CN113604047A - Preparation method of boron nitride graphene oxide polyimide composite material - Google Patents
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 45
- 229910052582 BN Inorganic materials 0.000 title claims abstract description 39
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 239000004642 Polyimide Substances 0.000 title claims abstract description 24
- 229920001721 polyimide Polymers 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000945 filler Substances 0.000 claims abstract description 19
- 150000004985 diamines Chemical class 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 9
- 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 7
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000002135 nanosheet Substances 0.000 claims abstract description 7
- 125000006158 tetracarboxylic acid group Chemical group 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 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 239000000178 monomer Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 25
- 239000011259 mixed solution Substances 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 230000010355 oscillation Effects 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 239000012286 potassium permanganate Substances 0.000 claims description 5
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 4
- 238000005266 casting Methods 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 3
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 claims description 3
- -1 4, 4' -biphenyltetracarboxylic anhydride Chemical class 0.000 claims description 3
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 3
- 238000004108 freeze drying Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims description 2
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052796 boron Inorganic materials 0.000 abstract description 6
- 230000001105 regulatory effect Effects 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 3
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- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 abstract 1
- 229920006351 engineering plastic Polymers 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 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 2
- 239000011229 interlayer Substances 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
-
- 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
-
- 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
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention relates to a preparation method of a boron nitride graphene oxide polyimide composite material. The preparation method of the composite material comprises the steps of firstly preparing graphene oxide by a chemical oxidation method, simultaneously preparing boron nitride nanosheets from micron boron nitride by a hydrothermal method, preparing the heat-conducting and insulating composite filler by utilizing pi-pi interaction between the boron nitride and the graphene oxide, adding tetracarboxylic dianhydride monomer of diamine into N, N-dimethylacetamide of the composite filler, preparing polyamic acid in situ, and finally drying a solvent of polyamic acid solution added with the boron nitride-graphene oxide composite filler, and then dehydrating and imidizing at high temperature to obtain the boron nitride-graphene oxide polyimide composite material. The microstructure of the filler particles is regulated and controlled by simultaneously regulating and controlling the proportion of the boron nitride and the graphene oxide, so that the composite material is regulated and controlledThe thermal conductivity of the material, the thermal conductivity of the composite material prepared by the invention is more than 0.6W/mK, and the resistivity is more than 1 x 1011Ωm。
Description
Technical Field
The invention relates to a preparation method of a boron nitride graphene oxide polyimide composite material, and belongs to the field of heat-conducting composite materials.
Background
Polyimide (PI) refers to a high-performance engineering plastic containing imide ring (-CO-N-CO-) in the main chain. Polyimide can be widely applied to the fields of aerospace, microelectronics, lithium ion battery separation membranes and the like, mainly because the high temperature resistance of polyimide can reach more than 400 ℃, and the polyimide has extremely long service life in the temperature range of-200 ℃ to 300 ℃, and due to the advantages, the polyimide is called as one of polymer materials with optimal comprehensive performance in engineering plastics. In addition, the polyimide is simple in synthesis method and excellent in performance, can be produced in batches in actual production, keeps the optimal performance, and is considered as engineering plastic with the optimal application prospect in the 21 st century.
In order to make the polyimide be better applied in the field of heat-conducting insulating materials, the key point for solving the problem is to add high-performance filler into a polyimide matrix, the method combines the high heat-conducting property and the thermal stability of the filler, keeps the excellent heat resistance, dielectric property and flexibility of the polyimide, and the obtained polyimide/filler composite material has excellent comprehensive performance. Boron nitride is a typical two-dimensional ceramic material because of its similar interlayer structure to graphene, also known as "white graphite". Boron nitride has excellent insulating properties, high thermal conductivity, excellent mechanical properties, and corrosion resistance. Graphene is also a two-dimensional material with high thermal conductivity, and graphene oxide, as a derivative of graphene, is connected with a large number of oxygen-containing groups on the sheet layer while a honeycomb two-dimensional planar structure is kept, so that the graphene oxide has better chemical activity and solubility. According to the invention, the heat conduction and insulation properties of the polyimide-based composite material are improved by introducing high-heat-conduction particle hexagonal boron nitride and graphene oxide. Due to the similar interlayer structure of the boron nitride and the graphene oxide, pi-pi interaction exists between the two layers, the combination is easier, and the interface thermal resistance is lower.
Disclosure of Invention
The invention aims to solve the problems that the existing polyimide has poor heat-conducting property and the electric conductivity of the polyimide is increased after the conductive filler or graphene and other fillers are added, and provides a preparation method of a boron nitride-graphene oxide polyimide composite material. The preparation method specifically comprises the steps of firstly preparing graphene oxide by a chemical oxidation method, simultaneously preparing boron nitride nanosheets from micron boron nitride by a hydrothermal method, preparing a heat-conducting and insulating composite filler by utilizing pi-pi interaction between the boron nitride and the graphene oxide, adding a tetracarboxylic acid dianhydride monomer of diamine into N, N-dimethylacetamide of the composite filler, preparing polyamic acid in situ, and finally drying a solvent in a polyamic acid solution added with the boron nitride-graphene oxide composite filler, and then dehydrating and imidizing at high temperature to obtain the boron nitride-graphene oxide polyimide composite material.
The preparation method of the boron nitride graphene oxide polyimide composite material is characterized by comprising the following steps of: the preparation method comprises the following steps:
(1) adding flake graphite, concentrated sulfuric acid and concentrated phosphoric acid into a flask, mechanically stirring at 100-400 r/min, adding potassium permanganate into the system while stirring, continuously stirring for 10-40 min after the addition is finished, then placing the system into a water bath at 40-80 ℃, stirring at the speed of 200-1000 r/min for reaction for 8-16 h, and pouring a mixed solution obtained after the reaction into a reaction kettle, wherein the volume ratio of the mixed solution to the concentrated sulfuric acid is 1: 1, stirring for 3-10 min at a stirring speed of 30-200 r/min, adding 30% of hydrogen peroxide into the system while stirring until the mixed solution turns golden yellow, standing the mixed solution for 8-30 h, pouring out the supernatant, washing the turbid solution below with deionized water again, centrifuging until the pH value is 5.5-7.0, and finally obtaining graphene oxide by a freeze drying method; wherein the dosage ratio of the flake graphite, the potassium permanganate, the concentrated sulfuric acid and the concentrated phosphoric acid is 1 g: 5-10 g: 100-200 mL: 10-20 mL;
(2) dispersing commercially available micron boron nitride in 2-10 mol/L sodium hydroxide solution to prepare 2-10 g/L dispersion, placing the dispersion in an ultrasonic bath with oscillation frequency of 26kHz and output power of 100-500W for 2-10 h, transferring the dispersion to a hydrothermal kettle, reacting at 130-180 ℃ for 4-12 h, naturally cooling to room temperature after the reaction is finished, washing the product to be neutral with deionized water, and placing the product in a vacuum oven at 60 ℃ for drying for 2-10 h to obtain boron nitride nanosheets;
(3) mixing graphene oxide and boron nitride nanosheets according to a mass ratio of 1: 3-10, adding the mixture into N, N-dimethylacetamide, and carrying out ultrasonic treatment for 2-10 hours in an ultrasonic bath with oscillation frequency of 26kHz and output power of 100-500W at room temperature to obtain the boron nitride graphene oxide filler, wherein the concentration of the graphene oxide is 0.1-0.5 wt%;
(4) under the protection of nitrogen atmosphere, adding a diamine monomer into the system in the step (3), then adding tetracarboxylic dianhydride in 0.5-1 h, stirring and reacting for 8-16 h at room temperature to obtain a mixed solution of boron nitride graphene oxide polyamic acid, wherein the diamine is more than one of p-phenylenediamine, 4,4 '-diaminodiphenyl ether, 4, 4' -diaminophenylsulfone and 4,4 '-diaminodiphenylmethane, the tetracarboxylic dianhydride is more than one of pyromellitic dianhydride, 4, 4' -biphenyltetracarboxylic anhydride and 3,3 ', 4, 4' -benzophenonetetracarboxylic dianhydride, and the molar ratio of the diamine to the tetracarboxylic dianhydride is 1: 1, the concentration of diamine is 0.1-0.5 mol/L;
(5) and (4) casting the mixed solution obtained in the step (4) on a glass plate, drying in an oven at 120-180 ℃ until the solvent is completely volatilized, then placing in a muffle furnace, preserving the heat at 280-330 ℃ for 1-3 h, naturally cooling to room temperature, and stripping the sample from the glass plate to obtain the composite film.
The invention has the beneficial effects that: according to the invention, boron nitride and graphene oxide are added simultaneously, so that boron nitride is coated on graphene oxide, a heat conduction path is constructed, an insulating layer is formed, the increase of the electrical conductivity of the system is prevented, the boron nitride-graphene oxide composite filler is formed, the composite filler is added into polyimide by an in-situ dispersion method to prepare the composite material, and the finally obtained composite material has adjustable heat conductivity and electrical resistivity by regulating the proportion of the fillers. The thermal conductivity of the composite material prepared by the invention is more than 0.6W/mK, and the resistivity is more than 1 x 1011Ωm。
Drawings
FIG. 1 is a schematic diagram of preparation of boron nitride graphene oxide composite filler
Detailed Description
The following examples of the preparation process of the present invention are presented, but the following examples are illustrative of the present invention and do not constitute any limitation to the claims of the present invention.
Example 1
(1) Adding 1.5g of flake graphite, 180mL of concentrated sulfuric acid and 20mL of concentrated phosphoric acid into a 500mL three-neck flask, mechanically stirring at 120r/min, adding 9g of potassium permanganate into the system while stirring, continuously stirring for 30min after the addition is finished, then placing the system into a water bath at 50 ℃ to stir and react for 12h at the speed of 600r/min, and pouring a mixed solution obtained after the reaction into a reaction kettle, wherein the volume ratio of the mixed solution to the concentrated sulfuric acid is 1: 1, stirring for 5min at a stirring speed of 60r/min, adding 30% of hydrogen peroxide into the system while stirring until the mixed solution turns golden yellow, standing the mixed solution for 20h, then pouring out the supernatant, washing the turbid solution below with deionized water again, centrifuging until the pH value is 6, and finally obtaining graphene oxide by a freeze-drying method;
(2) dispersing commercially available micron boron nitride in 5mol/L sodium hydroxide solution to prepare 4g/L dispersion, placing the dispersion in an ultrasonic bath with oscillation frequency of 26kHz and output power of 500W for 2h, transferring the dispersion to a hydrothermal kettle, reacting for 6h at 150 ℃, naturally cooling to room temperature after the reaction is finished, washing the product to be neutral by deionized water, and placing the product in a vacuum oven at 60 ℃ for drying for 8h to obtain boron nitride nanosheets;
(3) adding 0.1g of graphene oxide and 0.5g of boron nitride into 100g of N, N-dimethylacetamide, and carrying out ultrasonic treatment for 2h at room temperature in an ultrasonic bath with oscillation frequency of 26kHz and output power of 500W to obtain boron nitride graphene oxide filler;
(4) under the protection of nitrogen atmosphere, adding 2.1g of 4, 4' -diaminodiphenyl ether into the system in the step (4), then adding 2.3g of pyromellitic anhydride within 0.5h, and stirring and reacting for 12h at room temperature to obtain a mixed solution of boron nitride graphene oxide polyamic acid;
(5) casting the mixed solution obtained in the step (5) on a glass plate, drying in an oven at 150 ℃ until the solvent is completely volatilized, then placing in a muffle furnace, preserving the heat at 300 ℃ for 2h, naturally cooling to room temperature, stripping a sample from the glass plate to obtain the composite material, wherein the thermal conductivity of the composite material reaches 0.6W/mK, and the resistance is 2.0 multiplied by 1011Ωm。
Example 2
(1) In accordance with example 1, step (1);
(2) in accordance with example 1, step (2); (ii) a
(3) Adding 0.1g of graphene oxide and 5g of boron nitride into 100g of N, N-dimethylacetamide, and carrying out ultrasonic treatment for 2h in an ultrasonic bath with oscillation frequency of 26kHz and output power of 500W at room temperature to obtain boron nitride graphene oxide filler;
(4) in accordance with step (4) of example 1;
(5) in accordance with example 1, step (5); the thermal conductivity of the composite material reaches 0.7W/mK, and the resistance is 2.5 multiplied by 1011Ωm。
Example 3
(1) In accordance with example 1, step (1);
(2) in accordance with example 1, step (2);
(3) in accordance with example 1, step (3);
(4) under the protection of nitrogen atmosphere, 4.2g of 4, 4' -diaminodiphenyl ether is added into the system in the step (4), 4.6g of pyromellitic anhydride is added within 0.5h, and the mixture is stirred and reacted for 12h at room temperature to obtain a mixed solution of boron nitride graphene oxide polyamic acid;
(5) consistent with the step (5) of the example 1, the thermal conductivity of the composite material reaches 0.6W/mK, and the electric resistance is 1.8 multiplied by 1011Ωm。
Example 4
(1) In accordance with example 1, step (1);
(2) in accordance with example 1, step (2);
(3) in accordance with example 1, step (3);
(4) under the protection of nitrogen atmosphere, adding 2.6g of 4, 4' -diamino phenylsulfone into the system in the step (4), then adding 2.3g of pyromellitic dianhydride within 0.5h, and stirring and reacting at room temperature for 12h to obtain a mixed solution of boron nitride graphene oxide polyamic acid;
(5) consistent with the step (5) of the example 1, the thermal conductivity of the composite material reaches 0.6W/mK, and the electric resistance is 2.0 multiplied by 1011Ωm。
Example 5
(1) In accordance with example 1, step (1);
(2) in accordance with example 1, step (2);
(3) in accordance with example 1, step (3);
(4) in accordance with step (4) of example 1;
(5) casting the mixed solution obtained in the step (4) on a glass plate, drying in an oven at 160 ℃ until the solvent is completely volatilized, then placing in a muffle furnace, preserving the heat at 280 ℃ for 3h, naturally cooling to room temperature, stripping a sample from the glass plate to obtain the composite material, wherein the thermal conductivity of the composite material reaches 0.6W/mK, and the resistance is 2.0 multiplied by 1011Ωm。
Claims (1)
1. A preparation method of a boron nitride graphene oxide polyimide composite material is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) adding flake graphite, concentrated sulfuric acid and concentrated phosphoric acid into a flask, mechanically stirring at 100-400 r/min, adding potassium permanganate into the system while stirring, continuously stirring for 10-40 min after the addition is finished, then placing the system into a water bath at 40-80 ℃, stirring at the speed of 200-1000 r/min for reaction for 8-16 h, and pouring a mixed solution obtained after the reaction into a reaction kettle, wherein the volume ratio of the mixed solution to the concentrated sulfuric acid is 1: 1, stirring for 3-10 min at a stirring speed of 30-200 r/min, adding 30% of hydrogen peroxide into the system while stirring until the mixed solution turns golden yellow, standing the mixed solution for 8-30 h, pouring out the supernatant, washing the turbid solution below with deionized water again, centrifuging until the pH value is 5.5-7.0, and finally obtaining graphene oxide by a freeze drying method; wherein the dosage ratio of the flake graphite, the potassium permanganate, the concentrated sulfuric acid and the concentrated phosphoric acid is 1 g: 5-10 g: 100-200 mL: 10-20 mL;
(2) dispersing commercially available micron boron nitride in 2-10 mol/L sodium hydroxide solution to prepare 2-10 g/L dispersion, placing the dispersion in an ultrasonic bath with oscillation frequency of 26kHz and output power of 100-500W for 2-10 h, transferring the dispersion to a hydrothermal kettle, reacting at 130-180 ℃ for 4-12 h, naturally cooling to room temperature after the reaction is finished, washing the product to be neutral with deionized water, and placing the product in a vacuum oven at 60 ℃ for drying for 2-10 h to obtain boron nitride nanosheets;
(3) mixing graphene oxide and boron nitride nanosheets according to a mass ratio of 1: 3-10, adding the mixture into N, N-dimethylacetamide, and carrying out ultrasonic treatment for 2-10 hours in an ultrasonic bath with oscillation frequency of 26kHz and output power of 100-500W at room temperature to obtain the boron nitride graphene oxide filler, wherein the concentration of the graphene oxide is 0.1-0.5 wt%;
(4) under the protection of nitrogen atmosphere, adding a diamine monomer into the system in the step (3), then adding tetracarboxylic dianhydride in 0.5-1 h, stirring and reacting for 8-16 h at room temperature to obtain a mixed solution of boron nitride graphene oxide polyamic acid, wherein the diamine is more than one of p-phenylenediamine, 4,4 '-diaminodiphenyl ether, 4, 4' -diaminophenylsulfone and 4,4 '-diaminodiphenylmethane, the tetracarboxylic dianhydride is more than one of pyromellitic dianhydride, 4, 4' -biphenyltetracarboxylic anhydride and 3,3 ', 4, 4' -benzophenonetetracarboxylic dianhydride, and the molar ratio of the diamine to the tetracarboxylic dianhydride is 1: 1, the concentration of diamine is 0.1-0.5 mol/L;
(5) and (4) casting the mixed solution obtained in the step (4) on a glass plate, drying in an oven at 120-180 ℃ until the solvent is completely volatilized, then placing in a muffle furnace, preserving the heat at 280-330 ℃ for 1-3 h, naturally cooling to room temperature, and stripping the sample from the glass plate to obtain the composite film.
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