CN113754925B - Insulating base material-carbon nano tube hybrid material and preparation method and application thereof - Google Patents
Insulating base material-carbon nano tube hybrid material and preparation method and application thereof Download PDFInfo
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- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 144
- 239000000463 material Substances 0.000 title claims abstract description 131
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 94
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 167
- 239000003822 epoxy resin Substances 0.000 claims abstract description 166
- 239000000203 mixture Substances 0.000 claims abstract description 80
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000000945 filler Substances 0.000 claims abstract description 59
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000004100 electronic packaging Methods 0.000 claims abstract description 7
- 239000005022 packaging material Substances 0.000 claims abstract description 7
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 45
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 14
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 12
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 12
- 238000005245 sintering Methods 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 7
- 229940071536 silver acetate Drugs 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000009413 insulation Methods 0.000 abstract description 6
- 239000002131 composite material Substances 0.000 abstract description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 36
- 229910052582 BN Inorganic materials 0.000 description 34
- 230000000052 comparative effect Effects 0.000 description 32
- 238000012360 testing method Methods 0.000 description 20
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 11
- 238000011049 filling Methods 0.000 description 11
- 238000010292 electrical insulation Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 239000011810 insulating material Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000017525 heat dissipation Effects 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012772 electrical insulation material Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
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- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- 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
- C08K3/041—Carbon nanotubes
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- C08K3/38—Boron-containing compounds
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- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
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Abstract
The application relates to the technical field of preparation of heat-conducting insulating fillers, in particular to an insulating base material-carbon nanotube hybrid material and a preparation method and application thereof. An insulating base material-carbon nanotube hybrid material comprises a heat-conducting insulating base material serving as a base material, a connecting material and Carbon Nanotubes (CNTs), wherein the connecting material connects the heat-conducting insulating base material and the CNTs together; the connecting material of the heat-conducting insulating base material and the CNTs is a nano silver sintered body. The carbon nanotube hybrid material is easy to lap in the epoxy resin composition to form a heat conduction path, and simultaneously, because CNTs connected to the surface of a base material are separated by the heat conduction insulating base material and are not connected with each other, a composite system still keeps good electric insulation property and can be used for various electric insulation and electronic packaging materials.
Description
Technical Field
The application relates to the technical field of preparation of heat-conducting insulating fillers, in particular to an insulating base material-carbon nanotube hybrid material and a preparation method and application thereof.
Background
The insulating material is a key basic material of electrical equipment, and the performance of the insulating material directly influences the operational reliability and the service life of the equipment. In the operation process of the electrical equipment, heat generated by the current heat effect must be conducted or dissipated outwards in time through the insulating layer, otherwise, the temperature is increased, the working stability is affected, and even faults or accidents occur in severe cases. Modern electrical equipment tends to develop towards high power, small volume and light weight, and as a result of the trend, more heat is generated in the limited volume, and if the heat cannot be dissipated in time, the reliability and stability of the operation of the equipment are seriously affected. The adoption of the high-thermal-conductivity insulating material is the most effective way for solving the heat dissipation problem of the electrical equipment structure. The most widely used epoxy resins in electrical insulationHowever, the thermal conductivity of the pure epoxy resin material is low (about 0.20W (m.K)) -1 ) It is increasingly difficult to meet the timely and efficient heat dissipation requirements of modern electrical and electronic equipment, and becomes one of the major technical bottlenecks in the development of the electrical and electronic industry.
The filling type heat-conducting insulating epoxy resin has simple preparation process and lower production cost, thereby being widely applied. A commonly used thermally conductive and insulating filler is alumina (Al) 2 O 3 ) Boron Nitride (BN), magnesium oxide (MgO), aluminum nitride (AlN), and the like. Al (Al) 2 O 3 Because of its excellent electrical insulation, high thermal conductivity and low cost, it is widely used in electrical insulation materials. Al (Al) 2 O 3 Especially spherical Al 2 O 3 Dispersed in epoxy resins, high filling and low viscosity can be achieved due to low shear resistance. Although Al 2 O 3 Has high thermal conductivity (33-36W (m.K) -1 ) However, al is actually used 2 O 3 The thermal conductivity improvement of filled epoxies is quite limited. For example: when the filler volume content is 50%, al 2 O 3 The thermal conductivity of the epoxy resin composite material is about 1.30W (m.K) -1 Only pure Al 2 O 3 3.5% -4.0%, the advantage of high thermal conductivity of the filler is not fully exerted. BN has a thermal conductivity as high as 280W (m.K) -1 However, the thermal conductivity of BN-filled epoxy resins has also been improved only to a limited extent. For example: when the volume content of the filler is 15 percent, the thermal conductivity coefficient of the BN/epoxy resin composite material is 0.90W (m.K) -1 About, less than 0.4% of pure BN, and the advantage of high thermal conductivity of BN is not shown. Al (Al) 2 O 3 The thermal conductivity of BN-filled epoxy composites has been improved only to a limited extent, mainly because the thermally conductive fillers are isolated by the matrix and cannot be interconnected to form an effective thermally conductive path.
The Carbon Nanotubes (CNTs) have extremely high thermal conductivity and high length-diameter ratio, are easy to be mutually connected in a polymer matrix to form a heat conduction path, can obviously improve the thermal conductivity of the polymer under the condition of lower content, and are ideal fillers for improving the thermal conductivity of the polymer. However, CNTs have extremely high electrical conductivity and are not suitable for insulating and heat conducting occasions. In addition, the CNTs have large specific surface area and high surface energy, and are easy to agglomerate in a polymer matrix, so that the modification effect of the CNTs on the polymer is not ideal.
Disclosure of Invention
In view of the problems of the related art, the present application provides an insulating substrate-carbon nanotube hybrid material, and a preparation method and use thereof.
In a first aspect, the present application provides an insulating base material-carbon nanotube hybrid material, which is implemented by the following technical scheme:
an insulating base material-carbon nanotube hybrid material comprises a heat-conducting insulating base material serving as a base material, a connecting material and Carbon Nanotubes (CNTs), wherein the connecting material connects the heat-conducting insulating base material and the CNTs together; the connecting material of the heat-conducting insulating base material and the CNTs is a nano silver sintered body.
By adopting the technical scheme, the insulating base material-carbon nanotube hybrid material in the application is easy to be mutually lapped in the epoxy resin composition to form a heat conduction path, and simultaneously, because CNTs connected to the surface of the base material are separated by the heat conduction insulating base material and are not mutually connected, the composite system still keeps good electric insulation property, and can be used for various electric insulation and electronic packaging materials.
Preferably, the heat-conducting insulating base material is alpha-alumina (Al) 2 O 3 )。
Preferably, the thermally conductive and insulating substrate is Boron Nitride (BN).
By adopting the technical scheme, al can be prepared 2 O 3 The carbon nanotube hybrid material and the BN-carbon nanotube hybrid material are used as fillers in an epoxy resin system, can obviously improve the thermal conductivity of an epoxy resin condensate, still keep good electrical insulation, and have wide application prospect in the fields of electrical insulating materials and electronic packaging materials.
In a second aspect, the present application provides a method for preparing an insulating base material-carbon nanotube hybrid material, which is implemented by the following technical scheme:
a preparation method of an insulating substrate-carbon nanotube hybrid material comprises the following steps:
step one, dissolving 2-ethyl-4-methylimidazole (2E 4 MI) and silver acetate (AgAc) in dichloromethane to prepare Ag (2E 4 MI) 2 An Ac complex solution;
step two, ag (2E 4 MI) obtained in step one 2 Adding polyvinylpyrrolidone (PVP) and CNTs into the Ac complex solution, adding a heat-conducting insulating base material after ultrasonic dispersion is carried out for 1-4 hours, and then carrying out ultrasonic dispersion for 0.2-1 hour;
step three, after removing dichloromethane by distilling the dispersion liquid obtained in the step two under reduced pressure, carrying out high-temperature sintering treatment on the solid, wherein the high-temperature sintering temperature is 200-220 ℃;
and step four, crushing the solid obtained in the step three, dispersing the solid in ethanol, grinding, filtering and drying to obtain the heat-conducting insulating base material-CNTs hybrid material.
Preferably, the amount of the 2-ethyl-4-methylimidazole 2E4MI used in the first step is 0.02mol; the dosage of the silver acetate AgAc is 0.01mol; the amount of dichloromethane used was 400mL.
Preferably, when the thermally conductive and insulating substrate is alpha-alumina (Al) 2 O 3 ) In the second step, alpha-alumina (Al) 2 O 3 ) The dosage is 50g; CNTs and PVP were used in an amount of 0.5g each.
Preferably, when the thermally conductive and insulating substrate is Boron Nitride (BN), the amount of Boron Nitride (BN) used in step two is 5.0g, and the amounts of cnts and PVP are 0.5 g.
In a third aspect, the application of the insulating base material-carbon nanotube hybrid material provided by the present application is realized by the following technical scheme:
the application of the heat-conducting insulating base material-CNTs hybrid material is used as a heat-conducting insulating filler for various electrical insulating and electronic packaging materials.
By adopting the technical scheme, the electric insulating material and the electronic packaging material can be endowed with high heat conduction and good electric insulation property.
Preferably, the heat-conducting and insulating substrate-CNTs hybrid material is used as a heat-conducting and insulating filler for a heat-conducting and insulating epoxy resin composition; the heat-conducting and insulating epoxy resin composition comprises epoxy resin, a curing agent and a heat-conducting and insulating base material-CNTs hybrid material.
By adopting the technical scheme, the cured epoxy resin composition can be endowed with high heat conduction and good electrical insulation, the viscosity of an epoxy resin system can be reduced under the condition of obtaining the same heat conductivity, and the product has the characteristics of low viscosity and high heat conduction, and is convenient to process, produce, cast and package.
In summary, the present application has the following advantages:
1. the cured product obtained by applying the prepared heat-conducting insulating base material-carbon nanotube hybrid material as a filler to a heat-conducting insulating epoxy resin composition has the advantages of high heat conduction and good electric insulating property, and mainly comprises the heat-conducting insulating base material-carbon nanotube hybrid material which is easy to lap in the epoxy resin composition to form a heat-conducting path, and CNTs connected to the surface of the heat-conducting insulating base material are separated by the heat-conducting insulating base material and are not connected with each other, so that the epoxy resin composition system still keeps good electric insulating property, and the epoxy resin composition system can be used for various electric insulating and electronic packaging materials.
2. The heat-conducting insulating base material-carbon nano tube hybrid material provided by the application is filled in the epoxy resin composition, a heat-conducting path can be formed under the condition of less addition amount, the heat conductivity is obviously improved, and the high heat-conducting property of a cured product of the epoxy resin composition is ensured; under the condition of obtaining the same thermal conductivity, the viscosity of the heat-conducting insulating base material-carbon nano tube hybrid material/epoxy resin system is lower, and the product has the characteristics of low viscosity and high thermal conductivity, and is convenient to process, produce, cast and package.
3. The heat-conducting insulating base material-carbon nanotube hybrid material prepared in the application is of a heat-conducting insulating base material-carbon nanotube hybrid structure, so that the dispersibility of the carbon nanotubes in a resin matrix can be improved, the agglomeration is eliminated, and the advantage of high heat conductivity of the carbon nanotubes is fully exerted.
Detailed Description
The present application will be described in further detail with reference to examples.
Starting materials
Examples
Example 1
The hybrid material comprises a heat-conducting insulating base material serving as a base material, a connecting material and Carbon Nanotubes (CNTs), wherein the connecting material connects the heat-conducting insulating base material and the CNTs together. Wherein the connecting material of the heat-conducting insulating base material and the CNTs is a nano silver sintered body, and the heat-conducting insulating base material is alpha-alumina (Al) 2 O 3 ). Alpha-alumina (Al) 2 O 3 ) SA-10 alpha-alumina from Shanghai \29760.
Al (aluminum) 2 O 3 -a method for preparing a carbon nanotube hybrid material comprising the steps of:
the method comprises the following steps: adding 0.02mol of 2-ethyl-4-methylimidazole 2E4MI and 0.01mol of silver acetate AgAc into 400mL of dichloromethane at room temperature, magnetically stirring at the rotating speed of 240r/min for 1-2 hours until AgAc particles completely disappear to obtain clear and transparent Ag (2E 4 MI) 2 An Ac complex solution;
step two: in Ag (2E 4 MI) 2 And adding 0.5g of CNTs and 0.5g of PVP into the Ac complex solution, performing ultrasonic dispersion (the power of an ultrasonic generator is 1200W, the frequency is 20 kHz) for 3 hours, adding 50g of alpha-alumina, and continuing to perform ultrasonic dispersion for 0.5 hour to obtain a dispersion liquid.
Step three: and (4) carrying out reduced pressure distillation treatment on the dispersion liquid obtained in the step two, removing dichloromethane in the dispersion liquid, and then carrying out high-temperature sintering treatment on the solid, wherein the high-temperature sintering temperature is controlled at 210 ℃, and the high-temperature sintering time is 4 hours, so as to obtain the solid.
Step four: grinding the solid obtained in the third step in a three-roller machine (the roller distance of the three-roller machine is 30 mu m) for 3 times, dispersing in 400mL of ethanol, pouring into a basket grinder for grinding, grinding at the rotating speed of 2000r/min for 0.5 hour, filtering and drying to obtain Al 2 O 3 -CNTs hybrid material, al obtained 2 O 3 The density of the-CNTs hybrid material is 3.92 g/cc.
Al (aluminum) 2 O 3 Use of hybrid materials of carbon nanotubes, al 2 O 3 -carbon nanotube hybrid material as filler for thermally conductive and electrically insulating epoxy resin composition.
Preparation of epoxy resin composition: 93g of bisphenol A type epoxy resin (CYD 128), 7g of curing agent (OMICURE BC-120) and 200g of Al are mixed by weight 2 O 3 And (3) dispersing the-CNTs hybrid material at a high speed of 600rpm for 1 hour to obtain 300g of the heat-conducting and insulating epoxy resin composition.
Preparation of cured product of epoxy resin composition: the prepared heat-conducting insulating epoxy resin composition is defoamed for 1 hour under the vacuum condition of 80 ℃, and then is cured at the temperature of 130 ℃/4 hours to obtain a cured heat-conducting insulating epoxy resin. The obtained cured heat-conducting insulating epoxy resin is used for testing and analyzing the heat conductivity coefficient and the resistivity. Al in the obtained heat-conducting insulating epoxy resin condensate 2 O 3 The volume content of the-CNTs hybrid material was 38.0%.
Example 2
Example 2 differs from example 1 in that:
al (aluminum) 2 O 3 Use of hybrid materials of carbon nanotubes, al 2 O 3 -carbon nanotube hybrid material as filler for thermally conductive and electrically insulating epoxy resin composition.
Preparation of epoxy resin composition: 93g of bisphenol A type epoxy resin (CYD 128), 7g of curing agent (OMICURE BC-120) and 300g of Al by weight 2 O 3 And (3) dispersing the-CNTs hybrid material at a high speed of 600rpm for 1 hour to obtain 400g of the heat-conducting and insulating epoxy resin composition.
Preparation of cured product of epoxy resin composition: the prepared heat-conducting insulating epoxy resin composition is defoamed for 1 hour at 80 ℃ under a vacuum condition, and then is cured at 130 ℃/4 hours to obtain a cured heat-conducting insulating epoxy resin. The obtained cured heat-conducting insulating epoxy resin is used for testing and analyzing the heat conductivity coefficient and the resistivity. Al in the obtained heat-conducting insulating epoxy resin condensate 2 O 3 Volume content of-CNTs hybrid MaterialThe content was 47.9%.
Example 3
Example 3 differs from example 1 in that:
al (aluminum) 2 O 3 Use of hybrid materials of carbon nanotubes, al 2 O 3 -carbon nanotube hybrid materials as fillers for thermally conductive and insulating epoxy resin compositions.
Preparation of epoxy resin composition: 93g of bisphenol A type epoxy resin (CYD 128), 7g of curing agent (OMICURE BC-120) and 400g of Al 2 O 3 And (3) dispersing the-CNTs hybrid material at a high speed of 600rpm for 1 hour to obtain 500g of the heat-conducting and insulating epoxy resin composition.
Preparation of cured product of epoxy resin composition: the prepared heat-conducting insulating epoxy resin composition is defoamed for 1 hour at 80 ℃ under a vacuum condition, and then is cured at 130 ℃/4 hours to obtain a cured heat-conducting insulating epoxy resin. The obtained cured heat-conducting insulating epoxy resin is used for testing and analyzing the heat conductivity coefficient and the resistivity. Al in the obtained heat-conducting insulating epoxy resin condensate 2 O 3 The volume content of the-CNTs hybrid material is 55.0%.
Example 4
The hybrid material of the insulating base material and the carbon nano tube is a heat-conducting insulating base material, a connecting material and Carbon Nano Tubes (CNTs) which are used as base materials, wherein the connecting material connects the heat-conducting insulating base material and the CNTs together; the connecting material of the heat-conducting insulating base material and the CNTs is a nano silver sintered body. The thermally conductive and insulating substrate is Boron Nitride (BN), which is available from chemical research institute, inc. of Dandon, and is grade HF.
A preparation method of a Boron Nitride (BN) -carbon nanotube hybrid material comprises the following steps:
the method comprises the following steps: adding 0.02mol of 2-ethyl-4-methylimidazole 2E4MI and 0.01mol of silver acetate AgAc into 400mL of dichloromethane at room temperature, magnetically stirring at the rotating speed of 240r/min for 1-2 hours until AgAc particles completely disappear to obtain clear and transparent Ag (2E 4 MI) 2 An Ac complex solution;
step two: in Ag (2E 4M)I) 2 0.5g of CNTs and 0.5g of PVP are added into the Ac complex solution, ultrasonic dispersion (the power of an ultrasonic generator is 1200W, the frequency is 20 kHz) is adopted for 3 hours, 5g of boron nitride BN is added, and the ultrasonic dispersion is continued for 0.5 hour to obtain dispersion liquid.
Step three: and D, carrying out reduced pressure distillation treatment on the dispersion liquid obtained in the step two, removing dichloromethane in the dispersion liquid, and then carrying out high-temperature sintering treatment on the solid, wherein the high-temperature sintering temperature is controlled at 210 ℃, and the high-temperature sintering time is 4 hours, so as to obtain the solid.
Step four: and (3) putting the solid obtained in the third step into a three-roller machine (the roller spacing of the three-roller machine is 30 mu m), grinding and crushing for 3 times, dispersing in 400mL of ethanol, pouring into a basket type grinder, grinding for 0.5 hour at the rotating speed of 2000r/min, filtering and drying to obtain the BN-CNTs hybrid material. The material density was 2.62 g/cc.
An application of Boron Nitride (BN) -carbon nanotube hybrid material in preparing the heat-conducting and insulating epoxy resin composition and its solidified substance is disclosed.
Preparation of epoxy resin composition: 93g of bisphenol A type epoxy resin (CYD 128), 7g of curing agent (OMICURE BC-120), and 25g of BN-CNTs hybrid material are dispersed for 1 hour at a high speed of 600rpm to obtain 125g of heat-conducting insulating epoxy resin composition.
Preparation of cured product of epoxy resin composition: the prepared heat-conducting insulating epoxy resin composition is defoamed for 1 hour at 80 ℃ under a vacuum condition, and then is cured at 130 ℃/4 hours to obtain a cured heat-conducting insulating epoxy resin. The obtained cured heat-conducting insulating epoxy resin is used for testing and analyzing the heat conductivity coefficient and the resistivity. The volume content of BN-CNTs hybrid material in the obtained heat-conducting and insulating epoxy resin cured material is 10.27%.
Example 5
Example 5 differs from example 4 in that:
preparation of epoxy resin composition: 93g of bisphenol A type epoxy resin (CYD 128), 7g of curing agent (OMICURE BC-120), 35g of BN-CNTs hybrid material are dispersed for 1 hour at a high speed of 600rpm to obtain 135g of the heat-conducting insulating epoxy resin composition.
Preparation of cured product of epoxy resin composition: the prepared heat-conducting insulating epoxy resin composition is defoamed for 1 hour at 80 ℃ under a vacuum condition, and then is cured at 130 ℃/4 hours to obtain a cured heat-conducting insulating epoxy resin. The obtained cured heat-conducting insulating epoxy resin is used for testing and analyzing the heat conductivity coefficient and the resistivity. The volume content of the BN-CNTs hybrid material in the obtained heat-conducting and insulating epoxy resin cured product is 13.82%.
Example 6
Example 6 differs from example 4 in that:
preparation of epoxy resin composition: 93g of bisphenol A type epoxy resin (CYD 128), 7g of curing agent (OMICURE BC-120) and 45g of BN-CNTs hybrid material are dispersed for 1 hour at a high speed of 600rpm to obtain 145g of the heat-conducting insulating epoxy resin composition.
Preparation of cured product of epoxy resin composition: the prepared heat-conducting insulating epoxy resin composition is defoamed for 1 hour at 80 ℃ under a vacuum condition, and then is cured at 130 ℃/4 hours to obtain a cured heat-conducting insulating epoxy resin. The obtained cured heat-conducting insulating epoxy resin is used for testing and analyzing the heat conductivity coefficient and the resistivity. The volume content of the BN-CNTs hybrid material in the obtained cured heat-conducting insulating epoxy resin is 17.09%.
Comparative example
Comparative example 1
The preparation method of the cured product of the epoxy resin composition comprises the following specific steps:
the first step is as follows: by weight, 93g of bisphenol A type epoxy resin (CYD 128), 7g of curing agent (OMICURE BC-120), al 2 O 3 200g of/nano silver/CNTs mixed filler is dispersed for 1 hour at a high speed of 600rpm to obtain 300g of the heat-conducting and insulating epoxy resin composition. Wherein. Al (aluminum) 2 O 3 Mixing ratio of/Nano silver/CNTs to Al prepared in example 1 2 O 3 Al in-CNTs hybrid material 2 O 3 The ratio of nano silver to CNTs is the same, al 2 O 3 The mass ratio of nano silver to CNTs is as follows: 50:1.08:0.5.
the second step is that: the prepared heat-conducting insulating epoxy resin composition is defoamed for 1 hour at 80 ℃ under a vacuum condition, and then is cured at 130 ℃/4 hours to obtain a cured heat-conducting insulating epoxy resin. The obtained cured heat-conducting insulating epoxy resin is used for testing and analyzing the heat conductivity coefficient and the resistivity. The filler volume content of the cured product was 38.0%, which was the same as in example 1.
Comparative example 2
The preparation method of the cured product of the epoxy resin composition comprises the following specific steps:
the first step is as follows: by weight, 93g of bisphenol A type epoxy resin (CYD 128), 7g of curing agent (OMICURE BC-120), al 2 O 3 199.0g(Al 2 O 3 The density of (b) is 3.90 g/cc), and dispersed at a high speed of 600rpm for 1 hour to obtain the heat conductive and insulating epoxy resin composition.
The second step is that: the prepared heat-conducting insulating epoxy resin composition is defoamed for 1 hour at 80 ℃ under a vacuum condition, and then is cured at 130 ℃/4 hours to obtain a cured heat-conducting insulating epoxy resin. The obtained cured heat-conducting insulating epoxy resin is used for testing and analyzing the heat conductivity coefficient and the resistivity. The filler volume content of the cured product was 38.0%, which was the same as in example 1.
Comparative example 3
The preparation method of the cured product of the epoxy resin composition comprises the following specific steps:
the first step is as follows: by weight, 93g of bisphenol A type epoxy resin (CYD 128), 7g of curing agent (OMICURE BC-120), al were mixed 2 O 3 300g of/nano silver/CNTs mixed filler is dispersed for 1 hour at a high speed of 600rpm to obtain the heat-conducting and insulating epoxy resin composition. Wherein, al 2 O 3 Mixing ratio of/Nano silver/CNTs to Al prepared in example 1 2 O 3 Al in-CNTs hybrid material 2 O 3 The ratio of nano silver to CNTs is the same, and the mass ratio is as follows: 50/1.08/0.5.
The second step is that: the prepared heat-conducting insulating epoxy resin composition is defoamed for 1 hour at 80 ℃ under a vacuum condition, and then is cured at 130 ℃/4 hours to obtain a cured heat-conducting insulating epoxy resin. The obtained cured heat-conducting insulating epoxy resin is used for testing and analyzing the heat conductivity coefficient and the resistivity. The filler volume content of the cured product was 47.9%, which was the same as in example 2.
COMPARATIVE EXAMPLE 4 (COMPARATIVE EXAMPLES 2 to 2)
The preparation method of the cured product of the epoxy resin composition comprises the following specific steps:
the first step is as follows: by weight, 93g of bisphenol A type epoxy resin (CYD 128), 7g of curing agent (OMICURE BC-120), al 2 O 3 299g of filler, and dispersing for 1 hour at a high speed of 600rpm to obtain the heat-conducting and insulating epoxy resin composition.
The second step is that: the prepared heat-conducting insulating epoxy resin composition is defoamed for 1 hour at 80 ℃ under a vacuum condition, and then is cured at 130 ℃/4 hours to obtain a cured heat-conducting insulating epoxy resin. The obtained cured heat-conducting insulating epoxy resin is used for testing and analyzing the heat conductivity coefficient and the resistivity. The filler volume content of the cured product was 47.9%, which was the same as in example 2.
Comparative example 5
The preparation method of the cured product of the epoxy resin composition comprises the following specific steps:
the first step is as follows: by weight, 93g of bisphenol A type epoxy resin (CYD 128), 7g of curing agent (OMICURE BC-120), al were mixed 2 O 3 And (3) dispersing 400g of/nano silver/CNTs mixed filler at a high speed of 600rpm for 1 hour to obtain the heat-conducting and insulating epoxy resin composition. Wherein. Al (Al) 2 O 3 Mixing ratio of/Nano silver/CNTs to Al prepared in example 1 2 O 3 Al in-CNTs hybrid Material 2 O 3 The ratio of nano silver to CNTs is the same, al 2 O 3 The mass ratio of nano silver to CNTs is as follows: 50:1.08:0.5.
the second step is that: the prepared heat-conducting insulating epoxy resin composition is defoamed for 1 hour at 80 ℃ under a vacuum condition, and then is cured at 130 ℃/4 hours to obtain a cured heat-conducting insulating epoxy resin. The obtained cured heat-conducting insulating epoxy resin is used for testing and analyzing the heat conductivity coefficient and the resistivity. The filler volume content of the cured product was 55.0%, which was the same as in example 3.
COMPARATIVE EXAMPLE 6 (COMPARATIVE EXAMPLES 3 to 2)
The preparation method of the condensate of the epoxy resin composition comprises the following specific steps:
the first step is as follows: by weight93g of bisphenol A type epoxy resin (CYD 128), 7g of curing agent (OMICURE BC-120), al 2 O 3 399g of filler is dispersed for 1 hour at high speed of 600rpm to obtain the heat-conducting and insulating epoxy resin composition.
The second step is that: the prepared heat-conducting insulating epoxy resin composition is defoamed for 1 hour under the vacuum condition of 80 ℃, and then is cured at the temperature of 130 ℃/4 hours to obtain a cured heat-conducting insulating epoxy resin. The filler volume content of the cured product was 55.0%, which was the same as in example 3.
Comparative example 7
The preparation method of the cured product of the epoxy resin composition comprises the following specific steps:
the first step is as follows: 93g of bisphenol A type epoxy resin (CYD 128), 7g of curing agent (OMICURE BC-120), 25.0g of BN/nano silver/CNTs mixed filler are dispersed at high speed of 600rpm for 1 hour by weight to obtain 125g of heat-conducting insulating epoxy resin composition. The mixing ratio of BN/nano silver/CNTs is the same as the ratio of BN/nano silver/CNTs in the BN-CNTs hybrid material prepared in the example 4, and the mass ratio of BN/nano silver/CNTs in the BN-CNTs hybrid material is as follows: 5/1.08/0.5.
The second step is that: the prepared heat-conducting insulating epoxy resin composition is defoamed for 1 hour under the vacuum condition of 80 ℃, and then is cured at the temperature of 130 ℃/4 hours to obtain a cured heat-conducting insulating epoxy resin. The obtained cured heat-conducting insulating epoxy resin is used for testing and analyzing the heat conductivity coefficient and the resistivity. The filler volume content of the cured product was 10.27%, which was the same as in example 4.
Comparative example 8
The preparation method of the cured product of the epoxy resin composition comprises the following specific steps:
the first step is as follows: 93g of bisphenol A type epoxy resin (CYD 128), 7g of curing agent (OMICURE BC-120) and 21.94g of BN filler are dispersed at high speed of 600rpm for 1 hour by weight to obtain 121.94g of heat-conducting insulating epoxy resin composition.
The second step is that: the prepared heat-conducting insulating epoxy resin composition is defoamed for 1 hour under the vacuum condition of 80 ℃, and then is cured at the temperature of 130 ℃/4 hours to obtain a cured heat-conducting insulating epoxy resin. The obtained cured heat-conducting insulating epoxy resin is used for testing and analyzing the heat conductivity coefficient and the resistivity. The filler volume content of the cured product was 10.27%, which was the same as in example 4.
Comparative example 9
The preparation method of the condensate of the epoxy resin composition comprises the following specific steps:
the first step is as follows: 93g of bisphenol A type epoxy resin (CYD 128), 7g of curing agent (OMICURE BC-120), 35g of BN/nano silver/CNTs mixed filler are dispersed at high speed of 600rpm for 1 hour by weight to obtain 135g of heat-conducting insulating epoxy resin composition. The mixing ratio of BN/nano silver/CNTs is the same as the ratio of BN/nano silver/CNTs in the BN-CNTs hybrid material prepared in the example 4, and the mass ratio of BN/nano silver/CNTs in the BN-CNTs hybrid material is as follows: 5/1.08/0.5.
The second step is that: the prepared heat-conducting insulating epoxy resin composition is defoamed for 1 hour at 80 ℃ under a vacuum condition, and then is cured at 130 ℃/4 hours to obtain a cured heat-conducting insulating epoxy resin. The obtained cured heat-conducting insulating epoxy resin is used for testing and analyzing the heat conductivity coefficient and the resistivity. The filler volume content of the cured product was 13.82%, which was the same as in example 5.
Comparative example 10
The preparation method of the cured product of the epoxy resin composition comprises the following specific steps:
the first step is as follows: by weight, 93g of bisphenol A type epoxy resin (CYD 128), 7g of curing agent (OMICURE BC-120) and 30.74g of BN filler were dispersed at 600rpm for 1 hour to obtain 130.74g of a heat conductive and insulating epoxy resin composition.
The second step is that: the prepared heat-conducting insulating epoxy resin composition is defoamed for 1 hour at 80 ℃ under a vacuum condition, and then is cured at 130 ℃/4 hours to obtain a cured heat-conducting insulating epoxy resin. The obtained cured heat-conducting insulating epoxy resin is used for testing and analyzing the heat conductivity coefficient and the resistivity. The filler volume content of the cured product was 13.82%, which was the same as in example 5.
Comparative example 11
The preparation method of the cured product of the epoxy resin composition comprises the following specific steps:
the first step is as follows: 93g of bisphenol A type epoxy resin (CYD 128), 7g of curing agent (OMICURE BC-120), 45g of BN/nano silver/CNTs mixed filler are dispersed at high speed of 600rpm for 1 hour by weight to obtain 145g of the heat-conducting insulating epoxy resin composition. The mixing ratio of BN/nano silver/CNTs is the same as the ratio of BN/nano silver/CNTs in the BN-CNTs hybrid material prepared in the example 4, and the mass ratio of BN/nano silver/CNTs in the BN-CNTs hybrid material is as follows: 5/1.08/0.5.
The second step: the prepared heat-conducting insulating epoxy resin composition is defoamed for 1 hour at 80 ℃ under a vacuum condition, and then is cured at 130 ℃/4 hours to obtain a cured heat-conducting insulating epoxy resin. The obtained cured heat-conducting insulating epoxy resin is used for testing and analyzing the heat conductivity coefficient and the resistivity. The filler volume content of the cured product was 17.09% and the same as in example 6.
Comparative example 12
The preparation method of the cured product of the epoxy resin composition comprises the following specific steps:
the first step is as follows: 93g of bisphenol A type epoxy resin (CYD 128), 7g of curing agent (OMICURE BC-120) and 39.5g of BN filler are dispersed at high speed of 600rpm for 1 hour by weight to obtain 139.5g of the heat-conducting insulating epoxy resin composition.
The second step is that: the prepared heat-conducting insulating epoxy resin composition is defoamed for 1 hour under the vacuum condition of 80 ℃, and then is cured at the temperature of 130 ℃/4 hours to obtain a cured heat-conducting insulating epoxy resin. The obtained cured heat-conducting insulating epoxy resin is used for testing and analyzing the heat conductivity coefficient and the resistivity. The filler volume content of the cured product was 17.09%, which was the same as in example 6.
Performance test
Detection method/test method
1. Viscosity test of the composition: according to GB/T12007.4-1989 epoxy resin viscosity determination method.
2. Heat conductivity of the cured product: according to GB/T10295-2008 heat insulation material steady-state thermal resistance and related characteristic determination heat flow meter method.
3. Volume resistivity of a cured product: according to GB/T15662-1995 test method for volume resistivity of conductive and antistatic plastics.
Data analysis
Table 1 shows the viscosity of the epoxy resin compositions of examples 1 to 3 and comparative examples 1 to 6 and the thermal conductivity and volume resistivity test parameters of the cured products thereof
As can be seen by combining examples 1-3 and comparative examples 1-6 with Table 1, when the filler volume ratio is the same, al is used 2 O 3 The thermal conductivity of the epoxy resin filled with the-CNTs hybrid material (examples 1, 2 and 3) is obviously higher than that of Al 2 O 3 Thermal conductivity of filled epoxy resin (comparative examples 2, 4, 6), and use of Al 2 O 3 Thermal conductivity of epoxy resin filled with/nano silver/CNTs mixed filler (comparative examples 1, 3, 5).
In addition, al is used 2 O 3 The volume resistivity of the epoxy resin filled with the-CNTs hybrid material is smaller than that of the epoxy resin filled with Al 2 O 3 Volume resistivity of filled epoxy resin, but still has good electrical insulation properties (volume resistivity)>10 9 Ω·m)。
As can be seen by combining examples 1-3 and comparative examples 1-6 with Table 1, example 2 (Al) 2 O 3 The coefficient of thermal conductivity of the hybrid material filled with CNTs (carbon nanotubes) and filled with 47.9 percent of filler volume is 1.66W (m.K) -1 The viscosity was 464500cP. Comparative example 5 (Al) 2 O 3 The nano silver/CNTs mixed filler is filled, the volume content of the filler is 55.0 percent, and the thermal conductivity coefficient is 1.64W (m.K) -1 The viscosity was 923000cP, which is close to the thermal conductivity of example 2, and significantly greater than that of example 2. Comparative example 6 (Al) 2 O 3 Filling, 55.0 percent of filler volume content) has a heat conductivity coefficient of 1.52W (m.K) -1 The viscosity was 82100cP, which is lower than the thermal conductivity of example 2, and significantly higher than that of example 2.
Combining the above analysis, it can be seen that: this application and Al 2 O 3 、Al 2 O 3 Compared with nano silver/CNTs mixed filler, al 2 O 3 The epoxy resin system filled with the-CNTs hybrid material can obtain higher heat conductivity coefficient under lower filling amount(ii) a When the same or similar heat conductivity coefficient is obtained, the system viscosity is lower; the volume resistivity is slightly reduced, but still maintains good electrical insulation properties.
Table 2 shows the viscosity of the epoxy resin compositions of examples 4 to 6 and comparative examples 7 to 12 and the thermal conductivity and volume resistivity test parameters of the cured products thereof
It can be seen by combining examples 4-6 and comparative examples 7-12 and by combining Table 2 that the thermal conductivity of the epoxy resin filled with the BN-CNTs hybrid material (examples 4, 5, 6) is significantly greater than the thermal conductivity of the epoxy resin filled with BN (comparative examples 8, 10, 12) and the thermal conductivity of the epoxy resin filled with the BN/nanosilver/CNTs hybrid filler (comparative examples 7, 9, 11) when the filler volume ratio is the same. Although the volume resistivity of the epoxy resin filled with the BN-CNTs hybrid material is smaller than that of the epoxy resin filled with BN and that of the epoxy resin filled with the BN/nano-silver/CNTs mixed filler, the BN-CNTs hybrid material still has good electrical insulation performance (volume resistivity)>10 9 Ω·m)。
As can be seen by combining examples 4-6 and comparative examples 7-12 with Table 2, example 4 (BN-CNTs hybrid material filled, filler volume content 10.27%) has a thermal conductivity of 1.12W (m.K) -1 Viscosity was 60300cP. The thermal conductivity coefficients of comparative example 9 (BN/nano silver/CNTs mixed filler filling, filler volume content 13.82%), comparative example 10 (BN filling, filler volume content 13.82%), comparative example 12 (BN filling, filler volume content 17.09%) were 0.92W (m.K) -1 、0.76W(m·K) -1 、1.03W(m·K) -1 All of which are less than the thermal conductivity of example 4, but have viscosities of 119800cP, 102100cP and 796400cP, respectively, which are significantly greater than those of example 4. Example 5 (BN-CNTs hybrid filling, filler volume content 13.82%) has a thermal conductivity of 1.55W (m.K) -1 Viscosity was 143100cP. Comparative example 11 (BN/nano silver/CNTs mixed filler filling, filler volume content 17.09%), comparative example 12 (BN filling, filler volume contentAmount 17.09%) was 1.36W (m.K) -1 、1.03W(m·K) -1 Both were less than the thermal conductivity of example 5, but had viscosities of 986200cP and 796400cP, respectively, which were significantly greater than the viscosity of example 5.
Combining the above analysis, it can be seen that: compared with BN and BN/nano silver/CNTs mixed filler, the BN-CNTs hybrid material is filled in an epoxy resin system, and a higher heat conductivity coefficient can be obtained under the condition of lower filling amount; when the same or similar heat conductivity coefficient is obtained, the viscosity of the system is lower; the volume resistivity is slightly decreased, but the good electric insulation performance is still maintained.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (6)
1. A heat-conducting insulating base material-carbon nano tube hybrid material is characterized in that: the Carbon Nanotubes (CNTs) are connected with the heat-conducting insulating base material by the connecting material; the connecting material of the heat-conducting insulating base material and the CNTs is a nano-silver sintered body;
the preparation method of the heat-conducting insulating base material-CNTs hybrid material comprises the following steps:
step one, dissolving 2-ethyl-4-methylimidazole (2E 4 MI) and silver acetate (AgAc) in dichloromethane to prepare Ag (2E 4 MI) 2 An Ac complex solution;
step two, ag (2E 4 MI) obtained in step one 2 Adding polyvinylpyrrolidone (PVP) and CNTs into the Ac complex solution, adding a heat-conducting insulating base material after ultrasonic dispersion is carried out for 1-4 hours, and then carrying out ultrasonic dispersion for 0.2-1 hour;
step three, after removing dichloromethane by distilling the dispersion liquid obtained in the step two under reduced pressure, carrying out high-temperature sintering treatment on the solid, wherein the high-temperature sintering temperature is 200-220 ℃;
step four, the solid obtained in the step three is dispersed in ethanol after being crushed, ground, filtered and dried to obtain the heat-conducting insulating base material-CNTs hybrid material;
the heat-conducting insulating base material is alpha-aluminum oxide (Al) 2 O 3 ) Or Boron Nitride (BN).
2. The preparation method of the heat-conducting insulating base material-carbon nanotube hybrid material as claimed in claim 1, wherein the preparation method comprises the following steps: the method comprises the following steps:
step one, dissolving 2-ethyl-4-methylimidazole (2E 4 MI) and silver acetate (AgAc) in dichloromethane to prepare Ag (2E 4 MI) 2 An Ac complex solution;
step two, ag (2E 4 MI) obtained in step one 2 Adding polyvinylpyrrolidone (PVP) and CNTs into the Ac complex solution, adding a heat-conducting insulating base material after carrying out ultrasonic dispersion for 1-4 hours, and carrying out ultrasonic dispersion for 0.2-1 hour;
step three, after removing dichloromethane by distilling the dispersion liquid obtained in the step two under reduced pressure, carrying out high-temperature sintering treatment on the solid, wherein the high-temperature sintering temperature is 200-220 ℃;
step four, crushing the solid obtained in the step three, dispersing the solid in ethanol, grinding, filtering and drying to obtain the heat-conducting insulating base material-CNTs hybrid material;
the heat-conducting insulating base material is alpha-aluminum oxide (Al) 2 O 3 ) Or Boron Nitride (BN);
the dosage of the 2-ethyl-4-methylimidazole 2E4MI in the step one is 0.02mol; the dosage of the silver acetate AgAc is 0.01mol; the amount of dichloromethane used was 400mL.
3. The preparation method of the heat-conducting insulating base material-carbon nanotube hybrid material as claimed in claim 2, wherein: when the heat-conducting insulating base material is alpha-alumina (Al) 2 O 3 ) In the second step, alpha-alumina (Al) 2 O 3 ) The dosage is 50g; CNTs and PVP were used in amounts of 0.5g each.
4. The preparation method of the heat-conducting insulating base material-carbon nanotube hybrid material as claimed in claim 2, wherein: when the heat-conducting insulating base material is Boron Nitride (BN), in the second step, the amount of the Boron Nitride (BN) is 5.0g, and the amounts of the CNTs and the PVP are both 0.5 g.
5. Use of the thermal conductive insulating substrate-carbon nanotube hybrid material as defined in claim 1, wherein: the heat-conducting insulating base material-CNTs hybrid material is used as a heat-conducting insulating filler and is used for various electrical insulating and electronic packaging materials.
6. The use of the heat conducting and insulating substrate-CNTs hybrid material according to claim 5, characterized in that: the heat-conducting insulating base material-CNTs hybrid material is used as a heat-conducting insulating filler for a heat-conducting insulating epoxy resin composition; the heat-conducting and insulating epoxy resin composition comprises epoxy resin, a curing agent and the heat-conducting and insulating base material-CNTs hybrid material.
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