphite film Download PDFInfo
- Publication number
- CN112608474A CN112608474A CN202011351046.XA CN202011351046A CN112608474A CN 112608474 A CN112608474 A CN 112608474A CN 202011351046 A CN202011351046 A CN 202011351046A CN 112608474 A CN112608474 A CN 112608474A
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- China
- Prior art keywords
- polyimide film
- diamine monomer
- aminophenyl
- polyimide
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 73
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 32
- 239000010439 graphite Substances 0.000 title claims abstract description 32
- 239000000178 monomer Substances 0.000 claims abstract description 44
- 150000004985 diamines Chemical class 0.000 claims abstract description 39
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims abstract description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 3
- 125000004427 diamine group Chemical group 0.000 claims abstract 2
- 239000002002 slurry Substances 0.000 claims description 21
- 229920005575 poly(amic acid) Polymers 0.000 claims description 20
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 15
- 239000011347 resin Substances 0.000 claims description 15
- 229920005989 resin Polymers 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical compound C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 10
- 229910052791 calcium Inorganic materials 0.000 claims description 10
- 239000011575 calcium Substances 0.000 claims description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 9
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 8
- 108010025899 gelatin film Proteins 0.000 claims description 7
- 239000011256 inorganic filler Substances 0.000 claims description 7
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 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 claims description 5
- UUAXNIZLIORMNW-UHFFFAOYSA-N 2-(4-aminophenyl)pyrimidin-5-amine Chemical compound C1=CC(N)=CC=C1C1=NC=C(N)C=N1 UUAXNIZLIORMNW-UHFFFAOYSA-N 0.000 claims description 4
- LJQRDZHDYMOIIO-UHFFFAOYSA-N 4-[2-(4-aminophenyl)pyrimidin-5-yl]aniline Chemical group C1=CC(N)=CC=C1C1=CN=C(C=2C=CC(N)=CC=2)N=C1 LJQRDZHDYMOIIO-UHFFFAOYSA-N 0.000 claims description 4
- CETWTGTYZMPZFI-UHFFFAOYSA-N 4-[5-(4-aminophenyl)pyrazin-2-yl]aniline Chemical group C1=CC(N)=CC=C1C1=CN=C(C=2C=CC(N)=CC=2)C=N1 CETWTGTYZMPZFI-UHFFFAOYSA-N 0.000 claims description 4
- PFWDSZBMGYUMPB-UHFFFAOYSA-N 6-(4-aminophenyl)pyridin-3-amine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=N1 PFWDSZBMGYUMPB-UHFFFAOYSA-N 0.000 claims description 4
- UHRTVVGCBHYAAL-UHFFFAOYSA-N NC1=CC=C(C=C1)C1=NC=C(C=C1)C1=CC=C(C=C1)N Chemical group NC1=CC=C(C=C1)C1=NC=C(C=C1)C1=CC=C(C=C1)N UHRTVVGCBHYAAL-UHFFFAOYSA-N 0.000 claims description 4
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 238000010000 carbonizing Methods 0.000 claims description 3
- 238000005266 casting Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 229940043430 calcium compound Drugs 0.000 claims description 2
- 150000001674 calcium compounds Chemical class 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- IWVSKNFJIVKXHH-UHFFFAOYSA-N pyrazine;pyrimidine Chemical compound C1=CN=CN=C1.C1=CN=CC=N1 IWVSKNFJIVKXHH-UHFFFAOYSA-N 0.000 claims 1
- 239000004642 Polyimide Substances 0.000 abstract description 26
- 239000013078 crystal Substances 0.000 abstract description 4
- 230000001276 controlling effect Effects 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 14
- 238000003756 stirring Methods 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 238000005087 graphitization Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000007906 compression Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- -1 nitrogen-containing heterocyclic diamine Chemical class 0.000 description 5
- 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 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 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
- 238000002360 preparation method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 229910021383 artificial graphite Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000006835 compression Effects 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
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 238000009775 high-speed stirring Methods 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 125000000714 pyrimidinyl group Chemical group 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 206010039424 Salivary hypersecretion Diseases 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- JUNWLZAGQLJVLR-UHFFFAOYSA-J calcium diphosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])(=O)OP([O-])([O-])=O JUNWLZAGQLJVLR-UHFFFAOYSA-J 0.000 description 1
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 1
- 229940064002 calcium hypophosphite Drugs 0.000 description 1
- 229910001382 calcium hypophosphite Inorganic materials 0.000 description 1
- ROPDWRCJTIRLTR-UHFFFAOYSA-L calcium metaphosphate Chemical compound [Ca+2].[O-]P(=O)=O.[O-]P(=O)=O ROPDWRCJTIRLTR-UHFFFAOYSA-L 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229940043256 calcium pyrophosphate Drugs 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000019821 dicalcium diphosphate Nutrition 0.000 description 1
- 235000019700 dicalcium phosphate Nutrition 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 230000017525 heat dissipation Effects 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
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 208000026451 salivation Diseases 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 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 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 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 description 1
- 235000019731 tricalcium phosphate Nutrition 0.000 description 1
- 229940078499 tricalcium phosphate Drugs 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 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
- 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
- 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
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The polyimide film is obtained by polymerizing pyromellitic dianhydride, 4' -diaminodiphenyl ether and a second diamine monomer accounting for 1-50 mol% of the diamine monomer, wherein the second diamine monomer is a diamine monomer containing a nitrogen heterocycle, the imidization degree and the crystal orientation of polyimide are improved by regulating and controlling a formula, and the obtained polyimide graphite film has excellent thermal conductivity and mechanical properties.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a polyimide film and a graphite film.
Background
With the development of science and technology, the trend of electronic equipment towards thinning and the trend of internal circuit design towards densification is more and more obvious, and under the requirement, the heat dissipation design inside the equipment becomes a key. Because the graphite flake has characteristics such as radiating efficiency is high, occupation space is little, light in weight, along two directions uniform heat conduction, thereby can be with heat evenly distributed at two-dimensional plane effectual with heat transfer. Therefore, in recent years, it has attracted attention as a heat dissipating member for electronic devices, and many methods for producing graphite films have been developed which can be used for electronic devices and the like.
Polyimide has excellent performance, and the preparation of graphite film from polyimide is more and more important. A large number of artificial graphite films sintered from polyimide are currently used in electronic devices. However, the thermal conductivity and mechanical properties of the graphite film prepared from the existing PMDA/ODA type polyimide are not ideal, and the properties of the polyimide graphite film depend on the polyimide as the raw material, and on the basis, how to adjust and control the properties of the PMDA/ODA type polyimide to obtain the artificial graphite film with excellent thermal conductivity and mechanical properties is a subject which needs to be researched urgently.
Disclosure of Invention
Based on the technical problems in the prior art, the imidization degree and the crystal orientation of polyimide are improved through formula regulation, so that the polyimide graphite film obtained by the method has excellent thermal conductivity and mechanical properties.
The technical scheme of the invention is as follows:
a polyimide film is obtained by polymerizing pyromellitic dianhydride, 4' -diaminodiphenyl ether and a second diamine monomer accounting for 1-50 mol% of the diamine monomer, wherein the second diamine monomer is a diamine monomer containing a nitrogen heterocycle.
Preferably, the diamine monomer containing a nitrogen heterocycle is selected from imidazole-, pyridine-, pyrazine-or pyrimidine-containing diamine monomers.
Preferably, the imidazole-containing diamine monomer is one or two selected from the group consisting of 2- (4-aminophenyl) -5-aminobenzimidazole, 2 '-bis (4-aminophenyl) -5,5' -bibenzimidazole, and 1, 4-bis (5 '-aminobenzimidazole-2' -) benzene.
Preferably, the pyridine-containing diamine monomer is selected from 2, 5-bis (4-aminophenyl) pyridine or 2- (4-aminophenyl) -5-aminopyridine.
Preferably, the pyrimidine-containing diamine monomer is selected from 2, 5-bis (4-aminophenyl) pyrimidine or 2- (4-aminophenyl) -5-pyrimidinamine.
Preferably, the pyrazine-containing diamine monomer is 2, 5-bis (4-aminophenyl) pyrazine.
The polyimide film is prepared by the following steps:
s1, adding pyromellitic dianhydride into an organic solvent containing 4,4' -diaminodiphenyl ether and a second diamine monomer, and carrying out polymerization reaction to obtain polyamide acid slurry;
s2, adding the calcium-containing compound inorganic filler into an organic solvent, and uniformly dispersing to obtain calcium-containing compound slurry; adding transition metal oxide inorganic filler into an organic solvent, and uniformly dispersing to obtain slurry containing transition metal oxide;
s3, mixing the polyamic acid slurry with the calcium compound slurry and the transition metal oxide-containing slurry, filtering and defoaming to obtain mixed resin;
s4, casting and coating the mixed resin, removing part of the solvent to obtain a polyamic acid gel film, and performing biaxial tension and thermal imidization treatment to obtain the polyimide film.
Preferably, the organic solvent in the preparation method of the polyimide film is selected from one or more of N-methyl pyrrolidone, dimethyl sulfoxide, N-dimethylformamide and N, N-dimethylacetamide.
The invention also provides a graphite film which is obtained by carbonizing and roasting the polyimide film at high temperature.
Has the advantages that:
the technical team of the invention finds that the performance of the polyimide film is not only related to the structure of the polyimide molecule, but also influenced by the imidization degree to a great extent, and the common PMDA/ODA type polyimide has low imidization degree, poor crystal orientation and low birefringence, so that the graphite film prepared from the polyimide has unsatisfactory performance, heat conduction and mechanical properties.
According to the invention, nitrogen-containing heterocyclic diamine is introduced into a PMDA/ODA type polyimide system, so that not only is the molecular weight accumulation acting force increased and pi-pi conjugate accumulation increased, but also the imidization degree of a salivation section is improved by the nitrogen-containing heterocyclic diamine, so that the obtained polyimide has good crystal orientation and high birefringence of a polyimide film, and the correspondingly prepared graphite film has excellent heat conduction and mechanical properties.
Detailed Description
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.
Preparation of polyimide film
The raw materials used for the synthesis of the polyimide of the present invention include pyromellitic dianhydride (PMDA), 4,4' -Oxydianiline (ODA), and at least one second diamine monomer. The second diamine monomer is a nitrogen-containing heterocyclic diamine monomer. The nitrogen-containing heterocyclic diamine monomer is selected from diamine monomers containing imidazole, pyridine, pyrazine or pyrimidine structures.
The diamine monomer containing imidazole structure is selected from one or two of 2- (4-aminophenyl) -5-aminobenzimidazole, 2 '-bis (4-aminophenyl) -5,5' -bibenzimidazole and 1, 4-bis (5 '-aminobenzimidazole-2' -) benzene; the diamine monomer containing pyridine structure is selected from 2, 5-di (4-aminophenyl) pyridine or 2- (4-aminophenyl) -5-aminopyridine; the diamine monomer containing pyrimidine structure is selected from 2, 5-bis (4-aminophenyl) pyrimidine or 2- (4-aminophenyl) -5-pyrimidinamine; the diamine monomer containing pyrazine structure is 2, 5-di (4-aminophenyl) pyrazine.
The structural formula of the diamine monomer is as follows:
as for the content of the second diamine monomer, it is not preferable to be too high or too low, and it is preferable to range from 1 to 50% based on the total molar amount of the diamines, and too high or too low does not contribute to the adjustment of the properties of the polyimide film.
In addition to diamine and dianhydride, the graphite film is fired from the polyimide film, and two inorganic fillers are added when the polyimide film is synthesized. An inorganic filler is used as foaming agent, and is decomposed in the graphitization process of the polyimide film to generate gas, so that the graphite film is promoted to foam. 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, calcium carbonate, and the like. 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 sesquioxide, iron tetroxide, vanadium pentoxide, titanium dioxide, and the like.
When the polyimide is prepared, a polyimide precursor-polyamic acid is obtained by adopting a two-step method, and then the polyimide film is obtained by a thermal imidization method, a chemical imidization method or a combination of the thermal imidization and the chemical imidization. The thermal imidization method is preferred in the present invention.
The specific process for preparing polyamic acid can be specifically described as follows:
the order of addition or method of addition of the dianhydride monomer and the diamine monomer is not particularly limited, and for example, the diamine monomer may be dissolved in an organic solvent, and the dianhydride monomer may be added and subjected to a polymerization reaction at an appropriate reaction temperature to obtain a polyamic acid slurry; the amount of the diamine monomer added is usually 0.8mol or more and 1.2mol or less relative to 1mol of the dianhydride monomer; 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 20 to 40 ℃; with regard to the reaction time, it is generally from 1 to 10 h; 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 is preferably N-methylpyrrolidone, dimethylsulfoxide, N-dimethylformamide, N-dimethylacetamide, or the like.
The polymerization reaction is controlled by adding a small amount of an end-capping agent to the diamine monomer 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.
The method for manufacturing the polyimide film comprises the following steps: the polyamide acid resin is cast on an annular steel belt through a slit die head, a polyimide gel film is obtained after a part of 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 for the graphite film is imidized at high temperature during transverse stretching to obtain the polyimide film for the graphite film.
The properties of graphite 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. The thickness of the polyimide film to be used in the present invention is not particularly limited, and is preferably in the range of 5 μm to 200 μm, more preferably in the range of 10 μm to 150 μm.
For the preparation of graphite films
The graphite film can be obtained by carbonizing and roasting the polyimide film at high temperature.
The carbonization step is a step of obtaining a carbonized film by heat-treating the polyimide film at a temperature of from room temperature to 1600 ℃. The temperature of the heat treatment in the carbonization step is 800 ℃ or higher, preferably 900 ℃ or higher, and particularly preferably 1000 ℃ or higher.
The temperature for the high-temperature calcination is required to be within a suitable range, and usually the temperature is 2000 ℃ or higher, preferably 2200 ℃ or higher, and more preferably 2600 ℃ or higher. 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 process is required for the graphite film after high-temperature baking. By the compression process, the thickness unevenness caused by the expansion of the calcined graphite sheet can be reduced. Further, the compression step increases the density of the calcined graphite sheet, thereby improving 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.
Example 1
Polyimide film:
4,4' -diaminodiphenyl ether, pyromellitic dianhydride and 2- (4-aminophenyl) -5-aminobenzimidazole are reacted in N, N-dimethylacetamide in a molar ratio of 90:100:10 under stirring for 4 hours at 40 ℃ to obtain polyamic acid slurry with 20% of solid content;
adding calcium hydrophosphate as a filler with the average particle size of 3 mu m into N, N-dimethylacetamide, and dispersing by high-speed stirring to prepare calcium hydrophosphate slurry with the solid content of 10%; adding filler ferric oxide with the average particle size of 3 mu m into N, N-dimethylacetamide, and preparing ferric oxide slurry with the solid content of 10 percent by adopting high-speed stirring and dispersing;
adding calcium hydrophosphate slurry and ferric oxide slurry into the prepared polyamic acid slurry, and controlling the filler content in the calcium hydrophosphate slurry to be 0.5 percent of the solid weight of the polyimide film material and the filler content in the ferric oxide slurry to be 0.06 percent of the solid weight of the polyimide film material; stirring uniformly, filtering, defoaming, conveying the obtained mixed resin to a die head through a pipeline, casting on a steel belt, and removing the solvent at 150 ℃ to obtain the polyimide gel film. Firstly, longitudinally pulling up the polyimide gel film, then transversely stretching, controlling the stretching ratio to be 1.2, and imidizing at high temperature of 150 ℃ for 30s, 350 ℃ for 30s and 450 ℃ for 30s to obtain the polyimide film.
Graphite film:
the polyimide film obtained above was cut into a size of 300X 300mm, and graphite was placed on the film surface in a standing state to prepare a cylindrical closed holding container. Then, the temperature was raised to 1000 ℃ at 3 ℃/min in argon gas and the temperature was maintained for 1 hour to obtain a polyimide carbonized film, and the polyimide carbonized film was further heated to 2600 ℃ at 3 ℃/min and the temperature was maintained for 1 hour to bake the polyimide carbonized film, thereby graphitizing the polyimide carbonized film. The obtained graphite sheet was subjected to calendering treatment with a calender roll to obtain a graphite film.
Example 2
4,4' -diaminodiphenyl ether, pyromellitic dianhydride and 1, 4-bis (5' -aminobenzimidazole-2 ' -) benzene are reacted in N, N-dimethylacetamide in a molar ratio of 90:100:10 under stirring at 40 ℃ for 4 hours to obtain a polyamic acid resin solution with a solid content of 20%. Otherwise as in example 1.
Example 3
4,4' -diaminodiphenyl ether, pyromellitic dianhydride and 2,2' -bis (4-aminophenyl) -5,5' -bibenzimidazole react in N, N-dimethylacetamide in a molar ratio of 50:100:50 under stirring at 40 ℃ for 4h to obtain a polyamic acid resin solution with 20% of solid content. Otherwise as in example 1.
Example 4
4,4' -diaminodiphenyl ether, pyromellitic dianhydride and 2, 5-bis (4-aminophenyl) pyrimidine are reacted in N, N-dimethylacetamide in a molar ratio of 90:100:10 under stirring at 40 ℃ for 4h to obtain a polyamic acid resin solution with 20% of solid content. Otherwise as in example 1.
Example 5
4,4' -diaminodiphenyl ether, pyromellitic dianhydride and 2- (4-aminophenyl) -5-pyrimidinamine are reacted in N, N-dimethylacetamide in a molar ratio of 50:100:50 under stirring at 40 ℃ for 4h to obtain a polyamic acid resin solution with 20% of solid content. Otherwise as in example 1.
Example 6
4,4' -diaminodiphenyl ether, pyromellitic dianhydride and 2, 5-bis (4-aminophenyl) pyridine are reacted in N, N-dimethylacetamide in a molar ratio of 90:100:10 under stirring at 40 ℃ for 4h to obtain a polyamic acid resin solution with 20% of solid content. Otherwise as in example 1.
Example 7
4,4' -diaminodiphenyl ether, pyromellitic dianhydride and 2- (4-aminophenyl) -5-aminopyridine are reacted in N, N-dimethylacetamide in a molar ratio of 50:100:50 under stirring at 40 ℃ for 4h to obtain a polyamic acid resin solution with 20% of solid content. Otherwise as in example 1.
Example 8
4,4' -diaminodiphenyl ether, pyromellitic dianhydride and 2, 5-bis (4-aminophenyl) pyrazine are reacted in N, N-dimethylacetamide in a molar ratio of 50:100:50 under stirring at 40 ℃ for 4h to obtain a polyamic acid resin solution with 20% of solid content. Otherwise as in example 1.
Comparative example 1
4,4' -diaminodiphenyl ether, pyromellitic dianhydride and 2- (4-aminophenyl) -5-aminobenzimidazole are reacted in N, N-dimethylacetamide in a molar ratio of 40:100:60 under stirring at 40 ℃ for 4h to obtain a polyamic acid resin solution with 20% of solid content. Otherwise as in example 1.
Comparative example 2
4,4' -diaminodiphenyl ether and pyromellitic dianhydride are reacted in N, N-dimethylacetamide in a molar ratio of 1:1 under stirring at 40 ℃ for 4h to obtain a polyamic acid resin solution with a solid content of 20%. Otherwise as in example 1.
Test examples
The polyimide films and graphite films obtained in the above examples and comparative examples were subjected to performance tests in accordance with the following methods, and the test results are shown in table 1 below.
Polyimide film
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.
Degree of imidization of gel film: and (3) calculating the absorbance ratio between the symmetrical stretching vibration band of the imine carbonyl group and the benzene ring framework stretching vibration band as an internal standard.
Birefringence: the birefringence of the polyimide film was measured using a refractive index and film thickness measuring system (model 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 ℃ C., and the measured "(value of refractive index in TE mode) - (value of refractive index in TM mode)" was used as the birefringence)
Graphite film
Mechanical properties: the artificial graphite film thus produced was evaluated for tensile strength and elongation at break according to the method specified in astm d882, and tested using a universal tensile machine.
Thermal diffusivity: the measuring instrument is a diffusion method heat conduction instrument LFA467 produced by Germany Chinescen; the testing temperature is room temperature; the test mode is In-Plane; the light spot is 14 mm; the protective gas is nitrogen.
Table 1 performance test results of polyimide films and graphite films obtained in examples and comparative examples
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 (9)
1. The polyimide film is characterized by being obtained by polymerizing pyromellitic dianhydride, 4' -diaminodiphenyl ether and a second diamine monomer accounting for 1-50 mol% of the diamine monomer, wherein the second diamine monomer is a diamine monomer containing a nitrogen heterocyclic ring.
2. The polyimide film according to claim 1, wherein the diamine monomer containing a nitrogen heterocycle is selected from the group consisting of imidazole-, pyridine-, pyrazine-and pyrimidine-containing diamine monomers.
3. The polyimide film according to claim 2, wherein the imidazole-containing diamine monomer is one or two selected from the group consisting of 2- (4-aminophenyl) -5-aminobenzimidazole, 2 '-bis (4-aminophenyl) -5,5' -bibenzimidazole, and 1, 4-bis (5 '-aminobenzimidazole-2' -) benzene.
4. The polyimide film of claim 2 wherein the pyridine-containing diamine monomer is selected from the group consisting of 2, 5-bis (4-aminophenyl) pyridine and 2- (4-aminophenyl) -5-aminopyridine.
5. The polyimide film of claim 2 wherein the pyrimidine-containing diamine monomer is selected from the group consisting of 2, 5-bis (4-aminophenyl) pyrimidine and 2- (4-aminophenyl) -5-pyrimidinamine.
6. The polyimide film of claim 2, wherein the pyrazine-containing diamine monomer is 2, 5-bis (4-aminophenyl) pyrazine.
7. The polyimide film according to any one of claims 1 to 6, wherein the polyimide film is prepared by a method comprising the steps of:
s1, adding pyromellitic dianhydride into an organic solvent containing 4,4' -diaminodiphenyl ether and a second diamine monomer, and carrying out polymerization reaction to obtain polyamide acid slurry;
s2, adding the calcium-containing compound inorganic filler into an organic solvent, and uniformly dispersing to obtain calcium-containing compound slurry; adding transition metal oxide inorganic filler into an organic solvent, and uniformly dispersing to obtain slurry containing transition metal oxide;
s3, mixing the polyamic acid slurry with the calcium compound slurry and the transition metal oxide-containing slurry, filtering and defoaming to obtain mixed resin;
s4, casting and coating the mixed resin, removing part of the solvent to obtain a polyamic acid gel film, and performing biaxial tension and thermal imidization treatment to obtain the polyimide film.
8. The polyimide film according to claim 7, wherein the organic solvent is one or more selected from the group consisting of N-methylpyrrolidone, dimethylsulfoxide, N-dimethylformamide and N, N-dimethylacetamide.
9. A graphite film obtained by carbonizing the polyimide film according to any one of claims 1 to 8 and baking the film at a high temperature.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113717524A (en) * | 2021-08-31 | 2021-11-30 | 安徽国风塑业股份有限公司 | Polyimide film for preparing graphite film and preparation method thereof |
| CN115974067A (en) * | 2023-01-13 | 2023-04-18 | 富优特(山东)新材料科技有限公司 | High-thermal-conductivity graphite film of pyridine ring modified polyimide and preparation method thereof |
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