WO2023273192A1 - 一种改性二氧化硅填料及其制备方法 - Google Patents

一种改性二氧化硅填料及其制备方法 Download PDF

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WO2023273192A1
WO2023273192A1 PCT/CN2021/137826 CN2021137826W WO2023273192A1 WO 2023273192 A1 WO2023273192 A1 WO 2023273192A1 CN 2021137826 W CN2021137826 W CN 2021137826W WO 2023273192 A1 WO2023273192 A1 WO 2023273192A1
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coupling agent
silane coupling
preparation
set temperature
reaction product
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French (fr)
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王宁
朱朋莉
孙蓉
杜晓蒙
张磊聪
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Shenzhen Institute of Advanced Technology of CAS
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Shenzhen Institute of Advanced Technology of CAS
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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
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • 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
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3009—Physical treatment, e.g. grinding; treatment with ultrasonic vibrations
    • C09C1/3027—Drying, calcination
    • 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
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3081—Treatment with organo-silicon 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
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/309—Combinations of treatments provided for in groups C09C1/3009 - C09C1/3081
    • 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
    • C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
    • 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
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
    • 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

Definitions

  • the application relates to the technical field of chemical engineering, in particular to a modified silica filler and a preparation method thereof.
  • Silica filler has been widely used in electronic packaging materials such as underfill adhesives, epoxy molding compounds, and insulating adhesive films due to its low thermal expansion coefficient, good thermal stability, and chemical stability.
  • the thermal expansion coefficient of the resin material added with silica filler decreases with the increase of the silica filling amount, but the silica filler without surface modification is easy to be caused by the cohesion between the fillers and the filler in the case of high filling. Poor compatibility with the resin leads to increased viscosity and delamination of the system, resulting in failure of the composite.
  • the existing surface modification methods such as atmospheric pressure liquid phase (wet method) modification and dry method, all have the problem of low surface grafting amount.
  • the normal pressure liquid phase method (wet method) modification needs to consume a large amount of organic solvent, the silica filler and the silane coupling agent cannot be fully contacted, the reaction is not complete, and the amount of grafting on the surface is low; the dry method modification is likely to cause a lot of dust , The silica filler and the silane coupling agent cannot fully contact, the reaction is not complete, and the amount of grafting on the surface is low.
  • the main technical problem to be solved in this application is to provide a modified silica filler and its preparation method, so as to solve the problem of low surface grafting amount in the modification method of silica filler in the prior art.
  • a technical solution adopted by the present application is to provide a preparation method of modified silica filler, which preparation method includes: providing a silane coupling agent and silica powder with a set mass ratio; The coupling agent is added to the silica powder and stirred at the first set temperature to seal the reaction for the first set time to obtain the first reaction product; vacuum the first reaction product at the second set temperature Drying for a second set time yields a modified silica filler.
  • the silane coupling agent is added to the silica powder, and stirred at the first set temperature to seal the reaction for the first set time to obtain the first reaction product, including: adding the silane coupling agent to the two silicon oxide powder, and after adding a set volume of organic dispersant, stir at a set temperature at a set stirring speed to seal the reaction for a set time and obtain a first reaction product.
  • the silane coupling agent is added to the silica powder and stirred at the first set temperature to seal the reaction for the first set time , before obtaining the first reaction product, further comprising: heating the silicon dioxide powder to a third set temperature; wherein, the third set temperature is lower than the first set temperature; adding a silane coupling agent to the silicon dioxide powder , including: adding the silane coupling agent to the silica powder in the form of spraying.
  • the silane coupling agent is added to the silica powder, stirred at the first set temperature to seal the reaction for the first set time, after the first reaction product is obtained, the second set temperature is added to the second set temperature.
  • the first reaction product is vacuum-dried for a second set time, before obtaining the modified silica filler, further includes: separating the first reaction product with a set centrifugal speed.
  • the mass of the silicon dioxide powder is 0.5-5 g, and the set mass ratio of the silane coupling agent to the silicon dioxide powder is 0.1-0.5%.
  • the average particle size of the silica powder ranges from 0.2 to 5 ⁇ m.
  • the silane coupling agent is 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, bis(3-trimethoxysilylpropyl)amine, N-cyclohexyl- ⁇ - Aminopropyltrimethoxysilane, ⁇ -glycidyloxypropyltrimethoxysilane, 3-(2,3-epoxypropoxy)propylmethyldimethoxysilane, ⁇ -glycidyloxypropyl One or more mixtures of triethoxysilanes.
  • the organic dispersant is one or a mixture of methanol, ethanol, isopropanol and propanol.
  • the first set temperature is 120-180°C
  • the first set time is 0.5-24h
  • the second set temperature is 40-150°C
  • the second set time is 2-5h.
  • another technical solution adopted by the present application is to provide a modified silica filler, which is made by any one of the preparation methods described above.
  • the preparation method of the modified silica filler in this application provides a set mass ratio of silane coupling agent and silica powder, so that the silane coupling agent is added to the silica powder, Stir at the first set temperature, and seal the reaction for the first set time, so that the silicon dioxide powder can be fully contacted with the silane coupling agent, and the reaction is complete enough, so that the amount of the coupling agent can be reduced,
  • Obtaining the first reaction product not only reduces the preparation cost and improves economic benefits, but also avoids the phenomenon that the dispersibility of silica caused by excessive addition of coupling agent is reduced; further, at the second set temperature, the second The first reaction product is vacuum-dried for a second set time to obtain a modified silica filler, so that the modified silica filler can be obtained by making full use of the silane coupling agent, so as to greatly increase the surface grafting amount of the silica powder.
  • Fig. 1 is the schematic flow sheet of the first embodiment of the preparation method of the modified silica filler of the present application
  • Fig. 2 is the reaction schematic diagram of silicon dioxide and amine silane coupling agent in the present application
  • Fig. 3 is the schematic flow chart of the second embodiment of the preparation method of the modified silica filler of the present application.
  • Fig. 4 is a schematic diagram of diffuse reflection infrared transmittance corresponding to silica filler and silica filler modified by silane coupling agent in a specific application scenario of the present application;
  • Figure 5 is a schematic diagram of thermogravimetric analysis before and after the reaction of the silica filler modified by the silane coupling agent in Figure 4;
  • Fig. 6 is a schematic structural view of an embodiment of the modified silica filler of the present application.
  • FIG. 1 is a schematic flow diagram of the first embodiment of the preparation method of the modified silica filler of the present application.
  • the preparation method includes:
  • S11 Provide a silane coupling agent and silicon dioxide powder with a set mass ratio.
  • silica fillers have been widely used in electronic packaging materials such as underfill adhesives, epoxy molding compounds, and insulating adhesive films due to their low thermal expansion coefficient, good thermal and chemical stability, and the like.
  • the thermal expansion coefficient of the resin material added with silica filler decreases with the increase of silica filling amount, but the silica filler without surface modification is easy to be caused by the cohesion between fillers under the condition of high filling. Poor compatibility between the filler and the resin leads to an increase in the viscosity of the system and delamination, resulting in the failure of the composite material.
  • the grafted functional groups have good compatibility with the resin, thus ensuring the dispersion stability of the filler in the resin.
  • silicon dioxide powder an appropriate amount of silicon dioxide powder is provided, and based on the quality of the silicon dioxide powder, a silane coupling agent matching its mass ratio is prepared.
  • the silane coupling agent specifically refers to an organosilicon monomer having two or more different reactive groups in the molecule, which can cause chemical bonding (coupling) of organic materials and inorganic materials.
  • the molecular structure of the silane coupling agent is approximately in the shape of a regular tetrahedron, and the silicon atom is located at the apex, connecting three alkoxy groups (hydrolyzable groups) and a functional group (lipophilic group).
  • the corresponding silane couple can be equipped according to the mass ratio with the silicon dioxide powder, that is, the mass ratio is set to be 0.1-5%. joint agent.
  • the average particle diameter of the silicon dioxide powder is in the range of 0.2-5 ⁇ m.
  • the silane coupling agent is 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, bis(3-trimethoxysilylpropyl)amine, N-cyclohexyl - ⁇ -aminopropyltrimethoxysilane, ⁇ -glycidyloxypropyltrimethoxysilane (KBM-403), 3-(2,3-glycidoxy)propylmethyldimethoxysilane , ⁇ -glycidyl etheroxypropyltriethoxysilane and other reasonable silane coupling agents or a mixture of several, which is not limited in this application.
  • S12 Add the silane coupling agent to the silica powder, and stir at the first set temperature to seal the reaction for the first set time to obtain the first reaction product.
  • the silane coupling agent is added to the silica powder for mixing, for example, the silica powder and the silane coupling agent are placed in a pre-prepared three-necked flask, or any other reasonable chemical reaction container Finally, seal and heat the reaction vessel, so that the silane coupling agent and silicon dioxide powder reach the first set temperature, and simultaneously carry out high-speed stirring, so that the silane coupling agent and silicon dioxide powder can fully contact , and after continuing the reaction for the first set time, the corresponding first reaction product is obtained.
  • silicon dioxide powder and silane coupling agent are added into the hydrothermal reactor with Teflon lining in no order, so that the hydrothermal reactor can be sealed and heated , after heating the silane coupling agent and the silicon dioxide powder to a first set temperature and continuing to react for a first set time with stirring, a first reaction product is obtained.
  • the first reaction product is specifically a modified product after a dehydration condensation reaction occurs between silicon dioxide and a silane coupling agent.
  • FIG. 2 is a schematic diagram of the reaction between silicon dioxide and an amine silane coupling agent in this application.
  • hydroxyl groups on the surface of silica there are hydroxyl groups on the surface of silica, and adjacent hydroxyl groups are bonded to each other through hydrogen bonds. Isolated hydrogen atoms are highly electropositive and are easy to adsorb with electronegative atoms, and can undergo dehydration condensation reactions with hydroxyl-containing compounds.
  • the silane coupling agent is added to the silica powder for reaction, the alkoxy group in the silane coupling agent can react with the hydroxyl group on the surface of the silica to remove a small molecule of alcohol, thereby connecting with the silica with a chemical bond , and the lipophilic group (such as amino group) in the molecular formula can react with the polymer molecular chain to be filled.
  • the first set temperature is 120-180°C
  • the first set time is 0.5-24h.
  • the first reaction product is separated and kept at a second set temperature for vacuum drying, so as to obtain a surface-modified silica filler after vacuum drying for a second set time.
  • the silicon dioxide is the surface of the modified silicon dioxide that undergoes in-situ polymerization with the silane coupling agent as the starting point to form a compound graft-modified silicon dioxide product, so as to obtain improved Silica filler can greatly increase the surface grafting amount of silica powder.
  • the second set temperature is 40-150°C, and the second set time is 2-5h.
  • the above-mentioned S12 may specifically include: adding a silane coupling agent to the silica powder, and adding a set volume of organic dispersant, then using the set temperature at the first set temperature. Stir at a stirring speed to seal the reaction for a first set time to obtain a first reaction product.
  • the silane coupling agent in order to ensure that the chemical reaction between the silane coupling agent and the silica powder can be more uniform, that is, to make the distribution of the surface grafting amount of the silica powder more uniform, it is also possible to accommodate the silane coupling agent.
  • the reaction container of agent and silicon dioxide powder add the organic dispersant of set volume, so that silane coupling agent, silicon dioxide powder and organic dispersant are stirred at the first set temperature with a set stirring speed, The first reaction product is obtained after the silicon dioxide powder and the silane coupling agent fully and uniformly carry out the sealing reaction under the action of the organic dispersant for the first set time.
  • the organic dispersant is one or a mixture of any reasonable dispersants such as methanol, ethanol, isopropanol, propanol, etc., which is not limited in this application.
  • the set volume is 20-200mL.
  • it may specifically include: separating the first reaction product by using a set centrifugal speed.
  • the silane coupling agent is usually in a liquid state. After it reacts with the silica powder, especially after adding an organic dispersant to the silane coupling agent and the silica powder for reaction, the corresponding The first reaction product is separated from the liquid substance not participating in the reaction, for example, the solid-liquid separation is carried out by means of high-speed centrifugation, so as to separate the first reaction product.
  • the set centrifugal speed is 6000-8000r/min.
  • the above S13 may specifically include: performing vacuum suction filtration on the first reaction product to obtain a suction-filtration sample; washing the suction-filtration sample with pure water three times, and then using ethanol to wash the suction-filtration sample three times to obtain a washed sample; vacuum-dry the washed sample to obtain a modified silica filler; wherein, the drying temperature is controlled to be 40-150°C.
  • the above S13 may also include: making a resin composition by modifying silica filler, or any reasonable electronic package such as underfill glue, epoxy molding compound, insulating film, etc.
  • a resin composition by modifying silica filler, or any reasonable electronic package such as underfill glue, epoxy molding compound, insulating film, etc.
  • any reasonable electronic package such as underfill glue, epoxy molding compound, insulating film, etc.
  • FIG. 3 is a schematic flow diagram of the second embodiment of the preparation method of the modified silica filler of the present application.
  • the preparation method of the modified silica filler in this embodiment is a schematic flow diagram of a refinement example of the preparation method of the modified silica filler in Fig. 1, including the following steps:
  • S21 Provide a silane coupling agent and silicon dioxide powder with a set mass ratio.
  • S21 is the same as S11 in FIG. 1 , please refer to S11 and related text descriptions for details, and details will not be repeated here.
  • the silicon dioxide powder is added into the high-speed mixer to preheat it to reach the third preset temperature, so as to facilitate subsequent full reaction with the silane coupling agent.
  • the third set temperature is lower than the first set temperature.
  • the third set temperature is 90-110°C.
  • the silane coupling agent is added to the silica powder in the form of spraying, so that it is fully and uniformly contacted and mixed with the silica powder, and the silane coupling agent and the silica powder are heated to The first set temperature is accompanied by stirring, and the first reaction product is obtained after the sealed reaction for the first set time.
  • S24 is the same as S13 in FIG. 1 , please refer to S13 and related text descriptions for details, and details will not be repeated here.
  • silica powder Put 0.5-5g silica powder, 0.1-5% silane coupling agent and 20-50ml organic dispersant in sequence in a 100ml hydrothermal tank with Teflon lining
  • the reaction kettle is sealed for 0.5-24 hours of reaction at 120-180° C. with a stirring speed of 200-500 rpm.
  • the silica average particle size range is 0.2-5 microns;
  • the silane coupling agent can be 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, bis(3-trimethoxy silylpropyl)amine, N-cyclohexyl- ⁇ -aminopropyltrimethoxysilane, ⁇ -glycidyloxypropyltrimethoxysilane (KBM-403), 3-(2,3-cyclo Oxypropoxy)propylmethyldimethoxysilane, ⁇ -glycidyl etheroxypropyltriethoxysilane or a mixture of one or more of silane coupling agents with other functional groups;
  • the organic dispersant It can be one or a mixture of methanol, ethanol, isopropanol, and propanol.
  • the product of the hydrothermal reaction is separated by high-speed centrifugation at 6000-8000 rpm, and the centrifuged product is vacuum-dried at 40-150°C for 2-5 hours to obtain the final surface-modified silica filler.
  • the mass percent of silicon dioxide powder and the KBM-403 silane coupling agent of 3% and 20 milliliters of ethanol are sealed in a 100 milliliter hydrothermal reactor with a Teflon liner, in React at 150 degrees Celsius and 400 rpm stirring speed for 24 hours; separate the hydrothermal reaction product by high-speed centrifugation at 6000 rpm; vacuum dry the centrifuged product at 150 degrees Celsius for 5 hours to obtain the final surface-modified bismuth Silica filler, the TGA weight loss rate of the filler is 0.75%.
  • Fig. 4 is a schematic diagram of diffuse reflectance infrared transmittance corresponding to silica filler and silica filler modified by silane coupling agent in a specific application scenario of the present application
  • Fig. 5 is a schematic diagram of thermogravimetric analysis of the silica filler modified by the silane coupling agent in Fig. 4 before and after reaction.
  • the modified silica filler in Fig. 4 and Fig. 5 can be specifically understood as being prepared by the preparation method shown in the above-mentioned Example 4. It can be seen that the modified silica, that is, the surface of the silica filler modified by the silane coupling agent has obvious methyl and methylene infrared peaks, indicating that the silica surface has been successfully coated or bonded. KBM-403 silane coupling agent is attached to the branch. The weight loss rate of the modified silica is 0.75%, which also shows that the silica surface is coated or grafted with KBM-403 silane coupling agent.
  • the present application also provides a modified silica filler.
  • the modified silica filler is made by the preparation method described in any one of the above.
  • FIG. 6 is a schematic structural view of an embodiment of the modified silica filler of the present application.
  • the polymerization center in the modified silica filler is the lipophilic group (amino group) of the silane coupling agent, and the epoxy compound is connected through the amino group so that the surface of the silica can be contacted.
  • the surface of the modified silica filler provided by this application can be grafted with compounds of different properties through a silane coupling agent, which has the characteristics of uniform and complete graft coating and good dispersion, and can be more Well dispersed in the resin matrix to improve the fluidity of the resin composite system.
  • the preparation method of the modified silica filler in this application provides a set mass ratio of silane coupling agent and silica powder, so that the silane coupling agent is added to the silica powder, Stir at the first set temperature, and seal the reaction for the first set time, so that the silicon dioxide powder can be fully contacted with the silane coupling agent, and the reaction is complete enough, so that the amount of the coupling agent can be reduced,
  • Obtaining the first reaction product not only reduces the preparation cost and improves economic benefits, but also avoids the phenomenon that the dispersibility of silica caused by excessive addition of coupling agent is reduced; further, at the second set temperature, the second The first reaction product is vacuum-dried for a second set time to obtain a modified silica filler, so that the modified silica filler can be obtained by making full use of the silane coupling agent, so as to greatly increase the surface grafting amount of the silica powder.

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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)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Silicon Compounds (AREA)

Abstract

本申请公开了一种改性二氧化硅填料及其制备方法，其中，该制备方法包括：提供设定质量比值的硅烷偶联剂和二氧化硅粉末；将硅烷偶联剂加入到二氧化硅粉末中，在第一设定温度下进行搅拌，以密封反应第一设定时间，获得第一反应产物；在第二设定温度下对第一反应产物进行真空干燥第二设定时间，获得改性二氧化硅填料。上述方案，通过在密封环境下对添加有硅烷偶联剂的二氧化硅粉末进行搅拌，以使二氧化硅粉末能够充分地与硅烷偶联剂进行接触，进而使二者的反应足够完全，以能够充分利用硅烷偶联剂，大幅提高二氧化硅粉末的表面接枝量

Description

一种改性二氧化硅填料及其制备方法 技术领域
本申请涉及化学工程技术领域，特别是涉及一种改性二氧化硅填料及其制备方法。
 背景技术
二氧化硅填料由于具有热膨胀系数低，热稳定和化学稳定性好等特点，已广泛应用于底部填充胶、环氧模塑料、绝缘胶膜等电子封装材料中。添加了二氧化硅填料的树脂材料，其热膨胀系数随二氧化硅填充量的增加而降低，但不经表面改性的二氧化硅填料在高填充情况下，容易因填料间的内聚和填料与树脂间较差的相容性导致体系粘度的升高和分层，从而造成复合材料的失效。为减少二氧化硅填料间的内聚和提高填料与树脂基体间的界面相容性，通常需要用硅烷偶联剂对二氧化硅进行表面改性，根据树脂类型接枝一些有机官能团。基于相似相溶原理，接枝的官能团与树脂具有良好的相容性，从而保证了填料在树脂中的分散稳定性。
 技术问题
然而，现有的表面改性方法，如常压液相法（湿法）改性和干法改性，都存在表面接枝量不高的问题。其中，常压液相法（湿法）改性需要消耗大量有机溶剂，二氧化硅填料与硅烷偶联剂不能充分接触，反应不够完全，表面接枝量低；干法改性容易造成大量粉尘，二氧化硅填料与硅烷偶联剂不能充分接触，反应不够完全，表面接枝量低。
 技术解决方案
本申请主要解决的技术问题是提供一种改性二氧化硅填料及其制备方法，以解决现有技术中的二氧化硅填料的改性方法存在表面接枝量不高的问题。
为解决上述技术问题，本申请采用的一个技术方案是提供一种改性二氧化硅填料的制备方法，该制备方法包括：提供设定质量比值的硅烷偶联剂和二氧化硅粉末；将硅烷偶联剂加入到二氧化硅粉末中，在第一设定温度下进行搅拌，以密封反应第一设定时间，获得第一反应产物；在第二设定温度下对第一反应产物进行真空干燥第二设定时间，获得改性二氧化硅填料。
其中，将硅烷偶联剂加入到二氧化硅粉末中，在第一设定温度下进行搅拌，以密封反应第一设定时间，获得第一反应产物，包括：将硅烷偶联剂加入到二氧化硅粉末中，并加入设定容积的有机分散剂后，在第一设定温度下采用设定搅拌速度进行搅拌，以密封反应第一设定时间，获得第一反应产物。
其中，提供设定重量比值的硅烷偶联剂和二氧化硅粉末之后，将硅烷偶联剂加入到二氧化硅粉末中，在第一设定温度下进行搅拌，以密封反应第一设定时间，获得第一反应产物之前，还包括：将二氧化硅粉末加热至第三设定温度；其中，第三设定温度低于第一设定温度；将硅烷偶联剂加入到二氧化硅粉末中，包括：将硅烷偶联剂以喷雾的形式加入到二氧化硅粉末中。
其中，将硅烷偶联剂加入到二氧化硅粉末中，在第一设定温度下进行搅拌，以密封反应第一设定时间，获得第一反应产物之后，在第二设定温度下对第一反应产物进行真空干燥第二设定时间，获得改性二氧化硅填料之前，还包括：采用设定离心转速分离出第一反应产物。
其中，二氧化硅粉末的质量为0.5-5g，硅烷偶联剂与二氧化硅粉末的设定质量比值为0.1-0.5%。
其中，二氧化硅粉末的平均粒径范围为0.2-5µm。
其中，硅烷偶联剂为3-氨丙基三甲氧基硅烷、3-氨丙基三乙氧基硅烷、双(3-三甲氧基甲硅烷基丙基)胺、N-环己基-γ-氨丙基三甲氧基硅烷、γ-缩水甘油醚氧丙基三甲氧基硅烷、3-(2，3-环氧丙氧)丙基甲基二甲氧基硅烷、γ-缩水甘油醚氧丙基三乙氧基硅烷中的一种或几种的混合物。
其中，有机分散剂为甲醇、乙醇、异丙醇、丙醇中的一种或几种的混合物。
其中，第一设定温度为120-180℃，第一设定时间为0.5-24h；第二设定温度为40-150℃，第二设定时间为2-5h。
为解决上述技术问题，本申请采用的另一个技术方案是提供一种改性二氧化硅填料，该改性二氧化硅填料由上述任一项所述的制备方法制成。
 有益效果
区别于现有技术，本申请中的改性二氧化硅填料的制备方法通过提供设定质量比值的硅烷偶联剂和二氧化硅粉末，以将硅烷偶联剂加入到二氧化硅粉末中，在第一设定温度下进行搅拌，并密封反应第一设定时间，以使二氧化硅粉末能够充分地与硅烷偶联剂进行接触，而反应足够完全，从而能够降低偶联剂的用量，以获得第一反应产物，不仅降低了制备成本，提高了经济效益，还能避免因过量添加偶联剂导致的二氧化硅分散性降低的现象；进一步地，在第二设定温度下对第一反应产物进行真空干燥第二设定时间，以获得改性二氧化硅填料，从而能够充分利用硅烷偶联剂获得改性二氧化硅填料，以大幅提高二氧化硅粉末的表面接枝量。
 附图说明
为了更清楚地说明本申请实施例中的技术方案，下面将对实施例描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本申请的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1是本申请改性二氧化硅填料的制备方法第一实施方式的流程示意图；
图2是本申请中二氧化硅与胺类硅烷偶联剂的反应示意图；
图3是本申请改性二氧化硅填料的制备方法第二实施方式的流程示意图；
图4是本申请一具体应用场景中二氧化硅填料以及经硅烷偶联剂改性的二氧化硅填料对应的漫反射红外透过率示意图；
图5是图4中经硅烷偶联剂改性的二氧化硅填料反应前后的热重分析示意图；
图6是本申请改性二氧化硅填料一实施方式的结构示意图。
 本发明的实施方式
下面将结合本申请实施例中的附图，对本申请实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，均属于本申请保护的范围。
在本申请实施例中使用的术语是仅仅出于描述特定实施例的目的，而非旨在限制本申请。在本申请实施例和所附权利要求书中所使用的单数形式的“一种”、“所述”和“该”也旨在包括多数形式，除非上文清楚地表示其他含义，“多种”一般包含至少两种，但是不排除包含至少一种的情况。
应当理解，本文中使用的术语“和/或”仅仅是一种描述关联对象的关联关系，表示可以存在三种关系，例如，A和/或B，可以表示：单独存在A，同时存在A和B，单独存在B这三种情况。另外，本文中字符“/”，一般表示前后关联对象是一种“或”的关系。
应当理解，本文中使用的术语“包括”、“包含”或者其他任何变体意在涵盖非排他性的包含，从而使得包括一系列要素的过程、方法、物品或者设备不仅包括那些要素，而且还包括没有明确列出的其他要素，或者是还包括为这种过程、方法、物品或者设备所固有的要素。在没有更多限制的情况下，由语句“包括……”限定的要素，并不排除在包括所述要素的过程、方法、物品或者设备中还存在另外的相同要素。
下面结合附图和实施方式对本申请进行详细说明。
请参阅图1，图1是本申请改性二氧化硅填料的制备方法第一实施方式的流程示意图。在本实施方式中，该制备方法包括：
S11：提供设定质量比值的硅烷偶联剂和二氧化硅粉末。
可理解的，二氧化硅填料由于具有热膨胀系数低，热稳定和化学稳定性好等特点，已广泛应用于底部填充胶、环氧模塑料、绝缘胶膜等电子封装材料中。其中，添加了二氧化硅填料的树脂材料，其热膨胀系数随二氧化硅填充量的增加而降低，但不经表面改性的二氧化硅填料在高填充情况下，容易因填料间的内聚和填料与树脂间较差的相容性导致体系粘度的升高和分层，从而造成复合材料的失效。而为了减少二氧化硅填料间的内聚和提高填料与树脂基体间的界面相容性，通常还需要采用硅烷偶联剂对二氧化硅进行表面改性，以根据树脂类型接枝一些有机官能团。基于相似相溶原理，接枝的官能团与树脂具有良好的相容性，从而保证了填料在树脂中的分散稳定性。
具体地，提供合适份量的二氧化硅粉末，并以二氧化硅粉末的质量为基准，准备与其质量比值相适配的硅烷偶联剂。
其中，该硅烷偶联剂具体是指在分子中具有两种以上不同反应基的有机硅单体，它能使有机材料与无机材料发生化学键合(偶联)。硅烷偶联剂的分子结构近似为正四面体形，硅原子位于顶点位置，连接三个烷氧基团（易水解基团）和一个功能基团（亲油基团）。
在一可选的实施例中，在提供的二氧化硅粉末为0.5-5g时，可按与该二氧化硅粉末的质量比值，也即设定质量比值为0.1-5%配备相应的硅烷偶联剂。
可选地，该二氧化硅粉末的平均粒径范围为0.2-5µm。
可选地，该硅烷偶联剂为3-氨丙基三甲氧基硅烷、3-氨丙基三乙氧基硅烷、双(3-三甲氧基甲硅烷基丙基)胺、N-环己基-γ-氨丙基三甲氧基硅烷、γ-缩水甘油醚氧丙基三甲氧基硅烷(KBM-403)、3-(2，3-环氧丙氧)丙基甲基二甲氧基硅烷、γ-缩水甘油醚氧丙基三乙氧基硅烷等任意合理的硅烷偶联剂中的一种或几种的混合物，本申请对此不做限定。
S12：将硅烷偶联剂加入到二氧化硅粉末中，在第一设定温度下进行搅拌，以密封反应第一设定时间，获得第一反应产物。
进一步地，将硅烷偶联剂加入到二氧化硅粉末中进行混合，比如，依次将二氧化硅粉末和硅烷偶联剂放置于预先准备的三口烧瓶中，或其他任一合理的化学反应容器中后，进行密封，并对反应容器进行加热，而使硅烷偶联剂和二氧化硅粉末达到第一设定温度，并同时进行高速搅拌，以使硅烷偶联剂和二氧化硅粉末能够充分接触，而持续反应第一设定时间后，得到相应的第一反应产物。
在一可选的实施例中，将二氧化硅粉末和硅烷偶联剂不分次序的加入到带特氟龙内衬的水热反应釜中，以通过对该水热反应釜进行密封、加热，以将硅烷偶联剂和二氧化硅粉末加热至第一设定温度，并伴随搅拌持续反应第一设定时间后，获得第一反应产物。
其中，该第一反应产物具体为二氧化硅与硅烷偶联剂发生脱水缩合反应后的改性产物。
具体地，请参阅图2，图2是本申请中二氧化硅与胺类硅烷偶联剂的反应示意图。
其中，二氧化硅表面存在有羟基，相邻羟基彼此以氢键结合，孤立的氢原子正电性强，易与负电性原子吸附，能够与含羟基化合物发生脱水缩合反应。将硅烷偶联剂加入二氧化硅粉末中进行反应时，硅烷偶联剂中的烷氧基能够与二氧化硅表面的羟基发生反应，脱去一个小分子醇，从而和二氧化硅以化学键连接，而分子式中的亲油基团（如氨基）能够与被填充聚合物分子链发生反应。
可理解的，通过在硅烷偶联剂与二氧化硅粉末进行化学反应的过程中，在密封条件下，持续对其进行搅拌，以使二氧化硅粉末能够与硅烷偶联剂充分接触，而反应足够充分、完全，从而能够有效降低偶联剂的用量，以获得第一反应产物，且不仅能够降低相应的制备成本，提高经济效益，还能够避免因过量添加偶联剂导致的二氧化硅分散性降低的现象。
可选地，第一设定温度为120-180℃，第一设定时间为0.5-24h。
S13：在第二设定温度下对第一反应产物进行真空干燥第二设定时间，获得改性二氧化硅填料。
又进一步地，将第一反应产物分离出来，并使其维持在第二设定温度下进行真空干燥，以在对其真空干燥第二设定时间后，获得表面改性的二氧化硅填料。
可理解的，该二氧化硅即为改性二氧化硅表面以硅烷偶联剂为起点发生原位聚合而形成化合物接枝改性的二氧化硅产品，以通过充分利用硅烷偶联剂获得改性二氧化硅填料，大幅提高二氧化硅粉末的表面接枝量。
可选地，第二设定温度为40-150℃，第二设定时间为2-5h。
进一步地，在一实施例中，上述S12具体还可以包括：将硅烷偶联剂加入到二氧化硅粉末中，并加入设定容积的有机分散剂后，在第一设定温度下采用设定搅拌速度进行搅拌，以密封反应第一设定时间，获得第一反应产物。
可理解的，为保证硅烷偶联剂与二氧化硅粉末进行的化学反应能够更均匀，也即为使得二氧化硅粉末的表面接枝量的分布更均匀，还可以在容置有硅烷偶联剂和二氧化硅粉末的反应容器中，加入设定容积的有机分散剂，以在第一设定温度下采用设定搅拌速度对硅烷偶联剂、二氧化硅粉末以及有机分散剂进行搅拌，以使二氧化硅粉末和硅烷偶联剂在有机分散剂的作用下，充分并均匀地进行密封反应第一设定时间后，获得第一反应产物。
可选地，有机分散剂为甲醇、乙醇、异丙醇、丙醇等任意合理的分散剂中的一种或几种的混合物，本申请对此不做限定。
可选地，设定容积为20-200mL。
可选地，设定搅拌速度为200-500r/min（转/分钟）。
进一步地，在一实施例中，上述S12之后，S13之前，具体还可以包括：采用设定离心转速分离出第一反应产物。
可理解的，硅烷偶联剂通常为液体状态，在其与二氧化硅粉末进行反应后，尤其是在硅烷偶联剂和二氧化硅粉末中加入有机分散剂进行反应后，还需要将相应的第一反应产物，从未参与反应的液态物质中分离出来，比如，通过高速离心旋转的方式进行固液分离，以将第一反应产物分离出来。
可选地，该设定离心转速为6000-8000r/min。
进一步地，在一实施例中，上述S13具体还可以包括：对第一反应产物进行真空抽滤，获得抽滤样品；使用纯水对抽滤样品洗涤三次，再使用乙醇对抽滤样品洗涤三次，获得洗涤后的样品；对洗涤后的样品进行真空干燥，获得改性二氧化硅填料；其中，控制干燥温度为40-150℃。
进一步地，在一实施例中，上述S13之后，还可以包括：通过改性二氧化硅填料制成树脂组合物，或底部填充胶、环氧模塑料、绝缘胶膜等任一合理的电子封装材料中的一种，本申请对此不做限定。
请参阅图3，图3是本申请改性二氧化硅填料的制备方法第二实施方式的流程示意图。本实施方式的改性二氧化硅填料的制备方法是图1中的改性二氧化硅填料的制备方法的一细化实施例的流程示意图，包括如下步骤：
S21：提供设定质量比值的硅烷偶联剂和二氧化硅粉末。
其中，S21与图1中的S11相同，具体请参阅S11及其相关的文字描述，在此不再赘述。
S22：将二氧化硅粉末加热至第三设定温度。
具体地，将二氧化硅粉末加入到高速混料机中，以对其进行预加热，而使其达到第三设定温度，以利于后续与硅烷偶联剂进行充分反应。其中，该第三设定温度低于第一设定温度。
可选地，该第三设定温度为90-110℃。
S23：将硅烷偶联剂以喷雾的形式加入到二氧化硅粉末中，在第一设定温度下进行搅拌，以密封反应第一设定时间，获得第一反应产物。
进一步地，将硅烷偶联剂采用喷雾的形式加入到二氧化硅粉末中，以使其与二氧化硅粉末充分并均匀地进行接触、混合，并将硅烷偶联剂和二氧化硅粉末加热至第一设定温度，且伴随搅拌，密封反应第一设定时间后，获得第一反应产物。
S24：在第二设定温度下对第一反应产物进行真空干燥第二设定时间，获得改性二氧化硅填料。
其中，S24与图1中的S13相同，具体请参阅S13及其相关的文字描述，在此不再赘述。
为便于对本申请实施例进行理解，本申请提供了以下非限制性实施例，对本申请作进一步的详细说明。
实施例1
将0.5-5g二氧化硅粉末，与二氧化硅粉末的质量百分比为0.1-5%的硅烷偶联剂以及20-50毫升的有机分散剂依次装置于带特氟龙内衬的100毫升水热反应釜中，进行密封，以在120-180℃，并伴随200-500转/分钟的搅拌速度下，反应0.5-24小时。
其中，该二氧化硅平均粒径范围为0.2-5微米；该硅烷偶联剂可以是3-氨丙基三甲氧基硅烷、3-氨丙基三乙氧基硅烷、双(3-三甲氧基甲硅烷基丙基)胺、N-环己基-γ-氨丙基三甲氧基硅烷、γ-缩水甘油醚氧丙基三甲氧基硅烷(KBM-403)、3-(2，3-环氧丙氧)丙基甲基二甲氧基硅烷、γ-缩水甘油醚氧丙基三乙氧基硅烷或带其他官能团的硅烷偶联剂中的一种或几种的混合物；该有机分散剂可以是甲醇、乙醇、异丙醇、丙醇中的一种或几种的混合物。
进一步地，将水热反应的产物通过6000-8000转/分钟的高速离心分离出来，并将离心得到的产物通过40-150℃，2-5小时的真空干燥得到最终表面改性的二氧化硅填料。
实施例2
将0.5g平均粒径300纳米的二氧化硅粉末，与二氧化硅粉末的质量百分比为3%的KBM-403（γ-缩水甘油醚氧丙基三甲氧基硅烷）硅烷偶联剂，200毫升的乙醇添加至500毫升的三口烧瓶中，通过油浴或加压水浴，也即将密封的三口烧瓶置于热水或热油中，以通过热水或热油对三口烧瓶内部的KBM-403和二氧化硅粉末进行加热，以使其达到150℃，并在400转/分钟的搅拌速度以及18摄氏度冷水回流条件下，使二氧化硅粉末与KBM-403硅烷偶联剂反应24小时；将反应的产物通过6000转/分钟的高速离心分离出来；将离心产物通过150℃，5小时的真空干燥得到最终表面改性的二氧化硅填料，其中，改性二氧化硅填料填料的TGA（热重分析）失重率为0.23%。
实施例3
将0.5g平均粒径300纳米的二氧化硅粉末加入高速混料机，并预热至110摄氏度；以喷雾形式加入与二氧化硅粉末的质量百分比为3%的KBM-403硅烷偶联剂，然后将二氧化硅粉末和KBM-403加热至150℃，并保持400转/分钟搅拌速度进行反应1小时，其中，相应的反应的产物的TGA失重率为0.34%。
实施例4
将0.5g二氧化硅粉末，与二氧化硅粉末的质量百分比为3%的KBM-403硅烷偶联剂以及20毫升的乙醇密封于带特氟龙内衬的100毫升水热反应釜中，在150摄氏度、400转/分钟搅拌速度下反应24小时；将水热反应的产物通过6000转/分钟的高速离心分离出来；将离心产物通过150摄氏度，5小时的真空干燥得到最终表面改性的二氧化硅填料，填料的TGA失重率为0.75%。
进一步地，请参阅图4和图5，其中，图4是本申请一具体应用场景中二氧化硅填料以及经硅烷偶联剂改性的二氧化硅填料对应的漫反射红外透过率示意图，图5是图4中经硅烷偶联剂改性的二氧化硅填料反应前后的热重分析示意图。
其中，图4和图5中的改性的二氧化硅填料具体可理解为由上述实施例4所示出的制备方法制成得到。由此可知，修饰后的二氧化硅，也即经硅烷偶联剂改性的二氧化硅填料的表面带有明显的甲基、亚甲基红外峰，说明二氧化硅表面成功包覆或接枝上了KBM-403硅烷偶联剂。而修饰后的二氧化硅失重率为0.75%，也说明二氧化硅表面包覆或接枝上了KBM-403硅烷偶联剂。
对应地，本申请还提供了一种改性二氧化硅填料。其中，该改性二氧化硅填料由上述任一项所述的制备方法制成。
具体地，请参阅图6，图6是本申请改性二氧化硅填料一实施方式的结构示意图。
如图6所示，本实施方式中，改性二氧化硅填料中的聚合中心是硅烷偶联剂的亲油基团（氨基），通过氨基连接环氧化合物，以使二氧化硅表面能够接枝不同性能的化合物。
区别于现有技术，本申请所提供的改性二氧化硅填料的表面可通过硅烷偶联剂与不同性能的化合物进行接枝，具有接枝包覆均匀完全、分散程度好等特点，能够更好地分散于树脂基体中，以提高树脂复合体系的流动性。
区别于现有技术，本申请中的改性二氧化硅填料的制备方法通过提供设定质量比值的硅烷偶联剂和二氧化硅粉末，以将硅烷偶联剂加入到二氧化硅粉末中，在第一设定温度下进行搅拌，并密封反应第一设定时间，以使二氧化硅粉末能够充分地与硅烷偶联剂进行接触，而反应足够完全，从而能够降低偶联剂的用量，以获得第一反应产物，不仅降低了制备成本，提高了经济效益，还能避免因过量添加偶联剂导致的二氧化硅分散性降低的现象；进一步地，在第二设定温度下对第一反应产物进行真空干燥第二设定时间，以获得改性二氧化硅填料，从而能够充分利用硅烷偶联剂获得改性二氧化硅填料，以大幅提高二氧化硅粉末的表面接枝量。
以上所述仅为本申请的实施方式，并非因此限制本申请的专利范围，凡是利用本申请说明书及附图内容所作的等效结构或等效流程变换，或直接或间接运用在其他相关的技术领域，均同理包括在本申请的专利保护范围内。

Claims (10)

  1. 一种改性二氧化硅填料的制备方法，其特征在于，所述制备方法包括：
    提供设定质量比值的硅烷偶联剂和二氧化硅粉末；
    将所述硅烷偶联剂加入到所述二氧化硅粉末中，在第一设定温度下进行搅拌，以密封反应第一设定时间，获得第一反应产物；
    在第二设定温度下对所述第一反应产物进行真空干燥第二设定时间，获得所述改性二氧化硅填料。
  2. 根据权利要求1所述的制备方法，其特征在于，所述将所述硅烷偶联剂加入到所述二氧化硅粉末中，在第一设定温度下进行搅拌，以密封反应第一设定时间，获得第一反应产物，包括：
    将所述硅烷偶联剂加入到所述二氧化硅粉末中，并加入设定容积的有机分散剂后，在所述第一设定温度下采用设定搅拌速度进行搅拌，以密封反应所述第一设定时间，获得所述第一反应产物。
  3. 根据权利要求1所述的制备方法，其特征在于，所述提供设定重量比值的硅烷偶联剂和二氧化硅粉末之后，所述将所述硅烷偶联剂加入到所述二氧化硅粉末中，在第一设定温度下进行搅拌，以密封反应第一设定时间，获得第一反应产物之前，还包括：
    将所述二氧化硅粉末加热至第三设定温度；其中，所述第三设定温度低于所述第一设定温度；
    所述将所述硅烷偶联剂加入到所述二氧化硅粉末中，包括：
    将所述硅烷偶联剂以喷雾的形式加入到所述二氧化硅粉末中。
  4. 根据权利要求1或2所述的制备方法，其特征在于，所述将所述硅烷偶联剂加入到所述二氧化硅粉末中，在第一设定温度下进行搅拌，以密封反应第一设定时间，获得第一反应产物之后，所述在第二设定温度下对所述第一反应产物进行真空干燥第二设定时间，获得所述改性二氧化硅填料之前，还包括：
    采用设定离心转速分离出所述第一反应产物。
  5. 根据权利要求1-3中任一项所述的制备方法，其特征在于，
    所述二氧化硅粉末的质量为0.5-5g，所述硅烷偶联剂与所述二氧化硅粉末的所述设定质量比值为0.1-0.5%。
  6. 根据权利要求5所述的制备方法，其特征在于，
    所述二氧化硅粉末的平均粒径范围为0.2-5µm。
  7. 根据权利要求1-3中任一项所述的制备方法，其特征在于，
    所述硅烷偶联剂为3-氨丙基三甲氧基硅烷、3-氨丙基三乙氧基硅烷、双(3-三甲氧基甲硅烷基丙基)胺、N-环己基-γ-氨丙基三甲氧基硅烷、γ-缩水甘油醚氧丙基三甲氧基硅烷、3-(2，3-环氧丙氧)丙基甲基二甲氧基硅烷、γ-缩水甘油醚氧丙基三乙氧基硅烷中的一种或几种的混合物。
  8. 根据权利要求2所述的制备方法，其特征在于，
    所述有机分散剂为甲醇、乙醇、异丙醇、丙醇中的一种或几种的混合物。
  9. 根据权利要求1所述的制备方法，其特征在于，
    所述第一设定温度为120-180℃，所述第一设定时间为0.5-24h；所述第二设定温度为40-150℃，所述第二设定时间为2-5h。
  10. 一种改性二氧化硅填料，其特征在于，所述改性二氧化硅填料是由权利要求1-9中任一项所述的制备方法制成。
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Families Citing this family (4)

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Publication number Priority date Publication date Assignee Title
CN113604073A (zh) * 2021-06-29 2021-11-05 中国科学院深圳先进技术研究院 一种改性二氧化硅填料及其制备方法
CN114262528B (zh) * 2021-12-07 2023-04-18 中国科学院深圳先进技术研究院 一种二氧化硅的表面改性方法及应用
CN118772819B (zh) * 2024-09-05 2024-12-24 武汉市三选科技有限公司 一种高流动性的底部填充胶、其制备方法和倒装芯片
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Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08245835A (ja) * 1995-03-10 1996-09-24 Nec Corp シリカ粒子を含む樹脂組成物およびシリカ粒子の表面 処理方法
JPH1143320A (ja) * 1997-07-25 1999-02-16 Toshiba Ceramics Co Ltd シリカフィラーの製造方法ならびにフィラー用組成物およびその製造方法
JP2002146233A (ja) * 2000-11-07 2002-05-22 Denki Kagaku Kogyo Kk 表面処理された微細球状シリカ粉末および樹脂組成物
WO2006128793A1 (en) * 2005-06-01 2006-12-07 Small Particle Technology Gbg Ab Dispersible silica particles
JP2007171713A (ja) * 2005-12-26 2007-07-05 Tokuyama Corp 変性シリカ粉末
CN101089055A (zh) * 2007-07-12 2007-12-19 武汉理工大学 聚合物包覆二氧化硅复合微粒子的制备方法
CN102220036A (zh) * 2011-06-02 2011-10-19 北京化工大学 一种制备硅烷偶联剂改性白炭黑的方法
WO2017170660A1 (ja) * 2016-03-30 2017-10-05 株式会社フジミインコーポレーテッド カチオン変性シリカの製造方法およびカチオン変性シリカ分散体
CN111777874A (zh) * 2019-04-04 2020-10-16 深圳先进技术研究院 纳米二氧化硅及其表面改性方法
CN112662203A (zh) * 2020-11-27 2021-04-16 中国科学院深圳先进技术研究院 一种改性二氧化硅填料及其制备方法以及树脂组合物
CN113604073A (zh) * 2021-06-29 2021-11-05 中国科学院深圳先进技术研究院 一种改性二氧化硅填料及其制备方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018104634A (ja) * 2016-12-28 2018-07-05 ナミックス株式会社 表面処理シリカフィラー、および表面処理シリカフィラーを含有する樹脂組成物
CN110016242A (zh) * 2019-04-04 2019-07-16 深圳先进技术研究院 纳米二氧化硅的单分子层表面改性方法
CN112662011A (zh) * 2020-12-09 2021-04-16 深圳先进技术研究院 二氧化硅的改性方法、二氧化硅填料及环氧树脂复合材料
CN112662354A (zh) * 2020-12-09 2021-04-16 深圳先进技术研究院 二氧化硅填料及其制备方法、环氧树脂复合材料

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08245835A (ja) * 1995-03-10 1996-09-24 Nec Corp シリカ粒子を含む樹脂組成物およびシリカ粒子の表面 処理方法
JPH1143320A (ja) * 1997-07-25 1999-02-16 Toshiba Ceramics Co Ltd シリカフィラーの製造方法ならびにフィラー用組成物およびその製造方法
JP2002146233A (ja) * 2000-11-07 2002-05-22 Denki Kagaku Kogyo Kk 表面処理された微細球状シリカ粉末および樹脂組成物
WO2006128793A1 (en) * 2005-06-01 2006-12-07 Small Particle Technology Gbg Ab Dispersible silica particles
JP2007171713A (ja) * 2005-12-26 2007-07-05 Tokuyama Corp 変性シリカ粉末
CN101089055A (zh) * 2007-07-12 2007-12-19 武汉理工大学 聚合物包覆二氧化硅复合微粒子的制备方法
CN102220036A (zh) * 2011-06-02 2011-10-19 北京化工大学 一种制备硅烷偶联剂改性白炭黑的方法
WO2017170660A1 (ja) * 2016-03-30 2017-10-05 株式会社フジミインコーポレーテッド カチオン変性シリカの製造方法およびカチオン変性シリカ分散体
CN111777874A (zh) * 2019-04-04 2020-10-16 深圳先进技术研究院 纳米二氧化硅及其表面改性方法
CN112662203A (zh) * 2020-11-27 2021-04-16 中国科学院深圳先进技术研究院 一种改性二氧化硅填料及其制备方法以及树脂组合物
CN113604073A (zh) * 2021-06-29 2021-11-05 中国科学院深圳先进技术研究院 一种改性二氧化硅填料及其制备方法

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