CN113337126A - Heat-conducting insulating silicon rubber and preparation method and application thereof - Google Patents
Heat-conducting insulating silicon rubber and preparation method and application thereof Download PDFInfo
- Publication number
- CN113337126A CN113337126A CN202110646440.4A CN202110646440A CN113337126A CN 113337126 A CN113337126 A CN 113337126A CN 202110646440 A CN202110646440 A CN 202110646440A CN 113337126 A CN113337126 A CN 113337126A
- Authority
- CN
- China
- Prior art keywords
- heat
- spherical
- conducting
- conducting filler
- silicone oil
- 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
Images
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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
Abstract
The invention relates to the technical field of silicone rubber, in particular to heat-conducting insulating silicone rubber and a preparation method and application thereof. The heat-conducting insulating silicon rubber provided by the invention comprises heat-conducting filler and silicon rubber; the heat-conducting filler comprises spherical boron nitride aggregates formed by flaky boron nitride and spherical heat-conducting filler inserted into gaps of the spherical boron nitride aggregates; the spherical heat-conducting filler comprises aluminum nitride or spherical alumina; the raw materials for preparing the silicon rubber comprise vinyl-terminated silicone oil, hydrogen-containing silicone oil, an inhibitor and a catalyst; the mass ratio of the heat-conducting filler to the silicon rubber is 85:15. According to the invention, the spherical boron nitride aggregate formed by the flaky boron nitride forms a heat conduction path penetrating the out-of-plane direction, the spherical heat conduction filler forms a continuous three-dimensional heat conduction network structure in gaps of the spherical boron nitride aggregate, and the heat conductivity of the heat conduction insulating silicon rubber is obviously improved under the condition of 85% of addition amount. According to the description of the embodiment, the thermal conductivity of the heat-conducting insulating silicon rubber is more than 6W/(mK).
Description
Technical Field
The invention relates to the technical field of silicone rubber, in particular to heat-conducting insulating silicone rubber and a preparation method and application thereof.
Background
With the further improvement of the signal receiving and transmitting speed of electronic devices, the heat generated by the chip and the Radio Frequency (RF) chain increases rapidly, and how to realize rapid heat dissipation becomes an important factor for determining the performance of the devices. Thermal interface materials such as the heat conduction gasket, the heat conduction silicone grease and the heat conduction gel can effectively reduce the interface thermal resistance between the chip and the heat sink and promote the heat diffusion. At present, the heat conducting gasket is mainly prepared by blending high-content heat conducting filler (>90 vol%) and a high polymer material, but the improvement of the heat conductivity is limited. Meanwhile, an excessive filling amount of the thermally conductive filler may also result in an increase in density of the gasket and a decrease in workability.
Therefore, no good solution exists at present how to further improve the heat-conducting property of the heat-conducting silicone rubber material while reducing the filling amount of the heat-conducting filler of the heat-conducting silicone rubber material.
Disclosure of Invention
The invention aims to provide a heat-conducting insulating silicon rubber and a preparation method and application thereof; the heat-conducting insulating silicon rubber has lower content of heat-conducting filler and higher heat conductivity.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides heat-conducting insulating silicon rubber which comprises heat-conducting filler and silicon rubber;
the heat-conducting filler comprises spherical boron nitride aggregates formed by flaky boron nitride and spherical heat-conducting filler inserted into gaps of the spherical boron nitride aggregates; the spherical heat-conducting filler comprises spherical aluminum nitride or spherical aluminum oxide;
the raw materials for preparing the silicone rubber comprise vinyl-terminated silicone oil, hydrogen-containing silicone oil, an inhibitor and a catalyst;
the mass ratio of the heat-conducting filler to the silicon rubber is 85:15.
Preferably, the mass ratio of the vinyl-terminated silicone oil to the hydrogen-containing silicone oil to the inhibitor to the catalyst is (12-15): (2-3): (0.4-0.6): 1;
the hydrogen-containing silicone oil comprises lateral hydrogen-containing silicone oil and terminal hydrogen-containing silicone oil;
the mass ratio of the side hydrogen-containing silicone oil to the end hydrogen-containing silicone oil is (5.8-6.2): 1.
preferably, the particle size of the spherical boron nitride aggregate is 400-1000 μm; the particle size of the spherical heat-conducting filler is 30-150 mu m, and the average particle size is 80-100 mu m.
Preferably, the mass ratio of the spherical heat-conducting filler to the spherical boron nitride aggregate is (40-55): (30-45).
Preferably, the catalyst is chloroplatinic acid isopropanol catalyst, platinum complex catalyst or Karstedt catalyst;
the inhibitor is an organic inhibitor.
The invention also provides a preparation method of the heat-conducting insulating silicone rubber, which comprises the following steps:
mixing spherical heat-conducting filler with flaky boron nitride, carrying out first mixing on the obtained mixed heat-conducting filler, terminal vinyl silicone oil, hydrogen-containing silicone oil and inhibitor, and then carrying out second mixing on the mixture and a catalyst to obtain a heat-conducting filler/silicone rubber prepolymer; the spherical heat-conducting filler comprises spherical aluminum nitride or spherical aluminum oxide;
curing the heat-conducting filler/silicone rubber prepolymer to obtain the heat-conducting insulating silicone rubber;
the first mixing and the second mixing are carried out under the condition of stirring;
the stirring speed of the first mixing is 500-1000 rpm; the stirring speed of the second mixing is 1000-2200 rpm;
the mass ratio of the heat-conducting filler to the silicon rubber is 85:15.
Preferably, the particle size of the flaky boron nitride is 3-90 μm, the average particle size is 30-40 μm, and the specific surface area>0.24m2/g；
The particle size of the spherical heat-conducting filler is 30-150 mu m, the average particle size is 80-100 mu m, and the specific surface area<0.072m2/g。
Preferably, the second mixing process is to stir at 1000-1500 rpm for 1-3 min and then at 2000-2200 rpm for 0-5 min.
Preferably, the curing temperature is 120 ℃ and the curing time is 20-60 min.
The invention also provides application of the heat-conducting insulating silicone rubber in the technical scheme or the heat-conducting insulating silicone rubber prepared by the preparation method in the technical scheme in preparation of a thermal interface material.
The invention provides heat-conducting insulating silicon rubber which comprises heat-conducting filler and silicon rubber; the heat-conducting filler comprises spherical boron nitride aggregates formed by flaky boron nitride and spherical heat-conducting filler inserted into gaps of the spherical boron nitride aggregates; the spherical heat-conducting filler comprises spherical aluminum nitride or spherical aluminum oxide; the raw materials for preparing the silicone rubber comprise vinyl-terminated silicone oil, hydrogen-containing silicone oil, an inhibitor and a catalyst; the mass ratio of the heat-conducting filler to the silicon rubber is 85:15. According to the invention, the spherical boron nitride aggregate formed by the flaky boron nitride forms a heat conduction path penetrating the out-of-plane direction, the spherical aluminum nitride or the aluminum oxide forms a continuous three-dimensional heat conduction network structure in the gap of the spherical boron nitride aggregate, and the heat conductivity of the heat conduction insulation silicon rubber is obviously improved on the premise of 85% of the addition amount. According to the description of the embodiment, the thermal conductivity of the heat-conducting insulating silicon rubber is more than 6W/(m.K).
The invention also provides a preparation method of the heat-conducting insulating silicon rubber, which comprises the following steps: mixing spherical heat-conducting filler with flaky boron nitride, carrying out first mixing on the obtained mixed heat-conducting filler, terminal vinyl silicone oil, hydrogen-containing silicone oil and inhibitor, and then carrying out second mixing on the mixture and a catalyst to obtain a heat-conducting filler/silicone rubber prepolymer; the spherical heat-conducting filler comprises spherical aluminum nitride or spherical aluminum oxide; curing the heat-conducting filler/silicone rubber prepolymer to obtain the heat-conducting insulating silicone rubber; the first mixing and the second mixing are carried out under the condition of stirring; the stirring speed of the first mixing is 500-1000 rpm; the stirring speed of the second mixing is 1000-2200 rpm. By controlling the rotating speed in the first mixing process and the second mixing process, the spherical heat-conducting filler and the flaky heat-conducting filler are enabled to form large-size aggregates by taking spherical aluminum nitride or spherical aluminum oxide as a mother nucleus under the action of specific centrifugal force, and the spherical aluminum nitride or spherical aluminum oxide is distributed in gaps of the aggregates, so that the three-dimensional heat-conducting network structure is formed. And the preparation method is simple, easy to operate and suitable for industrial production.
Drawings
FIG. 1 is a diagram of a heat conductive filler/silicone rubber prepolymer prepared in example 2;
FIG. 2 is a cross-sectional electron microscope image of the heat-conducting insulating silicone rubber prepared in example 2;
FIG. 3 is an electron micrograph of the surface of the composite (after sanding with sandpaper) prepared in example 2 after stirring at 1500rpm for 3 min;
FIG. 4 is an electron micrograph of the surface of the composite material (after sanding) after 2min of stirring at 2000rpm in example 2.
FIG. 5 is a cross-sectional electron micrograph of the composite material of comparative example 1 after stirring at 1000rpm for 5min
Detailed Description
The invention provides heat-conducting insulating silicon rubber which comprises heat-conducting filler and silicon rubber;
the heat-conducting filler comprises spherical boron nitride aggregates formed by flaky boron nitride and spherical heat-conducting filler inserted into gaps of the spherical boron nitride aggregates; the spherical heat-conducting filler comprises spherical aluminum nitride or spherical aluminum oxide;
the raw materials for preparing the silicone rubber comprise vinyl-terminated silicone oil, hydrogen-containing silicone oil, an inhibitor and a catalyst;
the mass ratio of the heat-conducting filler to the silicon rubber is 85:15.
In the invention, the mass ratio of the spherical heat-conducting filler to the spherical boron nitride aggregate is preferably (40-55): (30-45), more preferably (45-50): (35-40).
In the invention, the particle size of the spherical boron nitride aggregate is preferably 400-1000 μm, and more preferably 600-800 μm.
In the invention, the particle size of the spherical heat-conducting filler is preferably 30-150 μm, and the average particle size is preferably 80-100 μm.
In the present invention, the above particle size range of the heat conductive filler may be more advantageous for inserting the sheet-shaped heat conductive filler into the gap of the spherical heat conductive filler.
In the invention, the raw materials for preparing the silicon rubber comprise vinyl-terminated silicone oil, hydrogen-containing silicone oil, an inhibitor and a catalyst; in the present invention, the catalyst is preferably a chloroplatinic acid isopropyl alcohol catalyst, a platinum complex catalyst or a Karstedt catalyst, more preferably a Karstedt catalyst; the inhibitor is preferably an organic inhibitor; the organic inhibitor is preferably GS5100 in model. In the present invention, the hydrogen-containing silicone oil preferably includes a side hydrogen-containing silicone oil and a terminal hydrogen-containing silicone oil; the mass ratio of the side hydrogen-containing silicone oil to the end hydrogen-containing silicone oil is preferably (5.8-6.2): 1, more preferably (5.9 to 6.1): 1, most preferably 6.0: 1. In the invention, the viscosity of the vinyl-terminated silicone oil is preferably 200-2500 cps; the hydrogen content of the side hydrogen-containing silicone oil is preferably 0.38-0.5%; the hydrogen content of the hydrogen-terminated silicone oil is preferably 0.2-0.3%.
In the invention, the mass ratio of the vinyl-terminated silicone oil, the hydrogen-containing silicone oil, the inhibitor and the catalyst is preferably (12-15): (2-3): (0.4-0.6): 1, more preferably: (13-15): (2-3): 0.5: 1, most preferably (14-15): (2-3): 0.5: 1.
in the invention, the vinyl-terminated silicone oil is a basic component for silicon rubber synthesis, the lateral hydrogen-containing silicone oil is used as a curing agent, the terminal hydrogen-containing silicone oil is used as a chain extender, the inhibitor is used for controlling vulcanization time, and the catalyst is used for promoting hydrosilylation. The silicone rubber prepared by the raw materials has the characteristics of low shrinkage and high elasticity, and the characteristics are favorable for preparing the heat-conducting composite material with high elasticity and low interface thermal resistance.
The invention also provides a preparation method of the heat-conducting insulating silicone rubber, which comprises the following steps:
mixing spherical heat-conducting filler with flaky boron nitride, carrying out first mixing on the obtained mixed heat-conducting filler, terminal vinyl silicone oil, hydrogen-containing silicone oil and inhibitor, and then carrying out second mixing on the mixture and a catalyst to obtain a heat-conducting filler/silicone rubber prepolymer; the spherical heat-conducting filler comprises spherical aluminum nitride or spherical aluminum oxide;
curing the heat-conducting filler/silicone rubber prepolymer to obtain the heat-conducting insulating silicone rubber;
the first mixing and the second mixing are carried out under the condition of stirring;
the stirring speed of the first mixing is 500-1000 rpm; the stirring speed of the second mixing is 1000-2200 rpm;
the mass ratio of the heat-conducting filler to the silicon rubber is 85:15.
In the present invention, all the starting materials for the preparation are commercially available products known to those skilled in the art unless otherwise specified.
Mixing spherical heat-conducting filler with flaky boron nitride, carrying out first mixing on the obtained mixed heat-conducting filler, terminal vinyl silicone oil, hydrogen-containing silicone oil and inhibitor, and then carrying out second mixing on the mixture and a catalyst to obtain a heat-conducting filler/silicone rubber prepolymer; the spherical heat-conducting filler comprises spherical aluminum nitride or spherical aluminum oxide.
In the present invention, the particle diameter of the flaky boron nitride is preferably 3 to 90 μm, the average particle diameter is preferably 30 to 40 μm, and the specific surface area is preferably>0.24m2/g。
In the present invention, the spherical heat conductive filler preferably has a particle size of 30 to 150 μm, an average particle size of 80 to 100 μm, and a specific surface area of 80 to 100 μm<0.072m2/g。
In the present invention, the mixing is preferably performed under stirring conditions, the rotation speed of the stirring is preferably 500rpm, and the time is preferably 5 min; the stirring is preferably carried out in a centrifugal debubbling machine.
In the invention, the first mixing is preferably carried out under vacuum, and the stirring speed of the first mixing is preferably 500-1000 rpm, and more preferably 1000 rpm; the time is preferably 1 to 10min, and more preferably 4 to 5 min. The first mixing is preferably carried out in a centrifugal debubbler.
After the first mixing is complete, the present invention preferably includes cooling; the cooling is preferably room temperature cooling.
In the present invention, the second mixing is preferably performed under vacuum, the stirring speed of the second mixing is preferably 1000 to 2200rpm, and the second mixing is preferably performed by stirring at 1000 to 1500rpm for 1 to 3min, then stirring at 2000 to 2200rpm for 0 to 5min, and more preferably by stirring at 1500rpm for 3min, then stirring at 2000rpm for 2 min.
In the present invention, the second mixing causes agglomeration of the boron nitride flakes with aluminum nitride as a core. The function of the stepwise stirring is to ensure the narrow size distribution of the spherical boron nitride agglomerates.
After the heat-conducting filler/silicone rubber prepolymer is obtained, the heat-conducting filler/silicone rubber prepolymer is cured to obtain the heat-conducting insulating silicone rubber.
The present invention preferably includes pressing the heat conductive filler/silicone rubber prepolymer before curing, and the pressing process is not particularly limited, and may be performed by a process known to those skilled in the art. In the specific embodiment of the invention, the heat-conducting filler/silicone rubber prepolymer is compacted in a mould.
In the invention, the curing temperature is preferably 120 ℃, and the curing time is preferably 20-60 min, and more preferably 30-40 min.
The invention also provides application of the heat-conducting insulating silicone rubber in the technical scheme or the heat-conducting insulating silicone rubber prepared by the preparation method in the technical scheme in preparation of a thermal interface material. The method of the present invention is not particularly limited, and the method may be performed by a method known to those skilled in the art.
The following will describe the heat conductive and insulating silicone rubber provided by the present invention, its preparation method and application in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1
35g of flaky boron nitride (particle diameter of 3 to 90 μm, average particle diameter of 33 μm, specific surface area of 0.24 m)2(g) and 50g of spherical aluminum nitride (particle diameter of 30-150 μm, average particle diameter of 88 μm, specific surface area of 0.072 m)2/g) was mixed and stirred in a centrifugal defoaming machine at 500rpm for 5 minutes to obtain a mixed heat conductive filler, 12.5g of terminal ethyleneMixing and stirring base silicone oil (the viscosity is 200cps), 0.33g of side hydrogen-containing silicone oil (the hydrogen-containing mass fraction is 0.38%), 2g of end hydrogen-containing silicone oil (the hydrogen-containing mass fraction is 0.32%) and 0.15g of inhibitor (GS5100) at the rotating speed of 1000rpm for 5min under vacuum, cooling at room temperature, finally mixing and stirring with 0.3g of platinum complex catalyst at the rotating speed of 1500rpm for 3min, and mixing and stirring at the rotating speed of 2000rpm for 2min to obtain a heat-conducting filler/silicone rubber prepolymer (the mass ratio of the heat-conducting filler to the silicone rubber is 85: 15);
compacting the heat-conducting filler/silicone rubber prepolymer in a mold, and curing for 30min at 120 ℃ to obtain the heat-conducting insulating silicone rubber.
The out-of-plane thermal diffusivity of the heat conductive and insulating silicone rubber was tested using a laser thermal conductivity meter (laser flash, TA, DXF500), the density of the heat conductive and insulating silicone rubber was tested using a density analyzer (PEAB, XS105DU, METTLER TOLEDO, Switzerland) according to ASTM1530, the specific heat capacity of the material was tested by DSCQ 2000; the test results are respectively: the out-of-plane thermal diffusivity is 3.07mm2(s) density of 2.161g/cm3The specific heat capacity is 0.8879J/(g DEG C); according to the formula k ═ α ρ CpThe thermal conductivity of the heat-conducting insulating silicon rubber is calculated to be 5.96W/(mK).
Example 2
40g of flaky boron nitride (particle diameter of 3 to 90 μm, average particle diameter of 33 μm, specific surface area of 0.24 m)2(g) and 45g of spherical aluminum nitride (particle diameter of 30-150 μm, average particle diameter of 88 μm, specific surface area of 0.072 m)2(g) mixing and stirring the mixture in a centrifugal defoaming machine at 500rpm for 5min, mixing and stirring the obtained mixed heat-conducting filler, 12.5g of terminal vinyl silicone oil (viscosity is 200cps), 0.33g of side hydrogen-containing silicone oil (hydrogen-containing mass fraction is 0.38%), 2g of terminal hydrogen-containing silicone oil (hydrogen-containing mass fraction is 0.32%) and 0.15g of inhibitor (GS5100) at 1000rpm under vacuum conditions for 5min, cooling at room temperature, and finally mixing and stirring the mixture with 0.3g of platinum complex catalyst at 1500rpm in sequence for 3min (the surface electron microscope image of the composite material obtained after the process is shown in figure 3), wherein spherical aluminum nitride is used as a mother nucleus, boron nitride forms aggregates around the aluminum nitride during stirring, and the mixture is stirred at 2000rpm for 2min (the composite material obtained after the process is shown in figure 3)As shown in fig. 4, a surface electron microscope image is shown in fig. 4), as the stirring is continued, the silicone rubber is used as an adhesive, and the size of the spherical boron nitride aggregate is gradually increased under the action of centrifugal force and friction force, so that the heat-conductive filler/silicone rubber prepolymer (the mass ratio of the heat-conductive filler to the silicone rubber is 85:15, the physical diagram is shown in figure 1);
compacting the heat-conducting filler/silicone rubber prepolymer in a mould, and curing for 30min at 120 ℃ to obtain the heat-conducting insulating silicone rubber (a cross-sectional electron microscope image is shown in figure 2), wherein the structure that aluminum nitride is inserted in gaps of spherical boron nitride aggregates is obtained by the preparation method disclosed by the invention as shown in figure 2.
The out-of-plane thermal diffusivity of the heat conductive and insulating silicone rubber was tested using a laser thermal conductivity meter (laser flash, TA, DXF500), the density of the heat conductive and insulating silicone rubber was tested using a density analyzer (PEAB, XS105DU, METTLER TOLEDO, Switzerland) according to ASTM1530, the specific heat capacity of the material was tested by DSCQ 2000; the test results are respectively: the out-of-plane thermal diffusivity is 3.58mm2(s) density of 2.071g/cm3The specific heat capacity is 0.8856J/(g DEG C); according to the formula k ═ α ρ CpThe thermal conductivity of the heat-conducting insulating silicon rubber is calculated to be 6.56W/(mK).
Example 3
40g of flaky boron nitride (particle diameter of 3 to 90 μm, average particle diameter of 33 μm, specific surface area of 0.24 m)2(g) and 45g of spherical aluminum nitride (particle diameter of 30-150 μm, average particle diameter of 88 μm, specific surface area of 0.072 m)2/g) mixing and stirring the mixture for 5min at 500rpm in a centrifugal defoaming machine, mixing and stirring the obtained mixed heat-conducting filler, 12.5g of terminal vinyl silicone oil (the viscosity is 2500cps), 0.38g of side hydrogen-containing silicone oil (the mass fraction of hydrogen is 0.38%), 1.95g of terminal hydrogen-containing silicone oil (the mass fraction of hydrogen is 0.32%) and 0.15g of inhibitor (GS5100) at the rotating speed of 1000rpm under a vacuum condition for 5min, cooling the mixture at room temperature, and finally mixing and stirring the mixture with 0.3g of platinum complex catalyst at the rotating speed of 1500rpm for 3min and at the rotating speed of 2000rpm for 1min to obtain a heat-conducting filler/silicone rubber prepolymer;
compacting the heat-conducting filler/silicone rubber prepolymer in a mold, and curing for 30min at 120 ℃ to obtain the heat-conducting insulating silicone rubber.
The out-of-plane thermal diffusivity of the heat conductive and insulating silicone rubber was tested using a laser thermal conductivity meter (laser flash, TA, DXF500), the density of the heat conductive and insulating silicone rubber was tested using a density analyzer (PEAB, XS105DU, METTLER TOLEDO, Switzerland) according to ASTM1530, the specific heat capacity of the material was tested by DSCQ 2000; the test results are respectively: the out-of-plane thermal diffusivity is 3.42mm2(s) density of 2.093g/cm3The specific heat capacity is 0.8831J/(g DEG C); according to the formula k ═ α ρ CpThe thermal conductivity of the heat-conducting insulating silicon rubber is calculated to be 6.32W/(mK).
Comparative example 1
40g of flaky boron nitride (particle diameter of 3 to 90 μm, average particle diameter of 33 μm, specific surface area of 0.24 m)2(g) and 45g of spherical aluminum nitride (particle diameter of 30-150 μm, average particle diameter of 88 μm, specific surface area of 0.072 m)2(g) mixing and stirring the mixture for 5min at 500rpm in a centrifugal defoaming machine, and mixing and stirring the obtained mixed heat-conducting filler, 12.5g of end vinyl silicone oil (the viscosity is 200cps), 0.38g of side hydrogen-containing silicone oil (the mass fraction of hydrogen is 0.38%), 1.95g of end hydrogen-containing silicone oil (the mass fraction of hydrogen is 0.32%), 0.15g of inhibitor (GS5100) and 0.3g of platinum complex catalyst for 5min under vacuum at 1000rpm to obtain a heat-conducting filler/silicone rubber prepolymer;
compacting the heat-conducting filler/silicone rubber prepolymer in a mould, and curing for 30min at 120 ℃ to obtain heat-conducting insulating silicone rubber (the mass ratio of the heat-conducting filler to the silicone rubber is 85: 15.28);
the heat-conducting insulating silicone rubber is subjected to SEM test, the test result is shown in FIG. 5, and as can be seen from FIG. 5, the heat-conducting insulating silicone rubber prepared by the invention does not form a structure in which aluminum nitride is inserted into gaps of spherical boron nitride aggregates.
The out-of-plane thermal diffusivity of the heat conductive and insulating silicone rubber was tested using a laser thermal conductivity meter (laser flash, TA, DXF500), the density of the heat conductive and insulating silicone rubber was tested using a density analyzer (PEAB, XS105DU, METTLER TOLEDO, Switzerland) according to ASTM1530, the specific heat capacity of the material was tested by DSCQ 2000; the test results are respectively: the out-of-plane thermal diffusivity is 1.64mm2(s) density of 2.078g/cm3The specific heat capacity is 0.8785J/(g DEG C); according to the formula k ═ α ρ CpThe thermal conductivity of the heat-conducting insulating silicon rubber is calculated to be 2.99W/(mK).
Comparative example 2
30g of flaky boron nitride (particle diameter of 3 to 90 μm, average particle diameter of 33 μm, specific surface area of 0.24 m)2(iii) 55g of spherical aluminum nitride (particle diameter of 30-150 μm, average particle diameter of 88 μm, and specific surface area of 0.072 m)2/g) mixing and stirring the mixture for 5min at 500rpm in a centrifugal defoaming machine, and mixing and stirring the obtained mixed heat-conducting filler, 12.5g of end vinyl silicone oil (the viscosity is 200cps), 0.38g of side hydrogen-containing silicone oil (the mass fraction of hydrogen is 0.38%), 1.95g of end hydrogen-containing silicone oil (the mass fraction of hydrogen is 0.32%), 0.15g of inhibitor (GS5100) and 0.3g of platinum catalyst for 5min under vacuum at the rotating speed of 1000rpm to obtain a heat-conducting filler/silicone rubber prepolymer;
compacting the heat-conducting filler/silicone rubber prepolymer in a mold, and curing for 30min at 120 ℃ to obtain the heat-conducting insulating silicone rubber.
The out-of-plane thermal diffusivity of the heat conductive and insulating silicone rubber was tested using a laser thermal conductivity meter (laser flash, TA, DXF500), the density of the heat conductive and insulating silicone rubber was tested using a density analyzer (PEAB, XS105DU, METTLER TOLEDO, Switzerland) according to ASTM1530, the specific heat capacity of the material was tested by DSCQ 2000; the test results are respectively: the out-of-plane thermal diffusion coefficient is 2.45mm2(s) density of 2.216g/cm3The specific heat capacity is 0.8974J/(g DEG C); according to the formula k ═ α ρ CpThe thermal conductivity of the heat-conducting insulating silicon rubber is calculated to be 4.67W/(mK).
Comparative example 3
85g of spherical aluminum nitride (the particle diameter is 30-150 mu m, the average particle diameter is 88 mu m, and the specific surface area is 0.072 m)212.5g of end vinyl silicone oil (the viscosity is 200cps), 0.33g of side hydrogen-containing silicone oil (the hydrogen-containing mass fraction is 0.38%), 2g of end hydrogen-containing silicone oil (the hydrogen-containing mass fraction is 0.32%), 0.15g of inhibitor (GS5100) and 0.3g of platinum complex catalyst are mixed and stirred for 5min under the vacuum condition at the rotating speed of 1000rpm to obtain the heat-conducting filler/silicone rubber prepolymer;
compacting the heat-conducting filler/silicone rubber prepolymer in a mold, and curing for 30min at 120 ℃ to obtain the heat-conducting insulating silicone rubber.
The out-of-plane thermal diffusivity of the heat conductive and insulating silicone rubber was tested using a laser thermal conductivity meter (laser flash, TA, DXF500), the density of the heat conductive and insulating silicone rubber was tested using a density analyzer (PEAB, XS105DU, METTLER TOLEDO, Switzerland) according to ASTM1530, the specific heat capacity of the material was tested by DSCQ 2000; the test results are respectively: the out-of-plane thermal diffusion coefficient is 1.21mm2(s) density of 2.314mm2(ii)/s, specific heat capacity of 0.8674J/(g ℃); according to the formula k ═ α ρ CpThe thermal conductivity of the heat-conducting insulating silicon rubber is calculated to be 2.43W/(mK).
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The heat-conducting insulating silicon rubber is characterized by comprising heat-conducting filler and silicon rubber;
the heat-conducting filler comprises spherical boron nitride aggregates formed by flaky boron nitride and spherical heat-conducting filler inserted into gaps of the spherical boron nitride aggregates; the spherical heat-conducting filler comprises spherical aluminum nitride or spherical aluminum oxide;
the raw materials for preparing the silicone rubber comprise vinyl-terminated silicone oil, hydrogen-containing silicone oil, an inhibitor and a catalyst;
the mass ratio of the heat-conducting filler to the silicon rubber is 85:15.
2. The heat-conducting insulating silicone rubber according to claim 1, wherein the mass ratio of the vinyl-terminated silicone oil, the hydrogen-containing silicone oil, the inhibitor and the catalyst is (12-15): (2-3): (0.4-0.6): 1;
the hydrogen-containing silicone oil comprises lateral hydrogen-containing silicone oil and terminal hydrogen-containing silicone oil;
the mass ratio of the side hydrogen-containing silicone oil to the end hydrogen-containing silicone oil is (5.8-6.2): 1.
3. the heat-conducting insulating silicone rubber according to claim 1, wherein the spherical boron nitride agglomerates have a particle size of 400 to 1000 μm;
the particle size of the spherical heat-conducting filler is 30-150 mu m, and the average particle size is 80-100 mu m.
4. The heat-conducting insulating silicone rubber according to claim 1 or 3, wherein the mass ratio of the spherical heat-conducting filler to the spherical boron nitride agglomerates is (40-55): (30-45).
5. The heat conductive insulating silicone rubber according to claim 1, wherein the catalyst is a chloroplatinic acid isopropyl alcohol catalyst, a platinum complex catalyst, or a Karstedt catalyst;
the inhibitor is an organic inhibitor.
6. The method for preparing a heat-conducting insulating silicone rubber according to any one of claims 1 to 5, characterized by comprising the steps of:
mixing spherical heat-conducting filler with flaky boron nitride, carrying out first mixing on the obtained mixed heat-conducting filler, terminal vinyl silicone oil, hydrogen-containing silicone oil and inhibitor, and then carrying out second mixing on the mixture and a catalyst to obtain a heat-conducting filler/silicone rubber prepolymer; the spherical heat-conducting filler comprises spherical aluminum nitride or spherical aluminum oxide;
curing the heat-conducting filler/silicone rubber prepolymer to obtain the heat-conducting insulating silicone rubber;
the first mixing and the second mixing are carried out under the condition of stirring;
the stirring speed of the first mixing is 500-1000 rpm; the stirring speed of the second mixing is 1000-2200 rpm;
the mass ratio of the heat-conducting filler to the silicon rubber is 85:15.
7. The method according to claim 6, wherein the flaky boron nitride has a particle size of 3 to 90 μm and an average particle sizeDiameter of 30-40 μm, specific surface area>0.24m2/g；
The particle size of the spherical heat-conducting filler is 30-150 mu m, the average particle size is 80-100 mu m, and the specific surface area<0.072m2/g。
8. The method according to claim 7, wherein the second mixing step is performed by stirring at 1000 to 1500rpm for 1 to 3min and then at 2000 to 2200rpm for 0 to 5 min.
9. The method according to claim 7, wherein the curing temperature is 120 ℃ and the curing time is 20 to 60 min.
10. Use of the heat-conducting and insulating silicone rubber according to any one of claims 1 to 6 or the heat-conducting and insulating silicone rubber prepared by the preparation method according to any one of claims 7 to 9 in preparation of a thermal interface material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110646440.4A CN113337126A (en) | 2021-06-10 | 2021-06-10 | Heat-conducting insulating silicon rubber and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110646440.4A CN113337126A (en) | 2021-06-10 | 2021-06-10 | Heat-conducting insulating silicon rubber and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113337126A true CN113337126A (en) | 2021-09-03 |
Family
ID=77475579
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110646440.4A Pending CN113337126A (en) | 2021-06-10 | 2021-06-10 | Heat-conducting insulating silicon rubber and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113337126A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113912914A (en) * | 2021-12-07 | 2022-01-11 | 北京石墨烯技术研究院有限公司 | Polymer-based composite heat conduction material and preparation method and application thereof |
| CN114426757A (en) * | 2022-01-20 | 2022-05-03 | 国网河北省电力有限公司电力科学研究院 | Resin material and preparation method thereof |
| CN114702828A (en) * | 2022-03-16 | 2022-07-05 | 深圳市傲川科技有限公司 | Boron nitride filled heat conduction interface material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030170446A1 (en) * | 2002-03-05 | 2003-09-11 | Polymatech Co. Ltd | Sheet for conducting heat |
| CN110776745A (en) * | 2019-10-09 | 2020-02-11 | 苏州欣天新精密机械有限公司 | Preparation method of thermal interface material |
| CN112457673A (en) * | 2020-11-09 | 2021-03-09 | 江苏集萃先进高分子材料研究所有限公司 | High-thermal-conductivity insulating silica gel gasket and preparation method thereof |
| CN112778766A (en) * | 2020-12-31 | 2021-05-11 | 广东皓明有机硅材料有限公司 | High-reliability high-thermal-conductivity silicone gel composition and preparation method and application thereof |
-
2021
- 2021-06-10 CN CN202110646440.4A patent/CN113337126A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030170446A1 (en) * | 2002-03-05 | 2003-09-11 | Polymatech Co. Ltd | Sheet for conducting heat |
| CN110776745A (en) * | 2019-10-09 | 2020-02-11 | 苏州欣天新精密机械有限公司 | Preparation method of thermal interface material |
| CN112457673A (en) * | 2020-11-09 | 2021-03-09 | 江苏集萃先进高分子材料研究所有限公司 | High-thermal-conductivity insulating silica gel gasket and preparation method thereof |
| CN112778766A (en) * | 2020-12-31 | 2021-05-11 | 广东皓明有机硅材料有限公司 | High-reliability high-thermal-conductivity silicone gel composition and preparation method and application thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113912914A (en) * | 2021-12-07 | 2022-01-11 | 北京石墨烯技术研究院有限公司 | Polymer-based composite heat conduction material and preparation method and application thereof |
| CN113912914B (en) * | 2021-12-07 | 2022-02-18 | 北京石墨烯技术研究院有限公司 | Polymer-based composite heat conduction material and preparation method and application thereof |
| CN114426757A (en) * | 2022-01-20 | 2022-05-03 | 国网河北省电力有限公司电力科学研究院 | Resin material and preparation method thereof |
| CN114426757B (en) * | 2022-01-20 | 2023-05-09 | 国网河北省电力有限公司电力科学研究院 | Resin material and preparation method thereof |
| CN114702828A (en) * | 2022-03-16 | 2022-07-05 | 深圳市傲川科技有限公司 | Boron nitride filled heat conduction interface material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113337126A (en) | Heat-conducting insulating silicon rubber and preparation method and application thereof | |
| CN109913185B (en) | Multilayer structure heat-conducting composite material containing heat-conducting film and preparation method thereof | |
| Bae et al. | The properties of AlN-filled epoxy molding compounds by the effects of filler size distribution | |
| CN110951254A (en) | Boron nitride composite high-thermal-conductivity insulating polymer composite material and preparation method thereof | |
| CN110922719A (en) | High-thermal-conductivity boron nitride/epoxy resin composite material and preparation method and application thereof | |
| CN112521754B (en) | MXene nanosheet compounded heat-conducting gel with thermal self-repairing performance and preparation method thereof | |
| CN113429796A (en) | Single-component high-thermal-conductivity silicone gel and preparation method thereof | |
| CN112724677A (en) | Dopamine modified boron nitride heat-conducting silicone grease and preparation method thereof | |
| CN112552688A (en) | High-thermal-conductivity organic silicon gel sheet and preparation method thereof | |
| CN112195016B (en) | Heat-conducting insulating carbon fiber silica gel gasket and preparation method thereof | |
| WO2021164225A1 (en) | Chemical and physical treatment method for filler with high thermal conductivity | |
| WO2022105646A1 (en) | Potting adhesive and preparation method therefor | |
| CN111363368A (en) | Fluid-like high-thermal-conductivity organic silicon gel and preparation method and application thereof | |
| WO2023197698A1 (en) | Heat-conduction-enhanced phase-change nanocapsule composite material, and preparation method therefor and use thereof | |
| CN114525100A (en) | High-thermal-conductivity low-viscosity epoxy pouring sealant and preparation method thereof | |
| CN112063020B (en) | Core-shell spherical heat-conducting filler and preparation method and application thereof | |
| CN112250996A (en) | Micro-nano epoxy resin electronic packaging material and preparation method and application thereof | |
| WO2021109730A1 (en) | Two-component organosilicon potting sealant and application method therefor | |
| CN115785864A (en) | PI-Al 2 O 3 Preparation method of PI-BN codoped high-thermal-conductivity epoxy resin composite material | |
| CN115746799A (en) | Preparation method of single-component heat-conducting gel with high heat conductivity | |
| CN115960548A (en) | Epoxy resin adhesive film for encapsulating chip and preparation method thereof | |
| CN115678286A (en) | Easily-filled and easily-repaired heat-conducting gel and preparation method thereof | |
| CN114605836A (en) | High-performance silicon oil-based flexible heat-conducting gasket and preparation method thereof | |
| CN107022194A (en) | A kind of multiple dimensioned Carbon Materials/silicon rubber interface Heat Conduction Material and preparation method | |
| CN111269690A (en) | Light heat-conducting filling and sealing foamed silica gel |
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 |