WO2021164225A1 - 一种高导热填料的化学和物理处理方法 - Google Patents

一种高导热填料的化学和物理处理方法 Download PDF

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WO2021164225A1
WO2021164225A1 PCT/CN2020/110987 CN2020110987W WO2021164225A1 WO 2021164225 A1 WO2021164225 A1 WO 2021164225A1 CN 2020110987 W CN2020110987 W CN 2020110987W WO 2021164225 A1 WO2021164225 A1 WO 2021164225A1
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thermal conductivity
high thermal
filler
physical
chemical
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PCT/CN2020/110987
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English (en)
French (fr)
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田付强
刘艳婷
夏宇
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苏州巨峰电气绝缘系统股份有限公司
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Publication of WO2021164225A1 publication Critical patent/WO2021164225A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • 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
    • 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
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/40—Compounds of aluminium
    • C09C1/407—Aluminium oxides or hydroxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/12—Treatment with organosilicon compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/32—Thermal properties
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • 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
    • 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
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • 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
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K

Definitions

  • the present invention relates to the field of thermally conductive fillers. More specifically, the present invention relates to a chemical and physical treatment method for highly thermally conductive fillers.
  • high thermal conductivity insulating materials have very broad application prospects in modern high-tech fields such as electrical equipment, microelectronics, LED lighting, solar energy, transportation, aerospace, national defense and military industry.
  • the development of high thermal conductivity insulating materials to solve the heat dissipation problem of electrical and electronic equipment is one of the research hotspots in the field of international electrical and electronic insulation.
  • For polymer materials there are mainly two ways to improve their thermal conductivity: One is to prepare intrinsic thermally conductive polymers, that is, the polymer itself has good thermal conductivity. This method is used in the preparation and processing of polymers.
  • a certain method is used to change the molecular and link structure of the polymer itself to obtain a special physical configuration, so as to improve its own thermal conductivity; the second is to prepare a filled thermally conductive polymer, that is, to use the polymer as the matrix , Add high thermal conductivity insulating filler, and prepare thermal conductive insulating polymer composite material through a certain process.
  • the composite material prepared by filling the resin matrix with inorganic thermally conductive filler has the characteristics of easy processing and molding, low price, and good thermal conductivity. This is currently the simplest and most effective method for preparing thermally conductive materials.
  • the first aspect of the present invention provides a chemical and physical treatment method for high thermal conductivity fillers, which includes the following steps:
  • step (1) Physically extruding the modified filler obtained in step (1); when the material obtained after the physical extruding is softly agglomerated, it needs to be physically crushed.
  • the number of extrusions of the physical extrusion treatment in the step (2) is greater than one.
  • the high thermal conductivity filler is selected from one or more of aluminum oxide, silicon oxide, aluminum nitride, boron nitride, zinc oxide, and silicon carbide.
  • the shape of the high thermal conductivity filler is selected from one or more of angular, spherical, flake, needle, and fibrous.
  • the particle size of the high thermal conductivity filler is 0.01-500um.
  • the modifier is selected from one or more of coupling agents, dispersants, and surfactants.
  • the amount of the modifier is 0.05-10w% of the high thermal conductivity filler.
  • the pressure of the high thermal conductivity filler during the physical extrusion process in the step (2) is 0.1-200 MPa.
  • the physical extrusion treatment in the step (2) is any one of ball milling, roll pressing, and plate pressing.
  • the extrusion time of the physical extrusion treatment in the step (2) is 1s-100h; the extrusion temperature is -60-100°C.
  • the second aspect of the present invention provides a modified high thermal conductivity filler prepared according to the chemical and physical treatment method of the high thermal conductivity filler.
  • the present invention has the following beneficial effects:
  • the chemical and physical method of the high thermal conductivity filler provided by the present invention can realize the chemical modification, physical shaping, and self-adaptive grading of the high thermal conductivity filler, can be used for the preparation of composite materials, and can greatly improve the filling of the filler in the resin, etc. Or reduce the viscosity of the glue solution, thereby improving the thermal conductivity of the resin and other matrix materials, and ensuring excellent manufacturability.
  • compositions, step, method, product, or device containing the listed elements is not necessarily limited to those elements, but may include other elements not explicitly listed or inherent in such a composition, step, method, product, or device Elements.
  • the first aspect of the present invention provides a chemical and physical treatment method of high thermal conductivity filler, which includes the following steps:
  • step (1) Physically extruding the modified filler obtained in step (1); when the material obtained after the physical extruding is softly agglomerated, it needs to be physically crushed.
  • Soft agglomeration is mainly caused by van der Waals force and Coulomb force between particles, so it can be mostly eliminated through some chemical action or applying mechanical energy.
  • the high thermal conductivity filler is selected from one or more of aluminum oxide, silicon oxide, aluminum nitride, boron nitride, zinc oxide, and silicon carbide.
  • the shape of the high thermal conductivity filler is selected from one or more of angular, spherical, sheet, needle, and fibrous; more preferably, the shape of the high thermal conductivity filler is flake and/or Angular.
  • the particle size of the high thermal conductivity filler is 0.01-500um.
  • the particle size of the high thermal conductivity filler of the present invention can be a single particle size or a combination of multiple particle sizes.
  • the modifier is selected from one or more of coupling agents, dispersants, and surfactants.
  • the modifier is a coupling agent and a dispersant; more preferably, the weight ratio of the coupling agent to the dispersant is 2:8-10:0.
  • the amount of the modifier is 0.05-10w% of the high thermal conductivity filler.
  • the high thermal conductivity filler was treated with a modifier, and when the amount of the modifier was 0.05-10w% of the high thermal conductivity filler, the thermal conductivity effect was better.
  • the applicant guessed that the possible reason was that the modifier processed the filler, so The thickness of the interface between the matrix and the filler is increased, and the bonding strength of the interface is correspondingly increased. Improving the dispersion process of the resin and the thermally conductive filler and increasing the bonding strength are helpful to the improvement of the thermal conductivity of the final composite material.
  • the content of modifier increases. Too much modifier increases the viscosity of the system and prevents the high thermal conductivity fillers from functioning. If the content of modifier is too small, the specific surface energy between the fillers is larger, which will cause agglomeration in the system. Defects in the thermal path.
  • the number of extrusions in the physical extrusion process in the step (2) is greater than one.
  • the pressure that the high thermal conductivity filler bears during the physical extrusion process in the step (2) is 0.1-200 MPa.
  • the physical extrusion treatment in the step (2) is any one of ball milling, roll pressing, and plate pressing.
  • chemical modification and physical modification can be combined, that is: adding modifier before or during ball milling, or adding modifier after proper time of ball milling to continue ball milling.
  • the extrusion time of the physical extrusion treatment in the step (2) is 1 s to 100 h; the extrusion temperature is -60 to 100°C.
  • the extrusion process of the high thermal conductivity filler and the extrusion pressure of 0.1-200MP can further improve the tensile strength and thermal conductivity of the composite material.
  • the mixing and curing process can effectively reduce the viscosity of the system and facilitate the crosslinking of the resin.
  • the second aspect of the present invention provides a modified high thermal conductivity filler prepared according to the chemical and physical treatment method of the high thermal conductivity filler.
  • the third aspect of the present invention provides a composite insulating material containing a modified high thermal conductivity filler.
  • the preparation method of the composite insulating material containing the modified high thermal conductivity filler includes: mixing the obtained modified high thermal conductivity filler with a resin, and then fully stirring and dispersing it.
  • the first embodiment of the present invention provides a composite insulating material containing a modified high thermal conductivity filler, which includes the following steps:
  • step (2) The modified filler obtained in step (1) is physically extruded by means of ball milling; the speed of the ball mill is 1500r/min, the extrusion time is 8h, the extrusion temperature is 60°C, and the pressure that the filler bears is 120MPa ;
  • step (3) Replace the powder obtained in step (3) with the filler obtained in step (1), and repeat step (5) to obtain glue 2;
  • step (3) Replace the powder obtained in step (3) with the high thermal conductivity hexagonal boron nitride that has not been treated in step (1), and repeat step (5) to obtain glue 3;
  • the viscosity of glue 1 is 3500 mPa ⁇ s
  • the viscosity of glue 2 is 152000 mPa ⁇ s
  • the viscosity of glue 3 is 935000 mPa ⁇ s.
  • the viscosity of glue 1 is only 1/267 of glue 3;
  • step (3) Weigh the filler obtained in step (3), gradually add it to 50g 128 epoxy resin, and use a centrifuge to continuously disperse it until dry powder appears, record the added filler content, and calculate the powder filling amount 1;
  • step (10) Replace the filler obtained in step (3) with the filler obtained in step (1), and repeat step (9) to obtain a filler filling amount of 2;
  • step (3) Replace the filler obtained in step (3) with the high thermal conductivity hexagonal boron nitride that has not been treated in step (1), and repeat step (9) to obtain a filler filling amount of 3;
  • the filler filling amount 1, 2, and 3 are 60%, 45%, and 40% respectively. This indicates that the method of the present invention can significantly increase the filling amount of boron nitride in the epoxy resin.
  • the second embodiment of the present invention provides a composite insulating material containing a modified high thermal conductivity filler, which includes the following steps:
  • the high thermal conductivity filler is surface-chemically modified with a modifier to obtain a modified filler;
  • the filler is angular alumina, the alumina particle size is 45 ⁇ m and 3 ⁇ m, and the mixing ratio is 3:2;
  • the modifier is a vinyl siloxane coupling agent, and the amount is 0.5 wt% of the high thermal conductivity filler;
  • step (2) Physically squeeze the modified filler obtained in step (1) by rolling; the pressure that the filler bears is 15MPa, the rotation speed is 2r/min, the temperature is 80°C, and the rolling time is 2h;
  • step (7) Replace the powder obtained in step (4) with the filler obtained in step (1), and repeat step (6) to obtain glue 2;
  • step (8) Replace the powder obtained in step (4) with the angular alumina that has not been treated in step (1), and repeat step (6) to obtain glue 3;
  • step (4) Weigh the filler obtained in step (4), gradually add it to 50g of 500mPa ⁇ s vinyl silicone oil with a viscosity of 500mPa ⁇ s, and use a centrifuge to continuously disperse it until dry powder appears, record the added filler content, and calculate the powder filling Quantity 1;
  • step (11) Replace the filler obtained in step (4) with the filler obtained in step (1), and repeat step (10) to obtain a filler filling amount of 2;
  • step (12) Replace the filler obtained in step (4) with the angular alumina that has not been treated in step (1), and repeat step (10) to obtain a filler filling amount of 3;
  • the filler filling amount 1, 2, and 3 are 91%, 83%, and 75%, respectively. This indicates that the method of the present invention can significantly increase the filling amount of the mixed alumina in the silicone oil.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

本发明涉及导热填料领域，更具体地，本发明涉及一种高导热填料的化学和物理处理方法，其包括下面步骤：(1)将高导热填料采用改性剂进行表面化学改性处理，得到改性填料；(2)对步骤(1)得到的改性填料进行物理挤压处理；物理挤压处理后得到的材料发生软团聚时，则需要进行物理粉碎。本发明提供的一种高导热填料的化学和物理方法能够实现对高导热填料的化学改性和物理整形、自适应级配，可用于复合材料制备，可以大幅度提高填料在树脂等中的填充量或降低胶液粘度，从而提高树脂等基体材料的热导率，并确保优异的工艺性。

Description

一种高导热填料的化学和物理处理方法
本申请要求了申请日为2020年02月21日，申请号为202010107935.5的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及导热填料领域，更具体地，本发明涉及一种高导热填料的化学和物理处理方法。
背景技术
目前高导热绝缘材料在电气设备、微电子、LED照明、太阳能、交通运输、航空航天、国防军工等现代高科技领域中有着十分广阔的应用前景。研制高导热绝缘材料，解决电气电子设备的散热问题，是国际电气电子绝缘领域的研究热点之一。对于聚合物材料而言提高其导热性能的方法主要有以下两种方式：一是制备本征型导热聚合物，即聚合物本身拥有良好的导热性能，这种方法是在聚合物的制备和加工过程中，采用一定的手段改变聚合物自身的分子及链接的结构来得到特殊的物理构型，以此来提高自身的热导率；二是制备填充型导热聚合物，即以聚合物为基体，添加高导热绝缘填料，通过一定工艺制备导热绝缘聚合物复合材料。用无机导热填料填充树脂基体的方法制得的复合材料具有易加工成型、价格低廉、导热性好等特点，这是目前来说制备导热材料的最简单、最有效的方法。随着聚合物基体中填料含量的增加，部分导热链、导热网会彼此相接和贯穿，最终形成贯穿整个基体的导热网络，此时填料也会变成连续相，填充型高分子复合材料的导热性能显著提高。因此，提高填料的填充量是提高聚合物基复合材料热导率的关键。然而，目前未经改性的导热填料或经过化学改性的填料，其填充量仍然不能满足导热技术发展的要求。此外，在一定的填充量下，如何降低胶液的粘度也是目前导热技术发展面临的一个重要问题。
发明内容
针对现有技术中存在的一些问题，本发明第一个方面提供了一种高导热填料的化学和物理处理方法，其包括下面步骤：
(1)将高导热填料采用改性剂进行表面化学改性处理，得到改性填料；
(2)对步骤(1)得到的改性填料进行物理挤压处理；物理挤压处理后得到的材料发生软团聚时，则需要进行物理粉碎。
作为本发明的一种优选地技术方案，所述步骤(2)中物理挤压处理的挤压次数大于1。
作为本发明的一种优选地技术方案，所述高导热填料选自氧化铝、氧化硅、氮化铝、氮化硼、氧化锌、碳化硅中的一种或多种。
作为本发明的一种优选地技术方案，所述高导热填料的形状选自角形、球形、片状、针状、纤维状中的一种或多种。
作为本发明的一种优选地技术方案，所述高导热填料的粒径为0.01～500um。
作为本发明的一种优选地技术方案，所述改性剂选自偶联剂、分散剂、表面活性剂中的一种或多种。
作为本发明的一种优选地技术方案所述改性剂用量为高导热填料的0.05～10w％。
作为本发明的一种优选地技术方案，所述步骤(2)中物理挤压处理时高导热填料所承受压强为0.1～200MPa。
作为本发明的一种优选地技术方案，所述步骤(2)中物理挤压处理的方式为球磨、辊压、板压中任一种。
作为本发明的一种优选地技术方案，所述步骤(2)中物理挤压处理的挤压时间为1s～100h；挤压温度为-60～100℃。
本发明第二个方面提供了一种根据所述高导热填料的化学和物理处理方法制备得到的改性高导热填料。
本发明与现有技术相比具有以下有益效果：
本发明提供的一种高导热填料的化学和物理方法能够实现对高导热填料的化学改性和物理整形、自适应级配，可用于复合材料制备，可以大幅度提高填料在树脂等中的填充量或降低胶液粘度，从而提高树脂等基体材料的热导率，并确保优异的工艺性。
具体实施方式
参选以下本发明的优选实施方法的详述以及包括的实施例可更容易地理解本发明的内容。除非另有限定，本文使用的所有技术以及科学术语具有与本发明所属领域普通技术人员通常理解的相同的含义。当存在矛盾时，以本说明书 中的定义为准。
本文中所用的术语“包含”、“包括”、“具有”、“含有”或其任何其它变形，意在覆盖非排它性的包括。例如，包含所列要素的组合物、步骤、方法、制品或装置不必仅限于那些要素，而是可以包括未明确列出的其它要素或此种组合物、步骤、方法、制品或装置所固有的要素。
当量、浓度、或者其它值或参数以范围、优选范围、或一系列上限优选值和下限优选值限定的范围表示时，这应当被理解为具体公开了由任何范围上限或优选值与任何范围下限或优选值的任一配对所形成的所有范围，而不论该范围是否单独公开了。例如，当公开了范围“1至5”时，所描述的范围应被解释为包括范围“1至4”、“1至3”、“1至2”、“1至2和4至5”、“1至3和5”等。当数值范围在本文中被描述时，除非另外说明，否则该范围意图包括其端值和在该范围内的所有整数和分数。
此外，本发明要素或组分前的不定冠词“一种”和“一个”对要素或组分的数量要求(即出现次数)无限制性。因此“一个”或“一种”应被解读为包括一个或至少一个，并且单数形式的要素或组分也包括复数形式，除非所述数量明显指单数形式。
本发明第一个方面提供了一种高导热填料的化学和物理处理方法，其包括下面步骤：
(1)将高导热填料采用改性剂进行表面化学改性处理，得到改性填料；
(2)对步骤(1)得到的改性填料进行物理挤压处理；物理挤压处理后得到的材料发生软团聚时，则需要进行物理粉碎。
软团聚：软团聚主要是由颗粒间的范德华力和库仑力所致，所以通过一些化学的作用或施加机械能的方式，就可以使其大部分消除。
步骤(1)
在一种实施方式中，所述高导热填料选自氧化铝、氧化硅、氮化铝、氮化硼、氧化锌、碳化硅中的一种或多种。
优选地，所述高导热填料的形状选自角形、球形、片状、针状、纤维状中的一种或多种；更有选地，所述高导热填料的形状为片状和/或角形。
在一种实施方式中，所述高导热填料的粒径为0.01～500um。
本发明所述高导热填料的粒径可以为单一粒径，也可以为多种粒径的复配。
在一种实施方式中，所述改性剂选自偶联剂、分散剂、表面活性剂中的一种或多种。
优选地，所述改性剂为偶联剂和分散剂；更优选地，所述偶联剂和分散剂的重量比为2∶8～10∶0。
在一种实施方式中，所述改性剂用量为高导热填料的0.05～10w％。
申请人意外地发现使用改性剂对高导热填料进行处理，且改性剂用量为高导热填料的0.05～10w％时导热效果较好，申请人猜测可能的原因是改性剂处理填料，使得基体与填料的界面厚度有所增加，界面粘结强度相应增加，改善树脂与导热填料的分散工艺和增加粘结强度，对最终复合材料导热性能的提高有帮助。改性剂含量增多，过多的改性剂增加了体系的粘度，阻碍高导热填料发挥作用，而改性剂的含量过少，填料之间的比表面能较大，在体系中团聚，造成导热通路的缺陷。
步骤(2)
在一种实施方式中，所述步骤(2)中物理挤压处理的挤压次数大于1。
优选地，所述步骤(2)中物理挤压处理时高导热填料所承受压强为0.1～200MPa。
优选地，所述步骤(2)中物理挤压处理的方式为球磨、辊压、板压中任一种。
本发明所述物理挤处理的方式为球磨时，可将化学改性与物理改性结合起来，即：在球磨前或球磨过程中加入改性剂，或球磨适当时间后再加入改性剂继续球磨。
在一种实施方式中，所述步骤(2)中物理挤压处理的挤压时间为1s～100h；挤压温度为-60～100℃。
申请人意外地发现对高导热填料进行挤压处理，且挤压压力为0.1～200MP能够进一步提高复合材料的拉伸强度和导热率，申请人认为可能的原因是经过挤压处理后，降低填料由于高的比表面能而发生团聚，有利于形成了滚珠-轴承结构或星形结构填料，有利于热量的传导，同时可能会降低填料带给体系的内摩擦作用，并且在树脂和高导热填料混合固化的过程中能够有效降低体系的粘 度，利于树脂的交联。
本发明第二个方面提供了一种根据所述高导热填料的化学和物理处理方法制备得到的改性高导热填料。
本发明第三个方面提供了一种含有改性高导热填料的复合绝缘材料。
在一种实施方式中，所述含有改性高导热填料的复合绝缘材料的制备方法包括：将得到的改性高导热填料与树脂混合，充分搅拌分散即得。
实施例
在下文中，通过实施例对本发明进行更详细地描述，但应理解，这些实施例仅仅是示例的而非限制性的。如果没有其它说明，下面实施例所用原料都是市售的。
实施例1
本发明实施1提供了一种含有改性高导热填料的复合绝缘材料，其包括下面步骤：
(1)将高导热填料采用改性剂进行表面化学改性处理，得到改性填料；所述填料为高导热六方氮化硼，片径为10μm；所述改性剂为KH560，用量为高导热填料的2wt％；
(2)对步骤(1)得到的改性填料采用球磨的方式进行物理挤压处理；球磨机转速为1500r/min，挤压时间为8h，挤压温度为60℃，填料所承受的压强为120MPa；
(3)将步骤(2)处理后的粉体进行过滤；
(4)以128环氧树脂为基体；
(5)称取步骤(3)得到的50g填料与50g的128环氧树脂，充分搅拌分散20min，得到胶液1；
(6)用步骤(1)得到的填料代替步骤(3)得到的粉体，重复步骤(5)，得到胶液2；
(7)用步骤(1)中未经任何处理的高导热六方氮化硼代替步骤(3)得到的粉体，重复步骤(5)，得到胶液3；
(8)采用旋转粘度计，在80℃下测试三种胶液的粘度。胶液1的粘度为3500mPa·s，胶液2的粘度为152000mPa·s，胶液3的粘度为935000mPa·s。胶 液1的粘度只有胶液3的1/267；
(9)称取步骤(3)得到的填料，逐步加入到50g 128环氧树脂中，并采用离心机不断分散，直到有干粉出现为止，记录加入填料含量，计算得出粉体填充量1；
(10)用步骤(1)得到的填料代替步骤(3)得到的填料，重复步骤(9)，得出填料填充量2；
(11)用步骤(1)中未经任何处理的高导热六方氮化硼代替步骤(3)得到的填料，重复步骤(9)，得出填料填充量3；
经计算，填料填充量1、2、3分别为60％、45％、40％。这表明本发明的方法可以显著提升氮化硼在环氧树脂中的填充量。
实施例2
本发明实施2提供了一种含有改性高导热填料的复合绝缘材料，其包括下面步骤：
(1)将高导热填料采用改性剂进行表面化学改性处理，得到改性填料；所述填料为角形氧化铝，氧化铝粒径为45μm和3μm，其混配比例为3∶2；所述改性剂为乙烯基硅氧烷偶联剂，用量为高导热填料的0.5wt％；
(2)对步骤(1)得到的改性填料采用辊压的方式进行物理挤压处理；填料所承受的压强为15MPa，转速为2r/min，温度为80℃，辊压时间为2h；
(3)将步骤(2)处理后的填料进行粉碎；
(4)重复步骤(2)和(3)，压强调整为20MPa；
(5)以粘度500mPa·s乙烯基硅油为基体；
(6)称取步骤(4)得到的70g填料与30g的乙烯基硅油，充分搅拌分散20min，得到胶液1；
(7)用步骤(1)得到的填料代替步骤(4)得到的粉体，重复步骤(6)，得到胶液2；
(8)用步骤(1)中未经任何处理的角形氧化铝代替步骤(4)得到的粉体，重复步骤(6)，得到胶液3；
(9)采用旋转粘度计，在80℃下测试三种胶液的粘度。胶液1的粘度为6500mPa·s，胶液2的粘度为46000mPa·s，胶液3的粘度为168000mPa·s。胶液 1的粘度只有胶液3的1/26；
(10)称取步骤(4)得到的填料，逐步加入到50g粘度500mPa·s乙烯基硅油中，并采用离心机不断分散，直到有干粉出现为止，记录加入填料含量，计算得出粉体填充量1；
(11)用步骤(1)的得到的填料代替步骤(4)得到的填料，重复步骤(10)，得出填料填充量2；
(12)用步骤(1)中未经任何处理的角形氧化铝代替步骤(4)得到的填料，重复步骤(10)，得出填料填充量3；
经计算，填料填充量1、2、3分别为91％、83％、75％。这表明本发明的方法可以显著提升混配氧化铝在硅油中的填充量。
前述的实例仅是说明性的，用于解释本发明所述方法的一些特征。所附的权利要求旨在要求可以设想的尽可能广的范围，且本文所呈现的实施例仅是根据所有可能的实施例的组合的选择的实施方式的说明。因此，申请人的用意是所附的权利要求不被说明本发明的特征的示例的选择限制。在权利要求中所用的一些数值范围也包括了在其之内的子范围，这些范围中的变化也应在可能的情况下解释为被所附的权利要求覆盖。

Claims (10)

  1. 一种高导热填料的化学和物理处理方法，其特征在于，其包括下面步骤：
    (1)将高导热填料采用改性剂进行表面化学改性处理，得到改性填料；
    (2)对步骤(1)得到的改性填料进行物理挤压处理；物理挤压处理后得到的材料发生软团聚时，则需要进行物理粉碎。
  2. 根据权利要求1所述高导热填料的化学和物理处理方法，其特征在于，所述步骤(2)中物理挤压处理的挤压次数大于1。
  3. 根据权利要求1所述高导热填料的化学和物理处理方法，其特征在于，所述高导热填料选自氧化铝、氧化硅、氮化铝、氮化硼、氧化锌、碳化硅中的一种或多种。
  4. 根据权利要求1所述高导热填料的化学和物理处理方法，其特征在于，所述高导热填料的形状选自角形、球形、片状、针状、纤维状中的一种或多种。
  5. 根据权利要求1所述高导热填料的化学和物理处理方法，其特征在于，所述高导热填料的粒径为0.01～500um。
  6. 根据权利要求1所述高导热填料的化学和物理处理方法，其特征在于，所述表面改性剂选自偶联剂、分散剂、表面活性剂中的一种或多种。
  7. 根据权利要求1所述高导热填料的化学和物理处理方法，其特征在于，所述改性剂用量为高导热填料的0.05～10w％。
  8. 根据权利要求1所述高导热填料的化学和物理处理方法，其特征在于，所述步骤(2)中物理挤压处理时高导热填料所承受压强为0.1～200MPa。
  9. 根据权利要求1所述高导热填料的化学和物理处理方法，其特征在于，所述步骤(2)中物理挤压处理的方式为球磨、辊压、板压中任一种。
  10. 根据权利要求1～9任一项所述高导热填料的化学和物理处理方法，其特征在于，所述步骤(2)中物理挤压处理的挤压时间为1s～100h；挤压温度为-60～100℃。
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