CN117430949A - Polyimide film with high heat conduction and low thermal expansion coefficient and preparation method thereof - Google Patents
Polyimide film with high heat conduction and low thermal expansion coefficient and preparation method thereof Download PDFInfo
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000000945 filler Substances 0.000 claims abstract description 80
- 150000001412 amines Chemical class 0.000 claims abstract description 56
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims abstract description 40
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000003756 stirring Methods 0.000 claims abstract description 28
- 235000010290 biphenyl Nutrition 0.000 claims abstract description 20
- 239000004305 biphenyl Substances 0.000 claims abstract description 20
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims abstract description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 239000002798 polar solvent Substances 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 7
- 238000001291 vacuum drying Methods 0.000 claims abstract description 7
- 239000002070 nanowire Substances 0.000 claims description 61
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 44
- 239000000243 solution Substances 0.000 claims description 34
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 20
- 238000005266 casting Methods 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 17
- 238000011065 in-situ storage Methods 0.000 claims description 17
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052786 argon Inorganic materials 0.000 claims description 11
- 229920003257 polycarbosilane Polymers 0.000 claims description 11
- 239000002243 precursor Substances 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 10
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 10
- 238000005229 chemical vapour deposition Methods 0.000 claims description 9
- SICLLPHPVFCNTJ-UHFFFAOYSA-N 1,1,1',1'-tetramethyl-3,3'-spirobi[2h-indene]-5,5'-diol Chemical compound C12=CC(O)=CC=C2C(C)(C)CC11C2=CC(O)=CC=C2C(C)(C)C1 SICLLPHPVFCNTJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000003980 solgel method Methods 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- IFUXXUAAJBKDGO-UHFFFAOYSA-N 2,3,5-trimethylbenzene-1,4-diamine Chemical compound CC1=CC(N)=C(C)C(C)=C1N IFUXXUAAJBKDGO-UHFFFAOYSA-N 0.000 claims description 4
- OOSCJVXJXSUBJN-UHFFFAOYSA-N 2,5-ditert-butylbenzene-1,4-diamine Chemical compound CC(C)(C)C1=CC(N)=C(C(C)(C)C)C=C1N OOSCJVXJXSUBJN-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 4
- MJAVQHPPPBDYAN-UHFFFAOYSA-N 2,6-dimethylbenzene-1,4-diamine Chemical compound CC1=CC(N)=CC(C)=C1N MJAVQHPPPBDYAN-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000035484 reaction time Effects 0.000 abstract description 3
- 150000003949 imides Chemical class 0.000 abstract 2
- -1 firstly Chemical compound 0.000 abstract 1
- 238000010345 tape casting Methods 0.000 abstract 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 152
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 130
- 239000004642 Polyimide Substances 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 239000011231 conductive filler Substances 0.000 description 7
- 239000004952 Polyamide Substances 0.000 description 6
- 229920002647 polyamide Polymers 0.000 description 6
- 238000001035 drying Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- 235000011130 ammonium sulphate Nutrition 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- ZHNUHDYFZUAESO-UHFFFAOYSA-N formamide Substances NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/10—Silicon-containing compounds
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to the technical field of polyimide film preparation, and provides a polyimide film with high heat conduction and low thermal expansion coefficient and a preparation method thereof, wherein the polyimide film comprises the following components in parts by weight: 5-40 parts of organic amine modified heat conducting filler, 50-120 parts of polar solvent, 2-10 parts of biphenyl dianhydride, 2-12 parts of p-phenylenediamine and the preparation method of the polyimide film comprises the following steps: under the protection of nitrogen, firstly, biphenyl dianhydride and p-phenylenediamine are placed in a polar solvent, uniformly stirred for polycondensation reaction, the reaction temperature is 30-50 ℃, the reaction time is 30-60 minutes, then, organic amine modified heat-conducting filler is added, after stirring and ultrasonic defoaming, tape casting treatment is carried out, and finally, heating and curing treatment is carried out in a vacuum drying oven. The imide film prepared by the invention has the advantages of high heat conduction and low thermal expansion coefficient, and improves the comprehensive performance and application scene of the imide film.
Description
Technical Field
The invention relates to the field of polyimide materials, in particular to a polyimide film with high heat conduction and low thermal expansion coefficient and a preparation method thereof.
Background
Polyimide is a highly regular polymer, and has the characteristics of excellent chemical stability, wear resistance, flame retardance, high temperature resistance, low temperature resistance, corrosion resistance, radiation resistance and the like, and therefore, polyimide also exhibits excellent mechanical properties and dielectric properties, and is widely used in various fields due to the excellent properties. In the aerospace field, polyimides are used to make high temperature structural members, thermal insulation materials, and electronic components. In the microelectronics and nanotechnology fields, polyimides can be used to make high performance electronic devices and nanomaterials. In the field of liquid crystal displays, polyimide is used as an alignment agent and an encapsulation material. In addition, polyimide is also used in the fields of separation membranes, lasers, optical devices, etc., and in summary, polyimide is widely recognized as an engineering plastic having great potential due to its excellent properties and various application fields.
With the advancement of technology, polyimide has faced challenges in the service environment of high thermal conductivity and low expansion coefficient. In particular, because polyimide molecular chains have high regularity, and their inter-molecular interactions are strong, resulting in a slower heat conduction rate, there is a need to find a suitable method to improve the thermal conductivity. In addition, the highly ordered structure of polyimide molecular chain makes it expand or contract greatly under temperature change, and the expansion coefficient needs to be reduced by controlling the process microstructure and other modes. To overcome these challenges, researchers are conducting research through approaches such as introducing thermally conductive fillers, changing molecular structures, optimizing synthesis processes and material formulations. Although the above approaches can improve the thermal conductivity and reduce the thermal expansion coefficient of polyimide to some extent, certain challenges remain, mainly in: (1) The heat conducting performance still needs to be improved, and although the introduction of the heat conducting filler can increase the heat conducting performance of polyimide, the selection and the addition amount of the heat conducting filler still need to be further optimized so as to improve the heat conducting effect. (2) The difference of thermal expansion coefficients is larger, so that more suitable heat conducting filler needs to be searched for to reduce the difference of thermal expansion coefficients, for example, chinese patent publication No. CN113999414A discloses a particle shape guide with different particle diametersThe thermal filler can enhance polyimide, so that the heat conducting property of polyimide can be improved to a certain extent, but the spherical granular heat conducting filler has a certain limitation in reducing the thermal expansion coefficient. (3) Weak interfacial bonding is another problem, and the heat conductive filler tends to be difficult to form firm interfacial bonding with polyimide, which may result in a decrease in heat conductive effect, as disclosed in chinese patent publication No. CN114058049a, which discloses that the silane coupling agent improves polyimide and the heat conductive filler SiO 2 Which may reduce the coefficient of thermal expansion of the polyimide to some extent. Therefore, future research needs to be conducted to solve these problems, and approaches such as improving selection and addition modes of the heat conducting filler, optimizing interface bonding and the like are needed to further improve the heat conducting property of polyimide and reduce the thermal expansion coefficient, so that a wider field and higher performance requirements can be provided for polyimide application.
Disclosure of Invention
The invention aims to provide a polyimide film with high heat conduction and low thermal expansion coefficient and a preparation method thereof, and solves the problems of low heat conductivity and high thermal expansion coefficient of the existing polyimide.
In order to achieve the above object, the present invention provides the following technical solutions:
the polyimide film with high heat conduction and low thermal expansion coefficient comprises the following components in parts by weight: 5-40 parts of organic amine modified heat conducting filler, 50-120 parts of polar solvent, 2-10 parts of biphenyl dianhydride and 2-12 parts of p-phenylenediamine.
Further, the organic amine is one or more of triethylamine, butylamine, isopropylamine, triethanolamine and ethylenediamine.
Further, the heat conducting filler is a micro-nano three-dimensional netlike SiC whisker-SiC nanowire.
Further, the preparation method of the heat conducting filler comprises the following steps: the preparation method comprises the steps of firstly preparing an SiC whisker preform by a sol-gel method, uniformly mixing 4-35 parts of SiC whisker, 20-30 parts of silicon solution and 20-30 parts of sodium dodecyl sulfonate by weight, adding 1-2.5 parts of ammonium persulfate, uniformly stirring, performing gel reaction to generate a blank, heating at 400-500 ℃ for 2h under an air environment to obtain the SiC whisker preform, then dipping 1.5-5 mol/L of catalyst solution on the SiC whisker preform, then at 1000 ℃, taking polycarbosilane as a precursor, taking argon as a carrier, and performing in-situ growth of SiC nanowire on the SiC whisker preform by a chemical vapor deposition method for 30-180 min to obtain the micro-nano three-dimensional network SiC whisker-SiC nanowire heat-conducting filler.
Further, the catalyst is one or a mixture of more of ferric chloride, ferric nitrate and ferric sulfate.
Further, the diameter of the SiC whisker is 1.5-5 mu m, the length is 15-30 mu m, the diameter of the SiC nanowire is 20-60 nm, the length is 600-5000 nm, and the mass ratio of the SiC whisker to the SiC nanowire is (5-20): 1.
Further, the preparation method of the organic amine modified heat conducting filler comprises the following steps: under the water bath condition of 50-80 ℃, 5-40 parts of heat conducting filler is added into 4-20 parts of organic amine in parts by weight, and is added into 40-80 parts of ethanol solvent, and the mixture is stirred for 2-4 hours, filtered, washed by ethanol and dried for 2-4 hours at 50-80 ℃ to obtain the organic amine modified heat conducting filler.
Further, the polar solvent is one or more of dimethylformamide and dimethylacetamide.
Further, the biphenyl dianhydride is one or more of 3,3', 4' -biphenyl tetracarboxylic dianhydride and 2,2', 3' -biphenyl tetracarboxylic dianhydride.
Further, the p-phenylenediamine is one or more of 2, 6-dimethyl p-phenylenediamine, 2,3, 5-trimethyl p-phenylenediamine and 2, 5-di-tert-butyl p-phenylenediamine.
The invention also provides a preparation method of the polyimide film with high heat conduction and low thermal expansion coefficient, which comprises the following steps:
s1, preparing an organic amine modified heat conduction filler: firstly, uniformly mixing 4-35 parts of SiC whisker, 20-30 parts of silicon solution and 20-30 parts of sodium dodecyl sulfonate according to the weight ratio, then adding 1-2.5 parts of ammonium sulfate and uniformly stirring to enable the solution to undergo a gel reaction to form a green body, and heating the green body in an air environment at 400-500 ℃ for 2 hours to remove colloid components to obtain a SiC whisker preform. Then, a catalyst solution of 1.5-5 mol/L is immersed on the SiC whisker preform, then polycarbosilane is used as a precursor, argon is used as a carrier, the growth time is 30-180 min, and the SiC nanowire is grown on the preform in situ, so that the three-dimensional netlike SiC whisker-SiC nanowire heat conduction filler is obtained. Finally, under the water bath condition of 50-80 ℃, 5-40 parts of heat conducting filler is added into 4-20 parts of organic amine in parts by weight, and is added into 40-80 parts of ethanol solvent, and the mixture is stirred for 2-4 hours, filtered, washed by ethanol and dried for 2-4 hours at 50-80 ℃ to obtain the organic amine modified heat conducting filler.
S2, preparing a polyamide acid PAA solution: 2 to 10 parts of biphenyl dianhydride and 2 to 12 parts of p-phenylenediamine are placed in 50 to 120 parts of polar solvent, the stirring speed is 50 to 100r/min, the polycondensation reaction is carried out under the protection of nitrogen, the temperature is 30 to 50 ℃, and the reaction time is 30 to 60 minutes.
S3, preparing a polyimide film: adding the organic amine modified heat-conducting filler obtained in the step S1 into the polyamide PAA solution obtained in the step S2, stirring for 4-6 hours, performing defoaming treatment by ultrasonic for 30 minutes, conveying the uniformly mixed solution into a casting machine for casting treatment after defoaming, and then respectively carrying out heat preservation on the film subjected to casting treatment in a vacuum drying box at each temperature point of 100 ℃ and 150 ℃ for 2 hours for curing treatment, thereby finally obtaining the polyimide film with high heat conduction and low thermal expansion coefficient.
The invention has at least the following beneficial effects:
firstly, the heat conducting filler selected by the invention is mainly based on the high heat conducting property and the low thermal expansion coefficient of the micro-nano three-dimensional network SiC whisker-SiC nanowire, the heat conducting efficiency of the polyimide film can be effectively improved on the heat conducting property, the low thermal expansion coefficient is helpful for reducing the thermal expansion coefficient of the film, the heat expansion matching property is improved, the heat conducting property and the heat stability of the film are helpful for optimizing, and the requirements of various application scenes are met.
Secondly, the micro-nano three-dimensional netlike SiC whisker-SiC nanowire is introduced into the polyimide film in structural design, so that the multi-scale combination of the micro-nano silicon carbide is realized, the design increases the distribution of the heat conducting filler in a three-dimensional space, avoids the aggregation of the nanowire and forms a three-dimensional heat conducting channel, in addition, the SiC whisker and the SiC nanowire are in an in-situ growth relationship, the bonding strength of the SiC whisker and the SiC nanowire is improved, the heat conducting performance is improved, the contact area between the SiC whisker and the SiC nanowire with high length-diameter ratio and polyimide can be increased at the other part, and the thermal expansion coefficient of polyimide is further reduced. Through optimizing the preparation conditions, the sizes and the distribution of the whiskers and the nanowires can be finely regulated and controlled, and the heat conduction performance and the thermal expansion coefficient of the film are further optimized.
In addition, the surfaces of the SiC whisker and the SiC nanowire modified by the organic amine contain amino groups, and the amino groups react with polyimide to form amide bonds, so that the interface binding force and compatibility of the filler and a polyimide matrix are improved. The method is favorable for further improving the exertion of the heat conducting property of the heat conducting filler in the polyimide film, reducing the heat resistance between the filler and the matrix, and simultaneously, the strong interface combination can also reduce the thermal expansion coefficient so as to meet the specific application requirements, so that the modification step provides powerful support for optimizing the comprehensive performance of the film.
Drawings
FIG. 1 is a SEM micrograph of three-dimensional network SiC whisker-SiC nanowire according to example 1 of the present invention;
FIG. 2 is a SEM microstructure photograph of three-dimensional network SiC whisker-SiC nanowire modified by organic amine in example 1 of the invention;
fig. 3 is an SEM microstructure photograph of the polyimide film prepared in example 1 of the present invention.
FIG. 4 is a SEM micrograph of three-dimensional network of SiC whiskers-SiC nanowires of example 5 of the invention.
Fig. 5 is an SEM microstructure photograph of the polyimide film prepared in comparative example 1 of the present invention.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.
Example 1
A polyimide film with high heat conduction and low thermal expansion coefficient comprises the following components in parts by weight: 6 parts of organic amine modified heat conducting filler, 50 parts of polar solvent, 3 parts of biphenyl dianhydride and 3 parts of p-phenylenediamine.
The organic amine is triethylamine, and the heat conducting filler is micro-nano three-dimensional netty SiC whisker-SiC nanowire.
The preparation method of the heat-conducting filler comprises the following steps: firstly preparing a SiC whisker preform by a sol-gel method, uniformly mixing 5.5 parts of SiC whisker, 20 parts of silicon solution and 20 parts of sodium dodecyl sulfonate by weight, then adding 1.5 parts of ammonium sulfate and uniformly stirring to enable the solution to undergo a gel reaction to form a blank, and heating the blank in an air environment at 450 ℃ for 2 hours to remove colloid components to obtain the SiC whisker preform. Then, 1.5mol/L catalyst solution is soaked on the SiC whisker preform, then polycarbosilane is used as a precursor, argon is used as a carrier, the growth time is 60min, and in-situ growth of SiC nanowires on the preform is realized, so that the three-dimensional netlike SiC whisker-SiC nanowire heat-conducting filler is obtained.
The catalyst is ferric chloride.
The diameter of the SiC whisker is 2 mu m, the length of the SiC whisker is 30 mu m, the diameter of the SiC nanowire is 40nm, the length of the SiC nanowire is 1500nm, the mass ratio of the SiC whisker to the SiC nanowire is 11:1, and the relationship between the SiC whisker and the SiC nanowire is in-situ growth relationship.
The preparation method of the organic amine modified heat-conducting filler comprises the following steps: under the water bath condition of 50 ℃,6 parts of heat conducting filler is added into 10 parts of organic amine in parts by weight, the mixture is added into 50 parts of ethanol solvent, the mixture is stirred for 3 hours, and after filtration, the mixture is washed by ethanol and dried for 3 hours at 60 ℃ to obtain the organic amine modified heat conducting filler.
The biphenyl dianhydride is 3,3', 4' -biphenyl tetracarboxylic dianhydride.
The p-phenylenediamine is 2, 5-di-tert-butyl.
The preparation method of the polyimide film with high heat conduction and low thermal expansion coefficient comprises the following steps: firstly, uniformly mixing 5.5 parts of SiC whisker, 20 parts of silicon solution and 20 parts of sodium dodecyl sulfonate according to the weight ratio, then adding 1.5 parts of ammonium sulfate, uniformly stirring to enable the solution to undergo a gel reaction to form a green body, and heating the green body in an air environment at 450 ℃ for 2 hours to remove colloid components to obtain the SiC whisker preform. Then, 1.5mol/L catalyst solution is soaked on the SiC whisker preform, then polycarbosilane is used as a precursor, argon is used as a carrier, the growth time is 60min, and in-situ growth of SiC nanowires on the preform is realized, so that the three-dimensional netlike SiC whisker-SiC nanowire heat-conducting filler is obtained. Finally, adding 6 parts of heat conducting filler into 10 parts of organic amine in parts by weight under the water bath condition of 50 ℃, adding into 50 parts of ethanol solvent, stirring for 3 hours, filtering, washing with ethanol, drying at 60 ℃ for 3 hours to obtain the organic amine modified heat conducting filler, placing 3 parts of biphenyl dianhydride and 3 parts of p-phenylenediamine into 50 parts of dimethylformamide, stirring at the speed of 60r/min, and carrying out polycondensation under the protection of nitrogen at the temperature of 30 ℃ for 30 minutes. Adding 6 parts of organic amine modified heat conducting filler into polyamide PAA solution, stirring for 5 hours, carrying out defoaming treatment by ultrasonic for 30 minutes, conveying the uniformly mixed solution into a casting machine for casting treatment after defoaming, and carrying out curing treatment on the film after casting treatment in a vacuum drying oven at each temperature point of 100 ℃ and 150 ℃ and 250 ℃ for 2 hours respectively, thus finally obtaining the polyimide film with high heat conduction and low thermal expansion coefficient.
Example 2
A polyimide film with high heat conduction and low thermal expansion coefficient comprises the following components in parts by weight:
20 parts of organic amine modified heat conducting filler, 65 parts of polar solvent, 4 parts of biphenyl dianhydride and 4 parts of p-phenylenediamine.
The organic amine is butylamine, and the heat conduction filler is micro-nano three-dimensional netlike SiC whisker-SiC nanowire.
The preparation method of the heat-conducting filler comprises the following steps: firstly preparing a SiC whisker preform by a sol-gel method, uniformly mixing 18 parts of SiC whisker, 25 parts of silicon solution and 30 parts of sodium dodecyl sulfonate in parts by weight, adding 2 parts of ammonium persulfate, uniformly stirring, performing gel reaction to generate a blank, heating at 450 ℃ for 2 hours in an air environment to obtain the SiC whisker preform, then soaking 3mol/L of catalyst solution in the SiC whisker preform, and then growing SiC nanowires on the SiC whisker preform in situ by a chemical vapor deposition method at 1000 ℃ by taking polycarbosilane as a precursor and argon as a carrier, wherein the growth time is 60min, thereby obtaining the micro-nano three-dimensional netlike SiC whisker-SiC nanowire heat-conducting filler.
The catalyst is ferric nitrate.
The diameter of the SiC whisker is 5 mu m, the length of the SiC whisker is 20 mu m, the diameter of the SiC nanowire is 40nm, the length of the SiC nanowire is 5000nm, the mass ratio of the SiC whisker to the SiC nanowire is 9:1, and the relationship between the SiC whisker and the SiC nanowire is in-situ growth relationship.
The preparation method of the organic amine modified heat-conducting filler comprises the following steps: under the water bath condition of 60 ℃, 20 parts of heat conduction filler is added into 10 parts of organic amine in parts by weight, the mixture is added into 67 parts of ethanol solvent, the mixture is stirred for 2.5 hours, and after filtration, the mixture is washed by ethanol and dried for 3.5 hours at 60 ℃, the organic amine modified heat conduction filler is obtained.
The biphenyl dianhydride is prepared by mixing 3,3', 4' -biphenyl tetracarboxylic dianhydride and 2,2', 3' -biphenyl tetracarboxylic dianhydride according to a mass ratio of 1:1.
The p-phenylenediamine is prepared by mixing 2, 6-dimethyl p-phenylenediamine and 2,3, 5-trimethyl p-phenylenediamine according to a mass ratio of 1:1.
The preparation method of the polyimide film with high heat conduction and low thermal expansion coefficient comprises the following steps: firstly, uniformly mixing 18 parts of SiC whisker, 25 parts of silicon solution and 30 parts of sodium dodecyl sulfonate according to weight proportion, adding 2 parts of ammonium persulfate, uniformly stirring, performing gel reaction to generate a blank, heating at 450 ℃ for 2 hours in an air environment to obtain a SiC whisker preform, then soaking 3mol/L of catalyst solution on the SiC whisker preform, and then performing in-situ growth of SiC nanowire on the SiC whisker preform by a chemical vapor deposition method at 1000 ℃ by taking polycarbosilane as a precursor and argon as a carrier, wherein the growth time is 60 minutes, thereby obtaining the micro-nano three-dimensional netlike SiC whisker-SiC nanowire heat-conducting filler. Then adding 20 parts of heat conducting filler into 10 parts of organic amine in parts by weight under the water bath condition of 60 ℃, adding 67 parts of ethanol solvent, stirring for 2.5 hours, filtering, washing with ethanol, drying at 60 ℃ for 3.5 hours to obtain the organic amine modified heat conducting filler, placing 4 parts of biphenyl dianhydride and 4 parts of p-phenylenediamine into 65 parts of dimethylformamide, stirring at the speed of 80r/min, and carrying out polycondensation reaction under the protection of nitrogen at the temperature of 38 ℃ for 50 minutes. Adding 20 parts of organic amine modified heat conducting filler into polyamide PAA solution, stirring for 5 hours, carrying out defoaming treatment by ultrasonic for 30 minutes, conveying the uniformly mixed solution into a casting machine for casting treatment after defoaming, and carrying out curing treatment on the film after casting treatment in a vacuum drying oven at each temperature point of 100 ℃ and 150 ℃ and 250 ℃ for 2 hours respectively, thus finally obtaining the polyimide film with high heat conduction and low thermal expansion coefficient.
Example 3
The polyimide film with high heat conduction and low thermal expansion coefficient comprises the following components in parts by weight: 30 parts of organic amine modified heat conducting filler, 80 parts of polar solvent, 6 parts of biphenyl dianhydride and 6 parts of p-phenylenediamine.
Further, the organic amine is a mixture of butylamine and isopropylamine.
Further, the heat conducting filler is a micro-nano three-dimensional netlike SiC whisker-SiC nanowire.
Further, the preparation method of the heat conducting filler comprises the following steps: the preparation method comprises the steps of firstly preparing a SiC whisker preform by a sol-gel method, uniformly mixing 28 parts of SiC whisker, 25 parts of silicon solution and 26 parts of sodium dodecyl sulfonate in parts by weight, adding 2.5 parts of ammonium persulfate, uniformly stirring, performing gel reaction to generate a blank, heating at 500 ℃ for 2h under an air environment to remove glue to obtain the SiC whisker preform, then soaking 2.5mol/L of catalyst solution in the SiC whisker preform, and then at 1000 ℃, taking polycarbosilane as a precursor and argon as a carrier, and performing in-situ growth of SiC nanowire on the SiC whisker preform by a chemical vapor deposition method for 60min to obtain the micro-nano three-dimensional netlike SiC whisker-SiC nanowire heat-conducting filler.
Further, the catalyst is a mixture of ferric chloride and ferric nitrate.
Further, the diameter of the SiC whisker is 4 mu m, the length of the SiC whisker is 25 mu m, the diameter of the SiC nanowire is 60nm, the length of the SiC nanowire is 4500nm, and the mass ratio of the SiC whisker to the SiC nanowire is 19:1.
Further, the relationship between the SiC whisker and the SiC nanowire is an in-situ growth relationship.
Further, the preparation method of the organic amine modified heat conducting filler comprises the following steps: under the water bath condition of 80 ℃, 30 parts of heat conducting filler is added into 20 parts of organic amine in parts by weight, the mixture is added into 80 parts of ethanol solvent, the mixture is stirred for 4 hours, and after filtration, the mixture is washed by ethanol and dried for 4 hours at 80 ℃ to obtain the organic amine modified heat conducting filler.
Further, the biphenyl dianhydride is prepared by mixing 3,3', 4' -biphenyl tetracarboxylic dianhydride and 2,2', 3' -biphenyl tetracarboxylic dianhydride according to a mass ratio of 1:2.
Further, the p-phenylenediamine is prepared by mixing 2,3, 5-trimethyl p-phenylenediamine and 2, 5-di-tert-butyl p-phenylenediamine according to a mass ratio of 1:2.
The preparation method of the polyimide film with high heat conduction and low thermal expansion coefficient comprises the following steps: firstly, uniformly mixing 28 parts of SiC whisker, 25 parts of silicon solution and 26 parts of sodium dodecyl sulfonate according to the weight ratio, adding 2.5 parts of ammonium persulfate, uniformly stirring, performing gel reaction to generate a blank, heating at 500 ℃ for 2 hours in an air environment to obtain a SiC whisker preform, then soaking 2.5mol/L of catalyst solution on the SiC whisker preform, and then performing in-situ growth of SiC nanowire on the SiC whisker preform by a chemical vapor deposition method at 1000 ℃ by taking polycarbosilane as a precursor and argon as a carrier, wherein the growth time is 60 minutes, thereby obtaining the micro-nano three-dimensional netlike SiC whisker-SiC nanowire heat-conducting filler. And finally, adding 30 parts of heat conducting filler into 20 parts of organic amine in parts by weight under the water bath condition of 80 ℃, adding into 80 parts of ethanol solvent, stirring for 4 hours, filtering, washing with ethanol, drying at 80 ℃ for 4 hours to obtain the organic amine modified heat conducting filler, placing 6 parts of biphenyl dianhydride and 6 parts of p-phenylenediamine into 80 parts of dimethylacetamide, stirring at the speed of 70r/min, and carrying out polycondensation under the protection of nitrogen at the temperature of 50 ℃ for 45 minutes. Adding an organic amine modified heat-conducting filler into a polyamide PAA solution, stirring for 6 hours, carrying out defoaming treatment by ultrasonic for 30 minutes, conveying the uniformly mixed solution into a casting machine for casting treatment after defoaming, and carrying out curing treatment on the film subjected to casting treatment in a vacuum drying oven at each temperature point of 100 ℃ and 150 ℃ and 250 ℃ for 2 hours respectively, thus obtaining the polyimide film with high heat conduction and low thermal expansion coefficient.
Example 4
The polyimide film with high heat conduction and low thermal expansion coefficient comprises the following components in parts by weight: 40 parts of organic amine modified heat conducting filler, 120 parts of polar solvent, 8 parts of biphenyl dianhydride and 8 parts of p-phenylenediamine.
Further, the organic amine is one or more of triethylamine, butylamine, isopropylamine, triethanolamine and ethylenediamine.
Further, the heat conducting filler is a micro-nano three-dimensional netlike SiC whisker-SiC nanowire.
Further, the preparation method of the heat conducting filler comprises the following steps: the preparation method comprises the steps of firstly preparing a SiC whisker preform by a sol-gel method, uniformly mixing 36 parts of SiC whisker, 30 parts of silicon solution and 30 parts of sodium dodecyl sulfonate in parts by weight, adding 2.5 parts of ammonium persulfate, uniformly stirring, performing gel reaction to generate a blank, heating at 500 ℃ for 2h in an air environment to remove glue to obtain the SiC whisker preform, then soaking 5mol/L of catalyst solution in the SiC whisker preform, and then growing SiC nanowires on the SiC whisker preform in situ by a chemical vapor deposition method at 1000 ℃ by taking polycarbosilane as a precursor and argon as a carrier, wherein the growth time is 180min to obtain the micro-nano three-dimensional netlike SiC whisker-SiC nanowire heat-conducting filler.
Further, the catalyst is one or a mixture of more of ferric chloride, ferric nitrate and ferric sulfate.
Further, the diameter of the SiC whisker is 5 mu m, the length of the SiC whisker is 30 mu m, the diameter of the SiC nanowire is 60nm, the length of the SiC nanowire is 5000nm, and the mass ratio of the SiC whisker to the SiC nanowire is 7:1.
Further, the relationship between the SiC whisker and the SiC nanowire is an in-situ growth relationship.
Further, the preparation method of the organic amine modified heat conducting filler comprises the following steps: under the water bath condition of 80 ℃, 40 parts of heat conducting filler is added into 20 parts of organic amine in parts by weight, the mixture is added into 75 parts of ethanol solvent, the mixture is stirred for 3 hours, and after filtration, the mixture is washed by ethanol and dried for 4 hours at 76 ℃ to obtain the organic amine modified heat conducting filler.
Further, the biphenyl dianhydride is 2,2', 3' -biphenyl tetracarboxylic dianhydride.
Further, the 2, 5-di-tert-butyl p-phenylenediamine.
The preparation method of the polyimide film with high heat conduction and low thermal expansion coefficient comprises the following steps: firstly, uniformly mixing 36 parts of SiC whisker, 30 parts of silicon solution and 30 parts of sodium dodecyl sulfonate according to weight proportion, adding 2.5 parts of ammonium persulfate, uniformly stirring, performing gel reaction to generate a blank, heating at 500 ℃ for 2 hours in an air environment to obtain a SiC whisker preform, then soaking 5mol/L of catalyst solution on the SiC whisker preform, then in-situ growing SiC nanowires on the SiC whisker preform by a chemical vapor deposition method at 1000 ℃ by taking polycarbosilane as a precursor and argon as a carrier, wherein the growth time is 180 minutes, and obtaining the micro-nano three-dimensional netlike SiC whisker-SiC nanowire heat-conducting filler. And finally, adding 40 parts of heat conducting filler into 20 parts of organic amine in parts by weight under the water bath condition of 80 ℃, adding into 75 parts of ethanol solvent, stirring for 3 hours, filtering, washing with ethanol, and drying at 76 ℃ for 4 hours to obtain the organic amine modified heat conducting filler. 8 parts of biphenyl dianhydride and 8 parts of p-phenylenediamine are placed in 120 parts of dimethylacetamide, the stirring speed is 100r/min, and the polycondensation reaction is carried out under the protection of nitrogen, wherein the temperature is 50 ℃, and the reaction time is 60 minutes. Adding an organic amine modified heat-conducting filler into a polyamide PAA solution, stirring for 6 hours, carrying out defoaming treatment by ultrasonic for 30 minutes, conveying the uniformly mixed solution into a casting machine for casting treatment after defoaming, and carrying out curing treatment on the film subjected to casting treatment in a vacuum drying oven at each temperature point of 100 ℃ and 150 ℃ and 250 ℃ for 2 hours respectively, thus obtaining the polyimide film with high heat conduction and low thermal expansion coefficient.
Example 5
Substantially the same as in example 1, except that the time for growing SiC nanowires was increased from 60min to 120min of example 1, otherwise unchanged.
Example 6
Substantially the same as in example 1, except that the component of SiC whiskers was increased from 5.5 parts to 10 parts of example 1, the others were unchanged.
Example 7
Substantially the same as in example 1, except that the organic amine was increased from 10 parts to 15 parts of example 1, the others were unchanged.
Comparative example 1
Substantially the same as in example 1, except that the SiC nanowire was not grown by chemical vapor deposition.
Comparative example 2
Substantially the same as in example 1, except that SiC whiskers were not employed, but an equal amount of SiC nanowires was directly added as a heat conductive filler.
Comparative example 3
Substantially the same as in example 1, except that the heat conductive coating was modified without using an organic amine.
The thermal conductivities, thermal expansion coefficients, and tensile strengths of examples 1 to 7, comparative examples 1 to 3, and conventional commercial polyimide films are shown in table 1, respectively.
The test methods for thermal conductivity and coefficient of thermal expansion are referred to the ASTM-D696 standard, and the test methods for tensile strength are referred to the ASTM-D882.
TABLE 1
Compared with the embodiment 1, the embodiments 2-4 increase the contents of the SiC whisker and the SiC nanowire which are heat conductive fillers, can increase the heat conductive property and the mechanical property of the polyimide film, and reduce the thermal expansion coefficient.
Compared with the embodiment 1, the thermal conductivity of the SiC nanowire heat conduction filler is reduced from 1.1W/(m.K) to 0.89W/(m.K), the thermal expansion coefficient is increased from 16ppm/K to 27.3ppm/K, and the tensile strength is reduced from 320MPa to 230MPa, so that the SiC nanowire can improve the mechanical property by improving the thermal conductivity of polyimide, reducing the thermal expansion coefficient.
Compared with the example 1, the thermal conductivity of the comparative example 2 is reduced from 1.1W/(m.K) to 0.79W/(m.K), the thermal expansion coefficient is increased from 16ppm/K to 24.9ppm/K, and the tensile strength is reduced from 320MPa to 253MPa, so that the SiC whisker can improve the mechanical property by improving the thermal conductivity of the polyimide, reducing the thermal expansion coefficient.
Comparative example 3 compared with example 1, without the organic amine modified thermally conductive filler, the thermal conductivity was reduced from 1.1W/(m.K) to 0.63W/(m.K), the thermal expansion coefficient was increased from 16ppm/K to 28.9ppm/K, and the tensile strength was reduced from 320MPa to 267MPa, demonstrating that organic amine modification can increase the interfacial bond of SiC and polyimide to improve mechanical properties and thermal conductivity, and reduce the thermal expansion coefficient.
FIG. 1 is a photograph of an SEM microstructure of a three-dimensional network SiC whisker-SiC nanowire in example 1 of the invention, and it can be seen that the SiC nanowire grown in situ is uniformly dispersed on the surface of the SiC whisker;
FIG. 2 is a SEM microstructure photograph of an organic amine modified three-dimensional network SiC whisker-SiC nanowire in example 1 of the invention, and the surface of the modified SiC whisker-SiC nanowire can be seen to have obvious modified particles;
fig. 3 is an SEM microstructure photograph of the polyimide film prepared in example 1 of the present invention, and it can be seen that the SiC whisker-SiC nanowire heat conductive filler is dispersed inside the matrix.
Fig. 4 is a photograph of SEM microstructure of three-dimensional network SiC whisker-SiC nanowires in example 5 of the present invention, and it can be clearly seen that the length of SiC nanowire filler increases with the extension of deposition time.
Fig. 5 is a SEM microstructure photograph of the polyimide film prepared in comparative example 1 of the present invention, and it can be clearly seen that there is no SiC nanowire filler.
Finally, it should be noted that: the above embodiments are only for illustrating the technical aspects of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the above embodiments, it should be understood by those of ordinary skill in the art that: all changes in the structure and details of the invention which may be made in the invention are encompassed by the scope of the invention as defined by the claims.
Claims (10)
1. A polyimide film with high heat conduction and low thermal expansion coefficient comprises the following components in parts by weight:
5-40 parts of organic amine modified heat conducting filler, 50-120 parts of polar solvent, 2-10 parts of biphenyl dianhydride and 2-12 parts of p-phenylenediamine.
2. The polyimide film with both high thermal conductivity and low thermal expansion coefficient according to claim 1, wherein said organic amine is one or more of triethylamine, butylamine, isopropylamine, triethanolamine and ethylenediamine.
3. The polyimide film with high heat conduction and low thermal expansion coefficient according to claim 1, wherein the heat conduction filler is micro-nano three-dimensional network SiC whisker-SiC nanowire.
4. The polyimide film with high heat conduction and low thermal expansion coefficient according to claim 1, wherein the preparation method of the heat conduction filler is as follows: the preparation method comprises the steps of firstly preparing an SiC whisker preform by a sol-gel method, uniformly mixing 4-35 parts of SiC whisker, 20-30 parts of silicon solution and 20-30 parts of sodium dodecyl sulfonate by weight, adding 1-2.5 parts of ammonium persulfate, uniformly stirring, performing gel reaction to generate a blank, heating at 400-500 ℃ for 2h under an air environment to obtain the SiC whisker preform, soaking the SiC whisker preform with 1.5-5 mol/L of catalyst solution, then at 1000 ℃ taking polycarbosilane as a precursor, taking argon as a carrier, and growing SiC nanowires on the SiC whisker preform in situ by a chemical vapor deposition method for 30-180 min to obtain the micro-nano three-dimensional network SiC whisker-SiC nanowire heat-conducting filler, wherein the catalyst is one or more of ferric chloride, ferric nitrate and ferric sulfate.
5. The polyimide film having both high thermal conductivity and low thermal expansion coefficient according to claim 3 or 4, wherein said SiC whisker has a diameter of 1.5 to 5 μm, a length of 15 to 30 μm, a diameter of 20 to 60nm, a length of 600 to 5000nm, and a mass ratio of (5 to 20): 1.
6. The polyimide film with high heat conduction and low thermal expansion coefficient according to claim 1, wherein the preparation method of the organic amine modified heat conduction filler is as follows:
under the water bath condition of 50-80 ℃, 5-40 parts of heat conducting filler is added into 4-20 parts of organic amine in parts by weight, and is added into 40-80 parts of ethanol solvent, and the mixture is stirred for 2-4 hours, filtered, washed by ethanol and dried for 2-4 hours at 50-80 ℃ to obtain the organic amine modified heat conducting filler.
7. The polyimide film having both high thermal conductivity and low thermal expansion coefficient according to claim 1, wherein said polar solvent is one or more of dimethylformamide and dimethylacetamide.
8. The polyimide film having both high thermal conductivity and low thermal expansion coefficient according to claim 1, wherein said biphenyl dianhydride is one or more of 3,3', 4' -biphenyl tetracarboxylic dianhydride and 2,2', 3' -biphenyl tetracarboxylic dianhydride.
9. The polyimide film having both high thermal conductivity and low thermal expansion coefficient according to claim 1, wherein said p-phenylenediamine is one or more of 2, 6-dimethyl-p-phenylenediamine, 2,3, 5-trimethyl-p-phenylenediamine, and 2, 5-di-t-butyl-p-phenylenediamine.
10. The method for producing a polyimide film having both high thermal conductivity and low thermal expansion coefficient according to any one of claims 1 to 4, comprising the steps of: firstly, placing 2-10 parts of biphenyl dianhydride and 2-12 parts of p-phenylenediamine in 50-120 parts of polar solvent, stirring at the speed of 50-100 r/min, carrying out polycondensation reaction under the protection of nitrogen at the temperature of 30-50 ℃ for 30-60 minutes, then adding 5-40 parts of organic amine modified heat conducting filler, stirring for 4-6 hours, carrying out defoaming treatment by ultrasonic for 30 minutes, conveying the uniformly mixed solution into a casting machine for casting treatment after the defoaming treatment, then carrying out curing treatment on the film after the casting treatment in a vacuum drying oven at each temperature point of 100 ℃ and 150 ℃ for 2 hours, and finally, demolding to obtain the polyimide film with high heat conduction and low thermal expansion coefficient.
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| CN105085914A (en) * | 2015-08-25 | 2015-11-25 | 中节能万润股份有限公司 | High-temperature-resistant polyimide and preparation method thereof |
| CN109153834A (en) * | 2016-05-20 | 2019-01-04 | 沙特基础工业全球技术有限公司 | Composite material including fluoroelastomer and polyimides prepares the method for composite material and the product comprising it |
| CN110776657A (en) * | 2019-11-05 | 2020-02-11 | 株洲时代新材料科技股份有限公司 | High-thermal-conductivity polyimide film and preparation method thereof |
| CN111793206A (en) * | 2020-06-09 | 2020-10-20 | 中天电子材料有限公司 | Preparation method of polyimide film and polyimide film |
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| CN105085914A (en) * | 2015-08-25 | 2015-11-25 | 中节能万润股份有限公司 | High-temperature-resistant polyimide and preparation method thereof |
| CN109153834A (en) * | 2016-05-20 | 2019-01-04 | 沙特基础工业全球技术有限公司 | Composite material including fluoroelastomer and polyimides prepares the method for composite material and the product comprising it |
| CN110776657A (en) * | 2019-11-05 | 2020-02-11 | 株洲时代新材料科技股份有限公司 | High-thermal-conductivity polyimide film and preparation method thereof |
| CN111793206A (en) * | 2020-06-09 | 2020-10-20 | 中天电子材料有限公司 | Preparation method of polyimide film and polyimide film |
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