CN112280307A - Preparation method of mixed double-coated boron nitride/graphene insulating and heat-conducting silicone grease - Google Patents
Preparation method of mixed double-coated boron nitride/graphene insulating and heat-conducting silicone grease Download PDFInfo
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Abstract
The invention relates to a preparation method of mixed double-coated boron nitride/graphene insulating and heat-conducting silicone grease, which comprises the steps of firstly adding boron nitride into a solvent, and stripping and dispersing the boron nitride by adopting ultrasonic-assisted high-speed shearing and stirring to prepare a large-particle boron nitride nanosheet dispersion liquid; adding part of the dispersion liquid into a grinding machine, and stripping and dispersing the dispersion liquid in a telecentric ball milling mode to prepare a small-particle boron nitride nanosheet dispersion liquid with a proper length-diameter ratio; adding alcohol and an organic solvent into deionized water while stirring, adding zinc nitrate and phenol, heating, and carrying out reduced pressure distillation to obtain a zinc carbolate/phenol mixed solution; and then adjusting the pH value, filtering, cleaning, drying and grinding the mixture after the reaction is finished, and uniformly mixing the mixture with organic silicone to obtain the zinc oxide-phenolic resin mixed double-coated boron nitride/graphene insulating heat-conducting silicone grease. The heat-conducting silicone grease prepared by the invention has excellent heat-conducting property, and the preparation method is simple, has strong controllability and is suitable for large-scale production.
Description
Technical Field
The invention belongs to the field of nanometer preparation, and particularly relates to a preparation method of mixed double-coated boron nitride/graphene insulating and heat-conducting silicone grease.
Background
With the continuous improvement of the integration level of electronic circuits, the working current density generated during the circuit operation is continuously increased, and with the continuous development of the technology, the electronic products are also increasingly developed in the aspects of densification and miniaturization. This leads to a large amount of thermal aggregation in highly integrated electronic chips, which places higher demands on the heat dissipation performance of dense high-power electronic components. Meanwhile, the electronic products also put high demands on the product insulation.
As graphene is published in 2004, it exhibits various excellent mechanical, optical and electrical properties, attracting the attention of scientists. Among them, graphene exhibits excellent unsurpassed performance in the field of heat conduction, and is suitable for heat dissipation materials, but since graphene also has excellent conductivity, the application range of graphene in electronic components is limited. The boron nitride sheet layer is a graphene-like material, and attracts people's attention because the boron nitride sheet layer is a hexagonal two-dimensional honeycomb lattice structure formed by sp2 hybridization like graphene. The boron nitride sheet material has excellent heat conducting performance and a large forbidden band width, so that the boron nitride sheet material has excellent insulating performance. The boron nitride lamellar material is applied to the heat-conducting silicone grease, so that the insulating heat-conducting silicone grease can be prepared, but the heat-conducting property of the insulating heat-conducting silicone grease still cannot meet the requirements of people. The reason is that the boron nitride sheets are not well overlapped, a good heat conduction path is not constructed, and interaction between the boron nitride sheets and a substrate interface hinders propagation of phonons, so that improvement of heat conduction performance is further limited.
In order to improve the heat-conducting property, on one hand, the particle size of the boron nitride nanosheets is regulated and controlled, the two boron nitride nanosheets with different particle sizes are compounded, so that the boron nitride nanosheets can be in full contact with each other to construct a heat-conducting path, and meanwhile, the efficiency of the heat-conducting path is improved by introducing a small amount of graphene, the content of the graphene is controlled, so that the heat-conducting path is not successfully constructed, and the insulating property of the heat-conducting silicone grease is not influenced. On the other hand, by adopting a mode of mixing and double-coating zinc oxide and phenolic resin, the interface effect of boron nitride and a matrix is reduced, the phonon propagation efficiency is improved, and the conductivity of graphene is further reduced. The zinc oxide-phenolic resin mixed double-coated boron nitride/graphene insulation heat-conducting silicone grease prepared by the invention has excellent heat-conducting property, and the preparation method provided by the invention is simple, strong in controllability and suitable for large-scale production.
Disclosure of Invention
The invention aims to provide a method for preparing insulating heat-conducting silicone grease by mixing zinc oxide/phenolic resin and double-coated boron nitride/graphene, aiming at the defect of low heat-conducting property of the existing insulating heat-conducting silicone grease.
The method for preparing the zinc oxide/phenolic resin mixed double-coated boron nitride/graphene insulating and heat-conducting silicone grease provided by the invention comprises the following steps: weighing boron nitride, a solvent and a dispersing agent, firstly adding the boron nitride into the solvent, and stripping and dispersing the boron nitride by adopting ultrasonic-assisted high-speed shearing and stirring to prepare a large-particle boron nitride nanosheet dispersion liquid; adding part of large-particle boron nitride nanosheet dispersion liquid into a grinding machine, stripping and dispersing the large-particle boron nitride nanosheet dispersion liquid in a telecentric ball milling mode, and reducing the particle size of the large-particle boron nitride nanosheet dispersion liquid through shearing to prepare small-particle boron nitride nanosheet dispersion liquid; weighing phenol, zinc nitrate, alcohol, an organic solvent and deionized water, adding the alcohol and the organic solvent into the deionized water while stirring, then adding the zinc nitrate and the phenol into the deionized water, heating the mixture to a certain temperature for reaction for a period of time, and carrying out reduced pressure distillation to obtain a zinc carbolate/phenol mixed solution; and then adjusting the pH value to 3-5, reacting for a period of time, and then filtering, cleaning, drying and grinding the mixture. And uniformly mixing the boron nitride/graphene insulating and heat conducting silicone grease with zinc oxide-phenolic resin mixed double coating.
The method comprises the following specific steps:
1) the preparation method comprises the steps of accurately weighing boron nitride, a solvent and a dispersing agent according to a formula, firstly adding the boron nitride into the solvent, and stripping and dispersing the boron nitride by adopting ultrasonic-assisted high-speed shearing and stirring to prepare the large-particle boron nitride nanosheet dispersion liquid. Wherein the mass ratio of the boron nitride to the solvent is 1: 1-1000; the mass ratio of the boron nitride to the dispersant is 1: 0.01-10; the solvent is any one or a mixture of more of N-methyl pyrrolidone, deionized water, ethanol, isopropanol and dimethylformamide; the dispersing agent is any one or a mixture of more of BYK220, BYK204, BYK102, BYK203, BYK192, BYK130, BYK110 and BYK 180; the ultrasonic power is 1000-8000W; adopting a Fluke FA25 high-shear dispersion emulsifying machine for high-speed shear dispersion, wherein the rotating speed is 5000-30000 r/min, and the processing time is 0.5-10 h; the average particle size of the large-particle boron nitride nanosheet dispersion is 5-10 microns;
2) adding part of the large-particle boron nitride nanosheet dispersion prepared in the step 1) into a grinding machine, and stripping and dispersing the large-particle boron nitride nanosheet dispersion in a telecentric ball milling mode to prepare the boron nitride nanosheet dispersion with a proper length-diameter ratio. Wherein, the telecentric ball milling dispersion adopts zirconia balls with the diameter of 0.05 to 0.2 micron as grinding media, the rotating speed is 500 to 8000 revolutions per minute, and the processing time is 0.5 to 10 hours; the boron nitride nanosheet dispersion with a proper length-diameter ratio has an average particle size of 0.7-5 microns and a length-diameter ratio of 50-800;
3) accurately weighing phenol, zinc nitrate, alcohol, an organic solvent and deionized water according to a formula, firstly adding the alcohol and the organic solvent into the deionized water, and stirring to form a uniformly mixed solution; and then adding zinc nitrate into the mixed solution, heating to a certain temperature (30-100 ℃) under the condition of stirring, slowly dripping phenol into the mixed solution, reacting for a period of time (0.5-10 hours) in the presence of a condensation pipe, and then carrying out reduced pressure distillation to obtain the zinc carbolate/phenol mixed solution. Wherein the alcohol is one or mixture of ethanol, isopropanol, butanol and octanol; the organic solvent is one or a mixture of diethyl ether, acetone, dichloromethane, petroleum ether, pentane and tetrahydrofuran; the mass ratio of the phenol to the zinc nitrate is 1: 0.1-50; the mass ratio of the phenol to the alcohol is 1: 1-500; the mass ratio of the alcohol to the organic solvent is 1: 0.1-10; the mass ratio of the alcohol to the deionized water is 1: 0.1-10;
4) uniformly mixing the boron nitride nanosheet dispersion liquid prepared in the step 1) and the step 2), adding a certain amount of graphene into the mixture, and performing ultrasonic treatment to uniformly disperse the graphene. Fully mixing the boron nitride/graphene dispersion liquid with the zinc carbolate/phenol mixed solution prepared in the step 3), adding a certain amount of formaldehyde, adjusting the pH value of the solution to 8-12 by using sodium hydroxide, and reacting at a certain temperature (30-100 ℃) for a certain time (1-24 hours) to prepare the boron nitride/graphene dispersion liquid double-coated by zinc oxide and phenolic aldehyde prepolymer. Wherein the mass ratio of the small-particle boron nitride nanosheet dispersion liquid to the large-particle boron nitride nanosheet dispersion liquid is 1: 0.01-100; the mass ratio of the graphene to the boron nitride nanosheet dispersion liquid is 1: 10-10000; the mass ratio of the boron nitride nanosheet dispersion liquid to the zinc carbolate/phenol mixed solution is 1: 0.01-100; the mass ratio of the formaldehyde to the zinc carbolate/phenol mixed solution is 1: 10-10000;
5) adding dilute sulfuric acid into the zinc oxide and phenolic aldehyde prepolymer double-coated boron nitride/graphene dispersion liquid prepared in the step 4), adjusting the pH value of the solution to 3-5, stirring and reacting for a period of time (0.5-10 h) at a certain temperature (30-100 ℃), filtering, cleaning and drying to obtain phenolic resin-zinc oxide mixed double-coated powder boron nitride/graphene powder. And (3) uniformly mixing the boron nitride/graphene insulating and heat conducting silicone grease with organic silicone to obtain the mixed double-coated boron nitride/graphene insulating and heat conducting silicone grease. Wherein the organic silicone is one or a mixture of more than two of dimethyl silicone oil, methyl toluene silicone oil, vinyl silicone oil, fluorine hydroxyl silicone oil, long-chain alkyl silicone oil or other modified silicone oil, and the viscosity range is 50-20000 cps; the mass ratio of the phenolic resin-zinc oxide mixed double-coated boron nitride/graphene powder to the silicone grease is 1: 0.01-10.
According to the invention, on one hand, two boron nitride nanosheets with different particle sizes are compounded by regulating the particle size and the length-diameter ratio of the boron nitride nanosheets, so that the boron nitride nanosheets can be in full contact with each other, and a heat conduction path is constructed; meanwhile, a small amount of graphene is introduced, the heat conduction path efficiency is improved, and meanwhile, the electric conduction path is not successfully constructed by controlling the content of the graphene, and the insulating property of the heat conduction silicone grease is not influenced. On the other hand, by adopting a mode of mixing and double-coating zinc oxide and phenolic resin, the interface effect of boron nitride and a matrix is reduced, the phonon propagation efficiency is improved, and the conductivity of graphene is further reduced. The zinc oxide-phenolic resin mixed double-coated boron nitride/graphene insulation heat-conducting silicone grease prepared by the invention has excellent heat-conducting property, and the preparation method provided by the invention is simple, strong in controllability and suitable for large-scale production.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 is an SEM image of a phenolic resin-zinc oxide mixed double-coated powder boron nitride/graphene powder of a product in example 1 of the present invention;
FIG. 2 is a graph showing the comparison of thermal conductivity between conventional commercially available thermal grease and the samples of the examples of the present invention.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
The first embodiment is as follows:
weighing boron nitride, a solvent and a dispersant (the solvent is N-methyl pyrrolidone, the dispersant is BYK204, the mass ratio of the boron nitride to the solvent is 1:100, and the mass ratio of the boron nitride to the dispersant is 1: 0.2), firstly adding the boron nitride into the solvent, and stripping and dispersing the boron nitride by ultrasonic (power is 3000W) assisted high-speed shearing stirring (rotating speed is 10000 r/min) (time is 3 h) to prepare the large-particle boron nitride nanosheet dispersion liquid (average particle size is 5 microns). And adding part of the prepared large-particle boron nitride nanosheet dispersion liquid into a grinding machine, stripping and dispersing the large-particle boron nitride nanosheet dispersion liquid in a telecentric ball milling mode (grinding media are zirconia balls with the diameter of 0.1 micrometer; the rotating speed is 2000 rpm, the processing time is 4 hours), and reducing the particle size of the large-particle boron nitride nanosheet dispersion liquid through shearing to prepare the boron nitride nanosheet dispersion liquid with the proper length-diameter ratio (the average particle size is 0.7 micrometer, and the length-diameter ratio is 50). Weighing phenol, zinc nitrate, alcohol, an organic solvent and deionized water (the alcohol is ethanol, the organic solvent is acetone, the mass ratio of the phenol to the zinc nitrate is 1:1, the mass ratio of the phenol to the alcohol is 1:50, the mass ratio of the alcohol to the organic solvent is 1:1, and the mass ratio of the alcohol to the deionized water is 1: 0.5), firstly adding the alcohol and the organic solvent into the deionized water, and stirring to form a uniformly mixed solution; then adding zinc nitrate into the mixed solution, heating to a certain temperature (8 ℃) under the condition of stirring, slowly dripping phenol into the mixed solution, reacting for a period of time (2 h) under the condition of a condenser pipe, and then carrying out reduced pressure distillation to obtain the zinc carbolate/phenol mixed solution. Uniformly mixing the prepared boron nitride nanosheet dispersion liquid with the large particle size and the small particle size (the mass ratio of the boron nitride nanosheet dispersion liquid with the small particle size to the boron nitride nanosheet dispersion liquid with the large particle size is 1: 1), then adding a certain amount of graphene (the mass ratio of the graphene to the boron nitride nanosheet dispersion liquid is 1: 500) into the mixture, and performing ultrasonic treatment to uniformly disperse the graphene and the boron nitride nanosheet dispersion liquid. The boron nitride/graphene double-coated phenolic aldehyde prepolymer dispersion liquid is fully mixed with a zinc carbolate/phenol mixed solution (the mass ratio of the boron nitride nanosheet dispersion liquid to the zinc carbolate/phenol mixed solution is 1: 1), then a certain amount of formaldehyde (the mass ratio of the formaldehyde to the zinc carbolate/phenol mixed solution is 1: 100) is added into the mixed solution, the pH value of the solution is adjusted to 10 through sodium hydroxide, and then the mixed solution is reacted at a certain temperature (90 ℃) for a certain time (4 hours) to prepare the zinc oxide and phenolic aldehyde prepolymer double-coated boron nitride/graphene dispersion liquid. Adjusting the pH value of zinc oxide and boron nitride/graphene dispersion liquid double-coated by the phenolic aldehyde prepolymer to 5 by using dilute sulfuric acid, stirring and reacting for a period of time (2 hours) at a certain temperature (80 ℃), filtering, cleaning and drying to obtain the phenolic resin-zinc oxide mixed double-coated powder boron nitride/graphene powder. The boron nitride/graphene insulating and heat conducting silicone grease is uniformly mixed with organic silicone (the organic silicone is dimethyl silicone oil, the viscosity range is 3000cps, the mass ratio of the phenolic resin-zinc oxide mixed double-coated boron nitride/graphene powder to the silicone grease is 1: 0.1), and then the mixed double-coated boron nitride/graphene insulating and heat conducting silicone grease is obtained.
Example two:
weighing boron nitride, a solvent and a dispersant (the solvent is isopropanol, the dispersant is BYK130, the mass ratio of the boron nitride to the solvent is 1:200, and the mass ratio of the boron nitride to the dispersant is 1: 0.3), firstly adding the boron nitride into the solvent, and carrying out stripping dispersion (the time is 2 h) on the boron nitride by using ultrasonic (the power is 5000W) assisted high-speed shearing stirring (the rotating speed is 20000 revolutions per minute), thus preparing the large-particle boron nitride nanosheet dispersion liquid (the average particle size is 8 microns). And adding part of the prepared large-particle boron nitride nanosheet dispersion liquid into a grinding machine, stripping and dispersing the large-particle boron nitride nanosheet dispersion liquid in a telecentric ball milling mode (grinding media are zirconia balls with the diameter of 0.05 micrometer; the rotating speed is 1800 rpm, the processing time is 5 hours), and reducing the particle size of the large-particle boron nitride nanosheet dispersion liquid through shearing to prepare the boron nitride nanosheet dispersion liquid with the proper length-diameter ratio (the average particle size is 2 micrometers, and the length-diameter ratio is 200). Weighing phenol, zinc nitrate, alcohol, an organic solvent and deionized water (the alcohol is isopropanol, the organic solvent is tetrahydrofuran, the mass ratio of the phenol to the zinc nitrate is 1:0.5, the mass ratio of the phenol to the alcohol is 1:100, the mass ratio of the alcohol to the organic solvent is 1:1.2, and the mass ratio of the alcohol to the deionized water is 1: 1), firstly adding the alcohol and the organic solvent into the deionized water, and stirring to form a uniformly mixed solution; then adding zinc nitrate into the mixed solution, heating to a certain temperature (85 ℃) under the condition of stirring, slowly dripping phenol into the mixed solution, reacting for a period of time (5 hours) under the condition of a condenser pipe, and then distilling under reduced pressure to obtain the zinc carbolate/phenol mixed solution. Uniformly mixing the prepared boron nitride nanosheet dispersion liquid with the large particle size and the small particle size (the mass ratio of the boron nitride nanosheet dispersion liquid with the small particle size to the boron nitride nanosheet dispersion liquid with the large particle size is 1: 0.8), adding a certain amount of graphene (the mass ratio of the graphene to the boron nitride nanosheet dispersion liquid is 1: 1000), and ultrasonically dispersing the graphene and the boron nitride nanosheet dispersion liquid uniformly. The boron nitride/graphene double-coated phenolic aldehyde prepolymer dispersion liquid is fully mixed with a zinc carbolate/phenol mixed solution (the mass ratio of the boron nitride nanosheet dispersion liquid to the zinc carbolate/phenol mixed solution is 1: 0.8), then a certain amount of formaldehyde (the mass ratio of the formaldehyde to the zinc carbolate/phenol mixed solution is 1: 200) is added into the mixed solution, the pH value of the solution is adjusted to 9 through sodium hydroxide, and then the mixed solution is reacted at a certain temperature (70 ℃) for a certain time (6 hours) to prepare the zinc oxide and phenolic aldehyde prepolymer double-coated boron nitride/graphene dispersion liquid. Adjusting the pH value of zinc oxide and boron nitride/graphene dispersion liquid double-coated by the phenolic aldehyde prepolymer to 5 by using dilute sulfuric acid, stirring and reacting for a period of time (5 hours) at a certain temperature (80 ℃), filtering, cleaning and drying to obtain the phenolic resin-zinc oxide mixed double-coated powder boron nitride/graphene powder. The boron nitride/graphene insulating and heat conducting silicone grease is uniformly mixed with organic silicone (the organic silicone is vinyl silicone oil, the viscosity range is 5000cps, the mass ratio of the phenolic resin-zinc oxide mixed double-coated boron nitride/graphene powder to the silicone grease is 1: 0.05), and then the mixed double-coated boron nitride/graphene insulating and heat conducting silicone grease is obtained.
Example three:
weighing boron nitride, a solvent and a dispersant (the solvent is ethanol, the dispersant is BYK180, the mass ratio of the boron nitride to the solvent is 1:50, and the mass ratio of the boron nitride to the dispersant is 1: 0.4), firstly adding the boron nitride into the solvent, and carrying out stripping and dispersion (the time is 3 h) on the boron nitride by using ultrasonic (the power is 4000W) assisted high-speed shearing and stirring (the rotating speed is 15000 r/min), thus preparing the large-particle boron nitride nanosheet dispersion liquid (the average particle size is 10 micrometers). And adding part of the prepared large-particle boron nitride nanosheet dispersion liquid into a grinding machine, stripping and dispersing the large-particle boron nitride nanosheet dispersion liquid in a telecentric ball milling mode (grinding media are zirconia balls with the diameter of 0.2 micrometer; the rotating speed is 3000 r/min, the processing time is 2 hours), and reducing the particle size through shearing to prepare the boron nitride nanosheet dispersion liquid with the proper length-diameter ratio (the average particle size is 5 micrometers, and the length-diameter ratio is 800). Weighing phenol, zinc nitrate, alcohol, an organic solvent and deionized water (the alcohol is a mixture of ethanol and isopropanol; the organic solvent is pentane; the mass ratio of the phenol to the zinc nitrate is 1: 0.7; the mass ratio of the phenol to the alcohol is 1: 120; the mass ratio of the alcohol to the organic solvent is 1: 1; and the mass ratio of the alcohol to the deionized water is 1: 0.8), firstly adding the alcohol and the organic solvent into the deionized water, and stirring to form a uniformly mixed solution; then adding zinc nitrate into the mixed solution, heating to a certain temperature (90 ℃) under the condition of stirring, slowly dripping phenol into the mixed solution, reacting for a period of time (5 hours) under the condition of a condenser pipe, and then carrying out reduced pressure distillation to obtain the zinc carbolate/phenol mixed solution. Uniformly mixing the prepared boron nitride nanosheet dispersion liquid with the large particle size and the small particle size (the mass ratio of the boron nitride nanosheet dispersion liquid with the small particle size to the boron nitride nanosheet dispersion liquid with the large particle size is 1: 1.3), adding a certain amount of graphene (the mass ratio of the graphene to the boron nitride nanosheet dispersion liquid is 1: 1000), and ultrasonically dispersing the graphene and the boron nitride nanosheet dispersion liquid uniformly. The boron nitride/graphene double-coated phenolic aldehyde prepolymer dispersion liquid is fully mixed with a zinc carbolate/phenol mixed solution (the mass ratio of the boron nitride nanosheet dispersion liquid to the zinc carbolate/phenol mixed solution is 1: 2), then a certain amount of formaldehyde (the mass ratio of the formaldehyde to the zinc carbolate/phenol mixed solution is 1: 200) is added into the mixed solution, the pH value of the solution is adjusted to 8 through sodium hydroxide, and then the mixed solution is reacted at a certain temperature (85 ℃) for a certain time (4 hours) to prepare the zinc oxide and phenolic aldehyde prepolymer double-coated boron nitride/graphene dispersion liquid. Adjusting the pH value of zinc oxide and boron nitride/graphene dispersion liquid double-coated by the phenolic aldehyde prepolymer to 5 by using dilute sulfuric acid, stirring and reacting for a period of time (3 hours) at a certain temperature (80 ℃), filtering, cleaning and drying to obtain the phenolic resin-zinc oxide mixed double-coated powder boron nitride/graphene powder. The boron nitride/graphene insulation heat-conducting silicone grease is uniformly mixed with organic silicone (the organic silicone is a mixture of methyl toluene silicone oil and long-chain alkyl silicone oil, the viscosity range is 10000cps, and the mass ratio of the phenolic resin-zinc oxide mixed double-coated boron nitride/graphene powder to the silicone grease is 1: 0.2) to obtain the mixed double-coated boron nitride/graphene insulation heat-conducting silicone grease.
Claims (6)
1. A preparation method of mixed double-coated boron nitride/graphene insulating and heat-conducting silicone grease is characterized by comprising the following specific steps:
1) accurately weighing boron nitride, a solvent and a dispersing agent according to a formula, firstly adding the boron nitride into the solvent, and stripping and dispersing the boron nitride by adopting ultrasonic-assisted high-speed shearing and stirring to prepare a large-particle boron nitride nanosheet dispersion liquid;
2) adding part of the large-particle boron nitride nanosheet dispersion prepared in the step 1) into a grinding machine, and stripping and dispersing the large-particle boron nitride nanosheet dispersion in a telecentric ball milling mode to prepare a small-particle boron nitride nanosheet dispersion with a proper length-diameter ratio;
3) accurately weighing phenol, zinc nitrate, alcohol, an organic solvent and deionized water according to a formula, firstly adding the alcohol and the organic solvent into the deionized water, and stirring to form a uniformly mixed solution; then adding zinc nitrate into the mixed solution, heating to a certain temperature (30-100 ℃) under the condition of stirring, slowly dripping phenol into the mixed solution, reacting for a period of time (0.5-10 hours) in the presence of a condenser pipe, and then carrying out reduced pressure distillation to obtain a zinc carbolate/phenol mixed solution;
4) uniformly mixing the boron nitride nanosheet dispersion liquid prepared in the steps 1) and 2), adding a certain amount of graphene, performing ultrasonic treatment to uniformly disperse the graphene, fully mixing the graphene with the zinc carbolate/phenol mixed solution prepared in the step 3), adding a certain amount of formaldehyde, adjusting the pH value of the solution to 8-12 by using sodium hydroxide, and reacting at a certain temperature (30-100 ℃) for a certain time (1-24 hours) to prepare a boron nitride/graphene dispersion liquid double-coated by zinc oxide and phenolic aldehyde prepolymer;
5) adding dilute sulfuric acid into the zinc oxide and phenolic aldehyde prepolymer double-coated boron nitride/graphene dispersion liquid prepared in the step 4), adjusting the pH value of the solution to 3-5, stirring and reacting at a certain temperature (30-100 ℃) for a period of time (0.5-10 hours), filtering, cleaning and drying to obtain phenolic resin-zinc oxide mixed double-coated powder boron nitride/graphene powder, and uniformly mixing the phenolic resin-zinc oxide mixed double-coated powder boron nitride/graphene powder with organic silicone to obtain the mixed double-coated boron nitride/graphene insulating heat-conducting silicone grease.
2. The preparation method of the mixed double-coated boron nitride/graphene insulating and heat conducting silicone grease as claimed in claim 1, wherein the mass ratio of the boron nitride to the solvent in the step 1) is 1: 1-1000; the mass ratio of the boron nitride to the dispersant is 1: 0.01-10; the solvent is any one or a mixture of more of N-methyl pyrrolidone, deionized water, ethanol, isopropanol and dimethylformamide; the dispersing agent is any one or a mixture of more of BYK220, BYK204, BYK102, BYK203, BYK192, BYK130, BYK110 and BYK 180; the ultrasonic power is 1000-8000W; the high-speed shearing dispersion adopts a Fluke FA25 high-shear dispersion emulsifying machine, the rotating speed is 5000-30000 r/min, and the processing time is 0.5-10 hours; the average particle size of the large-particle boron nitride nanosheet dispersion is 5-10 microns.
3. The preparation method of the mixed double-coated boron nitride/graphene insulating and heat conducting silicone grease according to claim 1, wherein in the step 2), zirconia balls with the diameter of 0.05-0.2 microns are used as grinding media for telecentric ball milling dispersion, the rotating speed is 500-8000 rpm, and the processing time is 0.5-10 hours; the boron nitride nanosheet dispersion with the appropriate length-diameter ratio has an average particle size of 0.7-5 microns and a length-diameter ratio of 50-800.
4. The method for preparing the mixed double-coated boron nitride/graphene insulating and heat conducting silicone grease according to claim 1, wherein the alcohol in the step 3) is one or a mixture of ethanol, isopropanol, butanol and octanol; the organic solvent is one or a mixture of diethyl ether, acetone, dichloromethane, petroleum ether, pentane and tetrahydrofuran; the mass ratio of the phenol to the zinc nitrate is 1: 0.1-50; the mass ratio of the phenol to the alcohol is 1: 1-500; the mass ratio of the alcohol to the organic solvent is 1: 0.1-10; the mass ratio of the alcohol to the deionized water is 1: 0.1-10.
5. The preparation method of the mixed double-coated boron nitride/graphene insulation and heat conduction silicone grease as claimed in claim 1, wherein the mass ratio of the boron nitride nanosheet dispersion with the appropriate length-diameter ratio to the large-particle boron nitride nanosheet dispersion in the step 4) is 1: 0.01-100; the mass ratio of the graphene to the boron nitride nanosheet dispersion liquid is 1: 10-10000; the mass ratio of the boron nitride nanosheet dispersion liquid to the zinc carbolate/phenol mixed solution is 1: 0.01-100; the mass ratio of the formaldehyde to the zinc carbolate/phenol mixed solution is 1: 10-10000.
6. The preparation method of the mixed double-coated boron nitride/graphene insulating and heat conducting silicone grease as claimed in claim 1, wherein the organic silicone in the step 5) is one or a mixture of more than two of dimethyl silicone oil, methyl toluene silicone oil, vinyl silicone oil, fluorine hydroxyl silicone oil, long-chain alkyl silicone oil or other modified silicone oil, and the viscosity range is 50-20000 cps; the mass ratio of the phenolic resin-zinc oxide mixed double-coated boron nitride/graphene powder to the silicone grease is 1: 0.01-10.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112876327A (en) * | 2021-02-03 | 2021-06-01 | 中国工程物理研究院化工材料研究所 | Method for preparing coated boron powder and coated boron powder |
| CN114734707A (en) * | 2022-04-25 | 2022-07-12 | 叶金蕊 | Heat-conducting ultrahigh voltage-resistant insulating composite material and preparation method thereof |
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2020
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112876327A (en) * | 2021-02-03 | 2021-06-01 | 中国工程物理研究院化工材料研究所 | Method for preparing coated boron powder and coated boron powder |
| CN114734707A (en) * | 2022-04-25 | 2022-07-12 | 叶金蕊 | Heat-conducting ultrahigh voltage-resistant insulating composite material and preparation method thereof |
| CN114734707B (en) * | 2022-04-25 | 2022-11-11 | 叶金蕊 | Heat-conducting ultrahigh voltage-resistant insulating composite material and preparation method thereof |
| WO2023206654A1 (en) * | 2022-04-25 | 2023-11-02 | 叶金蕊 | Heat-conducting ultrahigh-voltage-resistant insulating composite material and preparation method therefor |
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