CN111690259A - High-voltage-resistant organic silicon gel and preparation method and application thereof - Google Patents

High-voltage-resistant organic silicon gel and preparation method and application thereof Download PDF

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CN111690259A
CN111690259A CN202010589148.9A CN202010589148A CN111690259A CN 111690259 A CN111690259 A CN 111690259A CN 202010589148 A CN202010589148 A CN 202010589148A CN 111690259 A CN111690259 A CN 111690259A
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filler
component
modified
vinyl
coupling agent
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王婷婷
罗兵
徐永生
曾亮
齐放
刘洋
戴小平
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Hunan Guoxin Semiconductor Technology Co ltd
CSG Electric Power Research Institute
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Hunan Guoxin Semiconductor Technology Co ltd
Power Grid Technology Research Center of China Southern Power Grid Co Ltd
Research Institute of Southern Power Grid Co Ltd
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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
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • 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
    • 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
    • C08K2201/011—Nanostructured additives
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Abstract

The invention discloses a high-voltage-resistant organic silicon gel and a preparation method and application thereof, wherein the organic silicon gel comprises a component A and a component B, the component A is vinyl silicone oil, a catalyst and a filler A modified by the vinyl silicone oil, and the component B is the vinyl silicone oil, a cross-linking agent, an inhibitor and the filler B modified by the cross-linking agent, wherein the modified filler A is obtained by modifying the filler A by the vinyl silicone oil; the modified filler B is obtained by modifying the filler B with a crosslinking agent. The preparation method comprises the step of mixing the component A and the component B to prepare the high-voltage-resistant organic silicon gel. The high-voltage-resistant organic silicon gel has the advantages of high insulativity, high elasticity, low stress and the like, has very strong high-voltage-resistant capability, can prevent the breakdown of high-voltage current, can obviously improve the voltage-resistant performance of power electronic devices, has very important significance for improving the reliability of the power electronic devices, and has very high use value and good application prospect.

Description

High-voltage-resistant organic silicon gel and preparation method and application thereof
Technical Field
The invention belongs to the field of packaging materials, relates to a bi-component organic silicon gel for power electronic devices, and particularly relates to a high-voltage-resistant organic silicon gel and a preparation method and application thereof.
Background
The silicone gel refers to an organopolysiloxane composition having a straight chain as a main structure, among which organohydrogenpolysiloxanes containing silicon-bonded hydrogen atoms (Si — H), organopolysiloxanes having double bonds (e.g., bonded vinyl groups), and the like. The organic silicon gel has low elastic modulus and ultralow stress and small creep, but has stable chemical performance and low impurity content, so the organic silicon gel has small influence on a chip, a bonding wire or a wire frame in an electric power device, is very suitable for being used in encapsulation and sealing protection of medium-low voltage electric power devices, and is accepted by manufacturers.
With the continuous development of power electrical devices, the requirements for the packaging materials used in the packaging field are higher and higher, especially for the emergence of SiC power devices, so that more high-insulation silicone gels are needed to meet the market demands. At present, the withstand voltage of common organic silicon gel on the market is generally less than 18kV/mm, and the high-speed development of the development and application of novel electric power and electric devices cannot be met. Therefore, how to improve the voltage resistance of the silicone gel as much as possible on the basis of ensuring that the silicone gel has high elasticity and low stress is a problem to be solved urgently at present.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a high-voltage-resistant organic silicon gel with high insulation, high elasticity and low stress, and a preparation method and application thereof.
In order to solve the technical problems, the invention adopts the technical scheme that:
a high voltage resistant silicone gel comprises a component A and a component B;
the component A comprises the following raw material components in parts by weight:
60-100 parts of vinyl silicone oil;
0.05 to 2 portions of catalyst;
5-20 parts of modified filler A;
the component B comprises the following raw material components in parts by weight:
Figure BDA0002555743090000011
the modified filler A is obtained by modifying the filler A with vinyl silicone oil; the modified filler B is obtained by modifying the filler B with a crosslinking agent.
In the high-voltage resistant silicone gel, the modified filler A is prepared by the following steps:
(1) adding the filler A into a silane coupling agent modified solution for reaction, and removing the solvent to obtain a vinylated filler A;
(2) and (2) sequentially adding the vinyl filler A and the toluene obtained in the step (1) into vinyl silicone oil, stirring, adding an organic platinum catalyst for reaction, and carrying out solid-liquid separation to obtain the modified filler A.
The high-voltage-resistant organic silicon gel is further improved, in the step (1), the mass ratio of the filler A to the silane coupling agent modifying liquid is 2.0-5.0: 0.5; the filler A is nano alumina particles; the average grain diameter of the filler A is 50 nm-100 nm; the silane coupling agent modified liquid is prepared by mixing a silane coupling agent, isopropanol and toluene mixed solution; the mass percentage of the silane coupling agent in the silane coupling agent modified liquid is 10-30%; the silane coupling agent is KH 570; the mass ratio of the isopropanol to the toluene in the mixed solution of the isopropanol and the toluene is 0.3-0.5: 1; the reaction is carried out under the stirring condition with the rotating speed of 500 r/min-1500 r/min; the reaction temperature is 110-130 ℃; the reaction time is 3-5 h.
The high-voltage-resistant organic silicon gel is further improved, in the step (2), the mass ratio of the vinylation filler A, the vinyl silicone oil and the toluene is 100-50: 1-2: 150-200; the addition amount of the organic platinum catalyst is 0.1-1.0 per mill of the total mass of the vinylation filler A, the vinyl silicone oil and the toluene; the organic platinum catalyst is a platinum (0) -1, 3-divinyl tetramethyl disiloxane complex; the reaction is carried out under the protection of dry nitrogen or argon atmosphere; the reaction temperature is 110-125 ℃; the reaction time is 1.5-3 h.
In the high-voltage resistant silicone gel, the modified filler B is prepared by the following steps:
(a) adding the filler B into a silane coupling agent modified solution for reaction, and removing the solvent to obtain a vinylated filler B;
(b) and (B) sequentially adding the vinyl filler B and toluene obtained in the step (a) into a cross-linking agent, stirring, adding an organic platinum catalyst for reaction, and carrying out solid-liquid separation to obtain the modified filler B.
The high-voltage-resistant organic silicon gel is further improved, in the step (a), the mass ratio of the filler B to the silane coupling agent modifying liquid is 2.0-5.0: 0.5; the filler B is nano alumina particles; the average grain diameter of the filler B is 10 nm-50 nm; the silane coupling agent modified liquid is prepared by mixing a silane coupling agent, isopropanol and toluene mixed solution; the mass percentage of the silane coupling agent in the silane coupling agent modified liquid is 10-30%; the silane coupling agent is KH 570; the mass ratio of the isopropanol to the toluene in the mixed solution of the isopropanol and the toluene is 0.3-0.5: 1; the reaction is carried out under the stirring condition with the rotating speed of 500 r/min-1500 r/min; the reaction temperature is 110-130 ℃; the reaction time is 3-5 h.
The high-voltage-resistant organic silicon gel is further improved, in the step (B), the mass ratio of the vinyl filler B, the cross-linking agent and the toluene is 100-50: 1-2: 150-200; the addition amount of the organic platinum catalyst is 0.1-1.0 per mill of the total mass of the vinylation filler B, the cross-linking agent and the toluene; the reaction is carried out under the protection of dry nitrogen or argon atmosphere; the reaction temperature is 110-125 ℃; the reaction time is 1.5-3 h.
The high-voltage-resistant organic silicon gel is further improved, and the mass ratio of the component A to the component B is 0.8-1.2: 1.
In the high-voltage resistant silicone gel, the vinyl silicone oil is vinyl polydimethylsiloxane, the viscosity at room temperature is 1500 to 6500mPa & s, the mass content of vinyl is 0.05 to 4 percent, and the structure is represented by the following general formula:
Figure BDA0002555743090000031
wherein R is1Is one or more of hydrogen radical, methyl, ethoxy and vinyl, and a is an integer of 60-120.
In the above-mentioned high voltage resistant silicone gel, further improved, the catalyst is tris (triphenylphosphine) carbonyl rhodium (I) hydride complex; the mass percentage of rhodium in the tris (triphenylphosphine) carbonyl rhodium hydride (I) complex is 0.1-2%.
In the high-voltage resistant organic silicon gel, the cross-linking agent is side chain hydrogen-containing silicone oil, the room temperature viscosity is 100mPa & s-500 mPa & s, the content of hydrogen in the active silicon hydrogen bond is 0.05-2.0% of the total mass, and the structure is represented by the following general formula:
Figure BDA0002555743090000032
wherein R is2Is one or two of hydrogen radical and methyl, and b is an integer of 10-50; r3 is one or two of hydrogen group and ethoxy group, and c is an integer of 40-80.
In the high-voltage resistant silicone gel, the inhibitor is one of or a mixture of tetravinyl tetramethylcyclotetrasiloxane and ethynyl cyclohexanol in any proportion.
As a general technical concept, the present invention also provides a preparation method of the above high voltage resistant silicone gel, comprising the steps of:
s1, uniformly mixing vinyl silicone oil and a catalyst, adding the modified filler A, grinding, and removing impurities and bubbles to obtain a component A; adding the cross-linking agent and the inhibitor into the vinyl silicone oil, mixing uniformly, adding the modified filler B, grinding, and removing impurities and bubbles to obtain a component B;
and S2, mixing the component A and the component B obtained in the step S1, removing bubbles, and curing to obtain the high-voltage-resistant organic silicon gel.
In the preparation method of the high-voltage resistant organic silicon gel, in step S1, the grinding time in the preparation process of the component a is 30min to 60 min; the grinding time in the preparation process of the component B is 30-60 min.
As a general technical concept, the invention also provides application of the high-voltage-resistant organic silicon gel or the high-voltage-resistant organic silicon gel prepared by the preparation method in power electronic devices.
Compared with the prior art, the invention has the advantages that:
(1) the invention provides a high-voltage-resistant organic silicon gel which comprises a component A and a component B, wherein the component A is vinyl silicone oil, a catalyst and a filler A modified by the vinyl silicone oil, and the component B is vinyl silicone oil, a cross-linking agent, an inhibitor and a filler B modified by the cross-linking agent. In the invention, after the filler A is modified by the vinyl silicone oil, the filler A is effectively coated by the polydimethylsiloxane containing double bonds, which can improve the compatibility of the filler A and the vinyl silicone oil, so that the modified filler A is uniformly distributed in the vinyl silicone oil, namely in the component A; meanwhile, after the filler B is modified by the cross-linking agent, the filler B is effectively coated by polydimethylsiloxane containing Si-H active bonds, so that the compatibility of the filler B and the cross-linking agent can be improved, and the modified filler B is uniformly distributed in a mixed system of vinyl silicone oil and the cross-linking agent, namely in the component B; on the basis, the modified filler A and the modified filler B can be uniformly distributed in the silicone gel, so that the filler is favorable for participating in addition reaction with silicone oil in the silicone gel reaction process, the filler and the silicone gel form chemical crosslinking, effective protection is formed in the silicone gel, the voltage resistance of the silicone gel is improved, and breakdown under high-voltage current can be prevented. In addition, the vinyl silicone oil containing direct connection, the cross-linking agent and the chain extender are adopted, the original good insulativity, high elasticity and low stress of the organic silicon gel are kept, and meanwhile, the side chain groups in the adopted silicone oil, the cross-linking agent and other silicone oil contain hydrogen groups (-H) which can form a certain proportion of hydrogen bonds after the organic silicon gel is cured, so that the organic silicon gel is endowed with good rebound resilience and good self-repairing performance. The high-voltage-resistant organic silicon gel has the advantages of high insulativity, high elasticity, low stress and the like, more importantly, has very strong high-voltage-resistant capability, can prevent the breakdown of high-voltage current, can obviously improve the voltage-resistant performance of power electronic devices, has very important significance for improving the reliability of the power electronic devices, and has very high use value and very good application prospect.
(2) In the high-voltage-resistant organic silicon gel, the particle size of the filler is further optimized, wherein after the nano-alumina with the average particle size of 50-100 nm is modified by the vinyl silicone oil, the nano-particles are better coated by the polydimethylsiloxane containing double bonds, so that the compatibility of the filler A and the vinyl silicone oil is further improved, and the modified filler A can be more uniformly distributed in the organic silicon gel; meanwhile, after the nano-alumina with the average particle size of 10-50 nm is modified by the cross-linking agent, the nano-particles are better coated by the polydimethylsiloxane containing Si-H active bonds, and the compatibility of the filler B and the cross-linking agent is further improved, so that the modified filler B can be more uniformly distributed in a mixed system of the vinyl silicone oil and the cross-linking agent. Based on the above, the nano-alumina with different particle sizes modified by the vinyl silicone oil and the cross-linking agent can be more uniformly distributed in the silicone gel, which is more beneficial for the nano-alumina to participate in addition reaction with the silicone oil in the silicone gel reaction process, so that more effective protection can be formed in the silicone gel, the further breakdown of high-voltage current is prevented, and the voltage resistance of the silicone gel is further improved.
(3) The invention also provides a preparation method of the high-voltage-resistant organic silicon gel, which comprises the steps of preparing the vinyl silicone oil, the catalyst and the modified filler A into the component A, and preparing the vinyl silicone oil, the cross-linking agent, the inhibitor and the modified filler into the component B; and then mixing the component A and the component B to prepare the high-voltage-resistant organic silicon gel with high insulativity, high elasticity and low stress. The preparation method of the high-voltage-resistant organic silicon gel has the advantages of simple process, convenient operation, easily obtained raw materials, low requirement on equipment and the like, can realize large-scale preparation, is suitable for industrial production, and is beneficial to popularization and application of the high-voltage-resistant organic silicon gel.
Detailed Description
The invention is further described below with reference to specific preferred embodiments, without thereby limiting the scope of protection of the invention.
The materials and equipment used in the following examples are commercially available. In the examples of the present invention, unless otherwise specified, the processes used were conventional processes, the equipment used were conventional equipment, and the data obtained were average values of three or more experiments.
Example 1
A high-voltage-resistant silicone gel comprises a component A and a component B, wherein the mass ratio of the component A to the component B is 0.8: 1.
In the embodiment, the component A comprises the following raw material components in parts by weight:
60 parts of vinyl silicone oil;
0.05 part of a catalyst;
5 parts of modified filler A;
the component B comprises the following raw material components in parts by weight:
Figure BDA0002555743090000051
in this example, the vinyl silicone oil has the following structural formula:
Figure BDA0002555743090000052
wherein the vinyl silicone oil is purchased from Zhejiang Runzi and has a specific gravity of 0.96g/cm3The viscosity at room temperature is 1500 mPas, and the mass content of the vinyl is 0.05 percent.
In this example, the catalyst was a tris (triphenylphosphine) carbonyl rhodium (I) hydride complex, with the mass percentage of rhodium being 0.1%.
In this example, the structural formula of the crosslinker is as follows:
Figure BDA0002555743090000053
wherein the chain extender is purchased from Zhejiang Runzi and has a specific gravity of 0.96g/cm3The content of active silicon hydrogen bond hydrogen is 0.05% of the total mass, and the viscosity is 100 mPas.
In this example, the inhibitor is tetravinyltetramethylcyclotetrasiloxane.
In this embodiment, the modified filler a is obtained by modifying the filler a with vinyl silicone oil (the same as the vinyl silicone oil in the component a), where the filler a is nano alumina particles and has an average particle size of 50 nm. The preparation method of the modified filler A comprises the following steps:
(1) adding the filler A into the KH570 coupling agent modified solution according to the mass ratio of 2.0: 0.5, stirring and reacting for 3 hours at the rotation speed of 500r/min and the temperature of 110 ℃, and evaporating to remove the solvent to obtain the vinylated filler A; wherein the KH570 coupling agent modified solution is prepared by mixing a mixed solution of KH570 coupling agent, isopropanol and toluene; the KH570 coupling agent in the KH570 coupling agent modified solution accounts for 10 percent by mass; the mass ratio of the isopropanol to the toluene in the mixed solution of the isopropanol and the toluene is 0.3: 1.
(2) According to the mass ratio of the vinyl filler A to the vinyl silicone oil to the toluene of 100: 1: 150, wherein the addition amount of the organic platinum catalyst is 0.1 per mill of the total mass of the vinyl filler A, the vinyl silicone oil and the toluene, the vinyl filler A and the toluene obtained in the step (1) are sequentially added into the vinyl silicone oil, stirred, added with the organic platinum catalyst (platinum (0) -1, 3-divinyl tetramethyl disiloxane complex), reacted at 110 ℃ for 1.5h under the protection of dry nitrogen or argon atmosphere, and subjected to solid-liquid separation to obtain the modified filler A.
In this example, the structural formula of modified filler a is as follows:
Figure BDA0002555743090000061
in this embodiment, the modified filler B is obtained by modifying the filler B with a crosslinking agent (the same as the crosslinking agent in the component B), where the filler B is nano alumina particles and has an average particle size of 10 nm. The preparation method of the modified filler B comprises the following steps:
(1) adding the filler B into the KH570 coupling agent modified solution according to the mass ratio of 2.0: 0.5, stirring and reacting for 3 hours at the rotation speed of 500r/min and the temperature of 110 ℃, and evaporating to remove the solvent to obtain a vinylated filler B; wherein the KH570 coupling agent modified solution is prepared by mixing a mixed solution of KH570 coupling agent, isopropanol and toluene; the KH570 coupling agent in the KH570 coupling agent modified solution accounts for 10 percent by mass; the mass ratio of the isopropanol to the toluene in the mixed solution of the isopropanol and the toluene is 0.3: 1.
(2) According to the mass ratio of the vinyl filler B to the cross-linking agent to the toluene of 100: 1: 150, wherein the addition amount of the organic platinum catalyst is 0.1 per thousand of the total mass of the vinyl filler A to the cross-linking agent to the toluene, the vinyl filler B and the toluene obtained in the step (1) are sequentially added to the cross-linking agent, stirred, added with the organic platinum catalyst (platinum (0) -1, 3-divinyl tetramethyl disiloxane complex), reacted at 110 ℃ for 1.5h under the protection of dry nitrogen or argon atmosphere, and subjected to solid-liquid separation to obtain the modified filler B.
In this example, the structural formula of modified filler B is as follows:
Figure BDA0002555743090000071
the preparation method of the high-voltage-resistant silicone gel in the embodiment of the invention comprises the following steps:
s1, uniformly mixing vinyl silicone oil and a catalyst, adding the modified filler A, grinding and dispersing for 30min, and removing impurities and bubbles to obtain a component A; adding the vinyl silicone oil, the cross-linking agent and the inhibitor for a plurality of times, uniformly mixing, adding the modified filler B, grinding and dispersing for 30min, and removing impurities and bubbles to obtain the component B.
And S2, mixing the component A and the component B obtained in the step S1, removing bubbles, and curing to obtain the high-voltage-resistant organic silicon gel.
An application of the high-voltage-resistant silicone gel prepared in the embodiment in a power electronic device is specifically to use the high-voltage-resistant silicone gel for packaging protection of the power electronic device.
Example 2
A high-voltage-resistant silicone gel comprises a component A and a component B, wherein the mass ratio of the component A to the component B is 1.2: 1.
In the embodiment, the component A comprises the following raw material components in parts by weight:
100 parts of vinyl silicone oil;
2 parts of a catalyst;
20 parts of modified filler A;
the component B comprises the following raw material components in parts by weight:
Figure BDA0002555743090000072
in this example, the vinyl silicone oil has the following structural formula:
Figure BDA0002555743090000073
wherein the vinyl silicone oil is purchased from Zhejiang Runzi and has a specific gravity of 0.96g/cm3The viscosity at room temperature is 6500 mPas, and the mass content of the vinyl is 4%.
In this example, the catalyst was a tris (triphenylphosphine) carbonyl rhodium (I) hydride complex, with a rhodium content of 2% by mass.
In this example, the structural formula of the crosslinker is as follows:
Figure BDA0002555743090000074
wherein the chain extender is purchased from Zhejiang Runzi and has a specific gravity of 0.96g/cm3The content of active silicon hydrogen bond hydrogen is 2.0% of the total mass, and the viscosity is 500 mPas.
In this example, the inhibitor is ethynylcyclohexanol.
In this embodiment, the modified filler a is obtained by modifying the filler a with vinyl silicone oil (the same as the vinyl silicone oil in the component a), where the filler a is nano alumina particles and has an average particle size of 100 nm. The preparation method of the modified filler A comprises the following steps:
(1) adding the filler A into the KH570 coupling agent modified solution according to the mass ratio of 1.0: 0.1, stirring and reacting for 5 hours at the rotating speed of 1500r/min and the temperature of 130 ℃, and evaporating to remove the solvent to obtain the vinylated filler A; wherein the KH570 coupling agent modified solution is prepared by mixing a mixed solution of KH570 coupling agent, isopropanol and toluene; the KH570 coupling agent in the KH570 coupling agent modified solution accounts for 30 percent by mass; the mass ratio of the isopropanol to the toluene in the mixed solution of the isopropanol and the toluene is 0.5: 1.
(2) According to the mass ratio of 50: 1: 200 of the vinyl filler A, the vinyl silicone oil and the toluene, wherein the addition amount of the organic platinum catalyst is 1.0 per mill of the total mass of the vinyl filler A, the vinyl silicone oil and the toluene, the vinyl filler A and the toluene obtained in the step (1) are sequentially added into the vinyl silicone oil, stirred, added with the organic platinum catalyst (platinum (0) -1, 3-divinyl tetramethyl disiloxane complex), reacted at 125 ℃ for 3 hours under the protection of dry nitrogen or argon atmosphere, and subjected to solid-liquid separation to obtain the modified filler A.
In this example, the structural formula of modified filler a is as follows:
Figure BDA0002555743090000081
in this embodiment, the modified filler B is obtained by modifying the filler B with a crosslinking agent (the same as the crosslinking agent in the component B), where the filler B is nano alumina particles and has an average particle size of 50 nm. The preparation method of the modified filler B comprises the following steps:
(1) adding the filler B into the KH570 coupling agent modified solution according to the mass ratio of 1.0: 0.1, stirring and reacting for 5 hours at the rotating speed of 1500r/min and the temperature of 130 ℃, and evaporating to remove the solvent to obtain a vinylated filler B; wherein the KH570 coupling agent modified solution is prepared by mixing a mixed solution of KH570 coupling agent, isopropanol and toluene; the KH570 coupling agent in the KH570 coupling agent modified solution accounts for 30 percent by mass; the mass ratio of the isopropanol to the toluene in the mixed solution of the isopropanol and the toluene is 0.5: 1.
(2) According to the mass ratio of 50: 1: 200 of the vinyl filler B, the cross-linking agent and the toluene, wherein the addition amount of the organic platinum catalyst is 1.0 per mill of the total mass of the vinyl filler A, the cross-linking agent and the toluene, the vinyl filler B and the toluene obtained in the step (1) are sequentially added into the cross-linking agent, stirred, added with the organic platinum catalyst (platinum (0) -1, 3-divinyl tetramethyl disiloxane complex), reacted at 125 ℃ for 3 hours under the protection of dry nitrogen or argon atmosphere, and subjected to solid-liquid separation to obtain the modified filler B.
In this example, the structural formula of modified filler B is as follows:
Figure BDA0002555743090000091
the preparation method of the high-voltage-resistant silicone gel in the embodiment of the invention comprises the following steps:
s1, uniformly mixing vinyl silicone oil and a catalyst, adding the modified filler A, grinding and dispersing for 60min, and removing impurities and bubbles to obtain a component A; adding the vinyl silicone oil, the cross-linking agent and the inhibitor for a plurality of times, uniformly mixing, adding the modified filler B, grinding and dispersing for 60min, and removing impurities and bubbles to obtain the component B.
And S2, mixing the component A and the component B obtained in the step S1, removing bubbles, and curing to obtain the high-voltage-resistant organic silicon gel.
An application of the high-voltage-resistant silicone gel prepared in the embodiment in a power electronic device is specifically to use the high-voltage-resistant silicone gel for packaging protection of the power electronic device.
Example 3
A high-voltage-resistant silicone gel comprises a component A and a component B, wherein the mass ratio of the component A to the component B is 1: 1.
In the embodiment, the component A comprises the following raw material components in parts by weight:
80 parts of vinyl silicone oil;
1 part of a catalyst;
10 parts of modified filler A;
the component B comprises the following raw material components in parts by weight:
Figure BDA0002555743090000092
in this example, the vinyl silicone oil has the following structural formula:
Figure BDA0002555743090000093
wherein the vinyl silicone oil is purchased from Zhejiang Runzi and has a specific gravity of 0.96g/cm3The viscosity at room temperature is 3500 mPas, and the mass content of the vinyl is 0.8 percent.
In this example, the catalyst was a tris (triphenylphosphine) carbonyl rhodium (I) hydride complex, with the mass percentage of rhodium being 1%.
In this example, the structural formula of the crosslinker is as follows:
Figure BDA0002555743090000101
wherein the chain extender is purchased from Zhejiang Runzi and has a specific gravity of 0.96g/cm3The content of active silicon hydrogen bond hydrogen is 1% of the total mass, and the viscosity is 300 mPas.
In this example, the inhibitor is tetravinyltetramethylcyclotetrasiloxane.
In this embodiment, the modified filler a is obtained by modifying the filler a with vinyl silicone oil (the same as the vinyl silicone oil in the component a), where the filler a is nano alumina particles and has an average particle size of 80 nm. The preparation method of the modified filler A comprises the following steps:
(1) adding the filler A into the KH570 coupling agent modified solution according to the mass ratio of 7: 1, stirring and reacting for 4 hours at the rotation speed of 1000r/min and the temperature of 120 ℃, and evaporating to remove the solvent to obtain a vinyl filler A; wherein the KH570 coupling agent modified solution is prepared by mixing a mixed solution of KH570 coupling agent, isopropanol and toluene; the KH570 coupling agent in the KH570 coupling agent modified solution accounts for 10 percent by mass; the mass ratio of the isopropanol to the toluene in the mixed solution of the isopropanol and the toluene is 2.0: 5.
(2) According to the mass ratio of the vinyl filler A to the vinyl silicone oil to the toluene of 80: 1: 170, wherein the addition amount of the organic platinum catalyst is 0.5 per mill of the total mass of the vinyl filler A, the vinyl silicone oil and the toluene, the vinyl filler A and the toluene obtained in the step (1) are sequentially added into the vinyl silicone oil, stirred, added with the organic platinum catalyst (platinum (0) -1, 3-divinyl tetramethyl disiloxane complex), reacted at 120 ℃ for 2 hours under the protection of dry nitrogen or argon atmosphere, and subjected to solid-liquid separation to obtain the modified filler A.
In this example, the structural formula of modified filler a is as follows:
Figure BDA0002555743090000102
in this embodiment, the modified filler B is obtained by modifying the filler B with a crosslinking agent (the same as the crosslinking agent in the component B), wherein the filler B is nano alumina particles and has an average particle size of 30 nm. The preparation method of the modified filler B comprises the following steps:
(1) adding the filler B into the KH570 coupling agent modified solution according to the mass ratio of 7: 1, stirring and reacting for 4 hours at the rotation speed of 1000r/min and the temperature of 120 ℃, and evaporating to remove the solvent to obtain a vinyl filler B; wherein the KH570 coupling agent modified solution is prepared by mixing a mixed solution of KH570 coupling agent, isopropanol and toluene; the KH570 coupling agent in the KH570 coupling agent modified solution accounts for 10 percent by mass; the mass ratio of the isopropanol to the toluene in the mixed solution of the isopropanol and the toluene is 2.0: 5.
(2) According to the mass ratio of the vinyl filler B to the cross-linking agent to the toluene of 80: 1: 170, wherein the addition amount of the organic platinum catalyst is 0.5 per thousand of the total mass of the vinyl filler A to the cross-linking agent to the toluene, the vinyl filler B and the toluene obtained in the step (1) are sequentially added to the cross-linking agent, stirred, added with the organic platinum catalyst (platinum (0) -1, 3-divinyl tetramethyl disiloxane complex), reacted at 120 ℃ for 2 hours under the protection of dry nitrogen or argon atmosphere, and subjected to solid-liquid separation to obtain the modified filler B.
In this example, the structural formula of modified filler B is as follows:
Figure BDA0002555743090000111
the preparation method of the high-voltage-resistant silicone gel in the embodiment of the invention comprises the following steps:
s1, uniformly mixing vinyl silicone oil and a catalyst, adding the modified filler A, grinding and dispersing for 45min, and removing impurities and bubbles to obtain a component A; adding the vinyl silicone oil, the cross-linking agent and the inhibitor for a plurality of times, uniformly mixing, adding the modified filler B, grinding and dispersing for 45min, and removing impurities and bubbles to obtain the component B.
And S2, mixing the component A and the component B obtained in the step S1, removing bubbles, and curing to obtain the high-voltage-resistant organic silicon gel.
An application of the high-voltage-resistant silicone gel prepared in the embodiment in a power electronic device is specifically to use the high-voltage-resistant silicone gel for packaging protection of the power electronic device.
The high voltage resistant silicone gels prepared in examples 1-3 were subjected to performance testing, and the results are shown in table 1 below.
Table 1 results of performance test of silicone gels of examples 1 to 3 having different high voltage resistances
Item Detection standard Example 1 Example 2 Example 3
Viscosity (mPa. s) GB/T 2794-1995 4235 3826 4261
Penetration degree (0.1mm) GB/T 269-1991 35 38 36
Electric strength (kV/mm) GB/T 507-2002 32.0 34.1 31.3
Volume resistivity (omega cm) GB/T 1692-2008 3.1×1015 2.1×1015 3.0×1015
Modulus of elasticity (kPa) / 123 129 115
Thermal conductivity (W/(m.K)) GB/T 10295-2008 1.8 1.6 2.1
As shown in table 1, under different processing conditions, the volume resistivity and the electrical strength of the two-component high voltage resistant silicone gel (high voltage resistant silicone gel) for power electronic devices prepared in examples 1 to 3 of the present invention reach higher values, which indicates that the gels prepared according to the present invention have excellent electrical insulation performance and high voltage resistance, and the penetration degree and the elastic modulus are suitable, and indicates that the high voltage resistant silicone gel prepared according to the present invention maintains the advantages of high elasticity and low stress of the silicone gel. Therefore, the bi-component high-pressure-resistant organic silicon gel has the advantages of high insulativity, high elasticity, low stress and the like, can obviously improve the pressure resistance of power electronic devices (such as high-power semiconductor modules), has very important significance for improving the reliability of the power electronic devices, and has very high use value and very good application prospect.
The above examples are merely preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.

Claims (10)

1. A high voltage resistant silicone gel is characterized by comprising a component A and a component B;
the component A comprises the following raw material components in parts by weight:
60-100 parts of vinyl silicone oil;
0.05 to 2 portions of catalyst;
5-20 parts of modified filler A;
the component B comprises the following raw material components in parts by weight:
Figure FDA0002555743080000011
the modified filler A is obtained by modifying the filler A with vinyl silicone oil; the modified filler B is obtained by modifying the filler B with a crosslinking agent.
2. The high voltage resistant silicone gel according to claim 1, wherein the modified filler A is prepared by the following method:
(1) adding the filler A into a silane coupling agent modified solution for reaction, and removing the solvent to obtain a vinylated filler A;
(2) and (2) sequentially adding the vinyl filler A and the toluene obtained in the step (1) into vinyl silicone oil, stirring, adding an organic platinum catalyst for reaction, and carrying out solid-liquid separation to obtain the modified filler A.
3. The high-voltage-resistant silicone gel according to claim 2, wherein in step (1), the mass ratio of the filler A to the silane coupling agent modifying solution is 2.0-5.0: 0.5; the filler A is nano alumina particles; the average grain diameter of the filler A is 50 nm-100 nm; the silane coupling agent modified liquid is prepared by mixing a silane coupling agent, isopropanol and toluene mixed solution; the mass percentage of the silane coupling agent in the silane coupling agent modified liquid is 10-30%; the silane coupling agent is KH 570; the mass ratio of the isopropanol to the toluene in the mixed solution of the isopropanol and the toluene is 0.3-0.5: 1; the reaction is carried out under the stirring condition with the rotating speed of 500 r/min-1500 r/min; the reaction temperature is 110-130 ℃; the reaction time is 3-5 h;
in the step (2), the mass ratio of the vinylation filler A to the vinyl silicone oil to the toluene is 100-50: 1-2: 150-200; the addition amount of the organic platinum catalyst is 0.1-1.0 per mill of the total mass of the vinylation filler A, the vinyl silicone oil and the toluene; the organic platinum catalyst is a platinum (0) -1, 3-divinyl tetramethyl disiloxane complex; the reaction is carried out under the protection of dry nitrogen or argon atmosphere; the reaction temperature is 110-125 ℃; the reaction time is 1.5-3 h.
4. The high voltage resistant silicone gel according to claim 1, wherein the modified filler B is prepared by the following method:
(a) adding the filler B into a silane coupling agent modified solution for reaction, and removing the solvent to obtain a vinylated filler B;
(b) and (B) sequentially adding the vinyl filler B and toluene obtained in the step (a) into a cross-linking agent, stirring, adding an organic platinum catalyst for reaction, and carrying out solid-liquid separation to obtain the modified filler B.
5. The high-voltage-resistant silicone gel according to claim 4, wherein in step (a), the mass ratio of the filler B to the silane coupling agent modifying solution is 2.0-5.0: 0.5; the filler B is nano alumina particles; the average grain diameter of the filler B is 10 nm-50 nm; the silane coupling agent modified liquid is prepared by mixing a silane coupling agent, isopropanol and toluene mixed solution; the mass percentage of the silane coupling agent in the silane coupling agent modified liquid is 10-30%; the silane coupling agent is KH 570; the mass ratio of the isopropanol to the toluene in the mixed solution of the isopropanol and the toluene is 0.3-0.5: 1; the reaction is carried out under the stirring condition with the rotating speed of 500 r/min-1500 r/min; the reaction temperature is 110-130 ℃; the reaction time is 3-5 h;
in the step (B), the mass ratio of the vinyl filler B to the cross-linking agent to the toluene is 100-50: 1-2: 150-200; the addition amount of the organic platinum catalyst is 0.1-1.0 per mill of the total mass of the vinylation filler B, the cross-linking agent and the toluene; the reaction is carried out under the protection of dry nitrogen or argon atmosphere; the reaction temperature is 110-125 ℃; the reaction time is 1.5-3 h.
6. The high-voltage-resistant silicone gel according to any one of claims 1 to 5, wherein the mass ratio of the component A to the component B is 0.8 to 1.2: 1.
7. The high-voltage-resistant silicone gel according to any one of claims 1 to 5, wherein the vinyl silicone oil is vinyl polydimethylsiloxane, the room-temperature viscosity is 1500mPa · s to 6500mPa · s, the mass content of the vinyl group is 0.05% to 4%, and the structure is represented by the following general formula:
Figure FDA0002555743080000021
wherein R is1Is one or more of hydrogen group, methyl group, ethoxy group and vinyl group, and a is an integer of 60-120;
the catalyst is a tris (triphenylphosphine) carbonyl rhodium (I) hydride complex; the mass percentage of rhodium in the tris (triphenylphosphine) carbonyl rhodium hydride (I) complex is 0.1-2%;
the cross-linking agent is side chain hydrogen-containing silicone oil, the room temperature viscosity is 100-500 mPa.s, the content of hydrogen in the active silicon hydrogen bond is 0.05-2.0% of the total mass, and the structure is represented by the following general formula:
Figure FDA0002555743080000022
wherein R is2Is one or two of hydrogen radical and methyl, and b is an integer of 10-50; r3 is one or two of hydrogen group and ethoxy group, and c is an integer of 40-80;
the inhibitor is one of or a mixture of tetravinyl tetramethylcyclotetrasiloxane and ethynyl cyclohexanol in any proportion.
8. A method for preparing a high voltage resistant silicone gel according to any one of claims 1 to 7, comprising the steps of:
s1, uniformly mixing vinyl silicone oil and a catalyst, adding the modified filler A, grinding, and removing impurities and bubbles to obtain a component A; adding the cross-linking agent and the inhibitor into the vinyl silicone oil, mixing uniformly, adding the modified filler B, grinding, and removing impurities and bubbles to obtain a component B;
and S2, mixing the component A and the component B obtained in the step S1, removing bubbles, and curing to obtain the high-voltage-resistant organic silicon gel.
9. The method for preparing the high voltage resistant silicone gel according to claim 8, wherein in step S1, the grinding time in the preparation process of the component a is 30min to 60 min; the grinding time in the preparation process of the component B is 30-60 min.
10. Use of the high voltage resistant silicone gel according to any one of claims 1 to 7 or the high voltage resistant silicone gel prepared by the preparation method according to claim 8 or 9 in power electronic devices.
CN202010589148.9A 2020-06-24 2020-06-24 High-voltage-resistant organic silicon gel and preparation method and application thereof Pending CN111690259A (en)

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