CN115386111A - Polyimide film with good thermal conductivity and thermal stability and preparation method thereof - Google Patents
Polyimide film with good thermal conductivity and thermal stability and preparation method thereof Download PDFInfo
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- CN115386111A CN115386111A CN202210867701.XA CN202210867701A CN115386111A CN 115386111 A CN115386111 A CN 115386111A CN 202210867701 A CN202210867701 A CN 202210867701A CN 115386111 A CN115386111 A CN 115386111A
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000000178 monomer Substances 0.000 claims abstract description 28
- 150000004985 diamines Chemical class 0.000 claims abstract description 24
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 18
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 18
- QRZMXADUXZADTF-UHFFFAOYSA-N 4-aminoimidazole Chemical compound NC1=CNC=N1 QRZMXADUXZADTF-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000006185 dispersion Substances 0.000 claims abstract description 14
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011248 coating agent Substances 0.000 claims abstract description 13
- 238000000576 coating method Methods 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000003751 zinc Chemical class 0.000 claims abstract description 9
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 7
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 10
- 239000013153 zeolitic imidazolate framework Substances 0.000 claims description 10
- DEPDDPLQZYCHOH-UHFFFAOYSA-N 1h-imidazol-2-amine Chemical compound NC1=NC=CN1 DEPDDPLQZYCHOH-UHFFFAOYSA-N 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 2
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 2
- XPAQFJJCWGSXGJ-UHFFFAOYSA-N 4-amino-n-(4-aminophenyl)benzamide Chemical compound C1=CC(N)=CC=C1NC(=O)C1=CC=C(N)C=C1 XPAQFJJCWGSXGJ-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 2
- 238000004108 freeze drying Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000000203 mixture Substances 0.000 claims 1
- 238000001035 drying Methods 0.000 abstract description 4
- 239000004952 Polyamide Substances 0.000 abstract 1
- 239000002253 acid Substances 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- 229920002647 polyamide Polymers 0.000 abstract 1
- 239000004642 Polyimide Substances 0.000 description 19
- 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 12
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 11
- 238000005303 weighing Methods 0.000 description 8
- 239000011521 glass Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000002904 solvent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- 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
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- 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
- C08G73/101—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents
- C08G73/1017—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents in the form of (mono)amine
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- C—CHEMISTRY; METALLURGY
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- 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
- C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
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- 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
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- 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
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- 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 polyimide film with good thermal conductivity and thermal stability and a preparation method thereof, relating to the technical field of polyimide film preparation, wherein the preparation method comprises the following steps: dispersing graphene oxide into N, N-dimethylacetamide, adding zinc salt, aminoimidazole and methylimidazole, heating, and stirring for reaction; then adding hydrazine hydrate, stirring for reaction, cooling, centrifuging, washing and drying to obtain NH 2 -zifs @ rgo; mixing diamine monomer and NH 2 -ZIFs @ RGO is added into the organic solvent respectively to obtain diamine solution and NH 2 -zifs @ rgo dispersions; adding a dicarboxylic anhydride monomer into a diamine solution in batches, stirring for reaction, and then adding NH 2 -ZIFs @ RGO dispersion liquid, stirring for reaction, and finally adding a binary anhydride monomer for viscosity adjustment to obtain polyamic acid; and coating polyamic acid into a film, heating and imidizing the film in sections, and cooling the film to obtain the polyamide acid film. The PI film prepared by the invention has high heat conductivity coefficient and thermal stability, good mechanical property and good popularization and use value.
Description
Technical Field
The invention relates to the technical field of polyimide film preparation, in particular to a polyimide film with good thermal conductivity and thermal stability and a preparation method thereof.
Background
In recent years, polyimide (PI) has been regarded as important because of its outstanding comprehensive properties, multiple synthetic routes, wide application and good market prospects. However, polyimide has poor thermal conductivity, and the intrinsic thermal conductivity of a pure PI film is lower than 0.2W/(m · k), so that when the pure PI film is used as a supporting substrate of various elements, heat cannot be immediately led out, and heat is easily accumulated, thereby affecting the stability, the service life and the operation safety of the elements; some elements need to work for a long time even under high temperature conditions of more than 400 ℃, but the PI film is difficult to bear the high temperature at present. The lower thermal conductivity and thermal stability greatly limit the wider application of PI, so the development of PI films with high thermal conductivity and high thermal stability is a very important and urgent industrial demand.
Graphene is widely concerned about due to the ultrahigh thermal conductivity and good thermal stability, but graphene and a polymer have poor compatibility, a large number of interfaces are caused, and the thermal conductivity is limited; in addition, the graphene is easy to agglomerate in the polymer, is difficult to disperse uniformly, cannot form a good heat conduction channel, and has an undesirable heat conduction effect; in addition, the graphene has stronger conductive performance, and the insulating performance is greatly reduced after the graphene is added into a polymer, so that the application of the graphene is limited; and the thermal stability of the polymer is not obviously improved by singly using the graphene.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides the polyimide film with good thermal conductivity and thermal stability and the preparation method thereof.
The invention provides a preparation method of a polyimide film with good thermal conductivity and thermal stability, which comprises the following steps:
S1、NH 2 -zifs @ rgo preparation: dispersing graphene oxide into N, N-dimethylacetamide, adding zinc salt, aminoimidazole and methylimidazole, heating, and stirring for reaction; then adding hydrazine hydrate into the reaction system, stirring for reaction, cooling to room temperature, centrifuging, washing, and freeze-drying to obtain the aminated ZIF loaded graphene composite material NH 2 -ZIFs@RGO；
S2, preparing polyamic acid: reacting diamine monomer and NH 2 -ZIFs @ RGO is added into the organic solvent respectively to obtain diamine solution and NH 2 -zifs @ rgo dispersions; adding part of dicarboxylic anhydride monomer into diamine solution in batches, stirring for reaction, and then adding NH 2 -zifs @ rgo dispersion, stirring to react, finally adding the rest binary anhydride monomer for viscosity adjustment to obtain polyamic acid containing zifs @ rgo;
s3, preparing a polyimide film: coating polyamic acid containing ZIFs @ RGO to form a film, heating and imidizing the film in sections, and cooling the film to obtain the polyimide film.
Preferably, in S1, the particle size of the graphene oxide is 0.5-10 μm; the aminoimidazole is one or two of 2-aminoimidazole and 4-aminoimidazole.
Preferably, in S1, the mass ratio of graphene oxide to zinc salt is 1:2-5; the mass ratio of the total mass of the methylimidazole and the aminoimidazole to the zinc salt is 2-5:1; the mass ratio of the methylimidazole to the aminoimidazole is 1:0.1-0.5.
Preferably, in S1, adding zinc salt, aminoimidazole and methylimidazole, heating to 80-120 ℃, and stirring for reacting for 12-48h; then adding hydrazine hydrate into the reaction system, and stirring for reaction for 1-2h.
Preferably, in S2, the molar ratio of diamine monomer to dicarboxylic anhydride monomer is 1:1 to 1.05, NH 2 -ZIFs @ RGO to diamine monomer mass ratio of 0.1-0.5:1.
preferably, in S2, the dibasic anhydride monomer is added into the diamine solution in 2 to 3 batches, and the total amount of the added dibasic anhydride monomer in the batches accounts for 94 to 98 percent of the total mass of the dibasic anhydride monomer.
Preferably, in S2, part of the dibasic anhydride monomer is added into the diamine solution in batches, stirred and reacted for 1-2h, and then NH is added 2 -ZIFs @ RGO dispersion, stirring and reacting for 1-2h.
Preferably, in S2, the organic solvent is one of N, N-dimethylacetamide, N-dimethylformamide, and N-methylpyrrolidone;
the diamine monomer is one or two of p-phenylenediamine, 4 '-diaminodiphenyl ether and 4,4' -diaminobenzanilide;
the binary anhydride monomer is one of pyromellitic dianhydride, 3', 4' -biphenyl tetracarboxylic dianhydride and 4,4' -biphenyl ether dianhydride.
Preferably, in S3, the specific operation of the stepwise heating imidization treatment is as follows: keeping the temperature at 100 deg.C, 160 deg.C, 210 deg.C, 260 deg.C and 360 deg.C for 25-45min.
The invention also provides the polyimide film with good thermal conductivity and thermal stability, which is prepared by the method.
Has the beneficial effects that: the invention adopts aminoimidazole to replace partial methylimidazole to obtain aminated organic metal framework materials (ZIFs), and the ZIFs are grown on the surface of a graphene sheet layer by a hot solvent method so as to be loaded on graphene (RGO). Firstly, amino groups on ZIFs can participate in the polymerization reaction of diamine and a dicarboxylic anhydride monomer, an end capping effect is realized on a molecular chain, the thermal stability of a PI membrane can be improved, and the dicarboxylic anhydride is added in batches, so that the reaction is carried out more fully. Secondly, the organic ligand for synthesizing the ZIFs has good compatibility with a PI matrix polymer, so that RGO loaded with the ZIFs can be well dispersed in the PI matrix to form a good heat conduction channel, and the heat conductivity of the material is improved. In addition, the ZIFs loaded on the RGO surface can weaken the conductivity of the RGO, so that the inherent insulating property of the PI film can be maintained. The method has simple preparation process, and the prepared PI film has high heat conductivity coefficient and thermal stability, good mechanical property and good popularization and use value.
Detailed Description
The technical means of the present invention will be described in detail below with reference to specific examples.
Example 1
1) 0.5g GO was first dispersed in DMAC solvent with stirring for 1h, followed by 1.2g Zn (NO) 3 ) 2 ·6H 2 Adding O, 2.5g of 2-methylimidazole and 0.5g of 2-aminoimidazole into the solution, heating to 100 ℃ for reaction for 24 hours, then adding 8g of hydrazine hydrate into the solution for reaction for 1 hour, cooling the solution to room temperature, centrifugally washing the obtained solution for 2 times, and finally drying the obtained product in a freeze dryer for 3 hours to obtain NH 2 -zifs @ rgo composite;
2) 3g PDA and 7g ODA were added to 102g DMAC to dissolve, while 5g NH 2 -ZIFs @ RGO in 45g DMAC and in a disperser for 1 hour;
3) Weighing 13g PMDA, adding into the above diamine solution in 3 times, reacting at half an hour interval, and weighing 12.5g NH dispersed in 2) 2 Adding the dispersion of-ZIFs @ RGO into the solution to react for 1 hour, then adding 0.7g of PMDA to adjust the viscosity, stopping the reaction when the system viscosity reaches 60000 MPa.s, preparing polyamic acid containing ZIFs @ RGO, and carrying out vacuum defoaming treatment in a-1 Mpa oven;
4) Coating the defoamed polyamic acid on a glass plate of an automatic coating machine to form a film, wherein the thickness of the film is 50 mu m, finally carrying out imidization treatment, desolventizing at 100 ℃, 40min at 160 ℃, 40min at 210 ℃, 40min at 260 ℃, 40min at 360 ℃ for 40min, and cooling to obtain the polyimide film containing ZIFs @ RGO.
Example 2
1)NH 2 ZIFs @ RGO was prepared as in example 1;
2) 3g PDA and 7g ODA were dissolved in 96g DMAC while 5g NH was added 2 -ZIFs @ RGO in 45g DMAC and in a disperser for 2 hours;
3) Weighing 13g of PMDA, adding the PMDA into the diamine solution for reaction in 3 times at half an hour intervals, and then weighing 26.3g of NH dispersed in the 2) solution 2 -ZIFs @ RGO dispersion was added to the above solution to react for 1 hour, followed by addition of 0.7g PMDA to adjust viscosity, and the reaction was stopped when the system viscosity reached 60000 MPa.sPreparing polyamic acid containing ZIFs @ RGO, and carrying out vacuum defoaming treatment in a drying oven of-1 Mpa;
4) And (2) coating the defoamed polyamic acid on a glass plate of an automatic coating machine to form a film with the thickness of 50 mu m, finally carrying out imidization treatment, desolvating at 100 ℃, 40min at 160 ℃, 40min at 210 ℃, 40min at 260 ℃, 40min at 360 ℃, 40min at 360 ℃, and cooling to obtain the polyimide film containing ZIFs @ RGO.
Example 3
1)NH 2 ZIFs @ RGO was prepared as in example 1;
2) 3g PDA and 7g ODA were dissolved in 90g DMAC while 5g NH was added 2 -ZIFs @ RGO in 45g DMAC and in a disperser for 2 hours;
3) Weighing 13g of PMDA, adding into the diamine solution for reaction in 3 times at half an hour intervals, and weighing 41.8g of NH dispersed in 2) 2 Adding the dispersion of-ZIFs @ RGO into the solution to react for 1 hour, then adding 0.7g of PMDA to adjust the viscosity, stopping the reaction when the system viscosity reaches 60000 MPa-s to obtain polyamic acid containing the ZIFs @ RGO, and performing vacuum defoaming treatment in a-1 Mpa oven;
4) Coating the defoamed polyamic acid on a glass plate of an automatic coating machine to form a film, wherein the thickness of the film is 50 mu m, finally carrying out imidization treatment, desolventizing at 100 ℃, 40min at 160 ℃, 40min at 210 ℃, 40min at 260 ℃, 40min at 360 ℃ for 40min, and cooling to obtain the polyimide film containing ZIFs @ RGO.
Comparative example 1
1) Adding 3g of PDA and 7g of ODA into 108g of DMAC for dissolving, after reacting for 1 hour, adding 13g of PMDA into the solution in 3 times, evenly adding the solution at intervals of half an hour, then adding 0.7g of PMDA for adjusting the viscosity of the system to 60000 MPa.s to obtain polyamic acid, and carrying out vacuum defoaming treatment in an oven with the pressure of-1 MPa;
2) And (2) coating the defoamed polyamic acid on a glass plate of an automatic coating machine to form a film, wherein the thickness of the film is 50 microns, then removing the solvent for 40min at the temperature of 100 ℃, and finally carrying out imidization, wherein the imidization process comprises the steps of keeping the temperature at 160 ℃ for 40min, keeping the temperature at 210 ℃ for 40min, keeping the temperature at 260 ℃ for 40min, keeping the temperature at 360 ℃ for 40min, and cooling to obtain the polyimide film.
Comparative example 2
1) Preparation of zif8@ rgo: firstly, 0.5g of GO is dispersed in a DMAC solvent, and is stirred and dispersed for 1 hour; followed by 1.2g of Zn (NO) 3 ) 2 ·6H 2 Adding 3g of 2-methylimidazole and O into the solution, heating to 100 ℃ for reaction for 24 hours, then adding 8g of hydrazine hydrate into the solution for 1 hour, cooling the solution to room temperature, centrifugally washing the obtained solution for 2 times, and finally drying the obtained product in a freeze dryer for 3 hours to obtain the ZIF8@ RGO composite material;
2) Adding 3g of PDA and 7g of ODA into 102g of DMAC for dissolving, simultaneously dispersing 5g of ZIF8@ RGO into 45g of DMAC, and dispersing for 1 hour in a dispersion machine;
3) Weighing 13g of PMDA, uniformly adding the PMDA into the diamine solution for 3 times for reaction at intervals of half an hour, then weighing 12.5g of ZIF8@ RGO dispersion well dispersed in 2) and adding the dispersion into the solution for reaction for 1 hour, then adding 0.7g of PMDA for viscosity adjustment, stopping the reaction when the viscosity of the system reaches 60000 MPa.s, preparing the polyamic acid containing ZIF8@ RGO, and carrying out vacuum defoaming treatment in an oven of-1 Mpa;
4) And (2) coating the defoamed polyamic acid on a glass plate of an automatic coating machine to form a film with the thickness of 50 mu m, finally carrying out imidization treatment, desolvating at 100 ℃, 40min at 160 ℃, 40min at 210 ℃, 30min at 260 ℃, 40min at 360 ℃, 40min at 360 ℃, and cooling to obtain the polyimide film containing ZIF8@ RGO.
The thermal conductivity, TGA data, volume resistivity and mechanical properties of each of the polyimide films prepared in the examples of the present invention and the comparative examples were measured, and the results are shown in table 1.
TABLE 1 thermal conductivity, TGA data, volume resistivity, and mechanical property data for PI films
As can be seen from the data in the table, with the increase of the content of ZIFs @ RGO, the heat conductivity coefficient of the PI composite film is continuously increased, the thermal stability is greatly improved, and although the volume resistivity is reduced, the insulation performance is far higher than that of the standard insulation material 10 6 Volume resistivity of an order of magnitude; in addition, 2-methylimidazole is replaced by partial 2-aminoimidazole, and the performance of the ZIFs @ RGO/PI composite film is superior to that of the ZIF8@ RGO/PI composite film; and the reduction range of the tensile strength is not large, and the tensile strength can be basically maintained, which shows that the PI composite film maintains the excellent performance of the PI film.
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 polyimide film with good thermal conductivity and thermal stability is characterized by comprising the following steps:
S1、NH 2 -ZIFs @ RGO preparation: dispersing graphene oxide into N, N-dimethylacetamide, adding zinc salt, aminoimidazole and methylimidazole, heating, and stirring for reaction; then adding hydrazine hydrate into the reaction system, stirring for reaction, cooling to room temperature, centrifuging, washing, and freeze-drying to obtain the aminated ZIF loaded graphene composite material NH 2 -ZIFs@RGO；
S2, preparing polyamic acid: mixing diamine monomer and NH 2 -ZIFs @ RGO is added into the organic solvent respectively to obtain diamine solution and NH 2 -zifs @ rgo dispersions; adding part of dicarboxylic anhydride monomer into diamine solution in batches, stirring for reaction, and then adding NH 2 -zifs @ rgo dispersion, stirring for reaction, and finally adding the rest of the binary anhydride monomer for adjusting viscosity to obtain zifs @ rgo-containing polyamic acid;
s3, preparing a polyimide film: coating polyamic acid containing ZIFs @ RGO to form a film, heating and imidizing the film in sections, and cooling the film to obtain the polyimide film.
2. The method for preparing a polyimide film having good thermal conductivity and thermal stability according to claim 1, wherein in S1, the particle size of graphene oxide is 0.5 to 10 μm; the aminoimidazole is one or two of 2-aminoimidazole and 4-aminoimidazole.
3. The method for preparing a polyimide film having good thermal conductivity and thermal stability according to claim 1 or 2, wherein in S1, the mass ratio of graphene oxide to zinc salt is 1:2-5; the mass ratio of the total mass of the methylimidazole and the aminoimidazole to the zinc salt is 2-5:1; the mass ratio of the methylimidazole to the aminoimidazole is 1:0.1-0.5.
4. The method for preparing a polyimide film having good thermal conductivity and thermal stability according to any one of claims 1 to 3, wherein in S1, zinc salt, aminoimidazole and methylimidazole are added thereto, the temperature is raised to 80 to 120 ℃, and the mixture is stirred and reacted for 12 to 48 hours; then adding hydrazine hydrate into the reaction system, and stirring for reaction for 1-2h.
5. The method for producing a polyimide film excellent in thermal conductivity and thermal stability according to any one of claims 1 to 4, wherein in S2, the molar ratio of the diamine monomer to the dicarboxylic anhydride monomer is 1:1 to 1.05, NH 2 -ZIFs @ RGO to diamine monomer mass ratio of 0.1-0.5:1.
6. the method for preparing a polyimide film having excellent thermal conductivity and thermal stability according to any one of claims 1 to 5, wherein in S2, a portion of the dicarboxylic anhydride monomer is added to the diamine solution in 2 to 3 portions, and the total amount of the dicarboxylic anhydride monomer added in portions accounts for 94 to 98% of the total mass of the dicarboxylic anhydride monomer.
7. According to any one of claims 1 to 6The preparation method of the polyimide film with good thermal conductivity and thermal stability is characterized in that in S2, partial dicarboxylic anhydride monomers are added into diamine solution in batches, stirred and reacted for 1-2h, and then NH is added 2 -ZIFs @ RGO dispersion, stirring and reacting for 1-2h.
8. The method for preparing a polyimide film excellent in thermal conductivity and thermal stability according to any one of claims 1 to 7, wherein in S2, the organic solvent is one of N, N-dimethylacetamide, N-dimethylformamide, and N-methylpyrrolidone;
the diamine monomer is one or two of p-phenylenediamine, 4 '-diaminodiphenyl ether and 4,4' -diaminobenzanilide;
the binary anhydride monomer is one of pyromellitic dianhydride, 3', 4' -biphenyl tetracarboxylic dianhydride and 4,4' -biphenyl ether dianhydride.
9. The method for producing a polyimide film excellent in thermal conductivity and thermal stability according to any one of claims 1 to 8, wherein in S3, the specific operation of the stepwise thermal imidization treatment is as follows: keeping the temperature at 100 deg.C, 160 deg.C, 210 deg.C, 260 deg.C and 360 deg.C for 25-45min.
10. A polyimide film having good thermal conductivity and thermal stability, which is obtained by the method as claimed in any one of claims 1 to 9.
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| WO2022012076A1 (en) * | 2020-07-14 | 2022-01-20 | 广东工业大学 | Low-dielectric polyimide composite thin film material and preparation method therefor |
| CN114015231A (en) * | 2021-11-12 | 2022-02-08 | 安徽国风塑业股份有限公司 | High-thermal-conductivity polyimide film and preparation method thereof |
| CN114642975A (en) * | 2020-12-18 | 2022-06-21 | 中国石油化工股份有限公司 | Metal-organic framework mixed matrix membrane and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022012076A1 (en) * | 2020-07-14 | 2022-01-20 | 广东工业大学 | Low-dielectric polyimide composite thin film material and preparation method therefor |
| CN114642975A (en) * | 2020-12-18 | 2022-06-21 | 中国石油化工股份有限公司 | Metal-organic framework mixed matrix membrane and preparation method and application thereof |
| CN114015231A (en) * | 2021-11-12 | 2022-02-08 | 安徽国风塑业股份有限公司 | High-thermal-conductivity polyimide film and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| DANDAN HUANG等: "Synergistic effects of zeolite imidazole framework@graphene oxide composites in humidified mixed matrix membranes on CO2 separation", 《RSC ADVANCES》, pages 6099 - 6109 * |
| MINGMIN JIA等: "Amine-functionalized MOFs@GO as filler in mixed matrix membrane for selective CO2 separation", 《SEPARATION AND PURIFICATION TECHNOLOGY》, pages 63 - 69 * |
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