WO2022104949A1 - Thermally conductive composite material and preparation method therefor - Google Patents
Thermally conductive composite material and preparation method therefor Download PDFInfo
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- WO2022104949A1 WO2022104949A1 PCT/CN2020/135164 CN2020135164W WO2022104949A1 WO 2022104949 A1 WO2022104949 A1 WO 2022104949A1 CN 2020135164 W CN2020135164 W CN 2020135164W WO 2022104949 A1 WO2022104949 A1 WO 2022104949A1
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- Prior art keywords
- thermally conductive
- composite material
- polymer matrix
- conductive composite
- boron nitride
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Images
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
Definitions
- the invention belongs to the technical field of thermally conductive materials, and in particular relates to a thermally conductive composite material and a preparation method thereof.
- the printed circuit boards used in the field of microelectronics packaging are mostly made of polyimide, polyester and other materials, which not only have good electrical insulation properties, but also meet the requirements of different application scenarios for the mechanical strength of the substrate; another example is auxiliary chips.
- the matrix is mostly polyolefin or silica gel, and its good flexibility can greatly fill the gaps in the contact surface and reduce air thermal resistance.
- heat exchange and heating engineering the use of polymers such as polyurethane can replace metal materials in environments that are prone to corrosion, high strength and toughness, reducing manufacturing costs and product weight.
- the main method to improve the thermal conductivity of polymers is to fill the polymer matrix with high thermal conductivity fillers, and through the fillers, a thermal conduction path is formed inside the polymer matrix to improve the overall thermal conductivity.
- thermally conductive fillers boron nitride has a graphene-like crystal structure consisting of alternating, covalently bonded six-membered ring layers of boron and nitrogen atoms, which have high thermal conductivity, wide band gap, and good stability. It is widely used in electronic packaging and high-power equipment.
- the thermal conductivity of polymer composites using unmodified boron nitride as thermally conductive fillers still needs to be improved.
- the present invention provides a thermally conductive composite material and a preparation method thereof, so as to solve the problem of poor thermal conductivity of the existing polymer composite material.
- one aspect of the present invention is to provide a thermally conductive composite material, comprising a polymer matrix and a thermally conductive filler filled in the polymer matrix, wherein the thermally conductive filler is an edge grafted with amino functional groups of boron nitride nanosheets.
- the mass percentage of the thermally conductive filler is 10% to 50%.
- the lateral size of the boron nitride nanosheet is 200nm-300nm, and the thickness is 3nm-4nm.
- epoxy resin is further added to the polymer matrix, and the mass percentage of the epoxy resin in the polymer matrix is 25%-30%.
- the polymer matrix is selected from cyanate ester resin, polyethylene, polyvinyl alcohol, polyimide, polymethyl methacrylate, polydimethylsiloxane, polycarbonate, polyurethane and silicone rubber one or more of them.
- Another aspect of the present invention is to provide a method for preparing the thermally conductive composite material as described above, comprising:
- thermally conductive filler dispersion by surface modification, the edges of boron nitride nanosheets are grafted with amino functional groups to obtain thermally conductive fillers; the thermally conductive fillers are dispersed in a dispersant to form a thermally conductive filler dispersion;
- Preparation of the polymer matrix solution polymerizing the corresponding monomers used to form the polymer matrix under the action of heating and a catalyst to obtain the polymer matrix solution;
- thermally conductive filler dispersion liquid added to the polymer matrix solution in a predetermined proportion and stirring and mixing to obtain a mixed slurry
- the mixed slurry is cured into a film to obtain the thermally conductive composite material.
- the preparation of the thermally conductive filler dispersion includes:
- the boron nitride nanosheet powder is washed and dried, and then added to the dispersion liquid for dispersion to obtain the thermally conductive filler dispersion liquid.
- the ball milling aid is sodium chloride or potassium chloride
- the ball milling process is carried out under the protective atmosphere of N or Ar
- the dispersant is deionized water, ethanol, acetone or 1,4-di Oxane.
- the preparation method further includes: adding epoxy resin to the polymer matrix solution to toughen and modify the polymer matrix.
- the polymer matrix is a cyanate resin
- the preparation of the polymer matrix solution includes:
- the cyanate ester monomer and the catalyst are added into the reaction vessel, and the reaction vessel is heated in an oil bath to make the cyanate ester monomer undergo a polymerization reaction to obtain the polymer matrix solution; wherein, the catalyst is dilaurin Dibutyltin acid or di-n-butyltin oxide.
- the step of curing the mixed slurry into a film includes: performing vacuum defoaming treatment on the mixed slurry, pouring the mixed slurry in a mold, then heating and solidifying, and demoulding after cooling to obtain the thermally conductive composite Material.
- the solidifying the mixed slurry to form a film includes: vacuum filtration of the mixed slurry to form a film, heating and solidifying the film-forming material, and cooling to obtain the thermally conductive composite material.
- the thermally conductive filler is a boron nitride nanosheet with an amino group (-NH 2 ) functional group grafted on the edge, thereby increasing the wettability of the boron nitride nanosheet filler, thereby improving the Mixing well with the polymer matrix can effectively improve the thermal conductivity of thermally conductive composites.
- the preparation method of the thermally conductive composite material provided in the embodiment of the present invention has the advantages of simple process flow and easy realization of process conditions, and is favorable for large-scale industrial application.
- Fig. 1 is the process flow diagram of the preparation method of the thermally conductive composite material in the embodiment of the present invention
- Fig. 2 is the test curve diagram of the thermal conductivity of the thermally conductive composite material in the embodiment of the present invention
- FIG. 3 is a test curve diagram of the mechanical properties of the thermally conductive composite material in the embodiment of the present invention.
- Embodiments of the present invention first provide a thermally conductive composite material, comprising a polymer matrix and a thermally conductive filler filled in the polymer matrix, wherein the thermally conductive filler is a boron nitride nanosheet with an amino functional group grafted on the edge.
- the mass percentage of the thermally conductive filler is 10% to 50%.
- the lateral size of the boron nitride nanosheet is 200nm-300nm, and the thickness is 3nm-4nm.
- the thermally conductive fillers in the thermally conductive composites are boron nitride nanosheets with amino ( -NH2 ) functional groups grafted on the edges, thereby increasing the wettability of the boron nitride nanosheet fillers and thus better mixing with the polymer matrix , which can effectively improve the thermal conductivity of thermally conductive composites.
- epoxy resin is further added to the polymer matrix, and the mass percentage of the epoxy resin in the polymer matrix is 25% to 30%.
- the epoxy resin is selected as E51 type epoxy resin, which has the advantages of high epoxy value and low viscosity.
- the polymer matrix is a cyanate resin, and polyethylene, polyvinyl alcohol, polyimide, polymethyl methacrylate, polydimethylsiloxane, polycarbonate can also be used , polyurethane and silicone rubber.
- the above resins may be used alone or in combination of two or more.
- the most preferred choice is bisphenol A type cyanate resin, using cyanate resin as the polymer matrix, which has good dielectric properties (lower dielectric loss and dielectric constant), and good heat and humidity resistance ( low water absorption), and has excellent bonding properties.
- the embodiment of the present invention also provides the above-mentioned preparation method of the thermally conductive composite material, referring to FIG. 1 , the preparation method includes:
- thermally conductive filler dispersion by surface modification, the edges of boron nitride nanosheets are grafted with amino functional groups to obtain thermally conductive fillers; the thermally conductive fillers are dispersed in a dispersant to form a thermally conductive filler dispersion.
- hexagonal boron nitride is used as raw material, urea is used as modifier, hexagonal boron nitride is mixed with urea, added with a ball milling aid, and then placed in a ball milling equipment to carry out ball milling process to obtain an amino group grafted on the edge.
- Functional group boron nitride nanosheet powder is washed and dried, and then added to the dispersion liquid for dispersion to obtain the thermally conductive filler dispersion liquid.
- the lateral dimension of the hexagonal boron nitride is 5 ⁇ m ⁇ 10 ⁇ m, and the thickness is about 200 nm.
- the ball milling aid can be selected to be sodium chloride or potassium chloride, the ball milling process is carried out under the protection of N2 or Ar atmosphere, and the dispersant can be selected to be water, ethanol, acetone or 1,4-dicarbonate. Oxane. Urea is used as modifier, and the hexagonal boron nitride is peeled off and modified by mechanical ball milling with the aid of ball milling aids to obtain boron nitride nanosheet powder with amino functional groups grafted on the edge.
- the lateral dimension of the sheet is 200 nm to 300 nm, and the thickness is 3 nm to 4 nm.
- sodium chloride or potassium chloride ball milling aids helps to provide stronger shear force during the ball milling process and promote the peeling of hexagonal boron nitride.
- sodium chloride or potassium chloride is easily soluble in water and can be removed after several washing and drying, which is non-polluting to the sample and is convenient and quick.
- washing and drying the boron nitride nano-sheet powder mainly removes excess urea and ball milling aids, and obtains pure boron nitride nano-powder.
- the specific process may be as follows: firstly dissolving the boron nitride nanosheet powder in deionized water, filtering and then drying, preferably repeating washing and drying for 2 to 3 times.
- the mass ratio of hexagonal boron nitride to urea and ball milling aid can be set in the range of 1-2:20-25:5-10, and the rotational speed of the ball mill can be set at 350r/min ⁇ Within the range of 500r/min, Al 2 O 3 or ZrO 2 or agate grinding balls can be used, the ball diameter can be 10mm and/or 1mm, the ball-to-material ratio is 1-5, and the ball-milling treatment at room temperature is 6-10 hours.
- boron nitride nanosheet powder Within the range of 500r/min, Al 2 O 3 or ZrO 2 or agate grinding balls can be used, the ball diameter can be 10mm and/or 1mm, the ball-to-material ratio is 1-5, and the ball-milling treatment at room temperature is 6-10 hours.
- the prepared boron nitride flake powder is dispersed in deionized water, washed and dried repeatedly to remove excess urea and ball milling aids, and the purified boron nitride nano-powder is dispersed in the dispersion to finally obtain stable thermal conductivity. Filler dispersion.
- the polymer matrix is selected from cyanate ester resin, polyethylene, polyvinyl alcohol, polyimide, polymethyl methacrylate, polydimethylsiloxane, polycarbonate, polyurethane and silicone rubber one or more of them.
- the heating can be selected in the form of oil bath heating, and the heating temperature and time are set according to the needs of the polymerization reaction of the corresponding monomer used to form the polymer matrix.
- epoxy resin is added to the polymer matrix solution, and the blend is formed by continuous heating and stirring.
- the thermal conductivity of the finally obtained thermally conductive composite can be improved. Mechanical properties, enhance its toughness.
- the epoxy resin is selected as E51 type epoxy resin, which has the advantages of high epoxy value and low viscosity.
- the polymer matrix is a cyanate ester resin
- the preparation of the polymer matrix solution includes: adding a cyanate ester monomer and a catalyst into a reaction vessel, and heating the reaction vessel in an oil bath to make The cyanate ester monomer undergoes a polymerization reaction to obtain the polymer matrix solution; wherein, the catalyst is dibutyltin dilaurate or di-n-butyltin oxide.
- Cyanate ester resin is used as the polymer matrix, which has good dielectric properties (low dielectric loss and dielectric constant), good heat and humidity resistance (low water absorption), and excellent bonding properties.
- the predetermined ratio needs to be determined according to the mass percentage of the thermally conductive filler in the thermally conductive composite material to be finally prepared.
- the mass percentage of the thermally conductive filler is 10% to 50%.
- Mode 1 The mixed slurry is subjected to vacuum defoaming treatment, the mixed slurry is poured into a mold, then heated and solidified, and the thermally conductive composite material is obtained by demoulding after cooling.
- Method 2 The mixed slurry is subjected to vacuum filtration to form a film, the film-forming material is heated and solidified, and the thermally conductive composite material is obtained after cooling.
- the thermal conductive filler of boron nitride nanosheets in the polymer matrix can form a regular orientation arrangement under the action of suction filtration, forming a good thermal conductivity.
- the thermal conductivity of the finally obtained thermally conductive composite material is further improved.
- the method of gradual heating and heating for example: first heating at a temperature of 120 °C for 2 hours, then heating to 150 °C for 2 hours, and then heating to 180 °C for 2 hours, Then the temperature was raised to 200°C for 2h.
- thermally conductive composite material and its preparation method will be described below with reference to specific embodiments. Those skilled in the art will understand that the following embodiments are only specific examples of the above-mentioned thermally conductive composite material and its preparation method of the present invention, and are not used for limit it all.
- Hexagonal boron nitride, urea and sodium chloride were mixed in a planetary ball mill in a mass ratio of 1:20:5. Under the protection of N 2 atmosphere, at a speed of 500r/min, the diameters of the used balls were 10mm and 10mm respectively. 1mm ZrO2 grinding balls, ball milled for 10 hours. The obtained powder is washed and dried with deionized water to remove excess urea and sodium chloride to obtain pure boron nitride nano-powder. The polymer was dispersed in deionized water, and finally a pure and stable thermally conductive filler was obtained. The urea added during the ball-milling process realizes the modification of boron nitride nanosheets by grafting -NH2 functional groups on their edges.
- the polymer matrix is selected as cyanate ester resin, and its preparation process is as follows:
- the thermally conductive filler dispersion liquid prepared in Example 1 was added to the polymer matrix solution (mixture of cyanate ester resin and epoxy resin) prepared in Example 2 in a predetermined proportion, and stirred and mixed to obtain a mixed slurry.
- the thermally conductive filler dispersion liquid is added at 10%, 20%, 30%, 40% and 50%.
- the mixed slurry is cured into a film to obtain a thermally conductive composite material: the mixed slurry is subjected to vacuum defoaming treatment for 30 minutes, and then the mixed slurry is poured into a preheated mold, and the mixed slurry is firstly heated at 120° C. The temperature is heated for 2 hours, then heated to 150 °C for 2 hours, then heated to 180 °C for 2 hours, and then heated to 200 °C for 2 hours.
- thermally conductive composite material samples A1, A2, A3, A4, and A5 with the mass percentages of thermally conductive fillers of 10%, 20%, 30%, 40%, and 50%, respectively, were prepared.
- thermal conductivity and mechanical properties of the thermally conductive composite samples A1 to A5 were tested, and the test results of thermal conductivity and tensile strength are shown in Figures 2 and 3 and Table 1 below.
- the mixed slurry is prepared and obtained by referring to the method of Example 3.
- the difference between this example and Example 3 is that the process of curing the mixed slurry to form a film is different.
- the process of curing film formation in this embodiment is as follows: adding acetone (other diluents can also be selected in other embodiments) to the mixed slurry for dilution, and vacuuming the diluted mixed slurry After filtration for 20 hours to form a film, the film-forming material was heated and cured. The heating process was the same as that of Example 3. After the curing process, it was naturally cooled to room temperature to obtain a thermally conductive composite material.
- thermally conductive composite material samples B1, B2, B3, B4, and B5 with the mass percentages of thermally conductive fillers of 10%, 20%, 30%, 40%, and 50%, respectively, were prepared.
- thermal conductivity and mechanical properties of the thermally conductive composite samples B1 to B5 were tested, and the test results of thermal conductivity and tensile strength are shown in Figures 2 and 3 and Table 2 below.
- Example 4 Comparing Example 3 and Example 4, it can be seen that under the same other process conditions, the thermally conductive composite material prepared by vacuum filtration to form a film in Example 4 has better thermal conductivity. This is because by vacuum filtration of the mixed slurry, the boron nitride nanosheet thermal conductive filler in the polymer matrix can form a regular orientation arrangement under the action of suction filtration, forming a good thermal conduction path, and further improving the final thermal conductivity obtained. Thermal conductivity of composite materials.
- the thermally conductive filler in this example uses unmodified boron nitride nanosheets.
- the unmodified boron nitride nanosheets are dissolved in deionized water, and the thermally conductive filler dispersion is obtained by stirring and dispersing. .
- the mass percentages of the thermally conductive filler (unmodified boron nitride nanosheets) prepared in this example are 10%, 20%, 30%, 40% and 50% thermally conductive composite samples C1, sample C2, sample C3, sample C4 and sample C5.
- thermal conductivity and mechanical properties of the thermally conductive composite samples C1 to C5 were tested, and the test results of thermal conductivity and tensile strength are shown in Figures 2 and 3 and Table 3 below.
- Table 3 Test data of thermal conductivity and mechanical properties of thermally conductive composites of comparative examples
- Example 3 Comparing Example 3 with the comparative example, it can be seen that under the same other process conditions, the use of boron nitride nanosheets with amino functional groups grafted on the edges in the technical scheme of the present invention is used as a thermally conductive filler, compared with the use of unmodified boron nitride nanosheets.
- Boron nitride nanosheets have better thermal conductivity as thermally conductive fillers. This is due to the fact that the amino (-NH 2 ) functional groups grafted on the edges increase the wettability of the boron nitride nanosheet fillers, thereby better mixing with the polymer matrix, which can effectively improve the thermal conductivity of the thermally conductive composites.
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Abstract
A thermally conductive composite material, comprising a polymer matrix and a thermally conductive filler applied into the polymer matrix for filling. The thermally conductive filler is a boron nitride nanosheet grafted with an amino functional group at an edge. A preparation method for the thermally conductive composite material comprises: preparing a thermally conductive filler dispersion, i.e., grafting an amino functional group at an edge of a boron nitride nanosheet by means of surface modification to obtain a thermally conductive filler, and dispersing the thermally conductive filler in a dispersant to form the thermally conductive filler dispersion; preparing a polymer matrix solution, i.e., polymerizing, under the action of heating and a catalyst, a corresponding monomer used for forming a polymer matrix, so as to obtain the polymer matrix solution; adding the thermally conductive filler dispersion to the polymer matrix solution according to a predetermined ratio, and stirring and mixing to obtain a mixture slurry; and curing the mixture slurry into a film, so as to obtain the thermally conductive composite material. The thermally conductive composite material has good thermal conductivity and mechanical properties.
Description
本发明属于导热材料技术领域，具体涉及一种导热复合材料及其制备方法。The invention belongs to the technical field of thermally conductive materials, and in particular relates to a thermally conductive composite material and a preparation method thereof.
5G时代的到来，使得电子设备向着越发轻薄和小型化的方向发展，其内部电子元器件的高度集成化及结构复杂化使得器件单位面积的发热功率大幅上升，而器件发热会严重影响设备的使用性能和寿命。有数据显示，55％的电子产品的失效问题是由于温度过高引起的。因此，电子设备的散热成为了亟待解决的问题。With the advent of the 5G era, electronic devices are developing in the direction of becoming thinner and smaller. The highly integrated and complex structure of internal electronic components has greatly increased the heating power per unit area of the device, and the heating of the device will seriously affect the use of the device. performance and longevity. Some data show that 55% of the failure problems of electronic products are caused by excessive temperature. Therefore, the heat dissipation of electronic devices has become an urgent problem to be solved.
相较于传统的金属和陶瓷材料，聚合物因其质量轻、成本低、良好的绝缘性能及加工性能等优点获得广泛应用。如微电子封装领域所使用的印刷电路板，其基板多为聚酰亚胺、聚酯等材料，既具有良好的电绝缘性能又可满足不同应用场景对基板力学强度的要求；再如辅助芯片散热的热界面材料，其基体多为聚烯烃或硅胶，良好的柔韧性可大大填补接触面的空隙，减少空气热阻。又如换热和采暖工程中，使用聚氨酯等聚合物可以替代金属材料应用于易腐蚀、高强度和韧性的环境中，减少制造成本和产品重量。但聚合物内部大量的缺陷和链缠结使得声子在传递过程中频繁发生界面散射，声子自由程大大降低，导致聚合物的热导率偏低(～0.2W/m·K)，从而限制了其在热管理领域的进一步应用。Compared with traditional metal and ceramic materials, polymers are widely used due to their light weight, low cost, good insulating properties and processing properties. For example, the printed circuit boards used in the field of microelectronics packaging are mostly made of polyimide, polyester and other materials, which not only have good electrical insulation properties, but also meet the requirements of different application scenarios for the mechanical strength of the substrate; another example is auxiliary chips. For thermal interface materials that dissipate heat, the matrix is mostly polyolefin or silica gel, and its good flexibility can greatly fill the gaps in the contact surface and reduce air thermal resistance. Another example is heat exchange and heating engineering, the use of polymers such as polyurethane can replace metal materials in environments that are prone to corrosion, high strength and toughness, reducing manufacturing costs and product weight. However, a large number of defects and chain entanglements inside the polymer cause frequent interface scattering of phonons during the transfer process, and the phonon free path is greatly reduced, resulting in a low thermal conductivity of the polymer (~0.2W/m·K), thus It limits its further application in the field of thermal management.
目前提高聚合物热导率的主要方法是向聚合物基体中填充高导热填料，通过填料在聚合物基体内部形成导热路径进而提高整体热导率。在众多导热填料中，氮化硼拥有类似石墨烯的晶体结构，由交替的、共价键合的硼原子和氮原子组成的六元环层组成，其具备高热导率、宽带隙以及良好稳定性而被广泛应用于电子封装及高电设备中。目前，使用未经改性的氮化硼作为导热填料的聚合物复合材料的导热性能还有待提升。At present, the main method to improve the thermal conductivity of polymers is to fill the polymer matrix with high thermal conductivity fillers, and through the fillers, a thermal conduction path is formed inside the polymer matrix to improve the overall thermal conductivity. Among many thermally conductive fillers, boron nitride has a graphene-like crystal structure consisting of alternating, covalently bonded six-membered ring layers of boron and nitrogen atoms, which have high thermal conductivity, wide band gap, and good stability. It is widely used in electronic packaging and high-power equipment. At present, the thermal conductivity of polymer composites using unmodified boron nitride as thermally conductive fillers still needs to be improved.
发明内容SUMMARY OF THE INVENTION
鉴于现有技术存在的不足，本发明提供一种导热复合材料及其制备方法， 以解决现有的聚合物复合材料的导热性能较差的问题。In view of the deficiencies in the prior art, the present invention provides a thermally conductive composite material and a preparation method thereof, so as to solve the problem of poor thermal conductivity of the existing polymer composite material.
为实现上述发明目的，本发明的一方面是提供了一种导热复合材料，包括聚合物基体以及填充在所述聚合物基体中的导热填料，其中，所述导热填料为边缘接枝有氨基官能团的氮化硼纳米片。In order to achieve the above object of the invention, one aspect of the present invention is to provide a thermally conductive composite material, comprising a polymer matrix and a thermally conductive filler filled in the polymer matrix, wherein the thermally conductive filler is an edge grafted with amino functional groups of boron nitride nanosheets.
其中，所述导热复合材料中，所述导热填料的质量百分比为10％～50％。Wherein, in the thermally conductive composite material, the mass percentage of the thermally conductive filler is 10% to 50%.
其中，所述氮化硼纳米片的横向尺寸为200nm～300nm，厚度为3nm～4nm。Wherein, the lateral size of the boron nitride nanosheet is 200nm-300nm, and the thickness is 3nm-4nm.
其中，所述聚合物基体中还添加有环氧树脂，所述环氧树脂在所述聚合物基体中的质量百分比为25％～30％。Wherein, epoxy resin is further added to the polymer matrix, and the mass percentage of the epoxy resin in the polymer matrix is 25%-30%.
其中，所述聚合物基体选自氰酸酯树脂、聚乙烯、聚乙烯醇、聚酰亚胺、聚甲基丙烯酸甲酯、聚二甲基硅氧烷、聚碳酸酯、聚氨酯以及硅橡胶中的一种或两种以上。Wherein, the polymer matrix is selected from cyanate ester resin, polyethylene, polyvinyl alcohol, polyimide, polymethyl methacrylate, polydimethylsiloxane, polycarbonate, polyurethane and silicone rubber one or more of them.
本发明的另一方面是提供一种如上所述的导热复合材料的制备方法，其包括：Another aspect of the present invention is to provide a method for preparing the thermally conductive composite material as described above, comprising:
导热填料分散液的制备：通过表面改性使氮化硼纳米片的边缘接枝有氨基官能团，获得导热填料；将所述导热填料于分散剂中分散形成导热填料分散液；Preparation of thermally conductive filler dispersion: by surface modification, the edges of boron nitride nanosheets are grafted with amino functional groups to obtain thermally conductive fillers; the thermally conductive fillers are dispersed in a dispersant to form a thermally conductive filler dispersion;
聚合物基体溶液的制备：将用于形成聚合物基体对应的单体在加热及催化剂作用下发生聚合反应，获得所述聚合物基体溶液；Preparation of the polymer matrix solution: polymerizing the corresponding monomers used to form the polymer matrix under the action of heating and a catalyst to obtain the polymer matrix solution;
将所述导热填料分散液按预定比例添加到所述聚合物基体溶液并搅拌混合，获得混合浆料；adding the thermally conductive filler dispersion liquid to the polymer matrix solution in a predetermined proportion and stirring and mixing to obtain a mixed slurry;
将所述混合浆料固化成膜，获得所述导热复合材料。The mixed slurry is cured into a film to obtain the thermally conductive composite material.
其中，所述导热填料分散液的制备包括：Wherein, the preparation of the thermally conductive filler dispersion includes:
以六方氮化硼为原料，采用尿素为改性剂，将六方氮化硼与尿素混合并加入球磨助剂后置于球磨设备中进行球磨工艺，获得边缘接枝有氨基官能团的氮化硼纳米片粉体；Using hexagonal boron nitride as raw material, using urea as modifier, mixing hexagonal boron nitride and urea, adding ball milling aids, and then placing them in ball milling equipment for ball milling to obtain boron nitride nanometers with amino functional groups grafted on the edges. tablet powder;
将所述氮化硼纳米片粉体洗涤并干燥后加入到分散液中分散，获得所述导热填料分散液。The boron nitride nanosheet powder is washed and dried, and then added to the dispersion liquid for dispersion to obtain the thermally conductive filler dispersion liquid.
其中，所述球磨助剂为氯化钠或氯化钾，所述球磨工艺是在N
2或Ar的保 护气氛下进行，所述分散剂为去离子水、乙醇、丙酮或1,4-二氧六环。
Wherein, the ball milling aid is sodium chloride or potassium chloride , the ball milling process is carried out under the protective atmosphere of N or Ar, and the dispersant is deionized water, ethanol, acetone or 1,4-di Oxane.
其中，所述制备方法还包括：向所述聚合物基体溶液中加入环氧树脂以对所述聚合物基体进行增韧改性。Wherein, the preparation method further includes: adding epoxy resin to the polymer matrix solution to toughen and modify the polymer matrix.
其中，所述聚合物基体为氰酸酯树脂，所述聚合物基体溶液的制备包括：Wherein, the polymer matrix is a cyanate resin, and the preparation of the polymer matrix solution includes:
将氰酸酯单体和催化剂加入反应容器中，对所述反应容器进行油浴加热使所述氰酸酯单体发生聚合反应，获得所述聚合物基体溶液；其中，所述催化剂为二月桂酸二丁基锡或双正丁基氧化锡。The cyanate ester monomer and the catalyst are added into the reaction vessel, and the reaction vessel is heated in an oil bath to make the cyanate ester monomer undergo a polymerization reaction to obtain the polymer matrix solution; wherein, the catalyst is dilaurin Dibutyltin acid or di-n-butyltin oxide.
其中，所述将所述混合浆料固化成膜包括：对所述混合浆料进行真空脱泡处理，将所述混合浆料浇筑于模具中然后加热固化，冷却后脱模获得所述导热复合材料。Wherein, the step of curing the mixed slurry into a film includes: performing vacuum defoaming treatment on the mixed slurry, pouring the mixed slurry in a mold, then heating and solidifying, and demoulding after cooling to obtain the thermally conductive composite Material.
其中，所述将所述混合浆料固化成膜包括：对所述混合浆料进行真空抽滤成膜，对成膜物加热固化，冷却后获得所述导热复合材料。Wherein, the solidifying the mixed slurry to form a film includes: vacuum filtration of the mixed slurry to form a film, heating and solidifying the film-forming material, and cooling to obtain the thermally conductive composite material.
本发明实施例提供的导热复合材料，其中的导热填料为边缘接枝有氨基(-NH
2)官能团的氮化硼纳米片，由此增加了氮化硼纳米片填料的润湿性，从而更好地与聚合物基体混合，能够有效地提升导热复合材料的热导率。
In the thermally conductive composite material provided by the embodiment of the present invention, the thermally conductive filler is a boron nitride nanosheet with an amino group (-NH 2 ) functional group grafted on the edge, thereby increasing the wettability of the boron nitride nanosheet filler, thereby improving the Mixing well with the polymer matrix can effectively improve the thermal conductivity of thermally conductive composites.
本发明实施例提供的导热复合材料的制备方法，其具有工艺流程简单、工艺条件易于实现的优点，有利于大规模的工业化应用。The preparation method of the thermally conductive composite material provided in the embodiment of the present invention has the advantages of simple process flow and easy realization of process conditions, and is favorable for large-scale industrial application.
图1是本发明实施例中的导热复合材料的制备方法的工艺流程图；Fig. 1 is the process flow diagram of the preparation method of the thermally conductive composite material in the embodiment of the present invention;
图2是本发明实施例中的导热复合材料的导热性能的测试曲线图；Fig. 2 is the test curve diagram of the thermal conductivity of the thermally conductive composite material in the embodiment of the present invention;
图3是本发明实施例中的导热复合材料的力学性能的测试曲线图。FIG. 3 is a test curve diagram of the mechanical properties of the thermally conductive composite material in the embodiment of the present invention.
为使本发明的目的、技术方案和优点更加清楚，下面结合附图对本发明的具体实施方式进行详细说明。这些优选实施方式的示例在附图中进行了例示。附图中所示和根据附图描述的本发明的实施方式仅仅是示例性的，并且本发明并不限于这些实施方式。In order to make the objectives, technical solutions and advantages of the present invention clearer, the specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings. Examples of these preferred embodiments are illustrated in the accompanying drawings. The embodiments of the invention shown in the drawings and described with reference to the drawings are merely exemplary and the invention is not limited to these embodiments.
在此，还需要说明的是，为了避免因不必要的细节而模糊了本发明，在附 图中仅仅示出了与根据本发明的方案密切相关的结构和/或处理步骤，而省略了与本发明关系不大的其他细节。Here, it should also be noted that, in order to avoid obscuring the present invention due to unnecessary details, only the structures and/or processing steps closely related to the solution according to the present invention are shown in the drawings, and the related structures and/or processing steps are omitted. Other details not relevant to the invention.
本发明实施例首先提供了一种导热复合材料，包括聚合物基体以及填充在所述聚合物基体中的导热填料，其中，所述导热填料为边缘接枝有氨基官能团的氮化硼纳米片。Embodiments of the present invention first provide a thermally conductive composite material, comprising a polymer matrix and a thermally conductive filler filled in the polymer matrix, wherein the thermally conductive filler is a boron nitride nanosheet with an amino functional group grafted on the edge.
在优选的方案中，所述导热复合材料中，所述导热填料的质量百分比为10％～50％。所述氮化硼纳米片的横向尺寸为200nm～300nm，厚度为3nm～4nm。In a preferred solution, in the thermally conductive composite material, the mass percentage of the thermally conductive filler is 10% to 50%. The lateral size of the boron nitride nanosheet is 200nm-300nm, and the thickness is 3nm-4nm.
导热复合材料中的导热填料为边缘接枝有氨基(-NH
2)官能团的氮化硼纳米片，由此增加了氮化硼纳米片填料的润湿性，从而更好地与聚合物基体混合，能够有效地提升导热复合材料的热导率。
The thermally conductive fillers in the thermally conductive composites are boron nitride nanosheets with amino ( -NH2 ) functional groups grafted on the edges, thereby increasing the wettability of the boron nitride nanosheet fillers and thus better mixing with the polymer matrix , which can effectively improve the thermal conductivity of thermally conductive composites.
在优选的方案中，所述聚合物基体中还添加有环氧树脂，所述环氧树脂在所述聚合物基体中的质量百分比为25％～30％。通过添加环氧树脂对聚合物基体进行改性，可以改善导热复合材料的力学性能，增强其韧性。更为优选的是，环氧树脂选择为E51型环氧树脂，其优点为环氧值高、粘度低。In a preferred solution, epoxy resin is further added to the polymer matrix, and the mass percentage of the epoxy resin in the polymer matrix is 25% to 30%. By adding epoxy resin to modify the polymer matrix, the mechanical properties of thermally conductive composites can be improved and their toughness can be enhanced. More preferably, the epoxy resin is selected as E51 type epoxy resin, which has the advantages of high epoxy value and low viscosity.
在优选的方案中，所述聚合物基体为氰酸酯树脂，还可使用聚乙烯、聚乙烯醇、聚酰亚胺、聚甲基丙烯酸甲酯、聚二甲基硅氧烷、聚碳酸酯、聚氨酯以及硅橡胶。以上树脂可单独使用或者可两者或更多者组合使用。最为优选的是选择为双酚A型氰酸酯树脂，使用氰酸酯树脂作为聚合物基体，其具有良好的介电性能(较低的介电损耗和介电常数)，耐湿热性能好(吸水率低)，且具有优异的粘结性能。In a preferred solution, the polymer matrix is a cyanate resin, and polyethylene, polyvinyl alcohol, polyimide, polymethyl methacrylate, polydimethylsiloxane, polycarbonate can also be used , polyurethane and silicone rubber. The above resins may be used alone or in combination of two or more. The most preferred choice is bisphenol A type cyanate resin, using cyanate resin as the polymer matrix, which has good dielectric properties (lower dielectric loss and dielectric constant), and good heat and humidity resistance ( low water absorption), and has excellent bonding properties.
本发明实施例还提供了如上所述的导热复合材料的制备方法，参阅图1，所述制备方法包括：The embodiment of the present invention also provides the above-mentioned preparation method of the thermally conductive composite material, referring to FIG. 1 , the preparation method includes:
S10、导热填料分散液的制备：通过表面改性使氮化硼纳米片的边缘接枝有氨基官能团，获得导热填料；将所述导热填料于分散剂中分散形成导热填料分散液。S10. Preparation of thermally conductive filler dispersion: by surface modification, the edges of boron nitride nanosheets are grafted with amino functional groups to obtain thermally conductive fillers; the thermally conductive fillers are dispersed in a dispersant to form a thermally conductive filler dispersion.
在优选的方案中，以六方氮化硼为原料，采用尿素为改性剂，将六方氮化硼与尿素混合并加入球磨助剂后置于球磨设备中进行球磨工艺，获得边缘接枝有氨基官能团的氮化硼纳米片粉体。然后将所述氮化硼纳米片粉体洗涤并干燥后加入到分散液中分散，获得所述导热填料分散液。In a preferred solution, hexagonal boron nitride is used as raw material, urea is used as modifier, hexagonal boron nitride is mixed with urea, added with a ball milling aid, and then placed in a ball milling equipment to carry out ball milling process to obtain an amino group grafted on the edge. Functional group boron nitride nanosheet powder. Then, the boron nitride nanosheet powder is washed and dried, and then added to the dispersion liquid for dispersion to obtain the thermally conductive filler dispersion liquid.
具体地，所述六方氮化硼的横向尺寸为5μm～10μm，厚度为200nm左右。所述球磨助剂可以选择为氯化钠或氯化钾，所述球磨工艺是在N
2或Ar气氛的保护下进行，所述分散剂可以选择为水、乙醇、丙酮或1,4-二氧六环。采用尿素作为改性剂，在球磨助剂的辅助下机械球磨实现对六方氮化硼的剥离和改性，获得边缘接枝有氨基官能团的氮化硼纳米片粉体，所述氮化硼纳米片的横向尺寸为200nm～300nm，厚度为3nm～4nm。
Specifically, the lateral dimension of the hexagonal boron nitride is 5 μm˜10 μm, and the thickness is about 200 nm. The ball milling aid can be selected to be sodium chloride or potassium chloride, the ball milling process is carried out under the protection of N2 or Ar atmosphere, and the dispersant can be selected to be water, ethanol, acetone or 1,4-dicarbonate. Oxane. Urea is used as modifier, and the hexagonal boron nitride is peeled off and modified by mechanical ball milling with the aid of ball milling aids to obtain boron nitride nanosheet powder with amino functional groups grafted on the edge. The lateral dimension of the sheet is 200 nm to 300 nm, and the thickness is 3 nm to 4 nm.
其中，加入氯化钠或氯化钾球磨助剂有助于球磨过程中提供更强的剪切力，促进六方氮化硼的剥离。此外，氯化钠或氯化钾易溶于水，经过几次洗涤干燥就可去除，对样品无污染且方便快捷。Among them, the addition of sodium chloride or potassium chloride ball milling aids helps to provide stronger shear force during the ball milling process and promote the peeling of hexagonal boron nitride. In addition, sodium chloride or potassium chloride is easily soluble in water and can be removed after several washing and drying, which is non-polluting to the sample and is convenient and quick.
其中，将所述氮化硼纳米片粉体洗涤并干燥主要是除去多余的尿素和球磨助剂，获得纯净的氮化硼纳米粉体。具体工艺可以是：将所述氮化硼纳米片粉体先溶于去离子水中，过滤后干燥，优选是重复洗涤干燥2～3次。Wherein, washing and drying the boron nitride nano-sheet powder mainly removes excess urea and ball milling aids, and obtains pure boron nitride nano-powder. The specific process may be as follows: firstly dissolving the boron nitride nanosheet powder in deionized water, filtering and then drying, preferably repeating washing and drying for 2 to 3 times.
更具体地，在球磨工艺中，六方氮化硼与尿素以及球磨助剂的质量比可以设置在1～2:20～25:5～10的范围内，球磨机的转速可以设置在350r/min～500r/min的范围内，可以使用Al
2O
3或ZrO
2或玛瑙研磨球，球径大小可以为10mm和/或1mm，球料比为1～5，常温球磨处理6-10小时，获得改性氮化硼纳米片粉体。将制得的氮化硼片粉体分散在去离子水中，反复洗涤干燥以除去多余的尿素和球磨助剂，将纯化后的氮化硼纳米粉体分散于分散液中，最终得到稳定的导热填料分散液。
More specifically, in the ball milling process, the mass ratio of hexagonal boron nitride to urea and ball milling aid can be set in the range of 1-2:20-25:5-10, and the rotational speed of the ball mill can be set at 350r/min～ Within the range of 500r/min, Al 2 O 3 or ZrO 2 or agate grinding balls can be used, the ball diameter can be 10mm and/or 1mm, the ball-to-material ratio is 1-5, and the ball-milling treatment at room temperature is 6-10 hours. boron nitride nanosheet powder. The prepared boron nitride flake powder is dispersed in deionized water, washed and dried repeatedly to remove excess urea and ball milling aids, and the purified boron nitride nano-powder is dispersed in the dispersion to finally obtain stable thermal conductivity. Filler dispersion.
S20、聚合物基体溶液的制备：将用于形成聚合物基体对应的单体在加热及催化剂作用下发生聚合反应，获得所述聚合物基体溶液。S20. Preparation of the polymer matrix solution: polymerizing the corresponding monomers used to form the polymer matrix under the action of heating and a catalyst to obtain the polymer matrix solution.
其中，所述聚合物基体选自氰酸酯树脂、聚乙烯、聚乙烯醇、聚酰亚胺、聚甲基丙烯酸甲酯、聚二甲基硅氧烷、聚碳酸酯、聚氨酯以及硅橡胶中的一种或两种以上。Wherein, the polymer matrix is selected from cyanate ester resin, polyethylene, polyvinyl alcohol, polyimide, polymethyl methacrylate, polydimethylsiloxane, polycarbonate, polyurethane and silicone rubber one or more of them.
在优选的方案中，所述加热可以选择为油浴加热的方式，加热的温度以及时间根据用于形成聚合物基体对应的单体发生聚合反应的需要设定。In a preferred solution, the heating can be selected in the form of oil bath heating, and the heating temperature and time are set according to the needs of the polymerization reaction of the corresponding monomer used to form the polymer matrix.
在优选的方案中，向所述聚合物基体溶液中加入环氧树脂，持续加热并搅拌形成共混物，通过添加环氧树脂对聚合物基体进行改性，可以改善最终获得的导热复合材料的力学性能，增强其韧性。更为优选的是，环氧树脂选择为E51型环氧树脂，其优点为环氧值高、粘度低。In a preferred solution, epoxy resin is added to the polymer matrix solution, and the blend is formed by continuous heating and stirring. By adding epoxy resin to modify the polymer matrix, the thermal conductivity of the finally obtained thermally conductive composite can be improved. Mechanical properties, enhance its toughness. More preferably, the epoxy resin is selected as E51 type epoxy resin, which has the advantages of high epoxy value and low viscosity.
在优选的方案中，所述聚合物基体为氰酸酯树脂，所述聚合物基体溶液的制备包括：将氰酸酯单体和催化剂加入反应容器中，对所述反应容器进行油浴加热使所述氰酸酯单体发生聚合反应，获得所述聚合物基体溶液；其中，所述催化剂为二月桂酸二丁基锡或双正丁基氧化锡。使用氰酸酯树脂作为聚合物基体，其具有良好的介电性能(较低的介电损耗和介电常数)，耐湿热性能好(吸水率低)，且具有优异的粘结性能。In a preferred solution, the polymer matrix is a cyanate ester resin, and the preparation of the polymer matrix solution includes: adding a cyanate ester monomer and a catalyst into a reaction vessel, and heating the reaction vessel in an oil bath to make The cyanate ester monomer undergoes a polymerization reaction to obtain the polymer matrix solution; wherein, the catalyst is dibutyltin dilaurate or di-n-butyltin oxide. Cyanate ester resin is used as the polymer matrix, which has good dielectric properties (low dielectric loss and dielectric constant), good heat and humidity resistance (low water absorption), and excellent bonding properties.
S30、将所述导热填料分散液按预定比例添加到所述聚合物基体溶液并搅拌混合，获得混合浆料。S30, adding the thermally conductive filler dispersion liquid to the polymer matrix solution in a predetermined proportion and stirring and mixing to obtain a mixed slurry.
其中，所述预定比例需要根据最终所要制备获得的导热复合材料中导热填料的质量百分比确定。在优选的方案中，所要制备获得的导热复合材料中，导热填料的质量百分比为10％～50％。Wherein, the predetermined ratio needs to be determined according to the mass percentage of the thermally conductive filler in the thermally conductive composite material to be finally prepared. In a preferred solution, in the thermally conductive composite material to be prepared, the mass percentage of the thermally conductive filler is 10% to 50%.
S40、将所述混合浆料固化成膜，获得所述导热复合材料。S40, curing the mixed slurry into a film to obtain the thermally conductive composite material.
其中，优选采用以下两种方式的其中之一进行固化成膜：Among them, it is preferable to use one of the following two ways to cure and form a film:
方式一：对所述混合浆料进行真空脱泡处理，将所述混合浆料浇筑于模具中然后加热固化，冷却后脱模获得所述导热复合材料。Mode 1: The mixed slurry is subjected to vacuum defoaming treatment, the mixed slurry is poured into a mold, then heated and solidified, and the thermally conductive composite material is obtained by demoulding after cooling.
方式二：对所述混合浆料进行真空抽滤成膜，对成膜物加热固化，冷却后获得所述导热复合材料。Method 2: The mixed slurry is subjected to vacuum filtration to form a film, the film-forming material is heated and solidified, and the thermally conductive composite material is obtained after cooling.
其中，更为优选的是使用方式二，通过对混合浆料进行真空抽滤，可以使聚合物基体中的氮化硼纳米片导热填料在抽滤作用下形成规则的取向排列，形成良好的导热通路，进一步提升最终获得的导热复合材料的导热性能。Among them, it is more preferable to use the second method. By vacuum filtration of the mixed slurry, the thermal conductive filler of boron nitride nanosheets in the polymer matrix can form a regular orientation arrangement under the action of suction filtration, forming a good thermal conductivity. The thermal conductivity of the finally obtained thermally conductive composite material is further improved.
其中，以上方式一和方式二的加热固化工艺中，优选使用逐步升温加热的方式，例如：首先在120℃的温度下加热2h，然后升温至150℃加热2h，再升温至180℃加热2h，再升温至200℃加热2h。Among them, in the heating and curing processes of the above methods 1 and 2, it is preferable to use the method of gradual heating and heating, for example: first heating at a temperature of 120 °C for 2 hours, then heating to 150 °C for 2 hours, and then heating to 180 °C for 2 hours, Then the temperature was raised to 200°C for 2h.
以下将结合具体的实施例来说明上述导热复合材料及其制备方法，本领域技术人员所理解的是，下述实施例仅是本发明上述导热复合材料及其制备方法的具体示例，而不用于限制其全部。The above-mentioned thermally conductive composite material and its preparation method will be described below with reference to specific embodiments. Those skilled in the art will understand that the following embodiments are only specific examples of the above-mentioned thermally conductive composite material and its preparation method of the present invention, and are not used for limit it all.
实施例1：导热填料分散液的制备Example 1: Preparation of Thermally Conductive Filler Dispersion
六方氮化硼与尿素以及氯化钠按照质量比为1：20：5混合放入行星式球磨 机中，在N
2气氛的保护下，以500r/min的转速，使用球径大小分别为10mm和1mm的ZrO
2研磨球，球磨处理10小时。将得到的粉体以去离子水中洗涤和干燥以除去多余的尿素和氯化钠，获得纯净的氮化硼纳米粉体，然后选择以去离子水为分散剂，将纯净的氮化硼纳米粉体分散于去离子水中，最终得到纯净且稳定的导热填料。球磨过程中加入的尿素实现对氮化硼纳米片的改性，在其边缘接枝-NH
2官能团。
Hexagonal boron nitride, urea and sodium chloride were mixed in a planetary ball mill in a mass ratio of 1:20:5. Under the protection of N 2 atmosphere, at a speed of 500r/min, the diameters of the used balls were 10mm and 10mm respectively. 1mm ZrO2 grinding balls, ball milled for 10 hours. The obtained powder is washed and dried with deionized water to remove excess urea and sodium chloride to obtain pure boron nitride nano-powder. The polymer was dispersed in deionized water, and finally a pure and stable thermally conductive filler was obtained. The urea added during the ball-milling process realizes the modification of boron nitride nanosheets by grafting -NH2 functional groups on their edges.
实施例2：聚合物基体溶液的制备Example 2: Preparation of polymer matrix solution
本实施例中，聚合物基体选择为氰酸酯树脂，其制备工艺如下：In the present embodiment, the polymer matrix is selected as cyanate ester resin, and its preparation process is as follows:
将双酚A型氰酸酯单体7g，催化剂(二月桂酸二丁基锡，0.05g)，将二者先后放入反应容器中，采用油浴加热，加热温度为90℃，加热时间30min，聚合反应完成后得到浅黄色透明的氰酸酯聚合体液体，即获得聚合物基体溶液。With bisphenol A type cyanate monomer 7g, catalyst (dibutyltin dilaurate, 0.05g), the two are successively put into the reaction vessel, and oil bath heating is adopted, and the heating temperature is 90 ° C, and the heating time is 30min. After the reaction is completed, a light yellow transparent cyanate ester polymer liquid is obtained, that is, a polymer matrix solution is obtained.
向制备得到的氰酸酯聚合体溶液中加入3g E51型环氧树脂，继续搅拌加热15min，获得氰酸酯树脂与环氧树脂的混合物。To the prepared cyanate ester polymer solution, add 3 g of E51 epoxy resin, continue stirring and heating for 15 min, to obtain a mixture of cyanate ester resin and epoxy resin.
实施例3：导热复合材料的制备Example 3: Preparation of Thermally Conductive Composite
将实施例1制备获得的导热填料分散液按预定比例添加到实施例2制备获得的聚合物基体溶液(氰酸酯树脂与环氧树脂的混合物)并搅拌混合，获得混合浆料。其中，根据最终所要制备获得的导热复合材料中导热填料的质量百分比为10％、20％、30％、40％和50％添加导热填料分散液。The thermally conductive filler dispersion liquid prepared in Example 1 was added to the polymer matrix solution (mixture of cyanate ester resin and epoxy resin) prepared in Example 2 in a predetermined proportion, and stirred and mixed to obtain a mixed slurry. Wherein, according to the mass percentage of the thermally conductive filler in the thermally conductive composite material to be finally prepared, the thermally conductive filler dispersion liquid is added at 10%, 20%, 30%, 40% and 50%.
将所述混合浆料固化成膜，获得导热复合材料：对所述混合浆料进行真空脱泡处理30min，然后将所述混合浆料浇筑于预热好的模具中，按照首先在120℃的温度下加热2h，然后升温至150℃加热2h，再升温至180℃加热2h，再升温至200℃加热2h的工艺加热固化，固化工艺结束后自然冷却至室温，脱模得到导热复合材料。The mixed slurry is cured into a film to obtain a thermally conductive composite material: the mixed slurry is subjected to vacuum defoaming treatment for 30 minutes, and then the mixed slurry is poured into a preheated mold, and the mixed slurry is firstly heated at 120° C. The temperature is heated for 2 hours, then heated to 150 °C for 2 hours, then heated to 180 °C for 2 hours, and then heated to 200 °C for 2 hours.
本实施例制备获得导热填料的质量百分比分别为10％、20％、30％、40％和50％的导热复合材料样品A1、样品A2、样品A3、样品A4和样品A5。In this example, the thermally conductive composite material samples A1, A2, A3, A4, and A5 with the mass percentages of thermally conductive fillers of 10%, 20%, 30%, 40%, and 50%, respectively, were prepared.
对导热复合材料样品A1至A5进行导热性能和力学性能测试，热导率和拉伸强度的测试结果参见图2和图3以及如下表1。The thermal conductivity and mechanical properties of the thermally conductive composite samples A1 to A5 were tested, and the test results of thermal conductivity and tensile strength are shown in Figures 2 and 3 and Table 1 below.
表1：实施例3的导热复合材料的导热性能和力学性能测试数据Table 1: Test data of thermal conductivity and mechanical properties of the thermally conductive composite material of Example 3
| 样品sample | A1A1 | A2A2 | A3A3 | A4A4 | A5A5 |
| 热导率(W/m·K)Thermal conductivity (W/m·K) | 1.061.06 | 1.131.13 | 1.421.42 | 2.112.11 | 1.831.83 |
| 拉伸强度(MPa)Tensile strength (MPa) | 80.080.0 | 87.587.5 | 94.194.1 | 89.389.3 | 86.886.8 |
实施例4：导热复合材料的制备Example 4: Preparation of Thermally Conductive Composite
参照实施例3的方式制备获得混合浆料，本实施例与实施例3的区别在于，将所述混合浆料固化成膜的工艺不相同。The mixed slurry is prepared and obtained by referring to the method of Example 3. The difference between this example and Example 3 is that the process of curing the mixed slurry to form a film is different.
具体地，本实施例的固化成膜的工艺具体是：向所述混合浆料加入丙酮(另外的实施例中也可以选择其他的稀释剂)进行稀释，对稀释后的混合浆料进行真空抽滤20h成膜，对成膜物加热固化，加热的过程与实施例3的相同，固化工艺结束后自然冷却至室温，得到导热复合材料。Specifically, the process of curing film formation in this embodiment is as follows: adding acetone (other diluents can also be selected in other embodiments) to the mixed slurry for dilution, and vacuuming the diluted mixed slurry After filtration for 20 hours to form a film, the film-forming material was heated and cured. The heating process was the same as that of Example 3. After the curing process, it was naturally cooled to room temperature to obtain a thermally conductive composite material.
本实施例制备获得导热填料的质量百分比分别为10％、20％、30％、40％和50％的导热复合材料样品B1、样品B2、样品B3、样品B4和样品B5。In this example, the thermally conductive composite material samples B1, B2, B3, B4, and B5 with the mass percentages of thermally conductive fillers of 10%, 20%, 30%, 40%, and 50%, respectively, were prepared.
对导热复合材料样品B1至B5进行导热性能和力学性能测试，热导率和拉伸强度的测试结果参见图2和图3以及如下表2。The thermal conductivity and mechanical properties of the thermally conductive composite samples B1 to B5 were tested, and the test results of thermal conductivity and tensile strength are shown in Figures 2 and 3 and Table 2 below.
表2：实施例4的导热复合材料的导热性能和力学性能测试数据Table 2: Test data of thermal conductivity and mechanical properties of the thermally conductive composite material of Example 4
| 样品sample | B1B1 | B2B2 | B3B3 | B4B4 | B5B5 |
| 热导率(W/m·K)Thermal conductivity (W/m·K) | 1.401.40 | 1.651.65 | 1.841.84 | 2.322.32 | 2.022.02 |
| 拉伸强度(MPa)Tensile strength (MPa) | 83.083.0 | 84.684.6 | 92.292.2 | 90.290.2 | 88.388.3 |
对比实施例3和实施例4可知，在其他工艺条件相同的情况下，实施例4采用真空抽滤成膜的方式制备获得的导热复合材料具有更好地的导热性能。这是由于通过对混合浆料进行真空抽滤，可以使聚合物基体中的氮化硼纳米片导热填料在抽滤作用下形成规则的取向排列，形成良好的导热通路，进一步提升最终获得的导热复合材料的导热性能。Comparing Example 3 and Example 4, it can be seen that under the same other process conditions, the thermally conductive composite material prepared by vacuum filtration to form a film in Example 4 has better thermal conductivity. This is because by vacuum filtration of the mixed slurry, the boron nitride nanosheet thermal conductive filler in the polymer matrix can form a regular orientation arrangement under the action of suction filtration, forming a good thermal conduction path, and further improving the final thermal conductivity obtained. Thermal conductivity of composite materials.
对比例Comparative ratio
与实施例3相比，本实施例中的导热填料采用的是未改性的氮化硼纳米片，将未改性的氮化硼纳米片溶解于去离子水中，搅拌分散获得导热填料分散液。Compared with Example 3, the thermally conductive filler in this example uses unmodified boron nitride nanosheets. The unmodified boron nitride nanosheets are dissolved in deionized water, and the thermally conductive filler dispersion is obtained by stirring and dispersing. .
除了导热填料分散液不同，本实施例的其他工艺完全参照实施例3的进行，本实施例制备获得导热填料(未改性的氮化硼纳米片)的质量百分比分别为10％、20％、30％、40％和50％的导热复合材料样品C1、样品C2、样品C3、样品C4和样品C5。Except for the difference in the dispersion liquid of the thermally conductive filler, the other processes in this example are completely carried out with reference to Example 3. The mass percentages of the thermally conductive filler (unmodified boron nitride nanosheets) prepared in this example are 10%, 20%, 30%, 40% and 50% thermally conductive composite samples C1, sample C2, sample C3, sample C4 and sample C5.
对导热复合材料样品C1至C5进行导热性能和力学性能测试，热导率和拉伸强度的测试结果参见图2和图3以及如下表3。The thermal conductivity and mechanical properties of the thermally conductive composite samples C1 to C5 were tested, and the test results of thermal conductivity and tensile strength are shown in Figures 2 and 3 and Table 3 below.
表3：对比例的导热复合材料的导热性能和力学性能测试数据Table 3: Test data of thermal conductivity and mechanical properties of thermally conductive composites of comparative examples
| 样品sample | C1C1 | C2C2 | C3C3 | C4C4 | C5C5 |
| 热导率(W/m·K)Thermal conductivity (W/m·K) | 0.890.89 | 1.021.02 | 1.251.25 | 2.482.48 | 1.631.63 |
| 拉伸强度(MPa)Tensile strength (MPa) | 78.678.6 | 83.283.2 | 88.188.1 | 85.485.4 | 84.584.5 |
将实施例3与对比例进行对比可知，在其他工艺条件相同的情况下，本发明技术方案中采用边缘接枝有氨基官能团的氮化硼纳米片为导热填料，相比于采用未改性的氮化硼纳米片作为导热填料具有更好地的导热性能。这是由于边缘接枝有氨基(-NH
2)官能团增加了氮化硼纳米片填料的润湿性，从而更好地与聚合物基体混合，能够有效地提升导热复合材料的热导率。
Comparing Example 3 with the comparative example, it can be seen that under the same other process conditions, the use of boron nitride nanosheets with amino functional groups grafted on the edges in the technical scheme of the present invention is used as a thermally conductive filler, compared with the use of unmodified boron nitride nanosheets. Boron nitride nanosheets have better thermal conductivity as thermally conductive fillers. This is due to the fact that the amino (-NH 2 ) functional groups grafted on the edges increase the wettability of the boron nitride nanosheet fillers, thereby better mixing with the polymer matrix, which can effectively improve the thermal conductivity of the thermally conductive composites.
以上所述仅是本申请的具体实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本申请原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本申请的保护范围。The above are only specific embodiments of the present application. It should be pointed out that for those skilled in the art, without departing from the principles of the present application, several improvements and modifications can also be made. It should be regarded as the protection scope of this application.
Claims (16)
- 一种导热复合材料，包括聚合物基体以及填充在所述聚合物基体中的导热填料，其中，所述导热填料为边缘接枝有氨基官能团的氮化硼纳米片。A thermally conductive composite material comprises a polymer matrix and a thermally conductive filler filled in the polymer matrix, wherein the thermally conductive filler is a boron nitride nanosheet with an amino functional group grafted on the edge.
- 根据权利要求1所述的导热复合材料，其中，所述导热复合材料中，所述导热填料的质量百分比为10％～50％。The thermally conductive composite material according to claim 1, wherein, in the thermally conductive composite material, the mass percentage of the thermally conductive filler is 10% to 50%.
- 根据权利要求1所述的导热复合材料，其中，所述氮化硼纳米片的横向尺寸为200nm～300nm，厚度为3nm～4nm。The thermally conductive composite material according to claim 1, wherein the boron nitride nanosheets have a lateral dimension of 200 nm to 300 nm and a thickness of 3 nm to 4 nm.
- 根据权利要求1所述的导热复合材料，其中，所述聚合物基体中还添加有环氧树脂，所述环氧树脂在所述聚合物基体中的质量百分比为25％～30％。The thermally conductive composite material according to claim 1, wherein epoxy resin is further added to the polymer matrix, and the mass percentage of the epoxy resin in the polymer matrix is 25%-30%.
- 根据权利要求1所述的导热复合材料，其中，所述聚合物基体选自氰酸酯树脂、聚乙烯、聚乙烯醇、聚酰亚胺、聚甲基丙烯酸甲酯、聚二甲基硅氧烷、聚碳酸酯、聚氨酯以及硅橡胶中的一种或两种以上。The thermally conductive composite material according to claim 1, wherein the polymer matrix is selected from the group consisting of cyanate ester resin, polyethylene, polyvinyl alcohol, polyimide, polymethyl methacrylate, polydimethylsiloxane One or more of alkane, polycarbonate, polyurethane and silicone rubber.
- 一种导热复合材料的制备方法，其中，包括：A preparation method of a thermally conductive composite material, comprising:导热填料分散液的制备：通过表面改性使氮化硼纳米片的边缘接枝有氨基官能团，获得导热填料；将所述导热填料于分散剂中分散形成导热填料分散液；Preparation of thermally conductive filler dispersion: by surface modification, the edges of boron nitride nanosheets are grafted with amino functional groups to obtain thermally conductive fillers; the thermally conductive fillers are dispersed in a dispersant to form a thermally conductive filler dispersion;聚合物基体溶液的制备：将用于形成聚合物基体对应的单体在加热及催化剂作用下发生聚合反应，获得所述聚合物基体溶液；Preparation of the polymer matrix solution: polymerizing the corresponding monomers used to form the polymer matrix under the action of heating and a catalyst to obtain the polymer matrix solution;将所述导热填料分散液按预定比例添加到所述聚合物基体溶液并搅拌混合，获得混合浆料；adding the thermally conductive filler dispersion liquid to the polymer matrix solution in a predetermined proportion and stirring and mixing to obtain a mixed slurry;将所述混合浆料固化成膜，获得所述导热复合材料。The mixed slurry is cured to form a film to obtain the thermally conductive composite material.
- 根据权利要求6所述的导热复合材料的制备方法，其中，所述导热填料分散液的制备包括：The method for preparing a thermally conductive composite material according to claim 6, wherein the preparation of the thermally conductive filler dispersion comprises:以六方氮化硼为原料，采用尿素作为改性剂，将六方氮化硼与尿素混合并加入球磨助剂后置于球磨设备中进行球磨工艺，获得边缘接枝有氨基官能团的氮化硼纳米片粉体；Using hexagonal boron nitride as raw material, using urea as modifier, mixing hexagonal boron nitride and urea, adding ball milling aids, and then placing them in ball milling equipment for ball milling to obtain boron nitride nanometers with amino functional groups grafted on the edges. tablet powder;将所述氮化硼纳米片粉体洗涤并干燥后加入到分散液中分散，获得所述导热填料分散液。The boron nitride nanosheet powder is washed and dried, and then added to the dispersion liquid for dispersion to obtain the thermally conductive filler dispersion liquid.
- 根据权利要求7所述的导热复合材料的制备方法，其中，所述球磨助剂为氯化钠或氯化钾，所述球磨工艺是在N 2或Ar的保护气氛下进行，所述分散剂为去离子水、乙醇、丙酮或1,4-二氧六环。 The method for preparing a thermally conductive composite material according to claim 7, wherein the ball milling aid is sodium chloride or potassium chloride , the ball milling process is carried out under a protective atmosphere of N or Ar, and the dispersant is For deionized water, ethanol, acetone or 1,4-dioxane.
- 根据权利要求6所述的导热复合材料的制备方法，其中，所述制备方法还包括：向所述聚合物基体溶液中加入环氧树脂以对所述聚合物基体进行增韧改性。The preparation method of the thermally conductive composite material according to claim 6, wherein the preparation method further comprises: adding epoxy resin to the polymer matrix solution to toughen and modify the polymer matrix.
- 根据权利要求9所述的导热复合材料的制备方法，其中，所述环氧树脂在所述聚合物基体中的质量百分比为25％～30％。The method for preparing a thermally conductive composite material according to claim 9, wherein the mass percentage of the epoxy resin in the polymer matrix is 25% to 30%.
- 根据权利要求6所述的导热复合材料的制备方法，其中，所述导热复合材料中，所述导热填料的质量百分比为10％～50％。The method for preparing a thermally conductive composite material according to claim 6, wherein, in the thermally conductive composite material, the mass percentage of the thermally conductive filler is 10% to 50%.
- 根据权利要求6所述的导热复合材料的制备方法，其中，所述氮化硼纳米片的横向尺寸为200nm～300nm，厚度为3nm～4nm。The method for preparing a thermally conductive composite material according to claim 6, wherein the boron nitride nanosheets have a lateral size of 200 nm to 300 nm and a thickness of 3 nm to 4 nm.
- 根据权利要求6所述的导热复合材料的制备方法，其中，所述聚合物基体选自氰酸酯树脂、聚乙烯、聚乙烯醇、聚酰亚胺、聚甲基丙烯酸甲酯、聚二甲基硅氧烷、聚碳酸酯、聚氨酯以及硅橡胶中的一种或两种以上。The method for preparing a thermally conductive composite material according to claim 6, wherein the polymer matrix is selected from the group consisting of cyanate ester resin, polyethylene, polyvinyl alcohol, polyimide, polymethyl methacrylate, polydimethyl methacrylate One or more of siloxane, polycarbonate, polyurethane and silicone rubber.
- 根据权利要求6所述的导热复合材料的制备方法，其中，所述聚合物基体为氰酸酯树脂，所述聚合物基体溶液的制备包括：The method for preparing a thermally conductive composite material according to claim 6, wherein the polymer matrix is a cyanate ester resin, and the preparation of the polymer matrix solution comprises:将氰酸酯单体和催化剂加入反应容器中，对所述反应容器进行油浴加热使所述氰酸酯单体发生聚合反应，获得所述聚合物基体溶液；其中，所述催化剂为二月桂酸二丁基锡或双正丁基氧化锡。The cyanate ester monomer and the catalyst are added into the reaction vessel, and the reaction vessel is heated in an oil bath to make the cyanate ester monomer undergo a polymerization reaction to obtain the polymer matrix solution; wherein, the catalyst is dilaurin Dibutyltin acid or di-n-butyltin oxide.
- 根据权利要求6所述的导热复合材料的制备方法，其中，将所述混合浆料固化成膜包括：对所述混合浆料进行真空脱泡处理，将所述混合浆料浇筑于模具中然后加热固化，冷却后脱模获得所述导热复合材料。The method for preparing a thermally conductive composite material according to claim 6, wherein curing the mixed slurry into a film comprises: performing vacuum defoaming treatment on the mixed slurry, pouring the mixed slurry in a mold, and then Heating to solidify, and demoulding after cooling to obtain the thermally conductive composite material.
- 根据权利要求6所述的导热复合材料的制备方法，其中，所述将所述混合浆料固化成膜包括：对所述混合浆料进行真空抽滤成膜，对成膜物加热固化，冷却后获得所述导热复合材料。The method for preparing a thermally conductive composite material according to claim 6, wherein said solidifying the mixed slurry into a film comprises: vacuum filtration of the mixed slurry to form a film, heating and solidifying the film-forming material, and cooling Then the thermally conductive composite material is obtained.
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