CN110746783A - High-temperature-resistant addition type organic silicon gel and preparation method thereof - Google Patents
High-temperature-resistant addition type organic silicon gel and preparation method thereof Download PDFInfo
- Publication number
- CN110746783A CN110746783A CN201911022758.4A CN201911022758A CN110746783A CN 110746783 A CN110746783 A CN 110746783A CN 201911022758 A CN201911022758 A CN 201911022758A CN 110746783 A CN110746783 A CN 110746783A
- Authority
- CN
- China
- Prior art keywords
- silicone oil
- oligomeric silsesquioxane
- component
- mass
- vinyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- 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
-
- 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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Silicon Polymers (AREA)
Abstract
The invention discloses a high-temperature resistant addition type organic silicon gel and a preparation method thereof, wherein the component A in the organic silicon gel comprises: 12-25 parts of vinyl silicone oil containing oligomeric silsesquioxane; the component B comprises the following raw material components in parts by mass: 40 to 90 parts of vinyl silicone oil containing oligomeric silsesquioxane, 10 to 35 parts of chain extender, 5 to 15 parts of cross-linking agent containing oligomeric silsesquioxane and 1 to 5 parts of high-temperature resistant coupling agent. The preparation method comprises the following steps: preparing a component A/B; mixing the A/B components and curing. The organic silicon gel has the advantages of high elasticity, low stress, excellent high-temperature heat resistance and the like, can obviously improve the reliability and the service life of the base material at high temperature, has very high use value and good application prospect, can realize large-scale preparation, is suitable for industrial production, and is beneficial to popularization and application of materials.
Description
Technical Field
The invention belongs to the field of organosilicon materials, and relates to a high-temperature-resistant addition type organosilicon gel and a preparation method thereof.
Background
The addition type silicone gel is essentially a composition of organopolysiloxane, organohydrogenpolysiloxane containing silicon-bonded hydrogen atoms (Si — H), organopolysiloxane having double bonds (e.g., bonded vinyl groups), and the like. Due to the special structure, the composite material has many excellent properties such as better heat resistance, weather resistance, cold resistance, electric insulation performance and the like, and has lower elastic modulus and ultralow stress; good elasticity is not easy to form stress on a chip, a bonding wire, a wire frame and the like, and is very suitable for being applied to packaging of a power module, so that the high-elasticity-resistance packaging material is accepted by most power module manufacturers and is widely applied to packaging protection of the high-power module.
The common failure of high power semiconductor modules is basically caused by thermal cycling, and the main reasons for module failure can be summarized as adhesion and cracks caused by mismatched Coefficients of Thermal Expansion (CTE) of various materials, and the filled silicone gel cannot withstand high temperature. For the CTE value of the encapsulation material used, the approach taken is to reduce the CTE value of the material as much as possible; the heat resistance of the filled silicone gel is improved as much as possible on the basis of keeping the original high elasticity and low stress. With the development of electronic information industry technology, the semiconductor power module is developed towards high power, high performance and high energy density, which means that the heat productivity of the power module will be further improved, which puts higher requirements on the stability and dielectric property of the filled silica gel at high temperature, and becomes one of the key influencing factors of the service life and reliability of the high-power module. Therefore, how to obtain the high-temperature-resistant addition type organic silicon gel with high elasticity, low stress and excellent high-temperature resistance has very important significance for prolonging the service life and improving the reliability of a high-power module.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a high-temperature-resistant addition type organic silicon gel with high elasticity, low stress and excellent high-temperature resistance and a preparation method thereof.
In order to solve the technical problems, the invention adopts the technical scheme that:
the high-temperature-resistant addition type organic silicon gel comprises a component A and a component B, wherein the component A comprises the following raw material components in parts by mass:
12-25 parts of vinyl silicone oil containing oligomeric silsesquioxane;
the component B comprises the following raw material components in parts by mass:
the high-temperature-resistant addition type organic silicon gel is further improved, and the mass ratio of the component A to the component B is 0.5-1.5: 10.
In the high-temperature resistant addition type organic silicon gel, the structural formula of the vinyl silicone oil containing oligomeric silsesquioxane is further improved as follows:
wherein R is1Is at least one of methyl, phenyl and ethoxy; r2Is at least one of methyl, phenyl and ethoxy; a is an integer of 200 to 800, b is an integer of 1 to 10, and c is an integer of 1 to 50; the vinyl silicone oil containing the oligomeric silsesquioxane has the purity of more than or equal to 99.9 percent and the viscosity of 800-8000 mPa & s; the vinyl silicone oil containing oligomeric silsesquioxane contains 0.05-2.5% of vinyl and 50-70% of phenyl by mass.
The high-temperature resistant addition type organic silicon gel is further improved, and the structural formula of the chain extender is as follows:
wherein R is3Is methyl,At least one of phenyl and ethoxy atoms; d is an integer of 20 to 50, e is an integer of 1 to 10; the purity of the chain extender is more than or equal to 99.9 percent, and the viscosity is 10mPa & s-500 mPa & s; the mass percentage of hydrogen in the chain extender is 0.02-0.2%, and the mass percentage of phenyl is 50-70%.
In the high-temperature resistant addition type organic silicon gel, the structural formula of the cross-linking agent containing the oligomeric silsesquioxane is further improved as follows:
wherein R is4Is at least one of methyl, phenyl and ethoxy; r5Is at least one of methyl, phenyl and ethoxy; f is an integer of 100 to 500, g is an integer of 1 to 10, and h is an integer of 1 to 50; the cross-linking agent containing the oligomeric silsesquioxane has the purity of more than or equal to 99.9 percent and the viscosity of 10-500 mPa & s; the cross-linking agent containing the oligomeric silsesquioxane contains 0.2-2.0% of hydrogen and 50-70% of phenyl by mass.
In the above-mentioned high-temperature resistant addition type silicone gel, further improved, the structural formula of the high-temperature resistant coupling agent is as follows:
wherein i is an integer of 1-10.
As a general technical concept, the present invention also provides a preparation method of the above high temperature resistant addition type silicone gel, comprising the steps of:
s1, mixing vinyl silicone oil containing oligomeric silsesquioxane with a catalyst, stirring, and removing impurities and bubbles to obtain a component A; mixing vinyl silicone oil containing oligomeric silsesquioxane, a chain extender, a cross-linking agent containing oligomeric silsesquioxane, an inhibitor and a high-temperature-resistant coupling agent, stirring, 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-temperature-resistant addition type organic silicon gel.
In the above preparation method, further improvement is provided, in step S1, the preparation method of the vinyl silicone oil containing oligomeric silsesquioxane comprises the following steps: sequentially adding vinyl POSS and toluene into vinyl silicone oil, stirring, adding an organic platinum catalyst, heating to 110-125 ℃ under the protection of dry nitrogen or argon atmosphere, reacting for 1.5-3 h, and purifying to obtain the vinyl silicone oil containing oligomeric silsesquioxane; the mass ratio of the vinyl silicone oil to the vinyl POSS to the toluene is 40-60: 1-5: 100-150; the addition amount of the organic platinum catalyst is 0.5-1 per mill of the total mass of the vinyl silicone oil, the vinyl POSS and the toluene.
In a further improvement of the above preparation method, in step S1, the preparation method of the oligomeric silsesquioxane-containing cross-linking agent comprises the following steps: sequentially adding vinyl POSS and toluene into hydrogen-containing silicone oil, stirring, adding an organic platinum catalyst, heating to 110-125 ℃ under the protection of dry nitrogen or argon atmosphere, reacting for 1.5-3 h, and purifying to obtain a cross-linking agent containing oligomeric silsesquioxane; the mass ratio of the hydrogen-containing silicone oil to the vinyl POSS to the toluene is 50-80: 1-3: 100-150; the addition amount of the organic platinum catalyst is 0.5-1 per mill of the total mass of the hydrogen-containing silicone oil, the vinyl POSS and the toluene.
In the step S1, the mass ratio of the vinyl silicone oil containing oligomeric silsesquioxane to the catalyst in the preparation method of the component a is 12-25: 0.01-1; the catalyst is at least one of acidified ruthenium compound, rhodium compound, palladium compound, iridium compound and platinum compound. The ruthenium-based compound, rhodium-based compound, palladium-based compound, iridium-based compound, and platinum-based compound described above are a ruthenium-based catalyst, a rhodium-based catalyst, a palladium-based catalyst, an iridium-based catalyst, and a platinum-based catalyst in this order, and can be used in the present invention. In addition, perchloric acid is generally used for acidification.
In the step S1, the mass ratio of the vinyl silicone oil containing oligomeric silsesquioxane to the inhibitor in the preparation method of the component B is 40-90: 0.01-1; the inhibitor is at least one of alkynol compounds, azo compounds and polyene compounds.
In a further improvement of the above preparation method, the inhibitor is at least one of 3-methyl-1-butyn-3-ol, trimethyl-1-pentyn-3-ol, benzotriazole, 4-methyl-4 '-hydroxyazobenzene, 4' -dihydroxyhydroazobenzene, diallyl maleate, tetramethyltetravinylcyclotetrasiloxane and tetramethyltrivinylcyclotetrasiloxane.
In a further improvement of the above preparation method, in step S1, the removal of the impurities and bubbles is performed under a negative pressure condition of < -0.1 MPa;
in the step S2, the removal of the bubbles is carried out under the negative pressure condition of < -0.1 MPa; the time for removing bubbles is 5 min-10 min; the curing temperature is 100-125 ℃; the curing time is 3-5 h.
In the present invention, the preparation process of the vinyl silicone oil containing oligomeric silsesquioxane is represented by the following general formula:
in the present invention, the process for preparing the oligomeric silsesquioxane-containing cross-linking agent is represented by the following general formula:
compared with the prior art, the invention has the advantages that:
(1) the invention provides a high-temperature-resistant addition type organic silicon gel, wherein vinyl silicone oil containing oligomeric silsesquioxane can improve the phenyl content of the vinyl silicone oil, and can be chemically bonded with the oligomeric silsesquioxane with a stable structure, so that the organic silicon gel has better high-temperature resistance; the cross-linking agent containing the oligomeric silsesquioxane can not only improve the phenyl content of vinyl silicone oil, but also can chemically bond the oligomeric silsesquioxane with stable structure, and increase cross-linking points, which endows the silicone gel with better thermal stability; therefore, the vinyl silicone oil containing the oligomeric silsesquioxane (POSS) and the cross-linking agent containing the oligomeric silsesquioxane (POSS) are compounded, so that the high-temperature resistant addition type organic silicone gel keeps lower elastic modulus and stress and has the characteristics of high elasticity and low stress; and the stability and dielectric property of the high-temperature resistant addition type organic silicon gel at high temperature are greatly improved, and the high-temperature resistant organic silicon gel has better high-temperature resistance. Furthermore, by compounding a high-temperature-resistant coupling agent (oligomer coupling agent) with good high-temperature resistance, the silicon gel can be ensured to have good adhesive force with different base materials at high temperature, and the high-temperature resistance of the silicon gel can be further improved. Meanwhile, as the chain extender is used as a bridge for further crosslinking the hydrogen-containing silicone oil and the vinyl silicone oil, the crosslinking density and the molecular structure stability can be improved by compounding the chain extender, so that the aim of improving the high temperature resistance of the silicone gel is fulfilled. Therefore, the high-temperature resistant addition type organic silicon gel obtained by the method not only keeps the characteristics of high elasticity and low stress, but also has excellent high-temperature resistance, so that the high-power semiconductor module packaged by the high-temperature resistant addition type organic silicon gel can effectively improve the reliability of the high-power semiconductor module at high temperature, and the service life of the module is prolonged. The high-temperature-resistant addition type organic silicon gel has the advantages of high elasticity, low stress, excellent high-temperature heat resistance and the like, is suitable for packaging protection of various base materials, can obviously improve the reliability and the service life of the base materials (such as a high-power semiconductor module) at high temperature, and has high use value and good application prospect.
(2) The invention also provides a preparation method of the high-temperature-resistant addition type organic silicon gel, firstly mixing a part of vinyl silicone oil containing oligomeric silsesquioxane with a catalyst to prepare a component A, and mixing the other part of vinyl silicone oil containing oligomeric silsesquioxane with a chain extender, a cross-linking agent containing oligomeric silsesquioxane, an inhibitor and a high-temperature-resistant coupling agent to prepare a component B; and then mixing the component A and the component B, and curing to obtain the high-temperature-resistant addition type organic silicon gel. In the preparation process, the catalyst and the inhibitor influence each other, the catalyst is used for accelerating the reaction speed, the inhibitor is used for delaying the reaction speed, and the proper process time can be adjusted through the matching of a catalysis-inhibition system, so that the preparation of the high-temperature resistant addition type organic silicon gel with high elasticity, low stress and excellent high-temperature heat resistance is facilitated. The preparation method 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 favorable for popularization and application of the high-temperature-resistant addition type organic silicon gel material.
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 temperature resistant addition type organic silicon gel comprises a component A and a component B, wherein the mass ratio of the component A to the component B is 0.5: 10; the component A comprises the following raw material components in parts by mass:
15 parts of vinyl silicone oil containing oligomeric silsesquioxane;
the component B comprises the following raw material components in parts by mass:
in this example, the structural formula of the vinyl silicone oil containing oligomeric silsesquioxane is as follows:
wherein the vinyl silicone oil containing the oligomeric silsesquioxane has the purity of 99.9 percent and the viscosity of 1500mPa & s; the vinyl silicone oil containing the oligomeric silsesquioxane contains 2.5% by mass of vinyl and 50% by mass of phenyl.
In this example, the structural formula of the chain extender is as follows:
wherein the purity of the chain extender is 99.9 percent, and the viscosity is 100mPa & s; the mass percentage of hydrogen in the chain extender is 0.02%, and the mass percentage of phenyl is 50%.
In this example, the structural formula of the oligomeric silsesquioxane-containing cross-linking agent is as follows:
wherein the cross-linking agent containing the oligomeric silsesquioxane has the purity of 99.9 percent and the viscosity of 100 mPas; the cross-linking agent containing the oligomeric silsesquioxane contains 0.2% by mass of hydrogen and 50% by mass of phenyl.
In this example, the high temperature-resistant coupling agent is oligomeric gamma- (methacryloyloxy) propyl trimethoxysilane, which has the following structural formula:
a method for preparing the high temperature resistant addition type silicone gel in the above embodiment includes the following steps:
(1) adding 0.01 part by mass of catalyst (specifically, Japanese Xinyue Kanst platinum catalyst with the concentration of 3000 ppm) into 15 parts by mass of vinyl silicone oil containing oligomeric silsesquioxane, stirring uniformly, and removing impurities and bubbles under the negative pressure condition of < -0.1MPa to obtain component A.
(2) Adding 40 parts by mass of vinyl silicone oil containing oligomeric silsesquioxane, 10 parts by mass of chain extender, 5 parts by mass of cross-linking agent containing oligomeric silsesquioxane, 0.01 part by mass of inhibitor (specifically 3-methyl-1-butyn-3-ol) and 1 part by mass of high-temperature-resistant coupling agent into a mixing kettle in sequence, stirring uniformly, and removing impurities and bubbles under the negative pressure condition of less than-0.1 MPa to obtain the component B.
(3) And (3) mixing the component A obtained in the step (1) with the component B obtained in the step (2), defoaming for 8min under the negative pressure condition of < -0.1MPa, and curing for 4h at 125 ℃ to obtain the high-temperature-resistant addition type silicone gel.
In this example, the preparation process of the vinyl silicone oil containing oligomeric silsesquioxane is as follows: weighing 50 parts by mass of vinyl silicone oil into a single-mouth bottle, slowly adding 3 parts by mass of vinyl POSS, adding 100 parts by mass of dry toluene, adopting dry nitrogen protection, uniformly mixing under magnetic stirring, adding a Japan Xinyue Kanstel platinum catalyst with the concentration of 5000ppm (the addition amount of the organic platinum catalyst is 0.5 per mill of the total mass of the vinyl silicone oil, the vinyl POSS and the toluene), heating to 110 ℃, reacting for 1.5h, and purifying a reaction product to obtain the vinyl silicone oil containing oligomeric silsesquioxane.
In this example, the oligomeric silsesquioxane-containing crosslinker was prepared as follows: weighing 50 parts by mass of hydrogen-containing silicone oil into a single-mouth bottle, slowly adding 1 part by mass of vinyl POSS, adding 100 parts by mass of dry toluene, adopting dry nitrogen protection, uniformly mixing under magnetic stirring, adding 5000ppm of Japanese Behcard platinum catalyst (the addition amount of the organic platinum catalyst is 0.5 per mill of the total mass of the vinyl silicone oil, the vinyl POSS and the toluene), heating to 110 ℃, reacting for 1.5h, and purifying a reaction product to obtain the cross-linking agent containing the oligomeric silsesquioxane.
Example 2
A high temperature resistant addition type organic silicon gel comprises a component A and a component B, wherein the mass ratio of the component A to the component B is 1: 10; the component A comprises the following raw material components in parts by mass:
20 parts of vinyl silicone oil containing oligomeric silsesquioxane;
the component B comprises the following raw material components in parts by mass:
in this example, the structural formula of the vinyl silicone oil containing oligomeric silsesquioxane is as follows:
wherein the vinyl silicone oil containing the oligomeric silsesquioxane has the purity of 99.9 percent and the viscosity of 3500mPa & s; the vinyl silicone oil containing the oligomeric silsesquioxane contains 1.0 mass percent of vinyl and 60 mass percent of phenyl.
In this example, the structural formula of the chain extender is as follows:
wherein the purity of the chain extender is 99.9 percent, and the viscosity is 300mPa & s; the mass percentage of hydrogen in the chain extender is 0.2%, and the mass percentage of phenyl is 70%.
In this example, the structural formula of the oligomeric silsesquioxane-containing cross-linking agent is as follows:
wherein the cross-linking agent containing the oligomeric silsesquioxane has the purity of 99.9 percent and the viscosity of 300mPa & s; the cross-linking agent containing the oligomeric silsesquioxane contains 2.0% by mass of hydrogen and 60% by mass of phenyl.
In this example, the high temperature-resistant coupling agent is oligomeric gamma- (methacryloyloxy) propyl trimethoxysilane, which has the following structural formula:
a method for preparing the high temperature resistant addition type silicone gel in the above embodiment includes the following steps:
(1) adding 0.5 part by mass of catalyst (specifically 3500ppm Japanese Xinyue Kansted platinum catalyst) into 20 parts by mass of vinyl silicone oil containing oligomeric silsesquioxane, stirring uniformly, and removing impurities and bubbles under the negative pressure condition of < -0.1MPa to obtain component A.
(2) Adding 75 parts by mass of vinyl silicone oil containing oligomeric silsesquioxane, 25 parts by mass of chain extender, 10 parts by mass of cross-linking agent containing oligomeric silsesquioxane, 0.5 part by mass of inhibitor (specifically 4-methyl-4' -hydroxyazobenzene) and 3 parts by mass of high-temperature-resistant coupling agent into a mixing kettle in sequence, uniformly stirring, and removing impurities and bubbles under the negative pressure condition of less than-0.1 MPa to obtain the component B.
(3) And (3) mixing the component A obtained in the step (1) with the component B obtained in the step (2), defoaming for 5min under the negative pressure condition of < -0.1MPa, and curing for 3h at 100 ℃ to obtain the high-temperature-resistant addition type silicone gel.
In this example, the preparation process of the vinyl silicone oil containing oligomeric silsesquioxane is as follows: weighing 40 parts by mass of vinyl silicone oil into a single-mouth bottle, slowly adding 2 parts by mass of vinyl POSS, adding 100 parts by mass of dry toluene, adopting dry nitrogen protection, uniformly mixing under magnetic stirring, adding 5000ppm of Japanese Behcard platinum catalyst (the addition amount of the organic platinum catalyst is 0.8 per mill of the total mass of the vinyl silicone oil, the vinyl POSS and the toluene), heating to 125 ℃, reacting for 2 hours, and purifying a reaction product to obtain the vinyl silicone oil containing oligomeric silsesquioxane.
In this example, the oligomeric silsesquioxane-containing crosslinker was prepared as follows: weighing 60 parts by mass of hydrogen-containing silicone oil in a single-mouth bottle, slowly adding 2 parts by mass of vinyl POSS, adding 100 parts by mass of dry toluene, adopting dry nitrogen protection, uniformly mixing under magnetic stirring, adding 5000ppm of Japanese Behcard platinum catalyst (the addition amount of the organic platinum catalyst is 0.8 per mill of the total mass of the vinyl silicone oil, the vinyl POSS and the toluene), heating to 120 ℃, reacting for 2 hours, and purifying a reaction product to obtain the cross-linking agent containing the oligomeric silsesquioxane.
Example 3
A high temperature resistant addition type organic silicon gel comprises a component A and a component B, wherein the mass ratio of the component A to the component B is 1.5: 10; the component A comprises the following raw material components in parts by mass:
25 parts of vinyl silicone oil containing oligomeric silsesquioxane;
the component B comprises the following raw material components in parts by mass:
in this example, the structural formula of the vinyl silicone oil containing oligomeric silsesquioxane is as follows:
wherein the vinyl silicone oil containing the oligomeric silsesquioxane has the purity of 99.9 percent and the viscosity of 8000mPa & s; the vinyl silicone oil containing oligomeric silsesquioxane contains 0.05% by mass of vinyl and 70% by mass of phenyl.
In this example, the structural formula of the chain extender is as follows:
wherein the purity of the chain extender is 99.9 percent, and the viscosity is 500mPa & s; the mass percentage of hydrogen in the chain extender is 0.1%, and the mass percentage of phenyl is 60%.
In this example, the structural formula of the oligomeric silsesquioxane-containing cross-linking agent is as follows:
wherein the cross-linking agent containing the oligomeric silsesquioxane has the purity of 99.9 percent and the viscosity of 500mPa & s; the cross-linking agent containing the oligomeric silsesquioxane contains 1.2% by mass of hydrogen and 70% by mass of phenyl.
In this example, the high temperature-resistant coupling agent is oligomeric gamma- (methacryloyloxy) propyl trimethoxysilane, which has the following structural formula:
a method for preparing the high temperature resistant addition type silicone gel in the above embodiment includes the following steps:
(1) adding 1 part by mass of catalyst (specifically, Japanese Xinyue Kanst platinum catalyst with the concentration of 5000 ppm) into 25 parts by mass of vinyl silicone oil containing oligomeric silsesquioxane, stirring uniformly, and removing impurities and bubbles under the negative pressure condition of < -0.1MPa to obtain the component A.
(2) Sequentially adding 90 parts by mass of vinyl silicone oil containing oligomeric silsesquioxane, 35 parts by mass of chain extender, 15 parts by mass of cross-linking agent containing oligomeric silsesquioxane, 1 part by mass of inhibitor (particularly diallyl maleate) and 5 parts by mass of high-temperature-resistant coupling agent into a mixing kettle, uniformly stirring, and removing impurities and bubbles under the negative pressure condition of less than-0.1 MPa to obtain the component B.
(3) And (3) mixing the component A obtained in the step (1) with the component B obtained in the step (2), defoaming for 10min under the negative pressure condition of < -0.1MPa, and curing for 5h at 125 ℃ to obtain the high-temperature-resistant addition type silicone gel.
In this example, the preparation process of the vinyl silicone oil containing oligomeric silsesquioxane is as follows: weighing 60 parts by mass of vinyl silicone oil into a single-mouth bottle, slowly adding 1 part by mass of vinyl POSS, adding 150 parts by mass of dry toluene, adopting dry nitrogen protection, uniformly mixing under magnetic stirring, adding a Japan Xinyue Kanstel platinum catalyst with the concentration of 5000ppm (the addition amount of the organic platinum catalyst is 1 per mill of the total mass of the vinyl silicone oil, the vinyl POSS and the toluene), heating to 120 ℃, reacting for 2 hours, and purifying a reaction product to obtain the vinyl silicone oil containing the oligomeric silsesquioxane.
In this example, the oligomeric silsesquioxane-containing crosslinker was prepared as follows: weighing 80 parts by mass of hydrogen-containing silicone oil into a single-mouth bottle, slowly adding 3 parts by mass of vinyl POSS, adding 150 parts by mass of dry toluene, adopting dry nitrogen protection, uniformly mixing under magnetic stirring, adding a Japanese Behcard platinum catalyst with the concentration of 5000ppm (the addition amount of the organic platinum catalyst is 1 per mill of the total mass of the vinyl silicone oil, the vinyl POSS and the toluene), heating to 125 ℃, reacting for 2 hours, and purifying a reaction product to obtain the cross-linking agent containing the oligomeric silsesquioxane.
The performance of the high temperature resistant addition silicone gels prepared in examples 1-3 were tested and the results are shown in table 1.
TABLE 1 Performance test results for high temperature resistant addition silicone gels prepared in inventive examples 1-3
As can be seen from table 1, the mechanical properties (penetration and elastic modulus) and the insulating properties (electrical strength and volume resistivity) of the high temperature resistant addition type silicone gels prepared in examples 1 to 3 of the present invention were substantially maintained under various processing conditions, which indicates that the high temperature resistant addition type silicone gels of the present invention have excellent high temperature resistance; generally, the better the mechanical properties and insulation retention at 220 ℃, the better the high temperature resistance of the high temperature resistant addition type silicone gel. Meanwhile, as can be seen from table 1, the weight loss ratio of the high temperature resistant addition type silicone gel prepared in examples 1 to 3 of the present invention is less in change under various treatment conditions, and the less the weight loss ratio is under long-term high temperature storage, the less the small molecules and volatile substances of the silicone gel are, the more stable the molecular structure is, and thus the high temperature resistant addition type silicone gel of the present invention has excellent high temperature resistance. The following problems generally exist in the existing conventional addition type organic silicon gel products: after aging at 220 ℃/1000h, the mechanical property is reduced by more than 40%, the insulating property is reduced by more than 30%, the problems of poor high temperature resistance and the like exist, and the phenomena of yellowing, hardening and the like can occur. In addition, the high temperature addition type silicone gels prepared in inventive examples 1-3 retained the high elasticity and low stress properties of the silicone gels. Compared with the conventional addition type organic silicon gel product, the high-temperature addition type organic silicon gel provided by the invention not only maintains the characteristics of high elasticity and low stress, but also has excellent high-temperature resistance. Therefore, the high-temperature addition type organic silicon gel has the advantages of high elasticity, low stress, excellent high-temperature resistance and the like, can be suitable for packaging protection of various base materials, can remarkably improve the reliability and service life of the base materials (such as a high-power semiconductor module) at high temperature, has high use value and good application prospect, and has very important significance for improving the service life and reliability of the high-power module.
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. The high-temperature-resistant addition type organic silicon gel comprises a component A and a component B, and is characterized in that the component A comprises the following raw material components in parts by mass:
12-25 parts of vinyl silicone oil containing oligomeric silsesquioxane;
the component B comprises the following raw material components in parts by mass:
2. the high-temperature-resistant addition type silicone gel according to claim 1, wherein the mass ratio of the component A to the component B is 0.5-1.5: 10.
3. The high temperature resistant addition silicone gel of claim 2, wherein the oligomeric silsesquioxane-containing vinyl silicone oil has the following structural formula:
wherein R is1Is at least one of methyl, phenyl and ethoxy; r2Is at least one of methyl, phenyl and ethoxy; a is an integer of 200 to 800, b is an integer of 1 to 10, and c is an integer of 1 to 50; the vinyl silicone oil containing the oligomeric silsesquioxane has the purity of more than or equal to 99.9 percent and the viscosity of 800-8000 mPa & s; the vinyl silicone oil containing oligomeric silsesquioxane contains 0.05-2.5% of vinyl and 50-70% of phenyl by mass.
4. The high temperature resistant addition type silicone gel according to any one of claims 1 to 3, wherein the structural formula of the chain extender is as follows:
wherein R is3Is at least one of methyl, phenyl and ethoxy atoms; d is an integer of 20 to 50, e is an integer of 1 to 10; the purity of the chain extender is more than or equal to 99.9 percent, and the viscosity is 10mPa & s-500 mPa & s; the mass percentage of hydrogen in the chain extender is 0.02-0.2%, and the mass percentage of phenyl is 50-70%;
the structural formula of the crosslinking agent containing the oligomeric silsesquioxane is as follows:
wherein R is4Is at least one of methyl, phenyl and ethoxy; r5Is at least one of methyl, phenyl and ethoxy; f is an integer of 100 to 500, g is an integer of 1 to 10, and h is an integer of 1 to 50; the cross-linking agent containing the oligomeric silsesquioxane has the purity of more than or equal to 99.9 percent and the viscosity of 10-500 mPa & s; the cross-linking agent containing the oligomeric silsesquioxane contains 0.2-2.0% of hydrogen and 50-70% of phenyl by mass;
the structural formula of the high-temperature-resistant coupling agent is as follows:
5. A method for preparing the high temperature resistant addition type silicone gel according to any one of claims 1 to 4, comprising the steps of:
s1, mixing vinyl silicone oil containing oligomeric silsesquioxane with a catalyst, stirring, and removing impurities and bubbles to obtain a component A; mixing vinyl silicone oil containing oligomeric silsesquioxane, a chain extender, a cross-linking agent containing oligomeric silsesquioxane, an inhibitor and a high-temperature-resistant coupling agent, stirring, 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-temperature-resistant addition type organic silicon gel.
6. The method according to claim 5, wherein in step S1, the method for preparing the vinyl silicone oil containing oligomeric silsesquioxane comprises the following steps: sequentially adding vinyl POSS and toluene into vinyl silicone oil, stirring, adding an organic platinum catalyst, heating to 110-125 ℃ under the protection of dry nitrogen or argon atmosphere, reacting for 1.5-3 h, and purifying to obtain the vinyl silicone oil containing oligomeric silsesquioxane; the mass ratio of the vinyl silicone oil to the vinyl POSS to the toluene is 40-60: 1-5: 100-150; the addition amount of the organic platinum catalyst is 0.5-1 per mill of the total mass of the vinyl silicone oil, the vinyl POSS and the toluene.
7. The method according to claim 6, wherein in step S1, the method for preparing the oligomeric silsesquioxane-containing cross-linking agent comprises the steps of: sequentially adding vinyl POSS and toluene into hydrogen-containing silicone oil, stirring, adding an organic platinum catalyst, heating to 110-125 ℃ under the protection of dry nitrogen or argon atmosphere, reacting for 1.5-3 h, and purifying to obtain a cross-linking agent containing oligomeric silsesquioxane; the mass ratio of the hydrogen-containing silicone oil to the vinyl POSS to the toluene is 50-80: 1-3: 100-150; the addition amount of the organic platinum catalyst is 0.5-1 per mill of the total mass of the hydrogen-containing silicone oil, the vinyl POSS and the toluene.
8. The preparation method according to any one of claims 5 to 7, wherein in the step S1, the mass ratio of the vinyl silicone oil containing oligomeric silsesquioxane to the catalyst in the preparation method of the component A is 12-25: 0.01-1; the catalyst is at least one of acidified ruthenium compounds, rhodium compounds, palladium compounds, iridium compounds and platinum compounds;
in the preparation method of the component B, the mass ratio of the vinyl silicone oil containing the oligomeric silsesquioxane to the inhibitor is 40-90: 0.01-1; the inhibitor is at least one of alkynol compounds, azo compounds and polyene compounds.
9. The method according to claim 8, wherein the inhibitor is at least one of 3-methyl-1-butyn-3-ol, trimethyl-1-pentyn-3-ol, benzotriazole, 4-methyl-4 '-hydroxyazobenzene, 4' -dihydroxyhydroazobenzene, diallyl maleate, tetramethyltetravinylcyclotetrasiloxane, and tetramethyltrivinylcyclotetrasiloxane.
10. The method according to any one of claims 5 to 7, wherein in the step S1, the removal of the impurities and bubbles is performed under a negative pressure condition of < -0.1 MPa;
in the step S2, the removal of the bubbles is carried out under the negative pressure condition of < -0.1 MPa; the time for removing bubbles is 5 min-10 min; the curing temperature is 100-125 ℃; the curing time is 3-5 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911022758.4A CN110746783A (en) | 2019-10-25 | 2019-10-25 | High-temperature-resistant addition type organic silicon gel and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911022758.4A CN110746783A (en) | 2019-10-25 | 2019-10-25 | High-temperature-resistant addition type organic silicon gel and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110746783A true CN110746783A (en) | 2020-02-04 |
Family
ID=69279898
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911022758.4A Pending CN110746783A (en) | 2019-10-25 | 2019-10-25 | High-temperature-resistant addition type organic silicon gel and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110746783A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111153922A (en) * | 2020-01-03 | 2020-05-15 | 吉林奥来德光电材料股份有限公司 | Compound, composition for packaging photoelectric device, preparation method, packaging film, electronic device and packaging method |
| CN113444449A (en) * | 2021-07-15 | 2021-09-28 | 惠州市永卓科技有限公司 | Ultraviolet-cured solvent-free release silicone oil and preparation method thereof |
| CN116876242A (en) * | 2023-08-23 | 2023-10-13 | 广州市云轩新材料科技有限公司 | Silica gel for long-acting elliptical printing machine and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009108288A (en) * | 2007-10-09 | 2009-05-21 | Ube Ind Ltd | Composition for transparent heat-resistant resin, transparent heat-resistant resin and preparation method of transparent heat-resistant resin |
| JP4826160B2 (en) * | 2005-07-28 | 2011-11-30 | ナガセケムテックス株式会社 | Optical element sealing resin composition |
| CN103003367A (en) * | 2010-11-04 | 2013-03-27 | 株式会社大赛璐 | Curable resin composition and cured product |
| CN103073890A (en) * | 2011-10-25 | 2013-05-01 | 日东电工株式会社 | Silicone resin composition, encapsulating layer, reflector, and optical semiconductor device |
| CN104327273A (en) * | 2014-10-22 | 2015-02-04 | 上海大学 | Organic silicon potting adhesive containing POSS group and preparation method of organic silicon potting adhesive |
| CN106479189A (en) * | 2016-09-21 | 2017-03-08 | 沈阳化工大学 | A kind of silicone rubber containing phenyl three silylation cage-type silsesquioxane |
| CN107573696A (en) * | 2017-09-26 | 2018-01-12 | 株洲时代新材料科技股份有限公司 | A kind of high-power IGBT encapsulation high-temperature resistant silicone gel and its preparation method and application |
-
2019
- 2019-10-25 CN CN201911022758.4A patent/CN110746783A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4826160B2 (en) * | 2005-07-28 | 2011-11-30 | ナガセケムテックス株式会社 | Optical element sealing resin composition |
| JP2009108288A (en) * | 2007-10-09 | 2009-05-21 | Ube Ind Ltd | Composition for transparent heat-resistant resin, transparent heat-resistant resin and preparation method of transparent heat-resistant resin |
| CN103003367A (en) * | 2010-11-04 | 2013-03-27 | 株式会社大赛璐 | Curable resin composition and cured product |
| CN103073890A (en) * | 2011-10-25 | 2013-05-01 | 日东电工株式会社 | Silicone resin composition, encapsulating layer, reflector, and optical semiconductor device |
| CN104327273A (en) * | 2014-10-22 | 2015-02-04 | 上海大学 | Organic silicon potting adhesive containing POSS group and preparation method of organic silicon potting adhesive |
| CN106479189A (en) * | 2016-09-21 | 2017-03-08 | 沈阳化工大学 | A kind of silicone rubber containing phenyl three silylation cage-type silsesquioxane |
| CN107573696A (en) * | 2017-09-26 | 2018-01-12 | 株洲时代新材料科技股份有限公司 | A kind of high-power IGBT encapsulation high-temperature resistant silicone gel and its preparation method and application |
Non-Patent Citations (3)
| Title |
|---|
| 国家质量监督检验检疫总局: "《中华人民共和国国家标准》", 31 January 2003, 中国标准出版社 * |
| 夏征农等: "《大辞海》", 31 December 2015, 上海辞书出版社 * |
| 邝生鲁等: "《现代精细化工 高新技术与产品合成工艺》", 31 December 1997, 科学技术文献出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111153922A (en) * | 2020-01-03 | 2020-05-15 | 吉林奥来德光电材料股份有限公司 | Compound, composition for packaging photoelectric device, preparation method, packaging film, electronic device and packaging method |
| CN113444449A (en) * | 2021-07-15 | 2021-09-28 | 惠州市永卓科技有限公司 | Ultraviolet-cured solvent-free release silicone oil and preparation method thereof |
| CN116876242A (en) * | 2023-08-23 | 2023-10-13 | 广州市云轩新材料科技有限公司 | Silica gel for long-acting elliptical printing machine and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110746783A (en) | High-temperature-resistant addition type organic silicon gel and preparation method thereof | |
| CN109337644B (en) | Addition type room-temperature bonding two-component pouring sealant and preparation method thereof | |
| EP3929242A1 (en) | Thermally conductive composition and method for producing same | |
| CN111234771A (en) | Single-component addition type silicone gel and preparation method thereof | |
| CN114045152A (en) | Organic silicon die bonding adhesive for die bonding of LED | |
| CN113372728B (en) | Silicone resin composition, cured product thereof, and LED element | |
| EP0509515B1 (en) | Curable organopolysiloxane gel composition | |
| CN115772264B (en) | Alkoxy-terminated polysiloxane with self-adhesive property, and preparation method and application thereof | |
| CN115505268B (en) | Organic silicon insulating gel for packaging semiconductor module and preparation process thereof | |
| CN111363516A (en) | Ultraviolet-curing organic silicon coating adhesive and preparation method thereof | |
| CN111410932B (en) | Methyl organosilicon adhesive with excellent flexibility and strong adhesion for LED | |
| CN114621726A (en) | Low-density ultrahigh-fluidity heat-conducting pouring sealant and preparation method thereof | |
| CN111690259A (en) | High-voltage-resistant organic silicon gel and preparation method and application thereof | |
| CN113861934A (en) | Industrial glue for electronic and electric appliances | |
| CN116606608B (en) | Heat conducting filler, double-component organic silicon pouring sealant containing heat conducting filler and preparation method of double-component organic silicon pouring sealant | |
| CN112409980B (en) | Polyorganosiloxane composition for packaging solar cell module and preparation method thereof | |
| CN112341989B (en) | Heat-conducting silver adhesive and preparation method thereof | |
| CN114752346B (en) | Transparent silica gel for laser optical fiber encapsulation and preparation method thereof | |
| CN116462974B (en) | Heat-conducting silica gel sheet and preparation method thereof | |
| CN113416519B (en) | Organic silicon gel for encapsulating IGBT module | |
| CN114456771B (en) | LED insulation condensation type die bonding adhesive and preparation method thereof | |
| CN113528082B (en) | Silicone gel composition, silicone gel comprising same, packaging structure and semiconductor device | |
| CN116023903A (en) | Addition type organic silicon gel for power semiconductor module and preparation method thereof | |
| CN114854366B (en) | Anti-poisoning organic silicon die bond adhesive for LED | |
| CN118006130A (en) | High-temperature-resistant transparent gel for IGBT (insulated gate bipolar transistor) and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200204 |