CN112574468B - Heat-conducting polymer composite material with multi-layer continuous network structure and preparation method thereof - Google Patents

Heat-conducting polymer composite material with multi-layer continuous network structure and preparation method thereof Download PDF

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CN112574468B
CN112574468B CN201910941137.XA CN201910941137A CN112574468B CN 112574468 B CN112574468 B CN 112574468B CN 201910941137 A CN201910941137 A CN 201910941137A CN 112574468 B CN112574468 B CN 112574468B
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heat
network
conducting
composite material
conducting filler
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CN112574468A (en
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秦盟盟
陈莉
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Jinan Yingwei New Materials Technology Partnership LP
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Tianjin University of Technology
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Abstract

The invention discloses a heat-conducting polymer composite material with a multilayer continuous network structure and a preparation method thereof, wherein a network C is prepared, and the network C is subjected to a loading method for 2-50 times, wherein each loading method comprises the following steps: the preparation method comprises the steps of immersing the heat-conducting filler-loaded network C into the dispersion liquid A, taking out the heat-conducting filler-loaded network C, drying the heat-conducting filler-loaded network C at the temperature of 20-200 ℃ to obtain the heat-conducting polymer composite material, immersing the heat-conducting filler-loaded network C into the solution B, taking out the heat-conducting filler-loaded network C, and drying the heat-conducting filler-loaded network C at the temperature of 20-320 ℃ for 30-300 min to obtain the heat-conducting polymer composite material. The average distance between the polymer matrix of the obtained heat-conducting polymer composite material and the heat-conducting filler network is smaller, and the heat conductivity coefficient is higher.

Description

Heat-conducting polymer composite material with multi-layer continuous network structure and preparation method thereof
Technical Field
The invention belongs to the technical field of heat conduction materials, and particularly relates to a heat conduction polymer composite material with a multilayer continuous network structure and a preparation method thereof.
Background
With the rapid development of 5G communication, high-integration chips, artificial intelligence and the like, the power density and the heat production quantity of electronic devices are greatly improved, and if the heat management guarantee is not sufficient, the related devices are easy to age or damage in advance. The traditional metal heat conduction materials (such as aluminum, copper, etc.) have the limitations of high density, low specific heat conductivity (ratio of heat conductivity to material volume density), high thermal expansion coefficient, easy oxidation, etc., so that the ever-increasing heat dissipation requirements are difficult to meet. The polymer composite material based on the enhancement of the heat-conducting filler has lower density, excellent mechanical property, processing property and higher heat conductivity, and becomes a class of heat-conducting materials with the greatest development prospect in recent years, so that the polymer composite material has wide application prospect in the fields of energy, communication, electronics and the like.
High-thermal-conductivity materials such as graphene, carbon nanotubes and boron nitride have excellent thermal conductivity, so that the high-thermal-conductivity materials are widely used as fillers to improve the thermal conductivity of high polymer materials. The heat-conducting filler needs to form a continuous heat-conducting network in the polymer matrix, so that the interface thermal resistance can be effectively reduced, and the heat-conducting property of the composite material is improved. The process of forming the continuous heat conduction channel by adopting the traditional blending method needs to add a large amount of filler into a high polymer matrix, which can deeply affect the microstructure of the high polymer composite material and further damage the processability and the mechanical property of the high polymer composite material. Therefore, how to improve the utilization efficiency of the heat-conducting filler and enable the composite material to obtain higher heat-conducting performance at a lower filler addition level is a continuous challenge in the research of the heat-conducting polymer composite material.
In recent years, researchers at home and abroad improve the heat-conducting property of the composite material by constructing a three-dimensional continuous heat-conducting network. For example, Ding et al (Li X, Shao L, Song N, Shi L, Ding P. enhanced thermal-conductive and anti-drying properties of graphene composites by 3D graphene structures at low graphene content. composites Part A: Applied Science and manufacturing.2016; 88:305-14.) hydrothermally assemble graphene oxide to form a three-dimensional graphene network, and composite with nylon 6, the thermal conductivity of the composite material with 2 wt% graphene content reaches 0.85W/mK, which is 3 times that of the nylon 6 matrix. Bai et al (Zhuao Y, Wu Z, Bai S. study on thermal properties of graphene foam/graphene sheets polymers composites. composites Part A: Applied Science and manufacturing.2015; 72:200-6.) chemical vapor deposition was used to prepare three-dimensional graphene, with 0.7 wt% content of graphene increasing the thermal conductivity of the composite by nearly 2 times. These results indicate that the construction of the three-dimensional continuous heat-conducting network is an important factor for improving the heat-conducting performance of the composite material.
Researches show that the construction of the three-dimensional continuous heat-conducting network can weaken the interface scattering of phonons, promote the efficient transmission of phonons in the whole network and improve the heat-conducting property of the composite material; however, the density and distribution of the transmission path of the phonons, which are used as the carriers of the heat flow, are also the key for determining the heat flow transmission capability of the heat conduction network, thereby deeply influencing the three-dimensional heat conduction performance of the composite material. The existing research makes a series of progress in the aspects of construction of a three-dimensional continuous heat conduction network and improvement of heat conduction performance of a composite material, however, the existing three-dimensional continuous heat conduction network is single in structure, the average distance between a network framework and a polymer matrix is large, and the heat conduction filler is not beneficial to exerting the self high heat conduction characteristic. For example, Lin and the like utilize a graphene network to enhance the heat conduction performance of epoxy resin, wherein the mass fraction of graphene reaches 5%, and the heat conduction coefficient of the composite material is 1.52W/mK and is far lower than the theoretical heat conduction coefficient of graphene 5300W/mK, because the distance between the graphene heat conduction network and a polymer matrix is too large, heat is difficult to be rapidly transferred from the polymer matrix to the heat conduction network. Therefore, the development of the high-thermal-conductivity polymer composite material needs to build a three-dimensional continuous thermal conductive network, and more importantly, the research and development of the three-dimensional continuous thermal conductive network with high thermal conductivity are needed, so that the three-dimensional thermal conductivity of the composite material is greatly improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of a heat-conducting polymer composite material with a multilayer continuous network structure.
The invention also aims to provide the heat-conducting polymer composite material obtained by the preparation method, the heat-conducting polymer composite material takes a network C with a three-dimensional continuous network structure as a template, the surface of a network structure framework of the heat-conducting polymer composite material is sequentially and circularly loaded with the heat-conducting filler and the polymer matrix material (solute of polymer or polymer precursor solution), the heat-conducting filler and the polymer matrix material respectively form continuous networks, and the two networks are alternately deposited to form the heat-conducting polymer composite material with the multilayer continuous network structure.
The purpose of the invention is realized by the following technical scheme.
A preparation method of a heat-conducting polymer composite material with a multilayer continuous network structure comprises the following steps:
preparing a network C which is a material with a three-dimensional continuous network structure, and carrying out a loading method on the network C for 2-50 times, wherein each loading method comprises the following steps: immersing the mixture into the dispersion A for 1-30 min, taking out, drying at the temperature of 20-200 ℃ for 0.5-3 h to obtain a heat-conducting filler-loaded network C, immersing the heat-conducting filler-loaded network C into the solution B for 1-300 min, taking out, and drying at the temperature of 20-320 ℃ for 30-300 min to obtain a heat-conducting polymer composite material, wherein,
the preparation method of the dispersion liquid A comprises the following steps: dispersing a heat-conducting filler in the liquid D to obtain a mixture, and carrying out ultrasonic treatment on the mixture for 5-60 min by using a cell crusher to obtain a dispersion liquid A, wherein the concentration of the heat-conducting filler in the dispersion liquid A is 0.01-5 mg/mL, and the heat-conducting filler is a heat-conducting material with a heat conductivity coefficient larger than 10W/mK;
the solution B is a high polymer aqueous solution or a high polymer precursor solution, wherein the high polymer is polyvinyl alcohol, polyethylene glycol, cellulose, polyacrylic acid or polyurethane, and the mass fraction of the high polymer in the high polymer aqueous solution is 1-15%; the solute of the high-molecular precursor solution is polydimethylsiloxane, epoxy resin, polyamic acid or dopamine.
In the above technical solution, the network C is a polyurethane network, a melamine network, a polyimide network, a cellulose network, a polypropylene network, a nickel foam, a copper foam, or a carbon foam.
In the above technical solution, the heat conductive filler is a carbon nanotube, a carbon nanofiber, a silver nanofiber, a boron nitride nanotube, graphene, a boron nitride nanosheet, or a carbon nitride nanosheet.
In the technical scheme, the liquid D is acetone, tetrahydrofuran, ethyl acetate, isopropanol, N-methylpyrrolidone, N-dimethylformamide or dimethyl sulfoxide.
In the technical scheme, the power of ultrasonic treatment is 20-800W.
In the technical scheme, the centrifugation time is not more than 30 min.
In the technical scheme, the network C loaded with the heat-conducting filler is immersed in the solution B for 1-300 min, taken out and centrifuged, and the obtained product is dried at the temperature of 20-320 ℃ for 30-300 min, wherein the rotating speed of the centrifugation is less than or equal to 2000 r/min.
In the above technical scheme, when the solute of the polymer precursor solution is polydimethylsiloxane, epoxy resin, polyamic acid, the solvent of the polymer precursor solution is N-methylpyrrolidone, acetone, xylene;
and when the solute of the polymer precursor solution is dopamine, the solvent of the polymer precursor solution is Tris buffer solution.
The heat-conducting polymer composite material prepared by the preparation method.
In the technical scheme, the heat-conducting polymer composite material takes a network C as a framework, a heat-conducting filler layer and a polymer base material layer are loaded on the surface of the framework, the heat-conducting filler layer and the polymer base material layer are arranged in a staggered mode in the thickness direction of the load, the heat-conducting filler layer is formed by drying the dispersion liquid A, and the polymer base material layer is formed by drying the solution B.
The invention has the following beneficial effects:
the preparation method disclosed by the invention has the advantages that the required raw materials are simple and easy to obtain, the heat-conducting filler can form a multi-layer three-dimensional continuous heat-conducting network through a simple impregnation process, and the heat-conducting polymer composite materials with different heat-conducting properties can be obtained by controlling the number of times of loading. The average distance between the polymer matrix of the obtained heat-conducting polymer composite material and the heat-conducting filler network is smaller, and the heat conductivity coefficient is higher.
Drawings
FIG. 1 is a schematic process diagram of the production method of the present invention;
FIG. 2 is optical micrographs of (a) the thermally conductive polymer composite of example 1 and (b) the polymer composite of comparative example 1;
fig. 3 is a graph showing the relationship between the number of times N of loading and the thermal conductivity Y in example 2.
Detailed Description
A medicine purchase source:
acetone, xylene, tetrahydrofuran, ethyl acetate, isopropanol, N-methyl pyrrolidone, N-dimethylformamide, dimethyl sulfoxide and other chemical reagents are chemical pure and purchased from chemical technology limited of Jiangtian, Tianjin;
carbon nanotubes, carbon nanofibers, silver nanofibers, boron nitride nanotubes, graphene, boron nitride nanosheets, and carbon nitride nanosheets were purchased from Nanjing Xiancheng nanomaterial technology Co., Ltd;
polyvinyl alcohol, polyethylene glycol, cellulose, polyacrylic acid, polyurethane, polydimethylsiloxane, epoxy, polyamic acid, dopamine, and Tris buffer were purchased from tianjinliviateichow technologies, ltd;
polyurethane network, melamine network, polyimide network, cellulose network, polypropylene network, nickel foam, copper foam, carbon nanotube foam purchased from Tianjin Rivitta technology ltd, the pore size range of which is 50-200 microns;
and (3) testing the heat conductivity coefficient: the material is processed into a sample with the diameter of 50mm and the thickness of 3mm, and the heat conductivity coefficient of the material is tested by adopting a heat flow method.
The technical scheme of the invention is further explained by combining specific examples.
Example 1
As shown in fig. 1, a method for preparing a heat-conducting polymer composite material with a multilayer continuous network structure comprises the following steps:
a network C was prepared, which was a polyurethane network having a pore size of 150 μm. And (3) carrying out the load method on the network C for 50 times, wherein each load method comprises the following steps: immersing into the dispersion liquid A for 30min, taking out, drying at 20 ℃ for 0.5h to obtain a heat-conducting filler network C, immersing the heat-conducting filler network C into the solution B for 30min, taking out, centrifuging at 2000r/min for 30min, drying at 20 ℃ for 300min to obtain the heat-conducting polymer composite material, wherein,
the preparation method of the dispersion liquid A comprises the following steps: dispersing the heat-conducting filler in the liquid D to obtain a mixture, and carrying out ultrasonic treatment on the mixture for 60min by using a cell crusher to obtain a dispersion liquid A, wherein the power of the ultrasonic treatment is 20W, and the concentration of the heat-conducting filler in the dispersion liquid A is 0.01mg/mL (the heat-conducting filler is a carbon nano tube, and the heat-conducting coefficient of the heat-conducting filler is 500W/mK); liquid D is isopropyl alcohol.
The solution B is a polymer aqueous solution, wherein the polymer is polyvinyl alcohol, and the mass fraction of the polymer in the polymer aqueous solution is 15%.
Through tests, the heat conductivity coefficient of the heat-conducting polymer composite material is 3W/mK, and the mass fraction of the carbon nano tubes in the heat-conducting polymer composite material is 0.8%.
Comparative example 1
A preparation method of a high polymer composite material with a single heat-conducting filler network structure comprises the following steps:
1) a network C was prepared, which was a polyurethane network having a pore size of 150 μm.
2) The method for loading the carbon nano tubes is repeated for 50 times to obtain the polyurethane network loaded with the carbon nano tubes, wherein the method for loading the carbon nano tubes for each time comprises the following steps: immersing in the dispersion A for 50min, taking out, and drying at 20 deg.C for 0.5 h.
The preparation method of the dispersion liquid A comprises the following steps: dispersing the heat-conducting filler in the liquid D to obtain a mixture, and carrying out ultrasonic treatment on the mixture for 60min by using a cell crusher to obtain a dispersion liquid A, wherein the ultrasonic treatment power is 20W, and the concentration of the heat-conducting filler in the dispersion liquid A is 0.01 mg/mL; the heat conducting filler is carbon nano tube. Liquid D is isopropanol.
3) Repeating the polyvinyl alcohol loading method for 50 times by loading the carbon nanotube polyurethane network to obtain the high polymer composite material with the single heat-conducting filler network structure, wherein the polyvinyl alcohol loading method for each time comprises the following steps: soaking in the solution B for 5min, taking out, centrifuging at 2000r/min for 30min, and drying at 20 deg.C for 300 min. Wherein the solution B is a polymer aqueous solution, wherein the polymer is polyvinyl alcohol, and the mass fraction of the polymer in the polymer aqueous solution is 15%.
The heat conductivity coefficient of the polymer composite material with the single heat-conducting filler network structure in the comparative example 1 is tested to be 0.5W/mK, and the mass fraction of the carbon nano tubes in the polymer composite material with the single heat-conducting filler network structure in the comparative example 1 is tested to be 0.8%.
Fig. 2 is an optical micrograph, in which 2(a) is a thermally conductive polymer composite of example 1 and 2(b) is a polymer composite of comparative example 1. As can be seen from fig. 2, compared with the polymer composite material with a single network structure of the heat conductive filler, the network of the heat conductive filler in the heat conductive polymer composite material with a multi-layer continuous network structure of the present invention is denser, and the distance between the network of the heat conductive filler and the polymer matrix is smaller, such that the heat conductivity of the heat conductive polymer composite material in example 1 is much higher than that of the polymer composite material in comparative example 1.
Comparative example 2
A preparation method of a polyvinyl alcohol composite material dispersed with carbon nanotubes comprises the following steps:
the preparation method of the dispersion liquid A comprises the following steps: dispersing the heat-conducting filler in the liquid D to obtain a mixture, and carrying out ultrasonic treatment on the mixture for 60min by using a cell crusher to obtain a dispersion liquid A, wherein the power of ultrasonic treatment is 20W, and the concentration of the heat-conducting filler in the dispersion liquid A is 0.01 mg/mL; the heat conducting filler is carbon nano tube. Liquid D is isopropyl alcohol.
The solution B is a high polymer aqueous solution, wherein the high polymer is polyvinyl alcohol, and the mass fraction of the high polymer in the high polymer aqueous solution is 15%.
And (3) mixing the dispersion liquid A and the solution B according to the mass ratio of the carbon nano tubes to the polyvinyl alcohol of 0.8:99.2, stirring the obtained mixture at the temperature of 90 ℃ for 300min, stopping stirring, and drying at the temperature of 90 ℃ for 100min to obtain the polyvinyl alcohol composite material dispersed with the carbon nano tubes. The thermal conductivity of the polyvinyl alcohol composite material dispersed with carbon nanotubes of comparative example 2 was measured to be 0.3W/mK, and the mass fraction of carbon nanotubes in the polyvinyl alcohol composite material dispersed with carbon nanotubes of comparative example 2 was measured to be 0.8%.
From example 1 and comparative examples 1 to 2, it can be seen that the heat-conducting polymer composite material having a multi-layer continuous network structure has higher heat-conducting performance under the condition that the content of the heat-conducting filler (carbon nanotube) and the kind of the polymer matrix are the same.
Example 2
A preparation method of a heat-conducting polymer composite material with a multilayer continuous network structure comprises the following steps:
a network C is prepared, which is a melamine network with a pore size of 100 μm. And (3) carrying out a load method on the network C for 50 times, wherein each load method comprises the following steps: immersing the mixture into the dispersion liquid A for 1min, taking out, drying at 50 ℃ for 1h to obtain a heat-conducting filler loaded network C, immersing the heat-conducting filler loaded network C into the solution B for 20min, taking out, centrifuging at 1000r/min for 15min, drying at 50 ℃ for 200min to obtain a heat-conducting polymer composite material, wherein,
the preparation method of the dispersion liquid A comprises the following steps: dispersing the heat-conducting filler in the liquid D to obtain a mixture, and carrying out ultrasonic treatment on the mixture for 5min by using a cell crusher to obtain a dispersion liquid A, wherein the power of the ultrasonic treatment is 800W, and the concentration of the heat-conducting filler in the dispersion liquid A is 3mg/mL (the heat-conducting filler is a carbon nano tube, and the heat-conducting coefficient of the heat-conducting filler is 500W/mK); liquid D is acetone.
The solution B is a high polymer aqueous solution, wherein the high polymer is polyethylene glycol, and the mass fraction of the high polymer in the high polymer aqueous solution is 10%.
In the 50-time loading method, the thermal conductivity was measured every 10 times, and the relationship between the number of times of loading N and the thermal conductivity Y is shown in fig. 3. Therefore, the heat conductivity coefficient of the heat-conducting polymer composite material with the multilayer continuous network structure is in positive correlation with the frequency of the loading step.
Example 3
A preparation method of a heat-conducting polymer composite material with a multilayer continuous network structure comprises the following steps:
a network C, which is a cellulose network having a pore size of 50 μm, was prepared. And (3) carrying out a load method on the network C for 50 times, wherein each load method comprises the following steps: immersing into the dispersion A for 10min, taking out, drying at 50 deg.C for 3h to obtain a network C loaded with heat conductive filler, immersing into the solution B for 1min, taking out, centrifuging at 500r/min for 15min, drying at 50 deg.C for 30min to obtain a heat conductive polymer composite material,
the preparation method of the dispersion liquid A comprises the following steps: dispersing the heat-conducting filler in the liquid D to obtain a mixture, and carrying out ultrasonic treatment on the mixture for 30min by using a cell crusher to obtain a dispersion liquid A, wherein the power of the ultrasonic treatment is 500W, and the concentration of the heat-conducting filler in the dispersion liquid A is 5mg/mL (the heat-conducting filler is silver nanofiber, and the heat conductivity coefficient of the heat-conducting filler is 200W/mK); liquid D is tetrahydrofuran.
The solution B is a high polymer aqueous solution, wherein the high polymer is cellulose, and the mass fraction of the high polymer in the high polymer aqueous solution is 1%.
Through tests, the thermal conductivity coefficient of the thermal conductive polymer composite material of the embodiment is 2.8W/mK.
Example 4
A preparation method of a heat-conducting polymer composite material with a multilayer continuous network structure comprises the following steps:
a network C was prepared, which was a polyimide network having a pore size of 60 μm. And (3) carrying out a load method on the network C for 50 times, wherein each load method comprises the following steps: immersing the mixture into the dispersion liquid A for 10min, taking out, drying at 200 ℃ for 1h to obtain a heat-conducting filler loaded network C, immersing the heat-conducting filler loaded network C into the solution B for 1min, taking out, centrifuging at 100r/min for 5min, drying at 320 ℃ for 300min to obtain a heat-conducting polymer composite material, wherein,
the preparation method of the dispersion liquid A comprises the following steps: dispersing the heat-conducting filler in the liquid D to obtain a mixture, and carrying out ultrasonic treatment on the mixture for 30min by using a cell crusher to obtain a dispersion liquid A, wherein the power of ultrasonic treatment is 500W, and the concentration of the heat-conducting filler in the dispersion liquid A is 2mg/mL (the heat-conducting filler is graphene, and the heat conductivity coefficient of the heat-conducting filler is 1000W/mK); the liquid D is N-methylpyrrolidone.
The solution B is a polymer precursor solution, the solute of the polymer precursor solution is polyamic acid, the solvent of the polymer precursor solution is N-methyl pyrrolidone, and the mass fraction of the solute in the polymer precursor solution is 10%.
Through tests, the thermal conductivity coefficient of the thermal conductive polymer composite material of the embodiment is 4.5W/mK.
Example 5
A preparation method of a heat-conducting polymer composite material with a multilayer continuous network structure comprises the following steps:
a network C was prepared, which was a polypropylene network having a pore size of 200 μm. And (3) carrying out the load method on the network C for 30 times, wherein each load method comprises the following steps: immersing the mixture into the dispersion liquid A for 10min, taking out, drying at 50 ℃ for 1h to obtain a heat-conducting filler loaded network C, immersing the heat-conducting filler loaded network C into the solution B for 10min, taking out, centrifuging at 100r/min for 5min, drying at 60 ℃ for 100min to obtain a heat-conducting polymer composite material, wherein,
the preparation method of the dispersion liquid A comprises the following steps: dispersing the heat-conducting filler in the liquid D to obtain a mixture, and carrying out ultrasonic treatment on the mixture for 50min by using a cell crusher to obtain a dispersion liquid A, wherein the ultrasonic treatment power is 500W, and the concentration of the heat-conducting filler in the dispersion liquid A is 1mg/mL (the heat-conducting filler is a boron nitride nanosheet, and the heat-conducting coefficient of the heat-conducting filler is 200W/mK); liquid D is ethyl acetate.
The solution B is a high polymer aqueous solution, wherein the high polymer is polyacrylic acid, and the mass fraction of the high polymer in the high polymer aqueous solution is 10%.
Through tests, the thermal conductivity coefficient of the thermal conductive polymer composite material of the embodiment is 1.5W/mK.
Example 6
A preparation method of a heat-conducting polymer composite material with a multilayer continuous network structure comprises the following steps:
a network C was prepared, which was a nickel foam having a pore size of 200 μm. And (3) carrying out the load method on the network C for 50 times, wherein each load method comprises the following steps: immersing into the dispersion A for 10min, taking out, drying at 200 deg.C for 1h to obtain a network C loaded with heat conductive filler, immersing into the solution B for 300min, taking out, drying at 20 deg.C for 30min to obtain a heat conductive polymer composite material,
the preparation method of the dispersion liquid A comprises the following steps: dispersing the heat-conducting filler in the liquid D to obtain a mixture, and carrying out ultrasonic treatment on the mixture for 30min by using a cell crusher to obtain a dispersion liquid A, wherein the ultrasonic treatment power is 500W, and the concentration of the heat-conducting filler in the dispersion liquid A is 2mg/mL (the heat-conducting filler is a boron nitride nanosheet, and the heat-conducting coefficient of the heat-conducting filler is 200W/mK); liquid D is N, N-dimethylformamide.
The solution B is a polymer precursor solution, the solute of the polymer precursor solution is dopamine, the solvent of the polymer precursor solution is Tris buffer solution, and the mass fraction of the solute in the polymer precursor solution is 10%.
Through tests, the heat conductivity coefficient of the heat-conducting polymer composite material is 3.5W/mK.
Example 7
A preparation method of a heat-conducting polymer composite material with a multilayer continuous network structure comprises the following steps:
a network C was prepared, which was a carbon foam having a pore size of 200 μm. And carrying out a load method on the network C for 25 times, wherein the load method for each time is as follows: immersing into the dispersion A for 10min, taking out, drying at 200 deg.C for 1h to obtain a network C loaded with heat conductive filler, immersing into the solution B for 100min, taking out, drying at 50 deg.C for 30min to obtain a heat conductive polymer composite material,
the preparation method of the dispersion liquid A comprises the following steps: dispersing the heat-conducting filler in the liquid D to obtain a mixture, and carrying out ultrasonic treatment on the mixture for 30min by using a cell crusher to obtain a dispersion liquid A, wherein the power of the ultrasonic treatment is 500W, and the concentration of the heat-conducting filler in the dispersion liquid A is 2mg/mL (the heat-conducting filler is a carbon nitride nanosheet, and the heat conductivity coefficient of the heat-conducting filler is 50W/mK); and the liquid D is dimethyl sulfoxide.
The solution B is a high polymer aqueous solution, wherein the high polymer is polyurethane, and the mass fraction of the high polymer in the high polymer aqueous solution is 10%.
Through tests, the thermal conductivity coefficient of the thermal conductive polymer composite material of the embodiment is 2.5W/mK.
Example 8
A preparation method of a heat-conducting polymer composite material with a multilayer continuous network structure comprises the following steps:
a network C is prepared, which is a melamine network with a pore size of 100 μm. And (3) carrying out a load method on the network C for 2 times, wherein each load method comprises the following steps: immersing the mixture into the dispersion liquid A for 1min, taking out, drying at 50 ℃ for 1h to obtain a heat-conducting filler loaded network C, immersing the heat-conducting filler loaded network C into the solution B for 20min, taking out, centrifuging at 500r/min for 15min, drying at 100 ℃ for 120min to obtain a heat-conducting polymer composite material,
the preparation method of the dispersion liquid A comprises the following steps: dispersing the heat-conducting filler in the liquid D to obtain a mixture, and carrying out ultrasonic treatment on the mixture for 5min by using a cell crusher to obtain a dispersion liquid A, wherein the power of the ultrasonic treatment is 800W, and the concentration of the heat-conducting filler in the dispersion liquid A is 3mg/mL (the heat-conducting filler is carbon nanofiber, and the heat conductivity coefficient is 100W/mK); liquid D is acetone.
The solution B is a polymer precursor solution, the solute of the polymer precursor solution is polydimethylsiloxane, the solvent of the polymer precursor solution is acetone, and the mass fraction of the solute in the polymer precursor solution is 10%.
Through tests, the thermal conductivity coefficient of the thermal conductive polymer composite material of the embodiment is 0.5W/mK.
Example 9
A preparation method of a heat-conducting polymer composite material with a multilayer continuous network structure comprises the following steps:
a network C of copper foam having a pore size of 50 μm was prepared. And carrying out the load method on the network C for 10 times, wherein each load method comprises the following steps: immersing into the dispersion A for 10min, taking out, drying at 200 ℃ for 1h to obtain a network C loaded with heat-conducting filler, immersing the network C loaded with heat-conducting filler into the solution B for 10min, taking out, centrifuging at 100r/min for 5min, drying at 100 ℃ for 100min to obtain the heat-conducting polymer composite material, wherein,
the preparation method of the dispersion liquid A comprises the following steps: dispersing the heat-conducting filler in the liquid D to obtain a mixture, and carrying out ultrasonic treatment on the mixture for 30min by using a cell crusher to obtain a dispersion liquid A, wherein the power of ultrasonic treatment is 500W, and the concentration of the heat-conducting filler in the dispersion liquid A is 2mg/mL (the heat-conducting filler is graphene, and the heat conductivity coefficient is 1000W/mK); the liquid D is N-methylpyrrolidone.
The solution B is a polymer precursor solution, the solute of the polymer precursor solution is epoxy resin, the solvent of the polymer precursor solution is dimethylbenzene, and the mass fraction of the solute in the polymer precursor solution is 10%.
Through tests, the thermal conductivity coefficient of the thermal conductive polymer composite material of the embodiment is 3.9W/mK.
The heat-conducting polymer composite material with a multi-layer continuous network structure sequentially and circularly loads the heat-conducting filler and the polymer matrix material on the surface of a three-dimensional continuous network structure framework (network C), so that the heat-conducting filler and the polymer matrix material not only form three-dimensional continuous networks respectively, but also are alternately deposited, so that the heat-conducting polymer composite material not only has a high-heat-conducting three-dimensional filler network, but also has smaller average distance between the polymer matrix and the heat-conducting filler network, and heat can be transferred from the polymer matrix to the heat-conducting filler network in time and then is quickly transferred along the heat-conducting filler network, thereby showing higher heat-conducting performance; in addition, the content of the heat-conducting filler in the composite material can be controlled by controlling the times of the heat-conducting filler and the high polymer load, so that different heat-conducting properties can be obtained.
The invention being thus described by way of example, it should be understood that any simple alterations, modifications or other equivalent alterations as would be within the skill of the art without the exercise of inventive faculty, are within the scope of the invention.

Claims (4)

1. A preparation method of a heat-conducting polymer composite material with a multilayer continuous network structure is characterized by comprising the following steps:
preparing a network C which is a material with a three-dimensional continuous network structure, and carrying out a loading method on the network C for 2-50 times, wherein each loading method comprises the following steps: immersing the mixture into the dispersion liquid A for 1-30 min, taking out, drying at the temperature of 20-200 ℃ for 0.5-3 h to obtain a heat-conducting filler-loaded network C, immersing the heat-conducting filler-loaded network C into the solution B for 1-300 min, taking out, and drying at the temperature of 20-320 ℃ for 30-300 min to obtain a heat-conducting polymer composite material, wherein the network C is a polyurethane network, a melamine network, a polyimide network, a cellulose network, a polypropylene network, nickel foam, copper foam or carbon foam,
the preparation method of the dispersion liquid A comprises the following steps: dispersing a heat-conducting filler in a liquid D to obtain a mixture, and carrying out ultrasonic treatment on the mixture for 5-60 min by using a cell crusher to obtain a dispersion liquid A, wherein the concentration of the heat-conducting filler in the dispersion liquid A is 0.01-5 mg/mL, the heat-conducting filler is a heat-conducting material with a heat-conducting coefficient larger than 10W/mK, the heat-conducting filler is a carbon nano tube, a carbon nano fiber, a silver nano fiber, a boron nitride nano tube, graphene, a boron nitride nano sheet or a carbon nitride nano sheet, and the liquid D is acetone, tetrahydrofuran, ethyl acetate, isopropanol, N-methylpyrrolidone, N-dimethylformamide or dimethyl sulfoxide;
the solution B is a high polymer aqueous solution or a high polymer precursor solution, wherein the high polymer is polyvinyl alcohol, polyethylene glycol, cellulose, polyacrylic acid or polyurethane, and the mass fraction of the high polymer in the high polymer aqueous solution is 1-15%; the solute of the high-molecular precursor solution is polydimethylsiloxane, epoxy resin, polyamic acid or dopamine, when the solute of the high-molecular precursor solution is polydimethylsiloxane, epoxy resin or polyamic acid, the solvent of the high-molecular precursor solution is N-methylpyrrolidone, acetone or xylene, and when the solute of the high-molecular precursor solution is dopamine, the solvent of the high-molecular precursor solution is Tris buffer solution;
the heat conductivity coefficient of the heat-conducting polymer composite material with the multilayer continuous network structure is in positive correlation with the frequency of the loading step.
2. The method according to claim 1, wherein the power of the ultrasonic treatment is 20 to 800W.
3. The preparation method according to claim 2, wherein the network C loaded with the heat-conducting filler is immersed in the solution B for 1-300 min, taken out, centrifuged, and dried at 20-320 ℃ for 30-300 min, and the rotation speed of the centrifugation is less than or equal to 2000 r/min.
4. The method of claim 3, wherein the centrifugation time is no more than 30 min.
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