CN115505255A - Boron nitride polymer composite material and preparation method and application thereof - Google Patents

Boron nitride polymer composite material and preparation method and application thereof Download PDF

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CN115505255A
CN115505255A CN202211160582.0A CN202211160582A CN115505255A CN 115505255 A CN115505255 A CN 115505255A CN 202211160582 A CN202211160582 A CN 202211160582A CN 115505255 A CN115505255 A CN 115505255A
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boron nitride
composite material
polyurethane
nitride polymer
polymer composite
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柏浩
赵妮芳
高微微
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Shanxi Zhejiang University Institute Of New Materials And Chemical Industry
Zhejiang University ZJU
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Zhejiang University ZJU
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Abstract

The invention belongs to the technical field of thermal interface material preparation, and discloses a boron nitride polymer composite material, a preparation method and application thereof, wherein the boron nitride polymer composite material comprises the following steps: adding boron nitride nanosheets and a polymer into water, and performing ultrasonic dispersion to obtain a boron nitride polymer dispersion liquid; step (2), directionally freezing the boron nitride polymer dispersion liquid on the surface polished by sand paper to obtain a frozen block material; step (3), freeze-drying the frozen block material to remove ice crystals to obtain the boron nitride polymer porous material with a lamellar structure and a bridging structure; and (4) carrying out hot pressing on the boron nitride polymer porous material to obtain the boron nitride polymer composite material with a lamellar structure and a bridging structure. The method has the advantages of simple operation, low cost and easy large-scale production, and the obtained boron nitride polymer composite material has excellent in-plane and out-of-plane heat-conducting properties.

Description

Boron nitride polymer composite material and preparation method and application thereof
Technical Field
The application relates to the technical field of thermal interface material preparation, in particular to a boron nitride polymer composite material and a preparation method and application thereof.
Background
The high integration of high-power and high-frequency electronic devices can cause serious heat concentration problem, and serious threat is generated to the working stability and the safety and reliability of equipment. How to effectively and timely conduct out heat generated in the operation process of electronic devices has become a key technical problem limiting the development of the electronic packaging field.
To address the issue of heat dissipation, thermal interface materials are commonly used in electronic packages to reduce the contact resistance between the heat dissipating device and the heat generating device. An ideal thermal interface material needs to have an isotropic high thermal conductivity to ensure that heat can be efficiently transferred from the heat source to the heat sink in the out-of-plane direction and that localized heat can be quickly spread in-plane. The polymer material has the advantages of low density, electric insulation, good flexibility, easy processing and the like, and has wide application in the field of heat dissipation of electronic devices. However, pure polymers generally have low thermal conductivity and are far from meeting the current increasing heat dissipation requirements.
The polymer composite material is prepared by compounding the polymer and the high-thermal-conductivity filler, so that the thermal conductivity of the polymer can be effectively improved. Among them, the boron nitride nanosheet has many excellent properties such as high thermal conductivity, electrical insulation, good thermal stability and the like, and is one of ideal fillers for preparing high thermal conductivity polymer composite materials. The currently reported methods for preparing boron nitride polymer composite materials mainly comprise a vacuum filtration method, an electrostatic spinning method, a 3D printing method, a directional freezing method, a chemical vapor deposition method and the like. These methods cannot form an efficient three-dimensional heat conduction path, and cannot effectively improve the in-plane and out-of-plane heat conductivities at the same time, so that the requirements of high-efficiency heat dissipation of electronic devices cannot be met.
Disclosure of Invention
The embodiment of the application aims to provide a boron nitride polymer composite material, and a preparation method and application thereof, so as to solve the technical problem that the in-plane and out-of-plane thermal conductivity cannot be effectively improved simultaneously in the related technology, and the requirement on high-efficiency heat dissipation of an electronic device cannot be met.
According to a first aspect of embodiments herein, there is provided a method of preparing a boron nitride polymer composite material, comprising the steps of:
adding boron nitride nanosheets and a polymer into water, and performing ultrasonic dispersion to obtain a boron nitride polymer dispersion liquid;
step (2), directionally freezing the boron nitride polymer dispersion liquid on the surface polished by sand paper to obtain a frozen block material;
step (3), freeze-drying the frozen block material to remove ice crystals to obtain the boron nitride polymer porous material with a lamellar structure and a bridging structure;
and (4) carrying out hot pressing on the boron nitride polymer porous material to obtain the boron nitride polymer composite material with a lamellar structure and a bridging structure.
Preferably, the volume fraction of the boron nitride nanosheets in the dispersion is 2.5-10%, and the volume fraction of the polymer is 0.5-15%.
Preferably, the size of the boron nitride nanosheet is 3um to 5um.
Preferably, the polymer is selected from the group consisting of aqueous polyurethane, polyvinyl alcohol, nanocellulose.
Preferably, the freezing temperature of the directional freezing is-90 to-30 ℃.
Preferably, the freeze-drying time is 12 to 48 hours.
Preferably, the hot pressing temperature is 50-100 ℃, the pressure is 10-100 MPa, and the time is 5-30 min.
According to a second aspect of embodiments of the present application, there is provided a boron nitride polymer composite material prepared by the preparation method of the first aspect.
According to a third aspect of embodiments herein, there is provided a thermal interface material comprising the boron nitride polymer composite of the first aspect.
According to a fourth aspect of the embodiments of the present application, there is provided an electronic device, comprising a heat dissipating device and a heat generating device, wherein the thermal interface material of the first aspect is disposed between the heat dissipating device and the heat generating device.
The technical scheme provided by the embodiment of the application can have the following beneficial effects:
from the above embodiment, when the boron nitride polymer dispersion liquid is directionally frozen on the surface of the stainless steel sheet with the groove structure, under the combined influence of the vertical and horizontal temperature gradients, ice crystals grow along the direction perpendicular to the groove structure, and most of the boron nitride nanosheets and the polymer are squeezed by the growing ice crystals between two adjacent ice crystals to form a long-range oriented lamellar structure. Meanwhile, when the boron nitride polymer dispersion liquid reaches a certain concentration, due to the instability of ice crystal growth, a part of the boron nitride nanosheets and the polymer are captured by the growing ice crystals, so that a bridging structure is formed between the lamellae. After the freezing is completed, removing the ice crystals by freeze drying to obtain the boron nitride polymer porous material with a lamellar structure and a bridging structure. And obtaining the boron nitride polymer composite material with a lamellar structure and a bridging structure through simple hot pressing treatment.
As the boron nitride nanosheets with different sizes are different in difficulty degree of being captured by ice crystals, more boron nitride nanosheets can be captured by adjusting the sizes of the boron nitride nanosheets, so that the out-of-plane thermal conductivity is further improved.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the application.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the present application and together with the description, serve to explain the principles of the application.
FIG. 1 is an optical diagram of a directional freezer shown in accordance with one exemplary embodiment.
Fig. 2 is an optical diagram of a boron nitride polyurethane cellular material according to an exemplary embodiment 1.
Fig. 3 is an electron microscope image of a boron nitride polyurethane porous material according to an exemplary embodiment 1.
FIG. 4 is an optical diagram of a boron nitride polyurethane composite material according to an exemplary embodiment 1.
Fig. 5 is an electron microscope image of a boron nitride polyurethane composite material according to an exemplary embodiment 1.
Fig. 6 is an electron microscope image of a boron nitride polyurethane porous material according to an exemplary embodiment 2.
Fig. 7 is an electron microscope image of a boron nitride polyurethane porous material according to an exemplary embodiment 3.
Fig. 8 is an electron microscope image of a boron nitride polyurethane porous material shown according to an exemplary embodiment 4.
Fig. 9 is an electron micrograph of a boron nitride polyvinyl alcohol porous material shown according to an exemplary embodiment 5.
Fig. 10 is an electron micrograph of a boron nitride nanocellulose porous material shown in accordance with an exemplary embodiment 6.
Fig. 11 is an electron microscope image of a boron nitride polyurethane porous material shown in accordance with an exemplary embodiment 7.
Fig. 12 is an electron micrograph of a boron nitride polyurethane porous material shown according to an exemplary comparative example.
Detailed Description
Reference will now be made in detail to the exemplary embodiments, examples of which are illustrated in the accompanying drawings. The following description refers to the accompanying drawings in which the same numbers in different drawings represent the same or similar elements unless otherwise indicated. The embodiments described in the following exemplary embodiments do not represent all embodiments consistent with the present application.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in this application and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It should also be understood that the term "and/or" as used herein refers to and encompasses any and all possible combinations of one or more of the associated listed items.
The embodiment of the invention provides a preparation method of a boron nitride polymer composite material, which comprises the following steps:
adding boron nitride nanosheets and a polymer into water, and performing ultrasonic dispersion to obtain a boron nitride polymer dispersion liquid;
step (2), directionally freezing the boron nitride polymer dispersion liquid on the surface polished by sand paper to obtain a frozen block material;
step (3), freeze-drying the frozen block material to remove ice crystals to obtain the boron nitride polymer porous material with a lamellar structure and a bridging structure;
and (4) carrying out hot pressing on the boron nitride polymer porous material to obtain the boron nitride polymer composite material with a lamellar structure and a bridging structure.
In the technical scheme, when the boron nitride polymer dispersion liquid is directionally frozen on the surface of the stainless steel sheet with the groove structure, under the common influence of vertical and horizontal temperature gradients, ice crystals grow along the direction vertical to the groove structure, and most of boron nitride nanosheets and polymers are extruded between two adjacent ice crystals by the growing ice crystals to form a long-range oriented lamellar structure. Meanwhile, when the boron nitride polymer dispersion liquid reaches a certain concentration, due to the instability of ice crystal growth, a part of the boron nitride nanosheets and the polymer are captured by the growing ice crystals, so that a bridging structure is formed between the lamella layers. After the freezing is completed, removing the ice crystals by freeze drying to obtain the boron nitride polymer porous material with a lamellar structure and a bridging structure. And obtaining the boron nitride polymer composite material with a lamellar structure and a bridging structure through simple hot pressing treatment.
As the boron nitride nanosheets with different sizes are different in difficulty degree of being captured by ice crystals, more boron nitride nanosheets can be captured by adjusting the sizes of the boron nitride nanosheets, so that the out-of-plane thermal conductivity is further improved.
An optical diagram of a directional freezing device used in the example is shown in fig. 1, wherein 1 is a stainless steel sheet surface with a groove structure obtained by unidirectional sanding with sand paper, the mesh number of the sand paper is controlled to be 280-1500 meshes, 2 is a polymethyl methacrylate mold, the bottom of the stainless steel sheet surface 1 is directly contacted with a cold source, and the freezing temperature is controlled to be-90-30 ℃.
Example 1
(1) Adding 17.0g of boron nitride nanosheet (5 um) and 5.7g of 35% by mass of an aqueous polyurethane solution into 77.3g of water, and ultrasonically dispersing for 5 hours to obtain a uniformly dispersed boron nitride polyurethane dispersion liquid, wherein the volume fraction of the boron nitride nanosheet is 7.5% and the volume fraction of the polyurethane is 1.8%.
(2) Pouring the boron nitride polyurethane dispersion liquid obtained in the step (1) into a mold of a directional freezing device for directional freezing to obtain a frozen block material, wherein the freezing temperature is-60 ℃.
(3) And (3) freeze-drying the frozen block material obtained in the step (2) in a freeze-drying machine for 48h to remove ice crystals, so as to obtain the boron nitride polyurethane porous material with a lamellar structure and a bridging structure, wherein the optical photograph is shown in fig. 2, and the SEM photograph is shown in fig. 3.
(4) And (4) placing the boron nitride polyurethane porous material obtained in the step (3) into a mold, and carrying out hot pressing for 30min at 80 ℃ under the pressure of 100PMa to obtain the compact boron nitride polyurethane composite material. The composite material has a volume fraction of boron nitride of about 80% and a volume fraction of polyurethane of about 20%, and the optical photograph thereof is shown in FIG. 4 and the SEM photograph thereof is shown in FIG. 5.
The in-plane thermal conductivity of the prepared boron nitride polyurethane composite material is 39.0W m -1 K -1 Out-of-plane thermal conductivity of 11.5W m -1 K -1
Example 2
(1) Adding 5.7g of boron nitride nanosheet (5 um) and 1.9g of 35% by mass of aqueous polyurethane solution into 92.4g of water, and ultrasonically dispersing for 5 hours to obtain uniformly dispersed boron nitride polyurethane dispersion liquid, wherein the volume fraction of the boron nitride nanosheet is 2.5%, and the volume fraction of the polyurethane is 0.6%.
(2) Pouring the boron nitride polyurethane dispersion liquid obtained in the step (1) into a mold of a directional freezing device for directional freezing to obtain a frozen block material, wherein the freezing temperature is-60 ℃.
(3) And (3) freeze-drying the frozen block material obtained in the step (2) in a freeze-drying machine for 48h to remove ice crystals, so as to obtain the boron nitride polyurethane porous material with a lamellar structure and a bridging structure, wherein an SEM photograph of the boron nitride polyurethane porous material is shown in FIG. 6.
(4) And (4) placing the boron nitride polyurethane porous material obtained in the step (3) into a mold, and carrying out hot pressing for 30min at 80 ℃ under the pressure of 100PMa to obtain the compact boron nitride polyurethane composite material. The volume fraction of boron nitride in the composite material is about 80%, and the volume fraction of polyurethane is about 20%.
The in-plane thermal conductivity of the prepared boron nitride polyurethane composite material is 43.5W m -1 K -1 Out-of-plane thermal conductivity of 7.0W m -1 K -1
Example 3
(1) Adding 11.4g of boron nitride nanosheet (5 um) and 3.8g of 35% by mass of aqueous polyurethane solution into 84.9g of water, and ultrasonically dispersing for 5 hours to obtain uniformly dispersed boron nitride polyurethane dispersion liquid, wherein the volume fraction of the boron nitride nanosheet is 5% and the volume fraction of the polyurethane is 1.2%.
(2) Pouring the boron nitride polyurethane dispersion liquid obtained in the step (1) into a mold of a directional freezing device for directional freezing to obtain a frozen block material, wherein the freezing temperature is-60 ℃.
(3) And (3) freeze-drying the frozen block material obtained in the step (2) in a freeze-drying machine for 48h to remove ice crystals, so as to obtain the boron nitride polyurethane porous material with a lamellar structure and a bridging structure, wherein an SEM photograph of the boron nitride polyurethane porous material is shown in FIG. 7.
(4) And (4) placing the boron nitride polyurethane porous material obtained in the step (3) into a mold, and carrying out hot pressing for 30min at 80 ℃ under the pressure of 100PMa to obtain the compact boron nitride polyurethane composite material. The volume fraction of boron nitride in the composite material is about 80%, and the volume fraction of polyurethane is about 20%.
The in-plane thermal conductivity of the prepared boron nitride polyurethane composite material is 41.1W m -1 K -1 Out-of-plane thermal conductivity of 8.8W m -1 K -1
Example 4
(1) Adding 22.7g of boron nitride nanosheet (5 um) and 7.5g of 35% by mass of aqueous polyurethane solution into 69.8g of water, and ultrasonically dispersing for 5 hours to obtain uniformly dispersed boron nitride polyurethane dispersion liquid, wherein the volume fraction of the boron nitride nanosheet is 10% and the volume fraction of the polyurethane is 2.4%.
(2) Pouring the boron nitride polyurethane dispersion liquid obtained in the step (1) into a mold of a directional freezing device for directional freezing to obtain a frozen block material, wherein the freezing temperature is-60 ℃.
(3) And (3) freeze-drying the frozen block material obtained in the step (2) in a freeze-drying machine for 48h to remove ice crystals, so as to obtain the boron nitride polyurethane porous material with a lamellar structure and a bridging structure, wherein an SEM photograph of the boron nitride polyurethane porous material is shown in FIG. 8.
(4) And (4) placing the boron nitride polyurethane porous material obtained in the step (3) into a mold, and carrying out hot pressing for 30min at 80 ℃ under the pressure of 100PMa to obtain the compact boron nitride polyurethane composite material. The volume fraction of boron nitride in the composite material is about 80%, and the volume fraction of polyurethane is about 20%.
The in-plane thermal conductivity of the prepared boron nitride polyurethane composite material is 32.8W m -1 K -1 Out-of-plane thermal conductivity of 11.8W m -1 K -1
Example 5
(1) Adding 17.0g of boron nitride nanosheet (5 um) and 2.0g of polyvinyl alcohol powder into 81.0g of water, and ultrasonically dispersing for 5 hours to obtain uniformly dispersed boron nitride polyvinyl alcohol dispersion liquid, wherein the volume fraction of the boron nitride nanosheet is 7.5%, and the volume fraction of the polyvinyl alcohol is 1.8%.
(2) Pouring the boron nitride polyvinyl alcohol dispersion liquid obtained in the step (1) into a mould of an oriented freezing device for oriented freezing to obtain a frozen block material, wherein the freezing temperature is-60 ℃.
(3) And (3) freeze-drying the frozen block material obtained in the step (2) in a freeze-drying machine for 48h to remove ice crystals, so as to obtain the boron nitride polyvinyl alcohol porous material with a lamellar structure and a bridging structure, wherein an SEM picture of the boron nitride polyvinyl alcohol porous material is shown in FIG. 9.
(4) And (4) placing the boron nitride polyvinyl alcohol porous material obtained in the step (3) into a mould, and carrying out hot pressing for 30min at 100 ℃ under the pressure of 100PMa to obtain the compact boron nitride polyvinyl alcohol composite material. The volume fraction of boron nitride in the composite material is about 80%, and the volume fraction of polyvinyl alcohol is about 20%.
The in-plane thermal conductivity of the prepared boron nitride polyvinyl alcohol composite material is 38.0W m -1 K -1 Out-of-plane thermal conductivity of 9.87W m -1 K -1
Example 6
(1) Adding 17.0g of boron nitride nanosheet (5 um) and 39.6g of nanocellulose solution with the mass fraction of 5% into 43.4g of water, and ultrasonically dispersing for 5 hours to obtain uniformly dispersed boron nitride nanocellulose dispersion liquid, wherein the volume fraction of the boron nitride nanosheet is 7.5%, and the volume fraction of the nanocellulose is 1.8%.
(2) Pouring the boron nitride nano cellulose dispersion liquid obtained in the step (1) into a mould of a directional freezing device for directional freezing to obtain a frozen block material, wherein the freezing temperature is-60 ℃.
(3) And (3) freeze-drying the frozen block material obtained in the step (2) in a freeze-drying machine for 48h to remove ice crystals, so as to obtain the boron nitride nanocellulose porous material with a lamellar structure and a bridging structure, wherein the SEM photograph of the boron nitride nanocellulose porous material is shown in FIG. 10.
(4) And (4) placing the boron nitride nano cellulose porous material obtained in the step (3) in a mould, and carrying out hot pressing for 30min at 50 ℃ under the pressure of 100PMa to obtain the compact boron nitride nano cellulose composite material. The volume fraction of boron nitride in the composite material is about 80%, and the volume fraction of nano-cellulose is about 20%.
In-plane thermal conductivity of prepared boron nitride nano-cellulose composite materialIs 38.8W m -1 K -1 Out-of-plane thermal conductivity of 10.0W m -1 K -1
Example 7
(1) Adding 17.0g of boron nitride nanosheet (3 um) and 5.7g of 35% aqueous polyurethane solution into 77.3g of water, and ultrasonically dispersing for 5 hours to obtain uniformly dispersed boron nitride polyurethane dispersion liquid, wherein the volume fraction of the boron nitride nanosheet is 7.5%, and the volume fraction of the polyurethane is 1.8%.
(2) Pouring the boron nitride polyurethane dispersion liquid obtained in the step (1) into a mold of a directional freezing device for directional freezing to obtain a frozen block material, wherein the freezing temperature is-60 ℃.
(3) And (3) freeze-drying the frozen block material obtained in the step (2) in a freeze-drying machine for 48h to remove ice crystals, so as to obtain the boron nitride polyurethane porous material with a lamellar structure and a bridging structure, wherein an SEM photograph of the boron nitride polyurethane porous material is shown in FIG. 11.
(4) And (4) placing the boron nitride polyurethane porous material obtained in the step (3) into a mold, and carrying out hot pressing for 30min at 80 ℃ under the pressure of 100PMa to obtain the compact boron nitride polyurethane composite material. The volume fraction of boron nitride in the composite material is about 80%, and the volume fraction of polyurethane is about 20%.
The in-plane thermal conductivity of the prepared boron nitride polyurethane composite material is 28.3W m -1 K -1 Out-of-plane thermal conductivity of 6.2W m -1 K -1
Example 8
(1) Adding 17.0g of boron nitride nanosheet (5 um) and 5.7g of 35% aqueous polyurethane solution into 77.3g of water, and ultrasonically dispersing for 5 hours to obtain uniformly dispersed boron nitride polyurethane dispersion liquid, wherein the volume fraction of the boron nitride nanosheet is 7.5%, and the volume fraction of the polyurethane is 1.8%.
(2) Pouring the boron nitride polyurethane dispersion liquid obtained in the step (1) into a mold of a directional freezing device for directional freezing to obtain a frozen block material, wherein the freezing temperature is-30 ℃.
(3) And (3) freeze-drying the frozen block material obtained in the step (2) in a freeze-drying machine for 48h to remove ice crystals, so as to obtain the boron nitride polyurethane porous material with a lamellar structure and a bridging structure.
(4) And (4) placing the boron nitride polyurethane porous material obtained in the step (3) into a mold, and carrying out hot pressing for 30min at 80 ℃ under the pressure of 100PMa to obtain the compact boron nitride polyurethane composite material. The volume fraction of boron nitride in the composite material is about 80%, and the volume fraction of polyurethane is about 20%.
Example 9
(1) Adding 17.0g of boron nitride nanosheet (5 um) and 5.7g of 35% aqueous polyurethane solution into 77.3g of water, and ultrasonically dispersing for 5 hours to obtain uniformly dispersed boron nitride polyurethane dispersion liquid, wherein the volume fraction of the boron nitride nanosheet is 7.5%, and the volume fraction of the polyurethane is 1.8%.
(2) Pouring the boron nitride polyurethane dispersion liquid obtained in the step (1) into a mold of a directional freezing device for directional freezing to obtain a frozen block material, wherein the freezing temperature is-90 ℃.
(3) And (3) freeze-drying the frozen block material obtained in the step (2) in a freeze-drying machine for 48h to remove ice crystals, so as to obtain the boron nitride polyurethane porous material with a lamellar structure and a bridging structure.
(4) And (4) placing the boron nitride polyurethane porous material obtained in the step (3) into a mold, and carrying out hot pressing for 30min at 80 ℃ under the pressure of 100PMa to obtain the compact boron nitride polyurethane composite material. The volume fraction of boron nitride in the composite material is about 80%, and the volume fraction of polyurethane is about 20%.
Example 10
(1) Adding 17.0g of boron nitride nanosheet (5 um) and 5.7g of 35% by mass of an aqueous polyurethane solution into 77.3g of water, and ultrasonically dispersing for 5 hours to obtain a uniformly dispersed boron nitride polyurethane dispersion liquid, wherein the volume fraction of the boron nitride nanosheet is 7.5% and the volume fraction of the polyurethane is 1.8%.
(2) Pouring the boron nitride polyurethane dispersion liquid obtained in the step (1) into a mold of a directional freezing device for directional freezing to obtain a frozen block material, wherein the freezing temperature is-60 ℃.
(3) And (3) freeze-drying the frozen block material obtained in the step (2) in a freeze-drying machine for 12h to remove ice crystals, so as to obtain the boron nitride polyurethane porous material with a lamellar structure and a bridging structure.
(4) And (4) placing the boron nitride polyurethane porous material obtained in the step (3) into a mold, and carrying out hot pressing for 30min at 80 ℃ under the pressure of 100PMa to obtain the compact boron nitride polyurethane composite material. The volume fraction of boron nitride in the composite material is about 80%, and the volume fraction of polyurethane is about 20%.
Example 11
(1) Adding 17.0g of boron nitride nanosheet (5 um) and 5.7g of 35% by mass of an aqueous polyurethane solution into 77.3g of water, and ultrasonically dispersing for 5 hours to obtain a uniformly dispersed boron nitride polyurethane dispersion liquid, wherein the volume fraction of the boron nitride nanosheet is 7.5% and the volume fraction of the polyurethane is 1.8%.
(2) Pouring the boron nitride polyurethane dispersion liquid obtained in the step (1) into a mold of a directional freezing device for directional freezing to obtain a frozen block material, wherein the freezing temperature is-60 ℃.
(3) And (3) freeze-drying the frozen block material obtained in the step (2) in a freeze-drying machine for 48h to remove ice crystals, so as to obtain the boron nitride polyurethane porous material with a lamellar structure and a bridging structure.
(4) And (4) placing the boron nitride polyurethane porous material obtained in the step (3) into a mold, and hot-pressing for 5min at 80 ℃ under the pressure of 10PMa to obtain the compact boron nitride polyurethane composite material. The volume fraction of boron nitride in the composite material was about 70%, and the volume fraction of polyurethane was about 17.5%.
Comparative example
(1) Adding 17.0g of boron nitride nanosheet (5 um) and 5.7g of 35% aqueous polyurethane solution into 77.3g of water, and ultrasonically dispersing for 5 hours to obtain uniformly dispersed boron nitride polyurethane dispersion liquid, wherein the volume fraction of the boron nitride nanosheet is 7.5%, and the volume fraction of the polyurethane is 1.8%.
(2) Pouring the boron nitride polyurethane dispersion liquid obtained in the step (1) into a mold of a directional freezing device for directional freezing to obtain a frozen block material, wherein the freezing temperature is-196 ℃.
(3) And (3) freeze-drying the frozen block material obtained in the step (2) in a freeze-drying machine for 48h to remove ice crystals to obtain the boron nitride polyurethane porous material, wherein an SEM picture of the boron nitride polyurethane porous material is shown in figure 12, and the porous material does not have a lamellar structure and a bridging structure.
(4) And (4) placing the boron nitride polyurethane porous material obtained in the step (3) into a mold, and carrying out hot pressing for 30min at 80 ℃ under the pressure of 100PMa to obtain the compact boron nitride polyurethane composite material. The volume fraction of boron nitride in the composite material is about 80%, and the volume fraction of polyurethane is about 20%.
The in-plane thermal conductivity of the prepared boron nitride polyurethane composite material is 32.6W m -1 K -1 Out-of-plane thermal conductivity of 7.8W m -1 K -1
In conclusion, the boron nitride polymer composite material prepared by the embodiment of the invention has the following effects. According to the invention, through the design of the lamellar structure and the bridging structure, the out-of-plane thermal conductivity of the composite material can be remarkably improved while the high in-plane thermal conductivity is kept, the in-plane thermal conductivity of the composite material is 39.0W m-1K-1, and the out-of-plane thermal conductivity of the composite material is 11.5W m-1K-1 which is far higher than a literature value. In addition, the number of the bridging structures can be adjusted by adjusting the size of the boron nitride nanosheets, so that the thermal conductivity of the composite material can be finely adjusted.
Other embodiments of the present application will be apparent to those skilled in the art from consideration of the specification and practice of the disclosure disclosed herein. This application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the application and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the application being indicated by the following claims.
It will be understood that the present application is not limited to the precise arrangements described above and shown in the drawings and that various modifications and changes may be made without departing from the scope thereof. The scope of the application is limited only by the appended claims.

Claims (10)

1. The preparation method of the boron nitride polymer composite material is characterized by comprising the following steps of:
adding boron nitride nanosheets and a polymer into water, and performing ultrasonic dispersion to obtain a boron nitride polymer dispersion liquid;
step (2), directionally freezing the boron nitride polymer dispersion liquid on the surface polished by sand paper to obtain a frozen block material;
step (3), freeze-drying the frozen block material to remove ice crystals to obtain the boron nitride polymer porous material with a lamellar structure and a bridging structure;
and (4) carrying out hot pressing on the boron nitride polymer porous material to obtain the boron nitride polymer composite material with a lamellar structure and a bridging structure.
2. The method for preparing the boron nitride polymer composite material according to claim 1, wherein the volume fraction of the boron nitride nanosheets in the dispersion is 2.5-10%, and the volume fraction of the polymer is 0.5-15%.
3. The method of claim 1, wherein the boron nitride nanosheets are 3um to 5um in size.
4. The method of claim 1, wherein the polymer is selected from the group consisting of aqueous polyurethane, polyvinyl alcohol, and nanocellulose.
5. The method for preparing the boron nitride polymer composite material according to claim 1, wherein the freezing temperature of the directional freezing is-90 to-30 ℃.
6. The method of claim 1, wherein the freeze-drying time is 12-48 h.
7. The method for preparing the boron nitride polymer composite material according to claim 1, wherein the hot pressing temperature is 50-100 ℃, the pressure is 10-100 MPa, and the time is 5-30 min.
8. A boron nitride polymer composite material produced by the production method according to any one of claims 1 to 7.
9. A thermal interface material comprising the boron nitride polymer composite of claim 8.
10. An electronic device comprising a heat dissipating device and a heat generating device, wherein the thermal interface material of claim 9 is disposed between the heat dissipating device and the heat generating device.
CN202211160582.0A 2022-09-22 2022-09-22 Boron nitride polymer composite material and preparation method and application thereof Pending CN115505255A (en)

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