CN111333925A - High-thermal-conductivity boron nitride modified insulating rubber composite material and preparation method thereof - Google Patents
High-thermal-conductivity boron nitride modified insulating rubber composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of rubber materials, and discloses a high-thermal-conductivity boron nitride modified insulating rubber composite material which comprises the following formula raw materials and components: modified layered boron nitride nanosheets, hexyl methacrylate, concentrated natural latex, an emulsifier, an initiator, elemental sulfur, a surfactant, an accelerator and an activator. According to the high-heat-conductivity boron nitride modified insulating rubber composite material, the hydroxylated multilayer boron nitride nanosheets are rich in layered structures and contain a large number of hydroxyl groups, the epoxidized boron nitride nanosheets with high grafting rates and acrylamide are subjected to ring-opening reaction to obtain the alkenyl modified layered boron nitride nanosheets, and then the alkenyl modified layered boron nitride nanosheets and concentrated natural latex and hexyl methacrylate are subjected to alkenyl free radical polymerization reaction to obtain the modified rubber composite material.
Description
Technical Field
The invention relates to the technical field of rubber materials, in particular to a high-heat-conductivity boron nitride modified insulating rubber composite material and a preparation method thereof.
Background
The insulating material has high resistivity, is not conductive under allowable voltage, can generate phenomena of conduction, polarization, loss and the like under the action of certain external electric field intensity, can also generate aging after long-term use, is the basis and guarantee of the development of electrical products, is very important for the development of the electrical industry of a motor, and the development of high polymer materials directly influences the development of the insulating materials, such as polyimide, polyamide-imide, chloroprene rubber and the like, and has wide application in the industries of electricians, light industry, petrifaction, building materials and the like.
The rubber is a high-elasticity polymer material capable of being deformed reversibly, can generate larger deformation under the action of external force, can be recovered after the external force disappears, mainly comprises natural rubber, isoprene rubber, styrene butadiene rubber, chloroprene rubber and the like, is widely applied in the fields of transportation, industrial mines, military and national defense, electrical communication and the like, has good insulating property, but has higher and higher requirements on insulating rubber materials along with the continuous development of the electronic and electrical industry, has lower thermal conductivity and poorer thermal conductivity, cannot meet the industrial requirements of common rubber materials, has a graphite-like layered structure, has ultrahigh thermal conductivity and electrical resistivity, can be used as a filler to improve the thermal conductivity and insulating property of the rubber material, but has poor compatibility with the rubber, and is easy to agglomerate and agglomerate in the rubber material, the mechanical properties such as toughness of the material are affected.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a high-heat-conductivity boron nitride modified insulating rubber composite material and a preparation method thereof, which solve the problem of poor heat conductivity of rubber and solve the problem of poor compatibility of nano boron nitride and rubber.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a high-thermal-conductivity boron nitride modified insulating rubber composite material comprises the following formula raw materials in parts by weight: 1-4 parts of modified layered boron nitride nanosheet, 3-8 parts of hexyl methacrylate, 75-90 parts of concentrated natural latex, 1-3.5 parts of emulsifier, 3-6 parts of initiator, 0.5-1 part of elemental sulfur, 0.1-0.5 part of surfactant, 0.5-1 part of accelerator and 0.5-1 part of activator.
Preferably, the initiator potassium persulfate, the emulsifier sodium dodecyl sulfate, the surfactant polyoxyethylene fatty alcohol ether, the accelerator zinc diethyldithiocarbamate and the activator zinc oxide are used as raw materials.
Preferably, the preparation method of the modified layered boron nitride nanosheet is as follows:
(1) adding distilled water and a methanol solvent into a reaction bottle, adding boric acid and urea, stirring and dissolving, removing the solvent from the solution through freeze drying, placing a solid product in an atmosphere resistance furnace, introducing ammonia gas, heating at the rate of 5-10 ℃/min, carrying out heat preservation treatment at the temperature of 850-880 ℃ for 2-5h, grinding a calcined product to fine powder, placing the fine powder into distilled water, carrying out ultrasonic stripping treatment in an ultrasonic dispersion instrument at the temperature of 40-60 ℃ for 2-4h, wherein the ultrasonic frequency is 25-35KHz, filtering and drying the solution, and preparing the multilayer boron nitride nanosheet.
(2) Placing the multilayer boron nitride nanosheets in a mixed solvent of distilled water and ethanol, ultrasonically dispersing uniformly, transferring the solution into a high-pressure hydrothermal reaction kettle, placing the high-pressure hydrothermal reaction kettle in a forced air drier, heating to 160-200 ℃, reacting for 5-8h, filtering the solution to remove the solvent, and drying to obtain the hydroxylated boron nitride nanosheets.
(3) Introducing nitrogen into a reaction bottle, adding a toluene solvent and a hydroxylated boron nitride nanosheet, adding 3-glycidyl ether oxypropyltriethoxysilane after uniform ultrasonic dispersion, placing the reaction bottle in an oil bath pot, heating to 120 ℃ plus 140 ℃, stirring at a constant speed for reaction for 20-30h, filtering the solution to remove the solvent, washing a solid product with ethanol, and fully drying to prepare the 3-glycidyl ether oxypropyltriethoxysilane grafted epoxidized layered boron nitride nanosheet.
(4) Adding an acetone solvent and the epoxidized layered boron nitride nanosheet into a reaction bottle, adding acrylamide after uniform ultrasonic dispersion, placing the reaction bottle into an oil bath pot, heating to 70-90 ℃, uniformly stirring for reaction for 15-25h, carrying out reduced pressure distillation on the solution to remove the solvent, washing a solid product with ethanol, and fully drying to prepare the alkenyl modified layered boron nitride nanosheet.
Preferably, the mass ratio of the boric acid to the urea is 1: 28-35.
Preferably, the mass ratio of the hydroxylated boron nitride nanosheet to the 3-glycidyl ether oxypropyltriethoxysilane is 1: 0.2-0.6.
Preferably, the mass ratio of the epoxidized layered boron nitride nanosheet to the acrylamide is 1: 4-8.
Preferably, the ultrasonic dispersion appearance includes the top swing joint of instrument main part, instrument main part has top cap, top cap and slide rail swing joint, slide rail and pulley swing joint, and pulley swing joint has the regulation pole, adjusts pole swing joint and has regulator, regulator and fixation clamp swing joint, the inside fixedly connected with sound insulation protective layer of instrument main part, the inside both sides fixedly connected with ultrasonic emitter of sound insulation protective layer, the inside below fixedly connected with heating device in sound insulation protective layer.
Preferably, the preparation method of the high-thermal-conductivity boron nitride modified insulating rubber composite material comprises the following steps:
(1) introducing nitrogen into a reaction bottle, adding distilled water solvent, 75-90 parts of concentrated natural latex, 1-3.5 parts of emulsifier sodium dodecyl sulfate and 1-4 parts of modified layered boron nitride nanosheet, stirring uniformly, adding 3-8 parts of hexyl methacrylate and 3-6 parts of initiator potassium persulfate, stirring at 50-70 deg.C with uniform speed for 6-10h, adding 0.5-1 part of elemental sulfur, 0.1-0.5 part of surfactant polyoxyethylene fatty alcohol ether, 0.5-1 part of promoter zinc diethyldithiocarbamate and 0.5-1 part of activator zinc oxide into the solution, performing high-speed emulsification process, drying the solvent to form emulsion, filtering, defoaming, aging, pouring the emulsion into a film-forming mold, and heating for vulcanization to prepare the high-thermal-conductivity boron nitride modified insulating rubber composite material.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the high-thermal-conductivity boron nitride modified insulating rubber composite material is prepared by using boric acid as a boron source and urea as a nitrogen source through a freeze drying, ammonia gas atmosphere high-temperature heat treatment method and an ultrasonic stripping method, and has a rich layered structure and a larger specific surface area, hydrolysis of the multilayer boron nitride nanosheets is accelerated through a high-pressure hydrothermal method, so that a large number of hydroxyl groups are formed on the huge specific surface and in the rich layered structure of the boron nitride nanosheets, the hydroxyl groups are very easy to react with 3-glycidyl ether oxypropyltriethoxysilane to obtain epoxidized boron nitride nanosheets with a high grafting rate, the epoxy groups are subjected to a ring-opening reaction with amino groups in acrylamide to prepare alkenyl modified layered boron nitride nanosheets, the alkenyl modified layered boron nitride nanosheets are subjected to an alkenyl radical polymerization reaction with concentrated natural latex and hexyl methacrylate to finally obtain a modified rubber composite material, the boron nitride nanosheets are organically combined with rubber in a chemical bond combination mode, compatibility and dispersibility of the boron nitride nanosheets and the rubber are greatly improved, the resistivity and the thermal conductivity of the rubber are improved, and the rubber composite material prepared in examples 1-5 can reach 352.39.51.25.51.25.4K16-4.69×1016ohm cm, surface resistivity up to 1.19 × 1014-1.27×1014ohm·cm3Thereby enhancing the insulating property and the heat conducting property of the rubber material.
Drawings
FIG. 1 is a schematic front view of a reaction tank;
FIG. 2 is an enlarged schematic view of the adjustment lever;
fig. 3 is a schematic view of adjustment lever adjustment.
1. An instrument body; 2. a top cover; 3. a slide rail; 4. a pulley; 5. adjusting a rod; 6. a regulator; 7. a fixing clip; 8. a sound insulation protective layer; 9. an ultrasonic transmitter; 10. a heating device.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: a high-thermal-conductivity boron nitride modified insulating rubber composite material comprises the following formula raw materials in parts by weight: 1-4 parts of modified layered boron nitride nanosheet, 3-8 parts of hexyl methacrylate, 75-90 parts of concentrated natural latex, 1-3.5 parts of emulsifier, 3-6 parts of initiator, 0.5-1 part of elemental sulfur, 0.1-0.5 part of surfactant, 0.5-1 part of accelerator and 0.5-1 part of activator, wherein the initiator is potassium persulfate, the emulsifier is sodium dodecyl sulfate, the surfactant is polyoxyethylene fatty alcohol ether, the accelerator is zinc diethyldithiocarbamate and the activator is zinc oxide.
The preparation method of the modified layered boron nitride nanosheet comprises the following steps:
(1) adding distilled water and a methanol solvent into a reaction bottle, wherein the volume ratio of the distilled water to the methanol solvent is 1:2-4, adding boric acid and urea, the mass ratio of the boric acid to the urea is 1:28-35, stirring and dissolving, removing the solvent from the solution through freeze drying, placing a solid product into an atmosphere resistance furnace, introducing ammonia gas, carrying out heat preservation at the temperature rise rate of 5-10 ℃/min for 2-5h at the temperature of 850 plus 880 ℃, grinding the calcined product into fine powder, placing the fine powder into distilled water, carrying out ultrasonic stripping treatment at the temperature of 40-60 ℃ in an ultrasonic dispersion instrument, wherein the ultrasonic frequency is 25-35KHz, the ultrasonic dispersion instrument comprises an instrument main body, a top cover is movably connected above the instrument main body, the top cover is movably connected with a sliding rail, the sliding rail is movably connected with a pulley, an adjusting rod is movably connected with the adjusting rod, Regulator and fixation clamp swing joint, the inside fixedly connected with sound insulation protective layer of instrument main part, inside both sides fixedly connected with ultrasonic emitter of sound insulation protective layer, the inside below fixedly connected with heating device in sound insulation protective layer filter and dry the solution, prepare and obtain the multilayer boron nitride nanosheet.
(2) Placing the multilayer boron nitride nanosheets in a mixed solvent of distilled water and ethanol, ultrasonically dispersing uniformly, transferring the solution into a high-pressure hydrothermal reaction kettle, placing the high-pressure hydrothermal reaction kettle in a forced air drier, heating to 160-200 ℃, reacting for 5-8h, filtering the solution to remove the solvent, and drying to obtain the hydroxylated boron nitride nanosheets.
(3) Introducing nitrogen into a reaction bottle, adding a toluene solvent and a hydroxylated boron nitride nanosheet, adding 3-glycidoxypropyltriethoxysilane after uniform ultrasonic dispersion, wherein the mass ratio of the toluene solvent to the hydroxylated boron nitride nanosheet is 1:0.2-0.6, placing the reaction bottle into an oil bath pot, heating to 120 ℃ for 140 ℃, stirring at a constant speed for reaction for 20-30h, filtering the solution to remove the solvent, washing the solid product with ethanol, and fully drying to prepare the 3-glycidoxypropyltriethoxysilane grafted epoxidized layered boron nitride nanosheet.
(4) Adding an acetone solvent and the epoxidized layered boron nitride nanosheet into a reaction bottle, adding acrylamide after uniform ultrasonic dispersion, wherein the mass ratio of the acetone solvent to the epoxidized layered boron nitride nanosheet is 1:4-8, placing the reaction bottle into an oil bath pot, heating to 70-90 ℃, stirring at a constant speed for reaction for 15-25h, carrying out reduced pressure distillation on the solution to remove the solvent, washing a solid product with ethanol, and fully drying to prepare the alkenylated modified layered boron nitride nanosheet.
The preparation method of the high-thermal-conductivity boron nitride modified insulating rubber composite material comprises the following steps:
(1) introducing nitrogen into a reaction bottle, adding distilled water solvent, 75-90 parts of concentrated natural latex, 1-3.5 parts of emulsifier sodium dodecyl sulfate and 1-4 parts of modified layered boron nitride nanosheet, stirring uniformly, adding 3-8 parts of hexyl methacrylate and 3-6 parts of initiator potassium persulfate, stirring at 50-70 deg.C with uniform speed for 6-10h, adding 0.5-1 part of elemental sulfur, 0.1-0.5 part of surfactant polyoxyethylene fatty alcohol ether, 0.5-1 part of promoter zinc diethyldithiocarbamate and 0.5-1 part of activator zinc oxide into the solution, performing high-speed emulsification process, drying the solvent to form emulsion, filtering, defoaming, aging, pouring the emulsion into a film-forming mold, and heating for vulcanization to prepare the high-thermal-conductivity boron nitride modified insulating rubber composite material.
Example 1
(1) Preparation of multilayer boron nitride nanosheet component 1: adding distilled water and a methanol solvent into a reaction bottle, wherein the volume ratio of the distilled water to the methanol solvent is 1:2, adding boric acid and urea, the mass ratio of the boric acid to the urea is 1:28, stirring and dissolving, removing the solvent from the solution through freeze drying, placing a solid product into an atmosphere resistance furnace, introducing ammonia gas, keeping the temperature at a rate of 5 ℃/min, carrying out heat preservation treatment at 850 ℃ for 2h, grinding a calcined product into fine powder, placing the fine powder into distilled water, carrying out ultrasonic stripping treatment in an ultrasonic dispersion instrument at 40 ℃ for 2h, wherein the ultrasonic frequency is 25KHz, the ultrasonic dispersion instrument comprises an instrument main body, a top cover is movably connected above the instrument main body, the top cover is movably connected with a sliding rail, the sliding rail is movably connected with a pulley, the pulley is movably connected with an adjusting rod, the adjusting rod is movably connected with an adjuster, the adjuster is movably connected with a fixing clamp, a sound, And fixedly connecting a heating device below the inner part of the sound insulation protective layer, filtering and drying the solution, and preparing the multilayer boron nitride nanosheet component 1.
(2) Preparation of hydroxylated boron nitride nanosheet component 1: placing the multilayer boron nitride nanosheet component 1 in a mixed solvent of distilled water and ethanol, ultrasonically dispersing uniformly, transferring the solution into a high-pressure hydrothermal reaction kettle, placing the kettle in a forced air drier, heating to 160 ℃, reacting for 5 hours, filtering the solution to remove the solvent, and drying to obtain the hydroxylated boron nitride nanosheet component 1.
(3) Preparing an epoxidized layered boron nitride nanosheet component 1: introducing nitrogen into a reaction bottle, adding a toluene solvent and the hydroxylated boron nitride nanosheet component 1, ultrasonically dispersing uniformly, adding 3-glycidyl ether oxypropyltriethoxysilane, heating the reaction bottle to 120 ℃ in an oil bath kettle at a mass ratio of 1:0.2, stirring at a constant speed for reaction for 20 hours, filtering the solution to remove the solvent, washing a solid product with ethanol, and fully drying to prepare the 3-glycidyl ether oxypropyltriethoxysilane grafted epoxidized layered boron nitride nanosheet component 1.
(4) Preparing a modified layered boron nitride nanosheet component 1: adding an acetone solvent and the epoxidized layered boron nitride nanosheet component 1 into a reaction bottle, adding acrylamide after uniform ultrasonic dispersion, wherein the mass ratio of the acetone solvent to the epoxidized layered boron nitride nanosheet component 1 to 4-8, placing the reaction bottle into an oil bath pan, heating to 70 ℃, uniformly stirring for reaction for 15h, carrying out reduced pressure distillation on the solution to remove the solvent, washing a solid product with ethanol, and fully drying to prepare the alkenylated modified layered boron nitride nanosheet component 1.
(5) Preparing a high-thermal-conductivity boron nitride modified insulating rubber composite material 1: introducing nitrogen into a reaction bottle, adding distilled water solvent, 90 parts of concentrated natural latex, 1 part of emulsifier sodium dodecyl sulfate and 1 part of modified layered boron nitride nanosheet component 1, stirring uniformly, adding 3 parts of hexyl methacrylate and 3 parts of initiator potassium persulfate, stirring at a constant speed at 50 ℃ for reaction for 6 hours, adding 0.5 part of elemental sulfur, 0.1 part of surfactant polyoxyethylene fatty alcohol ether, 0.5 part of promoter zinc diethyldithiocarbamate and 0.5 part of activator zinc oxide into the solution, performing a high-speed emulsification process, drying the solvent to form a latex shape, filtering, defoaming and curing, pouring the latex material into a film forming mold, heating for vulcanization, and preparing the high-thermal-conductivity boron nitride modified insulating rubber composite material 1.
Example 2
(1) Preparation of multilayer boron nitride nanosheet component 2: adding distilled water and a methanol solvent into a reaction bottle, wherein the volume ratio of the distilled water to the methanol solvent is 1:2, adding boric acid and urea, the mass ratio of the boric acid to the urea is 1:28, stirring and dissolving, removing the solvent from the solution through freeze drying, placing a solid product into an atmosphere resistance furnace, introducing ammonia gas, keeping the temperature at the rate of 10 ℃/min, carrying out heat preservation treatment at 850 ℃ for 5h, grinding a calcined product into fine powder, placing the fine powder into distilled water, carrying out ultrasonic stripping treatment in an ultrasonic dispersion instrument at 40 ℃ for 4h, wherein the ultrasonic frequency is 35KHz, the ultrasonic dispersion instrument comprises an instrument main body, a top cover is movably connected above the instrument main body, the top cover is movably connected with a sliding rail, the sliding rail is movably connected with a pulley, the pulley is movably connected with an adjusting rod, the adjusting rod is movably connected with an adjuster, the adjuster is movably connected with a fixing clamp, a sound, And fixedly connecting a heating device below the inner part of the sound insulation protective layer, filtering and drying the solution, and preparing the multilayer boron nitride nanosheet component 2.
(2) Preparation of hydroxylated boron nitride nanosheet component 2: placing the multilayer boron nitride nanosheet component 2 in a mixed solvent of distilled water and ethanol, ultrasonically dispersing uniformly, transferring the solution into a high-pressure hydrothermal reaction kettle, placing the kettle in a forced air drier, heating to 160 ℃, reacting for 8 hours, filtering the solution to remove the solvent, and drying to obtain the hydroxylated boron nitride nanosheet component 2.
(3) Preparing an epoxidized layered boron nitride nanosheet component 2: introducing nitrogen into a reaction bottle, adding a toluene solvent and a hydroxylated boron nitride nanosheet component 2, ultrasonically dispersing uniformly, adding 3-glycidyl ether oxypropyltriethoxysilane, heating the reaction bottle to 120 ℃ in an oil bath kettle at a mass ratio of 1:0.2, stirring at a constant speed for reaction for 30 hours, filtering the solution to remove the solvent, washing a solid product with ethanol, and fully drying to prepare the 3-glycidyl ether oxypropyltriethoxysilane-grafted epoxidized layered boron nitride nanosheet component 2.
(4) Preparing a modified layered boron nitride nanosheet component 2: adding an acetone solvent and the epoxidized layered boron nitride nanosheet component 2 into a reaction bottle, adding acrylamide after uniform ultrasonic dispersion, wherein the mass ratio of the acetone solvent to the epoxidized layered boron nitride nanosheet component 2 is 1:4-8, placing the reaction bottle into an oil bath pan, heating to 70 ℃, uniformly stirring for reaction for 25h, carrying out reduced pressure distillation on the solution to remove the solvent, washing a solid product with ethanol, and fully drying to prepare the alkenylated modified layered boron nitride nanosheet component 2.
(5) Preparing a high-thermal-conductivity boron nitride modified insulating rubber composite material 2: introducing nitrogen into a reaction bottle, adding a distilled water solvent, 86 parts of concentrated natural latex, 1.5 parts of emulsifier sodium dodecyl sulfate and 1.5 parts of modified layered boron nitride nanosheet component 2, stirring uniformly, adding 4 parts of hexyl methacrylate and 3.5 parts of initiator potassium persulfate, stirring at a constant speed at 50 ℃ for reaction for 10 hours, adding 0.6 part of elemental sulfur, 0.3 part of surfactant polyoxyethylene fatty alcohol ether, 0.6 part of accelerator zinc diethyldithiocarbamate and 0.5-1 part of activator zinc oxide into the solution, performing a high-speed emulsification process, drying the solvent to form emulsion, filtering, defoaming and curing, pouring the emulsion into a film forming mold, heating and vulcanizing to obtain the high-heat-conductivity boron nitride modified insulating rubber composite material 2.
Example 3
(1) Preparation of multilayer boron nitride nanosheet component 3: adding distilled water and a methanol solvent into a reaction bottle, wherein the volume ratio of the distilled water to the methanol solvent is 1:2-4, adding boric acid and urea, the mass ratio of the boric acid to the urea is 1:28, stirring and dissolving, removing the solvent from the solution through freeze drying, placing a solid product into an atmosphere resistance furnace, introducing ammonia gas, carrying out heat preservation treatment at the temperature rising rate of 10 ℃/min for 5h at 850 ℃, grinding a calcined product into fine powder, placing the fine powder into distilled water, carrying out ultrasonic stripping treatment in an ultrasonic dispersion instrument at the temperature of 60 ℃ for 2h, wherein the ultrasonic frequency is 25KHz, the ultrasonic dispersion instrument comprises an instrument main body, a top cover is movably connected above the instrument main body, the top cover is movably connected with a sliding rail, the sliding rail is movably connected with a pulley, the pulley is movably connected with an adjusting rod, the adjusting rod is movably connected with an adjuster, the adjuster, and fixedly connecting ultrasonic emitters on two sides inside the sound insulation protective layer, fixedly connecting a heating device below the inner part of the sound insulation protective layer, filtering and drying the solution, and preparing to obtain the multilayer boron nitride nanosheet component 3.
(2) Preparation of hydroxylated boron nitride nanosheet component 3: placing the multilayer boron nitride nanosheet component 3 in a mixed solvent of distilled water and ethanol, ultrasonically dispersing uniformly, transferring the solution into a high-pressure hydrothermal reaction kettle, placing the kettle in a forced air drier, heating to 200 ℃, reacting for 5 hours, filtering the solution to remove the solvent, and drying to obtain the hydroxylated boron nitride nanosheet component 3.
(3) Preparing an epoxidized layered boron nitride nanosheet component 3: introducing nitrogen into a reaction bottle, adding a toluene solvent and a hydroxylated boron nitride nanosheet component 3, adding 3-glycidyl ether oxypropyltriethoxysilane after uniform ultrasonic dispersion, wherein the mass ratio of the toluene solvent to the hydroxylated boron nitride nanosheet component 3 is 1:0.2, placing the reaction bottle in an oil bath pot, heating to 140 ℃, stirring at a constant speed for reaction for 20 hours, filtering the solution to remove the solvent, washing a solid product with ethanol, and fully drying to prepare the 3-glycidyl ether oxypropyltriethoxysilane-grafted epoxidized layered boron nitride nanosheet component 3.
(4) Preparing a modified layered boron nitride nanosheet component 3: adding an acetone solvent and the epoxidized layered boron nitride nanosheet component 3 into a reaction bottle, adding acrylamide after uniform ultrasonic dispersion, wherein the mass ratio of the acetone solvent to the epoxidized layered boron nitride nanosheet component 3 is 1:4-8, placing the reaction bottle into an oil bath pot, heating to 90 ℃, uniformly stirring for reaction for 15h, carrying out reduced pressure distillation on the solution to remove the solvent, washing a solid product with ethanol, and fully drying to prepare the alkenylated modified layered boron nitride nanosheet component 3.
(5) Preparing a high-thermal-conductivity boron nitride modified insulating rubber composite material 3: introducing nitrogen into a reaction bottle, adding a distilled water solvent, 82 parts of concentrated natural latex, 2.2 parts of emulsifier sodium dodecyl sulfate and 2.5 parts of modified layered boron nitride nanosheet component 3, stirring uniformly, adding 3-8 parts of hexyl methacrylate and 4.5 parts of initiator potassium persulfate, stirring at a constant speed at 70 ℃ for reacting for 6 hours, adding 0.7 part of elemental sulfur, 0.2 part of surfactant polyoxyethylene fatty alcohol ether, 0.8 part of accelerator zinc diethyldithiocarbamate and 0.3 part of activator zinc oxide into the solution, performing a high-speed emulsification process, drying the solvent to form emulsion, filtering, defoaming and curing, pouring the emulsion into a film forming mold, heating and vulcanizing to obtain the high-heat-conductivity boron nitride modified insulating rubber composite material 3.
Example 4
(1) Preparation of multilayer boron nitride nanosheet component 4: adding distilled water and a methanol solvent into a reaction bottle, wherein the volume ratio of the distilled water to the methanol solvent is 1:3, adding boric acid and urea, the mass ratio of the boric acid to the urea is 1:32, stirring and dissolving, removing the solvent from the solution through freeze drying, placing a solid product into an atmosphere resistance furnace, introducing ammonia gas, keeping the temperature at the rate of 8 ℃/min, carrying out heat preservation treatment at 865 ℃ for 4h, grinding a calcined product into fine powder, placing the fine powder into distilled water, carrying out ultrasonic stripping treatment in an ultrasonic dispersion instrument at 50 ℃ for 2-4h, wherein the ultrasonic frequency is 30KHz, the ultrasonic dispersion instrument comprises an instrument main body, a top cover is movably connected above the instrument main body, the top cover is movably connected with a sliding rail, the sliding rail is movably connected with a pulley, the pulley is movably connected with an adjusting rod, the adjusting rod is movably connected with an adjuster, the adjuster, and fixedly connecting ultrasonic emitters on two sides inside the sound insulation protective layer, fixedly connecting a heating device below the inner part of the sound insulation protective layer, filtering and drying the solution, and preparing to obtain the multilayer boron nitride nanosheet component 4.
(2) Preparation of hydroxylated boron nitride nanosheet component 4: placing the multilayer boron nitride nanosheet component 4 in a mixed solvent of distilled water and ethanol, ultrasonically dispersing uniformly, transferring the solution into a high-pressure hydrothermal reaction kettle, placing the kettle in a forced air drier, heating to 180 ℃, reacting for 6 hours, filtering the solution to remove the solvent, and drying to obtain the hydroxylated boron nitride nanosheet component 4.
(3) Preparing an epoxidized layered boron nitride nanosheet component 4: introducing nitrogen into a reaction bottle, adding a toluene solvent and a hydroxylated boron nitride nanosheet component 4, ultrasonically dispersing uniformly, adding 3-glycidyl ether oxypropyltriethoxysilane, heating the reaction bottle to 130 ℃ in an oil bath kettle at a mass ratio of 1:0.4, stirring at a constant speed for reaction for 25 hours, filtering the solution to remove the solvent, washing a solid product with ethanol, and fully drying to prepare the 3-glycidyl ether oxypropyltriethoxysilane-grafted epoxidized layered boron nitride nanosheet component 4.
(4) Preparing a modified layered boron nitride nanosheet component 4: adding an acetone solvent and the epoxidized layered boron nitride nanosheet component 4 into a reaction bottle, adding acrylamide after uniform ultrasonic dispersion, wherein the mass ratio of the acetone solvent to the epoxidized layered boron nitride nanosheet component 4 to the acrylamide is 1:4-8, placing the reaction bottle into an oil bath pot, heating to 80 ℃, stirring at a constant speed for reaction for 20 hours, carrying out reduced pressure distillation on the solution to remove the solvent, washing a solid product with ethanol, and fully drying to prepare the alkenylated modified layered boron nitride nanosheet component 4.
(5) Preparing a high-thermal-conductivity boron nitride modified insulating rubber composite material 4: introducing nitrogen into a reaction bottle, adding a distilled water solvent, 78 parts of concentrated natural latex, 3 parts of emulsifier sodium dodecyl sulfate and 3.5 parts of modified layered boron nitride nanosheet component 4, stirring uniformly, adding 7 parts of hexyl methacrylate and 5.5 parts of initiator potassium persulfate, stirring at a constant speed at 60 ℃ for reacting for 8 hours, adding 0.8 part of elemental sulfur, 0.4 part of surfactant polyoxyethylene fatty alcohol ether, 0.8 part of accelerator zinc diethyldithiocarbamate and 0.9 part of activator zinc oxide into the solution, performing a high-speed emulsification process, drying the solvent to form emulsion, filtering, defoaming and curing, pouring the emulsion into a film forming mold, heating for vulcanization, and preparing the high-thermal-conductivity boron nitride modified insulating rubber composite material 4.
Example 5
(1) Preparation of multilayer boron nitride nanosheet component 5: adding distilled water and a methanol solvent into a reaction bottle, wherein the volume ratio of the distilled water to the methanol solvent is 1:4, adding boric acid and urea, the mass ratio of the boric acid to the urea is 1:35, stirring and dissolving, removing the solvent from the solution through freeze drying, placing a solid product into an atmosphere resistance furnace, introducing ammonia gas, keeping the temperature at the rate of 10 ℃/min, carrying out heat preservation treatment at 880 ℃ for 5h, grinding a calcined product into fine powder, placing the fine powder into distilled water, carrying out ultrasonic stripping treatment in an ultrasonic dispersion instrument at 60 ℃ for 4h, wherein the ultrasonic frequency is 35KHz, the ultrasonic dispersion instrument comprises an instrument main body, a top cover is movably connected above the instrument main body, the top cover is movably connected with a sliding rail, the sliding rail is movably connected with a pulley, the pulley is movably connected with an adjusting rod, the adjusting rod is movably connected with an adjuster, the adjuster is movably connected with a fixing clamp, a sound, And fixedly connecting a heating device below the inner part of the sound insulation protective layer, filtering and drying the solution, and preparing the multilayer boron nitride nanosheet component 5.
(2) Preparation of hydroxylated boron nitride nanosheet component 5: placing the multilayer boron nitride nanosheet component 5 in a mixed solvent of distilled water and ethanol, ultrasonically dispersing uniformly, transferring the solution into a high-pressure hydrothermal reaction kettle, placing the kettle in a forced air drier, heating to 200 ℃, reacting for 8 hours, filtering the solution to remove the solvent, and drying to obtain the hydroxylated boron nitride nanosheet component 5.
(3) Preparing an epoxidized layered boron nitride nanosheet component 5: introducing nitrogen into a reaction bottle, adding a toluene solvent and a hydroxylated boron nitride nanosheet component 5, adding 3-glycidyl ether oxypropyltriethoxysilane after uniform ultrasonic dispersion, wherein the mass ratio of the toluene solvent to the hydroxylated boron nitride nanosheet component 5 is 1:0.6, placing the reaction bottle in an oil bath pot, heating to 140 ℃, stirring at a constant speed for reaction for 30 hours, filtering the solution to remove the solvent, washing a solid product with ethanol, and fully drying to prepare the 3-glycidyl ether oxypropyltriethoxysilane-grafted epoxidized layered boron nitride nanosheet component 5.
(4) Preparing a modified layered boron nitride nanosheet component 5: adding an acetone solvent and the epoxidized layered boron nitride nanosheet component 5 into a reaction bottle, adding acrylamide after uniform ultrasonic dispersion, wherein the mass ratio of the acetone solvent to the epoxidized layered boron nitride nanosheet component 5 is 1:8, placing the reaction bottle into an oil bath pot, heating to 90 ℃, stirring at a constant speed for reaction for 25h, distilling the solution under reduced pressure to remove the solvent, washing a solid product with ethanol, and fully drying to prepare the alkenylated modified layered boron nitride nanosheet component 5.
(5) Preparing a high-thermal-conductivity boron nitride modified insulating rubber composite material 5: introducing nitrogen into a reaction bottle, adding distilled water solvent, 75 parts of concentrated natural latex, 3.5 parts of emulsifier sodium dodecyl sulfate and 4 parts of modified layered boron nitride nanosheet component 5, stirring uniformly, adding 8 parts of hexyl methacrylate and 6 parts of initiator potassium persulfate, stirring at a constant speed at 70 ℃ for reaction for 10 hours, adding 1 part of elemental sulfur, 0.5 part of surfactant polyoxyethylene fatty alcohol ether, 1 part of promoter zinc diethyldithiocarbamate and 1 part of activator zinc oxide into the solution, performing a high-speed emulsification process, drying the solvent to form a latex, filtering, defoaming and curing, pouring the latex material into a film forming mold, heating for vulcanization, and preparing the high-thermal-conductivity boron nitride modified insulating rubber composite material 5.
The boron nitride modified insulating rubber composite material 1-5 with high thermal conductivity prepared in the example 1-5 is subjected to a thermal conductivity test with the test standard of ASTM E1461; volume resistivity test and surface resistivity test, test standard ASTM D257.
In conclusion, the high-thermal-conductivity boron nitride modified insulating rubber composite material takes boric acid as a boron source and urea as a nitrogen source, and multilayer boron nitride nanosheets are prepared by freeze drying, an ammonia atmosphere high-temperature heat treatment method and an ultrasonic stripping method,the modified layered boron nitride nanosheet is prepared by carrying out ring-opening reaction on an epoxy group and an amino group in acrylamide to prepare an alkenylated modified layered boron nitride nanosheet, carrying out alkenyl radical polymerization reaction on the alkenylated modified layered boron nitride nanosheet and concentrated natural latex and hexyl methacrylate to finally obtain a modified rubber composite material, wherein the boron nitride nanosheet is organically combined with rubber in a chemical bond combination manner, the compatibility and the dispersibility of the boron nitride nanosheet and the rubber are greatly improved, the resistivity and the heat conductivity coefficient of the rubber are improved, the heat conductivity coefficient of the rubber composite material prepared in examples 1-5 is as high as 2.39-2.58W/m.K, and the resistivity is as high as 4.51. 4.51 × 10 by accelerating the hydrolysis of the multilayered boron nitride nanosheet through a high-pressure hydrothermal method16-4.69×1016ohm cm, surface resistivity up to 1.19 × 1014-1.27×1014ohm·cm3Thereby enhancing the insulating property and the heat conducting property of the rubber material.
Claims (8)
1. The high-thermal-conductivity boron nitride modified insulating rubber composite material comprises the following formula raw materials in parts by weight and components, and is characterized in that: 1-4 parts of modified layered boron nitride nanosheet, 3-8 parts of hexyl methacrylate, 75-90 parts of concentrated natural latex, 1-3.5 parts of emulsifier, 3-6 parts of initiator, 0.5-1 part of elemental sulfur, 0.1-0.5 part of surfactant, 0.5-1 part of accelerator and 0.5-1 part of activator.
2. The high thermal conductivity boron nitride modified insulating rubber composite material according to claim 1, wherein: the initiator potassium persulfate, the emulsifier sodium dodecyl sulfate, the surfactant polyoxyethylene fatty alcohol ether, the accelerator zinc diethyl dithiocarbamate and the activator zinc oxide.
3. The high thermal conductivity boron nitride modified insulating rubber composite material according to claim 1, wherein: the preparation method of the modified layered boron nitride nanosheet comprises the following steps:
(1) adding boric acid and urea into distilled water and a methanol solvent in a volume ratio of 1:2-4, stirring for dissolving, freeze-drying to remove the solvent, placing a solid product in an atmosphere resistance furnace, introducing ammonia gas, heating at a rate of 5-10 ℃/min, carrying out heat preservation treatment at 850-880 ℃ for 2-5h, grinding the calcined product to fine powder, placing the fine powder into the distilled water, carrying out ultrasonic stripping treatment in an ultrasonic dispersion instrument at 40-60 ℃ for 2-4h, wherein the ultrasonic frequency is 25-35KHz, filtering and drying to prepare the multilayer boron nitride nanosheet;
(2) placing the multilayer boron nitride nanosheets into a mixed solvent of distilled water and ethanol, transferring the solution into a hydrothermal reaction kettle after ultrasonic dispersion is uniform, heating to 160-200 ℃, reacting for 5-8h, filtering and drying to obtain hydroxylated boron nitride nanosheets;
(3) adding a hydroxylated boron nitride nanosheet into a toluene solvent, uniformly dispersing by ultrasonic, adding 3-glycidoxypropyltriethoxysilane, heating to 120-140 ℃ in a nitrogen atmosphere, uniformly stirring for reaction for 20-30h, filtering, washing and drying to prepare the 3-glycidoxypropyltriethoxysilane-grafted epoxidized layered boron nitride nanosheet;
(4) adding an epoxidized layered boron nitride nanosheet into an acetone solvent, adding acrylamide after uniform ultrasonic dispersion, heating to 70-90 ℃, reacting for 15-25h, removing the solvent, washing and drying to prepare the alkenylated modified layered boron nitride nanosheet.
4. The high thermal conductivity boron nitride modified insulating rubber composite material according to claim 3, wherein: the mass ratio of the boric acid to the urea is 1: 28-35.
5. The high thermal conductivity boron nitride modified insulating rubber composite material according to claim 3, wherein: the mass ratio of the hydroxylated boron nitride nanosheet to the 3-glycidyl ether oxypropyltriethoxysilane is 1: 0.2-0.6.
6. The high thermal conductivity boron nitride modified insulating rubber composite material according to claim 3, wherein: the mass ratio of the epoxidized layered boron nitride nanosheet to the acrylamide is 1: 4-8.
7. The high thermal conductivity boron nitride modified insulating rubber composite material according to claim 3, wherein: ultrasonic dispersion appearance includes the top swing joint of instrument main part, instrument main part has top cap, top cap and slide rail swing joint, slide rail and pulley swing joint, and pulley swing joint has the regulation pole, adjusts pole swing joint has regulator, regulator and fixation clamp swing joint, the inside fixedly connected with sound insulation protective layer of instrument main part, inside both sides fixedly connected with ultrasonic emitter of sound insulation protective layer, the inside below fixedly connected with heating device of sound insulation protective layer.
8. The high thermal conductivity boron nitride modified insulating rubber composite material according to claim 1, wherein: the preparation method of the high-thermal-conductivity boron nitride modified insulating rubber composite material comprises the following steps:
(1) adding 75-90 parts of concentrated natural latex, 1-3.5 parts of emulsifier sodium dodecyl sulfate and 1-4 parts of modified layered boron nitride nanosheet into distilled water solvent, stirring uniformly, adding 3-8 parts of hexyl methacrylate and 3-6 parts of initiator potassium persulfate, reacting at 50-70 ℃ for 6-10h in nitrogen atmosphere, adding 0.5-1 part of elemental sulfur, 0.1-0.5 part of surfactant polyoxyethylene fatty alcohol ether, 0.5-1 part of promoter zinc diethyldithiocarbamate and 0.5-1 part of activator zinc oxide into the solution, carrying out high-speed emulsification, drying the solvent to form emulsion, filtering, defoaming and curing, pouring the emulsion into a film forming mold, and heating for vulcanization to prepare the high-thermal-conductivity boron nitride modified insulating rubber composite material.
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| CN115028892A (en) * | 2022-06-10 | 2022-09-09 | 安徽建筑大学 | Three-dimensional structure modified boron nitride and preparation method and application thereof |
| CN115059806A (en) * | 2022-06-27 | 2022-09-16 | 青岛优派普环保科技股份有限公司 | PE pipe for fuel gas and preparation method thereof |
| CN117261377A (en) * | 2023-11-21 | 2023-12-22 | 汕头市韩领智造服饰有限公司 | Anti-penetration sweat stain-resistant quick-drying ultraviolet-resistant fabric and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115028892A (en) * | 2022-06-10 | 2022-09-09 | 安徽建筑大学 | Three-dimensional structure modified boron nitride and preparation method and application thereof |
| CN115059806A (en) * | 2022-06-27 | 2022-09-16 | 青岛优派普环保科技股份有限公司 | PE pipe for fuel gas and preparation method thereof |
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| CN117261377A (en) * | 2023-11-21 | 2023-12-22 | 汕头市韩领智造服饰有限公司 | Anti-penetration sweat stain-resistant quick-drying ultraviolet-resistant fabric and preparation method and application thereof |
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