CN113956683A - Heat-conducting insulating filler, preparation method thereof and heat-conducting insulating composite material - Google Patents
Heat-conducting insulating filler, preparation method thereof and heat-conducting insulating composite material Download PDFInfo
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Abstract
The invention relates to the field of heat dissipation materials, and discloses a heat-conducting insulating material and a preparation method thereof, a heat-conducting insulating composite material and a preparation method thereof, wherein the filler takes a heat-conducting substrate as a core, and an insulating shell layer is coated outside the heat-conducting substrate; the radial dimension D of the heat-conducting substrate is 5-100 mu m, and the coating thickness of the insulating shell layer is 2-2000 nm. Compared with the prior art, the high-thermal-conductivity insulating filler with a specific coating structure is prepared by adopting the thermal-conductivity matrix with high thermal conductivity and the inorganic material with good insulating property, and the comprehensive effect of the thermal conductivity and the insulating property of the thermal-conductivity insulating composite material prepared by the thermal-conductivity insulating filler is better by limiting the coating thickness and the radial size of the thermal-conductivity matrix.
Description
Technical Field
The invention relates to the technical field of heat dissipation materials, in particular to a heat conduction insulating filler, a preparation method thereof and a heat conduction insulating composite material.
Background
With the increasing number of high-power electronic devices, such as mobile phone 5G technology, the problem of heat generation is more and more prominent, and the problem of heat dissipation is urgently needed to be solved. When the power of the electronic equipment is higher, heat accumulation is generated, so that the performance of the equipment is reduced, and the service life is reduced, for example, the performance of the electronic equipment is reduced by 10 percent every time the temperature of the electronic equipment is increased by 2 ℃. However, if heat is dissipated through a thermally conductive material to reduce its temperature by 10 ℃, the service life will be doubled.
The addition of heat-conducting fillers in the high polymer material is a main method for preparing the heat-conducting composite material at present. The existing heat-conducting insulating composite material is mainly prepared by adding insulating inorganic materials such as boron nitride, aluminum nitride, magnesium oxide and the like, but the thermal conductivity of the aluminum oxide and the silicon oxide is low, and the price of the boron nitride is high.
CN110218449A discloses a preparation method of a heat-conducting and insulating composite material, which comprises the steps of loading simple substance silver on the surface of graphite fiber, taking the silver-loaded fiber and hexagonal boron nitride as fillers, and modifying the surfaces of the fillers by adopting a silane coupling agent.
CN105198436A discloses an insulating and heat-conducting inorganic nano composite ceramic, which is composed of the following raw materials in parts by mass: silicon carbide: silicon dioxide: filling material: auxiliary agent: 30% -45% of solvent: 10% -15%: 15% -30%: 1% -10%: 10% -30%; the filler is composed of the following raw materials in parts by mass: aluminum nitride: precipitating barium sulfate: 70% of kaolin: 25%: 5 percent, wherein the precipitated barium sulfate and the kaolin are sieved by a sieve with more than 6000 meshes; the auxiliary agent comprises the following substances in parts by mass: rheological aid: defoaming agent: wetting agent: a flattening auxiliary agent: thickening agent: 15% -30% of film-forming additive: 20% -30%: 15% -30%: 20% -30%: 15% -30%: 15-30 percent, and the sum of the mass percentage of all the auxiliary agents is 100 percent.
CN109880355A discloses an insulating heat-conducting modified nylon 6 composite material, which is prepared by the following method: 1) mixing PA6, high sphericity alumina, nano silicon carbide and nano boron nitride as raw materials in a high-speed mixer for 3 min; 2) extruding and granulating by a double-screw extruder; fully drying the granules to obtain the insulating heat-conducting modified nylon 6 composite material; in the step 1), the obtained mixture contains the following raw materials: 40-50 parts of PA6, 45-55 parts of high-sphericity alumina, 5-10 parts of nano silicon carbide and 5-10 parts of nano boron nitride.
Disclosure of Invention
The invention aims to overcome the defects of low thermal conductivity and high cost caused by adding insulating inorganic materials such as boron nitride, aluminum nitride, magnesium oxide and the like to prepare a heat-conducting insulating material in the prior art, and provides a heat-conducting insulating filler, a preparation method thereof and a heat-conducting insulating composite material. The heat-conducting insulating filler has the advantages of high heat conductivity and relatively low cost.
In order to achieve the above object, a first aspect of the present invention provides a heat conducting insulating filler, which takes a heat conducting substrate as a core, and an insulating shell layer is coated outside the heat conducting substrate; the radial dimension D of the heat-conducting substrate is 5-100 mu m, and the coating thickness of the insulating shell layer is 2-2000 nm.
A second aspect of the present invention provides a method for preparing a thermally conductive insulating filler, comprising: preparing a mixture of a heat-conducting matrix and sol-gel, wherein the sol-gel is coated on the surface of the heat-conducting matrix, and then filtering and drying the mixture to enable the sol-gel to form an insulating shell layer, so as to obtain a heat-conducting insulating filler;
wherein the radial dimension D of the heat-conducting matrix is 10-100 μm; the coating thickness of the insulating shell layer is 10-200 nm.
The third aspect of the invention provides a heat-conducting insulating filler prepared by the method.
A fourth aspect of the present invention provides a thermally conductive and insulating composite material comprising a resin matrix and the thermally conductive and insulating filler of the first or third aspect.
According to the invention, the high-thermal-conductivity insulating filler with a specific coating structure is prepared by adopting the thermal-conductivity matrix with high thermal conductivity and the inorganic material with good insulating property, and the comprehensive effect of the thermal conductivity and the insulating property of the thermal-conductivity insulating composite material prepared by the thermal-conductivity insulating filler is better by limiting the coating thickness and the radial size of the thermal-conductivity matrix; the thermal conductivity of the preferred heat-conducting insulating composite material is 2-7W/mk, and the electric resistance is 103-1013Ω。
Additional advantages and features of the present invention will be set forth in the detailed description which follows.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a heat-conducting insulating filler, which takes a heat-conducting substrate as a core, and an insulating shell layer is coated outside the heat-conducting substrate; the radial dimension D of the heat-conducting substrate is 5-100 mu m, and the coating thickness of the insulating shell layer is 2-2000 nm.
The inventor of the invention finds that the high-heat-conductivity insulating filler with a specific coating structure is prepared by adopting a heat-conductivity matrix with high heat conductivity and an inorganic material with good insulating property, and the heat-conductivity insulating filler with good comprehensive performance of heat conductivity and insulating property can be obtained by limiting the coating thickness and the radial dimension of the heat-conductivity matrix. Preferably, the radial dimension D of the heat-conducting matrix is 10-100 μm; the coating thickness of the insulating shell layer is 10-200 nm.
Preferably, the weight ratio of the insulating shell layer to the heat-conducting matrix is (4-20): (80-96).
The material of the heat-conducting matrix is particularly limited, preferably, the heat-conducting matrix comprises at least one of carbon powder, graphite, expanded graphite and mesophase pitch carbon fiber which are subjected to oxidation treatment, specifically, the heat-conducting matrix is obtained by oxidizing at least one of carbon powder, graphite, expanded graphite and mesophase pitch carbon fiber, and the materials have high heat conductivity, wide sources and low cost, and can enable the heat-conducting insulating filler to obtain excellent heat conductivity and insulating property. In the present invention, the carbon powder, graphite, expanded graphite and mesophase pitch carbon fiber are all commercially available, for example, the expanded graphite is available from Qingdao rock-ocean carbon materials, Inc.; the mesophase pitch carbon fibers can be purchased from Liaoning Nuo carbon materials Co.
Preferably, the insulating shell layer comprises silicon oxide and/or aluminum oxide.
A second aspect of the present invention provides a method for preparing a thermally conductive insulating filler, comprising: preparing a mixture of a heat-conducting matrix and sol-gel, wherein the sol-gel is coated on the surface of the heat-conducting matrix, and then filtering and drying the mixture to enable the sol-gel to form an insulating shell layer, so as to obtain a heat-conducting insulating filler;
wherein the radial dimension D of the heat-conducting matrix is 5-100 μm; the coating thickness of the insulating shell layer is 2-2000 nm.
In a preferred embodiment of the present invention, the method further comprises: carrying out oxidation treatment on the heat conduction material at the temperature of 450-650 ℃ to obtain the heat conduction matrix; the heat conductive material comprises at least one of carbon powder, graphite, expanded graphite and mesophase pitch carbon fiber.
Preferably, the conditions of the oxidation treatment include: the atmosphere is oxygen-containing gas, preferably air, the temperature is 500-650 ℃, and the time is 1-10h, more preferably 3-7 h.
The invention particularly limits the radial size of the heat-conducting matrix and the coating thickness of the insulating shell layer, and is beneficial to improving the comprehensive performance of the heat-conducting insulating composite material; preferably, the radial dimension D of the heat-conducting matrix is 10-100 μm; the coating thickness of the insulating shell layer is 10-200 nm.
The weight ratio of the insulating shell layer to the heat-conducting matrix is specially limited so as to improve the comprehensive performance of the heat-conducting insulating filler; preferably, the sol-gel is used in an amount such that the weight ratio of the insulating shell layer to the heat-conducting matrix is (4-20): (80-96).
The process of mixing the heat-conducting matrix and the sol-gel is particularly limited, the heat-conducting matrix can be mixed with the formed sol, the heat-conducting matrix can be added in the process of forming the sol to perform coating treatment while forming the sol, and the uniform and effective coating treatment can be better formed in the latter process.
Preferably, the sol-gel comprises a silica sol and/or an aluminum sol.
In a preferred embodiment of the present invention, the sol-gel is a silica sol, and the process of preparing the mixture of the thermally conductive substrate and the sol-gel includes: firstly, mixing a heat-conducting matrix with an ammonia organic solution for the first time to obtain a mixed solution, and then mixing tetraethoxysilane with the mixed solution for the second time.
The invention particularly limits the dosage of ammonia water and the content of tetraethoxysilane, and the dosage of the ammonia water and the tetraethoxysilane directly influences the coating thickness and the radial size and the content of the heat-conducting matrix. Preferably, the ammonia water organic solution contains ammonia water and an organic solvent, wherein the ammonia water accounts for 5-15 vol% of the ammonia water organic solution; the ethyl orthosilicate is 2-18 vol% of the ammonia water organic solution; the dosage of the heat-conducting substrate is 5-15g relative to 180mL of the organic solvent in the ammonia water organic solution. In the present invention, the organic solvent is not particularly limited, and an organic solvent that is known in the art, for example, ethanol, can be used.
Preferably, the primary mixing is carried out under stirring for a period of time of from 0.5 to 3 hours at a stirring speed of from 150 rpm to 250 rpm, more preferably at 200 rpm.
The invention particularly limits the time of the secondary mixing and stirring, and the stirring time directly influences the coating thickness and the radial size of the heat-conducting substrate; preferably, the secondary mixing is carried out under stirring for a period of time ranging from 0.5 to 20 hours, more preferably from 2 to 8 hours, at a stirring speed of 150 and 250 revolutions per minute, more preferably 200 revolutions per minute.
The third aspect of the invention provides a heat-conducting insulating filler prepared by the method. The heat-conducting insulating filler is completely the same as the heat-conducting insulating filler.
A fourth aspect of the present invention provides a thermally conductive and insulating composite material comprising a resin matrix and the thermally conductive and insulating filler of the first or third aspect.
The method for preparing the composite material is not particularly limited in the present invention, and the composite material can be prepared according to the methods existing in the field, for example, the heat-conducting and insulating filler is subjected to conventional banburying with the resin matrix and/or other auxiliary agents.
The weight ratio of the heat-conducting insulating filler to the resin matrix is particularly limited in the invention, so as to improve the comprehensive performance of the composite material. Preferably, the content of the thermally conductive and insulating filler is 20 to 90 wt% and the content of the resin matrix is 10 to 80 wt% with respect to the thermally conductive and insulating composite.
The resin matrix is not particularly limited in the present invention, and any resin existing in the art may be used; preferably, the resin matrix is selected from at least one of Polyethylene (PE), Linear Low Density Polyethylene (LLDPE), Low Density Polyethylene (LDPE), polypropylene (PP), Polyamide (PA), Polyphenylene Sulfide (PPs), Polyurethane (PU), and epoxy resin. The properties of the Polyethylene (PE), Linear Low Density Polyethylene (LLDPE), Low Density Polyethylene (LDPE), polypropylene (PP), Polyamide (PA), Polyphenylene Sulfide (PPs), Polyurethane (PU) and epoxy resin are not particularly limited, and those skilled in the art can freely select them according to actual needs. Preferably, the density of the low-density polyethylene is less than or equal to 92g/cm2Melt index at 190 ℃ and load of 2.16kg < 3g/10min, commercially available, e.g.LDPE (190 ℃ andthe melt index under the load of 2.16kg is 4g/10min, and the density is 0.924g/cm3) Purchased from Shenhua Baotou coal chemical industry, Ltd., and having a brand number of 5220. Preferably, the linear low density polyethylene has a density of 0.93g/cm or less2The melt index at 190 ℃ and a load of 2.16kg is < 3g/10 min. Commercially available, for example LLDPE (melt index at 190 ℃ and 2.16kg load of 2g/10min, density of 0.924 g/cm)3) Purchased from Shenhua Baotou coal chemical industry, Limited liability company under the trade name 7042.
The thermal conductivity of the composite material is 0.5-7W/mk, and the resistance is 100-1013Omega. The composite material prepared by the preferred scheme of the invention has the thermal conductivity of 2-7W/mk and the resistance of 103-1013Ω。
Preferably, the composite material further comprises an auxiliary agent; more preferably, the assistant is a silane coupling agent, and the silane coupling agent may be used in at least one type selected from the group consisting of KH550, KH540, KH792, KH602, KH560, KH570 and KH 590.
The invention makes special limitation on the dosage of the auxiliary agent so as to improve the comprehensive performance of the composite material; preferably, the amount of the auxiliary agent is 0.5-2 wt% with respect to the thermally conductive and insulating composite material.
The present invention will be described in detail below by way of examples. In the following examples, the thermal conductivity was measured by a relaxation resistant LF467 thermal conductivity tester and the electrical resistance was measured by a daily electrical resistance tester; the raw materials involved were all commercially available, except where stated otherwise, and were LLDPE (melt index at 190 ℃ and 2.16kg load of 2g/10min, density of 0.924 g/cm)3) Purchased from Shenhua Baotou coal chemical industry, Limited liability company under the trade name 7042.
Example 1
Firstly, 15g of carbon powder is taken to be oxidized for 3 hours at 550 ℃ in the air atmosphere to obtain the heat-conducting matrix. Measuring ammonia water, adding the ammonia water into 180mL of ethanol, and stirring for 5min to obtain an ammonia water ethanol solution with the ammonia water concentration of 15 vol%; and weighing 15g of heat-conducting matrix, adding the heat-conducting matrix into the ammonia water ethanol solution, and stirring for 0.5h at 200 revolutions per minute to obtain a mixed solution. Measuring tetraethoxysilane, adding the tetraethoxysilane into the mixed liquid, wherein the volume concentration of the tetraethoxysilane in the mixed liquid is 8 vol%, and stirring for 8 hours at 200 revolutions per minute. And filtering and drying to obtain the heat-conducting insulating filler.
The radial dimension D of the heat-conducting matrix is 20 mu m through testing; the coating thickness of the insulating shell layer is 100nm, and the weight ratio of the insulating shell layer to the heat-conducting substrate is 7.3: 92.7.
And banburying and mixing the heat-conducting insulating filler and LLDPE at 180 ℃ to obtain a heat-conducting insulating composite material, wherein the content of the heat-conducting insulating filler is 65 wt% and the content of the LLDPE is 35 wt% relative to the heat-conducting insulating composite material.
The thermal conductivity of the composite material is 6.2W/mk through testing, and the resistance is 1010Ω。
Example 2
Firstly, 15g of carbon powder is taken to be oxidized for 3 hours at 550 ℃ in the air atmosphere to obtain the heat-conducting matrix. Measuring ammonia water, adding the ammonia water into 180mL of ethanol, and stirring for 5min to obtain an ammonia water ethanol solution with the ammonia water concentration of 15 vol%; and weighing 15g of the heat-conducting matrix, adding the heat-conducting matrix into the ammonia water ethanol solution, and stirring for 0.5h at 200 revolutions per minute to obtain a mixed solution. Measuring tetraethoxysilane, adding the tetraethoxysilane into the mixed liquid, wherein the volume concentration of the tetraethoxysilane in the mixed liquid is 4 vol%, and stirring for 2 hours at 200 revolutions per minute. And filtering and drying to obtain the heat-conducting insulating filler.
The radial dimension D of the heat-conducting matrix is 20 mu m through testing; the coating thickness of the insulating shell layer is 80nm, and the weight ratio of the insulating shell layer to the heat-conducting substrate is 4.4: 95.6.
And banburying and mixing the heat-conducting insulating filler and LLDPE at 180 ℃ to obtain the heat-conducting insulating composite material, wherein the content of the heat-conducting insulating filler is 55 wt% and the content of the LLDPE is 45 wt% relative to the heat-conducting insulating composite material.
The thermal conductivity of the composite material is 5.5W/mk through testing, and the resistance is 103Ω。
Example 3
Firstly, taking 15g of carbon powder, and oxidizing for 3h at 550 ℃ in an air atmosphere to obtain the heat-conducting matrix. Measuring ammonia water, adding the ammonia water into 180mL of ethanol, and stirring for 5min to obtain an ammonia water ethanol solution with the ammonia water concentration of 15 vol%; and weighing 15g of the heat-conducting matrix, adding the heat-conducting matrix into the ammonia water ethanol solution, and stirring for 0.5h at 200 revolutions per minute to obtain a mixed solution. Measuring tetraethoxysilane, adding the tetraethoxysilane into the mixed liquid, wherein the volume concentration of the tetraethoxysilane in the mixed liquid is 8 vol%, and stirring for 8 hours at 200 revolutions per minute. And filtering and drying to obtain the heat-conducting insulating filler.
The radial dimension D of the heat-conducting matrix is 20 mu m through testing; the coating thickness of the insulating shell layer is 100nm, and the weight ratio of the insulating shell layer to the heat-conducting substrate is 7.3: 92.7.
Banburying and mixing the heat-conducting insulating filler and LLDPE at 180 ℃ to obtain a heat-conducting insulating composite material; wherein, relative to the heat-conducting and insulating composite material, the content of the heat-conducting and insulating filler is 55 wt%, and the content of LLDPE is 45 wt%.
The composite material is obtained by testing, the thermal conductivity is 4W/mk, and the resistance is 1010Ω。
Example 4
Preparing a heat-conducting insulating filler and a heat-conducting insulating composite material according to the method of the embodiment 1 respectively, except that the carbon powder is replaced by graphite with the same amount, the volume concentration of the tetraethoxysilane in the obtained mixed solution is 10 vol%, and the time of secondary mixing and stirring is 0.5 h; the composite composition shown in table 1 was used instead of the corresponding composition in example 1, and the test results are shown in table 1.
Example 5
Preparing a heat-conducting insulating filler and a heat-conducting insulating composite material according to the method of example 1 respectively, except that the carbon powder is replaced by the same amount of expanded graphite, the temperature of the oxidation treatment is 500 ℃, and the time is 6 hours; the time for secondary mixing and stirring is 18 hours; the composite composition shown in table 1 was used instead of the corresponding composition in example 1, and the test results are shown in table 1.
Example 6
A heat conductive insulating filler and a heat conductive insulating composite material were prepared according to the methods of example 1, respectively, except that the temperature of the oxidation treatment was 600 ℃, and the rest was the same as example 1. The composite composition shown in table 1 was used instead of the corresponding composition in example 1, and the test results are shown in table 1.
Example 7
Preparing a heat-conducting insulating filler and a heat-conducting insulating composite material according to the method of the embodiment 1 respectively, except that the volume concentration of the tetraethoxysilane in the obtained mixed solution is 16 vol%, and the time of secondary mixing and stirring is 4 hours; and an auxiliary agent KH550 is also added in the banburying mixing process, and the content of the auxiliary agent is 1 wt% relative to the heat-conducting and insulating composite material. The corresponding test results are shown in table 1.
Comparative example 1
Preparing a heat-conducting insulating filler and a heat-conducting insulating composite material according to the method of the embodiment 1, except that the oxidation treatment temperature is 300 ℃ and the time is 1 h; the composite composition shown in table 1 was used instead of the corresponding composition in example 1, and the test results are shown in table 1.
Comparative example 2
Preparing a heat-conducting insulating filler and a heat-conducting insulating composite material according to the method of example 1, except that the volume concentration of the tetraethoxysilane in the obtained mixed solution is 20 vol%, the time for primary mixing and stirring is 2 hours, and the time for secondary mixing and stirring is 22 hours; the composite composition shown in table 1 was used instead of the corresponding composition in example 1, and the test results are shown in table 1.
TABLE 1
As can be seen from the results of table 1, examples 1 to 7 using the present invention have excellent thermal conductivity and insulating properties.
As can be seen from comparison of example 1 and comparative examples 1 to 2, more excellent effects can be obtained by the scheme of the present invention.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. The heat-conducting insulating filler is characterized in that a heat-conducting base body is taken as a core, and an insulating shell layer is coated outside the heat-conducting base body; the radial dimension D of the heat-conducting substrate is 5-100 mu m, and the coating thickness of the insulating shell layer is 2-2000 nm.
2. The filler according to claim 1, wherein the thermally conductive matrix has a radial dimension D of 10-100 μ ι η, and the insulating shell layer has a coating thickness of 10-200 nm;
preferably, the weight ratio of the insulating shell layer to the heat-conducting matrix is (4-20): (80-96).
3. The filler of claim 1 or 2, wherein the thermally conductive matrix comprises at least one of an oxidized carbon powder, graphite, expanded graphite, and mesophase pitch carbon fibers;
preferably, the insulating shell layer comprises silicon oxide and/or aluminum oxide.
4. A method of preparing a thermally conductive insulating filler, comprising: preparing a mixture of a heat-conducting matrix and sol-gel, wherein the sol-gel is coated on the surface of the heat-conducting matrix, and then filtering and drying the mixture to enable the sol-gel to form an insulating shell layer, so as to obtain a heat-conducting insulating filler;
wherein the radial dimension D of the heat-conducting matrix is 5-100 μm; the coating thickness of the insulating shell layer is 2-2000 nm.
5. The method of claim 4, wherein the method further comprises: carrying out oxidation treatment on the heat conduction material at the temperature of 450-650 ℃ to obtain the heat conduction matrix; the heat conducting material comprises at least one of carbon powder, graphite, expanded graphite and mesophase pitch carbon fiber;
preferably, the conditions of the oxidation treatment include: the atmosphere is oxygen-containing gas, the temperature is 500-650 ℃, and the time is 1-10h, more preferably 3-7 h;
preferably, the radial dimension D of the heat-conducting substrate is 10-100 μm, and the coating thickness of the insulating shell layer is 10-200 nm;
preferably, the sol-gel is used in an amount such that the weight ratio of the insulating shell layer to the heat-conducting matrix is (4-20): (80-96).
6. The method of claim 4 or 5, wherein the sol-gel comprises silica sol and/or aluminum sol;
preferably, the sol-gel is a silica sol, and the process of preparing the mixture of the thermally conductive substrate and the sol-gel includes: firstly, mixing a heat-conducting matrix with an ammonia organic solution for the first time to obtain a mixed solution, and then mixing tetraethoxysilane with the mixed solution for the second time;
preferably, the ammonia water organic solution contains ammonia water and an organic solvent, wherein the ammonia water accounts for 5-15 vol% of the ammonia water organic solution; the ethyl orthosilicate is 2-18 vol% of the ammonia water organic solution; the dosage of the heat-conducting matrix is 5-15g relative to 180mL of the organic solvent;
preferably, the primary mixing is carried out under stirring, the stirring time is 0.5-3h, and the stirring speed is 150-;
preferably, the secondary mixing is carried out under stirring for a period of time ranging from 0.5 to 20 hours, more preferably from 2 to 8 hours, at a stirring speed of 150 rpm and 250 rpm.
7. A thermally conductive, electrically insulating filler prepared by the method of any one of claims 4 to 6.
8. A thermally conductive and insulating composite material, characterized in that the composite material comprises a resin matrix and the thermally conductive and insulating filler as claimed in any one of claims 1 to 3 and 7.
9. The composite of claim 8, wherein the thermally conductive and insulating filler is present in an amount of 20-90 wt% and the resin matrix is present in an amount of 10-80 wt% relative to the thermally conductive and insulating composite;
preferably, the resin matrix is selected from at least one of polyethylene, linear low density polyethylene, polypropylene, polyamide, polyphenylene sulfide, polyurethane, and epoxy resin;
preferably, the thermal conductivity of the composite material is 2-7W/mk, and the electric resistance is 103-1013Ω。
10. The composite material according to claim 8 or 9, wherein the composite material further comprises an auxiliary agent; the preferable auxiliary agent is a silane coupling agent;
preferably, the amount of the auxiliary agent is 0.5-2 wt% with respect to the thermally conductive and insulating composite material.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114988375A (en) * | 2022-06-06 | 2022-09-02 | 安徽壹石通材料科技股份有限公司 | Heat-conducting microsphere, preparation method thereof and polymer composite material |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4546028A (en) * | 1982-04-27 | 1985-10-08 | Compagnie D'informatique Militaire Spatiale & Aeronautique | Composite substrate with high heat conduction |
| CN103183889A (en) * | 2013-03-21 | 2013-07-03 | 上海交通大学 | High-thermal-conductivity and insulating polymer composite material and preparation method thereof |
| CN104559061A (en) * | 2015-01-09 | 2015-04-29 | 湖南大学 | High-thermal conductivity insulated carbon filler, high-thermal conductivity insulated epoxy resin composite material and preparation method thereof |
| CN104788909A (en) * | 2015-04-16 | 2015-07-22 | 四川大学 | Thermally conductive and insulating composite material and preparation method thereof |
| CN106380630A (en) * | 2016-08-29 | 2017-02-08 | 北京化工大学 | Preparation method and application of chemical-bonded thermally-conductive insulation composite filling material |
| CN107418206A (en) * | 2017-05-25 | 2017-12-01 | 成都新柯力化工科技有限公司 | A kind of high dispersive graphene heat conduction masterbatch and preparation method |
-
2020
- 2020-07-21 CN CN202010706082.7A patent/CN113956683B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4546028A (en) * | 1982-04-27 | 1985-10-08 | Compagnie D'informatique Militaire Spatiale & Aeronautique | Composite substrate with high heat conduction |
| CN103183889A (en) * | 2013-03-21 | 2013-07-03 | 上海交通大学 | High-thermal-conductivity and insulating polymer composite material and preparation method thereof |
| CN104559061A (en) * | 2015-01-09 | 2015-04-29 | 湖南大学 | High-thermal conductivity insulated carbon filler, high-thermal conductivity insulated epoxy resin composite material and preparation method thereof |
| CN104788909A (en) * | 2015-04-16 | 2015-07-22 | 四川大学 | Thermally conductive and insulating composite material and preparation method thereof |
| CN106380630A (en) * | 2016-08-29 | 2017-02-08 | 北京化工大学 | Preparation method and application of chemical-bonded thermally-conductive insulation composite filling material |
| CN107418206A (en) * | 2017-05-25 | 2017-12-01 | 成都新柯力化工科技有限公司 | A kind of high dispersive graphene heat conduction masterbatch and preparation method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114988375A (en) * | 2022-06-06 | 2022-09-02 | 安徽壹石通材料科技股份有限公司 | Heat-conducting microsphere, preparation method thereof and polymer composite material |
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