CN108976802B - Preparation method of heat-conducting insulating silicone grease - Google Patents
Preparation method of heat-conducting insulating silicone grease Download PDFInfo
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Abstract
The invention discloses a preparation method of heat-conducting insulating silicone grease, and belongs to the technical field of thermal interface materials. Weighing the following components in parts by weight: 70-80 parts of silicone oil, 10-12 parts of epoxidized soybean oil, 5-8 parts of catalyst, 10-18 parts of pretreated heat-conducting powder and 15-25 parts of modified carbon nano tube; mixing silicone oil and epoxidized soybean oil in a stirrer, adding a catalyst into the stirrer, pretreating the heat-conducting powder and the modified carbon nano tubes, and stirring and mixing for 30-60 min at the temperature of 45-65 ℃ and the rotating speed of 300-400 r/min to obtain the heat-conducting insulating silicone grease. The heat-conducting insulating silicone grease prepared by the technical scheme of the invention has the characteristics of excellent heat-conducting property and insulating property, and has wide prospect in the development of the thermal interface material industry.
Description
Technical Field
The invention discloses a preparation method of heat-conducting insulating silicone grease, and belongs to the technical field of thermal interface materials.
Background
The heat-conducting insulating silicone grease is formed by compounding metal oxide with excellent heat conductivity and insulating property and organic silica, has excellent heat conductivity and good electrical insulating property, is widely applied to contact surfaces between heating bodies and heat dissipation facilities in various electronic products and electrical equipment, and has the functions of heat transfer media and the properties of moisture prevention, dust prevention, corrosion prevention, shock prevention and the like. The heat-conducting insulating silicone grease is prepared from high-temperature-resistant silicone oil, high-heat-conducting insulating filler, functional auxiliary agents and the like. The high-heat-conductivity insulating paste is developed for heat dissipation and insulation of a switching power supply, a temperature controller, a power amplifying tube and a radiating fin with high requirements on heat conduction and temperature resistance, reduces the contact thermal resistance of a solid interface, improves interface heat exchange, and is applicable to the temperature range of-60 ℃ to +300 ℃.
The heat transfer surface between the electronic component and the heat dissipation plate or the radiator is not smooth, looks like a smooth chip surface and a radiator surface for dissipating heat of the nest temperature chip, and actually has a plurality of tiny pits and tiny impurities which can not be seen by naked eyes. When the surfaces of the two are in contact, the gaps or gaps between the surfaces are all air. Air has poor heat conduction capability and high thermal resistance, and other substances are required to be filled to reduce the thermal resistance and improve the performance of the radiator. Thus, heat transfer medium has grown in response to the fact that heat transfer grease is the most common heat transfer medium of our day, and is mainly used for filling the gap between the two contact surfaces to increase the contact area between the heat generating source and the heat sink.
With the continuous progress of LED manufacturing and packaging technology, the power of LEDs is increasing. The input power of the high-power LED is generally more than 1W, the chip area is 1mm multiplied by 1mm, and the heat flux density is 100W/cm2Above, the heat dissipation requirement is very high. The heat is transferred from the chip to the external environment and passes through a plurality of interfaces, and the gaps between the interfaces and the warping of the substrate influence the local heat dissipation of the key to form interface thermal resistance. Common interface materials include heat-conducting glue, heat-conducting silicone grease and heat-conducting film. The heat conducting gasket is easy to use, but cannot be applied to occasions with high heat dissipation requirements due to large thickness and large heat resistance. The heat-conducting silicone grease is filled between the accessories and the radiator, air in the middle is exhausted, the contact surface can be fully moistened, a very low thermal resistance interface is formed, and the quick 'fever' of a heating large household such as a CPU (central processing unit), a high-power LED and the like is facilitated. The heat-conducting silica gel and the heat-conducting silicone grease are filling media for intermediate heat transfer, have similar appearances and are different in that: the heat-conducting silica gel is a pouring sealant, the main component of the heat-conducting silica gel is silicon dioxide, the heat-conducting silica gel has very good viscosity, and the heat-conducting silica gel can be solidified at normal temperature; and the heat-conducting silicone grease can not be solidified and has no viscosity. Therefore, the heat conductive silicone is mainly used in the heat sink without the buckle or the fixing device, and the silicone grease is mainly used in the heat sink fixed by the buckleIn a heat dissipating device.
The traditional heat-conducting insulating silicone grease has the problem that the insulating property and the heat-conducting property are poor, so that the ideal effect cannot be achieved in the using process, and therefore, the problem that how to improve the insulating property and the heat-conducting property of the traditional heat-conducting insulating silicone grease cannot be further improved is solved.
Disclosure of Invention
The invention mainly solves the technical problems that: aiming at the defect that the insulating property and the heat conducting property of the traditional heat conducting insulating silicone grease can not be further improved, the preparation method of the heat conducting insulating silicone grease is provided.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of magnetic-sensitive rubber comprises the following specific preparation steps:
a preparation method of heat-conducting insulating silicone grease comprises the following specific preparation steps:
(1) mixing a carbon nano tube and absolute ethyl alcohol according to a mass ratio of 1: 300-1: 320, mixing, performing ultrasonic dispersion, adjusting the pH value to 8-10, stirring for reaction to obtain a carbon nano tube mixture, adjusting the pH value of the carbon nano tube mixture to be neutral, performing suction filtration, washing and drying to obtain a pretreated carbon nano tube;
(2) mixing the pretreated carbon nano tube with an ethanol water solution according to the mass ratio of 1: 300-1: 320, adding ammonia water with the mass 2-4 times that of the pretreated carbon nano tubes, performing ultrasonic dispersion, dripping an ethyl orthosilicate mixture with the mass 4-6 times that of the pretreated carbon nano tubes while performing ultrasonic dispersion, and stirring and mixing to obtain a pretreated carbon nano tube mixture; mixing the pretreated carbon nanotube mixture and the silane coupling agent mixture according to the mass ratio of 300: 1-300: 4, mixing, stirring and mixing, performing suction filtration, and washing to obtain a pre-modified carbon nano tube;
(3) mixing the pre-modified carbon nano tube with water according to the mass ratio of 1: 200-1: 400, adjusting the pH value to 4.0-4.8, adding hydroxyl silicone oil with the mass of 0.4-0.5 times that of the pre-modified carbon nano tube, stirring and mixing, aging, filtering, washing and drying to obtain a modified carbon nano tube blank;
(4) mixing the modified carbon nanotube blank and water according to the mass ratio of 1: 100-1: 200, adding aminosilane with the mass of 0.3-0.5 times of that of the modified carbon nanotube blank, stirring and mixing, cooling, adjusting the pH value to 6.5-6.8, filtering and drying to obtain a modified carbon nanotube;
(5) weighing the following components in parts by weight: 70-80 parts of silicone oil, 10-12 parts of epoxidized soybean oil, 5-8 parts of catalyst, 10-18 parts of pretreated heat-conducting powder and 15-25 parts of modified carbon nano tube; mixing silicone oil and epoxy soybean oil, adding a catalyst, pretreating the heat-conducting powder and the modified carbon nano tube, and stirring and mixing to obtain the heat-conducting insulating silicone grease.
The carbon nano tube in the step (1) has an average tube diameter of 10-30 nm and a length of 0.5-100 μm.
The ethanol aqueous solution in the step (2) is prepared by mixing absolute ethanol and water according to a volume ratio of 4: 1, mixing to obtain an ethanol water solution.
The tetraethoxysilane mixture in the step (2) is prepared by mixing tetraethoxysilane and absolute ethyl alcohol according to the mass ratio of 1: 8-1: 10 to obtain an ethyl orthosilicate mixture.
The silane coupling agent mixture in the step (2) is prepared by mixing absolute ethyl alcohol and acetic acid according to a mass ratio of 1: 1, adding a silane coupling agent KH-570 with the mass of 0.4-0.6 time that of the absolute ethyl alcohol, and stirring and mixing to obtain a silane coupling agent mixture.
The catalyst in the step (5) is any one of nano magnesium oxide or nano zinc oxide.
The heat conducting powder is pretreated by mixing nano silicon nitride and nano aluminum nitride according to the mass ratio of 1: 1-2: 1, adding ethanol with the mass of 4-6 times of that of the nano silicon nitride and a silane coupling agent KH-570 with the mass of 0.3-0.4 time of that of the nano silicon nitride, adjusting the pH to 9.8-10.0, stirring and mixing, performing ultrasonic dispersion, and drying to obtain the pretreated heat-conducting powder.
The invention has the beneficial effects that:
(1) according to the invention, the modified carbon nano tube is added in the process of preparing the heat-conducting insulating silicone grease, firstly, the surface of the carbon nano tube is grafted with silicon dioxide after being modified, and after the modified carbon nano tube is added into a product, the silicon dioxide can be uniformly distributed in the product under the action of a silane coupling agent, so that the modified carbon nano tube is uniformly distributed in the product, further the heat-conducting property of the product is improved, in addition, the agglomeration of the carbon nano tube can be prevented due to the existence of the silicon dioxide, further the heat-conducting property of the product is further improved, secondly, after the modification treatment of the grafted silicon dioxide in the modified carbon nano tube, the hydroxyl on the surface of the silicon dioxide and hydroxyl silicone oil are dehydrated and condensed to form new combination, so that the hydrophobicity of the silicon dioxide is improved;
(2) according to the invention, epoxidized soybean oil and a catalyst are added in the process of preparing the heat-conducting insulating silicone grease, on one hand, hydroxy silicone oil in the modified carbon nano tubes is aminated in subsequent treatment and can form crosslinking with the epoxidized soybean oil under the action of the catalyst, so that a certain crosslinking network can be formed in the product, and further the heat conductivity of the product is improved.
Detailed Description
Mixing nano silicon nitride and nano aluminum nitride according to the mass ratio of 1: 1-2: 1, mixing the materials in a beaker, adding ethanol which is 4-6 times of the mass of the nano silicon nitride and a silane coupling agent KH-570 which is 0.3-0.4 times of the mass of the nano silicon nitride into the beaker, adjusting the pH of the materials in the beaker to 9.8-10.0 by using a sodium hydroxide solution with the mass fraction of 5-10%, stirring and mixing the materials for 3-4 hours at the temperature of 55-65 ℃ and the rotating speed of 300-400 r/min, ultrasonically dispersing the materials for 15-20 minutes at the frequency of 50-55 kHz, drying the materials in the beaker for 3-4 hours at the temperature of 120-130 ℃ to obtain pretreated heat-conducting powder; mixing a carbon nano tube and absolute ethyl alcohol according to a mass ratio of 1: 300-1: 320, performing ultrasonic dispersion for 20-30 min under the condition that the frequency is 50-55 kHz, adjusting the pH value of a mixture of the carbon nano tube and absolute ethyl alcohol to 8-10 by using a potassium hydroxide solution with the mass fraction of 15-18%, stirring and reacting for 8-9 h under the conditions that the temperature is 85-90 ℃ and the rotating speed is 300-400 r/min to obtain a carbon nano tube mixture, adjusting the pH value of the carbon nano tube mixture to be neutral by using hydrochloric acid with the mass fraction of 5-8%, performing suction filtration to obtain a filter cake, washing the filter cake for 5-10 times by using water, and performing vacuum drying for 4-5 h under the condition that the temperature is 70-80 ℃ to obtain a pretreated carbon nano tube; mixing the pretreated carbon nano tube with an ethanol water solution according to the mass ratio of 1: 300-1: 320, adding 25-28% ammonia water with the mass fraction being 2-4 times of the mass of the pretreated carbon nano tube into the conical flask, ultrasonically dispersing for 60-70 min under the condition of the frequency being 45-55 kHz, dripping an ethyl orthosilicate mixture with the mass being 4-6 times of the mass of the pretreated carbon nano tube into the conical flask under the condition of 5-12 mL/min under the condition of ultrasonic dispersion, and stirring and mixing for 15-18 h under the conditions that the temperature is 50-60 ℃ and the rotating speed is 300-400 r/min after dripping is finished to obtain a pretreated carbon nano tube mixture; mixing the pretreated carbon nanotube mixture and the silane coupling agent mixture according to the mass ratio of 300: 1-300: 4, mixing, stirring and mixing for 6-7 h at the temperature of 45-55 ℃ and the rotating speed of 300-350 r/min, performing suction filtration to obtain a pre-modified carbon nanotube blank, and washing the pre-modified carbon nanotube blank for 5-8 times by using water to obtain a pre-modified carbon nanotube; mixing the pre-modified carbon nano tube with water according to the mass ratio of 1: 200-1: 400, mixing the materials in a flask, adjusting the pH of the materials in the flask to 4.0-4.8 by using acetic acid with the mass fraction of 12-25%, adding hydroxyl silicone oil with the mass of 0.4-0.5 times that of the pre-modified carbon nano tube into the flask, stirring and mixing for 30-40 min under the conditions that the temperature is 45-65 ℃ and the rotating speed is 300-400 r/min, aging the materials in the flask for 1-3 h at room temperature, filtering to obtain filter residues, washing the filter residues for 8-12 times by using water, and drying for 30-40 min at the temperature of 60-70 ℃ to obtain a modified carbon nano tube blank; mixing the modified carbon nanotube blank and water according to the mass ratio of 1: 100-1: 200, adding aminosilane with the mass 0.3-0.5 times of that of the modified carbon nanotube blank into a three-neck flask, stirring and mixing for 4-5 hours at the temperature of 80-90 ℃ and the rotating speed of 260-320 r/min, cooling the temperature of the materials in the three-neck flask to 40-45 ℃, adjusting the pH value of the materials in the three-neck flask to 6.5-6.8 by using acetic acid with the mass fraction of 12-20%, filtering to obtain a pretreated modified carbon nanotube, and drying the pretreated modified carbon nanotube for 1-2 hours at the temperature of 60-70 ℃ in vacuum to obtain the modified carbon nanotube; weighing the following components in parts by weight: 70-80 parts of silicone oil, 10-12 parts of epoxidized soybean oil, 5-8 parts of catalyst, 10-18 parts of pretreated heat-conducting powder and 15-25 parts of modified carbon nano tube; mixing silicone oil and epoxidized soybean oil in a stirrer, adding a catalyst into the stirrer, pretreating the heat-conducting powder and the modified carbon nano tubes, and stirring and mixing for 30-60 min at the temperature of 45-65 ℃ and the rotating speed of 300-400 r/min to obtain the heat-conducting insulating silicone grease. The carbon nanotube has an average diameter of 10 to 30nm and a length of 0.5 to 100 μm. The ethanol aqueous solution is prepared by mixing absolute ethanol and water according to a volume ratio of 4: 1, mixing to obtain an ethanol water solution. The tetraethoxysilane mixture is prepared by mixing tetraethoxysilane and absolute ethyl alcohol according to the mass ratio of 1: 8-1: 10 to obtain an ethyl orthosilicate mixture. The silane coupling agent mixture is prepared by mixing anhydrous ethanol and acetic acid according to a mass ratio of 1: 1, adding a silane coupling agent KH-570 with the mass of 0.4-0.6 time that of the absolute ethyl alcohol, and stirring and mixing to obtain a silane coupling agent mixture. The catalyst is any one of nano magnesium oxide or nano zinc oxide.
Example 1
Mixing nano silicon nitride and nano aluminum nitride according to the mass ratio of 2: 1, mixing the materials in a beaker, adding ethanol with the mass 6 times that of the nano silicon nitride and a silane coupling agent KH-570 with the mass 0.4 time that of the nano silicon nitride into the beaker, adjusting the pH of the materials in the beaker to 10.0 by using a sodium hydroxide solution with the mass fraction of 10%, stirring and mixing the materials for 4 hours at the temperature of 65 ℃ and the rotating speed of 400r/min, performing ultrasonic dispersion for 20 minutes at the frequency of 55kHz, and drying the materials in the beaker for 4 hours at the temperature of 130 ℃ to obtain pretreated heat-conducting powder; mixing a carbon nano tube and absolute ethyl alcohol according to a mass ratio of 1: 320, mixing, performing ultrasonic dispersion for 30min under the condition of 55kHz, adjusting the pH of the mixture of the carbon nano tube and the absolute ethyl alcohol to 10 by using a potassium hydroxide solution with the mass fraction of 18%, stirring and reacting for 9h under the conditions of 90 ℃ and 400r/min to obtain a carbon nano tube mixture, adjusting the pH of the carbon nano tube mixture to be neutral by using hydrochloric acid with the mass fraction of 8%, performing suction filtration to obtain a filter cake, washing the filter cake for 10 times by using water, and performing vacuum drying for 5h under the condition of 80 ℃ to obtain the pretreated carbon nano tube; mixing the pretreated carbon nano tube with an ethanol water solution according to the mass ratio of 1: 320, mixing the mixture in a conical flask, adding ammonia water with the mass fraction of 28 percent, the mass of which is 4 times that of the pretreated carbon nano tube, into the conical flask, ultrasonically dispersing the mixture for 70min under the condition of 55kHz, dripping an ethyl orthosilicate mixture with the mass of 6 times that of the pretreated carbon nano tube into the conical flask under the condition of 12mL/min under the condition of ultrasonic dispersion, and stirring and mixing the mixture for 18h under the conditions of 60 ℃ and 400r/min of rotation speed after finishing dripping to obtain a pretreated carbon nano tube mixture; mixing the pretreated carbon nanotube mixture and the silane coupling agent mixture according to the mass ratio of 300: 4, mixing, stirring and mixing for 7 hours at the temperature of 55 ℃ and the rotating speed of 350r/min, performing suction filtration to obtain a pre-modified carbon nanotube blank, and washing the pre-modified carbon nanotube blank for 8 times by using water to obtain a pre-modified carbon nanotube; mixing the pre-modified carbon nano tube with water according to the mass ratio of 1: 400, mixing the mixture in a flask, adjusting the pH of the material in the flask to 4.8 by using 25% acetic acid, adding hydroxyl silicone oil with the mass of 0.5 time of that of the pre-modified carbon nano tube into the flask, stirring and mixing the mixture for 40min at the temperature of 65 ℃ and the rotating speed of 400r/min, aging the material in the flask for 3h at room temperature, filtering the mixture to obtain filter residue, washing the filter residue for 12 times by using water, and drying the filter residue for 40min at the temperature of 70 ℃ to obtain a modified carbon nano tube blank; mixing the modified carbon nanotube blank and water according to the mass ratio of 1: 200, adding aminosilane with the mass 0.5 time of that of the modified carbon nanotube blank into the three-neck flask, stirring and mixing for 5 hours at the temperature of 90 ℃ and the rotating speed of 320r/min, cooling the materials in the three-neck flask to 45 ℃, adjusting the pH value of the materials in the three-neck flask to 6.8 by using acetic acid with the mass fraction of 20%, filtering to obtain a pretreated modified carbon nanotube, and drying the pretreated modified carbon nanotube for 2 hours at the temperature of 70 ℃ in vacuum to obtain the modified carbon nanotube; weighing the following components in parts by weight: 80 parts of silicone oil, 12 parts of epoxidized soybean oil, 8 parts of catalyst, 18 parts of pretreated heat-conducting powder and 25 parts of modified carbon nano tube; mixing silicone oil and epoxy soybean oil in a stirrer, adding a catalyst into the stirrer, pretreating the heat-conducting powder and the modified carbon nano tubes, and stirring and mixing for 60min at the temperature of 65 ℃ and the rotating speed of 400r/min to obtain the heat-conducting insulating silicone grease. The carbon nano tube has an average tube diameter of 30nm and a length of 100 mu m. The ethanol aqueous solution is prepared by mixing absolute ethanol and water according to a volume ratio of 4: 1, mixing to obtain an ethanol water solution. The tetraethoxysilane mixture is prepared by mixing tetraethoxysilane and absolute ethyl alcohol according to the mass ratio of 1: 10 to obtain an ethyl orthosilicate mixture. The silane coupling agent mixture is prepared by mixing anhydrous ethanol and acetic acid according to a mass ratio of 1: 1, adding a silane coupling agent KH-570 with the mass of 0.6 time that of the absolute ethyl alcohol, and stirring and mixing to obtain a silane coupling agent mixture. The catalyst is nano magnesium oxide.
Example 2
Mixing nano silicon nitride and nano aluminum nitride according to the mass ratio of 2: 1, mixing the materials in a beaker, adding ethanol with the mass 6 times that of the nano silicon nitride and a silane coupling agent KH-570 with the mass 0.4 time that of the nano silicon nitride into the beaker, adjusting the pH of the materials in the beaker to 10.0 by using a sodium hydroxide solution with the mass fraction of 10%, stirring and mixing the materials for 4 hours at the temperature of 65 ℃ and the rotating speed of 400r/min, performing ultrasonic dispersion for 20 minutes at the frequency of 55kHz, and drying the materials in the beaker for 4 hours at the temperature of 130 ℃ to obtain pretreated heat-conducting powder; mixing a carbon nano tube and absolute ethyl alcohol according to a mass ratio of 1: 320, mixing, performing ultrasonic dispersion for 30min under the condition of 55kHz, adjusting the pH of the mixture of the carbon nano tube and the absolute ethyl alcohol to 10 by using a potassium hydroxide solution with the mass fraction of 18%, stirring and reacting for 9h under the conditions of 90 ℃ and 400r/min to obtain a carbon nano tube mixture, adjusting the pH of the carbon nano tube mixture to be neutral by using hydrochloric acid with the mass fraction of 8%, performing suction filtration to obtain a filter cake, washing the filter cake for 10 times by using water, and performing vacuum drying for 5h under the condition of 80 ℃ to obtain the pretreated carbon nano tube; mixing the pretreated carbon nano tube with an ethanol water solution according to the mass ratio of 1: 320, mixing the mixture in a conical flask, adding ammonia water with the mass fraction of 28 percent, the mass of which is 4 times that of the pretreated carbon nano tube, into the conical flask, ultrasonically dispersing the mixture for 70min under the condition of 55kHz, dripping an ethyl orthosilicate mixture with the mass of 6 times that of the pretreated carbon nano tube into the conical flask under the condition of 12mL/min under the condition of ultrasonic dispersion, and stirring and mixing the mixture for 18h under the conditions of 60 ℃ and 400r/min of rotation speed after finishing dripping to obtain a pretreated carbon nano tube mixture; mixing the pretreated carbon nanotube mixture and the silane coupling agent mixture according to the mass ratio of 300: 4, mixing, stirring and mixing for 7 hours at the temperature of 55 ℃ and the rotating speed of 350r/min, performing suction filtration to obtain a pre-modified carbon nanotube blank, and washing the pre-modified carbon nanotube blank for 8 times by using water to obtain a pre-modified carbon nanotube; mixing the pre-modified carbon nano tube with water according to the mass ratio of 1: 400, mixing the mixture in a flask, adjusting the pH of the material in the flask to 4.8 by using 25% acetic acid, adding hydroxyl silicone oil with the mass of 0.5 time of that of the pre-modified carbon nano tube into the flask, stirring and mixing the mixture for 40min at the temperature of 65 ℃ and the rotating speed of 400r/min, aging the material in the flask for 3h at room temperature, filtering the mixture to obtain filter residue, washing the filter residue for 12 times by using water, and drying the filter residue for 40min at the temperature of 70 ℃ to obtain the modified carbon nano tube; weighing the following components in parts by weight: 80 parts of silicone oil, 12 parts of epoxidized soybean oil, 8 parts of catalyst, 18 parts of pretreated heat-conducting powder and 25 parts of modified carbon nano tube; mixing silicone oil and epoxy soybean oil in a stirrer, adding a catalyst into the stirrer, pretreating the heat-conducting powder and the modified carbon nano tubes, and stirring and mixing for 60min at the temperature of 65 ℃ and the rotating speed of 400r/min to obtain the heat-conducting insulating silicone grease. The carbon nano tube has an average tube diameter of 30nm and a length of 100 mu m. The ethanol aqueous solution is prepared by mixing absolute ethanol and water according to a volume ratio of 4: 1, mixing to obtain an ethanol water solution. The tetraethoxysilane mixture is prepared by mixing tetraethoxysilane and absolute ethyl alcohol according to the mass ratio of 1: 10 to obtain an ethyl orthosilicate mixture. The silane coupling agent mixture is prepared by mixing anhydrous ethanol and acetic acid according to a mass ratio of 1: 1, adding a silane coupling agent KH-570 with the mass of 0.6 time that of the absolute ethyl alcohol, and stirring and mixing to obtain a silane coupling agent mixture. The catalyst is nano magnesium oxide.
Example 3
Mixing nano silicon nitride and nano aluminum nitride according to the mass ratio of 2: 1, mixing the materials in a beaker, adding ethanol with the mass 6 times that of the nano silicon nitride and a silane coupling agent KH-570 with the mass 0.4 time that of the nano silicon nitride into the beaker, adjusting the pH of the materials in the beaker to 10.0 by using a sodium hydroxide solution with the mass fraction of 10%, stirring and mixing the materials for 4 hours at the temperature of 65 ℃ and the rotating speed of 400r/min, performing ultrasonic dispersion for 20 minutes at the frequency of 55kHz, and drying the materials in the beaker for 4 hours at the temperature of 130 ℃ to obtain pretreated heat-conducting powder; mixing a carbon nano tube and absolute ethyl alcohol according to a mass ratio of 1: 320, mixing, performing ultrasonic dispersion for 30min under the condition of 55kHz, adjusting the pH of the mixture of the carbon nano tube and the absolute ethyl alcohol to 10 by using a potassium hydroxide solution with the mass fraction of 18%, stirring and reacting for 9h under the conditions of 90 ℃ and 400r/min to obtain a carbon nano tube mixture, adjusting the pH of the carbon nano tube mixture to be neutral by using hydrochloric acid with the mass fraction of 8%, performing suction filtration to obtain a filter cake, washing the filter cake for 10 times by using water, and performing vacuum drying for 5h under the condition of 80 ℃ to obtain the pretreated carbon nano tube; mixing the pretreated carbon nano tube with an ethanol water solution according to the mass ratio of 1: 320, mixing the mixture in a conical flask, adding ammonia water with the mass fraction of 28 percent, the mass of which is 4 times that of the pretreated carbon nano tube, into the conical flask, ultrasonically dispersing the mixture for 70min under the condition of 55kHz, dripping an ethyl orthosilicate mixture with the mass of 6 times that of the pretreated carbon nano tube into the conical flask under the condition of 12mL/min under the condition of ultrasonic dispersion, and stirring and mixing the mixture for 18h under the conditions of 60 ℃ and 400r/min of rotation speed after finishing dripping to obtain a pretreated carbon nano tube mixture; mixing the pretreated carbon nanotube mixture and the silane coupling agent mixture according to the mass ratio of 300: 4, mixing, stirring and mixing for 7 hours at the temperature of 55 ℃ and the rotating speed of 350r/min, performing suction filtration to obtain a pre-modified carbon nanotube blank, and washing the pre-modified carbon nanotube blank for 8 times by using water to obtain a pre-modified carbon nanotube; mixing the pre-modified carbon nano tube with water according to the mass ratio of 1: 400, mixing the mixture in a flask, adjusting the pH of the material in the flask to 4.8 by using 25% acetic acid, adding hydroxyl silicone oil with the mass of 0.5 time of that of the pre-modified carbon nano tube into the flask, stirring and mixing the mixture for 40min at the temperature of 65 ℃ and the rotating speed of 400r/min, aging the material in the flask for 3h at room temperature, filtering the mixture to obtain filter residue, washing the filter residue for 12 times by using water, and drying the filter residue for 40min at the temperature of 70 ℃ to obtain a modified carbon nano tube blank; mixing the modified carbon nanotube blank and water according to the mass ratio of 1: 200, adding aminosilane with the mass 0.5 time of that of the modified carbon nanotube blank into the three-neck flask, stirring and mixing for 5 hours at the temperature of 90 ℃ and the rotating speed of 320r/min, cooling the materials in the three-neck flask to 45 ℃, adjusting the pH value of the materials in the three-neck flask to 6.8 by using acetic acid with the mass fraction of 20%, filtering to obtain a pretreated modified carbon nanotube, and drying the pretreated modified carbon nanotube for 2 hours at the temperature of 70 ℃ in vacuum to obtain the modified carbon nanotube; weighing the following components in parts by weight: 80 parts of silicone oil, 8 parts of catalyst, 18 parts of pretreated heat-conducting powder and 25 parts of modified carbon nano tube; and putting the silicon oil into a stirrer, adding a catalyst into the stirrer, pretreating the heat-conducting powder and the modified carbon nano tubes, and stirring and mixing for 60min at the temperature of 65 ℃ and the rotating speed of 400r/min to obtain the heat-conducting insulating silicon grease. The carbon nano tube has an average tube diameter of 30nm and a length of 100 mu m. The ethanol aqueous solution is prepared by mixing absolute ethanol and water according to a volume ratio of 4: 1, mixing to obtain an ethanol water solution. The tetraethoxysilane mixture is prepared by mixing tetraethoxysilane and absolute ethyl alcohol according to the mass ratio of 1: 10 to obtain an ethyl orthosilicate mixture. The silane coupling agent mixture is prepared by mixing anhydrous ethanol and acetic acid according to a mass ratio of 1: 1, adding a silane coupling agent KH-570 with the mass of 0.6 time that of the absolute ethyl alcohol, and stirring and mixing to obtain a silane coupling agent mixture. The catalyst is nano magnesium oxide.
Example 4
Mixing nano silicon nitride and nano aluminum nitride according to the mass ratio of 2: 1, mixing the materials in a beaker, adding ethanol with the mass 6 times that of the nano silicon nitride and a silane coupling agent KH-570 with the mass 0.4 time that of the nano silicon nitride into the beaker, adjusting the pH of the materials in the beaker to 10.0 by using a sodium hydroxide solution with the mass fraction of 10%, stirring and mixing the materials for 4 hours at the temperature of 65 ℃ and the rotating speed of 400r/min, performing ultrasonic dispersion for 20 minutes at the frequency of 55kHz, and drying the materials in the beaker for 4 hours at the temperature of 130 ℃ to obtain pretreated heat-conducting powder; mixing a carbon nano tube and absolute ethyl alcohol according to a mass ratio of 1: 320, mixing, performing ultrasonic dispersion for 30min under the condition of 55kHz, adjusting the pH of the mixture of the carbon nano tube and the absolute ethyl alcohol to 10 by using a potassium hydroxide solution with the mass fraction of 18%, stirring and reacting for 9h under the conditions of 90 ℃ and 400r/min to obtain a carbon nano tube mixture, adjusting the pH of the carbon nano tube mixture to be neutral by using hydrochloric acid with the mass fraction of 8%, performing suction filtration to obtain a filter cake, washing the filter cake for 10 times by using water, and performing vacuum drying for 5h under the condition of 80 ℃ to obtain the pretreated carbon nano tube; mixing the pretreated carbon nano tube with an ethanol water solution according to the mass ratio of 1: 320, mixing the mixture in a conical flask, adding ammonia water with the mass fraction of 28 percent, the mass of which is 4 times that of the pretreated carbon nano tube, into the conical flask, ultrasonically dispersing the mixture for 70min under the condition of 55kHz, dripping an ethyl orthosilicate mixture with the mass of 6 times that of the pretreated carbon nano tube into the conical flask under the condition of 12mL/min under the condition of ultrasonic dispersion, and stirring and mixing the mixture for 18h under the conditions of 60 ℃ and 400r/min of rotation speed after finishing dripping to obtain a pretreated carbon nano tube mixture; mixing the pretreated carbon nanotube mixture and the silane coupling agent mixture according to the mass ratio of 300: 4, mixing, stirring and mixing for 7 hours at the temperature of 55 ℃ and the rotating speed of 350r/min, performing suction filtration to obtain a pre-modified carbon nanotube blank, and washing the pre-modified carbon nanotube blank for 8 times by using water to obtain a pre-modified carbon nanotube; mixing the pre-modified carbon nano tube with water according to the mass ratio of 1: 400, mixing the mixture in a flask, adjusting the pH of the material in the flask to 4.8 by using 25% acetic acid, adding hydroxyl silicone oil with the mass of 0.5 time of that of the pre-modified carbon nano tube into the flask, stirring and mixing the mixture for 40min at the temperature of 65 ℃ and the rotating speed of 400r/min, aging the material in the flask for 3h at room temperature, filtering the mixture to obtain filter residue, washing the filter residue for 12 times by using water, and drying the filter residue for 40min at the temperature of 70 ℃ to obtain a modified carbon nano tube blank; mixing the modified carbon nanotube blank and water according to the mass ratio of 1: 200, adding aminosilane with the mass 0.5 time of that of the modified carbon nanotube blank into the three-neck flask, stirring and mixing for 5 hours at the temperature of 90 ℃ and the rotating speed of 320r/min, cooling the materials in the three-neck flask to 45 ℃, adjusting the pH value of the materials in the three-neck flask to 6.8 by using acetic acid with the mass fraction of 20%, filtering to obtain a pretreated modified carbon nanotube, and drying the pretreated modified carbon nanotube for 2 hours at the temperature of 70 ℃ in vacuum to obtain the modified carbon nanotube; weighing the following components in parts by weight: 80 parts of silicone oil, 12 parts of epoxidized soybean oil, 18 parts of pretreated heat-conducting powder and 25 parts of modified carbon nano tubes; mixing silicone oil and epoxy soybean oil in a stirrer, pretreating the heat-conducting powder and the modified carbon nano tube, and stirring and mixing for 60min at the temperature of 65 ℃ and the rotating speed of 400r/min to obtain the heat-conducting insulating silicone grease. The carbon nano tube has an average tube diameter of 30nm and a length of 100 mu m. The ethanol aqueous solution is prepared by mixing absolute ethanol and water according to a volume ratio of 4: 1, mixing to obtain an ethanol water solution. The tetraethoxysilane mixture is prepared by mixing tetraethoxysilane and absolute ethyl alcohol according to the mass ratio of 1: 10 to obtain an ethyl orthosilicate mixture. The silane coupling agent mixture is prepared by mixing anhydrous ethanol and acetic acid according to a mass ratio of 1: 1, adding a silane coupling agent KH-570 with the mass of 0.6 time that of the absolute ethyl alcohol, and stirring and mixing to obtain a silane coupling agent mixture.
Comparative example: heat conductive and insulating silicone grease manufactured by Shanghai certain science and technology materials manufacturing Limited.
The heat-conducting insulating silicone grease obtained in examples 1 to 4 and the comparative product were subjected to performance testing, the specific testing method was as follows:
thermal conductivity: the test piece was measured by a thermal constant analyzer (transient hot wire method) according to GB/T10294 standard.
Volume resistivity: and (4) according to the GB/T1410 standard, a high-impedance meter is adopted to measure and detect the test piece.
Specific detection results are shown in table 1:
TABLE 1 detection results of properties of thermally conductive and insulating silicone grease
| Detecting items | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example |
| Thermal conductivity/W.m-1·Ｋ-1 | 3.98 | 3.65 | 2.77 | 2.03 | 1.16 |
| Volume resistivity/Ω · cm | 9.13×1016 | 8.90×1016 | 6.27×1016 | 3.84×1016 | 1.89×1016 |
As can be seen from the detection results in Table 1, the heat-conducting insulating silicone grease prepared by the technical scheme of the invention has the characteristics of excellent heat-conducting property and insulating property, and has a wide prospect in the development of the thermal interface material industry.
Claims (7)
1. A preparation method of heat-conducting insulating silicone grease is characterized by comprising the following specific preparation steps:
(1) mixing a carbon nano tube and absolute ethyl alcohol according to a mass ratio of 1: 300-1: 320, mixing, performing ultrasonic dispersion, adjusting the pH value to 8-10, stirring for reaction to obtain a carbon nano tube mixture, adjusting the pH value of the carbon nano tube mixture to be neutral, performing suction filtration, washing and drying to obtain a pretreated carbon nano tube;
(2) mixing the pretreated carbon nano tube with an ethanol water solution according to the mass ratio of 1: 300-1: 320, adding ammonia water with the mass 2-4 times that of the pretreated carbon nano tubes, performing ultrasonic dispersion, dripping an ethyl orthosilicate mixture with the mass 4-6 times that of the pretreated carbon nano tubes while performing ultrasonic dispersion, and stirring and mixing to obtain a pretreated carbon nano tube mixture; mixing the pretreated carbon nanotube mixture and the silane coupling agent mixture according to the mass ratio of 300: 1-300: 4, mixing, stirring and mixing, performing suction filtration, and washing to obtain a pre-modified carbon nano tube;
(3) mixing the pre-modified carbon nano tube with water according to the mass ratio of 1: 200-1: 400, adjusting the pH value to 4.0-4.8, adding hydroxyl silicone oil with the mass of 0.4-0.5 times that of the pre-modified carbon nano tube, stirring and mixing, aging, filtering, washing and drying to obtain a modified carbon nano tube blank;
(4) mixing the modified carbon nanotube blank and water according to the mass ratio of 1: 100-1: 200, adding aminosilane with the mass of 0.3-0.5 times of that of the modified carbon nanotube blank, stirring and mixing, cooling, adjusting the pH value to 6.5-6.8, filtering and drying to obtain a modified carbon nanotube;
(5) weighing the following components in parts by weight: 70-80 parts of silicone oil, 10-12 parts of epoxidized soybean oil, 5-8 parts of catalyst, 10-18 parts of pretreated heat-conducting powder and 15-25 parts of modified carbon nano tube; mixing silicone oil and epoxy soybean oil, adding a catalyst, pretreating the heat-conducting powder and the modified carbon nano tube, and stirring and mixing to obtain the heat-conducting insulating silicone grease.
2. The method for preparing the heat-conducting insulating silicone grease as claimed in claim 1, wherein: the carbon nano tube in the step (1) has an average tube diameter of 10-30 nm and a length of 0.5-100 μm.
3. The method for preparing the heat-conducting insulating silicone grease as claimed in claim 1, wherein: the ethanol aqueous solution in the step (2) is prepared by mixing absolute ethanol and water according to a volume ratio of 4: 1, mixing to obtain an ethanol water solution.
4. The method for preparing the heat-conducting insulating silicone grease as claimed in claim 1, wherein: the tetraethoxysilane mixture in the step (2) is prepared by mixing tetraethoxysilane and absolute ethyl alcohol according to the mass ratio of 1: 8-1: 10 to obtain an ethyl orthosilicate mixture.
5. The method for preparing the heat-conducting insulating silicone grease as claimed in claim 1, wherein: the silane coupling agent mixture in the step (2) is prepared by mixing absolute ethyl alcohol and acetic acid according to a mass ratio of 1: 1, adding a silane coupling agent KH-570 with the mass of 0.4-0.6 time that of the absolute ethyl alcohol, and stirring and mixing to obtain a silane coupling agent mixture.
6. The method for preparing the heat-conducting insulating silicone grease as claimed in claim 1, wherein: the catalyst in the step (5) is any one of nano magnesium oxide or nano zinc oxide.
7. The method for preparing the heat-conducting insulating silicone grease as claimed in claim 1, wherein: the heat conducting powder is pretreated by mixing nano silicon nitride and nano aluminum nitride according to the mass ratio of 1: 1-2: 1, adding ethanol with the mass of 4-6 times of that of the nano silicon nitride and a silane coupling agent KH-570 with the mass of 0.3-0.4 time of that of the nano silicon nitride, adjusting the pH to 9.8-10.0, stirring and mixing, performing ultrasonic dispersion, and drying to obtain the pretreated heat-conducting powder.
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