WO2020029533A1 - 改性六方氮化硼及其制备方法和用途 - Google Patents

改性六方氮化硼及其制备方法和用途 Download PDF

Info

Publication number
WO2020029533A1
WO2020029533A1 PCT/CN2018/125304 CN2018125304W WO2020029533A1 WO 2020029533 A1 WO2020029533 A1 WO 2020029533A1 CN 2018125304 W CN2018125304 W CN 2018125304W WO 2020029533 A1 WO2020029533 A1 WO 2020029533A1
Authority
WO
WIPO (PCT)
Prior art keywords
boron nitride
hexagonal boron
polyvinyl alcohol
modified hexagonal
modified
Prior art date
Application number
PCT/CN2018/125304
Other languages
English (en)
French (fr)
Inventor
朱朋莉
黎华源
李刚
赵涛
孙蓉
Original Assignee
深圳先进技术研究院
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 深圳先进技术研究院 filed Critical 深圳先进技术研究院
Publication of WO2020029533A1 publication Critical patent/WO2020029533A1/zh

Links

Classifications

    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients
    • 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
    • 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
    • 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

Definitions

  • the present application belongs to the field of modified materials, and relates to a modified hexagonal boron nitride and a preparation method and application thereof.
  • Polymer materials are often used as packaging materials for electronic components and integrated circuits because of their ease of processing, high mechanical strength, and low cost.
  • the random winding and vibration of molecular chains increase the scattering during photon transmission, which increases the Interfacial thermal resistance makes the thermal conductivity of the polymer itself less than 0.5w ⁇ m -1 K -1 , which cannot meet the requirements for the thermal conductivity of electronic components; the currently commonly used solution is to incorporate a high thermal conductivity inorganic into the polymer filler.
  • CN103435895A discloses a method for preparing an insulating and highly thermally conductive composite material, which uses high-density polyethylene as a matrix, and adds three kinds of thermally conductive fillers and processing aids of different particle sizes, such as aluminum nitride, alumina, and boron nitride. Premixed in a high-speed machine, melt-blended, extruded, and pelletized into a twin-screw extruder to obtain a granular insulating high thermal conductivity composite material, but the inorganic filler auxiliary in the composite material prepared by this method is among them The dispersion is not uniform.
  • Hexagonal boron nitride has a layered structure similar to graphite, so it is also called “white graphite”. It has excellent thermal conductivity. In addition, the band gap is 5.6eV, which also provides good insulation. Hexagonal boron nitride Therefore, it has become one of the most promising thermal conductive fillers in the field of electronic packaging.
  • hexagonal boron nitride lacks functional groups that can undergo chemical reactions, has strong chemical inertness, and has poor compatibility with polymers, which is not conducive to dispersibility in polymers, which in turn affects the formation of thermally conductive networks, making hexagonal boron nitride
  • the efficiency of improving the thermal conductivity of polymers is relatively low, so surface modification of them has become the key to preparing high thermal conductivity composite materials.
  • the current methods of modifying hexagonal boron nitride are mainly divided into covalent modification and non-covalent modification.
  • Covalent modification is generally divided into two steps, first is to oxidize hexagonal boron nitride, introduce hydroxyl groups, and then graft some complex functional groups or molecules;
  • CN104892968A discloses a high thermal conductivity hexagonal boron nitride / polyimide composite material A method for the preparation, which utilizes a diisocyanate and an aromatic diamine reagent to obtain an aminated hexagonal boron nitride in a DMA or DMF solvent; such methods usually cause a structural change of the hexagonal boron nitride, affecting its thermal / electrical properties, And covalent modification will use many toxic, corrosive and volatile solvents, which is not good for the environment.
  • non-covalent modification of hexagonal boron nitride does not change its spatial structure and can retain its original properties, and in most cases these processes are reversible; non-covalent modification includes organic substances (such as dopamine, Polyimide, silane coupling agent) coats hexagonal boron nitride, and modifies functional inorganic particles (such as silicon dioxide, iron trioxide) on the surface of hexagonal boron nitride.
  • organic substances such as dopamine, Polyimide, silane coupling agent
  • CN106189165A discloses a method for preparing a high thermal conductivity insulating hexagonal boron nitride / polycarbonate composite material, which firstly ultrasonically increases the electronegativity of hexagonal boron nitride in water, and then uses cationic polymethacrylamide to modify it. Properties, and finally added to the polycarbonate matrix to obtain a composite material.
  • CN106674603A discloses a thermally conductive hexagonal boron nitride hybrid material, which is covered with a polymer layer on a hexagonal boron nitride envelope and silver nanoparticles are supported on the polymer layer. Although the thermal conductivity is good, The silver particles are added, which results in increased cost and a more complicated preparation method.
  • the introduction of silver nanoparticles will increase the conductivity of the material.
  • the polymer's hexagonal boron nitride improves the compatibility of the hexagonal boron nitride in the matrix, but because the polymer layer is coated on the surface of the hexagonal boron nitride, the thermal conductivity of the hexagonal boron nitride will be reduced. It cannot meet application requirements.
  • the purpose of this application is to provide a modified hexagonal boron nitride and a preparation method and application thereof.
  • the highly thermally conductive material silver
  • reducing the thickness of the cladding layer there is no known prediction of a person skilled in the art that omitting silver will cause a decrease in thermal conductivity and reduce the thickness of the cladding layer.
  • the dispersibility of the modified hexagonal boron nitride in the material is reduced.
  • the modified hexagonal boron nitride provided in the present application can be uniformly dispersed in the polyvinyl alcohol substrate and increases the thermal conductivity of the polyvinyl alcohol.
  • the present application provides a modified hexagonal boron nitride, wherein the modified hexagonal boron nitride uses polyethyleneimine as a coating layer;
  • the thickness of the coating layer of the modified hexagonal boron nitride is 4-6 nm, for example, 4.5 nm, 5 nm, 5.5 nm, and the like.
  • the modified hexagonal boron nitride provided in this application is polyethyleneimine-coated hexagonal boron nitride, and the thickness of the coating layer is 4-6 nm.
  • the modified hexagonal boron nitride provided in this application omits the silver nanoparticles
  • the thickness of the cladding layer is reduced, and the thermal conductivity of hexagonal boron nitride is not affected, and the modified hexagonal boron nitride provided in the present application still has good dispersibility in the substrate.
  • the mass percentage content of the polyethyleneimine is 3-5%, such as 3.5%, 4%, 4.5%, and the like.
  • the present application provides a method for preparing the modified hexagonal boron nitride according to the first aspect, the preparation method includes: mixing the hexagonal boron nitride and polyethyleneimine, and then centrifuging, washing, and drying To obtain the modified hexagonal boron nitride.
  • the mass ratio of the hexagonal boron nitride and polyethyleneimine is (9-10): 1, for example, 9.2.1, 9.5: 1, 9.7: 1, and the like.
  • the thickness of the coating layer of the modified hexagonal boron nitride is well controlled in the range of 4-6 nm.
  • the solvent used in the preparation method is a mixed solvent formed by deionized water and anhydrous ethanol at a mass ratio of (4-6): 3, such as 4.5: 3, 5: 3, 5.5: 3, and the like.
  • the mixing includes firstly stirring for 1-3h (for example, 1.5h, 2h, 2.5h, etc.) and then continuously stirring for 23-25h (for example, 23.5h, 24h, 24.5h, etc.).
  • polyethyleneimine can more uniformly cover the surface of hexagonal boron nitride, thereby ensuring that the modified hexagonal boron nitride can be more uniformly dispersed in the polymer matrix.
  • the centrifugation rate is 2000-3000 rpm, such as 2200 rpm, 2500 rpm, 2700 rpm, etc.
  • the centrifugation time is 3-5 min, such as 3.5 min, 4 min, 4.5 min, and the like.
  • This application uses a centrifugation rate of 2000-3000rpm and a centrifugation time of 3-5min.
  • the modified hexagonal boron nitride may be tightly stacked together, or the centrifugation rate may be too fast.
  • the polyethyleneimine adsorbed on the surface of the hexagonal boron nitride was detached from the surface of the hexagonal boron nitride.
  • the drying temperature is 50-60 ° C, such as 52 ° C, 55 ° C, 58 ° C, and the like.
  • the preparation method includes the following steps:
  • Hexagonal boron nitride and polyethyleneimine are mixed at a mass ratio of (9-10): 1, and a mixed solvent formed by deionized water and anhydrous ethanol at a mass ratio of (4-6): 3 is added , After ultrasonic stirring for 1-3h, continue to magnetically stir for 23-25h to obtain a preliminary product of modified hexagonal boron nitride;
  • the modified hexagonal boron nitride preliminary product obtained in step (1) is centrifuged at a centrifugation rate of 2000-3000 rpm, washed to remove polyethyleneimine not coated on the surface of the hexagonal boron nitride, and then at 50-60 ° C. Drying to obtain the modified hexagonal boron nitride.
  • the coating layer of the modified hexagonal boron nitride obtained in this application can be uniformly coated on the surface of the hexagonal boron nitride, and the thickness of the coating layer is in the range of 4-6 nm.
  • the present application provides a thermally conductive polyvinyl alcohol composite material, which is dispersed with the modified hexagonal boron nitride as described in the first aspect.
  • the volume ratio of the modified hexagonal boron nitride to the polyvinyl alcohol is 1: (4-5), such as 1: 4.2, 1: 4.5, 1: 4.7, and the like.
  • the density of the modified hexagonal boron nitride and the polyvinyl alcohol are greatly different, and the filling capacity of the modified hexagonal boron nitride to the polyvinyl alcohol can be better represented by the volume ratio.
  • the present application provides a method for preparing a thermally conductive polyvinyl alcohol composite material according to the third aspect, the preparation method comprising: mixing a formula amount of polyvinyl alcohol and modified hexagonal boron nitride in deionized water, Then defoaming, coating, and drying to obtain the thermally conductive polyvinyl alcohol composite material.
  • the modified hexagonal boron nitride provided in the present application can improve the thermal conductivity of the polymer matrix, and the application uses a coating method to obtain a thermally conductive polyvinyl alcohol composite material.
  • the coating process can make the sheet of modified hexagonal boron nitride along the
  • the orientation of the scraper is beneficial to the formation of the heat conduction network, which can further improve the efficiency of improving the thermal conductivity of the polymer by the modified hexagonal boron nitride.
  • the mass ratio of the polyvinyl alcohol and the deionized water is 1: (8-10), such as 1: 8.5, 1: 9, 1: 9.5, and the like.
  • the mass ratio of polyvinyl alcohol and deionized water is within this range, it has a better dissolving effect.
  • the content of deionized water is small, the resulting solution has a higher viscosity, which may affect the coating process of the material.
  • the content of ion water is large, the viscosity of the solution is too low, which may also affect the subsequent process of the material.
  • the mixing is magnetic stirring at 60-65 ° C (for example, 62 ° C, 63 ° C, 64 ° C, etc.) for 4-5h (for example, 4.2h, 4.5h, 4.7h, etc.).
  • the coating rate is 4-6 mm / s.
  • the slower coating rate (4-6mm / s) selected in this application can result in a more uniform composite film thickness and better orientation of the modified hexagonal boron nitride. If the coating rate is lower than 4mm / s, Will reduce production efficiency.
  • the drying method is to dry in a vacuum oven at 50-60 ° C (for example, 52 ° C, 55 ° C, 58 ° C, etc.) for 5-6h (for example, 5.2h, 5.5h, 5.8h, etc.) , And then dried in a blast oven at 60-70 ° C (for example, 62 ° C, 65 ° C, 68 ° C, etc.) for 10-12h (for example, 10.5h, 11h, 11.5h, etc.).
  • a vacuum oven for example, 52 ° C, 55 ° C, 58 ° C, etc.
  • 5-6h for example, 5.2h, 5.5h, 5.8h, etc.
  • 60-70 ° C for example, 62 ° C, 65 ° C, 68 ° C, etc.
  • 10-12h for example, 10.5h, 11h, 11.5h, etc.
  • the present application provides the application of the thermally conductive polyvinyl alcohol composite material according to the third aspect in an electronic component or an packaging material of an integrated circuit.
  • the thermally conductive polyvinyl alcohol composite material provided by the present application has a high thermal conductivity (greater than 7.4 W ⁇ m -1 K -1 ), which can meet the requirements of electronic components for thermal conductivity.
  • the modified hexagonal boron nitride provided in this application is polyethyleneimine-coated hexagonal boron nitride, and the thickness of the coating layer is 4-6 nm.
  • the modified hexagonal boron nitride provided in this application omits the silver nanometer.
  • the particles also reduced the thickness of the coating layer, did not affect the thermal conductivity of hexagonal boron nitride, and it still has good dispersibility in the polymer substrate;
  • This application selects an optional technical solution so that the coating layer of the modified hexagonal boron nitride can be uniformly coated on the surface of the hexagonal boron nitride, and the coating layer thickness is in the range of 4-6nm;
  • thermal conductivity of the thermally conductive polyvinyl alcohol composite material provided in this application is relatively high, above 7.4 W ⁇ m -1 K -1 , which can meet the requirements for the thermal conductivity of electronic components.
  • a thermally conductive polyvinyl alcohol composite material wherein the volume ratio of modified hexagonal boron nitride to polyvinyl alcohol is 1: 4.
  • the preparation method is as follows:
  • Hexagonal boron nitride and polyethyleneimine are mixed at a mass ratio of 9: 1, and a mixed solvent of deionized water and anhydrous ethanol at a mass ratio of 5: 3 is added, and the magnetic stirring is continued after 2 hours of ultrasonic stirring 24h, the preliminary product of modified hexagonal boron nitride was obtained;
  • step (2) The modified hexagonal boron nitride preliminary product obtained in step (1) is centrifuged at a centrifugal speed of 2500 rpm, washed to remove polyethyleneimine not coated on the surface of the hexagonal boron nitride, and then dried at 50 ° C to obtain Modified hexagonal boron nitride
  • the mass ratio of polyvinyl alcohol to deionized water is 1: 9.
  • Example 1 The difference from Example 1 is only that in step (1), the mass ratio of hexagonal boron nitride and polyethyleneimine is 10: 1.
  • the solvent is a mixed solvent (Example 3) formed by deionized water and anhydrous ethanol at a mass ratio of 4: 3, and the solvent is deionized water and anhydrous.
  • a mixed solvent of ethanol at a mass ratio of 6: 3 (Example 4)
  • a solvent of deionized water and anhydrous ethanol at a mass ratio of 1: 1 (Example 5)
  • a solvent of deionized water and A mixed solvent of anhydrous ethanol at a mass ratio of 7: 3 Example 6
  • Example 7 The difference from Example 1 lies in that in step (1), direct ultrasonication is performed for 26 hours (Example 7), and direct magnetic stirring is performed for 26 hours (Example 8).
  • Example 9 The difference from Example 1 is only that in step (2), the centrifugation rate is 2000 rpm (Example 9), the centrifugation rate is 3000 rpm (Example 10), and the centrifugation rate is 4000 rpm (Example 11).
  • Example 12 The difference from Example 1 is only that in step (3), the coating rate is 4 mm / s (Example 12), the coating rate is 6 mm / s (Example 13), and the coating rate is 8 mm / s ( Example 14).
  • a thermally conductive polyvinyl alcohol composite material wherein the volume ratio of the modified hexagonal boron nitride to the polyvinyl alcohol is 1: 5.
  • the preparation method is as follows:
  • Hexagonal boron nitride and polyethyleneimine are mixed at a mass ratio of 9: 1, and a mixed solvent formed by deionized water and anhydrous ethanol at a mass ratio of 5: 3 is added, and the magnetic stirring is continued for 1 hour. 25h, preliminary product of modified hexagonal boron nitride was obtained;
  • step (2) The modified hexagonal boron nitride preliminary product obtained in step (1) is centrifuged at a centrifugal speed of 2500 rpm, washed to remove polyethyleneimine not coated on the surface of the hexagonal boron nitride, and then dried at 60 ° C to obtain Modified hexagonal boron nitride.
  • the mass ratio of polyvinyl alcohol to deionized water is 1: 8.
  • Example 1 The difference from Example 1 is that the composite material is prepared by directly using the unmodified hexagonal boron nitride and polyvinyl alcohol provided in Example 1 without performing steps (1) and (2).
  • step (1) hexagonal boron nitride and polyethyleneimine are mixed at a mass ratio of 5: 2 (hexagonal boron nitride provided by CN106674603 and polymerized (Mass ratio).
  • Example 1 The difference from Example 1 is that, in this comparative example, in step (1), hexagonal boron nitride and polyethyleneimine were mixed at a mass ratio of 12: 1.
  • Example 1 The difference from Example 1 is only that the coating in step (3) is replaced with a simple film laying (a simple film laying is only necessary to pour the solution directly into the mold).
  • Coating thickness The modified hexagonal boron nitride obtained in Examples 1-15 and Comparative Examples 1-4 was characterized by transmission electron microscopy to determine the coating thickness;
  • Thermal conductivity ⁇ The thermal diffusion coefficient ⁇ (m 2 ⁇ s -1 ) of the material is measured by a laser thermal conductivity meter, the density ⁇ (Kg ⁇ m -3 ) of the material is measured by a density balance, and the differential scanning calorimetry is used.
  • the thickness of the coating layer of the modified hexagonal boron nitride dispersed in the thermally conductive polyvinyl alcohol composite material obtained in this application is in the range of 4-6 nm, and the quality of the coating layer is the modified hexagonal boron nitride 3-5% by mass, and the thermal conductivity of the thermally conductive polyvinyl alcohol composite material obtained in this application is above 7.4W ⁇ m -1 K -1 , which can meet the application requirements; it can be known from Example 1 and Comparative Examples 1-2
  • the thickness of the coating layer of the modified hexagonal boronitride obtained in this application In the range of 4-6nm, when the cladding layer is thick, the thermal conductivity of the composite material decreases.
  • the modified hexagonal boron nitride coating is thicker, but the hexagonal boron nitride is because of the thicker coating.
  • the presence of the layer polymer reduces its thermal conductivity, which in turn affects the thermal conductivity of the composite material. From Example 1 and Comparative Example 3, it can be seen that when the modified hexagonal boron nitride coating is thin, it will affect the modified hexagonal nitrogen. Dispersibility of Boron in the substrate; from Example 1 and Comparative Example 4 Comparison shows that in the preparation of a composite material, using a coating process help to improve the thermal conductivity of the composite material.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)

Abstract

一种改性六方氮化硼及其制备方法和用途，所述改性六方氮化硼以聚乙烯亚胺为包覆层；其中，所述改性六方氮化硼的包覆层厚度为4‑6nm，具有很好的导热性能，且可以在聚合物基底中较好的分散性。

Description

改性六方氮化硼及其制备方法和用途 技术领域
本申请属于改性材料领域，涉及一种改性六方氮化硼及其制备方法和用途。
背景技术
半个多世纪以来，电子元件一直朝着微型化、多功能化发展，功率密度的提高和特征尺寸的减小使得电子元件工作时产生的热量迅速积累，电子设备的温度随之增加，过高的温度会影响设备的正常工作，降低设备的使用寿命。因此，需要开发出新型的高导热复合材料来把电子设备工作产生的热量散发出去。
聚合物材料因为易于加工，机械强度大以及成本低等优点而常被用作电子元件和集成电路的封装材料，然而，因为分子链的随机缠绕和振动增大了光子传输时的散射，增加了界面热阻，使得聚合物本身的热导率低于0.5w·m -1K -1，不能满足电子元件对导热性能的要求；目前常用的解决办法是往聚合物中掺入高导热的无机填料。CN103435895A公开了一种制备绝缘高导热复合材料的方法，其以高密度聚乙烯为基体，添加氮化铝、氧化铝、氮化硼三种不同粒径的导热填料和加工助剂，一并投入在高速机中预混合，进过双螺杆挤出机熔融共混、挤出、造粒，得到颗粒型绝缘高导热复合材料，但此种方法制备得到的复合材料中的无机填料助剂在其中分散并不均匀。
六方氮化硼，具有和石墨相似的层状结构，故又称“白色石墨”，其具有优异的导热性能，另外，禁带宽度为5.6eV使其同时具备良好的绝缘性，六方氮化硼因此成为电子封装领域最有应用前景的导热填料之一。然而六方氮化硼 表面缺乏能发生化学反应的官能团，化学惰性强，与聚合物的相容性较差，不利于在聚合物中的分散性，进而影响导热网络的形成，使得六方氮化硼对聚合物热导率的提升效率较低，因此对其进行表面改性成为制备高导热复合材料的关键。目前改性六方氮化硼的方法主要分为共价改性和非共价改性。共价改性一般分为两步，先是氧化六方氮化硼，引入羟基，然后再接枝上一些复杂的官能团或者分子；CN104892968A公开了一种高导热六方氮化硼/聚酰亚胺复合材料的制备方法，其利用二异氰酸酯、芳香二胺试剂在DMA或DMF溶剂中得到了氨基化的六方氮化硼；这类方法通常会引起六方氮化硼的结构变化，影响其热学/电学性能，而且共价改性会用许多有毒、腐蚀和易挥发的溶剂，对环境不利。相反，对六方氮化硼的非共价改性不会改变其空间结构，可以保留它的原有性能，而且大多数情况下这些过程属于可逆的；非共价改性包括有机物(如多巴胺、聚酰亚胺、硅烷偶联剂)包覆六方氮化硼，在六方氮化硼表面修饰功能无机粒子(如二氧化硅，四氧化三铁)等。CN106189165A公开了一种高导热绝缘六方氮化硼/聚碳酸酯复合材料的制备方法，其先将六方氮化硼在水中超声增加其电负性，然后利用阳离子聚甲基丙烯酰胺对其进行改性，最后加入聚碳酸酯基体中得到复合材料。CN106674603A公开了一种导热六方氮化硼杂化材料，其在六方氮化硼包面包覆有聚合物层，且在聚合物层上负载有银纳米颗粒，虽然导热性较好，但是由于在其中加入了银颗粒，导致成本增加，制备方法较复杂，并且由于热界面材料本身对于绝缘性也有较高要求，引入银纳米颗粒会增加材料的导电性；而去掉银纳米颗粒后的包覆有聚合物的六方氮化硼虽然改善了六方氮化硼在基体中的相容性问题，但是由于在六方氮化硼表面包覆了聚合物层，反而会降低六方氮化硼的导热性，使其不能满足应用要求。
目前需要开发一种新的改性六方氮化硼填料，使其既能满足导热性要求，又可以在基体中很好的分散。
发明内容
以下是对本文详细描述的主题的概述。本概述并非是为了限制权利要求的保护范围。
本申请的目的在于提供一种改性六方氮化硼及其制备方法和用途。在本申请中，在省略了高导热材料(银)且减薄了包覆层的厚度之后，并没有出现本领域技术人员公知预测的省略银会造成导热性能的降低且减少包覆层厚度会造成改性六方氮化硼在材料中的分散性下降的问题，反而本申请提供的改性六方氮化硼在聚乙烯醇基材中可以均匀分散并增加了聚乙烯醇的导热性能。
为达此目的，本申请采用以下技术方案：
第一方面，本申请提供了一种改性六方氮化硼，所述改性六方氮化硼以聚乙烯亚胺为包覆层；
其中，所述改性六方氮化硼的包覆层厚度为4-6nm，例如4.5nm、5nm、5.5nm等。
本申请提供的改性六方氮化硼为聚乙烯亚胺包覆的六方氮化硼，包覆层厚度为4-6nm，本申请提供的改性六方氮化硼在省略了银纳米粒子的同时降低了包覆层的厚度，并没有影响六方氮化硼的导热性能，且本申请提供的改性六方氮化硼在基底中仍然具有较好的分散性。
可选地，在改性六方氮化硼中，所述聚乙烯亚胺的质量百分含量为3-5％，例如3.5％、4％、4.5％等。
第二方面，本申请提供了如第一方面所述的改性六方氮化硼的制备方法，所述制备方法包括：将六方氮化硼和聚乙烯亚胺混合，然后离心、洗涤、烘 干，得到所述改性六方氮化硼。
可选地，所述六方氮化硼和聚乙烯亚胺的质量比为(9-10)∶1，例如9.2∶1、9.5∶1、9.7∶1等。
本申请通过控制六方氮化硼和聚乙烯亚胺的质量比来很好的控制改性六方氮化硼的包覆层厚度在4-6nm范围内。
可选地，所述制备方法使用的溶剂为去离子水与无水乙醇以质量比为(4-6)∶3形成的混合溶剂，例如4.5∶3、5∶3、5.5∶3等。
可选地，所述混合包括先在超声搅拌1-3h(例如1.5h、2h、2.5h等)然后继续磁力搅拌23-25h(例如23.5h、24h、24.5h等)。
本申请通过选用特定的混合溶剂和特定的混合方式可以使聚乙烯亚胺更均匀地包覆在六方氮化硼表面，进而可以确保改性六方氮化硼可以更均匀的分散在聚合物基体中。
可选地，所述离心的速率为2000-3000rpm，例如2200rpm、2500rpm、2700rpm等，所述离心的时间为3-5min，例如3.5min、4min、4.5min等。
本申请选用2000-3000rpm的离心速率和3-5min的离心时间相配合，当离心速率过快时，可能会使改性的六方氮化硼紧密堆叠在一起，也可能会由于离心速率过快使吸附在六方氮化硼表面的聚乙烯亚胺脱离六方氮化硼表面。
可选地，所述烘干的温度为50-60℃，例如52℃、55℃、58℃等。
作为可选技术方案，所述制备方法包括如下步骤：
(1)将六方氮化硼和聚乙烯亚胺按质量比为(9-10)∶1混合，并加入去离子水与无水乙醇以质量比为(4-6)∶3形成的混合溶剂，超声搅拌1-3h后继续磁力搅拌23-25h，得到改性六方氮化硼初步产物；
(2)将步骤(1)得到的改性六方氮化硼初步产物以2000-3000rpm的离心 速率离心，洗涤除去未包覆在六方氮化硼表面的聚乙烯亚胺，然后在50-60℃下烘干得到所述改性六方氮化硼。
当本申请选用可选技术方案时，本申请得到的改性六方氮化硼的包覆层可以很均匀的包覆在六方氮化硼表面，且包覆层厚度在4-6nm范围内。
第三方面，本申请提供了一种导热聚乙烯醇复合材料，所述导热聚乙烯醇复合材料分散有如第一方面所述的改性六方氮化硼。
可选地，在复合材料中，所述改性六方氮化硼与聚乙烯醇的体积比为1∶(4-5)，例如1∶4.2、1∶4.5、1∶4.7等。
在本申请中，改性六方氮化硼与聚乙烯醇的密度相差较大，利用体积比可以更好的体现改性六方氮化硼对聚乙烯醇的填充能力。
第四方面，本申请提供了如第三方面所述的导热聚乙烯醇复合材料的制备方法，所述制备方法包括：将配方量的聚乙烯醇和改性六方氮化硼在去离子水中混合，然后脱泡、涂布、烘干，得到所述导热聚乙烯醇复合材料。
本申请提供的改性六方氮化硼可以提高聚合物基体的导热性能，而本申请采用涂布的方式得到导热聚乙烯醇复合材料，涂布工艺可以使片状的改性六方氮化硼沿刮刀方向取向，有利于导热网络的形成，从而可以进一步提高改性六方氮化硼对聚合物热导率的提升效率。
可选地，所述聚乙烯醇和去离子水的质量比为1∶(8-10)，例如1∶8.5、1∶9、1∶9.5等。
聚乙烯醇和去离子水的质量比在此范围内时，具有较好的溶解效果，当去离子水含量较少时，最后得到的溶液粘度较大，可能会影响材料的涂布等过程，去离子水含量较大时，溶液粘度过低，同样可能会影响材料的后续工艺。
可选地，所述混合为在60-65℃(例如62℃、63℃、64℃等)下磁力搅拌 4-5h(例如4.2h、4.5h、4.7h等)。
可选地，所述涂布的速率为4-6mm/s。例如4.5mm/s、5mm/s、5.5mm/s等。
本申请选用较慢的涂布速率(4-6mm/s)可以是得到的复合材料薄膜厚度更为均一，且改性六方氮化硼的取向更好，若涂布速率低于4mm/s，则会降低生产效率。
可选地，所述烘干的方法为先在50-60℃(例如52℃、55℃、58℃等)的真空烘箱中烘干5-6h(例如5.2h、5.5h、5.8h等)，然后在60-70℃(例如62℃、65℃、68℃等)等的鼓风烘箱中烘干10-12h(例如10.5h、11h、11.5h等)。
第五方面，本申请提供了如第三方面所述的导热聚乙烯醇复合材料在电子元件或集成电路的封装材料中的应用。
本申请提供的导热聚乙烯醇复合材料的热导率较高(大于7.4W·m -1K -1)，可以满足电子元件对导热性能的要求。
相对于相关技术，本申请具有以下有益效果：
(1)本申请提供的改性六方氮化硼为聚乙烯亚胺包覆的六方氮化硼，包覆层厚度为4-6nm，本申请提供的改性六方氮化硼在省略了银纳米粒子的同时降低了包覆层的厚度，并没有影响六方氮化硼的导热性能，且其仍旧在聚合物基底中具有较好的分散性；
(2)本申请通过选用可选技术方案使得到的改性六方氮化硼的包覆层可以很均匀的包覆在六方氮化硼表面，且包覆层厚度在4-6nm范围内；
(3)本申请提供的导热聚乙烯醇复合材料热导率较高，在7.4W·m -1K -1以上，可以满足电子元件对导热性能的要求。
在阅读并理解了详细描述后，可以明白其他方面。
具体实施方式
下面通过具体实施方式来进一步说明本申请的技术方案。本领域技术人员应该明了，所述实施例仅仅是帮助理解本申请，不应视为对本申请的具体限制。
实施例1
一种导热聚乙烯醇复合材料，其中改性六方氮化硼与聚乙烯醇的体积比为1∶4。
制备方法如下：
(1)将六方氮化硼和聚乙烯亚胺按质量比为9∶1混合，并加入去离子水与无水乙醇以质量比为5∶3形成的混合溶剂，超声搅拌2h后继续磁力搅拌24h，得到改性六方氮化硼初步产物；
(2)将步骤(1)得到的改性六方氮化硼初步产物以2500rpm的离心速率离心，洗涤除去未包覆在六方氮化硼表面的聚乙烯亚胺，然后在50℃下烘干得到改性六方氮化硼；
(3)将配方量的聚乙烯醇和改性六方氮化硼和去离子水在65℃下磁力搅拌4h，然后脱泡、在5mm/s的速率下涂布，然后先在50℃的真空烘箱中烘干6h，然后在60℃的鼓风烘箱中烘干10h，得到导热聚乙烯醇复合材料；
其中，聚乙烯醇和去离子水的质量比为1∶9。
实施例2
与实施例1的区别仅在于，在步骤(1)中，六方氮化硼和聚乙烯亚胺的质量比为10∶1。
实施例3-6
与实施例1的区别仅在于，在步骤(1)中，溶剂为去离子水与无水乙醇以质量比为4∶3形成的混合溶剂(实施例3)、溶剂为去离子水与无水乙醇以质量比为6∶3形成的混合溶剂(实施例4)、溶剂为去离子水与无水乙醇以质量比为1∶1形成的混合溶剂(实施例5)、溶剂为去离子水与无水乙醇以质量比为7∶3形成的混合溶剂(实施例6)。
实施例7-8
与实施例1的区别仅在于，在步骤(1)中，直接超声26h(实施例7)、直接磁力搅拌26h(实施例8)。
实施例9-11
与实施例1的区别仅在于，在步骤(2)中，离心速率为2000rpm(实施例9)、离心速率为3000rpm(实施例10)、离心速率为4000rpm(实施例11)。
实施例12-14
与实施例1的区别仅在于，在步骤(3)中，涂布速率为4mm/s(实施例12)、涂布速率为6mm/s(实施例13)、涂布速率为8mm/s(实施例14)。
实施例15
一种导热聚乙烯醇复合材料，其中改性六方氮化硼与聚乙烯醇的体积比为1∶5。
制备方法如下：
(1)将六方氮化硼和聚乙烯亚胺按质量比为9∶1混合，并加入去离子水与无水乙醇以质量比为5∶3形成的混合溶剂，超声搅拌1h后继续磁力搅拌25h，得到改性六方氮化硼初步产物；
(2)将步骤(1)得到的改性六方氮化硼初步产物以2500rpm的离心速率离心，洗涤除去未包覆在六方氮化硼表面的聚乙烯亚胺，然后在60℃下烘干得 到改性六方氮化硼。
(3)将配方量的聚乙烯醇和改性六方氮化硼和去离子水在60℃下磁力搅拌5h，然后脱泡、在5mm/s的速率下涂布，然后先在60℃的真空烘箱中烘干5h，然后在70℃的鼓风烘箱中烘干12h，得到导热聚乙烯醇复合材料；
其中，聚乙烯醇和去离子水的质量比为1∶8。
对比例1
与实施例1的区别仅在于，不进行步骤(1)、(2)，直接利用实施例1提供的未改性的六方氮化硼与聚乙烯醇制备成复合材料。
对比例2
与实施例1的区别仅在于，在本对比例中，在步骤(1)中，六方氮化硼和聚乙烯亚胺按质量比为5∶2进行混合(CN106674603提供的六方氮化硼与聚合物的质量比)。
对比例3
与实施例1的区别仅在于，在本对比例中，在步骤(1)中，六方氮化硼和聚乙烯亚胺按质量比为12∶1进行混合。
对比例4
与实施例1的区别仅在于，将步骤(3)涂布替换为简单铺膜(简单铺膜为将溶液直接倒入模具中即可)。
性能测试
对实施例1-15和对比例1-4提供的改性六方氮化硼和导热聚乙烯醇复合材料进行性能测试：
(1)包覆层厚度：对实施例1-15和对比例1-4得到的改性六方氮化硼进行 透射电镜表征，确定包覆层厚度；
(2)包覆层质量：利用热重分析仪进行测试；
(3)包覆层是否均匀包覆：利用TEM观察改性六方氮化硼的包覆层厚度是否均匀：
(4)热导率λ：利用激光导热仪测试材料的热扩散系数α(m 2·s -1)，利用密度天平测试材料的密度ρ(Kg·m -3)，利用差示扫描量热仪测试材料的比热容c(J·Kg -1·K -1)，其中，由下述公式计算热导率：
λ＝α·ρ·c
性能测试结果见表1：
表1
Figure PCTCN2018125304-appb-000001
Figure PCTCN2018125304-appb-000002
通过实验和性能测试可知，本申请得到的导热聚乙烯醇复合材料中分散的改性六方氮化硼的包覆层厚度在4-6nm范围内，包覆层的质量为改性六方氮化硼质量的3-5％，且本申请得到的导热聚乙烯醇复合材料的热导率在7.4W·m -1K -1以上，可以满足应用要求；由实施例1和对比例1-2可知，在制备改性六方氮化硼过程中，六方氮化硼和聚乙烯亚胺的质量比在本申请提供的质量比范围内时，本申请得到的改性六方氮化硼的包覆层厚度在4-6nm范围内，当包覆层较厚时，复合材料的导热性能降低，推测可能的原因是改性六方氮化硼包覆层较厚，六方氮化硼反而因为较厚的包覆层聚合物的存在使其导热性能下降，进而影响了复合材料的导热性能；由实施例1和对比例3可知，当改性六方氮化硼包覆层较薄时，会影响改性六方氮化硼在基材中的分散性；由实施例1和对比例4的对比可知，在制备复合材料时，采用涂布工艺有利于复合材料热导率的提高。
申请人声明，本申请通过上述实施例来说明本申请的改性六方氮化硼及其 制备方法和用途，但本申请并不局限于上述详细方法，即不意味着本申请必须依赖上述详细方法才能实施。

Claims (12)

  1. 一种改性六方氮化硼，其中，所述改性六方氮化硼包括六方氮化硼，以及包覆在所述六方氮化硼外侧的聚乙烯亚胺包覆层；
    所述改性六方氮化硼的包覆层厚度为4-6nm。
  2. 根据权利要求1所述的改性六方氮化硼，其中，在改性六方氮化硼中，所述聚乙烯亚胺的质量百分含量为3-5％。
  3. 根据权利要求1或2所述的改性六方氮化硼的制备方法，其中，所述制备方法包括：将六方氮化硼和聚乙烯亚胺混合，然后离心、洗涤、烘干，得到所述改性六方氮化硼；
    所述六方氮化硼和聚乙烯亚胺的质量比为(9-10)∶1。
  4. 根据权利要求3所述的制备方法，其中，所述制备方法使用的溶剂为去离子水与无水乙醇以质量比为(4-6)∶3形成的混合溶剂；
    可选地，所述混合包括先在超声搅拌1-3h然后继续磁力搅拌23-25h。
  5. 根据权利要求3或4所述的制备方法，其中，所述离心的速率为2000-3000rpm，所述离心的时间为3-5min；
    可选地，所述烘干的温度为50-60℃。
  6. 根据权利要求3-5中的任一项所述的制备方法，其中，所述制备方法包括如下步骤：
    (1)将六方氮化硼和聚乙烯亚胺按质量比为(9-10)∶1混合，并加入去离子水与无水乙醇以质量比为(4-6)∶3形成的混合溶剂，超声搅拌1-3h后继续磁力搅拌23-25h，得到改性六方氮化硼初步产物；
    (2)将步骤(1)得到的改性六方氮化硼初步产物以2000-3000rpm的离心速率离心，洗涤除去未包覆在六方氮化硼表面的聚乙烯亚胺，然后在50-60℃下烘干得到所述改性六方氮化硼。
  7. 一种导热聚乙烯醇复合材料，其中，所述导热聚乙烯醇复合材料分散有权利要求1或2所述的改性六方氮化硼。
  8. 根据权利要求7所述的导热聚乙烯醇复合材料，其中，在复合材料中，所述改性六方氮化硼与聚乙烯醇的体积比为1∶(4-5)。
  9. 根据权利要求7或8所述的导热聚乙烯醇复合材料的制备方法，其中，所述制备方法包括：将配方量的聚乙烯醇和改性六方氮化硼在去离子水中混合，然后脱泡、涂布、烘干，得到所述导热聚乙烯醇复合材料。
  10. 根据权利要求9所述的制备方法，其中，所述聚乙烯醇和去离子水的质量比为1∶(8-10)。
  11. 根据权利要求9或10所述的制备方法，其中，所述涂布的速率为4-6mm/s；
    可选地，所述混合为在60-65℃下磁力搅拌4-5h；
    可选地，所述烘干的方法为先在50-60℃的真空烘箱中烘干5-6h，然后在60-70℃的鼓风烘箱中烘干10-12h。
  12. 根据权利要求7或8所述的导热聚乙烯醇复合材料在电子元件或集成电路的封装材料中的应用。
PCT/CN2018/125304 2018-08-07 2018-12-29 改性六方氮化硼及其制备方法和用途 WO2020029533A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201810890654.4 2018-08-07
CN201810890654.4A CN109161051B (zh) 2018-08-07 2018-08-07 改性六方氮化硼及其制备方法和用途

Publications (1)

Publication Number Publication Date
WO2020029533A1 true WO2020029533A1 (zh) 2020-02-13

Family

ID=64895205

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2018/125304 WO2020029533A1 (zh) 2018-08-07 2018-12-29 改性六方氮化硼及其制备方法和用途

Country Status (2)

Country Link
CN (1) CN109161051B (zh)
WO (1) WO2020029533A1 (zh)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115491785B (zh) * 2022-09-09 2023-12-15 江苏三联新材料股份有限公司 一种多组分功能纤维的制备方法
CN116143526B (zh) * 2022-12-30 2023-12-08 新化县顺达电子陶瓷有限公司 一种高导热5g信号基站用陶瓷材料

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103849008A (zh) * 2012-11-29 2014-06-11 深圳先进技术研究院 杂化颗粒、聚合物基复合材料及其制备方法与应用
CN105461963A (zh) * 2014-09-11 2016-04-06 佛山市三水金戈新型材料有限公司 一种表面有机改性的氮化硼粉体及其制备方法和应用
CN106674603A (zh) * 2016-12-29 2017-05-17 中国科学院深圳先进技术研究院 导热六方氮化硼杂化材料及其制备方法与应用
CN106832751A (zh) * 2016-12-30 2017-06-13 梅庆波 一种高导热绝缘材料的制备方法
CN107189348A (zh) * 2017-05-11 2017-09-22 华中科技大学 一种环氧树脂导热复合材料及其制备与应用

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8105690B2 (en) * 1998-03-03 2012-01-31 Ppg Industries Ohio, Inc Fiber product coated with particles to adjust the friction of the coating and the interfilament bonding
CN101503560B (zh) * 2009-01-16 2012-02-22 上海师范大学 一种碳纳米管/聚合物/金属硫化物纳米复合材料的制备方法
WO2012027194A2 (en) * 2010-08-25 2012-03-01 Saint-Gobain Ceramics And Plastics, Inc. Boron nitride with attached mettalic particles, methods of making, and uses thereof
KR101328495B1 (ko) * 2011-12-28 2013-11-13 전자부품연구원 음이온성 고분자가 표면처리된 세라믹 입자 및 표면처리방법
CN107200815B (zh) * 2017-05-05 2019-02-12 常州大学 一种SiO2微胶囊改性水性丙烯酸防腐乳液的制备工艺

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103849008A (zh) * 2012-11-29 2014-06-11 深圳先进技术研究院 杂化颗粒、聚合物基复合材料及其制备方法与应用
CN105461963A (zh) * 2014-09-11 2016-04-06 佛山市三水金戈新型材料有限公司 一种表面有机改性的氮化硼粉体及其制备方法和应用
CN106674603A (zh) * 2016-12-29 2017-05-17 中国科学院深圳先进技术研究院 导热六方氮化硼杂化材料及其制备方法与应用
CN106832751A (zh) * 2016-12-30 2017-06-13 梅庆波 一种高导热绝缘材料的制备方法
CN107189348A (zh) * 2017-05-11 2017-09-22 华中科技大学 一种环氧树脂导热复合材料及其制备与应用

Also Published As

Publication number Publication date
CN109161051A (zh) 2019-01-08
CN109161051B (zh) 2020-08-28

Similar Documents

Publication Publication Date Title
WO2022104949A1 (zh) 导热复合材料及其制备方法
Han et al. A hybrid material approach toward solution‐processable dielectrics exhibiting enhanced breakdown strength and high energy density
Guo et al. High thermal conductive poly (vinylidene fluoride)-based composites with well-dispersed carbon nanotubes/graphene three-dimensional network structure via reduced interfacial thermal resistance
Zhang et al. Improved thermal and electrical properties of epoxy resin composites by dopamine and silane coupling agent modified hexagonal BN
Cheng et al. Low dielectric polyimide/fluorinated ethylene propylene (PI/FEP) nanocomposite film for high‐frequency flexible circuit board application
Hosier et al. The effects of water on the dielectric properties of silicon-based nanocomposites
CN104830031B (zh) 一种兼具导热和抗静电特性的环氧树脂复合材料及其制备方法
Li et al. Electrically insulating ZnOs/ZnOw/silicone rubber nanocomposites with enhanced thermal conductivity and mechanical properties
WO2020029533A1 (zh) 改性六方氮化硼及其制备方法和用途
CN106519516B (zh) 一种基于石蜡包覆钛酸钡纳米颗粒的介电复合材料及其制备方法
George et al. Influence of matrix polarity on the properties of ethylene vinyl acetate–carbon nanofiller nanocomposites
CN112011137A (zh) 一种石墨烯/水溶性聚合物复合材料及其制备方法
Liu et al. In-situ construction of dense thermal conduction networks endow the polymeric composites with advanced thermal management capability and superior dielectric properties
Tang et al. High-temperature-resistant barium strontium titanate@ Ag/poly (arylene ether nitrile) composites with enhanced dielectric performance and high mechanical strength
Ji et al. Mussel inspired interfacial modification of boron nitride/carbon nanotubes hybrid fillers for epoxy composites with improved thermal conductivity and electrical insulation properties
CN115710394A (zh) 一种抗静电聚乙烯复合材料及其制备方法和应用
Li et al. Conducting and stretchable emulsion styrene butadiene rubber composites using SiO2@ Ag core-shell particles and polydopamine coated carbon nanotubes
WO2022242132A1 (zh) 一种电池隔膜用材料、材料制备方法及电池隔膜
WO2024140413A1 (zh) 一种高抗冲聚苯乙烯复合材料及其制备方法和制品
Zhang et al. Improved mechanical, thermal properties and ideal dielectric properties of polyimide composite films by incorporation of boron nitride nanosheets and aramid nanofibers
Yi et al. Antioxidating and reinforcing effect of polydopamine functionalized silica on natural rubber latex films
Yu et al. Improved dispersion and interfacial interaction of SiO2@ polydopamine fillers in polytetrafluoroethylene composites for reduced thermal expansion and suppressed dielectric deterioration
You et al. Enhanced thermal conductivity in boron nitride incorporated polyethylene/polymethyl methacrylate composites via double percolation structure
JP4264804B2 (ja) 導電性樹脂組成物
Zeng et al. Preparation and characterization of CNTs/CaCu3Ti4O12/silicone rubber composites with improved dielectric and mechanical properties

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18929539

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18929539

Country of ref document: EP

Kind code of ref document: A1

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 12-07-2021)

122 Ep: pct application non-entry in european phase

Ref document number: 18929539

Country of ref document: EP

Kind code of ref document: A1