CN112662011A - Modification method of silicon dioxide, silicon dioxide filler and epoxy resin composite material - Google Patents
Modification method of silicon dioxide, silicon dioxide filler and epoxy resin composite material Download PDFInfo
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- CN112662011A CN112662011A CN202011461979.4A CN202011461979A CN112662011A CN 112662011 A CN112662011 A CN 112662011A CN 202011461979 A CN202011461979 A CN 202011461979A CN 112662011 A CN112662011 A CN 112662011A
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
Abstract
The invention provides a method for modifying silicon dioxide, which comprises the following steps: stirring and dispersing silicon dioxide particles in a dispersing agent to obtain a silicon dioxide dispersion liquid; adding a silane coupling agent and an acid catalyst into the silicon dioxide dispersion liquid to obtain a mixed reaction liquid; wherein the silane coupling agent is a biped silane coupling agent; and (3) carrying out a high-temperature reflux reaction process on the mixed reaction solution, cooling, and then sequentially carrying out centrifugal washing process and drying process treatment to obtain the surface-modified silicon dioxide particles. The invention also provides the silica filler prepared by the method and an epoxy resin composite material containing the silica filler. The modified silicon dioxide is added into an epoxy resin matrix as a filler, so that the compatibility and the dispersibility of the silicon dioxide filler in a resin base material are improved, the viscosity of the epoxy resin composite material is effectively reduced, and the epoxy resin composite material has excellent viscosity stability.
Description
Technical Field
The invention belongs to the technical field of polymer composite materials, and particularly relates to a modification method of silicon dioxide and a silicon dioxide filler, and also relates to an epoxy resin composite material containing the silicon dioxide filler.
Background
New forms of electronic products such as bio-micro-electromechanical systems, artificial intelligent micro-robots, wearable electronic devices, 5G communication electronic devices, light and thin notebooks, ultra-thin mobile phones and the like are more and more frequently appeared in daily life of people. The miniaturization, lightness, thinness and high operation speed of electronic devices make the chip develop towards high integration, miniaturization and high reliability. The underfill is a key one of plastic electronic packaging materials, can reduce the mismatch of thermal expansion coefficients between a Chip and a substrate, provides adhesive force, protects a solder Ball and the like, is used for underfill of CSP (Chip Scale Package)/BGA (Ball grid array Package), has the characteristics of good process operability, easy maintenance, good shock resistance, good vibration resistance and the like, greatly improves the reliability of electronic products, and is also expanded to be applied to increase the mechanical strength of the CSP. As the density of mobile electronic products is higher and higher, the underfill technology is gradually improved, and more underfill materials are developed.
Epoxy resin composites are a common underfill, generally composed of an epoxy resin, a curing agent, and a silica filler. With the trend of miniaturization of electronic products, the pitch of the CSP is becoming smaller and smaller, the pitch of the solder balls is also becoming smaller and smaller, and the underfill needs to have a low thermal expansion coefficient after curing, so that a larger filling amount of silica filler is required. Silica is inorganic and has a large amount of silanol groups on the surface, so that the silica is easy to agglomerate in organic matrix epoxy resin, when the resin matrix is filled in a large amount, the composite material has high viscosity, and the high-viscosity underfill can cause the operation difficulty of the packaging process to be increased.
Disclosure of Invention
In view of the defects in the prior art, the invention provides a method for modifying silica and a corresponding silica filler obtained by the method so as to solve the problem that the viscosity of a composite material is too high when the filling amount of the existing silica filler is large.
In order to achieve the above object, the present invention provides a method for modifying silica, comprising:
stirring and dispersing silicon dioxide particles in a dispersing agent to obtain a silicon dioxide dispersion liquid;
adding a silane coupling agent and an acid catalyst into the silicon dioxide dispersion liquid to obtain a mixed reaction liquid; wherein the silane coupling agent is a biped silane coupling agent;
and (3) carrying out a high-temperature reflux reaction process on the mixed reaction solution, cooling, and then sequentially carrying out centrifugal washing process and drying process treatment to obtain the surface-modified silicon dioxide particles.
Wherein the dispersant is selected from any one or more than two of methanol, ethanol and toluene.
Wherein the silicon dioxide particles are spherical silicon dioxide particles, and the particle size of the silicon dioxide particles is 400 nm-600 nm.
Wherein the biped silane coupling agent is selected from any one or more than two of phenyl hexaethoxysilane, methyl hexaethoxysilane, ethyl hexaethoxysilane, octyl hexaethoxysilane, vinyl hexaethoxysilane and aminopropyl hexaethoxysilane.
Wherein the mass ratio of the silica particles to the silane coupling agent is (10-50): 1.
The acid catalyst is selected from any one or more than two of formic acid, acetic acid, succinic acid and oxalic acid, and the addition amount of the acid catalyst is such that the pH value of the mixed reaction liquid is 3-5.
Wherein the high-temperature reflux reaction process is carried out in a condensation reflux device, the reaction temperature is 60-100 ℃, and the reaction time is 3-20 h.
The invention also provides a silica filler, which is surface-modified silica particles prepared by the silica modification method.
Another aspect of the present invention is to provide an epoxy resin composite material, comprising an epoxy resin matrix and a filler, wherein the epoxy resin matrix comprises an epoxy resin and a curing agent, and the filler is a silica filler as described above.
Wherein the epoxy resin is selected from any one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, alicyclic epoxy resin, novolac epoxy resin and naphthalene ring-containing epoxy resin, and the curing agent is selected from any one or more of methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, hexahydrophthalic anhydride, triethylene tetramine, tetraethylene pentamine, m-xylene diamine, trimethyl hexamethylene diamine, 2-methyl pentamethylene diamine, 4 '-diamino-3, 3' -diethyl diphenylmethane and bis (methylthio) toluene diamine.
Wherein in the epoxy resin matrix, the mass ratio of the epoxy resin to the curing agent is (2-5) to 1; the mass ratio of the epoxy resin matrix to the silica filler is 10: (3-5).
According to the modification method of the silicon dioxide, provided by the embodiment of the invention, the modifying agent is selected from a biped silane coupling agent, the molecule of the biped silane coupling agent contains six siloxy groups, and the biped silane coupling agent can react with more silanol groups on the surface of the silicon dioxide after being hydrolyzed, so that more functional groups are grafted on the surface of the silicon dioxide. The modified silica is added into an epoxy resin matrix as a filler, so that the compatibility and the dispersibility of the silica filler in a resin base material are improved, the viscosity of the epoxy resin composite material is effectively reduced, and the epoxy resin composite material has excellent viscosity stability.
Drawings
FIG. 1 is a process flow diagram of a method of modifying silica in an embodiment of the invention;
FIG. 2 is an SEM photograph of unmodified silica particles in example 1 of the present invention;
FIG. 3 is an SEM image of a silica filler prepared according to example 1 of the present invention;
FIG. 4 shows that the shear rate of the epoxy resin composite material prepared in example 1 of the present invention is 0-200S-1Viscosity profile under conditions;
FIG. 5 is an SEM image of a silica filler prepared according to example 2 of the present invention;
FIG. 6 is an SEM image of a silica filler prepared according to example 3 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention are described in detail below with reference to the accompanying drawings. Examples of these preferred embodiments are illustrated in the accompanying drawings. The embodiments of the invention shown in the drawings and described in accordance with the drawings are exemplary only, and the invention is not limited to these embodiments.
It should be noted that, in order to avoid obscuring the present invention with unnecessary details, only the structures and/or processing steps closely related to the scheme according to the present invention are shown in the drawings, and other details not so relevant to the present invention are omitted.
The embodiment of the invention firstly provides a modification method of silicon dioxide, as shown in fig. 1, the modification method comprises the following steps:
and S10, stirring and dispersing the silicon dioxide particles in the dispersing agent to obtain the silicon dioxide dispersion liquid.
Specifically, the silica particles are spherical silica particles, and the particle size of the silica particles is preferably 400nm to 600nm, and more preferably 500 nm.
Specifically, the dispersant is selected from any one or more of methanol, ethanol and toluene.
S20, adding a silane coupling agent and an acid catalyst into the silicon dioxide dispersion liquid to obtain a mixed reaction liquid; wherein the silane coupling agent is a biped silane coupling agent.
Specifically, the biped silane coupling agent is selected from any one or more of phenyl hexamethoxysilane, methyl hexaethoxysilane, ethyl hexaethoxysilane, octyl hexaethoxysilane, vinyl hexaethoxysilane and aminopropyl hexamethoxysilane.
In the step, the amount of the added silane coupling agent is such that the mass ratio of the silica particles to the silane coupling agent is (10-50): 1.
Specifically, the acid catalyst is selected from any one or more than two of formic acid, acetic acid, succinic acid and oxalic acid, and the adding amount of the acid catalyst is such that the pH value of the mixed reaction liquid is 3-5.
In a preferred embodiment, a magnetic stirrer is added to the mixed reaction solution for magnetic stirring.
And S30, carrying out a high-temperature reflux reaction process on the mixed reaction liquid, cooling, and then sequentially carrying out centrifugal washing process and drying process treatment to obtain the surface-modified silicon dioxide particles.
In a preferred scheme, the high-temperature reflux reaction process is carried out in a condensation reflux device, the reaction temperature is 60-100 ℃, and the reaction time is 3-20 h.
In a preferred embodiment, the detergent used in the centrifugal washing process is absolute ethyl alcohol; the temperature of the drying process is 100-300 ℃, and the time is 3-24 h.
The embodiment of the invention provides a silica filler, wherein the silica filler is surface-modified silica particles prepared by adopting the silica modification method, and the silica filler is used as a filler of an epoxy resin composite material.
The embodiment of the invention also provides an epoxy resin composite material, which comprises an epoxy resin matrix and a filler, wherein the epoxy resin matrix comprises epoxy resin and a curing agent, and the filler is the silica filler described in the embodiment of the invention.
In a preferred embodiment, the epoxy resin is selected from any one or two or more of bisphenol a type epoxy resin, bisphenol F type epoxy resin, alicyclic epoxy resin, novolac type epoxy resin and naphthalene ring-containing epoxy resin, and the curing agent is selected from any one or two or more of methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, triethylenetetramine, tetraethylenepentamine, m-xylylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, 4 '-diamino-3, 3' -diethyldiphenylmethane and bis (methylthio) toluenediamine.
In a preferable scheme, in the epoxy resin matrix, the mass ratio of the epoxy resin to the curing agent is (2-5): 1; the mass ratio of the epoxy resin matrix to the silica filler is 10: (3-5).
The preparation process of the epoxy resin composite material comprises the following steps:
(1) and mixing the epoxy resin and the curing agent according to the mass ratio of (2-5) to 1, and fully and uniformly mixing by using a planetary mixer to prepare the epoxy resin matrix.
(2) And mixing the epoxy resin matrix and the silicon dioxide filler according to the mass ratio of 10: and (3) uniformly mixing the components in the ratio of (3) to (5) by using a high-speed planetary mixer to obtain the epoxy resin composite material.
Example 1
Modification of silica and silica filler obtained
Selecting the materials with the volume ratio of 95: and 5, adding 100mL of ethanol and water mixed liquid serving as a dispersing solvent into a single-neck flask of a modification device, wherein the modification device adopts a condensation reflux magnetic stirring device. Adding 20g of silicon dioxide powder with the particle size of 500nm into the single-neck flask, adding a magnetic stirrer, and uniformly stirring.
Adding 1g of phenylethyl hexamethoxysilane into the single-neck flask, dropwise adding formic acid to enable the pH value of the mixed solution to be 4, heating the single-neck flask to 90 ℃, carrying out magnetic stirring, condensation and reflux reaction for 5 hours, then collecting a liquid mixture in a centrifugal flask, centrifuging at high speed in a centrifuge, separating liquid from silicon dioxide powder, collecting the silicon dioxide powder, carrying out ultrasonic cleaning and centrifugation on the silicon dioxide powder by using absolute ethyl alcohol, repeating the steps for 3 times, and drying in an oven at 150 ℃ for 5 hours to obtain the surface modified silicon dioxide. Wherein the high temperature drying also promotes the grafting reaction of the silane coupling agent with the silica.
The SEM topography of the unmodified silica is shown in fig. 2, and the SEM topography of the modified silica of this example is shown in fig. 3.
Second, epoxy resin composite material and preparation process thereof
Bisphenol F epoxy resin and a curing agent 4,4 '-diamino-3, 3' -diethyl diphenylmethane are prepared into a uniform epoxy resin matrix according to the mass ratio of 2.5:1, and are uniformly mixed in a planetary mixer. The first part of modified silica in this example was used as a filler and mixed with the epoxy resin matrix at a mass ratio of 3:10, and the mixture was uniformly mixed in a high-speed planetary mixer in a vacuum state and air bubbles were removed to prepare an epoxy resin composite material.
Viscosity test of epoxy resin composite material
The liquid epoxy resin composite material prepared in this example was subjected to viscosity measurement with a parallel plate rheometer. During testing, the distance between two plates of the flat-plate rheometer is 0.2mm, and the shear rate is 0-200S-1The test temperature was 25 ℃. FIG. 4 shows that the shear rate of the epoxy resin composite material prepared in this embodiment is 0-200S-1Viscosity curve under conditions wherein the shear rate is 50S-1The viscosity at that time was 7.0Pa · S, and the shear rate was 100S-1The viscosity was 6.9 pas.
Referring to the graph of fig. 4, the epoxy resin composite material prepared in this example has a low viscosity and excellent viscosity stability.
Example 2
Modification of silica and silica filler obtained
Selecting the materials with the volume ratio of 95: and 5, adding 100mL of ethanol and water mixed liquid serving as a dispersing solvent into a single-neck flask of a modification device, wherein the modification device adopts a condensation reflux magnetic stirring device. Adding 30g of silicon dioxide powder with the particle size of 500nm into the single-neck flask, adding a magnetic stirrer, and uniformly stirring.
Adding 1g of octyl hexaethoxysilane into the single-neck flask, dropwise adding formic acid to enable the pH value of the mixed solution to be 5, heating the single-neck flask to 60 ℃, carrying out magnetic stirring, condensing, refluxing and reacting for 20 hours, then collecting a liquid mixture in a centrifuge bottle, centrifuging at high speed in a centrifuge, separating liquid from silicon dioxide powder, collecting the silicon dioxide powder, carrying out ultrasonic cleaning and centrifuging on the silicon dioxide powder by using absolute ethyl alcohol, repeating for 3 times, and drying in an oven at 150 ℃ for 5 hours to obtain the surface modified silicon dioxide.
The SEM topography of the modified silica of this example is shown in fig. 5.
Second, epoxy resin composite material and preparation process thereof
Bisphenol F epoxy resin and a curing agent 4,4 '-diamino-3, 3' -diethyl diphenylmethane are prepared into a uniform epoxy resin matrix according to the mass ratio of 2.5:1, and are uniformly mixed in a planetary mixer. The first part of modified silica in this example was used as a filler and mixed with the epoxy resin matrix at a mass ratio of 4:10, and the mixture was uniformly mixed in a high-speed planetary mixer in a vacuum state and air bubbles were removed to prepare an epoxy resin composite material.
The epoxy resin composite material prepared in this example was subjected to a viscosity test in the manner as described in example 1. The shear rate of the epoxy resin composite material of the embodiment is 50S-1The viscosity at that time was 8.0Pa · S, and the shear rate was 100S-1The viscosity was 7.4 pas.
Example 3
Modification of silica and silica filler obtained
Selecting the materials with the volume ratio of 95: and 5, adding 100mL of ethanol and water mixed liquid serving as a dispersing solvent into a single-neck flask of a modification device, wherein the modification device adopts a condensation reflux magnetic stirring device. Adding 40g of silicon dioxide powder with the particle size of 500nm into the single-neck flask, adding a magnetic stirrer, and uniformly stirring.
Adding 1g of vinyl hexaethoxysilane into the single-neck flask, dropwise adding formic acid to enable the pH value of the mixed solution to be 3, heating the single-neck flask to 100 ℃, carrying out magnetic stirring, condensation and reflux reaction for 3 hours, then collecting a liquid mixture in a centrifuge bottle, centrifuging at high speed in a centrifuge, separating liquid from silicon dioxide powder, collecting the silicon dioxide powder, carrying out ultrasonic cleaning and centrifugation on the silicon dioxide powder by using absolute ethyl alcohol, repeating the steps for 3 times, and drying in an oven at 150 ℃ for 5 hours to obtain the surface modified silicon dioxide.
The SEM topography of the modified silica of this example is shown in fig. 6.
Second, epoxy resin composite material and preparation process thereof
Bisphenol F epoxy resin and a curing agent 4,4 '-diamino-3, 3' -diethyl diphenylmethane are prepared into a uniform epoxy resin matrix according to the mass ratio of 10:4, and are uniformly mixed in a planetary mixer. The first part of modified silica in this example was used as a filler and mixed with the epoxy resin matrix at a mass ratio of 5:10, and the mixture was uniformly mixed in a high-speed planetary mixer under vacuum and bubbles were removed to prepare an epoxy resin composite material.
The epoxy resin composite material prepared in this example was subjected to a viscosity test in the manner as described in example 1. The shear rate of the epoxy resin composite material of the embodiment is 50S-1The viscosity at that time was 8.2 pas and the shear rate was 100S-1The viscosity was 7.9 pas.
In summary, in the method for modifying silica provided in the embodiment of the present invention, the modified silica is added to the epoxy resin matrix as a filler, so that the compatibility and dispersibility of the silica filler in the resin matrix are improved, the viscosity of the epoxy resin composite material is effectively reduced, and the viscosity stability is excellent.
The foregoing is directed to embodiments of the present application and it is noted that numerous modifications and adaptations may be made by those skilled in the art without departing from the principles of the present application and are intended to be within the scope of the present application.
Claims (10)
1. A method for modifying silica, comprising:
stirring and dispersing silicon dioxide particles in a dispersing agent to obtain a silicon dioxide dispersion liquid;
adding a silane coupling agent and an acid catalyst into the silicon dioxide dispersion liquid to obtain a mixed reaction liquid; wherein the silane coupling agent is a biped silane coupling agent;
and (3) carrying out a high-temperature reflux reaction process on the mixed reaction solution, cooling, and then sequentially carrying out centrifugal washing process and drying process treatment to obtain the surface-modified silicon dioxide particles.
2. The method of modifying silica according to claim 1, wherein the dispersant is one or more selected from the group consisting of methanol, ethanol, and toluene.
3. The method of claim 1, wherein the silane coupling agent is one or more selected from the group consisting of phenylhexaethoxysilane, methylhexaethoxysilane, ethylhexaethoxysilane, octylhexaethoxysilane, vinylhexaethoxysilane, and aminopropylhexamethoxysilane.
4. The method for modifying silica according to claim 3, wherein the mass ratio of the silica particles to the silane coupling agent is (10-50): 1.
5. The method of modifying silica according to claim 3, wherein the acid catalyst is one or more selected from formic acid, acetic acid, succinic acid and oxalic acid, and is added in an amount such that the pH of the mixed reaction solution is 3 to 5.
6. The method for modifying silicon dioxide according to any one of claims 1 to 5, wherein the high-temperature reflux reaction process is carried out in a condensation reflux device, the reaction temperature is 60 ℃ to 100 ℃, and the reaction time is 3h to 20 h.
7. A silica filler, characterized in that it is a surface-modified silica particle prepared by a process for modifying silica according to any one of claims 1 to 6.
8. An epoxy resin composite comprising an epoxy resin matrix and a filler, wherein the epoxy resin matrix comprises an epoxy resin and a curing agent, and the filler is the silica filler of claim 7.
9. The epoxy resin composite according to claim 8, wherein the epoxy resin is selected from any one or more of bisphenol a type epoxy resin, bisphenol F type epoxy resin, alicyclic epoxy resin, novolac type epoxy resin, and naphthalene ring-containing epoxy resin, and the curing agent is selected from any one or more of methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, triethylenetetramine, tetraethylenepentamine, m-xylylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, 4 '-diamino-3, 3' -diethyldiphenylmethane, and bis (methylthio) toluenediamine.
10. The epoxy resin composite material according to claim 8 or 9, wherein the mass ratio of the epoxy resin to the curing agent in the epoxy resin matrix is (2-5): 1; the mass ratio of the epoxy resin matrix to the silica filler is 10: (3-5).
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
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| CN202011461979.4A CN112662011A (en) | 2020-12-09 | 2020-12-09 | Modification method of silicon dioxide, silicon dioxide filler and epoxy resin composite material |
| PCT/CN2020/136728 WO2022120907A1 (en) | 2020-12-09 | 2020-12-16 | Silica modification method, silica filler, and epoxy resin composite material |
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| CN202011461979.4A CN112662011A (en) | 2020-12-09 | 2020-12-09 | Modification method of silicon dioxide, silicon dioxide filler and epoxy resin composite material |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113604073A (en) * | 2021-06-29 | 2021-11-05 | 中国科学院深圳先进技术研究院 | Modified silicon dioxide filler and preparation method thereof |
| CN114292614A (en) * | 2022-03-02 | 2022-04-08 | 西陇科学股份有限公司 | Preparation method of modified silicon dioxide-epoxy resin composite slurry |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1834100A (en) * | 2005-11-11 | 2006-09-20 | 浙江大学 | Bisilane coupler contg. sulfur and nitrogen element and prepn. thereof |
| US20120322925A1 (en) * | 2011-06-15 | 2012-12-20 | Lion Copolymer, Llc | Functionalized silica for silica wet masterbatches and styrene butadiene rubber compositions |
| CN104114627A (en) * | 2011-08-16 | 2014-10-22 | 蓝星有机硅法国公司 | Method for preparing a silica grafted with an organosilicon compound |
| CN111777874A (en) * | 2019-04-04 | 2020-10-16 | 深圳先进技术研究院 | Nano silicon dioxide and surface modification method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200913181A (en) * | 2007-07-10 | 2009-03-16 | Arakawa Chem Ind | Optical semiconductor-sealing composition |
| CN105400475B (en) * | 2015-12-21 | 2019-05-24 | 广东工业大学 | The method that leak repairing fills the preparation method of glue and carries out house leak repairing using it |
| CN106916418B (en) * | 2015-12-25 | 2020-07-07 | 广东生益科技股份有限公司 | Thermosetting resin composition, prepreg, metal foil-clad laminate and printed circuit board |
| CN105504688B (en) * | 2016-01-08 | 2018-05-01 | 武汉理工大学 | A kind of F grades of motor embedding composite ceramics/epoxy resin composite material and preparation method thereof |
| CN106928656B (en) * | 2017-03-06 | 2019-01-29 | 武汉理工大学 | Nano-silicon dioxide modified RFI epoxy resin film and preparation method thereof |
-
2020
- 2020-12-09 CN CN202011461979.4A patent/CN112662011A/en active Pending
- 2020-12-16 WO PCT/CN2020/136728 patent/WO2022120907A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1834100A (en) * | 2005-11-11 | 2006-09-20 | 浙江大学 | Bisilane coupler contg. sulfur and nitrogen element and prepn. thereof |
| US20120322925A1 (en) * | 2011-06-15 | 2012-12-20 | Lion Copolymer, Llc | Functionalized silica for silica wet masterbatches and styrene butadiene rubber compositions |
| CN104114627A (en) * | 2011-08-16 | 2014-10-22 | 蓝星有机硅法国公司 | Method for preparing a silica grafted with an organosilicon compound |
| CN111777874A (en) * | 2019-04-04 | 2020-10-16 | 深圳先进技术研究院 | Nano silicon dioxide and surface modification method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113604073A (en) * | 2021-06-29 | 2021-11-05 | 中国科学院深圳先进技术研究院 | Modified silicon dioxide filler and preparation method thereof |
| CN114292614A (en) * | 2022-03-02 | 2022-04-08 | 西陇科学股份有限公司 | Preparation method of modified silicon dioxide-epoxy resin composite slurry |
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| WO2022120907A1 (en) | 2022-06-16 |
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