CN115011125A - High-thermal-conductivity antioxidant wave-absorbing silicone rubber composite material and preparation method thereof - Google Patents
High-thermal-conductivity antioxidant wave-absorbing silicone rubber composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-thermal-conductivity antioxidant wave-absorbing silicone rubber composite material and a preparation method thereof, wherein the silicone 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 flaky 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 silicon rubber has high-efficiency wave-absorbing performance and excellent heat-conducting capability. The heat-conducting property is improved by adjusting the dosage of the coupling agent and compounding the heat-conducting fillers with different shapes and different scales, and the oxidation resistance and the corrosion resistance are improved by performing high-temperature bluing modification treatment on the wave-absorbing filler. The highest thermal conductivity can reach 2.7 W.m ‑1 ·k ‑1 The minimum Reflection Loss (RL) can reach-48.5 dB, and the hardness (Shore A) is less than 45. The heat-conducting wave-absorbing silicone rubber material disclosed by the invention has the advantages of good elasticity, simple preparation process, readily available raw materials, low cost, good processability and 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 anti-oxidation wave-absorbing silicone rubber composite material and a preparation method thereof.
Background
With the development of society, power electronic equipment is continuously developing towards large capacity, high integration and high power density, and the appearance of the equipment is gradually developing towards miniaturization and light weight. This will lead to the rapid accumulation of heat generated by the power electronic devices and the failure of effective discharge, which will seriously affect the performance and life of the electronic devices. Therefore, there is a need to solve the heat dissipation problem generated during the application of electronic devices and electrical energy devices. The heat conduction material is adopted to absorb and dissipate redundant heat on the equipment element, so that the overheating phenomenon of the electronic device in a narrow environment is avoided, the surface layer heat is uniformly diffused along the surface direction, and the accident of a point heat source is effectively avoided.
Meanwhile, electromagnetic radiation generated by modern electronic equipment during working not only seriously harms human health, but also can cause electromagnetic wave cross interference among electronic components with different frequencies in the equipment, thereby causing the electromagnetic compatibility problem and the damage of sensitive devices, and meanwhile, the electromagnetic radiation can cause the information leakage problem, and the problem needs to be solved by attaching wave-absorbing materials on the surfaces of the electronic components.
The electronic equipment has narrow internal space, and the heat conduction material occupies the gap space on the surface of the device, so that the wave-absorbing materials cannot be used in a superposed manner. Therefore, achieving both efficient heat dissipation and absorption of electromagnetic radiation in the confined space of electronic equipment has become a significant challenge for researchers. On the other hand, the flying speed of weapons such as airplanes and missiles is faster and faster in the use process, a large amount of heat is generated by the friction between special parts such as skin and the like and air, and in order to achieve the stealth effect, the wave-absorbing material is required to be high-temperature resistant and oxidation resistant, but actually, the wave-absorbing material cannot be used at high temperature for a long time due to the poor oxidation resistance of some wave-absorbing materials. In order to meet the market requirement and solve the problem, it is necessary to develop a new generation of heat absorption and conduction wave absorption composite material with high heat conductivity, excellent wave absorption capability, oxidation resistance and easy processing performance.
Disclosure of Invention
In view of the above, the invention aims to provide a high-thermal-conductivity antioxidant wave-absorbing silicone rubber composite material and a preparation method thereof.
The invention provides the following technical scheme:
a high-thermal-conductivity antioxidant wave-absorbing silicone rubber composite material is prepared from the following raw materials in parts by mass:
basic silicone oil: 100 portions of
A crosslinking agent: 2 to 6 portions of
Catalyst: 0.5 to 2 portions of
Inhibitor (B): 0.2 to 0.5 portion
Spherical heat-conducting filler: 50 to 300 parts
Flake heat-conducting filler: 20 to 300 portions of
Wave-absorbing filler: 50 to 300 parts
Preferably, the basic silicone oil is straight-chain vinyl silicone oil, the vinyl content is 0.02mol/100g, and the viscosity at 25 ℃ is 500mPa & s; the cross-linking agent is hydrogen-containing silicone oil, the hydrogen content is 0.5mol/100g, and the viscosity at 25 ℃ is 80 mPas.
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, 1, 3, 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 powder, spherical alumina and spherical aluminum nitride powder, and the particle size is 20-60 microns.
Preferably, the flaky heat conducting filler is flaky boron nitride, the diameter of each flaky heat conducting filler is 10-50 mu m, and the thickness of each flaky heat conducting filler is 8 nm-3 mu m.
Preferably, the wave-absorbing filler is one of carbonyl iron powder, ferrite, permalloy powder and iron-silicon-aluminum ferrite, and the particle size is 2-80 μm.
The invention also provides a preparation method of the high-thermal-conductivity antioxidant wave-absorbing silicone rubber composite material, which comprises the following steps:
(1) pretreatment of the filler: modifying the spherical heat-conducting filler and the flaky heat-conducting filler by using a heat-conducting filler modifier to respectively obtain modified spherical heat-conducting powder and modified flaky heat-conducting powder; modifying the wave-absorbing filler by using a wave-absorbing filler modifier to obtain modified wave-absorbing powder;
(2) and (3) mixing of fillers: mixing the modified filler obtained in the step (1) for 10min by using a high-speed mixer to prepare a heat-conducting wave-absorbing filler;
(3) mixing a matrix and a filler: uniformly mixing basic silicone oil, a cross-linking agent, a catalyst, an inhibitor and the heat-conducting wave-absorbing filler obtained in the step (2) by using a vacuum defoaming machine at the rotating speed of 3000rpm, and defoaming for 15min to obtain a base material;
(4) and (3) vulcanization molding: pouring the base material obtained in the step (3) into a pre-prepared forming die for forming and shaping, and vulcanizing in a drying oven at 100-140 ℃ for 10-30 min to obtain the heat-conducting wave-absorbing silicone rubber material.
Preferably, the thermally conductive filler modifier of step (1) is a silane coupling agent, which is one or more of gamma-aminopropyltriethoxysilane (KH550), gamma-glycidoxypropyltrimethoxysilane (KH560), gamma- (methacryloyloxy) propyltrimethoxysilane (KH570), N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane (KH792), and isopropyl tris (dioctylpyrophosphate) 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 is as follows: the mass ratio of the silane coupling agent to the heat-conducting filler is 1-3: 100, the silane coupling agent is diluted by an alcohol-water solution, the spherical heat-conducting filler or the flaky heat-conducting filler is added, the mixture is treated at 50-150 ℃ for 20-120 min and then taken out, the mixture is placed in a vacuum drying oven at 50-150 ℃ and treated for 1-4 h, and the coupling agent and the filler are reacted completely to obtain the modified spherical heat-conducting powder or the modified flaky heat-conducting powder.
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 ultrasonically oscillating the mixed solution for 30 minutes;
(2) mixing deionized water and a bluing agent, uniformly stirring to obtain a bluing liquid, then dropwise adding the bluing liquid into the carbonyl iron powder mixed liquid, and stirring at a stirring speed of 250r/min for 30, 60 or 90min under the condition of a water bath at a constant temperature of 50 ℃;
(3) and after the reaction is finished, standing the system, pouring out the upper transparent solution, cleaning for 3 times by using absolute ethyl alcohol, drying in a drying box, and sieving to obtain blued carbonyl iron powder, namely the modified wave-absorbing filler.
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 0.5-10 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-thermal-conductivity antioxidant wave-absorbing silicone rubber composite material and a preparation method thereof, and particularly comprises the following steps:
(1) the high-thermal-conductivity antioxidant wave-absorbing silicone rubber composite material takes liquid silicone oil as a matrix material to prepare a flexible silicone rubber matrix, has the advantages of low cost and simple preparation method, and has high-efficiency wave-absorbing performance and excellent heat-conducting capacity by mixing the wave-absorbing agent and the heat-conducting filler in the silicone rubber matrix, so that the problems of heat dissipation and electromagnetic wave absorption can be solved in a limited space;
(2) the wettability of the heat-conducting filler and the matrix is improved by adjusting the using amount of the coupling agent; the heat-conducting property is improved by the synergistic effect of the complex formulation of the heat-conducting fillers with different shapes and different scales, the spherical graphite micro powder with uniform particle size distribution is cooperated with the flaky boron nitride with larger specific surface area, a heat-conducting passage is easy to form in a silicon rubber matrix, the using amount of the heat-conducting filler can be obviously reduced, the density of the silicon rubber composite material can be further reduced, and the heat-conducting property is improved;
(3) the wave-absorbing filler is subjected to high-temperature bluing modification treatment, so that the dielectric constant can be reduced, and the impedance matching between the wave-absorbing material and a space medium is improved; the dispersity of the wave-absorbing filler is improved; the oxidation resistance and corrosion resistance of the magnetic wave absorbing agent under high temperature can be effectively improved; the prepared wave-absorbing heat-conducting composite material gasket has longer service life in high-temperature environment, marine corrosion environment and some extremely severe environments;
(4) the heat-conducting wave-absorbing silicone rubber composite material has good heat-conducting property and wave-absorbing property, good flexibility, large elasticity and shock-absorbing property, and the heat conductivity can reach 2.7 W.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 silicone rubber material disclosed by the invention is simple in preparation process, easy to obtain raw materials, low in cost, good in processability, suitable for large-scale popularization and application, wide in application prospect, and especially suitable for the fields of precision electronic equipment such as 5G communication equipment, artificial intelligence equipment, wireless energy transmission devices, microwave medical devices and new energy batteries.
Drawings
FIG. 1 is a flow chart of a preparation process of a high-thermal-conductivity anti-oxidation wave-absorbing silicone rubber composite material;
FIG. 2 is a scanning electron microscope image of spherical graphite powder;
FIG. 3 is a scanning electron micrograph of lamellar boron nitride;
FIG. 4 is a scanning electron microscope image of carbonyl iron powder;
FIG. 5 is a flow chart of a process for bluing carbonyl iron powder;
FIG. 6 is a graph of reflection loss of a composite material after 24 hours of salt spray tests on carbonyl iron powder treated by different processes.
Detailed Description
The invention will be further explained and illustrated with reference to specific examples.
Example 1
The high-thermal-conductivity antioxidant wave-absorbing silicone rubber composite material disclosed by embodiment 1 of the invention comprises the following raw materials in parts by weight:
basic silicone oil: 100 portions of
A crosslinking agent: 6 portions of
Catalyst: 1 part of
Inhibitor (B): 0.5 portion
Spherical heat conductive filler (particle diameter 33 μm): 150 portions of
Plate-like heat conductive filler (plate diameter 30 μm, thickness 2 μm): 50 portions of
Wave-absorbing filler (particle size 4.5 μm): 100 portions of
Referring to fig. 1, fig. 1 is a flow chart of a preparation process of the high thermal conductivity antioxidant wave-absorbing silicone rubber composite material, and as shown in the figure, the preparation method of the thermal conductivity wave-absorbing silicone rubber material comprises the following steps:
(1) preparing alcohol aqueous solution with a certain concentration by using 6 parts of gamma-aminopropyltriethoxysilane (KH550), treating 200 parts of spherical heat-conducting filler and 200 parts of flaky heat-conducting filler at 100 ℃ for 50min respectively, taking out, placing the spherical heat-conducting filler and the flaky heat-conducting filler in a vacuum drying oven at 100 ℃ for 2h, and completely reacting a silane coupling agent and the fillers to obtain modified spherical heat-conducting filler and modified flaky heat-conducting filler respectively, wherein the scanning electron microscope image of the spherical heat-conducting filler is shown in figure 2, and the scanning electron microscope image of the flaky heat-conducting filler is shown in figure 3;
(2) referring to fig. 4-5, fig. 4 is a scanning electron microscope image of carbonyl iron powder, fig. 5 is a flowchart of carbonyl iron powder modification treatment, as shown in the figure200 parts of wave-absorbing filler is dispersed in 500ml of absolute ethyl alcohol, and the mixed solution is subjected to ultrasonic oscillation 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 a bluing liquid; and finally, dropwise adding the uniformly stirred bluing liquid into the carbonyl iron powder mixed solution, and stirring for 30min at a stirring speed of 250r/min under the water bath condition of constant temperature of 50 ℃, wherein a scanning electron microscope image of the carbonyl iron powder is shown in fig. 3. After the reaction is finished, standing the system, pouring out the upper layer transparent solution, washing for 3 times by using absolute ethyl alcohol, drying in a drying oven, and sieving to obtain the wave-absorbing filler subjected to bluing treatment, namely the modified wave-absorbing filler;
(3) and (3) mixing the filler: adding the fillers obtained in the steps (1) and (2) into a high-speed mixer according to the mass parts, and mixing for 10min to obtain the heat-conducting wave-absorbing filler;
(4) mixing a matrix and a 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) by using a vacuum defoaming machine at the rotating speed of 3000rpm, and defoaming for 15min to obtain a base material;
(5) and (3) vulcanization molding: pouring the base material obtained in the step (4) into a pre-prepared forming die for forming and shaping, and vulcanizing in a drying oven at 120 ℃ for 20min to obtain the heat-conducting wave-absorbing silicone 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 portions of
A crosslinking agent: 6 portions of
Catalyst: 1 part of
Inhibitor (B): 0.5 portion
Spherical heat conductive filler (particle diameter 33 μm): 150 portions of
Plate-like heat conductive filler (plate diameter 30 μm, thickness 2 μm): 50 portions 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 6 parts of gamma-aminopropyltriethoxysilane (KH550), treating 200 parts of spherical heat-conducting filler and 200 parts of flaky heat-conducting filler at 100 ℃ for 50min respectively, taking out, then placing in a vacuum drying oven at 100 ℃ for treatment for 2h to ensure that a coupling agent completely reacts with the fillers, and obtaining the modified spherical heat-conducting filler and the modified flaky heat-conducting filler respectively;
(2) and (3) mixing the filler: mixing the filler obtained in the step (1) for 10min by using a high-speed mixer according to the mass parts to prepare a heat-conducting mixed filler;
(3) mixing a matrix and a filler: uniformly mixing the basic glycerol, the cross-linking agent, the catalyst, the inhibitor and the heat-conducting mixed filler in the step (2) in parts by mass at a rotating speed of 3000rpm by using a vacuum defoaming machine, and defoaming for 15min to obtain a base material;
(4) and (3) vulcanization molding: pouring the base material obtained in the step (3) into a pre-prepared forming die for forming and shaping, and vulcanizing in a drying oven at 120 ℃ for 20min to obtain the heat-conducting wave-absorbing silicone rubber material.
Example 2
The high-thermal-conductivity antioxidant wave-absorbing silicone rubber composite material disclosed by embodiment 2 of the invention comprises the following raw materials in parts by weight:
basic silicone oil: 100 portions of
A crosslinking agent: 6 portions of
Catalyst: 1 part of
Inhibitor (B): 0.3 part
Spherical heat conductive filler (particle diameter 33 μm): 50 portions of
Plate-like heat conductive filler (plate diameter 30 μm, thickness 2 μm): 90 portions of
Wave-absorbing filler (particle size 4.5 μm): 160 portions of
The preparation method of the high-thermal-conductivity anti-oxidation wave-absorbing silicone rubber composite material comprises the following steps:
(1) preparing alcohol aqueous solution with a certain concentration by using 5 parts of gamma-aminopropyltriethoxysilane (KH550), treating 200 parts of spherical heat-conducting filler and 200 parts of flaky heat-conducting filler at 100 ℃ for 50min respectively, taking out, then placing in a vacuum drying oven at 100 ℃ for treatment for 2h to ensure that a coupling agent completely reacts with the fillers to obtain modified spherical heat-conducting filler and modified flaky heat-conducting filler respectively;
(2) will be provided withDispersing 200 parts of wave-absorbing filler in 500ml of absolute ethyl alcohol, and ultrasonically oscillating 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 a bluing liquid; finally, dropwise adding the uniformly stirred bluing liquid into the carbonyl iron powder mixed liquid, and stirring for 60min at a stirring speed of 250r/min under the condition of a water bath at a constant temperature of 50 ℃; after the reaction is finished, standing the system, pouring out the upper layer transparent solution, washing for 3 times by using absolute ethyl alcohol, drying in a drying oven, and sieving to obtain the wave-absorbing filler subjected to bluing treatment, namely the modified wave-absorbing filler;
(3) and (3) mixing of fillers: mixing the fillers obtained in the steps (1) and (2) for 10min by using a high-speed mixer according to the mass parts to prepare the heat-conducting wave-absorbing filler;
(4) mixing a matrix and a filler: uniformly mixing the basic glycerol, the cross-linking agent, the catalyst, the inhibitor and the heat-conducting wave-absorbing filler in the step (3) in parts by mass at a rotating speed of 3000rpm by using a vacuum defoaming machine, and defoaming for 15min to obtain a base material;
(5) and (3) vulcanization molding: pouring the base material obtained in the step (4) into a pre-prepared forming die for forming and shaping, and vulcanizing in a drying oven at 120 ℃ for 20min to obtain the heat-conducting wave-absorbing silicone 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 portions of
A crosslinking agent: 6 portions of
Catalyst: 1 part of
Inhibitor (b): 0.3 part of
Spherical heat conductive filler (particle diameter 33 μm): 50 portions of
Wave-absorbing filler (particle size 4.5 μm): 160 portions of
A preparation method of a heat-conducting wave-absorbing silicon rubber material comprises the following steps:
(1) preparing an alcohol water solution with a certain concentration by using 5 parts of gamma-aminopropyltriethoxysilane (KH550), treating 200 parts of spherical heat-conducting filler at 100 ℃ for 50min, taking out, then placing in a vacuum drying oven at 100 ℃ for 2h, and completely reacting a coupling agent and the filler to obtain the modified spherical heat-conducting filler;
(2) dispersing 200 parts of wave-absorbing filler in 500ml of absolute ethyl alcohol, and ultrasonically oscillating 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 a bluing liquid, finally, dropwise adding the bluing liquid after stirring uniformly into the carbonyl iron powder mixed liquid, and stirring for 60min at a stirring speed of 250r/min under the condition of a water bath with a constant temperature of 50 ℃; after the reaction is finished, standing the system, pouring out the upper layer transparent solution, washing for 3 times by using absolute ethyl alcohol, drying in a drying oven, and sieving to obtain the wave-absorbing filler subjected to bluing treatment, namely the modified wave-absorbing filler;
(3) and (3) mixing the filler: mixing the fillers obtained in the steps (1) and (2) for 10min by using a high-speed mixer according to the mass parts to prepare the heat-conducting wave-absorbing filler;
(4) mixing a matrix and a 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) by using a vacuum defoaming machine at the rotating speed of 3000rpm, and defoaming for 15min to obtain a base material;
(5) and (3) vulcanization molding: pouring the base material obtained in the step (4) into a pre-prepared forming die for forming and shaping, and vulcanizing in a drying oven at 120 ℃ for 20min to obtain the heat-conducting wave-absorbing silicone rubber material.
Example 3
The high-thermal-conductivity antioxidant wave-absorbing silicone rubber composite material disclosed by the embodiment 3 of the invention comprises the following raw materials in parts by weight:
100 portions of basic silicone oil
A crosslinking agent: 5 portions of
Catalyst: 0.8 portion of
Inhibitor (b): 0.3 part
Spherical thermally conductive filler (33 μm): 120 portions of
Plate-like heat conductive filler (plate diameter 15 μm, thickness 1 μm): 30 portions of
Wave-absorbing filler (particle size 2.5 μm): 150 portions of
The preparation method of the high-thermal-conductivity anti-oxidation wave-absorbing silicone rubber composite material comprises the following steps:
(1) preparing an alcohol aqueous solution with a certain concentration by using 6 parts of gamma-aminopropyltriethoxysilane (KH550), treating 200 parts of spherical heat-conducting filler and 200 parts of flaky heat-conducting filler at 100 ℃ for 50min respectively, taking out, then placing in a vacuum drying oven at 100 ℃ for treatment for 2h to ensure that a coupling agent completely reacts with the fillers, and obtaining the modified spherical heat-conducting filler and the modified flaky heat-conducting filler respectively;
(2) dispersing 200 parts of wave-absorbing filler in 500ml of absolute ethyl alcohol, and ultrasonically oscillating 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 evenly to obtain a bluing liquid, finally, dropwise adding the bluing liquid stirred evenly into the carbonyl iron powder mixed liquid, and stirring for 30min at a stirring speed of 250r/min under the condition of a water bath at a constant temperature of 50 ℃. After the reaction is finished, standing the system, pouring out the upper layer transparent solution, cleaning for 3 times by using absolute ethyl alcohol, drying in a drying oven, and sieving to obtain the blued wave-absorbing filler, namely the modified wave-absorbing filler;
(3) and (3) mixing of fillers: mixing the fillers obtained in the steps (1) and (2) for 10min by using a high-speed mixer according to the mass parts to prepare the heat-conducting wave-absorbing filler;
(4) mixing a matrix and a 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) by using a vacuum defoaming machine at the rotating speed of 3000rpm, and defoaming for 15min to obtain the base material.
(5) And (3) vulcanization molding: pouring the base material obtained in the step (4) into a pre-prepared forming die for forming and shaping, and vulcanizing in a drying oven at 120 ℃ for 20min to obtain the heat-conducting wave-absorbing silicone 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 portions of
A crosslinking agent: 5 portions of
Catalyst: 0.8 portion of
Inhibitor (b): 0.3 part
Spherical thermally conductive filler (33 μm): 120 portions of
Plate-like heat conductive filler (plate diameter 15 μm, thickness 1 μm): 30 portions of
Wave-absorbing filler (particle size 2.5 μm): 150 portions 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 6 parts of gamma-aminopropyltriethoxysilane (KH550), treating 200 parts of spherical heat-conducting filler and 200 parts of flaky heat-conducting filler at 100 ℃ for 50min respectively, taking out, then placing in a vacuum drying oven at 100 ℃ for treatment for 2h to ensure that a coupling agent completely reacts with the fillers, and obtaining the modified spherical heat-conducting filler and the modified flaky heat-conducting filler respectively;
(2) putting 200 parts of wave-absorbing filler into acetone, mechanically stirring for 30min, ultrasonically treating for 15min, and vacuum drying at 80 ℃ for 4 h;
(3) and (3) mixing of fillers: mixing the fillers obtained in the steps (1) and (2) for 10min by using a high-speed mixer according to the mass parts to prepare the heat-conducting wave-absorbing filler;
(4) mixing a matrix and a 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) by using a vacuum defoaming machine at the rotating speed of 3000rpm, and defoaming for 15min to obtain a base material;
(5) and (3) vulcanization molding: pouring the base material obtained in the step (4) into a pre-prepared forming die for forming and shaping, and vulcanizing in a drying oven at 120 ℃ for 20min to obtain the heat-conducting wave-absorbing silicone rubber material.
Example 4
The high-thermal-conductivity antioxidant wave-absorbing silicone rubber composite material disclosed by embodiment 4 of the invention comprises the following raw materials in parts by weight:
basic silicone oil: 100 portions of
A crosslinking agent: 6 portions of
Catalyst: 1 part of
Inhibitor (B): 0.3 part
Spherical thermally conductive filler (33 μm): 50 portions of
Plate-like heat conductive filler (plate diameter 15 μm, thickness 1 μm): 150 portions of
Wave-absorbing filler (particle size 2.5 μm): 100 portions of
A preparation method of a heat-conducting wave-absorbing silicon rubber material comprises the following steps:
(1) preparing alcohol aqueous solution with a certain concentration by using 5 parts of gamma- (methacryloyloxy) propyl trimethoxy silane (KH570), treating 200 parts of spherical heat-conducting filler and 200 parts of flaky heat-conducting filler at 100 ℃ for 50min respectively, taking out, then placing in a vacuum drying oven at 100 ℃ for 2h, and completely reacting a coupling agent with the fillers to obtain modified spherical heat-conducting filler and modified flaky heat-conducting filler respectively;
(2) dispersing 200 parts of wave-absorbing filler in 500ml of absolute ethyl alcohol, and ultrasonically oscillating the mixed solution for 30 minutes to obtain a wave-absorbing filler mixed solution; 500 parts of deionized water, 16.5 parts of NaOH and 5 parts of NaNO 3 1 part of Na 3 PO 4 Mixing, stirring uniformly to obtain a bluing liquid, finally, dropwise adding the bluing liquid after stirring uniformly into the carbonyl iron powder mixed liquid, and stirring for 30min at a stirring speed of 250r/min under the condition of a water bath with a constant temperature of 50 ℃; after the reaction is finished, standing the system, pouring out the upper layer transparent solution, washing for 3 times by using absolute ethyl alcohol, drying in a drying oven, and sieving to obtain the wave-absorbing filler subjected to bluing treatment, namely the modified wave-absorbing filler;
(3) and (3) mixing of fillers: mixing the fillers obtained in the steps (1) and (2) for 10min by using a high-speed mixer according to the mass parts to prepare the heat-conducting wave-absorbing filler;
(4) mixing a matrix and a 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) by using a vacuum defoaming machine at the rotating speed of 3000rpm, and defoaming for 15min to obtain a base material;
(5) and (3) vulcanization molding: pouring the base material obtained in the step (4) into a pre-prepared forming die for forming and shaping, and vulcanizing in a drying oven at 100 ℃ for 40min to obtain the heat-conducting wave-absorbing silicone rubber material.
Example 5
The high-thermal-conductivity antioxidant wave-absorbing silicone rubber composite material disclosed by the embodiment 5 of the invention comprises the following raw materials in parts by weight:
basic silicone oil: 100 portions of
A crosslinking agent: 6 portions of
Catalyst: 1 part of
Inhibitor (B): 0.3 part
Spherical thermally conductive filler (33 μm): 150 portions of
Plate-like heat conductive filler (plate diameter 30 μm, thickness 2 μm): 50 portions of
Wave-absorbing filler (particle size 4.5 μm): 100 portions of
The preparation method of the high-thermal-conductivity antioxidant wave-absorbing silicone rubber composite material comprises the following steps:
(1) preparing alcohol aqueous solution with a certain concentration by using 6 parts of gamma- (methacryloyloxy) propyl trimethoxy silane (KH570), treating 200 parts of spherical heat-conducting filler and 200 parts of flaky heat-conducting filler for 50min at 100 ℃, taking out, then placing in a vacuum drying oven at 100 ℃, treating for 2h to ensure that a coupling agent completely reacts with the fillers, and respectively obtaining the modified spherical heat-conducting filler and the modified flaky heat-conducting filler:
(2) dispersing 200 parts of wave-absorbing filler in 500ml of absolute ethyl alcohol, and ultrasonically oscillating the mixed solution for 30 minutes to obtain a wave-absorbing filler mixed solution; 500 parts of deionized water, 16.5 parts of NaOH and 5 parts of NaNO 3 1 part of Na 3 PO 4 Mixing and stirring uniformly to obtain a bluing liquid, finally dripping the bluing liquid which is stirred uniformly into the carbonyl iron powder mixed liquid, and stirring for 30min at a stirring speed of 250r/min under the condition of a water bath with a constant temperature of 50 ℃. After the reaction is finished, standing the system, pouring out the upper layer transparent solution, washing for 3 times by using absolute ethyl alcohol, drying in a drying oven, and sieving to obtain the wave-absorbing filler subjected to bluing treatment, namely the modified wave-absorbing filler;
(3) and (3) mixing of fillers: mixing the fillers obtained in the steps (1) and (2) for 15min by using a high-speed mixer according to the mass parts to prepare the heat-conducting wave-absorbing filler;
(4) mixing a matrix and a 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) by using a vacuum defoaming machine at the rotating speed of 3000rpm, and defoaming for 20min to obtain a base material;
(5) and (3) vulcanization molding: pouring the base material obtained in the step (4) into a pre-prepared forming die for forming and shaping, and vulcanizing in a drying oven at 100 ℃ for 40min to obtain the heat-conducting wave-absorbing silicone rubber material.
Referring to fig. 6, fig. 6 is a graph of reflection loss of a composite material after a salt spray test for 24 hours on carbonyl iron powder 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, the reflection loss and the hardness of the silicone rubber composite materials are tested, and the obtained experimental result data 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 embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, so as to understand the technical solutions of the present invention specifically and in detail, but not to be understood as the limitation of the protection scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. It should be understood that the technical solutions provided by the present invention, which are obtained by logical analysis, reasoning or limited experiments, are within the scope of the appended claims. Therefore, the protection scope of the present patent shall be subject to the content of the appended claims, and the description and drawings can be used to explain the content of the claims.
Claims (10)
1. The high-thermal-conductivity antioxidant wave-absorbing silicone rubber composite material is characterized by being prepared from the following raw materials in parts by mass: basic silicone oil: 100 parts of a crosslinking agent: 2-6 parts of catalyst: 0.5-2 parts of inhibitor: 0.2-0.5 parts of spherical heat-conducting filler: 50-300 parts of flaky heat-conducting filler: 20-300 parts of wave-absorbing filler: 50-300 parts.
2. The high-thermal-conductivity antioxidant wave-absorbing silicone rubber composite material as claimed in claim 1, wherein the base silicone oil is straight-chain vinyl silicone oil, the vinyl content is 0.02mol/100g, and the viscosity at 25 ℃ is 500mPa · s; the cross-linking agent is hydrogen-containing silicone oil, the hydrogen content is 0.5mol/100g, and the viscosity at 25 ℃ is 80 mPas.
3. The silicone rubber composite material with high thermal conductivity, oxidation resistance and wave absorption as claimed in claim 1, wherein the catalyst is a platinum catalyst, and the catalyst is one or more of an isopropanol solution of chloroplatinic acid, a platinum-1, 3-divinyl-1, 1, 3, 3-tetramethyldisiloxane complex, a platinum-vinyltrimethoxysilane complex and a platinum-vinyltriethoxysilane complex.
4. The high-thermal-conductivity antioxidant wave-absorbing silicone rubber composite material as claimed in 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. The high-thermal-conductivity antioxidant wave-absorbing silicone rubber composite material as claimed in claim 1, 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 μm.
6. The high-thermal-conductivity antioxidant wave-absorbing silicone rubber composite material as claimed in claim 1, wherein the flaky thermal conductive filler is flaky boron nitride, the diameter of the flaky thermal conductive filler is 10-50 μm, and the thickness of the flaky thermal conductive filler is 8 nm-3 μm.
7. The high-thermal-conductivity antioxidant wave-absorbing silicone rubber composite material as claimed in claim 1, wherein the wave-absorbing filler is one of carbonyl iron powder, ferrite, permalloy powder and sendust ferrite, and the particle size is 2-80 μm.
8. A preparation method of the high-thermal-conductivity antioxidant wave-absorbing silicone rubber composite material as claimed in any one of claims 1 to 7, comprising the following steps:
(1) pretreatment of the filler: modifying the spherical heat-conducting filler and the flaky heat-conducting filler by using a heat-conducting filler modifier to respectively obtain modified spherical heat-conducting powder and modified flaky heat-conducting powder; modifying the wave-absorbing filler by using a wave-absorbing filler modifier to obtain modified wave-absorbing powder;
(2) and (3) mixing of fillers: mixing the modified filler obtained in the step (1) for 10min by using a high-speed mixer to prepare a heat-conducting wave-absorbing filler;
(3) mixing a matrix and a filler: uniformly mixing basic silicone oil, a cross-linking agent, a catalyst, an inhibitor and the heat-conducting wave-absorbing filler obtained in the step (2) by using a vacuum defoaming machine at the rotating speed of 3000rpm, and defoaming for 15min to obtain a base material;
(4) and (3) vulcanization molding: pouring the base material obtained in the step (3) into a pre-prepared forming die for forming and shaping, and vulcanizing in a drying oven at 100-140 ℃ for 10-30 min to obtain the high-thermal-conductivity anti-oxidation wave-absorbing silicone rubber composite material.
9. The preparation method of the high-thermal-conductivity antioxidant wave-absorbing silicone rubber composite material according to claim 8, wherein the thermal-conductive filler modifier in the step (1) is a silane coupling agent which is one or more of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma- (methacryloyloxy) propyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane and isopropyl tri (dioctyl pyrophosphato-oxy) titanate; the wave-absorbing filler modifier is one or more of sodium hydroxide, sodium nitrite and trisodium phosphate.
10. The preparation method of the silicone rubber composite material with high thermal conductivity, oxidation resistance and wave absorption according to claim 8,
the specific preparation method of the modified heat-conducting filler in the step (1) comprises the following steps:
diluting a silane coupling agent with an alcohol water solution, adding a heat-conducting filler, treating at 50-150 ℃ for 20-120 min, taking out, then placing in a vacuum drying oven at 50-150 ℃ for 1-4 h, and completely reacting the silane coupling agent with the filler to obtain a modified heat-conducting filler;
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 ultrasonically oscillating the mixed solution for 30 minutes;
(2) mixing deionized water and a bluing agent, uniformly stirring to obtain a bluing liquid, then dropwise adding the bluing liquid into the carbonyl iron powder mixed liquid, and stirring at a stirring speed of 250r/min for 30, 60 or 90min under the condition of a water bath at a constant temperature of 50 ℃;
(3) and after the reaction is finished, standing the system, pouring out the upper layer transparent solution, cleaning for 3 times by using absolute ethyl alcohol, drying in a drying oven, and sieving to obtain blued carbonyl iron powder, namely the modified wave-absorbing filler.
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