CN114196063A - Low-dielectric polyimide film and preparation method thereof - Google Patents
Low-dielectric polyimide film and preparation method thereof Download PDFInfo
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- CN114196063A CN114196063A CN202111516368.XA CN202111516368A CN114196063A CN 114196063 A CN114196063 A CN 114196063A CN 202111516368 A CN202111516368 A CN 202111516368A CN 114196063 A CN114196063 A CN 114196063A
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000178 monomer Substances 0.000 claims abstract description 78
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 39
- 150000004985 diamines Chemical class 0.000 claims abstract description 39
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000011347 resin Substances 0.000 claims abstract description 35
- 229920005989 resin Polymers 0.000 claims abstract description 35
- 239000011259 mixed solution Substances 0.000 claims abstract description 29
- 238000005266 casting Methods 0.000 claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 24
- 239000002096 quantum dot Substances 0.000 claims abstract description 23
- 239000004952 Polyamide Substances 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 21
- 229920002647 polyamide Polymers 0.000 claims abstract description 21
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 9
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 9
- 239000004088 foaming agent Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 239000000758 substrate Substances 0.000 claims abstract description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 30
- 239000006185 dispersion Substances 0.000 claims description 19
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 16
- 229910021389 graphene Inorganic materials 0.000 claims description 14
- 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 description 10
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- WUPRYUDHUFLKFL-UHFFFAOYSA-N 4-[3-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(OC=2C=CC(N)=CC=2)=C1 WUPRYUDHUFLKFL-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
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- 238000007710 freezing Methods 0.000 claims description 3
- 230000008014 freezing Effects 0.000 claims description 3
- 239000003361 porogen Substances 0.000 claims description 3
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 claims description 2
- LBPVOEHZEWAJKQ-UHFFFAOYSA-N 3-[4-(3-aminophenoxy)phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 LBPVOEHZEWAJKQ-UHFFFAOYSA-N 0.000 claims description 2
- FYYYKXFEKMGYLZ-UHFFFAOYSA-N 4-(1,3-dioxo-2-benzofuran-5-yl)-2-benzofuran-1,3-dione Chemical compound C=1C=C2C(=O)OC(=O)C2=CC=1C1=CC=CC2=C1C(=O)OC2=O FYYYKXFEKMGYLZ-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- PGGDRKNQBAILPU-UHFFFAOYSA-N 4-[3-[4-amino-2-(trifluoromethyl)phenoxy]phenoxy]-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC(N)=CC=C1OC1=CC=CC(OC=2C(=CC(N)=CC=2)C(F)(F)F)=C1 PGGDRKNQBAILPU-UHFFFAOYSA-N 0.000 claims description 2
- GCJYASPNRCBMLH-UHFFFAOYSA-N 4-[3-[4-amino-3-(trifluoromethyl)phenoxy]phenoxy]-2-(trifluoromethyl)aniline Chemical compound C1=C(C(F)(F)F)C(N)=CC=C1OC1=CC=CC(OC=2C=C(C(N)=CC=2)C(F)(F)F)=C1 GCJYASPNRCBMLH-UHFFFAOYSA-N 0.000 claims description 2
- HHLMWQDRYZAENA-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropan-2-yl]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)(C(F)(F)F)C(F)(F)F)C=C1 HHLMWQDRYZAENA-UHFFFAOYSA-N 0.000 claims description 2
- KMKWGXGSGPYISJ-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1 KMKWGXGSGPYISJ-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 claims description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 230000009477 glass transition Effects 0.000 abstract description 3
- 238000004891 communication Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 238000003825 pressing Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- BIXGISJFDUHZEB-UHFFFAOYSA-N 2-[9,9-bis(4-methylphenyl)fluoren-2-yl]-9,9-bis(4-methylphenyl)fluorene Chemical compound C1=CC(C)=CC=C1C1(C=2C=CC(C)=CC=2)C2=CC(C=3C=C4C(C5=CC=CC=C5C4=CC=3)(C=3C=CC(C)=CC=3)C=3C=CC(C)=CC=3)=CC=C2C2=CC=CC=C21 BIXGISJFDUHZEB-UHFFFAOYSA-N 0.000 description 6
- 239000004642 Polyimide Substances 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000004377 microelectronic Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004427 diamine group Chemical group 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- 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
- 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
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/009—Use of pretreated compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
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Abstract
The invention discloses a low dielectric polyimide film and a preparation method thereof, and the low dielectric polyimide film comprises the following steps: s1, carrying out polymerization reaction on the aminated graphene quantum dot powder, the diamine monomer and the dicarboxylic anhydride monomer in an organic solvent, and then adding a pore-foaming agent to uniformly mix to obtain a polyamide acid resin mixed solution; s2, defoaming the polyamic acid resin mixed solution, and casting the polyamic acid resin mixed solution on a substrate to form a self-supporting film; s3, longitudinally stretching the self-supporting film, then performing thermal imidization treatment, and transversely stretching the self-supporting film while performing thermal imidization to obtain the low dielectric polyimide film. The invention can obtain the polyimide film with low dielectric constant, good mechanical property, high glass transition temperature and high thermal stability, and can be applied to electronic equipment of high-frequency communication.
Description
Technical Field
The invention relates to the technical field of polyimide materials, in particular to a low dielectric polyimide film and a preparation method thereof.
Background
In recent years, with the rapid development of the downstream electronic industry, the smart terminal industry is developing rapidly towards lightness, thinness and miniaturization, the antenna manufacturing material in 4G era adopts a PI film, and in the face of higher signal transmission requirements in 5G era, a mobile phone antenna material with lower dielectric constant and dielectric loss is required to meet the data transmission speed and quality, and the MPI has processing capability comparable to LCP and lower cost in 5G signal processing.
In order to meet the requirements of the development of microelectronic technology on products, reducing the dielectric constant of interlayer materials becomes an important means for reducing the signal delay time. However, the original silicon dioxide (dielectric constant is about 4.3) and the common polyimide material (dielectric constant is about 3.4) have been difficult to meet the development requirements of the microelectronic technology at the present stage.
However, polyimide itself has excellent heat resistance, mechanical properties, chemical stability, radiation resistance and good dielectric properties, and is an ideal interlayer material. Therefore, the development of new low dielectric polyimides has become a research hotspot in the field by reducing the dielectric constant of the polyimides, and is also one of the key technologies for the development of microelectronic products.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a low dielectric polyimide film and a preparation method thereof.
The invention provides a preparation method of a low dielectric polyimide film, which comprises the following steps:
s1, carrying out polymerization reaction on the aminated graphene quantum dot powder, the diamine monomer and the dicarboxylic anhydride monomer in an organic solvent, and then adding a pore-foaming agent to uniformly mix to obtain a polyamide acid resin mixed solution;
s2, defoaming the polyamic acid resin mixed solution, and casting the polyamic acid resin mixed solution on a substrate to form a self-supporting film;
s3, longitudinally stretching the self-supporting film, then performing thermal imidization treatment, and transversely stretching the self-supporting film while performing thermal imidization to obtain the low dielectric polyimide film.
Preferably, the ratio of the aminated graphene quantum dot powder to the organic solvent is (5-50) mg: 1L; the molar ratio of the diamine monomer to the dicarboxylic anhydride monomer is 1: (0.9 to 1.1); the mass ratio of the sum of the diamine monomer and the dicarboxylic anhydride monomer to the organic solvent is (1.5-2.5): 10; the viscosity of the polyamic acid resin mixed solution is 100-200 Pa & S.
Preferably, the mass of the pore-foaming agent accounts for 5-20% of the sum of the mass of the aminated graphene quantum dot powder, the diamine monomer and the dicarboxylic anhydride monomer.
Preferably, the porogen is 1, 2-dimethoxyethane.
Preferably, the diamine monomer is at least one of 4,4 '-diaminodiphenyl ether, 3,4' -diaminodiphenyl ether, 1, 3-bis (4 '-aminophenoxy) benzene, 1, 4-bis (3' -aminophenoxy) benzene, 1, 3-bis (2-trifluoromethyl-4-aminophenoxy) benzene, 1, 3-bis (3-trifluoromethyl-4-aminophenoxy) benzene, 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane;
the binary anhydride monomer is at least one of 3,3',4,4' -biphenyl tetracarboxylic dianhydride, 2,3,3',4' -biphenyl tetracarboxylic dianhydride, 3,3',4,4' -diphenyl ether tetracarboxylic dianhydride, 2,3,3',4' -diphenyl ether tetracarboxylic dianhydride, 4,4'- (hexafluoro-isopropenyl) tetracarboxylic dianhydride, 4,4' - (4,4 '-isopropyl-diphenoxy) tetracarboxylic dianhydride and 4,4' -diphenyl sulfone tetracarboxylic dianhydride;
the organic solvent is at least one of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran and acetone.
Preferably, the preparation method of the aminated graphene quantum dot powder comprises the following steps: and carrying out ultrasonic treatment, freezing treatment and cell disruption treatment on the graphene oxide aqueous dispersion, mixing the graphene oxide aqueous dispersion with an ammonia water solution, carrying out hydrothermal reaction, carrying out solid-liquid separation, and removing impurities and drying the obtained solid product to obtain the graphene oxide aqueous dispersion.
Preferably, the temperature of the hydrothermal reaction is 100-180 ℃, and the reaction time is 2-8 h; the mass fraction of the graphene oxide aqueous dispersion is 500-1000 mg/L; the volume ratio of the graphene oxide aqueous dispersion to the ammonia water solution is (2-6): 1.
preferably, the concentration of the ammonia water solution is 25-30%.
The graphene oxide can be prepared by a conventional hummers method or a modified hummers method. The method specifically comprises the following steps:
(1) adding NaNO3(0.25g) and H2SO4(25mL) was added to a dry beaker and then placed in an ice bath. When the temperature of the system dropped below 5.0 ℃, graphite powder (0.50g) was added and stirred for 30 minutes. Thereafter, KMnO was slowly added4(3.0 g). Stirring for 2 hours, and keeping the temperature below 5.0 ℃. The beaker was then transferred to a 35 ℃ water bath and stirring was continued for 2 hours. Then slowly dropping the reaction product into a beaker filled with deionized water (100mL), and keeping continuous stirring in the dropping process;
(2) the temperature is increased to 95 ℃ and kept for 30 minutes, then the obtained brownish black product is quickly poured into 120mL of ice water to reduce the temperature and stop the reaction, after standing for 5 minutes, a proper amount of hydrogen peroxide (30 percent, about 30mL) is added, and stirring is kept until the color of the solution is changed from brown to golden yellow;
(3) centrifuging, washing the precipitate with HCl solution (1: 10 by volume) until the supernatant is free of SO4 2-Ion (Using BaCl)2Solution measurement), then centrifuged, and the precipitate was washed with deionized water until the pH of the supernatant was 7.0;
(4) and transferring the precipitate to a beaker, adding a certain amount of deionized water, ultrafiltering to remove redundant ions, immersing the precipitate in the deionized water for 3-4 days to remove excessive impurities, then carrying out ultrasonic treatment for 30 minutes, finally drying the obtained product in a 50 ℃ oven for 48 hours, and uniformly dispersing the obtained solid in the deionized water to obtain the yellowish-brown GO (graphene oxide) water dispersion with the concentration of 0.50 mg/mL.
Preferably, in S2, the casting temperature is 130-180 ℃ and the casting speed is 3-6 m/min.
Preferably, in S3, the thermal imidization treatment includes: heating from room temperature to 290-320 ℃ in a stepwise manner to perform thermal imidization; preferably, in S3, the thermal imidization treatment includes: raising the temperature from room temperature to 60-80 ℃, preserving heat for 0.5-1 h, raising the temperature to 100-130 ℃, preserving heat for 0.5-1 h, raising the temperature to 160-180 ℃, preserving heat for 0.5-1 h, raising the temperature to 200-220 ℃, preserving heat for 0.5-1 h, raising the temperature to 250-270 ℃, preserving heat for 0.5-1 h, raising the temperature to 290-320 ℃, and preserving heat for 0.5-1 h.
Preferably, in S3, the speed of longitudinal stretching is 1.6-2.1 m/min, and the stretching ratio is 0.9-1.2.
Preferably, in S3, the amplitude modulation of the transverse stretching is 280-310 mm.
A low dielectric polyimide film is obtained by the preparation method.
The invention has the following beneficial effects:
the invention provides a low dielectric polyimide film and a preparation method thereof, wherein micromolecule 1, 2-dimethoxyethane is used as a pore-foaming agent, the pore-foaming agent has the characteristics of good mixing property with polyamic acid, low depolymerization temperature and stable property, air pores with uniform size and smaller pore diameter can be easily obtained by pore-foaming after imidization, and the polyimide film with low dielectric constant can be obtained; the aminated graphene quantum dots (af-GODs) are used as additives, the af-GODs have large specific surface area, the structure of the af-GODs is a net structure, the af-GODs contain diamine structures after modification, the volume and the structural integrity of polymers can be greatly improved after polycondensation, the mechanical property of the polyimide film can be improved, the aminated graphene quantum dots have large side groups and relatively rigid structures, and the glass transition temperature and the thermal stability of materials can be improved, so that the polyimide film with low dielectric constant, good mechanical property, high glass transition temperature and thermal stability is obtained, the polyimide film can be applied to electronic equipment for high-frequency communication, and the related problems of signal delay and the like which can occur in the 5G use of the existing polyimide film are solved.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
In the following examples and comparative examples, aminated graphene quantum dot powders were prepared as follows:
carrying out ultrasonic treatment, freezing treatment and cell disruption treatment on GO water dispersion (90mL and 500mg/L), mixing with ammonia water (27mL and 25%) solution, placing the obtained solution into a polytetrafluoroethylene (Teflon) autoclave with the capacity of 150mL, carrying out hydrothermal reaction at the temperature of 160 ℃ for 1h, cooling to room temperature, carrying out suction filtration by using a 0.22um filter membrane, washing the obtained filter cake with deionized water for several times, dispersing in the deionized water to obtain af-GQDs water dispersion, heating the af-GQDs water dispersion at the temperature of 65 ℃ to remove excessive NH3And then dried to remove water to obtain af-GQDs powder.
The preparation method of the GO water dispersion comprises the following steps:
(1) adding NaNO3(0.25g) and H2SO4(25mL) was added to a dry beaker and then placed in an ice bath. When the temperature of the system dropped below 5.0 ℃, graphite powder (0.50g) was added and stirred for 30 minutes. Thereafter, KMnO was slowly added4(3.0 g). Stirring for 2 hours, and keeping the temperature below 5.0 ℃. The beaker was then transferred to a 35 ℃ water bath and stirring was continued for 2 hours. Then slowly dropping the reaction product into a beaker filled with deionized water (100mL), and keeping continuous stirring in the dropping process;
(2) the temperature is increased to 95 ℃ and kept for 30 minutes, then the obtained brownish black product is quickly poured into 120mL of ice water to reduce the temperature and stop the reaction, after standing for 5 minutes, a proper amount of hydrogen peroxide (30 percent, about 30mL) is added, and stirring is kept until the color of the solution is changed from brown to golden yellow;
(3) centrifuging, washing the precipitate with HCl solution (1: 10 by volume) until the supernatant is free of SO4 2-Ion (Using BaCl)2Solution measurement), then centrifuged, and the precipitate was washed with deionized water until the pH of the supernatant was 7.0;
(4) and transferring the precipitate to a beaker, adding a certain amount of deionized water, ultrafiltering to remove redundant ions, immersing the precipitate in the deionized water for 3-4 days to remove excessive impurities, then carrying out ultrasonic treatment for 30 minutes, finally drying the obtained product in a 50 ℃ oven for 48 hours, and uniformly dispersing the obtained solid in the deionized water to obtain the yellowish-brown GO (graphene oxide) water dispersion with the concentration of 0.50 mg/mL.
Example 1
A preparation method of a low dielectric polyimide film comprises the following steps:
s1, dissolving a diamine monomer in N, N-dimethylacetamide, adding aminated graphene quantum dot powder for uniform dispersion, adding a dicarboxylic anhydride monomer for polymerization reaction in batches, adding 1, 2-dimethoxyethane for uniform mixing after the reaction is finished, and obtaining a polyamide acid resin mixed solution with the viscosity of 100-200 Pa & S, wherein the ratio of aminated graphene quantum dot powder to N, N-dimethylacetamide is 5 mg: 1L, diamine monomer consisting of BDAF and RODA according to a molar ratio of 1:1, dicarboxylic anhydride monomer consisting of PMDA and BPADA according to a molar ratio of 1:1, and diamine monomer and dicarboxylic anhydride monomer according to a molar ratio of 1:1, the mass ratio of the sum of the diamine monomer and the dicarboxylic anhydride monomer to the N, N-dimethylacetamide is 1: the mass of the 4, 1, 2-dimethoxyethane accounts for 13% of the sum of the mass of the aminated graphene quantum dot powder, the diamine monomer and the dicarboxylic anhydride monomer;
s2, placing the polyamide acid resin mixed solution in an oven for vacuum defoaming for 12h, pressing the polyamide acid resin mixed solution into a die head through a pipeline, adjusting the thickness of the die head, and uniformly casting the resin onto a mirror surface steel belt to form a self-supporting film, wherein the casting temperature is 150 ℃ and the casting speed is 5 m/min;
s3, longitudinally stretching the self-supporting film, wherein the longitudinal stretching speed is 2m/min, the stretching ratio is 1, then drawing and pressing the self-supporting film into a splint, and entering an imidization furnace for thermal imidization, wherein the thermal imidization comprises the following specific steps: and (3) heating from room temperature to 70 ℃, preserving heat for 40min, heating to 120 ℃, preserving heat for 40min, heating to 170 ℃, preserving heat for 40min, heating to 210 ℃, preserving heat for 40min, heating to 260 ℃, preserving heat for 40min, heating to 300 ℃, preserving heat for 40min, performing transverse stretching while performing thermal imidization, wherein the amplitude modulation of the transverse stretching is 300mm, and obtaining the low dielectric polyimide film.
Example 2
A preparation method of a low dielectric polyimide film comprises the following steps:
s1, dissolving a diamine monomer in N, N-dimethylacetamide, adding aminated graphene quantum dot powder for uniform dispersion, adding a dicarboxylic anhydride monomer for polymerization reaction in batches, adding 1, 2-dimethoxyethane for uniform mixing after the reaction is finished, and obtaining a polyamide acid resin mixed solution with the viscosity of 100-200 Pa & S, wherein the ratio of aminated graphene quantum dot powder to N, N-dimethylacetamide is 50 mg: 1L, diamine monomer consisting of BDAF and RODA according to a molar ratio of 1:1, dicarboxylic anhydride monomer consisting of PMDA and BPADA according to a molar ratio of 1:1, and diamine monomer and dicarboxylic anhydride monomer according to a molar ratio of 1: 0.9, the mass ratio of the sum of the diamine monomer and the dicarboxylic anhydride monomer to the N, N-dimethylacetamide is 1: the mass of the 4, 1, 2-dimethoxyethane accounts for 13% of the sum of the mass of the aminated graphene quantum dot powder, the diamine monomer and the dicarboxylic anhydride monomer;
s2, placing the polyamide acid resin mixed solution in an oven for vacuum defoaming for 12h, pressing the polyamide acid resin mixed solution into a die head through a pipeline, adjusting the thickness of the die head, and uniformly casting the resin onto a mirror surface steel belt to form a self-supporting film, wherein the casting temperature is 150 ℃ and the casting speed is 5 m/min;
s3, longitudinally stretching the self-supporting film, wherein the longitudinal stretching speed is 2m/min, the stretching ratio is 1, then drawing and pressing the self-supporting film into a splint, and entering an imidization furnace for thermal imidization, wherein the specific steps of the thermal imidization are as follows: raising the temperature from room temperature to 60 ℃, preserving heat for 1h, raising the temperature to 100 ℃, preserving heat for 1h, raising the temperature to 160 ℃, preserving heat for 1h, raising the temperature to 200 ℃, preserving heat for 1h, raising the temperature to 250 ℃, preserving heat for 1h, raising the temperature to 290 ℃, preserving heat for 1h, performing transverse stretching while performing thermal imidization, wherein the amplitude modulation of the transverse stretching is 300mm, and obtaining the low dielectric polyimide film.
Example 3
A preparation method of a low dielectric polyimide film comprises the following steps:
s1, dissolving a diamine monomer in N, N-dimethylacetamide, adding aminated graphene quantum dot powder for uniform dispersion, adding a dicarboxylic anhydride monomer for polymerization reaction in batches, adding 1, 2-dimethoxyethane for uniform mixing after the reaction is finished, and obtaining a polyamide acid resin mixed solution with the viscosity of 100-200 Pa & S, wherein the ratio of aminated graphene quantum dot powder to N, N-dimethylacetamide is 20 mg: 1L, diamine monomer consisting of BDAF and RODA according to a molar ratio of 1:1, dicarboxylic anhydride monomer consisting of PMDA and BPADA according to a molar ratio of 1:1, and diamine monomer and dicarboxylic anhydride monomer according to a molar ratio of 1: 0.9, the mass ratio of the sum of the diamine monomer and the dicarboxylic anhydride monomer to the N, N-dimethylacetamide is 1: the mass of the 4, 1, 2-dimethoxyethane accounts for 13% of the sum of the mass of the aminated graphene quantum dot powder, the diamine monomer and the dicarboxylic anhydride monomer;
s2, placing the polyamide acid resin mixed solution in an oven for vacuum defoaming for 12h, pressing the polyamide acid resin mixed solution into a die head through a pipeline, adjusting the thickness of the die head, and uniformly casting the resin onto a mirror surface steel belt to form a self-supporting film, wherein the casting temperature is 150 ℃ and the casting speed is 5 m/min;
s3, longitudinally stretching the self-supporting film, wherein the longitudinal stretching speed is 2m/min, the stretching ratio is 1, then drawing and pressing the self-supporting film into a splint, and entering an imidization furnace for thermal imidization, wherein the specific steps of the thermal imidization are as follows: raising the temperature from room temperature to 80 ℃, preserving heat for 0.5h, raising the temperature to 130 ℃, preserving heat for 0.5h, raising the temperature to 180 ℃, preserving heat for 0.5h, raising the temperature to 220 ℃, preserving heat for 0.5h, raising the temperature to 270 ℃, preserving heat for 0.5h, raising the temperature to 320 ℃, preserving heat for 0.5h, performing transverse stretching while performing thermal imidization, wherein the amplitude modulation of the transverse stretching is 300mm, and obtaining the low dielectric polyimide film.
The performance of the film was tested as follows:
and (3) thickness testing: testing the thickness of each part of the film by using a film thickness tester, and obtaining the thickness of the film by taking the average value;
elongation at break, tensile strength: stretching a film sample by using a tensile strength tester, recording the maximum tensile stress when the film is broken as the tensile strength in unit MPa, and simultaneously reading the breaking elongation of the film from the tester;
modulus of elasticity: testing the elastic modulus of the film by using an elastic modulus tester;
dielectric constant and dielectric loss: the polyimide solution was coated on a polytetrafluoroethylene sheet, and the dielectric constant and dielectric loss of the film were measured at 50GHz in a dielectric constant measuring instrument.
The low dielectric polyimide film obtained above had a thickness of 35. + -.5. mu.m, a tensile strength of 150MPa, an elongation at break of 17%, an elastic modulus of 4.2GPa, a dielectric constant of 2.5 and a dielectric dissipation factor of 0.003.
Comparative example 1
Comparative example 1 differs from example 3 only in that: the method is characterized in that amination graphene quantum dot powder and 1, 2-dimethoxyethane are not added, and the method comprises the following specific steps:
a preparation method of a polyimide film comprises the following steps:
s1, dissolving diamine monomer in N, N-dimethylacetamide, and adding dicarboxylic anhydride monomer in batches for polymerization reaction to obtain a polyamide acid resin mixed solution with the viscosity of 100-200 Pa & S, wherein the diamine monomer is composed of BDAF and RODA according to the molar ratio of 1:1, the dicarboxylic anhydride monomer is composed of PMDA and BPADA according to the molar ratio of 1:1, and the molar ratio of the diamine monomer to the dicarboxylic anhydride monomer is 1: 0.9, the mass ratio of the sum of the diamine monomer and the dicarboxylic anhydride monomer to the N, N-dimethylacetamide is 1: 4;
s2, placing the polyamide acid resin mixed solution in an oven for vacuum defoaming for 12h, pressing the polyamide acid resin mixed solution into a die head through a pipeline, adjusting the thickness of the die head, and uniformly casting the resin onto a mirror surface steel belt to form a self-supporting film, wherein the casting temperature is 150 ℃ and the casting speed is 5 m/min;
s3, longitudinally stretching the self-supporting film, wherein the longitudinal stretching speed is 2m/min, the stretching ratio is 1, then drawing and pressing the self-supporting film into a splint, and entering an imidization furnace for thermal imidization, wherein the specific steps of the thermal imidization are as follows: raising the temperature from room temperature to 80 ℃, preserving heat for 0.5h, raising the temperature to 130 ℃, preserving heat for 0.5h, raising the temperature to 180 ℃, preserving heat for 0.5h, raising the temperature to 220 ℃, preserving heat for 0.5h, raising the temperature to 270 ℃, preserving heat for 0.5h, raising the temperature to 320 ℃, preserving heat for 0.5h, performing transverse stretching while performing thermal imidization, wherein the amplitude modulation of the transverse stretching is 300mm, and obtaining the low dielectric polyimide film.
The low dielectric polyimide film prepared by the method has the thickness of 35 +/-5 mu m, the tensile strength of 100MPa, the elongation at break of 10 percent, the elastic modulus of 2.5GPa, the dielectric constant of 3.0 and the dielectric loss factor of 0.005.
Comparative example 2
Comparative example 2 differs from example 3 only in that: 1, 2-dimethoxyethane was not added, and the details were as follows:
a preparation method of a low dielectric polyimide film comprises the following steps:
s1, dissolving a diamine monomer in N, N-dimethylacetamide, adding aminated graphene quantum dot powder to disperse uniformly, adding a dicarboxylic anhydride monomer in batches to perform polymerization reaction, and obtaining a polyamide acid resin mixed solution with the viscosity of 100-200 Pa · S, wherein the ratio of the aminated graphene quantum dot powder to the N, N-dimethylacetamide is 20 mg: 1L, diamine monomer consisting of BDAF and RODA according to a molar ratio of 1:1, dicarboxylic anhydride monomer consisting of PMDA and BPADA according to a molar ratio of 1:1, and diamine monomer and dicarboxylic anhydride monomer according to a molar ratio of 1: 0.9, the mass ratio of the sum of the diamine monomer and the dicarboxylic anhydride monomer to the N, N-dimethylacetamide is 1: 4;
s2, placing the polyamide acid resin mixed solution in an oven for vacuum defoaming for 12h, pressing the polyamide acid resin mixed solution into a die head through a pipeline, adjusting the thickness of the die head, and uniformly casting the resin onto a mirror surface steel belt to form a self-supporting film, wherein the casting temperature is 150 ℃ and the casting speed is 5 m/min;
s3, longitudinally stretching the self-supporting film, wherein the longitudinal stretching speed is 2m/min, the stretching ratio is 1, then drawing and pressing the self-supporting film into a splint, and entering an imidization furnace for thermal imidization, wherein the specific steps of the thermal imidization are as follows: raising the temperature from room temperature to 80 ℃, preserving heat for 0.5h, raising the temperature to 130 ℃, preserving heat for 0.5h, raising the temperature to 180 ℃, preserving heat for 0.5h, raising the temperature to 220 ℃, preserving heat for 0.5h, raising the temperature to 270 ℃, preserving heat for 0.5h, raising the temperature to 320 ℃, preserving heat for 0.5h, performing transverse stretching while performing thermal imidization, wherein the amplitude modulation of the transverse stretching is 300mm, and obtaining the low dielectric polyimide film.
The low dielectric polyimide film obtained above had a thickness of 35. + -.5. mu.m, a tensile strength of 160MPa, an elongation at break of 17%, an elastic modulus of 4.4GPa, a dielectric constant of 2.9 and a dielectric loss factor of 0.004.
Comparative example 3
Comparative example 3 differs from example 3 only in that: the method is characterized in that no aminated graphene quantum dot powder is added, and specifically comprises the following steps:
a preparation method of a low dielectric polyimide film comprises the following steps:
s1, dissolving diamine monomer in N, N-dimethylacetamide, adding dicarboxylic anhydride monomer in batches for polymerization, adding 1, 2-dimethoxyethane after the reaction is finished, and mixing uniformly to obtain a polyamide acid resin mixed solution with the viscosity of 100-200 Pa.s, wherein the diamine monomer is composed of BDAF and RODA according to the molar ratio of 1:1, the dicarboxylic anhydride monomer is composed of PMDA and BPADA according to the molar ratio of 1:1, and the molar ratio of the diamine monomer to the dicarboxylic anhydride monomer is 1: 0.9, the mass ratio of the sum of the diamine monomer and the dicarboxylic anhydride monomer to the N, N-dimethylacetamide is 1: the mass of the 4, 1, 2-dimethoxyethane accounts for 13 percent of the sum of the mass of the diamine monomer and the mass of the dicarboxylic anhydride monomer;
s2, placing the polyamide acid resin mixed solution in an oven for vacuum defoaming for 12h, pressing the polyamide acid resin mixed solution into a die head through a pipeline, adjusting the thickness of the die head, and uniformly casting the resin onto a mirror surface steel belt to form a self-supporting film, wherein the casting temperature is 150 ℃ and the casting speed is 5 m/min;
s3, longitudinally stretching the self-supporting film, wherein the longitudinal stretching speed is 2m/min, the stretching ratio is 1, then drawing and pressing the self-supporting film into a splint, and entering an imidization furnace for thermal imidization, wherein the specific steps of the thermal imidization are as follows: raising the temperature from room temperature to 80 ℃, preserving heat for 0.5h, raising the temperature to 130 ℃, preserving heat for 0.5h, raising the temperature to 180 ℃, preserving heat for 0.5h, raising the temperature to 220 ℃, preserving heat for 0.5h, raising the temperature to 270 ℃, preserving heat for 0.5h, raising the temperature to 320 ℃, preserving heat for 0.5h, carrying out transverse stretching while carrying out thermal imidization, wherein the amplitude modulation of the transverse stretching is 300mm, and obtaining the low dielectric polyimide film.
The low dielectric polyimide film obtained above had a thickness of 35. + -.5. mu.m, a tensile strength of 95MPa, an elongation at break of 10%, an elastic modulus of 2.5GPa, a dielectric constant of 2.5 and a dielectric dissipation factor of 0.003.
As can be seen from the comparison between example 3 and comparative examples 1 to 3, the use of the aminated graphene quantum dots and the porogen 1, 2-dimethoxyethane can reduce the dielectric property of the film and enhance the mechanical property of the film. The aminated graphene quantum dots have large and regular structures, so that the mechanical property of the film is greatly improved due to the introduction of the aminated graphene quantum dots, and the dielectricity of the film is reduced to a certain extent due to the introduction of large side groups; the introduction of the pore-foaming agent 1, 2-dimethoxyethane reduces the dielectric property of the film, and the small molecules are depolymerized at high temperature to generate bubble holes in the film, so that the dielectric property of the film is reduced.
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 preparation method of a low dielectric polyimide film is characterized by comprising the following steps:
s1, carrying out polymerization reaction on the aminated graphene quantum dot powder, the diamine monomer and the dicarboxylic anhydride monomer in an organic solvent, and then adding a pore-foaming agent to uniformly mix to obtain a polyamide acid resin mixed solution;
s2, defoaming the polyamic acid resin mixed solution, and casting the polyamic acid resin mixed solution on a substrate to form a self-supporting film;
s3, longitudinally stretching the self-supporting film, then performing thermal imidization treatment, and transversely stretching the self-supporting film while performing thermal imidization to obtain the low dielectric polyimide film.
2. The method for preparing the low dielectric polyimide film according to claim 1, wherein the ratio of the aminated graphene quantum dot powder to the organic solvent is (5-50) mg: 1L; the molar ratio of the diamine monomer to the dicarboxylic anhydride monomer is 1: (0.9 to 1.1); the mass ratio of the sum of the diamine monomer and the dicarboxylic anhydride monomer to the organic solvent is (1.5-2.5): 10; the viscosity of the polyamic acid resin mixed solution is 100-200 Pa & S.
3. The preparation method of the low dielectric polyimide film as claimed in claim 1, wherein the mass of the pore-forming agent is 5-20% of the sum of the mass of the aminated graphene quantum dot powder, the diamine monomer and the dicarboxylic anhydride monomer.
4. The method of claim 1, wherein the porogen is 1, 2-dimethoxyethane.
5. The method of preparing a low dielectric polyimide film according to claim 1, the diamine monomer is at least one of 4,4 '-diaminodiphenyl ether, 3,4' -diaminodiphenyl ether, 1, 3-bis (4 '-aminophenoxy) benzene, 1, 4-bis (3' -aminophenoxy) benzene, 1, 3-bis (2-trifluoromethyl-4-aminophenoxy) benzene, 1, 3-bis (3-trifluoromethyl-4-aminophenoxy) benzene, 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane and 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane;
the binary anhydride monomer is at least one of 3,3',4,4' -biphenyl tetracarboxylic dianhydride, 2,3,3',4' -biphenyl tetracarboxylic dianhydride, 3,3',4,4' -diphenyl ether tetracarboxylic dianhydride, 2,3,3',4' -diphenyl ether tetracarboxylic dianhydride, 4,4'- (hexafluoro-isopropenyl) tetracarboxylic dianhydride, 4,4' - (4,4 '-isopropyl-diphenoxy) tetracarboxylic dianhydride and 4,4' -diphenyl sulfone tetracarboxylic dianhydride;
the organic solvent is at least one of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran and acetone.
6. The method for preparing the low dielectric polyimide film according to claim 1, wherein the method for preparing the aminated graphene quantum dot powder comprises the following steps: and carrying out ultrasonic treatment, freezing treatment and cell disruption treatment on the graphene oxide aqueous dispersion, mixing the graphene oxide aqueous dispersion with an ammonia water solution, carrying out hydrothermal reaction, carrying out solid-liquid separation, and removing impurities and drying the obtained solid product to obtain the graphene oxide aqueous dispersion.
7. The method for preparing the low dielectric polyimide film according to claim 6, wherein the hydrothermal reaction is carried out at a temperature of 100 to 180 ℃ for 1 to 8 hours; the mass fraction of the graphene oxide aqueous dispersion is 500-1000 mg/L; the volume ratio of the graphene oxide aqueous dispersion to the ammonia water solution is (2-6): 1.
8. the method for preparing a low dielectric polyimide film according to claim 1, wherein the casting temperature is 130 to 180 ℃ and the casting speed is 3 to 6m/min in S2.
9. The method of preparing a low dielectric polyimide film according to claim 1, wherein the thermal imidization treatment is preferably performed in S3 by: heating from room temperature to 290-320 ℃ in a stepwise manner to perform thermal imidization; preferably, in S3, the thermal imidization treatment includes: raising the temperature from room temperature to 60-80 ℃, preserving heat for 0.5-1 h, raising the temperature to 100-130 ℃, preserving heat for 0.5-1 h, raising the temperature to 160-180 ℃, preserving heat for 0.5-1 h, raising the temperature to 200-220 ℃, preserving heat for 0.5-1 h, raising the temperature to 250-270 ℃, preserving heat for 0.5-1 h, raising the temperature to 290-320 ℃, and preserving heat for 0.5-1 h.
10. A low dielectric polyimide film obtained by the production method according to any one of claims 1 to 9.
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