CN112250917A - Preparation method of high-thermal-conductivity natural rubber composite material - Google Patents
Preparation method of high-thermal-conductivity natural rubber composite material Download PDFInfo
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Abstract
The invention relates to the technical field of rubber, and discloses a preparation method of a high-thermal-conductivity natural rubber composite material. The method comprises the following steps: 1) placing hexagonal boron nitride in a muffle furnace for high-temperature treatment, and then adding the hexagonal boron nitride into an ethanolamine solvent for ultrasonic oscillation to obtain hexagonal boron nitride nanosheets; 2) preparing metal organic framework-hexagonal boron nitride composite particles; 3) preparing a metal organic framework-hexagonal boron nitride composite particle suspension, adding the metal organic framework-hexagonal boron nitride composite particle suspension into natural latex to obtain a natural latex mixed solution, dropwise adding a calcium chloride solution into the natural latex mixed solution to perform emulsion breaking to obtain a rubber master batch, and sequentially mixing and open-milling the rubber master batch to obtain the high-thermal-conductivity natural rubber composite material. The natural rubber composite material prepared by the invention not only has good heat-conducting property, but also obviously improves the mechanical strength of the rubber composite material.
Description
Technical Field
The invention relates to the technical field of rubber materials, in particular to a preparation method of a high-thermal-conductivity natural rubber composite material.
Background
The natural rubber is of the order ofThe general rubber with longest service time and widest application range in the world mainly comprises isoprene and has a molecular formula of (C)5H8)nThe molar mass is generally between 1000-100000, the polyisoprene content of natural rubber is usually above 97%, besides, it also contains a small amount of non-rubber substances such as protein, saccharide and fly. Natural rubber has a number of excellent physical properties, such as good resilience, insulation, water barrier, air tightness, tensile properties, etc. Besides, it has excellent chemical properties of alkali resistance, acid resistance, heat resistance and the like, and is widely applied to various fields. Such as automobile tires, engine sealing rings in the transportation industry, rain shoes, hot water bags, surgical gloves and infusion tubes in daily life, and even parts of missiles, rockets, satellites and aviation aircraft carriers in the advanced state of national defense science and technology. Along with the development of science and technology, people put forward new demand again to the application of rubber, in the electronic packaging field, electronic components during operation can produce a large amount of heats, these heats need in time to be dispelled, traditional heat dissipation material is metal electrically conductive material, can not with electronic components direct contact, therefore the radiating effect is not good, and soft natural rubber can with electronic components direct contact, this makes it become the more suitable substitute of metal heat dissipation material, but the natural rubber thermal diffusivity is relatively poor, this heat conductivility that just needs to improve it. In addition, as the tire is an important field of natural rubber application, the tire can generate a large amount of heat in the high-speed running process of an automobile, and the internal temperature of the tire is rapidly increased due to the poor heat conduction performance of the natural rubber, so that the aging of the tire is accelerated, and traffic accidents are caused. Therefore, the problems to be solved in the transportation industry are to improve the thermal conductivity of rubber and reduce the temperature of tires.
Chinese patent publication No. CN103589005 discloses a method for preparing illite smectite mixed layer clay/natural rubber composite rubber, which comprises preparing natural illite smectite mixed layer clay into slurry, adding the slurry into natural latex suspension, flocculating and granulating to obtain illite smectite mixed layer clay/natural rubber composite colloidal particles, and drying the colloidal particles to obtain illite smectite mixed layer clay/natural rubber composite rubber. Chinese patent publication No. CN105348585 discloses a white carbon black/natural rubber masterbatch, a preparation method thereof and a white carbon black/natural rubber composite material. The rubber composite materials obtained in the above patent documents have good mechanical properties, but have poor heat conductivity, and thus limit the range of applications of the rubber materials.
Chinese patent publication No. CN111499935 discloses a modified graphene oxide/natural rubber high thermal conductivity composite material, which is prepared by modifying a prepared hexagonal boron nitride nanosheet, mixing the modified hexagonal boron nitride nanosheet with a graphene oxide dispersion to form a hexagonal boron nitride nanosheet modified graphene oxide dispersion, blending the hexagonal boron nitride nano modified graphene oxide dispersion with natural latex, demulsifying to form a masterbatch, plastifying, mixing and vulcanizing the masterbatch to form the high thermal conductivity natural rubber composite material. Although the hexagonal boron nitride nanosheet modified graphene oxide forms a conductive network in rubber, the dispersion performance of the hexagonal boron nitride nanosheet modified graphene oxide in the rubber is poor, and the heat transfer between the heat conducting particles is slow due to the large distance between the heat conducting particles, so that the further improvement of the heat conducting performance of the rubber is limited.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides a preparation method of a high-thermal-conductivity natural rubber composite material. The natural rubber composite material prepared by the invention not only has good heat-conducting property, but also obviously improves the mechanical strength of the rubber composite material.
In order to achieve the purpose, the invention adopts the following technical scheme: a preparation method of a high-thermal-conductivity natural rubber composite material comprises the following steps:
1) placing hexagonal boron nitride in a muffle furnace for high-temperature treatment, cooling to obtain hexagonal boron nitride powder, adding the hexagonal boron nitride powder into an ethanolamine solvent, placing the ethanolamine solvent in an ultrasonic cleaner for ultrasonic oscillation, and centrifuging, washing and drying to obtain hexagonal boron nitride nanosheets;
2) adding zinc nitrate hexahydrate into a methanol solution, stirring and dissolving to obtain a zinc nitrate solution, adding hexagonal boron nitride nanosheets and carbon nanotubes into the zinc nitrate solution, and uniformly dispersing by ultrasonic oscillation to obtain a suspension; adding 2-methylimidazole into a methanol solution, stirring and dissolving to obtain a 2-methylimidazole solution, dropwise adding the 2-methylimidazole solution into the suspension, stirring and reacting at room temperature for 1-3 hours under a dark condition, and centrifuging, washing and drying after the reaction is finished to obtain metal organic framework-hexagonal boron nitride composite particles;
3) adding the metal organic framework-hexagonal boron nitride composite particles into deionized water, uniformly stirring and dispersing to obtain a metal organic framework-hexagonal boron nitride composite particle suspension, adding the metal organic framework-hexagonal boron nitride composite particle suspension into natural latex, uniformly stirring and mixing to obtain a natural latex mixed solution, dropwise adding a calcium chloride solution into the natural latex mixed solution to perform emulsion breaking, and then placing the natural latex mixed solution into an oven to dry to obtain a rubber master batch; and (3) mixing and open milling the rubber master batch in sequence to prepare the high-thermal-conductivity natural rubber composite material.
The hexagonal boron nitride nanosheets and the carbon nanotubes have excellent thermal conductivity, and the ultra-high specific surface area and the high aspect ratio of the hexagonal boron nitride nanosheets enable the thermal conductivity of the material to be improved at a low filling amount. The problem that the hexagonal boron nitride nanosheets and the carbon nanotubes are directly filled into the rubber material is that the hexagonal boron nitride nanosheets and the carbon nanotubes are dispersed in the rubber material in a disordered manner, a regular heat conduction network structure is not easy to form, the heat transfer efficiency between heat conduction particles is low, and the hexagonal boron nitride nanosheets and the carbon nanotubes are easy to agglomerate, so that the improvement effect of the hexagonal boron nitride nanosheets and the carbon nanotubes on the heat conduction performance of the rubber material is influenced. In contrast, the hexagonal boron nitride nanosheet is prepared by an ultrasonic oscillation stripping method, the metal organic framework is prepared by reacting 2-methylimidazole with zinc nitrate, the hexagonal boron nitride nanosheet and the carbon nanotube are embedded into and on the surface of the metal organic framework by taking the metal organic framework as a carrier, so that the hexagonal boron nitride nanosheet and the carbon nanotube are combined with the metal organic framework, part of the carbon nanotube is vertically embedded on the surface of the metal organic framework to form a protruding structure, and the metal organic framework-hexagonal boron nitride composite particle with the heat conducting property and the protruding structure of the carbon nanotube is prepared. The surface of the metal organic framework-hexagonal boron nitride composite particles has a convex structure, so that the metal organic framework-hexagonal boron nitride composite particles are not easy to agglomerate, the dispersity of the heat-conducting particles in the rubber material is improved, and the heat-conducting property of the rubber material is improved.
The hexagonal boron nitride nanosheets inside the metal organic framework-hexagonal boron nitride composite particles are connected with the hexagonal boron nitride nanosheets through the carbon nano tubes, so that the heat conduction efficiency between the hexagonal boron nitride nanosheets is improved, the metal organic framework-hexagonal boron nitride composite particles with high heat conduction performance are further obtained, and the heat conduction performance of the rubber material is improved. On the other hand, the metal organic framework-hexagonal boron nitride composite particles with the carbon nanotube heat conduction protruding structure are uniformly dispersed in the rubber material, so that a heat conduction network with a certain regular structure can be formed, and the heat conduction efficiency of the rubber material is improved; in addition, the heat-conducting protruding structure formed by the carbon nano tubes on the surface of the metal organic framework-hexagonal boron nitride heat-conducting composite particle can shorten the interval between the heat-conducting particles, further improve the heat-conducting efficiency of the rubber material and further improve the heat-conducting performance of the rubber material.
Preferably, the hexagonal boron nitride in the step 1) is placed in a muffle furnace, the high-temperature treatment temperature is 100-300 ℃, and the high-temperature treatment time is 3-6 h.
Preferably, the ultrasonic oscillation power in the step 1) is 80-100W, and the ultrasonic oscillation time is controlled to be 10-15 h.
Preferably, the mass ratio of the zinc nitrate hexahydrate, the hexagonal boron nitride nanosheets and the carbon nanotubes in the step 2) is 1:0.3-0.5: 0.06-0.1.
Preferably, the mixing mass ratio of the zinc nitrate hexahydrate and the 2-methylimidazole in the step 2) is 1: 6-9.
Preferably, the mass ratio of the metal-organic framework-hexagonal boron nitride composite particles to the natural latex in the step 3) is 1: 60-80.
Preferably, the pretreatment of the hexagonal boron nitride nanosheets in the step 1) comprises the following steps:
adding the hexagonal boron nitride nanosheets into a sodium hydroxide solution, heating the solution to 120 ℃ in an oil bath, stirring the solution for reaction for 3-5 hours, and performing centrifugal separation, washing and drying to obtain hydroxylated hexagonal boron nitride nanosheets; adding an epoxy silane coupling agent into a mixed solution of ethanol and water, adjusting the pH value of the system to 4-6, heating in a water bath to 50-60 ℃, stirring for hydrolysis for 30-50min to obtain epoxy silane coupling agent hydrolysate, adding hydroxylated hexagonal boron nitride nanosheets into the epoxy silane coupling agent hydrolysate, stirring for reaction for 1-3h, and performing centrifugal separation, washing and drying to obtain alkylated hexagonal boron nitride nanosheets; adding hyaluronic acid into deionized water, stirring and dissolving to prepare a hyaluronic acid aqueous solution, adding an alkylated hexagonal boron nitride nanosheet into the hyaluronic acid aqueous solution, adding a stannic chloride catalyst, stirring and reacting at 75-85 ℃ for 2-5h, and performing centrifugal separation, washing and drying to obtain the nano-silver-doped zinc oxide.
In the process of preparing the metal organic framework-hexagonal boron nitride composite particle, the invention has the problem that the prepared metal organic framework-hexagonal boron nitride composite particle has lower load of the hexagonal boron nitride nanosheet, so that the heat-conducting property of the metal organic framework-hexagonal boron nitride composite particle is influenced. In order to further solve the problem, the method comprises the steps of firstly carrying out alkaline treatment on the hexagonal boron nitride nanosheets to enable the hexagonal boron nitride nanosheets to load hydroxyl groups, then hydrolyzing the hydroxyl groups obtained by using an epoxy silane coupling agent to carry out dehydration condensation on the hydroxyl groups loaded on the hexagonal boron nitride nanosheets, grafting the epoxy silane coupling agent on the hexagonal boron nitride nanosheets to enable the hexagonal boron nitride nanosheets to load the epoxy groups, carrying out ring-opening reaction on the epoxy groups and the hydroxyl groups on hyaluronic acid molecules to graft hyaluronic acid on the surfaces of the hexagonal boron nitride nanosheets, and enabling the hexagonal boron nitride nanosheets to be subjected to nano-grade boron nitride surface treatmentHyaluronic acid is loaded on the surface of the sheet, hexagonal boron nitride nanosheet loaded with hyaluronic acid and Zn on metal organic framework2+And electrostatic interaction is generated, so that more hexagonal boron nitride nanosheets are combined with the metal organic framework in the preparation process of the metal organic framework-hexagonal boron nitride composite particle, the loading capacity of the hexagonal boron nitride nanosheets on the metal organic framework is improved, and the heat-conducting property of the metal organic framework-hexagonal boron nitride composite particle is further improved.
Preferably, the sodium hydroxide solution has a mass concentration of 0.5 to 1.0%.
Preferably, the mass ratio of the hydroxylated hexagonal boron nitride nanosheets to the epoxy silane coupling agent is 1: 0.2-0.6.
Preferably, the mass concentration of the hyaluronic acid aqueous solution is 0.1-0.5%.
Therefore, compared with the prior art, the invention has the following beneficial effects:
(1) the surface of the organic framework-hexagonal boron nitride composite particles has a convex structure, so that the metal organic framework-hexagonal boron nitride composite particles are not easy to agglomerate, the dispersity of the heat-conducting particles in the rubber material is improved, and the heat-conducting property of the rubber material is improved; (2) the hexagonal boron nitride nanosheets and the hexagonal boron nitride nanosheets in the metal organic framework-hexagonal boron nitride composite particles are connected through the carbon nano tubes, so that the heat conduction efficiency among the hexagonal boron nitride nanosheets is improved, the metal organic framework-hexagonal boron nitride composite particles with high heat conduction performance are further obtained, and the heat conduction of the rubber material is improved; (3) the metal organic framework-hexagonal boron nitride composite particles with the carbon nanotube heat conduction protruding structure are uniformly dispersed in the rubber material, so that a heat conduction network with a certain regular structure can be formed, and the heat conduction efficiency of the rubber material is improved; the heat-conducting protruding structure formed by the carbon nano tubes on the surface of the metal organic framework-hexagonal boron nitride heat-conducting composite particle can shorten the interval between the heat-conducting particles, further improve the heat-conducting efficiency of the rubber material and further improve the heat-conducting performance of the rubber material.
Drawings
FIG. 1 is a graph of the surface temperature of rubber composites of example 1, comparative example 1 and comparative example 2 over time during the infrared thermographic temperature-rise test.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples. In the present invention, unless otherwise specified, raw materials, equipment, and the like used are commercially available or commonly used in the art, and the methods in the examples are conventional in the art unless otherwise specified.
Example 1
The preparation method of the high-thermal-conductivity natural rubber composite material comprises the following steps:
1) placing hexagonal boron nitride in a muffle furnace, performing high-temperature treatment at 300 ℃ for 3h, cooling to obtain hexagonal boron nitride powder, adding the hexagonal boron nitride powder into an ethanolamine solvent according to the mass-to-volume ratio of 1g/70mL, placing in an ultrasonic cleaner, performing ultrasonic oscillation at 100W for 10h, centrifuging, washing and drying to obtain a hexagonal boron nitride nanosheet;
preprocessing hexagonal boron nitride nanosheets:
adding the hexagonal boron nitride nanosheet into a sodium hydroxide solution with the mass concentration of 0.5%, heating to 100 ℃ in an oil bath, stirring for reacting for 5 hours, and performing centrifugal separation, washing and drying to obtain a hydroxylated hexagonal boron nitride nanosheet; mixing ethanol and water according to the volume ratio of 10:2 to obtain a mixed solution of ethanol and water, adding an epoxy silane coupling agent KH-560 into the mixed solution of ethanol and water, wherein the mass ratio of the epoxy silane coupling agent KH-560 to the mixed solution is 1:30, adjusting the pH of the system to 6, heating in a water bath to 50 ℃, stirring for hydrolysis for 50min to obtain an epoxy silane coupling agent hydrolysate, adding a hydroxylated hexagonal boron nitride nanosheet into the epoxy silane coupling agent hydrolysate, wherein the mass ratio of the hydroxylated hexagonal boron nitride nanosheet to the epoxy silane coupling agent KH-560 is 1:0.5, stirring for reaction for 2h, and carrying out centrifugal separation, washing and drying to obtain an alkylated hexagonal boron nitride nanosheet; adding hyaluronic acid into deionized water, stirring and dissolving to prepare a hyaluronic acid aqueous solution with the mass concentration of 0.4%, adding the alkylated hexagonal boron nitride nanosheets into the hyaluronic acid aqueous solution according to the mass-volume ratio of 1g/80mL, adding a stannic chloride catalyst, wherein the addition amount of stannic chloride is 3 wt% of the hyaluronic acid, stirring and reacting for 4 hours at 80 ℃, and performing centrifugal separation, washing and drying to obtain pretreated hexagonal boron nitride nanosheets;
2) adding zinc nitrate hexahydrate into a methanol solution according to the mass-volume ratio of 1g/70mL, stirring and dissolving to obtain a zinc nitrate solution, adding pretreated hexagonal boron nitride nanosheets and carbon nanotubes into the zinc nitrate solution, wherein the mass ratio of the zinc nitrate hexahydrate to the hexagonal boron nitride nanosheets to the carbon nanotubes is 1:0.4:0.09, and uniformly dispersing by ultrasonic oscillation to obtain a suspension; adding 2-methylimidazole into a methanol solution according to the mass-volume ratio of 1g/50mL, stirring and dissolving to obtain a 2-methylimidazole solution, dropwise adding the 2-methylimidazole solution into the suspension, wherein the mixing mass ratio of zinc nitrate hexahydrate and 2-methylimidazole is 1:8, stirring and reacting for 2.5 hours at room temperature under the condition of keeping out of the sun, and centrifuging, washing and drying after the reaction is finished to obtain the metal organic framework-hexagonal boron nitride composite particles;
3) adding metal organic framework-hexagonal boron nitride composite particles into deionized water according to the mass-volume ratio of 1g/100mL, stirring and dispersing uniformly to obtain a metal organic framework-hexagonal boron nitride composite particle suspension, adding the metal organic framework-hexagonal boron nitride composite particle suspension into natural latex with the solid content of 50%, wherein the mass ratio of the metal organic framework-hexagonal boron nitride composite particles to the natural latex is 1:65, stirring and mixing uniformly to obtain a natural latex mixed solution, dropwise adding a calcium chloride aqueous solution with the mass concentration of 3% into the natural latex mixed solution to perform emulsion breaking, and then placing the natural latex mixed solution into an oven for drying to obtain a rubber master batch; and (3) mixing and open milling the rubber master batch in sequence to prepare the high-thermal-conductivity natural rubber composite material.
Example 2
The preparation method of the high-thermal-conductivity natural rubber composite material comprises the following steps:
1) placing hexagonal boron nitride in a muffle furnace, performing high-temperature treatment at 100 ℃ for 6 hours, cooling to obtain hexagonal boron nitride powder, adding the hexagonal boron nitride powder into an ethanolamine solvent according to the mass-volume ratio of 1g/70mL, placing in an ultrasonic cleaner, performing ultrasonic oscillation at 80W for 15 hours, centrifuging, washing and drying to obtain hexagonal boron nitride nanosheets;
preprocessing hexagonal boron nitride nanosheets:
adding the hexagonal boron nitride nanosheet into a sodium hydroxide solution with the mass concentration of 1.0%, heating to 120 ℃ in an oil bath, stirring for reacting for 3 hours, and performing centrifugal separation, washing and drying to obtain a hydroxylated hexagonal boron nitride nanosheet; mixing ethanol and water according to the volume ratio of 10:2 to obtain a mixed solution of ethanol and water, adding an epoxy silane coupling agent KH-560 into the mixed solution of ethanol and water, wherein the mass ratio of the epoxy silane coupling agent KH-560 to the mixed solution is 1:30, adjusting the pH value of the system to 4, heating in a water bath to 60 ℃, stirring for hydrolysis for 30min to obtain an epoxy silane coupling agent hydrolysate, adding hydroxylated hexagonal boron nitride nanosheets into the epoxy silane coupling agent hydrolysate, wherein the mass ratio of the hydroxylated hexagonal boron nitride nanosheets to the epoxy silane coupling agent KH-560 is 1:0.3, stirring for reaction for 1.5h, and carrying out centrifugal separation, washing and drying to obtain alkylated hexagonal boron nitride nanosheets; adding hyaluronic acid into deionized water, stirring and dissolving to prepare a hyaluronic acid aqueous solution with the mass concentration of 0.2%, adding the alkylated hexagonal boron nitride nanosheets into the hyaluronic acid aqueous solution according to the mass-volume ratio of 1g/80mL, adding a stannic chloride catalyst, wherein the addition amount of stannic chloride is 3 wt% of the hyaluronic acid, stirring and reacting for 3 hours at 80 ℃, and performing centrifugal separation, washing and drying to obtain pretreated hexagonal boron nitride nanosheets;
2) adding zinc nitrate hexahydrate into a methanol solution according to the mass-volume ratio of 1g/70mL, stirring and dissolving to obtain a zinc nitrate solution, adding pretreated hexagonal boron nitride nanosheets and carbon nanotubes into the zinc nitrate solution, wherein the mass ratio of the zinc nitrate hexahydrate to the hexagonal boron nitride nanosheets to the carbon nanotubes is 1:0.4:0.07, and uniformly dispersing by ultrasonic oscillation to obtain a suspension; adding 2-methylimidazole into a methanol solution according to the mass-volume ratio of 1g/50mL, stirring and dissolving to obtain a 2-methylimidazole solution, dropwise adding the 2-methylimidazole solution into the suspension, wherein the mixing mass ratio of zinc nitrate hexahydrate and 2-methylimidazole is 1:7, stirring and reacting for 2 hours at room temperature under the condition of keeping out of the sun, and centrifuging, washing and drying after the reaction is finished to obtain the metal organic framework-hexagonal boron nitride composite particles;
3) adding metal organic framework-hexagonal boron nitride composite particles into deionized water according to the mass-volume ratio of 1g/100mL, stirring and dispersing uniformly to obtain a metal organic framework-hexagonal boron nitride composite particle suspension, adding the metal organic framework-hexagonal boron nitride composite particle suspension into natural latex with the solid content of 50%, wherein the mass ratio of the metal organic framework-hexagonal boron nitride composite particles to the natural latex is 1:75, stirring and mixing uniformly to obtain a natural latex mixed solution, dropwise adding a calcium chloride aqueous solution with the mass concentration of 3% into the natural latex mixed solution to perform emulsion breaking, and then placing the natural latex mixed solution into an oven for drying to obtain a rubber master batch; and (3) mixing and open milling the rubber master batch in sequence to prepare the high-thermal-conductivity natural rubber composite material.
Example 3
The preparation method of the high-thermal-conductivity natural rubber composite material comprises the following steps:
1) placing hexagonal boron nitride in a muffle furnace, performing high-temperature treatment at 200 ℃ for 5h, cooling to obtain hexagonal boron nitride powder, adding the hexagonal boron nitride powder into an ethanolamine solvent according to the mass-to-volume ratio of 1g/70mL, placing in an ultrasonic cleaner, performing ultrasonic oscillation at 90W for 12h, centrifuging, washing and drying to obtain a hexagonal boron nitride nanosheet;
preprocessing hexagonal boron nitride nanosheets:
adding the hexagonal boron nitride nanosheet into a sodium hydroxide solution with the mass concentration of 0.8%, heating to 110 ℃ in an oil bath, stirring for reacting for 4 hours, and performing centrifugal separation, washing and drying to obtain a hydroxylated hexagonal boron nitride nanosheet; mixing ethanol and water according to the volume ratio of 10:2 to obtain a mixed solution of ethanol and water, adding an epoxy silane coupling agent KH-560 into the mixed solution of ethanol and water, wherein the mass ratio of the epoxy silane coupling agent KH-560 to the mixed solution is 1:30, adjusting the pH value of the system to 5, heating in a water bath to 55 ℃, stirring for hydrolysis for 40min to obtain an epoxy silane coupling agent hydrolysate, adding a hydroxylated hexagonal boron nitride nanosheet into the epoxy silane coupling agent hydrolysate, wherein the mass ratio of the hydroxylated hexagonal boron nitride nanosheet to the epoxy silane coupling agent KH-560 is 1:0.6, stirring for reaction for 3h, and carrying out centrifugal separation, washing and drying to obtain an alkylated hexagonal boron nitride nanosheet; adding hyaluronic acid into deionized water, stirring and dissolving to prepare a hyaluronic acid aqueous solution with the mass concentration of 0.5%, adding the alkylated hexagonal boron nitride nanosheets into the hyaluronic acid aqueous solution according to the mass-volume ratio of 1g/80mL, adding a stannic chloride catalyst, wherein the addition amount of stannic chloride is 3 wt% of the hyaluronic acid, stirring and reacting for 5 hours at 85 ℃, and performing centrifugal separation, washing and drying to obtain pretreated hexagonal boron nitride nanosheets;
2) adding zinc nitrate hexahydrate into a methanol solution according to the mass-volume ratio of 1g/70mL, stirring and dissolving to obtain a zinc nitrate solution, adding pretreated hexagonal boron nitride nanosheets and carbon nanotubes into the zinc nitrate solution, wherein the mass ratio of the zinc nitrate hexahydrate to the hexagonal boron nitride nanosheets to the carbon nanotubes is 1:0.5:0.1, and uniformly dispersing by ultrasonic oscillation to obtain a suspension; adding 2-methylimidazole into a methanol solution according to the mass-volume ratio of 1g/50mL, stirring and dissolving to obtain a 2-methylimidazole solution, dropwise adding the 2-methylimidazole solution into the suspension, wherein the mixing mass ratio of zinc nitrate hexahydrate and 2-methylimidazole is 1:9, stirring and reacting for 3 hours at room temperature under the condition of keeping out of the sun, and centrifuging, washing and drying after the reaction is finished to obtain the metal organic framework-hexagonal boron nitride composite particles;
3) adding metal organic framework-hexagonal boron nitride composite particles into deionized water according to the mass-volume ratio of 1g/100mL, stirring and dispersing uniformly to obtain a metal organic framework-hexagonal boron nitride composite particle suspension, adding the metal organic framework-hexagonal boron nitride composite particle suspension into natural latex with the solid content of 50%, wherein the mass ratio of the metal organic framework-hexagonal boron nitride composite particles to the natural latex is 1:60, stirring and mixing uniformly to obtain a natural latex mixed solution, dropwise adding a calcium chloride aqueous solution with the mass concentration of 3% into the natural latex mixed solution to perform emulsion breaking, and then placing the natural latex mixed solution into an oven for drying to obtain a rubber master batch; and (3) mixing and open milling the rubber master batch in sequence to prepare the high-thermal-conductivity natural rubber composite material.
Example 4
The preparation method of the high-thermal-conductivity natural rubber composite material comprises the following steps:
1) placing hexagonal boron nitride in a muffle furnace, performing high-temperature treatment at 200 ℃ for 5h, cooling to obtain hexagonal boron nitride powder, adding the hexagonal boron nitride powder into an ethanolamine solvent according to the mass-to-volume ratio of 1g/70mL, placing in an ultrasonic cleaner, performing ultrasonic oscillation at 90W for 12h, centrifuging, washing and drying to obtain a hexagonal boron nitride nanosheet;
preprocessing hexagonal boron nitride nanosheets:
adding the hexagonal boron nitride nanosheet into a sodium hydroxide solution with the mass concentration of 0.8%, heating to 110 ℃ in an oil bath, stirring for reacting for 4 hours, and performing centrifugal separation, washing and drying to obtain a hydroxylated hexagonal boron nitride nanosheet; mixing ethanol and water according to the volume ratio of 10:2 to obtain a mixed solution of ethanol and water, adding an epoxy silane coupling agent KH-560 into the mixed solution of ethanol and water, wherein the mass ratio of the epoxy silane coupling agent KH-560 to the mixed solution is 1:30, adjusting the pH value of the system to 5, heating in a water bath to 55 ℃, stirring for hydrolysis for 40min to obtain an epoxy silane coupling agent hydrolysate, adding a hydroxylated hexagonal boron nitride nanosheet into the epoxy silane coupling agent hydrolysate, wherein the mass ratio of the hydroxylated hexagonal boron nitride nanosheet to the epoxy silane coupling agent KH-560 is 1:0.2, stirring for reaction for 1h, and carrying out centrifugal separation, washing and drying to obtain an alkylated hexagonal boron nitride nanosheet; adding hyaluronic acid into deionized water, stirring and dissolving to prepare a hyaluronic acid aqueous solution with the mass concentration of 0.1%, adding the alkylated hexagonal boron nitride nanosheets into the hyaluronic acid aqueous solution according to the mass-volume ratio of 1g/80mL, adding a stannic chloride catalyst, wherein the addition amount of stannic chloride is 3 wt% of the hyaluronic acid, stirring and reacting for 2 hours at 75 ℃, and performing centrifugal separation, washing and drying to obtain pretreated hexagonal boron nitride nanosheets;
2) adding zinc nitrate hexahydrate into a methanol solution according to the mass-volume ratio of 1g/70mL, stirring and dissolving to obtain a zinc nitrate solution, adding pretreated hexagonal boron nitride nanosheets and carbon nanotubes into the zinc nitrate solution, wherein the mass ratio of the zinc nitrate hexahydrate to the hexagonal boron nitride nanosheets to the carbon nanotubes is 1:0.3:0.06, and uniformly dispersing by ultrasonic oscillation to obtain a suspension; adding 2-methylimidazole into a methanol solution according to the mass-volume ratio of 1g/50mL, stirring and dissolving to obtain a 2-methylimidazole solution, dropwise adding the 2-methylimidazole solution into the suspension, wherein the mixing mass ratio of zinc nitrate hexahydrate and 2-methylimidazole is 1:6, stirring and reacting for 1h at room temperature under the condition of keeping out of the sun, and centrifuging, washing and drying after the reaction is finished to obtain the metal organic framework-hexagonal boron nitride composite particles;
3) adding metal organic framework-hexagonal boron nitride composite particles into deionized water according to the mass-volume ratio of 1g/100mL, stirring and dispersing uniformly to obtain a metal organic framework-hexagonal boron nitride composite particle suspension, adding the metal organic framework-hexagonal boron nitride composite particle suspension into natural latex with the solid content of 50%, wherein the mass ratio of the metal organic framework-hexagonal boron nitride composite particles to the natural latex is 1:80, stirring and mixing uniformly to obtain a natural latex mixed solution, dropwise adding a calcium chloride aqueous solution with the mass concentration of 3% into the natural latex mixed solution to perform emulsion breaking, and then placing the natural latex mixed solution into an oven for drying to obtain a rubber master batch; and (3) mixing and open milling the rubber master batch in sequence to prepare the high-thermal-conductivity natural rubber composite material.
Comparative example 1
Comparative example 1 differs from example 1 in the absence of step 2) while replacing the metal-organic framework-hexagonal boron nitride composite particles in step 3) with hexagonal boron nitride nanoplates.
Comparative example 2
Comparative example 2 differs from example 1 in that the hexagonal boron nitride nanoplates were not pre-treated in step 1).
Comparative example 3
Comparative example 3 differs from example 1 in that no thermally conductive filler is added to the rubber.
Testing of rubber composite Properties
1. And (3) testing mechanical properties:
the tensile strength and the tensile breaking elongation of the rubber composite material are measured by using a universal tensile testing machine, the test is carried out by adopting the GB/T528-2009 standard, the used test sample is a dumbbell-shaped sample strip, the tensile rate is 500mm/10min, the tear strength of the rubber composite material is measured by using the universal tensile testing machine, the test is carried out by adopting the GB/T529-2008 standard, and the used sample is a Y-shaped sample strip.
2. Testing the heat conduction performance:
the heat conductivity coefficient refers to the heat transferred by 1 square meter of area within a certain time when the temperature difference of the surfaces of two sides of the material is microfiltered for 1K under the condition of stable heat transfer, and the unit is W/m.K, and the heat conductivity coefficient is a main physical parameter for representing the heat conductivity of the material. The method adopts a steady state method to test the heat conductivity coefficient of the natural rubber, cuts a rubber sample into small wafers with the thickness of 2mm and the diameter of 30mm, measures the heat conductivity of the sample by a DRL-I heat conductivity coefficient tester, tests each sample for three times, and takes an average value to obtain a final result.
3. Infrared thermal imaging temperature rise test:
and (3) recording the temperature of the object which rises or falls within the same time by using an infrared thermal imager so as to reflect the heat conducting property of the object. Firstly, preparing a stainless steel plate with the thickness of 5mm, keeping the temperature of the steel plate at 90 ℃ by using a heating plate, enabling the temperature of the surface of the steel plate to be uniform, then placing samples with the same thickness on the surface of the steel plate, and recording the temperature of the surface of the sample at intervals of 10s by using an infrared thermal imaging instrument.
According to the test results, the rubber composite material prepared in the embodiment has better thermal conductivity and comprehensive mechanical property than the rubber materials prepared in the comparative examples 1-3. The invention proves that the heat-conducting property of the rubber material can be greatly improved and the comprehensive mechanical strength of the rubber material can be improved by adding the metal organic framework-hexagonal boron nitride composite particles into the natural rubber. The heat conducting performance of the rubber composite material prepared in the embodiment is superior to that of the comparative example 1, because the metal organic framework-hexagonal boron nitride composite particles with the carbon nanotube heat conducting protruding structures are uniformly dispersed in the rubber material, a heat conducting network with a certain regular structure can be formed, and the heat conducting efficiency of the rubber material is improved; the heat-conducting protruding structure formed by the carbon nano tubes on the surface of the metal organic framework-hexagonal boron nitride heat-conducting composite particle can shorten the interval between the heat-conducting particles, further improve the heat-conducting efficiency of the rubber material and further improve the heat-conducting performance of the rubber material. The heat-conducting property of the rubber material prepared in the embodiment is superior to that of the rubber material prepared in the comparative example 2, and the fact that the heat-conducting property of the rubber material can be improved by pretreating the hexagonal boron nitride nanosheet is proved. The tensile strength and the tear strength of the rubber composite material prepared in the embodiment are superior to those of the rubber composite material prepared in the comparative example 1 and the comparative example 3, because the metal organic framework-hexagonal boron nitride composite particles can play a role in reinforcing the rubber material, and the convex structures on the metal organic framework-hexagonal boron nitride composite particles can increase the bonding force of natural rubber and heat conducting particles, so that the mechanical strength of the rubber composite material is further improved.
The surface temperature change curve of the infrared thermal imaging temperature rise test material in the graph of fig. 1 can be obtained, and the surface temperature of the rubber composite material in the example 1 has higher temperature in the same time in the temperature rise process compared with the surface temperature of the rubber composite material in the comparative example 1 and the surface temperature of the rubber composite material in the comparative example 2, so that the rubber composite material prepared in the example 1 has better heat conducting property.
Claims (10)
1. The preparation method of the high-thermal-conductivity natural rubber composite material is characterized by comprising the following steps of:
1) placing hexagonal boron nitride in a muffle furnace for high-temperature treatment, cooling to obtain hexagonal boron nitride powder, adding the hexagonal boron nitride powder into an ethanolamine solvent, placing the ethanolamine solvent in an ultrasonic cleaner for ultrasonic oscillation, and centrifuging, washing and drying to obtain hexagonal boron nitride nanosheets;
2) adding zinc nitrate hexahydrate into a methanol solution, stirring and dissolving to obtain a zinc nitrate solution, adding hexagonal boron nitride nanosheets and carbon nanotubes into the zinc nitrate solution, and uniformly dispersing by ultrasonic oscillation to obtain a suspension; adding 2-methylimidazole into a methanol solution, stirring and dissolving to obtain a 2-methylimidazole solution, dropwise adding the 2-methylimidazole solution into the suspension, stirring and reacting at room temperature for 1-3 hours under a dark condition, and centrifuging, washing and drying after the reaction is finished to obtain metal organic framework-hexagonal boron nitride composite particles;
3) adding the metal organic framework-hexagonal boron nitride composite particles into deionized water, uniformly stirring and dispersing to obtain a metal organic framework-hexagonal boron nitride composite particle suspension, adding the metal organic framework-hexagonal boron nitride composite particle suspension into natural latex, uniformly stirring and mixing to obtain a natural latex mixed solution, dropwise adding a calcium chloride solution into the natural latex mixed solution to perform emulsion breaking, and then placing the natural latex mixed solution into an oven to dry to obtain a rubber master batch; and (3) mixing and open milling the rubber master batch in sequence to prepare the high-thermal-conductivity natural rubber composite material.
2. The preparation method of the natural rubber composite material with high thermal conductivity as claimed in claim 1, wherein the hexagonal boron nitride is placed in a muffle furnace in the step 1) at the high temperature of 100-300 ℃ for 3-6 h.
3. The method for preparing the natural rubber composite material with high thermal conductivity according to claim 1, wherein the ultrasonic oscillation power in the step 1) is 80-100W, and the ultrasonic oscillation time is controlled within 10-15 h.
4. The preparation method of the high-thermal-conductivity natural rubber composite material according to claim 1, wherein the mass ratio of the zinc nitrate hexahydrate, the hexagonal boron nitride nanosheets and the carbon nanotubes in the step 2) is 1:0.3-0.5: 0.06-0.1.
5. The preparation method of the natural rubber composite material with high thermal conductivity according to claim 1, wherein the mixing mass ratio of the zinc nitrate hexahydrate and the 2-methylimidazole in the step 2) is 1: 6-9.
6. The preparation method of the natural rubber composite material with high thermal conductivity according to claim 1, wherein the mass ratio of the metal-organic framework-hexagonal boron nitride composite particles to the natural rubber latex in the step 3) is 1: 60-80.
7. The preparation method of the high-thermal-conductivity natural rubber composite material according to claim 1, wherein the step 1) of pretreating the hexagonal boron nitride nanosheets comprises the following steps:
adding the hexagonal boron nitride nanosheets into a sodium hydroxide solution, heating the solution to 120 ℃ in an oil bath, stirring the solution for reaction for 3-5 hours, and performing centrifugal separation, washing and drying to obtain hydroxylated hexagonal boron nitride nanosheets; adding an epoxy silane coupling agent into a mixed solution of ethanol and water, adjusting the pH value of the system to 4-6, heating in a water bath to 50-60 ℃, stirring for hydrolysis for 30-50min to obtain epoxy silane coupling agent hydrolysate, adding hydroxylated hexagonal boron nitride nanosheets into the epoxy silane coupling agent hydrolysate, stirring for reaction for 1-3h, and performing centrifugal separation, washing and drying to obtain alkylated hexagonal boron nitride nanosheets; adding hyaluronic acid into deionized water, stirring and dissolving to prepare a hyaluronic acid aqueous solution, adding an alkylated hexagonal boron nitride nanosheet into the hyaluronic acid aqueous solution, adding a stannic chloride catalyst, stirring and reacting at 75-85 ℃ for 2-5h, and performing centrifugal separation, washing and drying to obtain the nano-silver-doped zinc oxide.
8. The method for preparing the natural rubber composite material with high thermal conductivity according to claim 7, wherein the mass concentration of the sodium hydroxide solution is 0.5-1.0%.
9. The preparation method of the high-thermal-conductivity natural rubber composite material as claimed in claim 7, wherein the mass ratio of the hydroxylated hexagonal boron nitride nanosheets to the epoxy silane coupling agent is 1: 0.2-0.6.
10. The method for preparing a high thermal conductivity natural rubber composite material as claimed in claim 7, wherein the mass concentration of the hyaluronic acid aqueous solution is 0.1-0.5%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113583449A (en) * | 2021-08-26 | 2021-11-02 | 航天特种材料及工艺技术研究所 | Modified organic silicon composite material and preparation method and application thereof |
| CN115558460A (en) * | 2021-12-30 | 2023-01-03 | 上海都昱新材料科技有限公司 | Pouring sealant for photovoltaic module and preparation method thereof |
| CN115612189A (en) * | 2022-10-28 | 2023-01-17 | 青岛科技大学 | Low-temperature vulcanized rubber material and preparation method thereof |
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2020
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113583449A (en) * | 2021-08-26 | 2021-11-02 | 航天特种材料及工艺技术研究所 | Modified organic silicon composite material and preparation method and application thereof |
| CN115558460A (en) * | 2021-12-30 | 2023-01-03 | 上海都昱新材料科技有限公司 | Pouring sealant for photovoltaic module and preparation method thereof |
| CN115558460B (en) * | 2021-12-30 | 2023-11-28 | 上海都昱新材料科技有限公司 | Pouring sealant for photovoltaic module and preparation method thereof |
| CN115612189A (en) * | 2022-10-28 | 2023-01-17 | 青岛科技大学 | Low-temperature vulcanized rubber material and preparation method thereof |
| CN115612189B (en) * | 2022-10-28 | 2023-11-17 | 青岛科技大学 | Low-temperature vulcanized rubber material and preparation method thereof |
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