阅读说明：本技术 一种耐高温加成型有机硅凝胶及其制备方法 (High-temperature-resistant addition type organic silicon gel and preparation method thereof ) 是由 曾亮 齐放 戴小平 于 2019-10-25 设计创作，主要内容包括：本发明公开了一种耐高温加成型有机硅凝胶及其制备方法,该有机硅凝胶中A组分包括：12份～25份含低聚倍半硅氧烷的乙烯基硅油；B组分按照质量份计包括以下原料组分：40份～90份含低聚倍半硅氧烷的乙烯基硅油、10份～35份扩链剂、5份～15份含低聚倍半硅氧烷的交联剂、1份～5份耐高温偶联剂。其制备方法包括：制备A/B组分；将A/B组分混合、固化。本发明有机硅凝胶具有弹性高、应力低、高温耐热性能优异等优点,能够显著提高基材在高温下的可靠性和使用寿命,有着很高的使用价值和很好的应用前景,其制备方法可实现大规模制备,适合于工业化生产,有利于材料的推广应用。(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.)

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.

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.