WO2020037902A1 - Preparation method of high-dispersion graphene-based heat conductive silica gel - Google Patents

Preparation method of high-dispersion graphene-based heat conductive silica gel Download PDF

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WO2020037902A1
WO2020037902A1 PCT/CN2018/121697 CN2018121697W WO2020037902A1 WO 2020037902 A1 WO2020037902 A1 WO 2020037902A1 CN 2018121697 W CN2018121697 W CN 2018121697W WO 2020037902 A1 WO2020037902 A1 WO 2020037902A1
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graphene
solution
silica gel
coupling agent
thermally conductive
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French (fr)
Chinese (zh)
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文芳
杨波
李悦
黄国家
张双红
翟伟
***
郭华超
李爽
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广州特种承压设备检测研究院
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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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • 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
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic
    • 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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  • the invention relates to the field of thermally conductive materials, in particular to a method for preparing a highly dispersed graphene-based thermally conductive silica gel.
  • thermal silica gel As a kind of elastic material between the heat source and the heat sink, thermal silica gel has the important function of expelling air and speeding up heat dissipation. It has good heat dissipation, shock absorption, chemical resistance, and a wide operating temperature (-90 ⁇ 250 °C). ), Can maintain flexibility and stability in extreme and harsh environments, and is very suitable for flexible bonding, positioning, heat dissipation, insulation and insulation of LED lighting, electromagnetic shielding, electronic information, communication equipment, aerospace, automotive and household appliances. Sealed for use.
  • Thermally conductive silica gel usually needs to be filled with a high thermal conductivity filler into the polysiloxane polymer matrix to form a uniformly dispersed system to obtain high thermal conductivity.
  • Common fillers are metals, metal oxides and nitrides, and these traditional The thermal conductivity of the filler can no longer meet the requirements of the market for thermal management materials. Excessive filling amount will also affect the mechanical properties of the silicone.
  • graphene As a new type of thermally conductive filler, graphene has a two-dimensional honeycomb structure formed by the deposition of a single layer of sp 2 hybrid carbon atoms. The thickness of a single layer is only 0.335 nm, and the specific surface area can reach 2630 m 2 ⁇ g -1 . The thinnest and hardest nanomaterial, with the advantages of ultra-high carrier mobility, excellent thermal conductivity, high specific surface area and high flexibility. Graphene only absorbs 2.3% of light. The conductivity is as high as 5300W / (m ⁇ K), so using graphene to fill the silica gel matrix can prepare high thermal conductivity materials, which have far better thermal conductivity than other fillers, and have broad application prospects.
  • thermally conductive fillers prepared by virtue of the synergistic effect between thermally conductive fillers are beneficial to improve the thermal conductivity of thermally conductive silica gel, but existing research cannot fully utilize graphite. Synergistic mechanism between ene and other thermally conductive fillers. 4. Among aluminas with different morphologies, spherical alumina is used as a filler to prepare the thermally conductive silica gel with the best thermal conductivity.
  • the preparation methods of spherical alumina include sol-gel method, drop-ball method, template method, etc.
  • the spherical alumina prepared by the gel method has a wide range of particle diameters, high sphericity, and good dispersibility, but has serious agglomeration after sintering.
  • the drop ball method is a further improvement of the sol-emulsion-gel method in the process.
  • Alumina has high purity and best dispersibility, but has a narrow size range and usually large particle size.
  • the template method is suitable for preparing hollow spheres, which requires higher template agents, has more steps in the preparation process, and has a higher cost.
  • the object of the present invention is to provide a method for preparing a highly dispersed graphene-based thermally conductive silica gel, which can improve the dispersibility of graphene as a thermally conductive filler and improve its thermal conductivity.
  • the object of the present invention is achieved by the following technical scheme: a method for preparing a highly dispersed graphene-based thermally conductive silica gel, including the following steps:
  • the dispersibility of thermally conductive fillers exerts its thermal conductivity.
  • the principle is as follows: The surface of graphene oxide is negatively charged because it is rich in -OH and -COOH, and combines with positively charged Al 3+ with a strong ionic bond, so that Al 3+ is uniformly loaded on the surface of graphene oxide; After adding the precipitant, Al 3+ deposits Al 2 O 3 on the surface of graphene oxide by coordination bond force; after calcination at high temperature, graphene oxide is reduced to form graphene, and electrostatic force is exerted on Al 2 O 3 Combined to form a composite product with good dispersibility and thermal conductivity.
  • graphene forms a bridge structure between Al 2 O 3 particles to form a graphene / Al 2 O 3 composite filler in a polymer matrix.
  • the close-packed structure can promote the formation of a thermally conductive mesh chain structure and reduce the interface thermal resistance, thereby improving the thermal conductivity of the thermally conductive silica gel.
  • Al 2 O 3 adheres uniformly to the surface of graphene, which can not only utilize the excellent thermal conductivity of graphene, but also improve the thermal conductivity of Al 2 O 3 as a single filler.
  • the defect that the rate is not high, and at the same time, the electrical insulation of Al 2 O 3 can be used to prevent the composite material from reaching the threshold of the electroosmotic flow and obtain a better synergy effect.
  • the present invention uses a uniform precipitation method to prepare spherical alumina powder, which has the advantages of low raw material cost, simple process, simple operation, and low equipment requirements.
  • a mass ratio of graphene to Al 2 O 3 is 1: (10 to 40). If the content of graphene is too large, it is difficult to ensure the dispersibility of graphene in the composite conductive filler. If the dispersibility of graphene cannot be guaranteed, it will cause the prepared thermal silica gel to form voids and greatly reduce the thermal conductivity. Too much, it is difficult to ensure the insulation of the composite conductive filler, because graphene has good electrical conductivity, and its excessive content will reduce the insulation; if the graphene content is too small, it is difficult to improve the thermal conductivity of the thermally conductive silica gel.
  • the optimal mass ratio of graphene to Al 2 O 3 is 1:30.
  • step S1 the ratio of the concentration of the precipitating agent in the B solution to the concentration of the aluminum salt in the A solution is (2-6): 1. If the amount of the precipitant is too large, insolubility is likely to occur; if the amount of the precipitant is too small, it is difficult to ensure the complete precipitation of aluminum ions, and other impurities may be generated.
  • the precipitant is preferably ammonium bicarbonate, ammonium carbonate, urea or hexamethylenetetramine.
  • the aluminum salt is preferably aluminum sulfate, ammonium aluminum sulfate, or potassium potassium sulfate dodecahydrate.
  • step S1 during the mixing of the A solution and the B solution, an alkaline solution is added to control the pH to be 5 to 9, and the mixture is stirred at 70 to 110 ° C for 30 to 50 hours.
  • the alkaline solution is preferably ammonia water, sodium hydroxide solution or sodium carbonate solution.
  • step S1 the calcining process is as follows: firstly, pre-calcining at 300-500 ° C for 3-8 hours in an argon atmosphere; and grinding and then calcining at 900-1500 ° C for 2-5 hours in an argon atmosphere.
  • the coupling agent solution is prepared by dissolving the coupling agent in ethanol, and the volume fraction of the coupling agent is 1-8%.
  • the coupling agent is preferably a silane coupling agent, and specifically may be ⁇ - (methacryloyloxy) propyltrimethoxysilane, ⁇ - (2,3-glycidoxy) propyltrimethoxysilane, Any of ⁇ - (methacryloyloxy) propyltrimethoxysilane.
  • the mass ratio of the graphene / Al 2 O 3 composite filler to the coupling agent is 100: (1-20).
  • the thermal conductivity of the coupling agent is poor. It acts to couple the filler and the polymer matrix and reduce the interface thermal resistance. If the amount of the coupling agent is too large, the proportion will be too low to reduce the thermal conductivity; if the amount of the coupling agent is too small, then It is difficult to achieve effective coupling between the filler and the matrix, which increases the interface thermal resistance.
  • step S2 before adding the graphene / Al 2 O 3 composite filler to the coupling agent solution, first add glacial acetic acid to control the pH to be 3-5.
  • the mass ratio of the coupling agent-modified graphene / Al 2 O 3 composite filler, the silicone rubber matrix, and the auxiliary agent is (45 to 65): (51 to 27): (4 to 8). ). Too much filler is likely to cause uneven dispersion and form voids; too little filler is difficult to effectively improve the thermal conductivity of thermally conductive silica gel.
  • the material obtained at the above ratio has good thermal conductivity.
  • the mass ratio of the graphene / Al 2 O 3 composite filler, the silicone rubber matrix and the additive is 60: 35: 5, the material has the best thermal conductivity.
  • the silicone rubber matrix is preferably a methyl vinyl silicone rubber, a dimethyl silicone rubber, or a methylphenyl vinyl silicone rubber.
  • the auxiliary agent may be a structure control agent, a reinforcing agent, a vulcanizing agent, or a catalyst.
  • the structure control agent is preferably a hydroxy silicone oil, methylphenylmethoxy silicone oil or methyl hydroxy silicone oil.
  • the reinforcing agent is preferably fumed silica, kaolin, quartz powder, calcium silicate, zirconium silicate, zinc oxide or iron oxide.
  • the vulcanizing agent is preferably benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di-tert-butyl peroxide. alkyl.
  • the catalyst is preferably a platinum catalyst or an isopropanol solution of chloroplatinic acid.
  • step S3 is specifically: adding the coupling agent-modified graphene / Al 2 O 3 composite filler, a silicone rubber matrix, and an auxiliary agent to a high-speed open mill, vacuum mixing for 3 to 6 hours, and thinning 2 to 6 hours. Five times, and then using a vulcanization apparatus at 120 to 300 ° C. for 3 to 8 hours to obtain a highly dispersed graphene-based thermal silica gel.
  • FIG. 1 is a SEM image of the graphene / Al 2 O 3 composite filler in Example 1.
  • FIG. 1 is a SEM image of the graphene / Al 2 O 3 composite filler in Example 1.
  • the invention provides a method for preparing a high-dispersion graphene-based thermal silica gel, including the following steps:
  • a precipitant is weighed to prepare a solution having a concentration of 0.1 to 5 mol / L
  • the ratio of the concentration of the precipitating agent to the concentration of the aluminum salt is (2-6): 1, and ethylene glycol polymer is added as a dispersant at a concentration of 0.1-10% to form a B solution; and then the A solution and the B solution are mixed
  • control the solution pH to 5-9 maintain the temperature at 70-110 ° C, and stir for 30-50 hours to obtain a gray precipitate; then filter the gray precipitate with deionized water and It is washed 3 to 6 times with anhydrous ethanol, dried and pre-fired at 300-500 ° C for 3-8 hours in an argon atmosphere. After grinding, it is calcined at 900-1500 ° C for 2-5 hours in an argon atmosphere.
  • a graphene / Al 2 O 3 composite filler was obtained.
  • the reaction fully obtained a gray precipitate, washed 3 times with deionized water and absolute ethanol, and dried for 3 hours at 300 ° C in an argon atmosphere after drying. It was calcined in an argon atmosphere at 1000 ° C. for 2 h to obtain a graphene / Al 2 O 3 composite filler.
  • reaction fully obtained a gray precipitate, washed 4 times with deionized water and absolute ethanol, dried at 350 ° C in an argon atmosphere for 5 hours, and then placed after grinding. It was calcined in an argon atmosphere at 1100 ° C for 3 hours to obtain a graphene / Al 2 O 3 composite filler.
  • a method for preparing a high-dispersion graphene-based thermal silica gel of this comparative example includes the following steps:
  • a method for preparing a high-dispersion graphene-based thermal silica gel of this comparative example includes the following steps:
  • a method for preparing a high-dispersion graphene-based thermal silica gel of this comparative example includes the following steps:
  • FIG. 1 is a SEM image of the graphene / Al 2 O 3 composite filler in Example 1.
  • the graphene sheet is thin, showing a yarn shape, and has high dispersibility;
  • Al 2 O 3 is a spherical nanoparticle uniformly dispersed in the graphene sheet;
  • graphene and Al 2 O 3 particles Closely fit, the two cooperate with each other to form a uniformly dispersed composite filler.
  • graphene forms a bridge structure between Al 2 O 3 particles, forming a tight packing of the graphene / Al 2 O 3 composite filler in the polymer matrix.
  • the structure can promote the formation of a thermally conductive mesh chain structure, reduce the interface thermal resistance, and thereby improve the thermal conductivity of the thermally conductive silica gel.
  • Al 2 O 3 is evenly attached to the surface of graphene, which can not only utilize the excellent thermal conductivity of graphene, improve the defect of low thermal conductivity of Al 2 O 3 as a single filler, but also use the electrical insulation of Al 2 O 3 . Prevent the composite material from reaching the electroosmotic threshold and obtain better synergistic effects.
  • the invention uses a uniform precipitation method to prepare spherical alumina powder, which has the advantages of low raw material cost, simple process, simple operation, and low requirements on equipment.

Abstract

The invention relates to the preparation method for a high-dispersion graphene-based heat conductive silica gel, comprising: (1) adding a graphite oxide into water, and ultrasonically dispersing to form a graphene oxide aqueous suspension; adding an aluminum salt into the graphene oxide aqueous suspension, and ultrasonically dispersing to form a solution A; preparing a precipitant solution, and adding a dispersing agent to form a solution B; mixing the solutions A and B, stirring to give a grey precipitate, and then filtering, washing, drying and calcining the grey precipitate to give a graphene/Al 2O 3 composite filler; (2) preparing a coupling agent solution, adding the graphene/Al 2O 3 composite filler, stirring, filtering, washing, and drying to give a graphene/Al 2O 3 composite filler modified by the coupling agent; (3) mixing the graphene/Al 2O 3 composite filler modified by the coupling agent with a silicone rubber matrix and an auxiliary, and then vulcanizing to give the high-dispersion graphene-based heat conductive silica gel. The invention can improve the dispersibility of the graphene as a heat conductive filler and improve its heat conductivity.

Description

一种高分散石墨烯基导热硅胶的制备方法Preparation method of high-dispersion graphene-based thermal silica gel 技术领域Technical field
本发明涉及导热材料领域，尤其涉及一种高分散石墨烯基导热硅胶的制备方法。The invention relates to the field of thermally conductive materials, in particular to a method for preparing a highly dispersed graphene-based thermally conductive silica gel.
背景技术Background technique
随着半导体、电子元器件不断往微型化、轻型化和高效化方向发展，热困扰问题加剧，迫切需要良好的散热措施来解决。导热硅胶作为一种填充热源和散热器之间的弹性材料，具有驱逐空气和加快散热的重要作用，其良好的散热、减震、耐化学腐蚀性和较宽的使用温度(-90～250℃)，能在极限和苛刻环境中保持弹性和使用稳定性，非常适合LED照明、电磁屏蔽、电子信息、通讯设备、航空航天、汽车和家用电器等领域的弹性粘接、定位、散热、绝缘及密封使用。With the continuous development of semiconductors and electronic components in the direction of miniaturization, lightness and efficiency, the problem of thermal distress has intensified, and good heat dissipation measures are urgently needed to solve it. As a kind of elastic material between the heat source and the heat sink, thermal silica gel has the important function of expelling air and speeding up heat dissipation. It has good heat dissipation, shock absorption, chemical resistance, and a wide operating temperature (-90 ～ 250 ℃). ), Can maintain flexibility and stability in extreme and harsh environments, and is very suitable for flexible bonding, positioning, heat dissipation, insulation and insulation of LED lighting, electromagnetic shielding, electronic information, communication equipment, aerospace, automotive and household appliances. Sealed for use.
导热硅胶通常需要应用导热性良好的填料填充到聚硅氧烷高分子基体中，形成均匀分散的体系，以获得高导热性，常用的填料为金属、金属氧化物及氮化物等，而这些传统填料的导热性已不能满足现在市场对热管理材料的要求，过多的填充量也会影响硅胶的机械性能。Thermally conductive silica gel usually needs to be filled with a high thermal conductivity filler into the polysiloxane polymer matrix to form a uniformly dispersed system to obtain high thermal conductivity. Common fillers are metals, metal oxides and nitrides, and these traditional The thermal conductivity of the filler can no longer meet the requirements of the market for thermal management materials. Excessive filling amount will also affect the mechanical properties of the silicone.
石墨烯作为一种新型导热填料，具有单层sp 2杂化的碳原子堆积形成的二维蜂窝状结构，单层厚度仅为0.335nm，比表面积可达2630m 2·g -1，是世界上最薄、也是最坚硬的纳米材料，具有超高的载流子迁移率、优异的热导率、高比表面积和高柔韧性等优点，石墨烯仅吸收2.3％的光，单层石墨烯热导率高达5300W/(m·K)，因此采用石墨烯填充到硅胶基体中，可以制备出高导热性材料，导热性能远远优于其他填料，具有广阔的应用前景。 As a new type of thermally conductive filler, graphene has a two-dimensional honeycomb structure formed by the deposition of a single layer of sp 2 hybrid carbon atoms. The thickness of a single layer is only 0.335 nm, and the specific surface area can reach 2630 m 2 · g -1 . The thinnest and hardest nanomaterial, with the advantages of ultra-high carrier mobility, excellent thermal conductivity, high specific surface area and high flexibility. Graphene only absorbs 2.3% of light. The conductivity is as high as 5300W / (m · K), so using graphene to fill the silica gel matrix can prepare high thermal conductivity materials, which have far better thermal conductivity than other fillers, and have broad application prospects.
但是，目前石墨烯基导热硅胶面临的问题是：1、石墨烯极容易团聚，在填充基体内部会因为团聚而影响导热通路的形成，这是由于石墨烯比表面积较大，导致其具有较高的表面能，在分散过程中容易发生缠绕和团聚，很难与其他材料形成均匀的分散体系，石墨烯层数越少，其导热性能越好，因此石墨烯在基体中的分散性问题严重影响石墨烯基导热硅胶的导热性能。2、单独采用石墨烯填充导热硅胶，填料与基体界面之间存在一定的空隙，内部热量传输过程中，界面作用引起界面热阻，直接影响体系的热导率。3、不同材质，不同尺寸，不同维度的导热填料相互混杂，凭借导热填料间的协同效应制备出的导热填料，有利于提升导热硅胶的热导率，但是现有的研究并不能完全发挥出石墨烯与其他导热填料间的协同机制。4、不同形貌的氧化铝中，球形氧化铝作为填料所制备的导热硅胶具有最佳的导热性能，球形氧化铝的制备方法主要有溶胶凝胶法、滴球法、模板法等，采用溶胶凝胶法制备的球形氧化铝，粒径范围较广，球形率高，分散性较好，但是烧结后团聚严重；滴球法是对溶胶-乳液-凝胶法在 工艺上的进一步改进，制备的氧化铝纯度高，分散性最好，但是尺寸范围窄，通常粒径较大；模板法适用于制备空心球体，其对模板剂的要求较高，制备过程步骤多，成本较高。However, the current problems of graphene-based thermally conductive silica gel are: 1. Graphene is extremely easy to agglomerate, and it will affect the formation of thermal conduction paths due to agglomeration in the filled matrix. This is because graphene has a large specific surface area, which leads to its high Surface energy, easy to entangle and agglomerate during the dispersion process, it is difficult to form a uniform dispersion system with other materials, the fewer the number of graphene layers, the better its thermal conductivity, so the problem of graphene dispersion in the matrix is seriously affected Thermal conductivity of graphene-based thermal silica. 2. Graphene alone is used to fill the thermally conductive silica gel. There is a certain gap between the filler and the substrate interface. During the internal heat transfer process, the interface action causes the interface thermal resistance, which directly affects the thermal conductivity of the system. 3. Different materials, different sizes, and different dimensions of thermally conductive fillers are mixed with each other. The thermally conductive fillers prepared by virtue of the synergistic effect between thermally conductive fillers are beneficial to improve the thermal conductivity of thermally conductive silica gel, but existing research cannot fully utilize graphite. Synergistic mechanism between ene and other thermally conductive fillers. 4. Among aluminas with different morphologies, spherical alumina is used as a filler to prepare the thermally conductive silica gel with the best thermal conductivity. The preparation methods of spherical alumina include sol-gel method, drop-ball method, template method, etc. The spherical alumina prepared by the gel method has a wide range of particle diameters, high sphericity, and good dispersibility, but has serious agglomeration after sintering. The drop ball method is a further improvement of the sol-emulsion-gel method in the process. Alumina has high purity and best dispersibility, but has a narrow size range and usually large particle size. The template method is suitable for preparing hollow spheres, which requires higher template agents, has more steps in the preparation process, and has a higher cost.
发明内容Summary of the Invention
基于此，本发明的目的在于，提供一种高分散石墨烯基导热硅胶的制备方法，能够提高石墨烯作为导热填料的分散性，改善其导热性能。Based on this, the object of the present invention is to provide a method for preparing a highly dispersed graphene-based thermally conductive silica gel, which can improve the dispersibility of graphene as a thermally conductive filler and improve its thermal conductivity.
本发明的目的是通过以下技术方案实现的：一种高分散石墨烯基导热硅胶的制备方法，包括以下步骤：The object of the present invention is achieved by the following technical scheme: a method for preparing a highly dispersed graphene-based thermally conductive silica gel, including the following steps:
S1：将氧化石墨加入水中，超声剥离形成氧化石墨烯水悬液；将铝盐加入所述氧化石墨烯水悬液中，超声分散，形成A溶液；配制沉淀剂溶液，并加入分散剂，形成B溶液；将所述A溶液与B溶液混合，搅拌，得到灰色沉淀，然后对所述灰色沉淀进行过滤、清洗、烘干、煅烧，得到石墨烯/Al 2O 3复合填料； S1: adding graphite oxide to water and ultrasonically peeling to form a graphene oxide aqueous suspension; adding an aluminum salt to the graphene oxide aqueous suspension and dispersing ultrasonically to form a solution A; preparing a precipitant solution and adding a dispersant to form Solution B; mixing the solution A and solution B and stirring to obtain a gray precipitate, and then filtering, washing, drying, and calcining the gray precipitate to obtain a graphene / Al 2 O 3 composite filler;
S2：配制偶联剂溶液，加入所述石墨烯/Al 2O 3复合填料，然后进行搅拌、过滤、清洗、烘干，得到偶联剂修饰的石墨烯/Al 2O 3复合填料； S2: preparing a coupling agent solution, adding the graphene / Al 2 O 3 composite filler, and then stirring, filtering, washing, and drying to obtain a coupling agent-modified graphene / Al 2 O 3 composite filler;
S3：将所述偶联剂修饰的石墨烯/Al 2O 3复合填料与硅橡胶基体和助剂混合，然后硫化，得到高分散石墨烯基导热硅胶。 S3: The graphene / Al 2 O 3 composite filler modified by the coupling agent is mixed with a silicone rubber matrix and an auxiliary agent, and then vulcanized to obtain a highly dispersed graphene-based thermally conductive silica gel.
相对于现有技术，本发明的有益效果如下：Compared with the prior art, the beneficial effects of the present invention are as follows:
1、本发明采用分散性较好的氧化石墨烯作为原料，其表面含有丰富的含氧官能团，平面上含有-OH和C-O-C，而在其片层边缘含有C＝O和-COOH，具有良好的浸润性和表面活性，利用氧化石墨烯的活性官能团，原位合成氧化石墨烯/Al 2O 3复合物，经过高温烧结还原处理，得到分散性良好的石墨烯基材料，能够有效避免石墨烯作为导热填料的分散性问题，发挥其导热性能。其中的原理如下：氧化石墨烯表面因含丰富的-OH和-COOH而带负电，与带正电的Al 3+以较强的离子键结合，使Al 3+均匀负载于氧化石墨烯表面；加入沉淀剂后，Al 3+以配位键作用力使Al 2O 3沉积在氧化石墨烯表面；经过高温煅烧，氧化石墨烯被还原形成石墨烯，与Al 2O 3之间以静电作用力结合，形成具有良好分散性及导热性的复合产物。 1. The present invention uses graphene oxide with good dispersibility as a raw material, the surface of which is rich in oxygen-containing functional groups, -OH and COC on the plane, and C = O and -COOH on the edge of the sheet, which has a good Wettability and surface activity, using graphene oxide's active functional groups, in-situ synthesis of graphene oxide / Al 2 O 3 composite, and high temperature sintering and reduction treatment, to obtain a graphene-based material with good dispersion, which can effectively avoid graphene as The dispersibility of thermally conductive fillers exerts its thermal conductivity. The principle is as follows: The surface of graphene oxide is negatively charged because it is rich in -OH and -COOH, and combines with positively charged Al 3+ with a strong ionic bond, so that Al 3+ is uniformly loaded on the surface of graphene oxide; After adding the precipitant, Al 3+ deposits Al 2 O 3 on the surface of graphene oxide by coordination bond force; after calcination at high temperature, graphene oxide is reduced to form graphene, and electrostatic force is exerted on Al 2 O 3 Combined to form a composite product with good dispersibility and thermal conductivity.
2、通过本发明制得的石墨烯/Al 2O 3复合填料中，石墨烯在Al 2O 3颗粒之间形成桥连结构，形成石墨烯/Al 2O 3复合填料在聚合物基体中的紧密堆积结构，能够促使形成导热网链结构，降低界面热阻，从而提高导热硅胶的热导率。 2. In the graphene / Al 2 O 3 composite filler prepared by the present invention, graphene forms a bridge structure between Al 2 O 3 particles to form a graphene / Al 2 O 3 composite filler in a polymer matrix. The close-packed structure can promote the formation of a thermally conductive mesh chain structure and reduce the interface thermal resistance, thereby improving the thermal conductivity of the thermally conductive silica gel.
3、通过本发明制得的石墨烯/Al 2O 3复合填料中，Al 2O 3均匀附着在石墨烯表面，不仅能够利用石墨烯优异的导热性能，改善Al 2O 3作为单一填料热导率不高的缺陷，同时能够利用的Al 2O 3电绝缘性，防止复合材料达到电渗流阈值，获得较好的协同效应。 3. In the graphene / Al 2 O 3 composite filler prepared by the present invention, Al 2 O 3 adheres uniformly to the surface of graphene, which can not only utilize the excellent thermal conductivity of graphene, but also improve the thermal conductivity of Al 2 O 3 as a single filler. The defect that the rate is not high, and at the same time, the electrical insulation of Al 2 O 3 can be used to prevent the composite material from reaching the threshold of the electroosmotic flow and obtain a better synergy effect.
4、本发明采用均匀沉淀法制备球形氧化铝粉体，具有原料成本低、工艺简单、操作简便、对设备要求低的优点。4. The present invention uses a uniform precipitation method to prepare spherical alumina powder, which has the advantages of low raw material cost, simple process, simple operation, and low equipment requirements.
进一步地，步骤S1中，所述石墨烯/Al 2O 3复合填料中，石墨烯与Al 2O 3的质量比为1:(10～40)。若石墨烯的含量过多，则难以保证复合导电填料中石墨烯的分散性，如果不能保证石墨烯的分散性，会导致制备的导热硅胶形成空隙，大大降低导热性；且若石墨烯的含量过多，则难以保证复合导电填料的绝缘性，因为石墨烯具有良好的导电性，其含量过多，会降低绝缘性；若石墨烯含量过少，则难以提高导热硅胶的导热性。石墨烯与Al 2O 3的最佳质量比为1:30。 Further, in step S1, in the graphene / Al 2 O 3 composite filler, a mass ratio of graphene to Al 2 O 3 is 1: (10 to 40). If the content of graphene is too large, it is difficult to ensure the dispersibility of graphene in the composite conductive filler. If the dispersibility of graphene cannot be guaranteed, it will cause the prepared thermal silica gel to form voids and greatly reduce the thermal conductivity. Too much, it is difficult to ensure the insulation of the composite conductive filler, because graphene has good electrical conductivity, and its excessive content will reduce the insulation; if the graphene content is too small, it is difficult to improve the thermal conductivity of the thermally conductive silica gel. The optimal mass ratio of graphene to Al 2 O 3 is 1:30.
进一步地，步骤S1中，所述B溶液中沉淀剂的浓度与所述A溶液中铝盐的浓度的比为(2～6):1。若沉淀剂的量过多，则易出现不溶现象；若沉淀剂的量过少，则难以保证铝离子完全沉淀，可能产生其他杂质。所述沉淀剂优选为碳酸氢铵、碳酸铵、尿素或六次甲基四胺。所述铝盐优选为硫酸铝、硫酸铝铵或十二水合硫酸铝钾。Further, in step S1, the ratio of the concentration of the precipitating agent in the B solution to the concentration of the aluminum salt in the A solution is (2-6): 1. If the amount of the precipitant is too large, insolubility is likely to occur; if the amount of the precipitant is too small, it is difficult to ensure the complete precipitation of aluminum ions, and other impurities may be generated. The precipitant is preferably ammonium bicarbonate, ammonium carbonate, urea or hexamethylenetetramine. The aluminum salt is preferably aluminum sulfate, ammonium aluminum sulfate, or potassium potassium sulfate dodecahydrate.
进一步地，步骤S1中，在A溶液与B溶液混合过程中，加入碱溶液控制pH为5～9，在70～110℃下搅拌30～50h。所述碱溶液优选为氨水、氢氧化钠溶液或碳酸钠溶液。Further, in step S1, during the mixing of the A solution and the B solution, an alkaline solution is added to control the pH to be 5 to 9, and the mixture is stirred at 70 to 110 ° C for 30 to 50 hours. The alkaline solution is preferably ammonia water, sodium hydroxide solution or sodium carbonate solution.
进一步地，步骤S1中，所述煅烧过程为：先置于氩气氛围中300～500℃预烧3～8h；研磨后再置于氩气氛围中900～1500℃煅烧2～5h。Further, in step S1, the calcining process is as follows: firstly, pre-calcining at 300-500 ° C for 3-8 hours in an argon atmosphere; and grinding and then calcining at 900-1500 ° C for 2-5 hours in an argon atmosphere.
进一步地，步骤S2中，所述偶联剂溶液的配制过程为：将偶联剂溶于乙醇中，所述偶联剂的体积分数为1～8％。所述偶联剂优选为硅烷偶联剂，具体可以是γ-(甲基丙烯酰氧)丙基三甲氧基硅烷、γ-(2，3-环氧丙氧)丙基三甲氧基硅烷、γ-(甲基丙烯酰氧)丙基三甲氧基硅烷中的任意一种。Further, in step S2, the coupling agent solution is prepared by dissolving the coupling agent in ethanol, and the volume fraction of the coupling agent is 1-8%. The coupling agent is preferably a silane coupling agent, and specifically may be γ- (methacryloyloxy) propyltrimethoxysilane, γ- (2,3-glycidoxy) propyltrimethoxysilane, Any of γ- (methacryloyloxy) propyltrimethoxysilane.
进一步地，步骤S2中，所述石墨烯/Al 2O 3复合填料与偶联剂的质量比为100:(1～20)。偶联剂导热性较差，作用为偶联填料与高分子基体，减少界面热阻，若偶联剂的量过多，占比过大会降低导热性；若偶联剂的量过少，则难以实现填料与基体之间的有效偶联，使界面热阻增大。 Further, in step S2, the mass ratio of the graphene / Al 2 O 3 composite filler to the coupling agent is 100: (1-20). The thermal conductivity of the coupling agent is poor. It acts to couple the filler and the polymer matrix and reduce the interface thermal resistance. If the amount of the coupling agent is too large, the proportion will be too low to reduce the thermal conductivity; if the amount of the coupling agent is too small, then It is difficult to achieve effective coupling between the filler and the matrix, which increases the interface thermal resistance.
进一步地，步骤S2中，在偶联剂溶液中加入所述石墨烯/Al 2O 3复合填料前，先加入冰醋酸控制pH为3～5。 Further, in step S2, before adding the graphene / Al 2 O 3 composite filler to the coupling agent solution, first add glacial acetic acid to control the pH to be 3-5.
进一步地，步骤S3中，所述偶联剂修饰的石墨烯/Al 2O 3复合填料、硅橡胶基体和助剂的质量比为(45～65):(51～27):(4～8)。过多的填料容易造成分散不均，形成空隙；过少的填料难以有效改善导热硅胶的导热性。在上述配比下获得的材料具有良好的导热性，当石墨烯/Al 2O 3复合填料、硅橡胶基体和助剂的质量比为60:35:5时，材料的导热性最佳。所述硅橡胶基体优选为甲基乙烯基硅橡胶、二甲基硅橡胶或甲基苯基乙烯基硅橡胶。所述助剂可以是结构控 制剂、补强剂、硫化剂或催化剂。所述结构控制剂优选为羟基硅油、甲基苯基甲氧基硅油或甲基羟基硅油。所述补强剂优选为气相白炭黑、高岭土、石英粉、硅酸钙、硅酸锆、氧化锌或氧化铁。所述硫化剂优选为过氧化苯甲酰、2,4-二氯过氧化苯甲酰、过氧化二叔丁基、2,5-二甲基-2,5-二叔丁基过氧化己烷。所述催化剂优选为铂金催化剂或氯铂酸的异丙醇溶液。 Further, in step S3, the mass ratio of the coupling agent-modified graphene / Al 2 O 3 composite filler, the silicone rubber matrix, and the auxiliary agent is (45 to 65): (51 to 27): (4 to 8). ). Too much filler is likely to cause uneven dispersion and form voids; too little filler is difficult to effectively improve the thermal conductivity of thermally conductive silica gel. The material obtained at the above ratio has good thermal conductivity. When the mass ratio of the graphene / Al 2 O 3 composite filler, the silicone rubber matrix and the additive is 60: 35: 5, the material has the best thermal conductivity. The silicone rubber matrix is preferably a methyl vinyl silicone rubber, a dimethyl silicone rubber, or a methylphenyl vinyl silicone rubber. The auxiliary agent may be a structure control agent, a reinforcing agent, a vulcanizing agent, or a catalyst. The structure control agent is preferably a hydroxy silicone oil, methylphenylmethoxy silicone oil or methyl hydroxy silicone oil. The reinforcing agent is preferably fumed silica, kaolin, quartz powder, calcium silicate, zirconium silicate, zinc oxide or iron oxide. The vulcanizing agent is preferably benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di-tert-butyl peroxide. alkyl. The catalyst is preferably a platinum catalyst or an isopropanol solution of chloroplatinic acid.
进一步地，步骤S3具体为：将所述偶联剂修饰的石墨烯/Al 2O 3复合填料、硅橡胶基体和助剂加入到高速开炼机中，真空混合3～6h，通薄2～5次，然后采用硫化仪在120～300℃下二次硫化3～8h，得到高分散石墨烯基导热硅胶。 Further, step S3 is specifically: adding the coupling agent-modified graphene / Al 2 O 3 composite filler, a silicone rubber matrix, and an auxiliary agent to a high-speed open mill, vacuum mixing for 3 to 6 hours, and thinning 2 to 6 hours. Five times, and then using a vulcanization apparatus at 120 to 300 ° C. for 3 to 8 hours to obtain a highly dispersed graphene-based thermal silica gel.
为了更好地理解和实施，下面结合附图和实施例说明本发明。For better understanding and implementation, the present invention is described below with reference to the drawings and embodiments.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为实施例1中的石墨烯/Al 2O 3复合填料的SEM图。 FIG. 1 is a SEM image of the graphene / Al 2 O 3 composite filler in Example 1. FIG.
具体实施方式detailed description
本发明提供了一种高分散石墨烯基导热硅胶的制备方法，包括以下步骤：The invention provides a method for preparing a high-dispersion graphene-based thermal silica gel, including the following steps:
(1)称取氧化石墨，加入到去离子水中，氧化石墨的质量分数为0.01～10％，超声剥离形成氧化石墨烯水悬液；然后称取铝盐，加入所述氧化石墨烯水悬液中，控制产物中石墨烯与Al 2O 3的质量比为1:(10～40)，超声分散0.5～2h，形成A溶液；称取沉淀剂，配制成浓度为0.1～5mol/L的溶液，沉淀剂浓度与铝盐浓度的比为(2～6):1，加入乙二醇聚合物作为分散剂，浓度为0.1～10％，形成B溶液；然后将所述A溶液与B溶液混合，伴随搅拌并加入一定量的碱溶液，控制溶液pH为5～9，维持温度为70～110℃，搅拌30～50h，得到灰色沉淀；然后对所述灰色沉淀进行过滤，用去离子水和无水乙醇清洗3～6次，烘干后在氩气氛围中300～500℃预烧3～8h，研磨后再置于氩气氛围中900～1500℃煅烧2～5h。得到石墨烯/Al 2O 3复合填料。 (1) Weigh graphite and add it to deionized water. The mass fraction of graphite oxide is 0.01 to 10%. Ultrasonic peeling forms a graphene oxide aqueous suspension. Then weigh the aluminum salt and add the graphene oxide aqueous suspension. In the control, the mass ratio of graphene to Al 2 O 3 in the product is controlled to be 1: (10 to 40), and the solution is dispersed for 0.5 to 2 hours under ultrasound to form a solution A. A precipitant is weighed to prepare a solution having a concentration of 0.1 to 5 mol / L The ratio of the concentration of the precipitating agent to the concentration of the aluminum salt is (2-6): 1, and ethylene glycol polymer is added as a dispersant at a concentration of 0.1-10% to form a B solution; and then the A solution and the B solution are mixed With stirring and adding a certain amount of alkali solution, control the solution pH to 5-9, maintain the temperature at 70-110 ° C, and stir for 30-50 hours to obtain a gray precipitate; then filter the gray precipitate with deionized water and It is washed 3 to 6 times with anhydrous ethanol, dried and pre-fired at 300-500 ° C for 3-8 hours in an argon atmosphere. After grinding, it is calcined at 900-1500 ° C for 2-5 hours in an argon atmosphere. A graphene / Al 2 O 3 composite filler was obtained.
(2)量取偶联剂，溶解于乙醇中，偶联剂的体积分数为1～8％；搅拌下加入冰醋酸控制pH为3～5，再加入步骤(1)制得的石墨烯/Al 2O 3复合填料，控制石墨烯/Al 2O 3复合填料与偶联剂的质量比为100:(1～20)；然后搅拌1～4h，过滤并用醇清洗，60～80℃烘干，得到偶联剂修饰的石墨烯/Al 2O 3复合填料。 (2) Measure the coupling agent, dissolve it in ethanol, the volume fraction of the coupling agent is 1-8%; add glacial acetic acid under stirring to control the pH to 3-5, and then add the graphene prepared in step (1) / Al 2 O 3 composite filler, control the mass ratio of graphene / Al 2 O 3 composite filler and coupling agent to 100: (1 ～ 20); then stir for 1 ～ 4h, filter and wash with alcohol, and dry at 60 ～ 80 ℃ To obtain a graphene / Al 2 O 3 composite filler modified by a coupling agent.
(3)将步骤(2)制得的偶联剂修饰的石墨烯/Al 2O 3复合填料与硅橡胶基体和助剂按照(45～65):(51～27):(4～8)的质量比加入到高速开炼机中，真空混合3～6h，通薄2～5次，然后采用硫化仪在120～300℃下二次硫化3～8h，得到高分散石墨烯基导热硅胶。 (3) The coupling agent-modified graphene / Al 2 O 3 composite filler prepared in step (2) and the silicone rubber matrix and auxiliary agent are in accordance with (45 to 65): (51 to 27): (4 to 8) The mass ratio was added to a high-speed open mill, vacuum-mixed for 3-6 hours, thinned 2-5 times, and then vulcanized at 120-300 ° C for 3-8 hours using a vulcanizer to obtain a highly dispersed graphene-based thermal silica gel.
以下通过具体实施例进一步说明。It will be further described below through specific embodiments.
实施例1Example 1
本实施例的一种高分散石墨烯基导热硅胶的制备方法，包括以下步骤：A method for preparing a highly-dispersed graphene-based thermal silica gel in this embodiment includes the following steps:
(1)称取0.2g氧化石墨，加入到500mL去离子水中，超声剥离形成氧化石墨烯水悬液；然后加入25.66g硫酸铝，超声分散1h，形成A溶液；然后称取23.72g碳酸氢铵，配置成浓度为0.6mol/L的溶液，加入5mL聚乙二醇400，充分搅拌，形成B溶液；然后将A溶液缓慢滴加到B溶液中，伴随搅拌并加入一定量的碱溶液，调控溶液pH为6.5，维持温度为85℃，电磁搅拌12h，反应充分得到灰色沉淀，用去离子水和无水乙醇清洗3次，烘干后在氩气氛围中300℃预烧3h，研磨后再置于氩气氛围中1000℃煅烧2h，得到石墨烯/Al 2O 3复合填料。 (1) Weigh 0.2g of graphite oxide, add it to 500mL of deionized water, ultrasonically peel to form a graphene oxide aqueous suspension; then add 25.66g of aluminum sulfate, ultrasonically disperse for 1h to form A solution; then weigh 23.72g of ammonium bicarbonate , Configure a solution with a concentration of 0.6mol / L, add 5mL of polyethylene glycol 400, and stir thoroughly to form the B solution; then slowly add the A solution to the B solution, with stirring and add a certain amount of alkali solution to control The pH of the solution was 6.5, the temperature was maintained at 85 ° C, and electromagnetic stirring was performed for 12 hours. The reaction fully obtained a gray precipitate, washed 3 times with deionized water and absolute ethanol, and dried for 3 hours at 300 ° C in an argon atmosphere after drying. It was calcined in an argon atmosphere at 1000 ° C. for 2 h to obtain a graphene / Al 2 O 3 composite filler.
(2)量取5mL偶联剂，溶解到200mL乙醇中，搅拌下加入一定量的冰醋酸，控制溶液pH为3，加入30g上述反应制得的石墨烯/Al 2O 3复合填料，电磁搅拌1.5h后，过滤并用乙醇清洗，60℃烘干，得到偶联剂修饰的石墨烯/Al 2O 3复合填料。 (2) Measure 5mL of coupling agent, dissolve in 200mL of ethanol, add a certain amount of glacial acetic acid under stirring, control the solution pH to 3, add 30g of graphene / Al 2 O 3 composite filler prepared by the above reaction, and stir by electromagnetic After 1.5 h, it was filtered, washed with ethanol, and dried at 60 ° C. to obtain a graphene / Al 2 O 3 composite filler modified by a coupling agent.
(3)采用上述偶联剂修饰的石墨烯/Al 2O 3复合填料、甲基乙烯基硅橡胶基体以及一定量的助剂按质量比为59:35:6，加入到高速开炼机中，真空混合3h，通薄2次，然后采用硫化仪180℃下硫化3h，得到高分散石墨烯基导热硅胶。 (3) The graphene / Al 2 O 3 composite filler modified by the above coupling agent, a methyl vinyl silicone rubber matrix, and a certain amount of additives are added to the high-speed open mill at a mass ratio of 59: 35: 6. , Vacuum mixing for 3h, thinning twice, and then vulcanizing at 180 ° C for 3h using a vulcanizer to obtain a highly dispersed graphene-based thermal silica gel.
实施例2Example 2
本实施例的一种高分散石墨烯基导热硅胶的制备方法，包括以下步骤：A method for preparing a highly-dispersed graphene-based thermal silica gel in this embodiment includes the following steps:
(1)称取0.5g氧化石墨，加入到500mL去离子水中，超声剥离形成氧化石墨烯水悬液；然后加入51.33g硫酸铝，超声分散2h，形成A溶液；然后称取43.24g碳酸铵，配置成浓度为0.9mol/L的溶液，加入10mL聚乙二醇2000，充分搅拌，形成B溶液；然后将A溶液缓慢滴加到B溶液中，伴随搅拌并加入一定量的碱溶液，调控溶液pH为7，维持温度为90℃，电磁搅拌24h，反应充分得到灰色沉淀，用去离子水和无水乙醇清洗4次，烘干后在氩气氛围中350℃预烧5h，研磨后再置于氩气氛围中1100℃煅烧3h，得到石墨烯/Al 2O 3复合填料。 (1) Weigh 0.5 g of graphite oxide, add it to 500 mL of deionized water, and ultrasonically peel to form a graphene oxide aqueous suspension; then add 51.33 g of aluminum sulfate and ultrasonically disperse for 2 h to form A solution; then weigh 43.24 g of ammonium carbonate, Prepare a solution with a concentration of 0.9mol / L, add 10mL polyethylene glycol 2000, and stir thoroughly to form the B solution; then slowly add the A solution to the B solution, and add a certain amount of alkali solution with stirring to adjust the solution The pH was 7, the temperature was maintained at 90 ° C, and electromagnetic stirring was performed for 24 hours. The reaction fully obtained a gray precipitate, washed 4 times with deionized water and absolute ethanol, dried at 350 ° C in an argon atmosphere for 5 hours, and then placed after grinding. It was calcined in an argon atmosphere at 1100 ° C for 3 hours to obtain a graphene / Al 2 O 3 composite filler.
(2)量取10mL偶联剂，溶解到250mL乙醇中，搅拌下加入一定量的冰醋酸，控制溶液pH为4，加入60g上述反应制得的石墨烯/Al 2O 3复合填料，电磁搅拌2h后，过滤并用乙醇清洗，65℃烘干，得到偶联剂修饰的石墨烯/Al 2O 3复合填料。 (2) Measure 10 mL of coupling agent, dissolve it in 250 mL of ethanol, add a certain amount of glacial acetic acid under stirring, control the pH of the solution to 4, add 60 g of graphene / Al 2 O 3 composite filler prepared by the above reaction, and stir by electromagnetic stirring After 2 h, it was filtered, washed with ethanol, and dried at 65 ° C. to obtain a graphene / Al 2 O 3 composite filler modified by a coupling agent.
(3)采用上述偶联剂修饰的石墨烯/Al 2O 3复合填料、二甲基硅橡胶基体以及一定量的助剂按质量比为60:35:5，加入到高速开炼机中，真空混合4h，通薄4次，然后采用硫化仪190℃下硫化5h，得到高分散石墨烯基导热硅胶。 (3) The graphene / Al 2 O 3 composite filler modified by the above coupling agent, a dimethyl silicone rubber matrix, and a certain amount of additives are added to the high-speed open mill at a mass ratio of 60: 35: 5. It was mixed in vacuum for 4h, thinned 4 times, and then vulcanized at 190 ° C for 5h using a vulcanizer to obtain a highly dispersed graphene-based thermal silica gel.
实施例3Example 3
本实施例的一种高分散石墨烯基导热硅胶的制备方法，包括以下步骤：A method for preparing a highly-dispersed graphene-based thermal silica gel in this embodiment includes the following steps:
(1)称取0.7g氧化石墨，加入到500mL去离子水中，超声剥离形成氧化石墨烯水悬液；然后加入94.86g硫酸铝铵，超声分散3h，形成A溶液；然后称取36.04g尿素，配置成浓度为1.2mol/L的溶液，加入15mL聚乙二醇6000，充分搅拌，形成B溶液；然后将A溶液缓慢滴加到B溶液中，伴随搅拌并加入一定量的碱溶液，调控溶液pH为7.5，维持温度为95℃，电磁搅拌48h，反应充分得到灰色沉淀，用去离子水和无水乙醇清洗5次，烘干后在氩气氛围中400℃预烧8h，研磨后再置于氩气氛围中1200℃煅烧4h，得到石墨烯/Al 2O 3复合填料。 (1) Weigh 0.7g of graphite oxide, add it to 500mL of deionized water, ultrasonically peel to form a graphene oxide suspension; then add 94.86g of ammonium aluminum sulfate, and ultrasonically disperse for 3h to form A solution; then weigh 36.04g of urea, Prepare a solution with a concentration of 1.2mol / L, add 15mL of polyethylene glycol 6000, and stir thoroughly to form the B solution; then slowly add the A solution to the B solution, and add a certain amount of alkali solution with stirring to adjust the solution The pH was 7.5, the temperature was maintained at 95 ° C, and electromagnetic stirring was performed for 48 hours. The reaction fully obtained a gray precipitate, washed 5 times with deionized water and absolute ethanol, dried and pre-burned at 400 ° C for 8 hours in an argon atmosphere. It was calcined at 1200 ° C for 4 h in an argon atmosphere to obtain a graphene / Al 2 O 3 composite filler.
(2)量取15mL偶联剂，溶解到500mL乙醇中，搅拌下加入一定量的冰醋酸，控制溶液pH为5，加入80g上述反应制得的石墨烯/Al 2O 3复合填料，电磁搅拌3h后，过滤并用乙醇清洗，70℃烘干，得到偶联剂修饰的石墨烯/Al 2O 3复合填料。 (2) Measure 15 mL of coupling agent, dissolve it in 500 mL of ethanol, add a certain amount of glacial acetic acid under stirring, control the solution pH to 5, add 80 g of graphene / Al 2 O 3 composite filler prepared by the above reaction, and stir by electromagnetic stirring After 3 h, it was filtered, washed with ethanol, and dried at 70 ° C. to obtain a graphene / Al 2 O 3 composite filler modified by a coupling agent.
(3)采用上述偶联剂修饰的石墨烯/Al 2O 3复合填料、二甲基硅橡胶基体以及一定量的助剂按质量比为61:34:5，加入到高速开炼机中，真空混合6h，通薄5次，然后采用硫化仪200℃下硫化6h，得到高分散石墨烯基导热硅胶。 (3) The graphene / Al 2 O 3 composite filler modified by the above coupling agent, a dimethyl silicone rubber matrix, and a certain amount of additives are added to the high-speed open mill at a mass ratio of 61: 34: 5. It was mixed in vacuum for 6 hours, thinned 5 times, and then vulcanized at 200 ° C for 6 hours using a vulcanizer to obtain highly dispersed graphene-based thermal silica gel.
对比例1Comparative Example 1
本对比例的一种高分散石墨烯基导热硅胶的制备方法，包括以下步骤：A method for preparing a high-dispersion graphene-based thermal silica gel of this comparative example includes the following steps:
(1)称取0.2g石墨烯，加入到500mL去离子水中，超声分散形成石墨烯水悬液；然后加入25.66g硫酸铝，超声分散1h，形成A溶液；然后称取23.72g碳酸氢铵，配置成浓度为0.6mol/L的溶液，加入5mL聚乙二醇400，充分搅拌，形成B溶液；然后将A溶液缓慢滴加到B溶液中，伴随搅拌并加入一定量的碱溶液，调控溶液pH为6.5，维持温度为85℃，电磁搅拌12h，反应充分得到灰色沉淀，用去离子水和无水乙醇清洗3次，烘干后在氩气氛围中300℃预烧3h，研磨后再置于氩气氛围中1000℃煅烧2h，得到石墨烯/Al 2O 3复合填料。 (1) Weigh 0.2g of graphene and add it to 500mL of deionized water and ultrasonically disperse to form a graphene aqueous suspension; then add 25.66g of aluminum sulfate and ultrasonically disperse for 1h to form A solution; then weigh 23.72g of ammonium bicarbonate, Dispose into a solution with a concentration of 0.6mol / L, add 5mL of polyethylene glycol 400, and stir thoroughly to form the B solution; then slowly add the A solution to the B solution, and add a certain amount of alkali solution with stirring to adjust the solution The pH is 6.5, the temperature is maintained at 85 ° C, and the mixture is stirred for 12 hours by electromagnetic stirring. The reaction fully obtains a gray precipitate. It is washed 3 times with deionized water and absolute ethanol. It was calcined in an argon atmosphere at 1000 ° C. for 2 h to obtain a graphene / Al 2 O 3 composite filler.
(2)量取5mL偶联剂，溶解到200mL乙醇中，搅拌下加入一定量的冰醋酸，控制溶液pH为3，加入30g上述反应制得的石墨烯/Al 2O 3复合填料，电磁搅拌1.5h后，过滤并用乙醇清洗，60℃烘干，得到偶联剂修饰的石墨烯/Al 2O 3复合填料。 (2) Measure 5mL of coupling agent, dissolve in 200mL of ethanol, add a certain amount of glacial acetic acid under stirring, control the solution pH to 3, add 30g of graphene / Al 2 O 3 composite filler prepared by the above reaction, and stir by electromagnetic After 1.5 h, it was filtered, washed with ethanol, and dried at 60 ° C. to obtain a graphene / Al 2 O 3 composite filler modified by a coupling agent.
(3)采用上述偶联剂修饰的石墨烯/Al 2O 3复合填料、甲基乙烯基硅橡胶基体以及一定量的助剂按质量比为59:35:6，加入到高速开炼机中，真空混合3h，通薄2次，然后采用硫化仪180℃下硫化3h，得到石墨烯基导热硅胶。 (3) The graphene / Al 2 O 3 composite filler modified by the above coupling agent, a methyl vinyl silicone rubber matrix, and a certain amount of additives are added to the high-speed open mill at a mass ratio of 59: 35: 6. , Vacuum mixing for 3h, thinning twice, and then vulcanizing at 180 ° C for 3h using a vulcanizer to obtain graphene-based thermal silica gel.
对比例2Comparative Example 2
本对比例的一种高分散石墨烯基导热硅胶的制备方法，包括以下步骤：A method for preparing a high-dispersion graphene-based thermal silica gel of this comparative example includes the following steps:
(1)称取0.5g石墨烯，加入到500mL去离子水中，超声剥离形成石墨烯水悬液；然后加入51.33g硫酸铝，超声分散2h，形成A溶液；然后称取43.24g碳酸铵，配置成浓度为0.9mol/L 的溶液，加入10mL聚乙二醇2000，充分搅拌，形成B溶液；然后将A溶液缓慢滴加到B溶液中，伴随搅拌并加入一定量的碱溶液，调控溶液pH为7，维持温度为90℃，电磁搅拌24h，反应充分得到灰色沉淀，用去离子水和无水乙醇清洗4次，烘干后在氩气氛围中350℃预烧5h，研磨后再置于氩气氛围中1100℃煅烧3h，得到石墨烯/Al 2O 3复合填料。 (1) Weigh 0.5g of graphene, add it to 500mL of deionized water, and ultrasonically peel to form a graphene aqueous suspension; then add 51.33g of aluminum sulfate, and ultrasonically disperse for 2h to form A solution; then weigh 43.24g of ammonium carbonate, configure Into a solution with a concentration of 0.9mol / L, add 10mL of polyethylene glycol 2000, and stir thoroughly to form the B solution; then slowly add the A solution to the B solution, and add a certain amount of alkali solution with stirring to adjust the pH of the solution The temperature is 7 and the temperature is maintained at 90 ° C. The electromagnetic stirring is performed for 24 hours. The reaction fully obtains a gray precipitate. It is washed 4 times with deionized water and absolute ethanol. After drying, it is pre-burned at 350 ° C for 5 hours in an argon atmosphere. Calcined in an argon atmosphere at 1100 ° C for 3 hours to obtain a graphene / Al 2 O 3 composite filler.
(2)量取10mL偶联剂，溶解到250mL乙醇中，搅拌下加入一定量的冰醋酸，控制溶液pH为4，加入60g上述反应制得的石墨烯/Al 2O 3复合填料，电磁搅拌2h后，过滤并用乙醇清洗，65℃烘干，得到偶联剂修饰的石墨烯/Al 2O 3复合填料。 (2) Measure 10 mL of coupling agent, dissolve it in 250 mL of ethanol, add a certain amount of glacial acetic acid under stirring, control the pH of the solution to 4, add 60 g of graphene / Al 2 O 3 composite filler prepared by the above reaction, and stir by electromagnetic stirring After 2 h, it was filtered, washed with ethanol, and dried at 65 ° C. to obtain a graphene / Al 2 O 3 composite filler modified by a coupling agent.
(3)采用上述偶联剂修饰的石墨烯/Al 2O 3复合填料、二甲基硅橡胶基体以及一定量的助剂按质量比为60:35:5，加入到高速开炼机中，真空混合4h，通薄4次，然后采用硫化仪190℃下硫化5h，得到石墨烯基导热硅胶。 (3) The graphene / Al 2 O 3 composite filler modified by the above coupling agent, a dimethyl silicone rubber matrix, and a certain amount of additives are added to the high-speed open mill at a mass ratio of 60: 35: 5. It was mixed in vacuum for 4h, thinned 4 times, and then vulcanized at 190 ° C for 5h using a vulcanizer to obtain graphene-based thermal silica gel.
对比例3Comparative Example 3
本对比例的一种高分散石墨烯基导热硅胶的制备方法，包括以下步骤：A method for preparing a high-dispersion graphene-based thermal silica gel of this comparative example includes the following steps:
(1)称取0.7g石墨烯，同时称取20.39g球形Al 2O 3，粉体干混后，得到石墨烯与Al 2O 3复合填料。 (1) Weigh 0.7g of graphene and 20.39g of spherical Al 2 O 3 at the same time. After the powder is dry-blended, graphene and Al 2 O 3 composite filler are obtained.
(2)量取5mL偶联剂，溶解到200mL乙醇中，搅拌下加入一定量的冰醋酸，控制溶液pH为3，加入30g上述反应制得的石墨烯与Al 2O 3复合填料，电磁搅拌1.5h后，过滤并用乙醇清洗，60℃烘干，得到偶联剂修饰的石墨烯与Al 2O 3复合填料。 (2) Measure 5 mL of coupling agent, dissolve it in 200 mL of ethanol, add a certain amount of glacial acetic acid under stirring, control the solution pH to 3, add 30 g of graphene and Al 2 O 3 composite filler prepared by the above reaction, and stir by electromagnetic After 1.5 h, it was filtered and washed with ethanol, and dried at 60 ° C. to obtain a coupling agent-modified graphene and Al 2 O 3 composite filler.
③采用上述偶联剂修饰的石墨烯与Al 2O 3复合填料、甲基乙烯基硅橡胶基体以及一定量的助剂按质量比为59:35:6，加入到高速开炼机中，真空混合3h，通薄2次，然后采用硫化仪180℃下硫化3h，得到石墨烯基导热硅胶。 ③ The graphene and Al 2 O 3 composite filler modified by the above coupling agent, a methyl vinyl silicone rubber matrix and a certain amount of additives are added to the high-speed open mill with a mass ratio of 59: 35: 6, and the vacuum is applied. Mix for 3h, pass through twice, and vulcanize at 180 ° C for 3h using a vulcanizer to obtain graphene-based thermal silica gel.
性能测试Performance Testing
请参阅图1，其为实施例1中的石墨烯/Al 2O 3复合填料的SEM图。从图中可以看出，石墨烯片层较薄，呈现出纱状，具有高分散性；Al 2O 3为球形纳米颗粒，均匀分散在石墨烯片层中；石墨烯与Al 2O 3颗粒紧密贴合，二者相互协同，形成均匀分散的复合填料。 Please refer to FIG. 1, which is a SEM image of the graphene / Al 2 O 3 composite filler in Example 1. As can be seen from the figure, the graphene sheet is thin, showing a yarn shape, and has high dispersibility; Al 2 O 3 is a spherical nanoparticle uniformly dispersed in the graphene sheet; graphene and Al 2 O 3 particles Closely fit, the two cooperate with each other to form a uniformly dispersed composite filler.
对实施例1～3以及对比例1～3制得的导热硅胶进行性能测试，测试方法采用国内外常用的标准测试方法，得到的结果如下表1所示。Performance tests were performed on the thermally conductive silica gels prepared in Examples 1 to 3 and Comparative Examples 1 to 3, and the test methods used standard test methods commonly used at home and abroad. The results obtained are shown in Table 1 below.
Figure PCTCN2018121697-appb-000001
Figure PCTCN2018121697-appb-000001
Figure PCTCN2018121697-appb-000002
Figure PCTCN2018121697-appb-000002
从表中可以看出，本发明实施例1～3的综合性能要优于对比例1～3。本发明的原料采用了氧化石墨烯，且通过均匀沉淀法合成了球形Al 2O 3，利用氧化石墨烯的活性官能团，原位合成氧化石墨烯/Al 2O 3复合物，经过高温烧结还原处理，得到分散性良好的石墨烯基材料，能够有效避免石墨烯作为导热填料的分散性问题，发挥其导热性能。通过本发明制得的石墨烯/Al 2O 3复合填料中，石墨烯在Al 2O 3颗粒之间形成桥连结构，形成石墨烯/Al 2O 3复合填料在聚合物基体中的紧密堆积结构，能够促使形成导热网链结构，降低界面热阻，从而提高导热硅胶的热导率。且Al 2O 3均匀附着在石墨烯表面，不仅能够利用石墨烯优异的导热性能，改善Al 2O 3作为单一填料热导率不高的缺陷，同时能够利用的Al 2O 3电绝缘性，防止复合材料达到电渗流阈值，获得较好的协同效应。此外，本发明采用均匀沉淀法制备球形氧化铝粉体，具有原料成本低、工艺简单、操作简便、对设备要求低的优点。 It can be seen from the table that the comprehensive performance of Examples 1 to 3 of the present invention is better than that of Comparative Examples 1 to 3. Graphene oxide is used as a raw material in the present invention, and spherical Al 2 O 3 is synthesized by a uniform precipitation method. The graphene oxide / Al 2 O 3 composite is synthesized in situ by using the active functional group of graphene oxide, and subjected to high temperature sintering reduction treatment To obtain a graphene-based material with good dispersibility, which can effectively avoid the problem of dispersibility of graphene as a thermally conductive filler and exert its thermal conductivity. In the graphene / Al 2 O 3 composite filler prepared by the present invention, graphene forms a bridge structure between Al 2 O 3 particles, forming a tight packing of the graphene / Al 2 O 3 composite filler in the polymer matrix. The structure can promote the formation of a thermally conductive mesh chain structure, reduce the interface thermal resistance, and thereby improve the thermal conductivity of the thermally conductive silica gel. And Al 2 O 3 is evenly attached to the surface of graphene, which can not only utilize the excellent thermal conductivity of graphene, improve the defect of low thermal conductivity of Al 2 O 3 as a single filler, but also use the electrical insulation of Al 2 O 3 . Prevent the composite material from reaching the electroosmotic threshold and obtain better synergistic effects. In addition, the invention uses a uniform precipitation method to prepare spherical alumina powder, which has the advantages of low raw material cost, simple process, simple operation, and low requirements on equipment.
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。The above-mentioned embodiments only express several implementation manners of the present invention, and their descriptions are more specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be noted that, for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can be made, which all belong to the protection scope of the present invention.

Claims (10)

  1. 一种高分散石墨烯基导热硅胶的制备方法，其特征在于：包括以下步骤：A method for preparing high-dispersion graphene-based thermal silica gel, which is characterized by comprising the following steps:
    S1：将氧化石墨加入水中，超声剥离形成氧化石墨烯水悬液；将铝盐加入所述氧化石墨烯水悬液中，超声分散，形成A溶液；配制沉淀剂溶液，并加入分散剂，形成B溶液；将所述A溶液与B溶液混合，搅拌，得到灰色沉淀，然后对所述灰色沉淀进行过滤、清洗、烘干、煅烧，得到石墨烯/Al 2O 3复合填料； S1: adding graphite oxide to water and ultrasonically peeling to form a graphene oxide aqueous suspension; adding an aluminum salt to the graphene oxide aqueous suspension and dispersing ultrasonically to form a solution A; preparing a precipitant solution and adding a dispersant to form Solution B; mixing the solution A and solution B and stirring to obtain a gray precipitate, and then filtering, washing, drying, and calcining the gray precipitate to obtain a graphene / Al 2 O 3 composite filler;
    S2：配制偶联剂溶液，加入所述石墨烯/Al 2O 3复合填料，然后进行搅拌、过滤、清洗、烘干，得到偶联剂修饰的石墨烯/Al 2O 3复合填料； S2: preparing a coupling agent solution, adding the graphene / Al 2 O 3 composite filler, and then stirring, filtering, washing, and drying to obtain a coupling agent-modified graphene / Al 2 O 3 composite filler;
    S3：将所述偶联剂修饰的石墨烯/Al 2O 3复合填料与硅橡胶基体和助剂混合，然后硫化，得到高分散石墨烯基导热硅胶。 S3: The graphene / Al 2 O 3 composite filler modified by the coupling agent is mixed with a silicone rubber matrix and an auxiliary agent, and then vulcanized to obtain a highly dispersed graphene-based thermally conductive silica gel.
  2. 根据权利要求1所述的高分散石墨烯基导热硅胶的制备方法，其特征在于：步骤S1中，所述石墨烯/Al 2O 3复合填料中，石墨烯与Al 2O 3的质量比为1:(10～40)。 The method for preparing a highly dispersed graphene-based thermally conductive silica gel according to claim 1, wherein in step S1, in the graphene / Al 2 O 3 composite filler, a mass ratio of graphene to Al 2 O 3 is 1: (10 to 40).
  3. 根据权利要求1或2所述的高分散石墨烯基导热硅胶的制备方法，其特征在于：步骤S1中，所述B溶液中沉淀剂的浓度与所述A溶液中铝盐的浓度的比为(2～6):1。The method for preparing a highly-dispersed graphene-based thermally conductive silica gel according to claim 1 or 2, wherein in step S1, the ratio of the concentration of the precipitant in the B solution to the concentration of the aluminum salt in the A solution is (2 ~ 6): 1.
  4. 根据权利要求3所述的高分散石墨烯基导热硅胶的制备方法，其特征在于：步骤S1中，在A溶液与B溶液混合过程中，加入碱溶液控制pH为5～9，在70～110℃下搅拌30～50h。The method for preparing high-dispersion graphene-based thermally conductive silica gel according to claim 3, wherein in step S1, during the mixing of the A solution and the B solution, an alkaline solution is added to control the pH to be 5 to 9, and the pH is between 70 to 110. Stir for 30-50 hours at ℃.
  5. 根据权利要求4所述的高分散石墨烯基导热硅胶的制备方法，其特征在于：步骤S1中，所述煅烧过程为：先置于氩气氛围中300～500℃预烧3～8h；研磨后再置于氩气氛围中900～1500℃煅烧2～5h。The method for preparing high-dispersion graphene-based thermally conductive silica gel according to claim 4, characterized in that: in step S1, the calcining process is: firstly pre-firing at 300-500 ° C for 3-8 hours in an argon atmosphere; grinding Then put it in an argon atmosphere for calcination at 900 ～ 1500 ℃ for 2 ～ 5h.
  6. 根据权利要求1所述的高分散石墨烯基导热硅胶的制备方法，其特征在于：步骤S2中，所述偶联剂溶液的配制过程为：将偶联剂溶于乙醇中，所述偶联剂的体积分数为1～8％。The method for preparing high-dispersion graphene-based thermally conductive silica gel according to claim 1, wherein in step S2, the preparation process of the coupling agent solution is: dissolving the coupling agent in ethanol, and coupling The volume fraction of the agent is 1 to 8%.
  7. 根据权利要求6所述的高分散石墨烯基导热硅胶的制备方法，其特征在于：步骤S2中，所述石墨烯/Al 2O 3复合填料与偶联剂的质量比为100:(1～20)。 The method for preparing a highly dispersed graphene-based thermally conductive silica gel according to claim 6, characterized in that in step S2, the mass ratio of the graphene / Al 2 O 3 composite filler to the coupling agent is 100: (1 to 20).
  8. 根据权利要求7所述的高分散石墨烯基导热硅胶的制备方法，其特征在于：步骤S2中，在偶联剂溶液中加入所述石墨烯/Al 2O 3复合填料前，先加入冰醋酸控制pH为3～5。 The method for preparing highly thermally conductive graphene-based dispersion of the silica in claim 7, wherein: step S2, the coupling agent was added in the solution before the graphene / Al 2 O 3 composite fillers, glacial acetic acid was added to Control the pH to 3 ~ 5.
  9. 根据权利要求1所述的高分散石墨烯基导热硅胶的制备方法，其特征在于：步骤S3中，所述偶联剂修饰的石墨烯/Al 2O 3复合填料、硅橡胶基体和助剂的质量比为(45～65):(51～27):(4～8)。 The method for preparing a highly dispersed graphene-based thermally conductive silica gel according to claim 1, wherein in step S3, the coupling agent-modified graphene / Al 2 O 3 composite filler, the silicone rubber matrix, and the additives The mass ratio is (45 to 65): (51 to 27): (4 to 8).
  10. 根据权利要求9所述的高分散石墨烯基导热硅胶的制备方法，其特征在于：步骤S3具体为：将所述偶联剂修饰的石墨烯/Al 2O 3复合填料、硅橡胶基体和助剂加入到高速开炼机 中，真空混合3～6h，通薄2～5次，然后采用硫化仪在120～300℃下二次硫化3～8h，得到高分散石墨烯基导热硅胶。 The method for preparing a highly dispersed graphene-based thermally conductive silica gel according to claim 9, wherein step S3 is specifically: graphene / Al 2 O 3 composite filler modified by the coupling agent, a silicone rubber matrix, and The agent is added to a high-speed open mill, vacuum-mixed for 3 to 6 hours, thinned 2 to 5 times, and then vulcanized at 120 to 300 ° C for 3 to 8 hours using a vulcanizer to obtain a highly dispersed graphene-based thermally conductive silica gel.
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