CN113549422A - Organic silicon pouring sealant and preparation method thereof - Google Patents
Organic silicon pouring sealant and preparation method thereof Download PDFInfo
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- CN113549422A CN113549422A CN202110864678.4A CN202110864678A CN113549422A CN 113549422 A CN113549422 A CN 113549422A CN 202110864678 A CN202110864678 A CN 202110864678A CN 113549422 A CN113549422 A CN 113549422A
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- C09J183/00—Adhesives based on 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; Adhesives based on derivatives of such polymers
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Abstract
The invention discloses an organic silicon pouring sealant and a preparation method thereof, wherein a heat-conducting filler is provided, and an epoxy group and an amino group are respectively connected to the surface of the heat-conducting filler; filling the heat-conducting filler into vinyl silicone oil, and stirring and reacting at the temperature of 120-150 ℃ for 0.5-4h to obtain the organic silicon-based adhesive, wherein a bead-shaped topological structure is formed among the heat-conducting fillers; mixing the organic silicon-based adhesive with a catalyst to obtain a component A; mixing the organic silicon-based adhesive with hydrogen-containing silicone oil and an inhibitor to obtain a component B; and mixing the component A with the component B to obtain the organic silicon pouring sealant. By the organic silicon pouring sealant and the preparation method thereof, the high-filling low-viscosity heat-conducting insulating organic silicon pouring sealant can be obtained.
Description
Technical Field
The invention relates to the technical field of pouring sealant, in particular to an organic silicon pouring sealant and a preparation method thereof.
Background
The pouring sealant is a high-molecular composite material for bonding, sealing and coating protection of electronic components, can effectively prevent erosion of water, dust and harmful gas to the electronic components, improves the stability of internal components, is widely applied to the fields of aerospace, automobiles, chips, LED packaging materials and the like with higher requirements on heat-conducting performance, and comprises epoxy resin pouring sealant and organic silicon resin pouring sealant in common market. The epoxy resin pouring sealant is gradually replaced by the organic silicon pouring sealant due to poor heat resistance, weather resistance and aging resistance, easy yellowing and brittleness and higher material storage cost.
Generally, the thermal conductivity of pure silicon rubber is low, and high-thermal-conductivity filler needs to be added into silicon rubber to increase the thermal conductivity coefficient of the composite material. However, the high filler loading inevitably causes the defects of difficult processing, poor fluidity, difficult defoaming, filler agglomeration, high cost and low mechanical strength of the organic silicon pouring sealant.
Disclosure of Invention
In view of the above disadvantages of the prior art, the present invention aims to provide an organosilicon potting adhesive and a preparation method thereof, which effectively solve the problems of high component viscosity and difficulty in defoaming during the preparation process of the organosilicon potting adhesive, and further improve the fluidity of the potting adhesive under the condition of ensuring high thermal conductivity and insulating property.
In order to achieve the above objects and other related objects, the present invention adopts the following technical solutions:
providing a heat-conducting filler;
respectively connecting an epoxy group and an amino group on the surface of the heat-conducting filler;
filling the heat-conducting filler into vinyl silicone oil, and stirring and reacting at the temperature of 120-150 ℃ for 0.5-4h to obtain the organic silicon-based adhesive, wherein a bead-shaped topological structure is formed among the heat-conducting fillers;
mixing the organic silicon-based adhesive with a catalyst to obtain a component A;
mixing the organic silicon-based adhesive with hydrogen-containing silicone oil and an inhibitor to obtain a component B;
and mixing the component A with the component B to obtain the organic silicon pouring sealant.
In some embodiments of the invention, the step of attaching an epoxy group to the surface of the thermally conductive filler comprises: adding silane coupling agent hydrolysate with epoxy groups into the heat-conducting filler to obtain the heat-conducting filler with epoxy groups on the surface.
In some embodiments of the invention, the step of attaching amino groups to the surface of the thermally conductive filler comprises: adding the silane coupling agent hydrolysate with amino groups into the heat-conducting filler to obtain the heat-conducting filler with amino groups on the surface.
In some embodiments of the invention, the epoxy silane coupling agent is one or a combination of two of gamma- (2, 3-glycidoxy) propyltrimethoxysilane, gamma-glycidoxytrimethylsilane.
In some embodiments of the invention, the aminosilane-bearing coupling agent is one or a combination of gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane, and N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane.
In some embodiments of the invention, the thermally conductive filler is one or a combination of alumina, boron nitride, aluminum nitride and silica.
In some embodiments of the invention, the inhibitor is one or a combination of acetylene, phenylacetylene, butynedioate, 1-ethynylcyclohexanol, 2-vinyl isopropanol, 2-ethylynbutan-2-ol, 3-phenyl-1-buten-3-ol, 1-ethynyl-1-cyclopentanol, and 1-ethynyl-1-cyclohexanol.
In some embodiments of the invention, the mass ratio of the A component to the B component is 1 (0.8-1.2).
In some embodiments of the invention, the thermally conductive filler has a particle size of 1 to 100 μm.
Another object of the present invention is to provide the above-mentioned organic silicon pouring sealant, which comprises component a and component B:
the component A comprises organic silicon adhesive and catalyst;
the component B comprises organic silicon-based adhesive, hydrogen-containing silicone oil and an inhibitor;
the organic silicon-based adhesive comprises a part of vinyl silicone oil chain segment which is fixed in the gap of the heat-conducting filler through the bead-shaped topological structure, and another part of vinyl silicone oil chain segment which is distributed around the heat-conducting filler and is close to the surface of the heat-conducting filler.
The invention provides an organic silicon pouring sealant and a preparation method thereof, and the organic silicon pouring sealant has the beneficial effects that: firstly, surface modification is carried out on a heat conduction material, so that the surface of a heat conduction filler is respectively connected with an epoxy group and an amino group; secondly, filling the heat-conducting filler with amino groups and epoxy groups into vinyl silicone oil, so that the epoxy groups and the amino groups are subjected to chemical reaction under certain conditions to generate strong chemical bond interaction, the heat-conducting filler generates strong interaction by virtue of the formed chemical bonds, gaps among the heat-conducting filler are shortened, the heat-conducting filler is flocculated into a bead-shaped topological structure, a part of vinyl silicone oil chain segments are fixed in the gaps of the heat-conducting filler, the other part of the chain segments are distributed around the filler and are close to the surface of the filler, and in the shearing and flowing process, the friction among filler clusters and between the filler clusters and the vinyl silicone oil is reduced, so that the viscosity of the composite material is effectively reduced; moreover, the preparation method of the organic silicon pouring sealant is simple, high in filling, low in viscosity and good in heat-conducting property.
Drawings
FIG. 1 is a schematic view showing the effect of a heat conductive filler having an epoxy group and a heat conductive filler having an amino group.
Description of reference numerals:
1-vinyl silicone oil chain, 2-heat-conducting filler with amino group, and 3-heat-conducting filler with epoxy group.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
It is to be understood that the present invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. Unless otherwise specified, "%" and "part(s)" shown in the following examples mean "% by mass" and "part(s) by mass", respectively.
The invention provides an organic silicon pouring sealant material which comprises a component A and a component B. The component A comprises organic silicon-based glue and a catalyst, wherein the organic silicon-based glue is 80-120 parts, and the catalyst is 0.1-1.2 parts. The component B comprises organic silicon-based glue, hydrogen-containing silicone oil and an inhibitor, wherein the organic silicon-based glue is 80-120 parts, the hydrogen-containing silicone oil is 1.0-4.0 parts, the hydrogen content of the hydrogen-containing silicone oil is 0.3-1.5%, and the inhibitor is 0.0015-0.003 parts. The particles form a special three-dimensional network structure due to interaction among the heat-conducting fillers in the organic silicon-based adhesive, so that a part of vinyl silicone oil chain segments are fixed in gaps among the fillers, and a part of the vinyl silicone oil chain segments are close to the surface of the heat-conducting fillers and distributed around the fillers.
The invention provides a preparation method of an organic silicon pouring sealant, which comprises the following steps of preparing a heat-conducting filler with an epoxy group on the surface and a heat-conducting filler with an amino group on the surface, wherein the preparation sequence of the heat-conducting filler with the epoxy group on the surface and the heat-conducting filler with the amino group on the surface is not limited. And then preparing an organic silicon-based adhesive by using the heat-conducting filler after surface treatment, finally preparing a component A by adding a catalyst into the organic silicon-based adhesive, preparing a component B by adding hydrogen-containing silicone oil and an inhibitor into the organic silicon-based adhesive, and uniformly mixing the component A and the component B to obtain the organic silicon pouring sealant.
In an embodiment of the present invention, the preparation method of the organic silicon pouring sealant includes the step (1) of preparing the heat conducting filler with epoxy groups on the surface, which specifically includes:
and (3) preparing hydrolysis liquid, namely adding absolute ethyl alcohol and deionized water into the silane coupling agent with the epoxy group, and hydrolyzing at a constant temperature of 20-40 ℃ for 20-40min to obtain the silane coupling agent hydrolysis solution with the epoxy group.
And (3) surface modification of the heat-conducting filler, namely adding the heat-conducting filler into a high-speed blender, and adding silane coupling agent hydrolysate with epoxy groups when the temperature of the heat-conducting filler is higher than 110 ℃, for example, at 110-180 ℃, wherein the modification can be carried out for 20-40min, so as to obtain the heat-conducting filler with epoxy groups on the surface, wherein the mass of the silane coupling agent with epoxy groups is 1-3% of that of the heat-conducting filler.
In an embodiment of the present invention, the preparation method of the organic silicon pouring sealant includes the step (2) of preparing the heat conducting filler with amino groups on the surface, which specifically includes:
and (3) preparing a hydrolysis solution, namely adding absolute ethyl alcohol and deionized water into the silane coupling agent with amino groups, and hydrolyzing at a constant temperature of 20-40 ℃ for 20-40min to obtain a silane coupling agent hydrolysis solution with amino groups.
And (3) surface modification of the heat-conducting filler, namely adding the heat-conducting filler into a high-speed blender, and adding silane coupling agent hydrolysate with amino groups when the temperature of the heat-conducting filler is higher than 110 ℃, for example, at 110-180 ℃, for modification for 20-40min to obtain the heat-conducting filler with amino groups on the surface, wherein the mass of the silane coupling agent is 1-3% of that of the heat-conducting filler.
In an embodiment of the present invention, the preparation method of the organic silicon pouring sealant includes the step (3) of preparing the organic silicon-based sealant, which specifically includes:
for example, 80-120 parts by weight of vinyl silicone oil is taken, and heat-conducting filler with epoxy groups on the surface and heat-conducting filler with amino groups on the surface, for example, 1150 parts of 570-.
In an embodiment of the present invention, the preparation method of the organic silicon pouring sealant includes the step (4) of preparing the organic silicon pouring sealant, which specifically includes:
adding the catalyst into the organic silicon-based adhesive, and uniformly mixing to obtain the component A.
Adding hydrogen-containing silicone oil and an inhibitor into the organic silicone-based adhesive, and uniformly mixing to obtain the component B.
Uniformly mixing the component A and the component B according to the mass ratio of 1 (0.8-1.2), and obtaining the high-filling low-viscosity heat-conducting and insulating organic silicon pouring sealant.
Specifically, in the preparation of the hydrolysate in the step (1), the volume ratio of the absolute ethyl alcohol to the epoxy silane coupling agent is, for example, 1 (0.8-1.5), and the molar ratio of the deionized water to the epoxy silane coupling agent is, for example, 1:1-5: 1. The hydrolysis temperature is 20-40 deg.C, and the hydrolysis time is 20-40min, and can be 30min in 30 deg.C constant temperature water bath. In the step (1) of surface modification of the heat-conducting filler, the stirring speed of the high-speed blender can be 1000-2000rpm, for example, the stirring speed is set to 1000rpm, and the stirring reaction is carried out for 30min at 120 ℃.
In various embodiments, the epoxy-bearing silane coupling agent is one or a combination of two of γ - (2, 3-glycidoxy) propyltrimethoxysilane and γ -glycidoxytrimethylsilane, for example, the volume ratio of γ - (2, 3-glycidoxy) propyltrimethoxysilane to absolute ethyl alcohol is 1:1, the volume ratio of γ -glycidoxytrimethylsilane to absolute ethyl alcohol is 1:1, the volume ratio of γ - (2, 3-glycidoxy) propyltrimethoxysilane, the volume ratio of γ -glycidoxytrimethylsilane to absolute ethyl alcohol is 1:1:2, and the like.
Specifically, in the preparation of the hydrolysate in the step (2), the volume ratio of the absolute ethyl alcohol to the coupling agent with the amino silane is 1 (0.8-1.5), and the molar ratio of the deionized water to the coupling agent with the amino silane is 1:1-5: 1. The hydrolysis temperature is 20-40 deg.C, and the hydrolysis time is 20-40min, such as 30min in 30 deg.C water bath. In the preparation of the hydrolysis liquid in the step (2), the stirring speed of the high-speed blender can be 1000-2000rpm, for example, the stirring speed is set to 1000rpm, and the stirring reaction is carried out for 30min at 120 ℃.
In different embodiments, the silane coupling agent with amino groups is one or more of gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane and N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane. For example, the volume ratio of gamma-aminopropyltrimethoxysilane to absolute ethyl alcohol may be 1:1, or the volume ratio of gamma-aminopropyltriethoxysilane to absolute ethyl alcohol may be 1:1, or the volume ratio of N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane to absolute ethyl alcohol may be 1:1, or the volume ratio of N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane to absolute ethyl alcohol may be 1:1, or the volume ratio of N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane to absolute ethyl alcohol may be 1:1, or the volume ratio of gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane to absolute ethyl alcohol may be 1:1:2, or the volume ratio of N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, The volume ratio of N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane to N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane to absolute ethyl alcohol is 1:2:3:6, etc.
In different embodiments, the heat conductive filler is one or a combination of alumina, boron nitride, aluminum nitride and silicon dioxide, the heat conductive filler is spherical, and the particle size of the heat conductive filler is 1-100 μm, for example. For example, the material can be spherical alumina, spherical boron nitride, spherical aluminum nitride, spherical silicon dioxide, a mixture of spherical alumina and spherical boron nitride, a mixture of spherical alumina, spherical boron nitride and spherical aluminum nitride, and the like.
Referring to fig. 1, the surface of the heat-conducting filler is modified to form the heat-conducting filler with the epoxy group and the heat-conducting filler with the amino group, in the stirring process, the epoxy group and the amino group are subjected to chemical reaction, the heat-conducting fillers generate strong interaction by means of formed chemical bonds to form a bead-shaped topological structure, a part of vinyl silicone oil chain segments are fixed in gaps of the heat-conducting filler, and the other part of vinyl silicone oil chain segments are distributed around the filler, so that the friction among filler clusters and between the filler clusters and the vinyl silicone oil is reduced in the shearing and flowing process, and the viscosity is reduced.
Specifically, in the step (3), 80-120 parts of vinyl silicone oil can be selected, for example, 1150 parts of thermal conductive filler with epoxy groups on the surface and thermal conductive filler with amino groups on the surface are 570-. For example, the mass ratio of the heat-conducting filler with epoxy groups on the surface to the heat-conducting filler with amino groups on the surface is 1:1, and the mixture is stirred for 30min at 140 ℃.
In different embodiments, the amount of the heat-conducting filler with the epoxy group on the surface and the amount of the heat-conducting filler with the amino group on the surface are different, and the heat-conducting filler is used for improving the heat-conducting property of the organic silicon pouring sealant and improving the heat-radiating effect. Meanwhile, the addition of the heat-conducting filler is excessive, which causes the defects of difficult processing, poor fluidity, difficult defoaming, filler agglomeration, high cost and low mechanical strength of the organic silicon pouring sealant, so the addition amount of the heat-conducting filler is controlled in the mass fraction.
Specifically, in the step (4), 80-120 parts of high-filling low-viscosity organosilicon-based adhesive in the component A can be selected, and 0.1-1.2 parts of catalyst can be selected. The high filling low viscosity organosilicon-based adhesive in the component B can be selected from 80 to 120 parts, the hydrogen-containing silicone oil can be preferably selected from 1.0 to 4.0 parts, and the inhibitor can be selected from 0.0015 to 0.003 part. The component A and the component B can be uniformly mixed according to the mass ratio of 1 (0.8-1.2), and the mass ratio can be 1: 1.
In different embodiments, the catalyst is one or a combination of Karstedt catalyst (Karstedt catalyst), Speier catalyst, rhodium catalyst, palladium catalyst and nickel catalyst, wherein the Karstedt catalyst can select the content of platinum to be 1000ppm-3000 ppm. For example, the catalyst may be Karstedt catalyst 1.2 parts, Speier catalyst 1.2 parts, rhodium catalyst 1.2 parts, palladium catalyst 1.2 parts, nickel catalyst 1.2 parts, Karstedt catalyst 0.6 part and Speier catalyst 0.6 part, Karstedt catalyst 0.4 part, rhodium catalyst 0.4 part and nickel catalyst 0.4 part, etc.
In different embodiments, the hydrogen content of the hydrogen-containing silicone oil is, for example, 0.3% to 1.5%, and may be, for example, 2 parts of hydrogen-containing silicone oil with a hydrogen content of 1.0%, or may be, for example, 2 parts of oil with a hydrogen content of 0.8%, and the like.
In various embodiments, the inhibitor is one or a combination of acetylene, phenylacetylene, butynedioate, 1-ethynylcyclohexanol, 2-vinyl isopropanol, 2-ethylbutynin-2-ol, 3-phenyl-1-buten-3-ol, 1-ethynyl-1-cyclopentanol, and 1-ethynyl-1-cyclohexanol. For example, acetylene may be 0.003 part, phenylacetylene may be 0.003 part, butynedioic acid ester may be 0.003 part, 1-ethynylcyclohexanol may be 0.003 part, 2-vinyl isopropanol may be 0.003 part, 2-ethylalkyn-2-ol may be 0.003 part, 3-phenyl-1-buten-3-ol may be 0.003 part, 1-ethynyl-1-cyclopentanol may be 0.003 part, 1-ethynyl-1-cyclohexanol may be 0.003 part, acetylene may be a mixture of 0.001 part and 0.002 part, and acetylene may be a mixture of 0.001 part, phenylacetylene 0.001 part and 0.001 part of 1-ethynyl-1-cyclohexanol may be used.
The invention will be explained in more detail below with reference to specific examples.
Example 1
(1) Preparing a heat-conducting filler with epoxy groups on the surface: 350g of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, 260g of absolute ethyl alcohol and 80g of deionized water are weighed into a beaker and stirred uniformly. And putting the beaker into a constant-temperature water bath kettle at the temperature of 30 ℃ for hydrolysis for 30min to obtain a hydrolysis solution with the epoxy silane coupling agent. Adding 35kg of spherical alumina with the particle size of 10 mu m into a high-speed blender, adjusting the rotating speed to 1000rpm, adding silane coupling agent hydrolysate with epoxy groups when the material temperature reaches 120 ℃, and modifying for 30min to obtain the alumina with the epoxy groups.
(2) Preparing a heat-conducting filler with amino groups on the surface: 400g of gamma-aminopropyltriethoxysilane, 335g of absolute ethanol and 98g of deionized water are weighed into a beaker and stirred uniformly. And putting the beaker into a constant-temperature water bath kettle at the temperature of 30 ℃ for hydrolysis for 30min to obtain a hydrolysis solution with the aminosilane coupling agent. Adding 40kg of spherical alumina with the particle size of 10 mu m into a high-speed blender, adjusting the rotating speed to 1000rpm, adding silane coupling agent hydrolysate with epoxy groups when the material temperature reaches 120 ℃, and modifying for 30min to obtain the alumina with amino groups.
(3) Preparing organic silicon-based adhesive: weighing 100 parts of vinyl silicone oil, adding 809 parts of alumina with epoxy groups on the surface and alumina with amino groups on the surface, wherein the mass ratio of the alumina with epoxy groups on the surface to the alumina with amino groups on the surface is 1:1, uniformly mixing, stirring at 140 ℃ for reaction for 0.5h, and cooling to room temperature to obtain the high-filling low-viscosity organic silicon-based adhesive.
(4) Preparing an organic silicon pouring sealant: 100g of the above silicone-based adhesive and 1.2g of Karstedt's catalyst having a platinum content of 1000ppm were weighed and mixed uniformly to obtain component A. 100g of organic silicon-based adhesive, 2.0g of hydrogen-containing silicone oil with the hydrogen content of 0.3 percent and 0.003g of 1-ethynylcyclohexanol are weighed and uniformly mixed to obtain a component B. A, B components with equal mass are uniformly mixed, and bubbles are removed in vacuum to obtain the organic silicon pouring sealant. Carrying out a shear viscosity test at 25 ℃; pouring the mixture into a mold to prepare a sample, and carrying out heat conductivity coefficient test.
Example 2
(1) Preparing a heat-conducting filler with epoxy groups on the surface: 350g of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, 260g of absolute ethyl alcohol and 80g of deionized water are weighed into a beaker and stirred uniformly. And putting the beaker into a constant-temperature water bath kettle at the temperature of 30 ℃ for hydrolysis for 30min to obtain a hydrolysis solution with the epoxy silane coupling agent. Adding 35kg of spherical alumina with the particle size of 10 mu m into a high-speed blender, adjusting the rotating speed to 1000rpm, adding silane coupling agent hydrolysate with epoxy groups when the material temperature reaches 120 ℃, and modifying for 30min to obtain the alumina with the epoxy groups.
(2) Preparing a heat-conducting filler with amino groups on the surface: 400g of gamma-aminopropyltriethoxysilane, 335g of absolute ethanol and 98g of deionized water are weighed into a beaker and stirred uniformly. And putting the beaker into a constant-temperature water bath kettle at the temperature of 30 ℃ for hydrolysis for 30min to obtain a hydrolysis solution with the aminosilane coupling agent. Adding 40kg of spherical alumina with the particle size of 10 mu m into a high-speed blender, adjusting the rotating speed to 1000rpm, adding silane coupling agent hydrolysate with epoxy groups when the material temperature reaches 120 ℃, and modifying for 30min to obtain the alumina with amino groups.
(3) Preparing organic silicon-based adhesive: weighing 100 parts of vinyl silicone oil, adding 809 parts of alumina with epoxy groups on the surface and alumina with amino groups on the surface, wherein the mass ratio of the alumina with epoxy groups on the surface to the alumina with amino groups on the surface is 1:1, uniformly mixing, stirring at 140 ℃ for reaction for 4h, and cooling to room temperature to obtain the high-filling low-viscosity organic silicon-based adhesive.
(4) Preparing an organic silicon pouring sealant: 100g of the above silicone-based adhesive and 1.2g of Karstedt's catalyst having a platinum content of 1000ppm were weighed and mixed uniformly to obtain component A. 100g of organic silicon-based adhesive, 2.0g of hydrogen-containing silicone oil with the hydrogen content of 0.3 percent and 0.003g of 1-ethynylcyclohexanol are weighed and uniformly mixed to obtain a component B. A, B components with equal mass are uniformly mixed, and bubbles are removed in vacuum to obtain the organic silicon pouring sealant. Carrying out a shear viscosity test at 25 ℃; pouring the mixture into a mold to prepare a sample, and carrying out heat conductivity coefficient test.
Example 3
(1) Preparing a heat-conducting filler with epoxy groups on the surface: 350g of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, 260g of absolute ethyl alcohol and 80g of deionized water are weighed into a beaker and stirred uniformly. And putting the beaker into a constant-temperature water bath kettle at the temperature of 30 ℃ for hydrolysis for 30min to obtain a hydrolysis solution with the epoxy silane coupling agent. Adding 35kg of spherical alumina with the particle size of 10 mu m into a high-speed blender, adjusting the rotating speed to 1000rpm, adding silane coupling agent hydrolysate with epoxy groups when the material temperature reaches 120 ℃, and modifying for 30min to obtain the aluminum nitride with the epoxy groups.
(2) Preparing a heat-conducting filler with amino groups on the surface: 400g of gamma-aminopropyltriethoxysilane, 335g of absolute ethanol and 98g of deionized water are weighed into a beaker and stirred uniformly. And putting the beaker into a constant-temperature water bath kettle at the temperature of 30 ℃ for hydrolysis for 30min to obtain a hydrolysis solution with the aminosilane coupling agent. Adding 40kg of spherical alumina with the particle size of 10 mu m into a high-speed blender, adjusting the rotating speed to 1000rpm, adding silane coupling agent hydrolysate with epoxy groups when the material temperature reaches 120 ℃, and modifying for 30min to obtain the alumina with amino groups.
(3) Preparing organic silicon-based adhesive: weighing 100 parts of vinyl silicone oil, adding 570 parts of alumina with epoxy groups on the surface and alumina with amino groups on the surface, wherein the mass ratio of the alumina with epoxy groups on the surface to the alumina with amino groups on the surface is 1:1, uniformly mixing, stirring at 140 ℃ for reaction for 0.5h, and cooling to room temperature to obtain the high-filling low-viscosity organic silicon-based adhesive.
(4) Preparing an organic silicon pouring sealant: 100g of the organic silicon pouring sealant base adhesive and 1.2g of Karstedt catalyst with the platinum content of 1000ppm are weighed and mixed uniformly to obtain the component A. 100g of organic silicon pouring sealant base adhesive, 2.0g of hydrogen-containing silicone oil with the hydrogen content of 0.3 percent and 0.003g of 1-ethynylcyclohexanol are weighed and uniformly mixed to obtain a component B. A, B components with equal mass are uniformly mixed, and bubbles are removed in vacuum to obtain the organic silicon pouring sealant. Carrying out a shear viscosity test at 25 ℃; pouring the mixture into a mold to prepare a sample, and carrying out heat conductivity coefficient test.
Comparative example 1
In comparative example 1, the high-filling low-viscosity silicone-based adhesive is directly obtained from the mixed components in example 1, and the silicone pouring sealant is prepared according to the formula of example 1 without stirring reaction. The remaining shear viscosity test and thermal conductivity test were the same as in example 1.
Comparative example 2
In comparative example 2, the high-filling low-viscosity silicone-based adhesive is directly obtained from the mixed components in example 3, and the silicone pouring sealant is prepared according to the formula of example 3 without stirring reaction. The remaining shear viscosity test and thermal conductivity test were the same as in example 3.
The viscosity and thermal conductivity property pairs for the samples obtained in each of the examples and comparative examples are shown in table 1:
TABLE 1 test result of normal temperature performance of organosilicon casting glue
As can be seen from Table 1, the comparison result between examples 1-2 and comparative example 1 shows that, since the reaction degree of the epoxy group-containing heat conductive filler and the amino group-containing heat conductive filler is different only in the step (3) of example 1-2 compared to comparative example 1, the control reaction time is different, the viscosity of the silicone potting compound is changed greatly, which indicates that the epoxy group-containing heat conductive filler and the amino group-containing heat conductive filler in the vinyl silicone oil generate strong interaction, the interaction between the fillers is increased with the increase of the reaction time, and the fillers are further flocculated to form filler clusters, the viscosity of the examples has a significant tendency to decrease compared to the comparative example, which indicates that the filler clusters gradually form a bead-connected topology structure, in the process of the vinyl silicone oil chain segment movement, the frictional resistance among the filler clusters and between the filler clusters and the vinyl silicone oil is reduced.
The comparison of example 3 with comparative example 2 shows that, since comparative example 2 is a silicone potting adhesive prepared according to the formulation of example 3, the silicone potting adhesive is directly obtained from the mixed components in example 3, and no reaction occurs between epoxy group and amino group. In comparison with example 3, the epoxy groups and the amino groups on the surface of the heat conductive filler react, and the viscosity is remarkably reduced. The addition amounts of the heat-conducting filler with epoxy groups and the heat-conducting filler with amino groups are different in example 3 and example 1, 570 parts of the heat-conducting filler is added in example 3, and 809 parts of the heat-conducting filler is added in example 1, and the viscosity of example 3 is better than that of example 1 through viscosity comparison, so that the amount of the heat-conducting filler can be reasonably changed according to the actual application requirements.
Although the heat conductivity of the organic silicon pouring sealant has no obvious variation trend, the organic silicon pouring sealant has a higher numerical value, and the performance that the organic silicon pouring sealant is low in viscosity and easy to process under the high-heat-conduction and insulation conditions is realized.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (10)
1. The preparation method of the organic silicon pouring sealant is characterized by comprising the following steps:
providing a heat-conducting filler;
respectively connecting an epoxy group and an amino group on the surface of the heat-conducting filler;
filling the heat-conducting filler into vinyl silicone oil, and stirring and reacting at the temperature of 120-150 ℃ for 0.5-4h to obtain the organic silicon-based adhesive, wherein a bead-shaped topological structure is formed among the heat-conducting fillers;
mixing the organic silicon-based adhesive with a catalyst to obtain a component A;
mixing the organic silicon-based adhesive with hydrogen-containing silicone oil and an inhibitor to obtain a component B;
and mixing the component A with the component B to obtain the organic silicon pouring sealant.
2. The method for preparing the silicone pouring sealant as claimed in claim 1, wherein the step of attaching epoxy groups to the surface of the thermal conductive filler comprises:
adding silane coupling agent hydrolysate with epoxy groups into the heat-conducting filler to obtain the heat-conducting filler with epoxy groups on the surface.
3. The method for preparing the silicone pouring sealant as claimed in claim 1, wherein the step of attaching amino groups to the surface of the heat conductive filler comprises:
adding the silane coupling agent hydrolysate with amino groups into the heat-conducting filler to obtain the heat-conducting filler with amino groups on the surface.
4. The method for preparing the silicone pouring sealant as claimed in claim 2, wherein the epoxy silane coupling agent is one or a combination of two of γ - (2, 3-glycidoxy) propyltrimethoxysilane and γ -glycidoxytrimethylsilane.
5. The method for preparing the organosilicon potting adhesive according to claim 3, wherein the aminosilane-containing coupling agent is one or a combination of more of gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane and N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane.
6. The method for preparing the silicone pouring sealant as claimed in claim 1, wherein the heat conductive filler is one or a combination of aluminum oxide, boron nitride, aluminum nitride and silicon dioxide.
7. The method for preparing the silicone pouring sealant as claimed in claim 1, wherein the inhibitor is one or more of acetylene, phenylacetylene, butynedioic acid ester, 1-ethynylcyclohexanol, 2-vinyl isopropanol, 2-ethylbutynin-2-ol, 3-phenyl-1-buten-3-ol, 1-ethynyl-1-cyclopentanol, and 1-ethynyl-1-cyclohexanol.
8. The method for preparing the silicone pouring sealant as claimed in claim 1, wherein the mass ratio of the component A to the component B is 1 (0.8-1.2).
9. The preparation method of the organic silicon pouring sealant as claimed in claim 1, characterized in that: the particle size of the heat-conducting filler is 1-100 mu m.
10. An organic silicon pouring sealant is characterized by comprising a component A and a component B,
the component A comprises organic silicon adhesive and catalyst;
the component B comprises organic silicon-based adhesive, hydrogen-containing silicone oil and an inhibitor;
the organic silicon-based adhesive comprises a part of vinyl silicone oil chain segment which is fixed in the gap of the heat-conducting filler through the bead-shaped topological structure, and another part of vinyl silicone oil chain segment which is distributed around the heat-conducting filler and is close to the surface of the heat-conducting filler.
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| CN114836168A (en) * | 2022-06-08 | 2022-08-02 | 合肥工业大学 | Organosilicon pouring sealant modified by anions and cations and preparation method thereof |
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