CN112812341B - High-thermal-conductivity composite particle/polyimide film with four-needle-shaped structure and preparation method thereof - Google Patents
High-thermal-conductivity composite particle/polyimide film with four-needle-shaped structure and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-thermal-conductivity composite particle/polyimide film with a four-needle structure, which comprises 1-60 parts by mass of a thermal conductive filler, 0.1-5 parts by mass of a surface treating agent and 50-600 parts by mass of a polyamic acid solution; the heat-conducting filler is prepared by coating boron nitride on the surface of zinc oxide, coating graphene on the outer layer, and welding and assembling the boron nitride dispersed on the surface of the zinc oxide to obtain composite particles with stable structures; the film is prepared by adding boron nitride into an organic solvent of diamine and dicarboxylic anhydride, uniformly mixing, carrying out in-situ polymerization reaction to prepare a mixed solution of polyamide acid and boron nitride, adding composite particles into the polyamide acid solution of boron nitride, carrying out vacuum defoaming, laying the mixture into a film, and carrying out programmed heating and thermal imidization to obtain the polyimide film with high thermal conductivity in the plane and outside the plane. The film has the characteristics of high heat conduction and electric insulation, simple preparation process and short forming period, and has wide application prospect in the field of electronic materials such as heat management materials, thermal interface materials and the like.
Description
Technical Field
The invention belongs to the technical field of polyimide films, and particularly relates to a high-thermal-conductivity composite particle/polyimide film with a four-needle structure and a preparation method thereof.
Background
In recent years, with the progress of integration, miniaturization, thinning and multi-functionalization of the electronic information industry, there is an urgent need to solve the problem of heat dissipation of electronic devices and equipment, and therefore, the development of a polymer composite material having high thermal conductivity has become a major issue.
The Polyimide (PI) has good heat resistance, oxidation resistance and mechanical property due to the stable heterocyclic structure contained in the molecular chain, is a good high-temperature-resistant insulating material, and is widely applied to the field of materials such as electronics, aerospace and the like. However, the self thermal conductivity of polyimide is low, and is between 0.1 and 0.2W/m.K, which makes it difficult to meet the heat dissipation requirement of electronic devices, so that the thermal conductivity of polyimide is further improved.
The main method for improving the heat conductivity of the polymer composite material is to introduce high-heat-conductivity filler into a polymer matrix, but other problems are brought at the same time, firstly, the filler in the polymer matrix needs higher filling amount to reach the percolation value, and an effective heat-conducting path is formed; secondly, the inorganic filler is easy to agglomerate in the polymer matrix, so that the mechanical property and the like of the inorganic filler are reduced; third, the poor compatibility of the inorganic filler with the polymer matrix increases its interfacial thermal resistance. In patent CN110452418A, boron nitride is used for coating alumina to synergistically enhance the heat conductivity of a polyimide film, the surface of the alumina is coated with boron nitride to improve the compatibility of a filler and a matrix, the alumina and the boron nitride in the matrix form an isolation structure, and then a filler network is built to improve the heat conductivity of the filler network, but the improvement of the heat conductivity of the research in the vertical direction of the film is limited. Therefore, in the aspect of polyimide heat-conducting films, the problem of simultaneously improving the in-plane and out-of-plane heat conductivity of the films is still a difficult point to be solved.
According to the invention, boron nitride and zinc oxide are subjected to surface treatment agent modification and calcination treatment, the boron nitride is adsorbed on the surface of the zinc oxide after electrostatic self-assembly to form a first layer of shell structure, graphene oxide is continuously adsorbed on the outer layer, and the boron nitride dispersed on the surface of the zinc oxide is welded by the graphene to form the composite particles with the tetrapod-like structure. The interface compatibility of the filler and a matrix can be effectively improved, the filler and boron nitride in the matrix are compounded, the boron nitride is self-oriented to form a layered structure, and then a multi-dimensional lapping network is formed with the zinc oxide four-needle-shaped composite particles, so that a high-efficiency heat conduction passage is constructed, the in-plane and out-of-plane heat conductivity of the polyimide composite film is improved, and the high-heat-conductivity polyimide composite film is prepared.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a high-thermal-conductivity composite particle/polyimide film with a four-needle structure and a preparation method thereof.
The technical scheme for realizing the purpose of the invention is as follows:
a high-thermal-conductivity composite particle/polyimide composite film with a four-needle structure is prepared from the following raw materials in parts by mass, 1-60 parts of thermal-conductive filler, 1-5 parts of surface treating agent and 50-600 parts of polyamide solution; the heat-conducting filler is a tetrapod-shaped heat-conducting filler which is prepared by welding graphene oxide with boron nitride and coating tetrapod-shaped zinc oxide by adopting an electrostatic self-assembly method.
The particle size of the zinc oxide is 5-100 mu m; the boron nitride is hexagonal boron nitride, and the particle size is 100nm-5 mu m; the particle size of the graphene oxide is 500nm-6 mu m.
The surface treating agent is one of HK560 silane coupling agent, polyethyleneimine and polydopamine.
The polyamic acid solution is prepared by dissolving diamine in an organic solvent and then adding dibasic anhydride into the diamine solution; the mass ratio of the dibasic anhydride to the diamine is 1:1-1.05, and the mass concentration of the polyamic acid solution is 15-25%.
The binary anhydride is one of pyromellitic dianhydride (PMDA), 3,3,4,4, biphenyl tetracarboxylic dianhydride, 2,3,3,4, biphenyl tetracarboxylic dianhydride, 3,3,4,4, benzophenone tetracarboxylic dianhydride, 2,3,6,7 and naphthalene tetracarboxylic dianhydride.
The diamine is one of p-phenylenediamine, m-phenylenediamine, diphenyldiamine, 4,4, diaminodiphenyl ether, p-xylylenediamine, 3,4, diaminodiphenyl ether, 4,4, diaminodiphenylmethane, 3,3 and dimethoxybenzidine.
The organic solvent is one of N, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone, dimethylacetamide and dimethyl sulfoxide.
The thickness of the film is 10-500 μm.
A preparation method of a composite particle/polyimide film with a high thermal conductivity and a four-needle structure comprises the following steps:
1) Preparation of surface treatment agent-modified zinc oxide: preparing a dispersion liquid by using absolute ethyl alcohol and deionized water, wherein the mass concentration of the absolute ethyl alcohol is 1-80%, and slowly adding a surface treatment agent into the dispersion liquid, wherein the mass part of the surface treatment agent is 1-10% of the dispersion liquid; stirring for hydrolysis, adding tetrapod-like zinc oxide, wherein the zinc oxide accounts for 5-80% of the dispersion liquid by mass, heating in a water bath, filtering and drying to obtain surface treatment agent modified zinc oxide;
2) Preparing modified boron nitride: weighing hexagonal boron nitride, calcining for 1-4h at 900-1200 ℃, then using deionized water as a dispersion, performing ultrasonic treatment, filtering and drying to obtain modified boron nitride;
3) Preparation of boron nitride coated zinc oxide: mixing modified boron nitride and modified zinc oxide according to the mass ratio of 1:1-10, weighing the modified boron nitride prepared in the step 2), adding deionized water, preparing boron nitride dispersion liquid with the concentration of 1-10mg/ml, adding zinc oxide modified by the surface treating agent prepared in the step 1) after ultrasonic treatment, stirring, filtering and drying to prepare the boron nitride-coated zinc oxide tetrapod-shaped heat-conducting filler;
4) Preparing zinc oxide coated with graphene oxide welding boron nitride: the mass ratio of the graphene oxide to the boron nitride coated zinc oxide composite particles is 0.5-1:10, weighing graphene oxide, adding deionized water, preparing graphene oxide dispersion liquid with the concentration of 1-10mg/ml, adding the graphene oxide dispersion liquid into the graphene oxide dispersion liquid after ultrasonic treatment to prepare boron nitride-coated zinc oxide composite particles, stirring, filtering and drying to prepare the graphene oxide-welded boron nitride-coated zinc oxide tetrapod-shaped heat-conducting filler;
5) Compounding boron nitride in the matrix: after boron nitride is uniformly dispersed in an organic solvent, adding diamine for dissolving, and then adding dibasic anhydride into the solution for in-situ polymerization reaction to prepare a polyamic acid solution containing boron nitride;
6) Adding the graphene oxide welded boron nitride coated zinc oxide tetrapod-like structure heat-conducting filler prepared in the step 4) into the boron nitride polyamic acid solution prepared in the step 5), uniformly stirring, and performing vacuum defoaming treatment;
7) And (3) paving a film by using the defoamed polyamic acid solution, performing thermal imidization treatment on the paved film, and cooling after complete thermal imidization to obtain the high-thermal-conductivity polyimide composite film.
Advantageous effects
The invention provides a high-thermal-conductivity composite particle/polyimide composite film with a four-needle structure and a preparation method thereof, wherein the preparation principle of the film is as follows: the zinc oxide is modified by a surface treating agent, the surface of the zinc oxide is subjected to positive charge through hydrolysis, then boron nitride is calcined at high temperature and subjected to ultrasonic treatment, more active points are exposed, and tube energy groups such as hydroxyl groups are introduced, so that the surface of the zinc oxide is subjected to negative charge. The method comprises the steps of coating boron nitride on the surface of zinc oxide through electrostatic self-assembly to form a first-layer shell structure, further continuing to adsorb graphene oxide electrostatically, welding the boron nitride dispersed on the surface of the zinc oxide by utilizing the graphene oxide, and forming a compact and stable high-heat-conductivity filler shell layer on the surface of the zinc oxide. The zinc oxide has a four-needle structure with a high length-diameter ratio and a multi-dimensional shape, is lapped into a three-dimensional heat conduction network in a polymer matrix, and realizes effective contact between the filler and the polymer matrix/the filler through boron nitride and graphene on the surface of the zinc oxide, so that the interface compatibility of the zinc oxide is improved, and the interface thermal resistance is reduced.
The composite film has the following advantages:
1. by hybridizing fillers with different sizes and shapes, a three-dimensional heat conduction path is easily formed in the composite film, and the high-heat-conductivity composite material is prepared under the condition of low filler content;
2. the boron nitride/graphene oxide coated zinc oxide is used for improving the dispersibility among the fillers and the compatibility between the fillers and a polymer matrix, effectively reducing the interface thermal resistance of the fillers, improving the mechanical property of the fillers and efficiently playing the inherent properties of the heat-conducting fillers;
3. the in-plane self-orientation trend of two-dimensional boron nitride in the imidization process in the matrix is utilized to form a boron nitride layered structure, and then the four-needle structure of zinc oxide is lapped with layered boron nitride to form a multi-dimensional heat conduction network in the vertical direction and the in-plane direction, so that the in-plane and out-of-plane heat conductivity of the polyimide film is effectively improved.
4. The method comprises the steps of coating boron nitride on the surface of zinc oxide through electrostatic self-assembly to form a first-layer shell structure, further continuing to adsorb graphene oxide through static electricity, welding the boron nitride dispersed on the surface of the zinc oxide through the graphene oxide, and forming a compact and stable high-heat-conductivity filler shell layer on the surface of the zinc oxide, so that composite particles with stable structures and better heat conductivity are prepared.
5. The main body of the heat-conducting filler mainly comprises zinc oxide and boron nitride, so that the cost is low, and a small amount of graphene oxide is added to form the high-heat-conducting and low-interface-thermal-resistance composite particles with a double-layer shell structure, so that the film material has the characteristic of optimized cost performance.
Drawings
FIG. 1 is a diagram of a heat conduction network mechanism of a polyimide film internal graphene oxide welded boron nitride-coated tetrapod-like zinc oxide composite particle and layered boron nitride;
fig. 1 shows that a multi-dimensional heat conducting network is formed by utilizing the effective lap joint between the four-needle structure of the composite particles and the layered boron nitride.
Detailed Description
The invention will be further elucidated with reference to the drawings and examples, without however being limited thereto.
Example 1
A preparation method of a composite particle/polyimide film with a high-thermal-conductivity four-needle-shaped structure comprises the following steps:
(1) Preparing surface treatment modified zinc oxide: preparing a dispersion liquid by using absolute ethyl alcohol and deionized water, wherein the mass concentration of the absolute ethyl alcohol is 80%, and slowly adding an HK560 silane coupling agent into the dispersion liquid, wherein the mass part of the HK560 silane coupling agent is 1% of the dispersion liquid; stirring for hydrolysis, adding zinc oxide, wherein the mass part of the zinc oxide is 80% of that of the dispersion liquid, heating in a water bath, filtering and drying to obtain silane coupling agent modified zinc oxide;
(2) Preparing modified boron nitride: weighing boron nitride, calcining for 6 hours at 900 ℃, then using deionized water as dispersion liquid, carrying out ultrasonic treatment for 4 hours, filtering and drying to obtain modified boron nitride;
(3) Preparing boron nitride coated zinc oxide: the mass ratio of the modified boron nitride to the modified zinc oxide is 1:1, weighing the modified boron nitride prepared in the step (2), adding deionized water, preparing boron nitride dispersion liquid with the concentration of 1mg/ml, adding KH560 modified zinc oxide prepared in the step (1) after ultrasonic treatment, stirring, filtering and drying to prepare the boron nitride coated zinc oxide heat-conducting filler with the tetrapod-like structure.
(4) Preparing zinc oxide coated with graphene oxide welding boron nitride: the mass ratio of the graphene oxide to the boron nitride coated zinc oxide composite particles is 0.5:10, weighing graphene oxide, adding deionized water, preparing graphene oxide dispersion liquid with the concentration of 1mg/ml, adding the graphene oxide dispersion liquid into the graphene oxide dispersion liquid after ultrasonic treatment, and performing stirring, filtering and drying to obtain the boron nitride-coated graphene oxide welded graphene oxide-zinc tetrapod-shaped heat-conducting filler;
(5) 7.2g of boron nitride was added to 80g of DMAC organic solvent and sonicated for 3 hours, followed by 8.615gODA. And (3) mechanically stirring to uniformly disperse the filler to prepare a reaction solvent containing boron nitride:
(6) 9.385g PMDA divided into 50%, 20%, 8% was added four times to the reaction solvent prepared in step 5 to perform in situ polymerization reaction, each time at an interval of 05h: the viscosity of the system is adjusted by the rest 2 percent of PDMA to reach 50000 MPa.s, and the polyamic acid solution containing boron nitride is prepared;
(7) Adding 3.6g of graphene oxide welded boron nitride coated zinc oxide heat-conducting filler into the polyamide acid solution containing boron nitride prepared in the step (5), mechanically stirring for about 3 hours, and placing the polyamide acid solution into a vacuum oven for defoaming treatment under-1 Mpa;
(8) And (2) paving a film by using the defoamed polyamic acid solution, putting the paved film into a high-temperature oven for thermal imidization, setting the heating rate of the oven to be 2 ℃/min, keeping the temperature of the oven for 20min from room temperature after the temperature of the oven rises to 40 ℃ until the temperature reaches 350 ℃, and cooling to obtain the high-thermal-conductivity polyimide film after complete thermal imidization.
The prepared polyimide film is tested for heat conductivity by a laser flash method, and the in-plane thermal conductivity of the film is 3.56W (m.K) -1 The out-of-plane thermal conductivity coefficient is 1.23W (m.K) -1 。
Example 2
A preparation method of a composite particle/polyimide film with a high thermal conductivity and a four-needle structure comprises the following steps:
(1) Preparing surface treatment modified zinc oxide: preparing a dispersion liquid by using absolute ethyl alcohol and deionized water, wherein the mass concentration of the absolute ethyl alcohol is 1%, and slowly adding polyethyleneimine into the dispersion liquid, wherein the mass part of the silane coupling agent is 5% of the dispersion liquid; stirring for dissolving, adding zinc oxide, wherein the mass part of the zinc oxide is 50% of the dispersion liquid, heating and stirring in a water bath at 60 ℃ for 2h, filtering and drying to obtain polyethyleneimine modified zinc oxide;
(2) Preparing modified boron nitride: weighing boron nitride, calcining for 1h at 1200 ℃, then using deionized water as dispersion liquid, carrying out ultrasonic treatment for 1h, filtering and drying to obtain modified boron nitride;
(3) Preparing boron nitride coated zinc oxide: the mass ratio of the modified boron nitride to the modified zinc oxide is 1:1, weighing the modified boron nitride prepared in the step (2), adding deionized water, preparing boron nitride dispersion liquid with the concentration of 10mg/ml, adding polyethyleneimine modified zinc oxide prepared in the step (1) after ultrasonic treatment, stirring, filtering and drying to prepare the boron nitride coated zinc oxide heat-conducting filler with the tetrapod-like structure.
(4) Preparing zinc oxide coated with graphene oxide welding boron nitride: the mass ratio of the graphene oxide to the boron nitride coated zinc oxide composite particles is 1:10, weighing graphene oxide, adding deionized water, preparing a graphene oxide dispersion liquid with the concentration of 10mg/ml, adding the graphene oxide dispersion liquid into the graphene oxide dispersion liquid after ultrasonic treatment, and performing stirring, filtering and drying to obtain the boron nitride-coated graphene oxide welded graphene oxide-boron nitride-coated zinc oxide-based tetrapod-shaped heat-conducting filler;
(5) 7.2g of boron nitride was added to 80g of DMAC organic solvent and sonicated for 3 hours, followed by 8.615gODA. And (3) mechanically stirring to uniformly disperse the filler to prepare a reaction solvent containing boron nitride:
(6) 9.385g PMDA divided into 50%, 20%, 8% was added four times to the reaction solvent prepared in step 1 to perform in situ polymerization reaction, each time at an interval of 05h: the viscosity of the system is adjusted by the residual 2 percent of PDMA to reach 50000 MPa.s, and the polyamic acid solution containing boron nitride is prepared;
(7) Adding 3.6g of graphene oxide welded boron nitride coated zinc oxide heat-conducting filler into the polyamide acid solution containing boron nitride prepared in the step (1), mechanically stirring for about 3 hours, and placing the polyamide acid solution into a vacuum oven for defoaming treatment under-1 Mpa;
(8) And (2) paving a film by using the defoamed polyamic acid solution, putting the paved film into a high-temperature oven for thermal imidization, setting the heating rate of the oven to be 2 ℃/min, keeping the temperature of the oven for 20min from room temperature after the temperature of the oven rises to 40 ℃ until the temperature reaches 350 ℃, and cooling to obtain the high-thermal-conductivity polyimide film after complete thermal imidization.
The prepared polyimide film is tested for heat conductivity by a laser flash method, and the in-plane heat conductivity coefficient of the film is 3.81W (m.K) -1 The out-of-plane thermal conductivity coefficient is 1.46W (m.K) -1 。
Example 3
A preparation method of a composite particle/polyimide film with a high-thermal-conductivity four-needle-shaped structure comprises the following steps:
(1) Preparing surface treatment modified zinc oxide: preparing a dispersion solution by using absolute ethyl alcohol and deionized water, wherein the mass concentration of the absolute ethyl alcohol is 1%, and slowly adding a dopamine monomer into the dispersion solution, wherein the mass part of dopamine is 10% of the dispersion solution; stirring for dissolving, adding zinc oxide, wherein the mass part of the zinc oxide is 50% of the dispersion liquid, regulating the pH to 8.5 by using a Tris solution, heating in a water bath at 60 ℃, stirring for 12 hours, filtering and drying to obtain polydopamine modified zinc oxide;
(2) Preparation of modified boron nitride: weighing boron nitride, calcining for 4 hours at the temperature of 1000 ℃, then using deionized water as a dispersion liquid, carrying out ultrasonic treatment for 2 hours, filtering and drying to obtain modified boron nitride;
(3) Preparing boron nitride coated zinc oxide: the mass ratio of the modified boron nitride to the modified zinc oxide is 1: and 5, weighing the modified boron nitride prepared in the step (2), adding deionized water, preparing a boron nitride dispersion liquid with the concentration of 5mg/ml, adding polydopamine-modified zinc oxide prepared in the step (1) after ultrasonic treatment, stirring, filtering and drying to prepare the boron nitride-coated zinc oxide heat-conducting filler with the tetrapod-like structure.
(4) Preparing zinc oxide coated with graphene oxide welding boron nitride: the mass ratio of the graphene oxide to the boron nitride coated zinc oxide composite particles is 1:10, weighing graphene oxide, adding deionized water, preparing graphene oxide dispersion liquid with the concentration of 2mg/ml, adding graphene oxide dispersion liquid into the graphene oxide dispersion liquid after ultrasonic treatment, and adding the graphene oxide coated with boron nitride obtained in the step 3), stirring, filtering and drying the graphene oxide dispersion liquid to obtain the tetrapod-structure heat-conducting filler of which the graphene oxide is welded with the boron nitride coated zinc oxide;
(5) 7.2g of boron nitride was added to 80g of DMAC organic solvent and sonicated for 3 hours, followed by 8.615gODA. And (3) mechanically stirring to uniformly disperse the filler to prepare a reaction solvent containing boron nitride:
(6) 9.385g PMDA divided into 50%, 20%, 8% was added four times to the reaction solvent prepared in step 1 to perform in situ polymerization reaction, each time at an interval of 05h: the viscosity of the system is adjusted by the residual 2 percent of PDMA to reach 50000 MPa.s, and the polyamic acid solution containing boron nitride is prepared;
(7) Adding 3.6g of heat-conducting filler of graphene oxide welded boron nitride coated zinc oxide into the polyamide acid solution containing boron nitride prepared in the step (1), mechanically stirring for about 3 hours, placing the mixture into a vacuum oven, and defoaming under-1 Mpa;
(8) And (2) paving a film by using the defoamed polyamic acid solution, putting the paved film into a high-temperature oven for thermal imidization, setting the heating rate of the oven to be 2 ℃/min, keeping the temperature of the oven for 20min from room temperature after the temperature of the oven rises to 40 ℃ until the temperature reaches 350 ℃, and cooling to obtain the high-thermal-conductivity polyimide film after complete thermal imidization.
The prepared polyimide film is subjected to heat conduction performance test by a laser flash method, and the in-plane heat conduction coefficient of the film is 4.13W (m.K) -1 The out-of-plane thermal conductivity coefficient is 1.67W (m.K) -1 。
Claims (8)
1. The high-thermal-conductivity composite particle/polyimide film with the four-needle structure is characterized by being prepared from the following raw materials in parts by mass, 1-60 parts by mass of thermal-conductive filler, 1-5 parts by mass of surface treating agent and 50-600 parts by mass of polyamic acid solution; the heat-conducting filler is graphene welded boron nitride coated tetrapod-like zinc oxide composite particles prepared by adopting an electrostatic self-assembly method;
the preparation method of the composite particle/polyimide film with the high thermal conductivity and the four-needle-shaped structure comprises the following steps:
1) Preparation of surface treatment agent-modified zinc oxide: preparing a dispersion liquid by using absolute ethyl alcohol and deionized water, wherein the mass concentration of the absolute ethyl alcohol is 1-80%, and slowly adding a surface treatment agent into the dispersion liquid, wherein the mass part of the surface treatment agent is 1-10% of the dispersion liquid; stirring for dissolving, adding tetrapod-like zinc oxide, wherein the mass part of the zinc oxide is 5-80% of the dispersion liquid, heating in a water bath, stirring, filtering and drying to obtain surface treatment agent modified zinc oxide;
2) Preparing modified boron nitride: weighing hexagonal boron nitride, calcining for 1-4h at 900-1200 ℃, using deionized water as a dispersion, performing ultrasonic treatment, filtering and drying to obtain modified boron nitride;
3) Preparation of boron nitride coated zinc oxide: mixing modified boron nitride and modified zinc oxide according to a mass ratio of 1:1-10, weighing the modified boron nitride prepared in the step 2), adding deionized water, preparing boron nitride dispersion liquid with the concentration of 1-10mg/ml, adding zinc oxide modified by the surface treating agent prepared in the step 1) after ultrasonic treatment, stirring, filtering and drying to prepare the boron nitride-coated zinc oxide tetrapod-shaped heat-conducting filler;
4) Preparing zinc oxide coated with graphene oxide welding boron nitride: the mass ratio of the graphene oxide to the boron nitride coated zinc oxide composite particles is (0.5-1): 10, weighing graphene oxide, adding deionized water, preparing graphene oxide dispersion liquid with the concentration of 1-10mg/ml, adding zinc oxide composite particles coated with boron nitride obtained in the step 3) after ultrasonic treatment, stirring, filtering and drying to obtain the tetrapod-shaped heat-conducting filler of which the graphene oxide is welded with the zinc oxide coated with the boron nitride;
5) Compounding boron nitride in the matrix: after boron nitride is uniformly dispersed in an organic solvent, adding diamine for dissolving, and then adding dibasic anhydride into the solution for in-situ polymerization reaction to prepare a polyamic acid solution containing boron nitride;
6) Adding the graphene oxide welded boron nitride coated zinc oxide tetrapod-like structure heat-conducting filler prepared in the step 4) into the boron nitride polyamic acid solution prepared in the step 5), uniformly stirring, and performing vacuum defoaming treatment;
7) And (3) paving a film by using the defoamed polyamic acid solution, performing thermal imidization treatment on the paved film, and cooling after complete thermal imidization to obtain the high-thermal-conductivity polyimide film.
2. The high thermal conductivity tetrapod-like structure composite microparticle/polyimide film as claimed in claim 1, wherein the particle size of said zinc oxide is 5-100 μm; the boron nitride is hexagonal boron nitride, and the particle size is 100nm-5 mu m; the particle size of the graphene oxide is 500nm-6 mu m.
3. The composite particle/polyimide film with a high thermal conductivity and a four-needle structure as claimed in claim 1, wherein the surface treatment agent is one of HK560 silane coupling agent, polyethyleneimine and polydopamine.
4. The high-thermal-conductivity composite particle/polyimide film with the tetrapod-like structure as claimed in claim 1, wherein the polyamic acid solution is prepared by dissolving diamine in an organic solvent and then adding dicarboxylic anhydride into the diamine solution; the mass ratio of the dibasic anhydride to the diamine is 1:1-1.05, and the mass concentration of the polyamic acid solution is 15-25%.
5. The high thermal conductivity tetrapod-structured composite particle/polyimide film according to claim 4, wherein the dicarboxylic anhydride is one of pyromellitic dianhydride, 3,3,4,4, biphenyl tetracarboxylic dianhydride, 2,3,3,4, biphenyl tetracarboxylic dianhydride, 3,3,4,4, benzophenone tetracarboxylic dianhydride, 2,3,6,7, and naphthalene tetracarboxylic dianhydride.
6. The composite particle/polyimide film with a high thermal conductivity and a four-needle structure as claimed in claim 4, wherein the diamine is one of p-phenylenediamine, m-phenylenediamine, biphenyldiamine, 4,4, -diaminodiphenyl ether, p-xylylenediamine, 3,4, -diaminodiphenyl ether, 4,4, -diaminodiphenylmethane, 3,3, -dimethoxybenzidine.
7. The composite particle/polyimide film with a high thermal conductivity and a four-needle structure according to claim 4, wherein the organic solvent is one of N, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone, dimethylacetamide and dimethylsulfoxide.
8. The high thermal conductivity tetrapod-like structured composite microparticle/polyimide film as claimed in claim 1, wherein the thickness of the film is 10 to 500 μm.
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