CN115386111B - 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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- 229920001721 polyimide Polymers 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000013153 zeolitic imidazolate framework Substances 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 239000000178 monomer Substances 0.000 claims abstract description 28
- 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 24
- 150000004985 diamines Chemical class 0.000 claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004952 Polyamide Substances 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 18
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 18
- 229920002647 polyamide 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
- 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
- 239000006185 dispersion Substances 0.000 claims abstract description 12
- 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
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 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
- 239000007788 liquid Substances 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
- 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
- 238000000034 method Methods 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-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
- 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
- 238000005576 amination reaction Methods 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 4
- 238000001035 drying Methods 0.000 abstract description 2
- 229920006122 polyamide resin Polymers 0.000 abstract 1
- 239000004642 Polyimide Substances 0.000 description 19
- 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
- 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 10
- 239000011521 glass Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000011701 zinc Substances 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
- 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
- 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
-
- 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
- C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
-
- 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
- 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
- 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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- 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
- C08J2487/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
Abstract
The invention discloses a polyimide film with good thermal conductivity and thermal stability and a preparation method thereof, and relates 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 into the mixture, heating the mixture, and stirring the mixture for reaction; then adding hydrazine hydrate, stirring for reaction, cooling, centrifuging, washing and drying to obtain NH 2 -zifs@rgo; diamine monomer and NH 2 Adding ZIFs@RGO into an organic solvent to obtain a diamine solution and NH 2 -zifs@rgo dispersion; adding dianhydride monomer into diamine solution in batches, stirring for reaction, and then adding NH 2 Stirring and reacting ZIFs@RGO dispersion liquid, and finally adding a dianhydride monomer to regulate viscosity to prepare polyamide acid; coating polyamide acid into a film, carrying out sectional heating imidization treatment, and cooling to obtain the polyamide resin. The PI film prepared by the invention has high heat conductivity 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
Polyimide (PI) has been receiving attention in recent years due to its outstanding combination of properties, various synthetic routes, and broad use and better 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 heat cannot be timely conducted out when the polyimide is used as a supporting base material of various elements, and heat is easy to accumulate, thereby influencing the stability, service life and operation safety of the elements; some components need to operate for a long period of time even at high temperatures above 400 ℃, but PI films currently cannot withstand such high temperatures. The lower heat conductivity and thermal stability greatly limit the wider application of PI, so the development of PI films with high heat conductivity and high thermal stability is an important and urgent industrial requirement.
Graphene is widely focused on due to the ultrahigh thermal conductivity and good thermal stability, but the poor compatibility of graphene and a polymer can cause a large number of interfaces and the heat conduction is limited; in addition, graphene is easy to agglomerate in the polymer, difficult to disperse uniformly, cannot form a good heat conduction channel, and has an unsatisfactory heat conduction effect; in addition, the graphene has strong conductive performance, and the insulating performance is greatly reduced after the graphene is added into the 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, and the prepared polyimide film has high thermal conductivity coefficient, good thermal stability and simple preparation method.
The preparation method of the polyimide film with good thermal conductivity and thermal stability provided by the invention comprises the following steps:
S1、NH 2 -zifs@rgo preparation: dispersing graphene oxide into N, N-dimethylacetamide, adding zinc salt, aminoimidazole and methylimidazole into the mixture, heating the mixture, and stirring the mixture for reaction; then adding hydrazine hydrate into the reaction system, stirring for reaction, cooling to room temperature, centrifuging, washing, freeze-drying to obtain the amination ZIF loaded graphene composite material NH 2 -ZIFs@RGO；
S2, polyamidePreparation of amino acid: diamine monomer and NH 2 Adding ZIFs@RGO into an organic solvent to obtain a diamine solution and NH 2 -zifs@rgo dispersion; adding part of dianhydride monomer into diamine solution in batches, stirring for reaction, and then adding NH 2 Stirring and reacting the ZIFs@RGO dispersion liquid, and finally adding the rest of the dianhydride monomer to adjust viscosity to prepare polyamide acid containing ZIFs@RGO;
s3, preparing a polyimide film: coating polyamide acid containing ZIFs@RGO to form a film, carrying out sectional heating imidization treatment, and cooling to obtain the polyamide acid.
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 methylimidazole and aminoimidazole to zinc salt is 2-5:1, a step of; the mass ratio of the methylimidazole to the aminoimidazole is 1:0.1-0.5.
Preferably, in S1, zinc salt, aminoimidazole and methylimidazole are added, the temperature is raised to 80-120 ℃, and stirring reaction is carried out for 12-48 hours; 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 dianhydride monomer is 1:1-1.05, NH 2 The mass ratio of ZIFs@RGO to diamine monomer is 0.1-0.5:1.
preferably, in S2, the dianhydride monomer is added into the diamine solution in 2-3 batches, and the total amount of the added dianhydride monomer in batches accounts for 94-98% of the total mass of the dianhydride monomer.
Preferably, in S2, part of the dianhydride monomer is added into the diamine solution in batches, stirred for reaction for 1-2h, and then NH is added 2 The ZIFs@RGO dispersion is stirred 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' -diaminoanilide;
the dianhydride 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 step-wise heating imidization treatment is as follows: respectively maintaining the temperature at 100deg.C, 160deg.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 prepared by the method.
The beneficial effects are that: according to the invention, partial methylimidazole is replaced by aminoimidazole to obtain an aminated organic metal framework material (ZIFs), and the ZIFs are grown on the surface of the graphene sheet layer by a thermal solvent method so as to be loaded on graphene (RGO). Firstly, amino on ZIFs can participate in polymerization reaction of diamine and dianhydride monomers, a blocking effect is achieved on a molecular chain, thermal stability of a PI film can be improved, and the dianhydride is added in batches to enable the reaction to be more fully carried out. And secondly, the organic ligand for synthesizing ZIFs has good compatibility with the PI matrix polymer, so that RGO loaded with 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, ZIFs loaded on the RGO surface can weaken the conductivity of the ZIFs, so that the inherent insulating property of the PI film can be maintained. The preparation method is simple in preparation process, and the prepared PI film is high in heat conductivity coefficient and heat stability, good in mechanical property and good in popularization and use value.
Detailed Description
The technical scheme of the invention is described in detail through specific embodiments.
Example 1
1) 0.5g GO was dispersed in DMAC solvent and stirred for 1h followed by 1.2. 1.2gZn (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, 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 materials;
2) 3g PDA and 7g ODA were added to 102g DMAC to dissolve, while 5gNH 2 ZIFs@RGO was dispersed in 45g DMAC and dispersed in a disperser for 1 hour;
3) 13g PMDA is weighed and added into the diamine solution for reaction for 3 times, each time is separated by half an hour, and then 12.5gNH dispersed in 2) is weighed 2 Adding ZIFs@RGO dispersion liquid into the solution for reacting for 1 hour, then adding 0.7g PMDA for viscosity adjustment, stopping the reaction when the viscosity of the system reaches 60000 MPa.s, preparing polyamide acid containing ZIFs@RGO, and carrying out vacuum defoaming treatment in a-1 MPa oven;
4) Coating the defoaming-treated polyamide acid on a glass plate of an automatic coating machine to form a film, enabling the film thickness to be 50 mu m, finally carrying out imidization treatment, desolvating at 100 ℃ for 40min, insulating at 160 ℃ for 40min, insulating at 210 ℃ for 40min, insulating at 260 ℃ for 40min, and cooling after completion to obtain the polyimide film containing ZIFs@RGO.
Example 2
1)NH 2 The preparation method of the-ZIFs@RGO is the same as that of example 1;
2) 3g PDA and 7g ODA were added to 96g DMAC to dissolve, while 5gNH 2 ZIFs@RGO was dispersed in 45g DMAC and dispersed in a disperser for 2 hours;
3) 13g of PMDA is weighed and added into the diamine solution for reaction for 3 times, each time is separated by half an hour, and then 26.3g of NH dispersed in 2) is weighed 2 Adding ZIFs@RGO dispersion liquid into the solution for reacting for 1 hour, then adding 0.7g PMDA for viscosity adjustment, stopping the reaction when the viscosity of the system reaches 60000 MPa.s, preparing polyamide acid containing ZIFs@RGO, and carrying out vacuum defoaming treatment in a-1 MPa oven;
4) Coating the defoaming-treated polyamide acid on a glass plate of an automatic coating machine to form a film, enabling the film thickness to be 50 mu m, finally carrying out imidization treatment, desolvating at 100 ℃ for 40min, insulating at 160 ℃ for 40min, insulating at 210 ℃ for 40min, insulating at 260 ℃ for 40min, and cooling after completion to obtain the polyimide film containing ZIFs@RGO.
Example 3
1)NH 2 The preparation method of the-ZIFs@RGO is the same as that of example 1;
2) 3g PDA and 7g ODA were added to 90g DMAC to dissolve, while 5gNH 2 ZIFs@RGO was dispersed in 45g DMAC and dispersed in a disperser for 2 hours;
3) 13g of PMDA is weighed and added into the diamine solution for reaction for 3 times, each time is separated by half an hour, and then 41.8gNH dispersed in 2) is weighed 2 Adding ZIFs@RGO dispersion liquid into the solution for reacting for 1 hour, then adding 0.7g PMDA for viscosity adjustment, stopping the reaction when the viscosity of the system reaches 60000 MPa.s, preparing polyamide acid containing ZIFs@RGO, and carrying out vacuum defoaming treatment in a-1 MPa oven;
4) Coating the defoaming-treated polyamide acid on a glass plate of an automatic coating machine to form a film, enabling the film thickness to be 50 mu m, finally carrying out imidization treatment, desolvating at 100 ℃ for 40min, insulating at 160 ℃ for 40min, insulating at 210 ℃ for 40min, insulating at 260 ℃ for 40min, and cooling after completion 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 dissolution, after reacting for 1 hour, adding 13g of PMDA into the solution for 3 times on average, each time for half an hour, then adding 0.7g of PMDA for viscosity adjustment, when the viscosity of the system reaches 60000 MPa.s, preparing polyamide acid, and carrying out vacuum defoaming treatment in a-1 Mpa oven;
2) Coating the defoaming-treated polyamic acid on a glass plate of an automatic coating machine to form a film, enabling the film thickness to be 50 mu m, then desolvating for 40min at 100 ℃, finally carrying out imidization treatment, wherein the imidization process is that the temperature is kept at 160 ℃ for 40min, the temperature is kept at 210 ℃ for 40min, the temperature is kept at 260 ℃ for 40min, and the temperature is kept at 360 ℃ for 40min, and cooling is carried out after the completion to obtain the polyimide film.
Comparative example 2
1) ZIF8@RGO preparation: dispersing 0.5g GO in a DMAC solvent, and stirring and dispersing for 1h; subsequently 1.2g Zn (NO) 3 ) 2 ·6H 2 Adding O and 3g of 2-methylimidazole into the solution, heating to 100 ℃ for reaction for 24 hours, 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 addingDrying the obtained product in a freeze dryer for 3 hours to obtain a ZIF8@RGO composite material;
2) 3g PDA and 7g ODA were added to 102g DMAC to dissolve, while 5g ZIF8@RGO was dispersed in 45g DMAC and dispersed in a disperser for 1 hour;
3) 13g of PMDA is weighed and added into the diamine solution for reaction for 3 times, each time at intervals of half an hour, then 12.5g of ZIF8@RGO dispersion liquid which is well dispersed in 2) is weighed and added into the solution for reaction for 1 hour, then 0.7g of PMDA is added for viscosity adjustment, the reaction is stopped when the viscosity of the system reaches 60000 MPa.s, polyamide acid containing ZIF8@RGO is prepared, and vacuum defoaming treatment is carried out in a-1 MPa oven;
4) Coating the defoaming-treated polyamide acid on a glass plate of an automatic coating machine to form a film, enabling the film thickness to be 50 mu m, finally carrying out imidization treatment, desolvating at 100 ℃ for 40min, insulating at 160 ℃ for 40min, insulating at 210 ℃ for 30min, insulating at 260 ℃ for 40min, and insulating at 360 ℃ for 40min, and cooling after completion to obtain the polyimide film containing ZIF8@RGO.
The thermal conductivity, TGA data, volume resistivity and mechanical properties of each polyimide film prepared in examples and comparative examples of the present invention 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 ZIFs@RGO content, the thermal conductivity of the PI composite film is continuously increased, the thermal stability is greatly improved, and the volume resistivity is reduced, but the insulating performance is far higher than that of the standard insulating material 10 6 Volume resistivity of the order of magnitude; in addition, partial 2-aminoimidazole is used for replacing 2-methylimidazole, and the performance of the ZIFs@RGO/PI composite film is better than that of ZIF8@RGO/PI composite film performance; and the tensile strength is not greatly reduced, and basically can be maintained, so that the PI composite film maintains the excellent performance of the PI film.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (8)
1. The preparation method of the 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 into the mixture, heating the mixture, and stirring the mixture for reaction; then adding hydrazine hydrate into the reaction system, stirring for reaction, cooling to room temperature, centrifuging, washing, freeze-drying to obtain the amination ZIF loaded graphene composite material NH 2 -ZIFs@RGO；
S2, preparing polyamide acid: diamine monomer and NH 2 Adding ZIFs@RGO into an organic solvent to obtain a diamine solution and NH 2 -zifs@rgo dispersion; adding part of dianhydride monomer into diamine solution in batches, stirring for reaction, and then adding NH 2 Stirring and reacting the ZIFs@RGO dispersion liquid, and finally adding the rest of the dianhydride monomer to adjust viscosity to prepare polyamide acid containing ZIFs@RGO;
s3, preparing a polyimide film: coating polyamide acid containing ZIFs@RGO to form a film, carrying out sectional heating imidization treatment, and cooling to obtain the polyamide acid;
the mass ratio of the methylimidazole to the aminoimidazole is 1:0.1-0.5;
in S1, the mass ratio of graphene oxide to zinc salt is 1:2-5; the mass ratio of the total mass of methylimidazole and aminoimidazole to zinc salt is 2-5:1, a step of;
in S2, the molar ratio of diamine monomer to dianhydride monomer is 1:1-1.05, NH 2 -ZIFs@The mass ratio of RGO to diamine monomer is 0.1-0.5:1.
2. the method for producing a polyimide film having excellent thermal conductivity and thermal stability according to claim 1, wherein in S1, the particle diameter 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 with good thermal conductivity and thermal stability according to claim 1, wherein in S1, zinc salt, aminoimidazole and methylimidazole are added, the temperature is raised to 80-120 ℃, and stirring reaction is carried out for 12-48 hours; then adding hydrazine hydrate into the reaction system, and stirring for reaction for 1-2h.
4. The method for preparing a polyimide film with good thermal conductivity and thermal stability according to claim 1, wherein in S2, part of the dianhydride monomer is added into the diamine solution in 2-3 batches, and the total amount of the added dianhydride monomer in batches is 94-98% of the total mass of the dianhydride monomer.
5. The method for producing a polyimide film having excellent thermal conductivity and thermal stability according to claim 1, wherein in S2, a part of the dianhydride monomer is added to the diamine solution in batches, the reaction is carried out for 1 to 2 hours with stirring, and then NH is added 2 The ZIFs@RGO dispersion is stirred for 1-2h.
6. The method for producing a polyimide film having excellent thermal conductivity and thermal stability according to claim 1, 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' -diaminoanilide;
the dianhydride monomer is one of pyromellitic dianhydride, 3', 4' -biphenyl tetracarboxylic dianhydride and 4,4' -biphenyl ether dianhydride.
7. The method for producing a polyimide film having excellent thermal conductivity and thermal stability according to claim 1, wherein in S3, the specific operation of the step of heating imidization treatment is as follows: respectively maintaining the temperature at 100deg.C, 160deg.C, 210 deg.C, 260 deg.C and 360 deg.C for 25-45min.
8. The polyimide film with good thermal conductivity and thermal stability prepared by the method of any one of claims 1 to 7.
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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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| 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 |
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