CN113667272B - Polymer-based high-thermal-conductivity material and preparation process thereof - Google Patents
Polymer-based high-thermal-conductivity material and preparation process thereof Download PDFInfo
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Abstract
The invention discloses a polymer-based high-thermal-conductivity material and a preparation process thereof. The process comprises the following steps: uniformly mixing the heat-conducting filler and the pore-forming agent to obtain a mixture, placing the mixture in a mold, carrying out compression molding, heating to obtain a heat-conducting framework; uniformly mixing the resin and the curing agent to obtain a mixed solution; and soaking the heat-conducting framework in the mixed liquid in a container, vacuumizing the container, standing and curing to obtain the polymer-based high-heat-conducting material. The invention compacts the heat-conducting filler mixed with the pore-foaming agent by a mould pressing forming method, heats the heat-conducting filler to be more than the melting point of the pore-foaming agent, the pore-foaming agent is changed into a molten state, the liquid pore-foaming agent flows to form holes, simultaneously plays a role of enhancing the heat-conducting filler in the flowing process, forms a firm porous heat-conducting framework, and is poured with low-viscosity liquid resin to be cured to form the insulating heat-conducting material. The preparation process provided by the invention has low requirements on the particle size and the shape of the heat-conducting filler, and saves the cost.
Description
Technical Field
The invention belongs to the technical field of chemical materials, and particularly relates to a polymer-based high-heat-conductivity material and a preparation process thereof.
Background
The rise of the fifth generation mobile network and the higher power density in the electronic equipment make the requirement of heat dissipation continuously increase, and if the heat management guarantee is not sufficient, the related devices are easy to age or damage in advance. There is an urgent need for polymer composites with excellent thermal conductivity, low dielectric constant, and low dielectric loss in microelectronics and wireless communication systems.
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 reinforced based on the heat-conducting filler has low density, excellent mechanical property, processing property and high heat conductivity, and becomes a heat-conducting material with 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 increase the thermal conductivity of high polymer materials. Hexagonal boron nitride (H-BN), due to its high thermal conductivity, wide band gap and high aspect ratio two-dimensional (2D) morphology, together with excellent electrical insulating properties, makes it an ideal candidate for the fabrication of polymer composites with high thermal conductivity enhancement.
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 fillers into a high polymer matrix, the high-content heat conduction fillers can increase the heat conductivity, but the increase of the cost can be inevitably caused by increasing the heat conductivity by increasing the content of the fillers, and meanwhile, the microstructure of the high polymer composite material can be deeply influenced, so that the processability and the mechanical property are reduced. When the heat-conducting filler is simply dispersed in the polymer, phonon scattering occurs continuously between the interface of the heat-conducting filler and the polymer in the heat-conducting process, so that heat loss is caused, and in order to improve the utilization efficiency of the heat-conducting filler of the high-molecular composite material and enable the composite material to obtain higher heat-conducting performance at a lower filler addition level, many researchers now adopt a heat-conducting framework constructed by connecting the heat-conducting filler in advance to construct a continuous heat-conducting path to improve the heat-conducting performance of the polymer-based heat-conducting composite material.
However, there are some barriers that can be breached in current research on BN thermal conductive frameworks: because the surface of the chemical inert BN filler has very few functional groups, heat conduction paths cannot be directly formed among BN, but the BN fillers are in physical contact or are crosslinked through a low-heat-conduction high-molecular adhesive, and interface thermal resistance is caused; chemical modification of BN surfaces has limited application due to the complexity of the manufacturing process.
Aiming at the problems, a new hole making method, namely a fusion hole making method, is adopted to construct a BN framework, heat-conducting fillers BN and urea are pressed together by a compression method by using BN and sacrificial material urea in a mould pressing mode, and meanwhile, pore-forming agents are fused and flow out in the heating process to form the porous heat-conducting framework. This method allows the formation of a thermally conductive path without the use of polymer material bonding, and the absence of polymers or dispersants between BN's in the preformed 3D-BN foam, avoids those with low intrinsic thermal conductivity to prevent direct filler-filler contact in the thermal path. Meanwhile, the molten urea increases the contact between BN fillers due to certain adhesiveness, so that a BN framework is enhanced, the defect of irregularity of the BN is filled, and the defect irregular interface between the BN framework and resin is reduced. And because the certain adhesion of urea for the skeleton has certain mechanical strength, has reduced the operation degree of difficulty, and better construction is changeed and is changed into the filling resin, can realize lower filler volume and adjustable shape.
The patent document with publication number CN111334001A discloses a boron nitride modified epoxy resin insulating material with high thermal conductivity and a preparation method thereof, tannic acid is firmly fixed on nano boron nitride by physical adsorption and chemical covalent bond modification, phenolic hydroxyl in the tannic acid and epoxy groups in ethylene glycol diglycidyl ether are subjected to ring-opening reaction, and then are crosslinked and polymerized with epoxy resin E44 and cured, and through the synergistic effect of physical acting force and chemical bond modification, the nano boron nitride is organically combined with the epoxy resin, so that the compatibility of the nano boron nitride and the epoxy resin is improved, and the epoxy resin material is endowed with excellent thermal conductivity and insulating property. This approach only solves the problem of compatibility of BN with epoxy resins. The problem of connection between the thermally conductive fillers is not solved.
Patent document CN111909490A discloses a heat conductive epoxy composite material containing an aerogel skeleton having a porous structure, in which a continuous structure using a heat conductive skeleton improves heat conductivity, but the improvement of heat conductivity is insufficient.
Patent document No. CN111499391 discloses a resin-impregnated boron nitride sintered body, but the sintering temperature is 1600 degrees or more, and the operation cost is high due to the high sintering temperature.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a polymer-based high-thermal-conductivity material and a preparation process thereof.
The invention aims to solve the problem that the heat-conducting property of the traditional polymer-based heat-conducting material cannot be further improved only by dispersing the heat-conducting filler in a polymer matrix.
The purpose of the invention is realized by at least one of the following technical solutions.
The polymer-based high-heat-conduction material provided by the invention consists of matrix resin and a heat-conduction framework. The heat-conducting framework is prepared by compression molding and heating at room temperature and high pressure of heat-conducting filler and pore-foaming agent which can be melted at a certain temperature.
The polymer-based high-thermal-conductivity material provided by the invention is an insulating high-modulus polymer-based thermal-conductivity material, and can be applied to supporting material packaging materials and the like.
The preparation process of the polymer-based high-thermal-conductivity material provided by the invention comprises the following steps:
(1) uniformly mixing the heat-conducting filler and the pore-forming agent to obtain a mixture, then placing the mixture into a mold, carrying out compression molding, heating and heating to obtain a heat-conducting framework;
(2) uniformly mixing resin and a curing agent to obtain a mixed solution;
(3) and (3) soaking the heat-conducting framework in the step (1) in the mixed liquid in the step (2) in a container, vacuumizing the container, standing and curing to obtain the polymer-based high heat-conducting material.
Further, the heat-conducting filler in the step (1) is one or more of boron nitride, aluminum oxide, zinc oxide, magnesium oxide, aluminum nitride and silicon carbide, and the pore-forming agent is urea.
Preferably, the thermal conductivity of the heat-conducting filler in the step (1) is 20-350W/(m.k).
Further preferably, the thermal conductivity of the heat-conducting filler in the step (1) is 100-.
Further, the mixture in the step (1) comprises the following components in parts by volume:
10-80 parts of heat-conducting filler;
20-90 parts of a pore-forming agent.
The pore-forming agent is a material capable of being melted, is heated at high temperature to be changed into liquid state, is melted and flows out, and is bonded in gaps of the heat-conducting filler in the flowing-out process, so that the heat conductivity is further increased.
Further, the compression molding pressure in the step (1) is 150-250MPa, and the compression molding time is 3-5 minutes.
Preferably, the pressure for compression molding in step (1) is 200MPa, and the compression molding time is 5 minutes.
Further, the temperature of the heating treatment in the step (1) is 140 ℃, -150 ℃, and the time of the heating treatment is 2-4 hours.
Preferably, the time of the heat treatment in the step (1) is 3 hours.
Further, the resin in the step (2) is one of epoxy resin, urethane acrylate, phenolic resin, urea resin and organic silicon resin;
in step (2), the curing agent is one or more of aliphatic amine, alicyclic amine, aromatic amine, acid anhydride, polyamide and resin curing agent.
Further, the mixed solution in the step (2) comprises the following components in parts by volume:
20-90 parts of resin;
10-80 parts of a curing agent.
The resin is curable at high temperature or normal temperature, has low viscosity and good fluidity before curing, and is convenient for vacuumizing and infiltrating into pores of the heat-conducting framework. The resin is a crosslinking curable resin.
Further, the volume ratio of the heat conducting framework to the mixed liquid in the step (3) is 1: 9-8: 2.
further, the curing treatment time in the step (3) is 12 hours, and the curing treatment is carried out in an environment of a vacuum degree of-0.1 MPa.
The invention provides a polymer-based high-thermal-conductivity material prepared by the preparation process.
The polymer-based high thermal conductive material provided by the invention can be used as a heat dissipation component of heat dissipation electronic components such as power devices. In particular, the composite material can be used for an insulating layer of a printed circuit board, a thermal interface material and a double-sided heat dissipation power module for an automobile.
The invention compacts the heat-conducting filler mixed with the pore-foaming agent by a mould pressing forming method, heats the heat-conducting filler to be more than the melting point of the pore-foaming agent, the pore-foaming agent is changed into a molten state, the liquid pore-foaming agent flows to form holes, simultaneously plays a role of enhancing the heat-conducting filler in the flowing process, forms a firm porous heat-conducting framework, and is poured with low-viscosity liquid resin to be cured to form the insulating heat-conducting material.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the preparation process provided by the invention has low requirements on the particle size and the shape of the heat-conducting filler, does not need to buy the heat-conducting filler with good regularity and large particle size for pursuing quality, and saves the cost.
(2) The preparation process provided by the invention is a new process, is more beneficial to the transmission of a heat carrier (phonon), can improve the heat conductivity of a product, and particularly, if a melting hole making process is added, the heat conductivity of the product can be even higher than that of a pure heat-conducting filler compression body molded in the same compression mode.
(3) In the preparation process provided by the invention, the obtained heat-conducting framework has certain strength, and the heat-conducting framework does not need to worry about the fracture of the framework in the transferring, gluing and curing processes.
Drawings
FIG. 1 is an SEM picture of a thermally conductive skeleton obtained by a 500 degree Celsius treatment in step (1) of comparative example 1;
FIG. 2 is an enlarged view of a portion of the box in FIG. 1;
FIG. 3 is a SEM image of the thermally conductive skeleton obtained from the step (1) of example 3 at 140 degrees Celsius;
FIG. 4 is an enlarged view of the box portion of FIG. 3;
FIG. 5 is a graph of the thermal conductivity results for the polymer-based high thermal conductivity materials prepared in examples 1-8 and the thermal conductivity material prepared in comparative example 2;
fig. 6 is an EDS image of carbon and boron elements in the polymer-based high thermal conductivity material prepared in example 1.
Detailed Description
The following examples are presented to further illustrate the practice of the invention, but the practice and protection of the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.
The invention discovers that the porous filler with the 3D framework (net structure) is added in the preparation process of the heat conduction material, so that the reinforcement effect of the framework material can be well utilized, and favorable conditions are created for realizing micro-area reinforcement by adding the subsequent heat conduction filler. However, the method for constructing a three-dimensional heat-conducting network in advance in the prior art is often limited by an effective construction method and harsh operating conditions, and a regular network with good communication effect cannot be formed in the polymer, so that the improvement of the heat-conducting coefficient is limited. The present inventors have provided the following technical solutions of the present invention based on the above findings.
The heat conductive filler is not limited to a heat conductive ceramic such as BN, which is insulating and difficult to sinter. The resin is not limited to epoxy resin, and a low viscosity high modulus thermosetting plastic is possible. The composite material comprises 10-80 parts by volume of porous filler and 20-90 parts by volume of polymer, and the change of the thermal conductivity of the composite material is shown in figure 1 along with the increase of the content of the heat-conducting filler. In the present invention, the shape of the porous filler is not particularly limited as long as the requirements of the present invention can be satisfied, and may be, for example, one selected from the group consisting of a square, a rectangle, a circle, and an irregular polygon in a sheet shape, and is preferably a square and/or a circle.
In the present invention, as the content of the thermally conductive filler increases, the change in the thermal conductivity of the composite material is shown in fig. 1.
The parts by weight (mass) used in the following examples may be given in units of g, kg, etc., by way of example, or may be any other amount commonly used in the art.
The volume fractions used in the following examples may be, for example, cubic centimeters, cubic decimeters, cubic meters, and the like, or any other amount commonly used in the art.
The resistivity of the polymer-based high-thermal-conductivity material prepared in the following example is detected by a hot-disc transient flat plate heat source method thermal conductivity meter method, and is tested according to a standard GB/T32064, and the volume resistivity of the material is tested by using an EST120 type digital high resistance meter, and is tested according to a standard GB/T1410-2006.
Example 1
A preparation process of a polymer-based high-thermal-conductivity material comprises the following steps:
(1) according to the volume parts, 10 parts of heat-conducting filler (boron nitride and BN are selected) and 90 parts of pore-forming agent (urea are selected) are taken, the heat-conducting filler and the pore-forming agent are uniformly mixed to obtain a mixture, then the mixture is placed in a mold, compression molding is carried out (the pressure is 200MPa, the time is 5 minutes), the temperature is increased, heating treatment is carried out (the temperature is 140 ℃, the time is 2 hours), and the heat-conducting framework is obtained;
(2) according to the mass parts, 75 parts of resin (epoxy resin 5015 is selected) and 25 parts of curing agent (epoxy resin curing agent 5015 is selected) are taken, and the resin and the curing agent are uniformly mixed (uniformly stirred and mixed for 5 minutes) to obtain a mixed solution (epoxy resin prepolymer);
(3) soaking the heat-conducting framework in the step (1) in the mixed liquid in the step (2) in a container, wherein the volume ratio of the heat-conducting framework to the mixed liquid is 1: and 9, vacuumizing the container, keeping the vacuum degree of the container at-0.1 MPa after vacuumizing, standing for curing (12 hours), and thus obtaining the polymer-based high-thermal-conductivity material.
Example 2
A preparation process of a polymer-based high-thermal-conductivity material comprises the following steps:
(1) according to the volume parts, 20 parts of heat-conducting filler (boron nitride and BN are selected) and 80 parts of pore-forming agent (urea are selected) are taken, the heat-conducting filler and the pore-forming agent are uniformly mixed to obtain a mixture, then the mixture is placed in a mold, compression molding is carried out (the pressure is 200MPa, the time is 5 minutes), the temperature is increased, heating treatment is carried out (the temperature is 140 ℃, the time is 2 hours), and the heat-conducting framework is obtained;
(2) according to the mass parts, 75 parts of resin (epoxy resin 5015 is selected) and 25 parts of curing agent (epoxy resin curing agent 5015 is selected) are taken, the resin and the curing agent are stirred and mixed uniformly, and the stirring time is 5 minutes, so that a mixed solution (epoxy resin prepolymer) is obtained;
(3) soaking the heat-conducting framework in the step (1) in the mixed liquid in the step (2) in a container, wherein the volume ratio of the heat-conducting framework to the mixed liquid is 2: and 8, vacuumizing the container, keeping the vacuum degree of the container at-0.1 MPa after vacuumizing, standing for curing (12 hours), and thus obtaining the polymer-based high-thermal-conductivity material.
Example 3
A preparation process of a polymer-based high-thermal-conductivity material comprises the following steps:
(1) according to the volume parts, 30 parts of heat-conducting filler (boron nitride and BN are selected) and 70 parts of pore-forming agent (urea are selected) are taken, the heat-conducting filler and the pore-forming agent are uniformly mixed to obtain a mixture, then the mixture is placed in a mold, compression molding is carried out (the pressure is 200MPa, the time is 5 minutes), the temperature is increased, heating treatment is carried out (the temperature is 140 ℃, the time is 2 hours), and the heat-conducting framework is obtained;
(2) taking 75 parts of resin (epoxy resin 5015) and 25 parts of curing agent (epoxy resin curing agent 5015), and uniformly stirring and mixing the resin and the curing agent for 5 minutes to obtain a mixed solution (epoxy resin prepolymer);
(3) and (3) soaking the heat-conducting framework in the step (1) in the mixed liquid in the step (2) in a container, wherein the volume ratio of the heat-conducting framework to the mixed liquid is 3/7, vacuumizing the container, keeping the vacuum degree of the container at-0.1 MPa after vacuumizing, and standing for curing (for 12 hours) to obtain the polymer-based high heat-conducting material.
Example 4
A preparation process of a polymer-based high-thermal-conductivity material comprises the following steps:
(1) according to the volume parts, 40 parts of heat-conducting filler (boron nitride and BN are selected) and 60 parts of pore-forming agent (urea are selected) are taken, the heat-conducting filler and the pore-forming agent are uniformly mixed to obtain a mixture, then the mixture is placed in a mold, compression molding is carried out (the pressure is 200MPa, the time is 5 minutes), the temperature is increased, heating treatment is carried out (the temperature is 140 ℃, the time is 2 hours), and the heat-conducting framework is obtained;
(2) according to the mass parts, 75 parts of resin (epoxy resin 5015 is selected) and 25 parts of curing agent (epoxy resin curing agent 5015 is selected) are taken, the resin and the curing agent are stirred and mixed uniformly, and the stirring time is 5 minutes, so that a mixed solution (epoxy resin prepolymer) is obtained;
(3) soaking the heat-conducting framework in the step (1) in the mixed liquid in the step (2) in a container, wherein the volume ratio of the heat-conducting framework to the mixed liquid is 4: and 6, vacuumizing the container, keeping the vacuum degree of the container to be-0.1 MPa after vacuumizing, standing for curing (12 hours), and thus obtaining the polymer-based high-thermal-conductivity material.
Example 5
(1) According to the volume parts, 50 parts of heat-conducting filler (boron nitride and BN are selected) and 50 parts of pore-forming agent (urea are selected) are taken and evenly mixed to obtain a mixture, then the mixture is placed in a mold and is subjected to compression molding (the pressure is 200MPa and the time is 5 minutes), and the temperature is increased for heating treatment (the temperature is 140 ℃ and the time is 2 hours) to obtain a heat-conducting framework;
(2) according to the mass parts, 75 parts of resin (epoxy resin 5015 is selected) and 25 parts of curing agent (epoxy resin curing agent 5015 is selected) are taken, the resin and the curing agent are stirred and mixed uniformly, and the stirring time is 5 minutes, so that a mixed solution (epoxy resin prepolymer) is obtained;
(3) soaking the heat-conducting framework in the step (1) in the mixed liquid in the step (2) in a container, wherein the volume ratio of the heat-conducting framework to the mixed liquid is 5: and 5, vacuumizing the container, keeping the vacuum degree of the container at-0.1 MPa after vacuumizing, standing for curing (12 hours), and thus obtaining the polymer-based high-thermal-conductivity material.
Example 6
(1) According to the volume parts, 60 parts of heat-conducting filler (boron nitride and BN are selected) and 40 parts of pore-forming agent (urea are selected) are taken, the heat-conducting filler and the pore-forming agent are uniformly mixed to obtain a mixture, then the mixture is placed in a mold, compression molding is carried out (the pressure is 200MPa and the time is 5 minutes), the temperature is increased, heating treatment is carried out (the temperature is 140 ℃ and the time is 2 hours), and the heat-conducting framework is obtained;
(2) taking 75 parts of resin (epoxy resin 5015) and 25 parts of curing agent (epoxy resin curing agent 5015), and uniformly stirring and mixing the resin and the curing agent for 5 minutes to obtain a mixed solution (epoxy resin prepolymer);
(3) soaking the heat-conducting framework in the step (1) in the mixed liquid in the step (2) in a container, wherein the volume ratio of the heat-conducting framework to the mixed liquid is 6: and 4, vacuumizing the container, keeping the vacuum degree of the container at-0.1 MPa after vacuumizing, standing for curing (12 hours), and thus obtaining the polymer-based high-thermal-conductivity material.
Example 7
(1) According to the volume parts, 70 parts of heat-conducting filler (boron nitride and BN are selected) and 30 parts of pore-forming agent (urea are selected) are taken, the heat-conducting filler and the pore-forming agent are uniformly mixed to obtain a mixture, then the mixture is placed in a mold, compression molding is carried out (the pressure is 200MPa, the time is 5 minutes), the temperature is increased, heating treatment is carried out (the temperature is 140 ℃, the time is 2 hours), and the heat-conducting framework is obtained;
(2) taking 75 parts of resin (epoxy resin 5015) and 25 parts of curing agent (epoxy resin curing agent 5015), and uniformly stirring and mixing the resin and the curing agent for 5 minutes to obtain a mixed solution (epoxy resin prepolymer);
(3) soaking the heat-conducting framework in the step (1) in the mixed liquid in the step (2) in a container, wherein the volume ratio of the heat-conducting framework to the mixed liquid is 7: and 3, vacuumizing the container, keeping the vacuum degree of the container at-0.1 MPa after vacuumizing, standing for curing (12 hours), and thus obtaining the polymer-based high-thermal-conductivity material.
Example 8
(1) According to the volume parts, 80 parts of heat-conducting filler (boron nitride and BN are selected) and 20 parts of pore-forming agent (urea are selected) are taken and evenly mixed to obtain a mixture, then the mixture is placed in a mold and is subjected to compression molding (the pressure is 200MPa, the time is 5 minutes), and the temperature is increased to carry out heating treatment (the temperature is 140 ℃ and the time is 2 hours) to obtain a heat-conducting framework;
(2) taking 75 parts of resin (epoxy resin 5015) and 25 parts of curing agent (epoxy resin curing agent 5015), and uniformly stirring and mixing the resin and the curing agent for 5 minutes to obtain a mixed solution (epoxy resin prepolymer);
(3) soaking the heat-conducting framework in the step (1) in the mixed liquid in the step (2) in a container, wherein the volume ratio of the heat-conducting framework to the mixed liquid is 8: and 2, vacuumizing the container, keeping the vacuum degree of the container to be-0.1 MPa after vacuumizing, standing for curing (12 hours), and thus obtaining the polymer-based high-thermal-conductivity material.
Example 9
A thermally conductive material was prepared according to the method of example 3, example 9 differing from example 3 only in that: the heat conductive filler of step (1) was changed to 21 parts Boron Nitride (BN) plus 9 parts alumina.
Example 10
A thermally conductive material was prepared according to the method of example 3, with example 10 differing from example 3 only in that: the heat conductive filler in the step (1) is changed into 21 parts of Boron Nitride (BN) and 9 parts of silicon carbide.
Comparative example 1
A thermally conductive material was prepared according to the method of example 3, with comparative example 1 differing from example 3 only in that: the temperature of the heat treatment in the step (1) is changed to 500 ℃.
Comparative example 2
A heat conductive material was prepared according to the method of example 1, and comparative example 2 differs from example 1 only in that: no thermally conductive filler is added.
Comparative example 3
(1) Taking 75 parts of resin (epoxy resin 5015) and 25 parts of curing agent (epoxy resin curing agent 5015), and uniformly mixing the resin and the curing agent (uniformly stirring and mixing for 5 minutes) to obtain a mixed solution (epoxy resin prepolymer);
(2) according to the volume parts, 10 parts of heat-conducting filler (boron nitride, BN is selected), 90 parts of the mixed liquid in the step (1) are taken, the heat-conducting filler is uniformly mixed in the mixed liquid in the step (1) in a container, and the volume ratio of the heat-conducting filler to the mixed liquid is 1: and 9, vacuumizing the container, keeping the vacuum degree of the container at-0.1 MPa after vacuumizing, and standing for curing (for 12 hours) to obtain the boron nitride/epoxy composite material.
Comparative example 4
According to the volume parts, 100 parts of heat-conducting filler (boron nitride and BN are selected) is placed in a mold, compression molding is carried out (the pressure is 200MPa, the time is 5 minutes), the temperature is increased, heating treatment is carried out (the temperature is 140 ℃, the time is 2 hours), and no epoxy resin is added.
Effect analysis
Table 1 below shows the results of the thermal conductivity and resistivity parameters of the polymer-based high thermal conductivity material prepared in each example.
TABLE 1
Example 8 was compared to comparative example 2: examples of the invention8 the thermal conductivity of the prepared polymer-based high thermal conductive material can reach up to 13.65 W.m-1·K-1Up to 65 times that of the polymer itself.
Example 1 compared to comparative example 3: with the same filler volume fraction of 10%, the boron nitride/epoxy composite material (polymer-based high thermal conductivity material) obtained in example 1 has a higher thermal conductivity (3.08 W.m)-1·K-1) The boron nitride/epoxy composite material (thermal conductivity 0.57 W.m) obtained by simple blending of comparative example 3 was used-1·K-1) 5.57 times of the thermal conductivity of the composite material, which proves that the process can effectively improve the thermal conductivity of the composite material.
By comparison of example 3 with comparative example 1:
FIG. 1 is an SEM picture of a thermally conductive skeleton obtained by a 500 degree Celsius treatment in step (1) of comparative example 1; fig. 2 is an enlarged picture of the box area of fig. 1.
FIG. 3 is an SEM image of a thermally conductive frame of example 3 processed at 140 degrees Celsius during step (1);
fig. 4 is an enlarged picture of the box area of fig. 3.
As can be seen from fig. 1, 2, 3 and 4: comparative example 1 heat treatment was carried out at 500 c, urea was completely removed due to the high temperature (500 c), BN and BN were only overlapped; on the other hand, when the heat treatment is performed at 140 ℃ in example 3, it can be seen that urea infiltrates among the BN, the urea bonds the heat conductive fillers BN together, irregular surface interfaces are filled, and the cross section looks smooth and flat. As can be seen from the data in Table 1, the final polymer-based high thermal conductivity material has higher thermal conductivity than the thermal conductivity material prepared in comparative example 1, the thermal conductivity is from 1.36 W.m.-1·K-1Increased to 5.32 W.m-1·K-1The improvement is nearly four times.
As can be seen from the data in Table 1, the product can maintain a high resistivity due to the addition of the insulating and heat-conducting filler, and the resistivity can be maintained at 1013Omega cm or more.
FIG. 5 is a graph of the thermal conductivity results for the polymer-based high thermal conductivity materials prepared in examples 1-8 and the thermal conductivity material prepared in comparative example 2; fig. 5 reflects the change of thermal conductivity with the change of the content of the thermally conductive filler, and it can be understood from fig. 5 that: as the amount of the heat conductive filler increases, the heat conductivity of the heat conductive material also increases.
Fig. 6 is an EDS image of carbon and boron in the polymer-based high thermal conductivity material prepared in example 1, and it can be seen from the EDS image of C element that there are voids between the resins, and a complete thermal conductivity path can be formed.
The above examples are only preferred embodiments of the present invention, which are intended to be illustrative and not limiting, and those skilled in the art should understand that they can make various changes, substitutions and alterations without departing from the spirit and scope of the invention.
Claims (6)
1. A preparation process of a polymer-based high-thermal-conductivity material is characterized by comprising the following steps:
(1) uniformly mixing the heat-conducting filler and urea to obtain a mixture, then placing the mixture in a mold, carrying out compression molding, heating to obtain a heat-conducting framework; the heat conducting filler is boron nitride;
the temperature of the heating treatment in the step (1) is 140-150 ℃, and the time of the heating treatment is 2-4 hours;
the mixture in the step (1) comprises the following components in parts by volume:
10-80 parts of heat-conducting filler;
20-90 parts of urea;
(2) uniformly mixing resin and a curing agent to obtain a mixed solution;
(3) soaking the heat-conducting framework in the step (1) in the mixed liquid in the step (2) in a container, vacuumizing the container, standing and curing to obtain the polymer-based high heat-conducting material;
and (3) the volume ratio of the heat-conducting framework to the mixed liquid is 1: 9-8: 2.
2. the process for preparing a polymer-based high thermal conductive material according to claim 1, wherein the pressure for the compression molding in step (1) is 150-250MPa, and the time for the compression molding is 3-5 minutes.
3. The process for preparing polymer-based high thermal conductive material according to claim 1, wherein the resin in step (2) is one of epoxy resin, urethane acrylate, phenolic resin, urea resin and silicone resin; the curing agent in the step (2) is more than one of aliphatic amine, alicyclic amine, aromatic amine, acid anhydride, polyamide and resin curing agent.
4. The process for preparing a polymer-based high thermal conductive material according to claim 1, wherein the mixed solution in the step (2) comprises the following components in parts by volume:
20-90 parts of resin;
10-80 parts of a curing agent.
5. The process for preparing a polymer-based high thermal conductive material according to claim 1, wherein the curing treatment in the step (3) is performed for 12 hours under an environment of a vacuum degree of-0.1 MPa.
6. A polymer-based high thermal conductive material produced by the production process according to any one of claims 1 to 5.
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