CN115011125B - High-heat-conductivity antioxidant wave-absorbing silicon rubber composite material and preparation method thereof - Google Patents
High-heat-conductivity antioxidant wave-absorbing silicon rubber composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-heat-conductivity antioxidant wave-absorbing silicon rubber composite material and a preparation method thereof, wherein the high-heat-conductivity antioxidant wave-absorbing silicon rubber composite material is prepared from the following raw materials in parts by mass: 100 parts of basic silicone oil and a cross-linking agent: 2-6 parts of catalyst: 0.5-2 parts of inhibitor: 0.2-0.5 part of spherical heat conducting filler: 50-300 parts of sheet-shaped heat-conducting filler: 20-300 parts of wave-absorbing filler: 50-300 parts. By mixing the wave-absorbing filler and the heat-conducting filler into the liquid silicone rubber matrix, the liquid silicone rubber has high-efficiency wave-absorbing performance and excellent heat-conducting capability. The heat conducting performance is improved by adjusting the dosage of the coupling agent and compounding the heat conducting fillers with different shapes and different dimensions, and the oxidation resistance and corrosion resistance of the wave-absorbing filler are improved by carrying out high-temperature bluing modification treatment. The heat conductivity can reach 2.7W.m at most ‑1 ·k ‑1 The minimum Reflection Loss (RL) can be up to-48.5 dB and the hardness (shore a) is less than 45. The heat-conducting wave-absorbing silicon rubber material disclosed by the invention has the advantages of good elasticity, simple preparation process, readily available raw materials, low cost and good processability, and has a good development prospect.
Description
Technical Field
The invention relates to the technical field of heat-conducting wave-absorbing materials, in particular to a high-heat-conducting antioxidant wave-absorbing silicon rubber composite material and a preparation method thereof.
Background
With the development of society, power electronic equipment is continuously developed to have high capacity, high integration and high power density, and simultaneously, the appearance of the equipment is gradually developed to be miniaturized and light. This will cause rapid accumulation of heat generated by the power electronic device and ineffective discharge, seriously affecting the usability and lifetime of the electronic device. Therefore, the problem of heat dissipation generated by the electronic device and the electrical energy device during application needs to be solved. The heat conduction material is generally adopted to absorb and dissipate redundant heat on the equipment element, so that the overheating phenomenon of an electronic device in a narrow environment is avoided, the surface heat is uniformly diffused along the surface direction, and the spot heat source accident is effectively avoided.
Meanwhile, electromagnetic radiation generated during operation of modern electronic equipment not only seriously damages human health, but also can cause electromagnetic wave cross interference among electronic components with different frequencies in the equipment, so that electromagnetic compatibility problem is caused, sensitive devices are damaged, meanwhile, information leakage problem can be generated due to electromagnetic wave radiation, and a wave absorbing material is attached to the surface of the electronic components to solve the problem.
The electronic equipment has a narrow internal space, the heat conduction material occupies the gap space on the surface of the device, and the wave absorbing material cannot be used in a superposition way. Therefore, achieving both efficient heat dissipation and absorption of electromagnetic radiation within the limited space of electronic equipment has become a major challenge for researchers. On the other hand, the weaponry such as an airplane, a missile and the like has higher and faster flying speed in the use process, and special parts such as a skin and the like rub with air to generate a large amount of heat, so that the wave-absorbing material is required to be high-temperature resistant and oxidation resistant in order to achieve the stealth effect, but in practice, the wave-absorbing material cannot be used for a long time at high temperature due to poor oxidation resistance of some wave-absorbing materials. In order to meet the market demand and solve the problem, it is very necessary to develop a new generation of heat-absorbing and heat-conducting wave-absorbing composite materials with high heat-conducting property, excellent wave-absorbing capability and oxidation resistance and easy processing property.
Disclosure of Invention
In view of the above, the invention aims to provide the high-heat-conductivity and oxidation-resistant wave-absorbing silicon rubber composite material and the preparation method thereof.
The invention provides the following technical scheme:
the high-heat-conductivity antioxidant wave-absorbing silicon rubber composite material is prepared from the following raw materials in parts by mass:
basic silicone oil: 100 parts of
Crosslinking agent: 2 to 6 portions
Catalyst: 0.5 to 2 parts
Inhibitors: 0.2 to 0.5 part
Spherical heat conductive filler: 50-300 parts
Sheet-like heat conductive filler: 20-300 parts
Wave-absorbing filler: 50-300 parts
Preferably, the base silicone oil is linear vinyl silicone oil, the vinyl content is 0.02mol/100g, and the viscosity at 25 ℃ is 500 mPa.s; the cross-linking agent is hydrogen-containing silicone oil, the hydrogen content is 0.5mol/100g, and the viscosity at 25 ℃ is 80 mPa.s.
Preferably, the catalyst is a platinum catalyst, which is one or more of an isopropanol solution of chloroplatinic acid, a platinum-1, 3-divinyl-1, 3-tetramethyldisiloxane complex, a platinum-vinyltrimethoxysilane complex and a platinum-vinyltriethoxysilane complex.
Preferably, the inhibitor is one or more of 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3, 5-dimethyl-1-hexyn-3-ol, 1-ethynyl-1-cyclohexanol and 3-phenyl-1-butyn-3-ol.
Preferably, the spherical heat conducting filler is one of spherical graphite powder, spherical aluminum oxide and spherical aluminum nitride powder, and the particle size is 20-60 mu m.
Preferably, the sheet-shaped heat-conducting filler is sheet-shaped boron nitride, the sheet diameter is 10-50 mu m, and the thickness is 8 nm-3 mu m.
Preferably, the wave-absorbing filler is one of carbonyl iron powder, ferrite, permalloy powder and Fe-Si-Al ferrite, and the particle size is 2-80 mu m.
The invention also provides a preparation method of the high-heat-conductivity antioxidant wave-absorbing silicon rubber composite material, which comprises the following steps:
(1) Pretreatment of filler: modifying the spherical heat conducting filler and the flaky heat conducting filler by using a heat conducting filler modifier to obtain modified spherical heat conducting powder and modified flaky heat conducting powder respectively; modifying the wave-absorbing filler by using a wave-absorbing filler modifier to obtain modified wave-absorbing powder;
(2) Mixing filler: mixing the modified filler in the step (1) for 10min by using a high-speed mixer to prepare the heat-conducting wave-absorbing filler;
(3) Mixing the matrix with the filler: uniformly mixing basic silicone oil, a cross-linking agent, a catalyst, an inhibitor and the heat conduction wave-absorbing filler obtained in the step (2) by using a vacuum deaerating machine at a rotating speed of 3000rpm, and deaerating for 15min to obtain a base material;
(4) And (3) vulcanization molding: pouring the base material in the step (3) into a pre-prepared forming mold for forming and shaping, and vulcanizing in a drying oven at 100-140 ℃ for 10-30 min to obtain the heat-conducting wave-absorbing silicon rubber material.
Preferably, the heat conductive filler modifier in the step (1) is a silane coupling agent, which is one or more of gamma-aminopropyl triethoxysilane (KH 550), gamma-glycidoxypropyl trimethoxysilane (KH 560), gamma- (methacryloyloxy) propyl trimethoxysilane (KH 570), N- (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane (KH 792) and isopropyl tri (dioctyl pyrophosphoryloxy) titanate (NDZ-201).
Preferably, the modifier of the wave-absorbing filler is sodium hydroxide (NaOH) or sodium nitrite (NaNO) 2 ) And trisodium phosphate (Na) 3 PO 4 ) One or more of them.
Preferably, the specific preparation method of the modified heat-conducting filler comprises the following steps: the mass ratio of the silane coupling agent to the heat conducting filler is 1-3:100, the silane coupling agent is diluted by alcohol aqueous solution, spherical heat conducting filler or flaky heat conducting filler is added, the mixture is taken out after being treated for 20-120 min at 50-150 ℃, and then the mixture is placed in a vacuum drying oven at 50-150 ℃ for 1-4 h, so that the coupling agent and the filler are completely reacted, and the modified spherical heat conducting powder or the modified flaky heat conducting powder is obtained.
Preferably, the specific preparation method of the modified wave-absorbing filler comprises the following steps:
(1) Dispersing the wave-absorbing filler in absolute ethyl alcohol, and carrying out ultrasonic oscillation on the mixed solution for 30 minutes;
(2) Mixing deionized water and a bluing agent and uniformly stirring to obtain a bluing liquid, then adding the bluing liquid into the carbonyl iron powder mixed liquid, and stirring for 30, 60 or 90min at a stirring speed of 250r/min under the water bath condition of constant temperature of 50 ℃;
(3) After the reaction is finished, the system is kept stand, the upper transparent solution is poured off, the system is washed for 3 times by absolute ethyl alcohol, and then dried in a drying box, and the carbonyl iron powder after bluing treatment, namely the modified wave-absorbing filler, is obtained through sieving.
Preferably, the bluing agent in the step (2) is prepared from the following raw materials in parts by weight: 20-100 parts of NaOH and 5-40 parts of NaNO 3 0.5 to 10 parts of Na 3 PO 4 The mass ratio of the bluing agent to the wave-absorbing filler is 1-5:10.
The invention discloses a high-heat-conductivity antioxidant wave-absorbing silicon rubber composite material and a preparation method thereof, in particular to a high-heat-conductivity antioxidant wave-absorbing silicon rubber composite material which is prepared from the following components in percentage by weight:
(1) The high-heat-conductivity antioxidant wave-absorbing silicon rubber composite material disclosed by the invention takes liquid silicone oil as a matrix material to prepare a flexible silicon rubber matrix, has the advantages of lower cost and simple preparation method, and can simultaneously solve the problems of heat dissipation and electromagnetic wave absorption in a limited space by mixing the wave-absorbing agent and the heat-conducting filler into the silicon rubber matrix, so that the silicon rubber composite gasket disclosed by the invention has high-efficiency wave-absorbing performance and excellent heat-conducting capacity;
(2) The wettability of the heat conducting filler and the matrix is improved by adjusting the dosage of the coupling agent; the heat conduction performance is improved through the synergistic effect of the compounding of the heat conduction fillers with different shapes and different dimensions, spherical graphite micro powder with uniform particle size distribution is synergistic with flaky boron nitride with larger specific surface area, a heat conduction path is easy to form in a silicon rubber matrix, the consumption of the heat conduction filler can be obviously reduced, the density of the silicon rubber composite material can be further reduced, and meanwhile, the heat conduction performance is improved;
(3) The high-temperature bluing modification treatment is carried out on the wave-absorbing filler, so that the dielectric constant can be reduced, and the impedance matching between the wave-absorbing material and the space medium can be improved; the dispersibility of the wave-absorbing filler is improved; can effectively improve the oxidation resistance and corrosion resistance of the magnetic wave absorber under the high temperature condition; the prepared heat-absorbing waveguide composite gasket has longer service life in high-temperature environment, marine corrosion environment and some extremely severe environments;
(4) The heat-conducting wave-absorbing silicon rubber composite material has good heat-conducting property and wave-absorbing property, good flexibility, high elasticity, shock absorption and highest heat conductivity of 2.7W.m -1 ·k -1 The minimum Reflection Loss (RL) can reach-48.5 dB, and the hardness (Shore A) is less than 45;
(5) The heat-conducting wave-absorbing silicon rubber material disclosed by the invention is simple in preparation process, easy in raw material acquisition, low in cost and good in processability, is suitable for large-scale popularization and application, has a wide application prospect, and is especially suitable for the fields of precision electronic equipment such as 5G communication equipment, artificial intelligent equipment, wireless energy transmission devices, microwave medical devices, new energy batteries and the like.
Drawings
FIG. 1 is a flow chart of a preparation process of a high-heat-conductivity antioxidant wave-absorbing silicon rubber composite material;
FIG. 2 is a scanning electron microscope image of spherical graphite powder;
FIG. 3 is a scanning electron microscope image of platy boron nitride;
FIG. 4 is a scanning electron microscope image of carbonyl iron powder;
FIG. 5 is a flow chart of a carbonyl iron powder bluing process;
fig. 6 is a graph showing the reflection loss of the composite material after the carbonyl iron powder treated by different processes is subjected to a salt spray test for 24 hours.
Detailed Description
The invention is further illustrated and described below in connection with specific examples.
Example 1
The high-heat-conductivity antioxidant wave-absorbing silicon rubber composite material disclosed by the embodiment 1 comprises the following raw materials in parts by weight:
basic silicone oil: 100 parts of
Crosslinking agent: 6 parts of
Catalyst: 1 part of
Inhibitors: 0.5 part
Spherical heat conductive filler (particle diameter 33 μm): 150 parts of
Sheet-like heat conductive filler (sheet diameter 30 μm, thickness 2 μm): 50 parts of
Wave-absorbing filler (particle size 4.5 μm): 100 parts of
Referring to fig. 1, fig. 1 is a flowchart of a preparation process of the high-thermal-conductivity antioxidant wave-absorbing silicon rubber composite material, and as shown in the figure, the preparation method of the thermal-conductive wave-absorbing silicon rubber material comprises the following steps:
(1) 6 parts of gamma-aminopropyl triethoxysilane (KH 550) is used for preparing an alcohol aqueous solution with a certain concentration, 200 parts of spherical heat-conducting filler and 200 parts of flaky heat-conducting filler are respectively treated at 100 ℃ for 50min and then taken out, a scanning electron microscope image of the spherical heat-conducting filler is shown as a figure 2, a scanning electron microscope image of the flaky heat-conducting filler is shown as a figure 3, the spherical heat-conducting filler and the flaky heat-conducting filler are placed in a vacuum drying oven at 100 ℃ and treated for 2h, so that the silane coupling agent and the filler are completely reacted, and modified spherical heat-conducting filler and modified flaky heat-conducting filler are respectively obtained;
(2) Referring to fig. 4-5, fig. 4 is a scanning electron microscope image of carbonyl iron powder, fig. 5 is a flow chart of carbonyl iron powder modification treatment, as shown in the drawing, 200 parts of wave-absorbing filler are dispersed in 500ml of absolute ethyl alcohol, and the mixed solution is subjected to ultrasonic vibration for 30 minutes to obtain wave-absorbing filler mixed solution; 500 parts of deionized water, 33 parts of NaOH and 10 parts of NaNO 3 2 parts of Na 3 PO 4 Mixing and stirring uniformly to obtain bluing liquid; and finally, dripping the uniformly stirred bluing liquid into the carbonyl iron powder mixed liquid, and stirring for 30min at a stirring speed of 250r/min under the water bath condition with the constant temperature of 50 ℃, wherein a scanning electron microscope diagram of the carbonyl iron powder is shown in figure 3. After the reaction is finished, standing the system, pouring out the upper transparent solution, washing for 3 times by using absolute ethyl alcohol, drying in a drying box, and sieving to obtain a blue-treated wave-absorbing filler, namely a modified wave-absorbing filler;
(3) Mixing filler: adding the filler obtained in the steps (1) and (2) into a high-speed mixer for mixing for 10min according to the mass parts, and obtaining the heat-conducting wave-absorbing filler;
(4) Mixing the matrix with the filler: uniformly mixing vinyl silicone oil, hydrogen-containing silicone oil, a platinum catalyst, an inhibitor and the heat-conducting wave-absorbing filler in the step (3) according to the mass parts by using a vacuum deaerating machine at a rotating speed of 3000rpm, and deaerating for 15min to obtain a base material;
(5) And (3) vulcanization molding: pouring the base material in the step (4) into a pre-prepared forming mold for forming and shaping, and vulcanizing for 20min in a drying oven at 120 ℃ to obtain the heat-conducting wave-absorbing silicon rubber material.
Comparative example 1
The heat-conducting wave-absorbing silicon rubber material comprises the following raw materials in parts by weight:
basic silicone oil: 100 parts of
Crosslinking agent: 6 parts of
Catalyst: 1 part of
Inhibitors: 0.5 part
Spherical heat conductive filler (particle diameter 33 μm): 150 parts of
Sheet-like heat conductive filler (sheet diameter 30 μm, thickness 2 μm): 50 parts of
A preparation method of a heat-conducting wave-absorbing silicon rubber material comprises the following steps:
(1) 6 parts of gamma-aminopropyl triethoxysilane (KH 550) is used for preparing an alcohol aqueous solution with a certain concentration, 200 parts of spherical heat-conducting filler and 200 parts of flaky heat-conducting filler are respectively treated at 100 ℃ for 50min and then taken out, and then the mixture is placed in a vacuum drying oven at 100 ℃ for 2h, so that the coupling agent and the filler react completely to respectively obtain modified spherical heat-conducting filler and modified flaky heat-conducting filler;
(2) Mixing filler: mixing the filler obtained in the step (1) for 10min by using a high-speed mixer according to the mass parts to obtain a heat-conducting mixed filler;
(3) Mixing the matrix with the filler: uniformly mixing basic glycerin, a cross-linking agent, a catalyst, an inhibitor and the heat-conducting mixed filler in the step (2) according to the mass parts by using a vacuum deaerating machine at a rotating speed of 3000rpm, and deaerating for 15min to obtain a base material;
(4) And (3) vulcanization molding: pouring the base material in the step (3) into a pre-prepared forming mold for forming and shaping, and vulcanizing for 20min in a drying oven at 120 ℃ to obtain the heat-conducting wave-absorbing silicon rubber material.
Example 2
The high-heat-conductivity antioxidant wave-absorbing silicon rubber composite material disclosed by the embodiment 2 comprises the following raw materials in parts by weight:
basic silicone oil: 100 parts of
Crosslinking agent: 6 parts of
Catalyst: 1 part of
Inhibitors: 0.3 part
Spherical heat conductive filler (particle diameter 33 μm): 50 parts of
Sheet-like heat conductive filler (sheet diameter 30 μm, thickness 2 μm): 90 parts of
Wave-absorbing filler (particle size 4.5 μm): 160 parts of
The preparation method of the high-heat-conductivity antioxidant wave-absorbing silicon rubber composite material comprises the following steps:
(1) Preparing an alcohol aqueous solution with a certain concentration by using 5 parts of gamma-aminopropyl triethoxysilane (KH 550), respectively treating 200 parts of spherical heat-conducting filler and 200 parts of flaky heat-conducting filler at 100 ℃ for 50min, taking out, then placing in a vacuum drying oven at 100 ℃ for 2h, and completely reacting the coupling agent with the filler to respectively obtain a modified spherical heat-conducting filler and a modified flaky heat-conducting filler;
(2) Dispersing 200 parts of wave-absorbing filler in 500ml of absolute ethyl alcohol, and carrying out ultrasonic oscillation on the mixed solution for 30 minutes to obtain a wave-absorbing filler mixed solution; 500 parts of deionized water, 33 parts of NaOH and 10 parts of NaNO 3 2 parts of Na 3 PO 4 Mixing and stirring uniformly to obtain bluing liquid; finally, dripping the bluing liquid after uniform stirring into carbonyl iron powder mixed liquid, and stirring for 60min at a stirring speed of 250r/min under the water bath condition of constant temperature of 50 ℃; after the reaction is finished, standing the system, pouring out the upper transparent solution, washing for 3 times by using absolute ethyl alcohol, drying in a drying box, and sieving to obtain a blue-treated wave-absorbing filler, namely a modified wave-absorbing filler;
(3) Mixing filler: mixing the fillers obtained in the steps (1) and (2) for 10 minutes by using a high-speed mixer according to the mass parts to obtain the heat-conducting wave-absorbing filler;
(4) Mixing the matrix with the filler: uniformly mixing basic glycerin, a cross-linking agent, a catalyst, an inhibitor and the heat-conducting wave-absorbing filler in the step (3) according to the mass parts by using a vacuum deaerating machine at a rotating speed of 3000rpm, and deaerating for 15min to obtain a base material;
(5) And (3) vulcanization molding: pouring the base material in the step (4) into a pre-prepared forming mold for forming and shaping, and vulcanizing for 20min in a drying oven at 120 ℃ to obtain the heat-conducting wave-absorbing silicon rubber material.
Comparative example 2
The heat-conducting wave-absorbing silicon rubber material comprises the following raw materials in parts by weight:
basic silicone oil: 100 parts of
Crosslinking agent: 6 parts of
Catalyst: 1 part of
Inhibitors: 0.3 part
Spherical heat conductive filler (particle diameter 33 μm): 50 parts of
Wave-absorbing filler (particle size 4.5 μm): 160 parts of
A preparation method of a heat-conducting wave-absorbing silicon rubber material comprises the following steps:
(1) Preparing an alcohol aqueous solution with a certain concentration by using 5 parts of gamma-aminopropyl triethoxysilane (KH 550), treating 200 parts of spherical heat-conducting filler at 100 ℃ for 50min, taking out, then placing in a vacuum drying oven at 100 ℃, and treating for 2h to enable the coupling agent to react with the filler completely, thus obtaining the modified spherical heat-conducting filler;
(2) Dispersing 200 parts of wave-absorbing filler in 500ml of absolute ethyl alcohol, and carrying out ultrasonic oscillation on the mixed solution for 30 minutes to obtain a wave-absorbing filler mixed solution; 500 parts of deionized water, 33 parts of NaOH and 10 parts of NaNO 3 2 parts of Na 3 PO 4 Mixing, stirring uniformly to obtain bluing liquid, finally dripping the bluing liquid after uniform stirring into carbonyl iron powder mixed liquid, and stirring for 60min at a stirring speed of 250r/min under the water bath condition of constant temperature of 50 ℃; after the reaction is finished, standing the system, pouring out the upper transparent solution, washing for 3 times by using absolute ethyl alcohol, drying in a drying box, and sieving to obtain a blue-treated wave-absorbing filler, namely a modified wave-absorbing filler;
(3) Mixing filler: mixing the fillers obtained in the steps (1) and (2) for 10 minutes by using a high-speed mixer according to the mass parts to obtain the heat-conducting wave-absorbing filler;
(4) Mixing the matrix with the filler: uniformly mixing vinyl silicone oil, hydrogen-containing silicone oil, a platinum catalyst, an inhibitor and the heat-conducting wave-absorbing filler in the step (3) according to the mass parts by using a vacuum deaerating machine at a rotating speed of 3000rpm, and deaerating for 15min to obtain a base material;
(5) And (3) vulcanization molding: pouring the base material in the step (4) into a pre-prepared forming mold for forming and shaping, and vulcanizing for 20min in a drying oven at 120 ℃ to obtain the heat-conducting wave-absorbing silicon rubber material.
Example 3
The high-heat-conductivity antioxidant wave-absorbing silicon rubber composite material disclosed by the embodiment 3 comprises the following raw materials in parts by weight:
100 parts of basic silicone oil
Crosslinking agent: 5 parts of
Catalyst: 0.8 part
Inhibitors: 0.3 part
Spherical heat conductive filler (33 μm): 120 parts of
Sheet-like heat conductive filler (sheet diameter 15 μm, thickness 1 μm): 30 parts of
Wave-absorbing filler (particle size 2.5 μm): 150 parts of
The preparation method of the high-heat-conductivity antioxidant wave-absorbing silicon rubber composite material comprises the following steps:
(1) 6 parts of gamma-aminopropyl triethoxysilane (KH 550) is used for preparing an alcohol aqueous solution with a certain concentration, 200 parts of spherical heat-conducting filler and 200 parts of flaky heat-conducting filler are respectively treated at 100 ℃ for 50min and then taken out, and then the mixture is placed in a vacuum drying oven at 100 ℃ for 2h, so that the coupling agent and the filler react completely to respectively obtain modified spherical heat-conducting filler and modified flaky heat-conducting filler;
(2) Dispersing 200 parts of wave-absorbing filler in 500ml of absolute ethyl alcohol, and carrying out ultrasonic oscillation on the mixed solution for 30 minutes to obtain a wave-absorbing filler mixed solution; 500 parts of deionized water, 33 parts of NaOH and 10 parts of NaNO 3 2 parts of Na 3 PO 4 Mixing, stirring to obtain bluing liquid, and adding the bluing liquid to carbonyl ironThe powder mixture was stirred for 30min at a stirring speed of 250r/min in a water bath at a constant temperature of 50 ℃. After the reaction is finished, standing the system, pouring out the upper transparent solution, washing for 3 times by using absolute ethyl alcohol, drying in a drying box, and sieving to obtain a blue-treated wave-absorbing filler, namely a modified wave-absorbing filler;
(3) Mixing filler: mixing the fillers obtained in the steps (1) and (2) for 10 minutes by using a high-speed mixer according to the mass parts to obtain the heat-conducting wave-absorbing filler;
(4) Mixing the matrix with the filler: and (3) uniformly mixing vinyl silicone oil, hydrogen-containing silicone oil, a platinum catalyst, an inhibitor and the heat-conducting wave-absorbing filler in the step (3) according to the mass parts by using a vacuum deaerating machine at a rotating speed of 3000rpm, and deaerating for 15min to obtain a base material.
(5) And (3) vulcanization molding: pouring the base material in the step (4) into a pre-prepared forming mold for forming and shaping, and vulcanizing for 20min in a drying oven at 120 ℃ to obtain the heat-conducting wave-absorbing silicon rubber material.
Comparative example 3
The heat-conducting wave-absorbing silicon rubber material comprises the following raw materials in parts by weight:
basic silicone oil: 100 parts of
Crosslinking agent: 5 parts of
Catalyst: 0.8 part
Inhibitors: 0.3 part
Spherical heat conductive filler (33 μm): 120 parts of
Sheet-like heat conductive filler (sheet diameter 15 μm, thickness 1 μm): 30 parts of
Wave-absorbing filler (particle size 2.5 μm): 150 parts of
A preparation method of a heat-conducting wave-absorbing silicon rubber material comprises the following steps:
(1) 6 parts of gamma-aminopropyl triethoxysilane (KH 550) is used for preparing an alcohol aqueous solution with a certain concentration, 200 parts of spherical heat-conducting filler and 200 parts of flaky heat-conducting filler are respectively treated at 100 ℃ for 50min and then taken out, and then the mixture is placed in a vacuum drying oven at 100 ℃ for 2h, so that the coupling agent and the filler react completely to respectively obtain modified spherical heat-conducting filler and modified flaky heat-conducting filler;
(2) Placing 200 parts of wave-absorbing filler into acetone, mechanically stirring for 30min, ultrasonically treating for 15min, and vacuum drying at 80 ℃ for 4h;
(3) Mixing filler: mixing the fillers obtained in the steps (1) and (2) for 10 minutes by using a high-speed mixer according to the mass parts to obtain the heat-conducting wave-absorbing filler;
(4) Mixing the matrix with the filler: uniformly mixing vinyl silicone oil, hydrogen-containing silicone oil, a platinum catalyst, an inhibitor and the heat-conducting wave-absorbing filler in the step (3) according to the mass parts by using a vacuum deaerating machine at a rotating speed of 3000rpm, and deaerating for 15min to obtain a base material;
(5) And (3) vulcanization molding: pouring the base material in the step (4) into a pre-prepared forming mold for forming and shaping, and vulcanizing for 20min in a drying oven at 120 ℃ to obtain the heat-conducting wave-absorbing silicon rubber material.
Example 4
The high-heat-conductivity antioxidant wave-absorbing silicon rubber composite material disclosed by the embodiment 4 comprises the following raw materials in parts by weight:
basic silicone oil: 100 parts of
Crosslinking agent: 6 parts of
Catalyst: 1 part of
Inhibitors: 0.3 part
Spherical heat conductive filler (33 μm): 50 parts of
Sheet-like heat conductive filler (sheet diameter 15 μm, thickness 1 μm): 150 parts of
Wave-absorbing filler (particle size 2.5 μm): 100 parts of
A preparation method of a heat-conducting wave-absorbing silicon rubber material comprises the following steps:
(1) Preparing an alcohol aqueous solution with a certain concentration by using 5 parts of gamma- (methacryloyloxy) propyl trimethoxy silane (KH 570), respectively treating 200 parts of spherical heat conducting filler and 200 parts of flaky heat conducting filler at 100 ℃ for 50min, taking out, then placing in a vacuum drying oven at 100 ℃ for 2h, and completely reacting the coupling agent with the filler to respectively obtain a modified spherical heat conducting filler and a modified flaky heat conducting filler;
(2) Dispersing 200 parts of wave-absorbing filler in 500ml of absolute ethyl alcohol, and carrying out ultrasonic oscillation on the mixed solution for 30 minutes to obtain a wave-absorbing filler mixed solution; 500 parts of deionized water and 16.5 parts of NaOH,5 parts of NaNO 3 1 part of Na 3 PO 4 Mixing, stirring uniformly to obtain bluing liquid, finally dripping the bluing liquid after uniform stirring into carbonyl iron powder mixed liquid, and stirring for 30min at a stirring speed of 250r/min under the water bath condition of constant temperature of 50 ℃; after the reaction is finished, standing the system, pouring out the upper transparent solution, washing for 3 times by using absolute ethyl alcohol, drying in a drying box, and sieving to obtain a blue-treated wave-absorbing filler, namely a modified wave-absorbing filler;
(3) Mixing filler: mixing the fillers obtained in the steps (1) and (2) for 10 minutes by using a high-speed mixer according to the mass parts to obtain the heat-conducting wave-absorbing filler;
(4) Mixing the matrix with the filler: uniformly mixing vinyl silicone oil, hydrogen-containing silicone oil, a platinum catalyst, an inhibitor and the heat-conducting wave-absorbing filler in the step (3) according to the mass parts by using a vacuum deaerating machine at a rotating speed of 3000rpm, and deaerating for 15min to obtain a base material;
(5) And (3) vulcanization molding: pouring the base material in the step (4) into a pre-prepared forming mold for forming and shaping, and vulcanizing for 40min in a drying oven at 100 ℃ to obtain the heat-conducting wave-absorbing silicon rubber material.
Example 5
The high-heat-conductivity antioxidant wave-absorbing silicon rubber composite material disclosed by the embodiment 5 comprises the following raw materials in parts by weight:
basic silicone oil: 100 parts of
Crosslinking agent: 6 parts of
Catalyst: 1 part of
Inhibitors: 0.3 part
Spherical heat conductive filler (33 μm): 150 parts of
Sheet-like heat conductive filler (sheet diameter 30 μm, thickness 2 μm): 50 parts of
Wave-absorbing filler (particle size 4.5 μm): 100 parts of
The preparation method of the high-heat-conductivity antioxidant wave-absorbing silicon rubber composite material comprises the following steps:
(1) 6 parts of gamma- (methacryloyloxy) propyl trimethoxysilane (KH 570) is used for preparing an alcohol aqueous solution with a certain concentration, 200 parts of spherical heat conducting filler and 200 parts of flaky heat conducting filler are respectively treated at 100 ℃ for 50min and then taken out, and then the mixture is placed in a vacuum drying oven at 100 ℃ for 2h, so that the coupling agent and the filler are completely reacted to respectively obtain a modified spherical heat conducting filler and a modified flaky heat conducting filler:
(2) Dispersing 200 parts of wave-absorbing filler in 500ml of absolute ethyl alcohol, and carrying out ultrasonic oscillation on the mixed solution for 30 minutes to obtain a wave-absorbing filler mixed solution; 500 parts of deionized water and 16.5 parts of NaOH and 5 parts of NaNO 3 1 part of Na 3 PO 4 Mixing, stirring uniformly to obtain bluing liquid, finally dripping the bluing liquid after uniform stirring into carbonyl iron powder mixed liquid, and stirring for 30min at a stirring speed of 250r/min under the water bath condition of constant temperature of 50 ℃. After the reaction is finished, standing the system, pouring out the upper transparent solution, washing for 3 times by using absolute ethyl alcohol, drying in a drying box, and sieving to obtain a blue-treated wave-absorbing filler, namely a modified wave-absorbing filler;
(3) Mixing filler: mixing the fillers obtained in the steps (1) and (2) for 15 minutes by using a high-speed mixer according to the mass parts to obtain the heat-conducting wave-absorbing filler;
(4) Mixing the matrix with the filler: uniformly mixing vinyl silicone oil, hydrogen-containing silicone oil, a platinum catalyst, an inhibitor and the heat-conducting wave-absorbing filler in the step (3) according to the mass parts by using a vacuum deaerating machine at a rotating speed of 3000rpm, and deaerating for 20min to obtain a base material;
(5) And (3) vulcanization molding: pouring the base material in the step (4) into a pre-prepared forming mold for forming and shaping, and vulcanizing for 40min in a drying oven at 100 ℃ to obtain the heat-conducting wave-absorbing silicon rubber material.
Referring to fig. 6, fig. 6 is a graph showing the reflection loss of the composite material after salt spray test for 24 hours after carbonyl iron powder is treated by different processes, and the performance of the silicone rubber composite materials prepared in examples 1 to 5 and comparative examples 1 to 3 is tested, specifically, the thermal conductivity, reflection loss and hardness of the silicone rubber composite materials are tested, and the obtained experimental results are shown in the following table:
| thermal conductivity (W.m) -1 ·k -1 ) | Reflection loss (dB) | Hardness (shore A) | |
| Example 1 | 2.0 | -33.8 | 39 |
| Comparative example 1 | 2.0 | -16.2 | 32 |
| Example 2 | 1.6 | -36.8 | 40 |
| Comparative example 2 | 0.4 | -36.8 | 31 |
| Example 3 | 1.5 | -34.5 | 41 |
| Comparative example 3 | 1.5 | -48.5 | 40 |
| Example 4 | 2.7 | -24.7 | 38 |
| Example 5 | 2.2 | -33.8 | 38 |
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples merely represent a few embodiments of the present invention, which facilitate a specific and detailed understanding of the technical solutions of the present invention, but are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. It should be understood that, based on the technical solutions provided by the present invention, those skilled in the art may obtain technical solutions through logical analysis, reasoning or limited experiments, which are all within the scope of protection of the appended claims. The scope of the patent is therefore intended to be covered by the appended claims, and the description and drawings may be interpreted as illustrative of the contents of the claims.
Claims (7)
1. The high-heat-conductivity antioxidant wave-absorbing silicon rubber composite material is characterized by being prepared from the following raw materials in parts by weight: basic silicone oil: 100 parts of cross-linking agent: 2-6 parts of catalyst: 0.5-2 parts of inhibitor: 0.2 to 0.5 part of modified spherical heat conducting filler: 50-300 parts of modified flaky heat conducting filler: 20-300 parts of modified wave absorbing powder: 50-300 parts;
the modified spherical heat conducting filler is obtained by modifying spherical heat conducting filler by using a heat conducting filler modifier, wherein the spherical heat conducting filler is one of spherical graphite powder, spherical aluminum oxide and spherical aluminum nitride powder, and the particle size is 20-60 mu m;
the modified flaky heat conducting filler is obtained by modifying the heat conducting filler by using a heat conducting filler modifier, wherein the flaky heat conducting filler is flaky boron nitride, the diameter of the flaky boron nitride is 10-50 mu m, and the thickness of the flaky boron nitride is 8 nm-3 mu m;
the heat conducting filler modifier is a silane coupling agent, which is one or more of gamma-aminopropyl triethoxysilane, gamma-glycidol ether oxypropyl trimethoxysilane, gamma- (methacryloyloxy) propyl trimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane and isopropyl tri (dioctyl pyrophosphoryloxy) titanate; the mass ratio of the silane coupling agent to the spherical heat conducting filler is 1-3:100, and the mass ratio of the silane coupling agent to the flaky heat conducting filler is 1-3:100;
the modified wave-absorbing powder is obtained by modifying wave-absorbing filler by using a wave-absorbing filler modifier, wherein the wave-absorbing filler is one of carbonyl iron powder, ferrite, permalloy powder and ferrosilicon ferrite, the particle size is 2-80 mu m, and the wave-absorbing filler modifier is sodium hydroxide, sodium nitrite and trisodium phosphate.
2. The high-heat-conductivity antioxidant wave-absorbing silicon rubber composite material according to claim 1, wherein the base silicone oil is linear vinyl silicone oil, the vinyl content is 0.02mol/100g, and the viscosity at 25 ℃ is 500 mPa.s; the cross-linking agent is hydrogen-containing silicone oil, the hydrogen content is 0.5mol/100g, and the viscosity at 25 ℃ is 80 mPa.s.
3. The high thermal conductivity antioxidant wave absorbing silicon rubber composite according to claim 1, wherein the catalyst is a platinum catalyst which is one or more of an isopropanol solution of chloroplatinic acid, a platinum-1, 3-divinyl-1, 3-tetramethyldisiloxane complex, a platinum-vinyltrimethoxysilane complex and a platinum-vinyltriethoxysilane complex.
4. The high thermal conductivity and oxidation resistance wave absorbing silicon rubber composite material according to claim 1, wherein the inhibitor is one or more of 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3, 5-dimethyl-1-hexyn-3-ol, 1-ethynyl-1-cyclohexanol and 3-phenyl-1-butyn-3-ol.
5. A method for preparing the high-heat-conductivity antioxidant wave-absorbing silicon rubber composite material according to any one of claims 1 to 4, comprising the following steps:
(1) Pretreatment of filler: modifying the spherical heat conducting filler and the flaky heat conducting filler by using a heat conducting filler modifier to obtain modified spherical heat conducting powder and modified flaky heat conducting powder respectively; modifying the wave-absorbing filler by using a wave-absorbing filler modifier to obtain modified wave-absorbing powder;
(2) Mixing filler: mixing the modified filler in the step (1) for 10min by using a high-speed mixer to prepare the heat-conducting wave-absorbing filler;
(3) Mixing the matrix with the filler: uniformly mixing basic silicone oil, a cross-linking agent, a catalyst, an inhibitor and the heat conduction wave-absorbing filler obtained in the step (2) by using a vacuum deaerating machine at a rotating speed of 3000rpm, and deaerating for 15min to obtain a base material;
(4) And (3) vulcanization molding: pouring the base material in the step (3) into a pre-prepared forming mold for forming and shaping, and vulcanizing for 10-30 min in a drying oven at 100-140 ℃ to obtain the high-heat-conductivity antioxidant wave-absorbing silicon rubber composite material.
6. The method for preparing the high-heat-conductivity antioxidant wave-absorbing silicon rubber composite material according to claim 5, wherein the heat-conducting filler modifier in the step (1) is a silane coupling agent which is one or more of gamma-aminopropyl triethoxysilane, gamma-glycidoxypropyl trimethoxysilane, gamma- (methacryloyloxy) propyl trimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane and isopropyl tri (dioctyl pyrophosphoryl) titanate; the wave-absorbing filler modifier is one or more of sodium hydroxide, sodium nitrite and trisodium phosphate.
7. The method for preparing the high-heat-conductivity antioxidant wave-absorbing silicon rubber composite material according to claim 5, wherein the method is characterized in that,
the specific preparation method of the modified heat-conducting filler in the step (1) comprises the following steps:
diluting the silane coupling agent with an alcohol aqueous solution, adding the heat-conducting filler, treating for 20-120 min at 50-150 ℃, taking out, then placing in a vacuum drying oven at 50-150 ℃, and treating for 1-4 h to enable the silane coupling agent to react with the filler completely, thus obtaining the modified heat-conducting filler;
the specific preparation method of the modified wave-absorbing powder comprises the following steps:
(1) Dispersing the wave-absorbing filler in absolute ethyl alcohol, and carrying out ultrasonic oscillation on the mixed solution for 30 minutes;
(2) Mixing deionized water and a bluing agent and uniformly stirring to obtain a bluing liquid, then adding the bluing liquid into the carbonyl iron powder mixed liquid, and stirring for 30, 60 or 90min at a stirring speed of 250r/min under the water bath condition of constant temperature of 50 ℃;
(3) After the reaction is finished, the system is kept stand, the upper transparent solution is poured off, the system is washed for 3 times by absolute ethyl alcohol, and then dried in a drying box, and the carbonyl iron powder after bluing treatment, namely the modified wave-absorbing powder, is obtained through sieving.
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