CN112812574A - Preparation method of high-thermal-conductivity boron nitride modified styrene butadiene rubber - Google Patents
Preparation method of high-thermal-conductivity boron nitride modified styrene butadiene rubber Download PDFInfo
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Abstract
The invention relates to the technical field of styrene-butadiene rubber, and discloses high-thermal-conductivity boron nitride modified styrene-butadiene rubber, wherein maleic anhydride reacts with styrene-butadiene rubber to obtain maleic anhydride modified styrene-butadiene rubber, boron nitride reacts with oleic acid to further react with m-chloroperoxybenzoic acid to obtain epoxidized boron nitride nanosheets, and further reacts with maleic anhydride modified styrene-butadiene rubber to obtain high-thermal-conductivity boron nitride modified styrene-butadiene rubber, the boron nitride nanosheets are uniformly dispersed in a styrene-butadiene rubber matrix through covalent connection, so that the interface bonding force of the boron nitride nanosheets and the styrene-butadiene rubber is improved, stress can be transferred, the mechanical property is improved, meanwhile, the uniformly dispersed boron nitride nanosheets accelerate phonon diffusion, the interface effect of the boron nitride nanosheets and the styrene-butadiene rubber is improved, the interface thermal resistance is reduced, and the high-thermal-conductivity boron nitride modified styrene-butadiene rubber has excellent mechanical properties, And (4) heat conducting property.
Description
Technical Field
The invention relates to the technical field of styrene butadiene rubber, in particular to a preparation method of boron nitride modified styrene butadiene rubber with high heat conductivity.
Background
Along with the development of society, highway traffic is increasingly developed, and the problem of energy shortage and environmental pollution is more and more serious, people urgently need a novel green tire with the characteristics of high wear resistance, high wet skid resistance, low heat generation, low rolling resistance and the like, wherein the styrene butadiene rubber obtained by emulsion polymerization has the advantages of excellent processing performance, low heat generation, low temperature flexibility, good traction performance, good wear resistance, excellent wet skid resistance and the like, and is widely applied in the fields of tires, adhesive tapes, rubber tubes, electric wires and cables, medical appliances and the like, but due to the structural limitation of molecular chains, the styrene butadiene rubber has poor heat conductivity and poor mechanical property, and the application range of the styrene butadiene rubber is limited.
The nano-filler such as zinc oxide, aluminum oxide, boron nitride nanosheets and the like has the advantages of ultra-high specific surface area, excellent mechanical property, better heat-conducting property and the like, and after the nano-filler is compounded with a polymer, the comprehensive properties such as the mechanical property, the heat-conducting property, the insulating property and the like of the polymer can be effectively enhanced, wherein the boron nitride nanosheets have a graphene-like structure and have excellent heat-conducting insulating property and mechanical property, after the boron nitride nanosheets are compounded with styrene butadiene rubber, the comprehensive property of the styrene butadiene rubber is remarkably improved, but the boron nitride nanosheets are inorganic nano-materials, the dispersibility and the interface bonding force in an organic styrene butadiene rubber matrix are poor, and the modification effect of the boron nitride nanosheets on the styrene butadiene rubber is greatly reduced.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a preparation method of high-thermal-conductivity boron nitride modified styrene-butadiene rubber, and solves the problems of poor thermal conductivity and poor mechanical property of styrene-butadiene rubber.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: the preparation method of the high-thermal-conductivity boron nitride modified styrene-butadiene rubber comprises the following steps:
(1) adding styrene butadiene rubber into a low-temperature double-roller open type rubber mixing mill, wrapping rollers, adding maleic anhydride and an initiator cumene hydroperoxide, uniformly mixing to obtain a mixed rubber, plasticating for 5-20min at 65-80 ℃, cooling to room temperature, washing with deionized water, and drying to obtain maleic anhydride modified styrene butadiene rubber;
(2) adding a deionized water-ethanol mixed solvent and oleic acid in a volume ratio of 1:1-3 into a three-necked bottle, placing the three-necked bottle in a water bath stirring device for uniform dispersion, adding boron nitride nanosheets, uniformly dispersing, transferring the mixture into a reaction kettle for reaction, performing centrifugal separation, washing the mixture with ethanol, and drying the mixture to obtain oleic acid modified boron nitride nanosheets;
(3) adding a dichloromethane-cyclohexane mixed solvent, oleic acid modified boron nitride nanosheets and m-chloroperoxybenzoic acid in a volume ratio of 1:1-3 into a three-necked bottle, placing the three-necked bottle in a water bath stirring device for uniform dispersion, carrying out reaction, centrifuging, washing with ethanol, and drying to obtain epoxidized boron nitride nanosheets;
(4) adding a trichloromethane solvent and maleic anhydride modified styrene-butadiene rubber into a three-neck flask, placing the three-neck flask into a water bath stirring device, stirring for 2.5-4h at 75-90 ℃, adding an epoxidized boron nitride nanosheet and a catalyst 2-methylimidazole, uniformly dispersing, reacting, precipitating a product with methanol, centrifuging, washing with ethanol, and drying to obtain boron nitride grafted styrene-butadiene rubber;
(5) adding boron nitride grafted styrene-butadiene rubber into a low-temperature double-roller open type rubber mixing mill, adding an activating agent zinc oxide, a peptizer stearic acid, an antioxidant tetra (3, 5-di-tert-butyl-4-hydroxyhydrocinnamic acid) pentaerythritol ester and an accelerator N-cyclohexyl-2-benzothiazole sulfonamide after roller wrapping, uniformly mixing to obtain a mixed rubber, plastifying at 70-85 ℃ for 10-25min, placing the product on a flat vulcanizing machine, and pressing at 140-170 ℃ and 13-16MPa for 20-35min to obtain the high-thermal-conductivity boron nitride modified styrene-butadiene rubber.
Preferably, the mass ratio of the styrene-butadiene rubber, the maleic anhydride and the cumene hydroperoxide in the step (1) is 100:6-12: 0.5-1.1.
Preferably, the mass ratio of the oleic acid to the boron nitride nanosheets in the step (2) is 2-5: 100.
Preferably, the reaction condition in the step (2) is that the reaction is carried out at 160-190 ℃ for 9-12 h.
Preferably, the mass ratio of the oleic acid modified boron nitride nanosheet to the m-chloroperoxybenzoic acid in the step (3) is 0.4-0.7: 100.
Preferably, the reaction condition in the step (3) is reflux reaction at 50-65 ℃ for 2.5-4 h.
Preferably, in the step (4), the mass ratio of the maleic anhydride modified styrene-butadiene rubber, the epoxidized boron nitride nanosheet and the 2-methylimidazole is 100:9-12: 1-2.5.
Preferably, the reaction condition in the step (4) is that the reaction is carried out for 1.5 to 3 hours at a temperature of between 80 and 95 ℃.
Preferably, in the step (5), the mass ratio of the boron nitride grafted styrene-butadiene rubber, the zinc oxide, the stearic acid, the pentaerythritol tetrakis (3, 5-di-tert-butyl-4-hydroxyhydrocinnamate) and the N-cyclohexyl-2-benzothiazole sulfonamide is 100:5-8:1-2:0.8-1.4: 0.6-1.2.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
according to the high-thermal-conductivity boron nitride modified styrene-butadiene rubber, under the action of an initiator cumene hydroperoxide, through mechanochemistry in a shear field, radicals are generated by double bonds of maleic anhydride and pi-pi double bonds on a benzene ring of the styrene-butadiene rubber, and a biradical coupling reaction is generated, so that the maleic anhydride is covalently grafted to the styrene-butadiene rubber to obtain the maleic anhydride modified styrene-butadiene rubber, through a hydrothermal reaction, carboxyl groups on oleic acid and hydroxyl groups on boron nitride nanosheets are subjected to an esterification reaction, so that oleic acid and the boron nitride nanosheets are covalently grafted to obtain oleic acid modified boron nitride nanosheets, the double bonds on the oleic acid are further epoxidized by m-chloroperoxybenzoic acid to obtain epoxidized boron nitride nanosheets, and rich epoxy groups are introduced.
According to the high-thermal-conductivity boron nitride modified styrene-butadiene rubber, under the catalytic action of 2-methylimidazole, maleic anhydride grafted by styrene-butadiene rubber generates a ring-opening reaction to generate a carboxylic acid nucleophile, meanwhile, 2-methylimidazole is combined with an epoxy group on a boron nitride nanosheet, so that the epoxy group is positively charged and further reacts with the carboxylic acid nucleophile to promote the ring-opening reaction of the epoxy group to generate an esterification reaction, the boron nitride grafted styrene-butadiene rubber composite material is obtained, the high-thermal-conductivity boron nitride modified styrene-butadiene rubber is further obtained, the boron nitride nanosheet is covalently grafted with the styrene-butadiene rubber, the dispersibility and the interfacial bonding force of the boron nitride nanosheet in a styrene-butadiene rubber matrix are improved, the boron nitride nanosheet is highly dispersed in the styrene-butadiene rubber matrix, and the agglomeration phenomenon of the.
According to the high-thermal-conductivity boron nitride modified styrene-butadiene rubber, through covalent connection, boron nitride nanosheets are uniformly dispersed in a styrene-butadiene rubber matrix, the interface area with the styrene-butadiene rubber is increased, and meanwhile, the interface bonding force between the boron nitride nanosheets and the styrene-butadiene rubber is increased, so that the interface strength between the boron nitride nanosheets and the styrene-butadiene rubber is increased, the physical/chemical crosslinking sites of the composite material are increased, the stress is transferred from the styrene-butadiene rubber matrix to the boron nitride grafted styrene-butadiene rubber, and the mechanical property of the composite material is improved.
According to the high-thermal-conductivity boron nitride modified styrene-butadiene rubber, through covalent connection, boron nitride nanosheets are uniformly dispersed in a styrene-butadiene rubber matrix, the effective volume of a composite material is increased, gaps between the boron nitride nanosheets and the styrene-butadiene rubber are reduced, the content of cavities of a thermal insulator is reduced, meanwhile, the uniformly dispersed boron nitride nanosheets and the boron nitride nanosheets have ultrahigh specific surface areas, a thermal flow area is remarkably increased, phonons are accelerated to diffuse in the composite material, and the covalent connection is realized, so that the interface effect of the boron nitride nanosheets and the styrene-butadiene rubber is improved, the interface thermal resistance is reduced, the thermal conductivity is improved, and the high-thermal-conductivity boron nitride modified styrene-butadiene rubber has excellent mechanical properties and thermal conductivity.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: a preparation method of boron nitride modified styrene butadiene rubber with high thermal conductivity comprises the following steps:
(1) adding styrene-butadiene rubber into a low-temperature double-roll open rubber mixing mill, wrapping a roll, adding maleic anhydride and an initiator cumene hydroperoxide, wherein the mass ratio of the styrene-butadiene rubber to the maleic anhydride to the cumene hydroperoxide is 100:6-12:0.5-1.1, uniformly mixing to obtain a mixed rubber, plasticating for 5-20min at 65-80 ℃, cooling to room temperature, washing with deionized water, and drying to obtain maleic anhydride modified styrene-butadiene rubber;
(2) adding a deionized water-ethanol mixed solvent and oleic acid in a volume ratio of 1:1-3 into a three-necked bottle, placing the three-necked bottle in a water bath stirring device for uniform dispersion, adding boron nitride nanosheets, wherein the mass ratio of the oleic acid to the boron nitride nanosheets is 2-5:100, uniformly dispersing, transferring the mixture into a reaction kettle, reacting for 9-12h at the temperature of 160-;
(3) adding a dichloromethane-cyclohexane mixed solvent, an oleic acid modified boron nitride nanosheet and m-chloroperoxybenzoic acid in a volume ratio of 1:1-3 into a three-necked bottle, wherein the mass ratio of the dichloromethane-cyclohexane mixed solvent to the oleic acid modified boron nitride nanosheet to the m-chloroperoxybenzoic acid is 0.4-0.7:100, placing the mixture into a water bath stirring device for uniform dispersion, carrying out reflux reaction at 50-65 ℃ for 2.5-4h, centrifuging, washing with ethanol, and drying to obtain an epoxidized boron nitride nanosheet;
(4) adding a trichloromethane solvent and maleic anhydride modified styrene-butadiene rubber into a three-necked bottle, placing the three-necked bottle in a water bath stirring device, stirring the three-necked bottle at 75-90 ℃ for 2.5-4h, adding epoxidized boron nitride nanosheets and a catalyst 2-methylimidazole, wherein the mass ratio of the maleic anhydride modified styrene-butadiene rubber to the epoxidized boron nitride nanosheets to the 2-methylimidazole is 100:9-12:1-2.5, uniformly dispersing the mixture, reacting the mixture at 80-95 ℃ for 1.5-3h, precipitating a product by using methanol, centrifuging the product, washing the product by using ethanol, and drying the product to obtain boron nitride grafted styrene-butadiene rubber;
(5) adding boron nitride grafted styrene-butadiene rubber into a low-temperature double-roll open type rubber mixing mill, adding an activating agent zinc oxide, a peptizer stearic acid, an antioxidant pentaerythritol tetra (3, 5-di-tert-butyl-4-hydroxyhydrocinnamic acid) and an accelerator N-cyclohexyl-2-benzothiazole sulfenamide after roll wrapping, wherein the mass ratio of the boron nitride grafted styrene-butadiene rubber, the zinc oxide, the stearic acid, the pentaerythritol tetra (3, 5-di-tert-butyl-4-hydroxyhydrocinnamic acid) and the N-cyclohexyl-2-benzothiazole sulfenamide is 100:5-8:1-2:0.8-1.4:0.6-1.2, uniformly mixing to obtain a mixed rubber, plastifying at 70-85 ℃ for 10-25min, placing the product on a flat vulcanizing machine, and vulcanizing at 140 ℃ and 170 ℃ -, And (3) pressing for 20-35min under 13-16MPa to obtain the high-heat-conductivity boron nitride modified styrene-butadiene rubber.
Example 1
(1) Adding styrene butadiene rubber into a low-temperature double-roller open type rubber mixing mill, wrapping rollers, adding maleic anhydride and an initiator cumene hydroperoxide, wherein the mass ratio of the styrene butadiene rubber to the maleic anhydride to the cumene hydroperoxide is 100:6:0.5, uniformly mixing to obtain a rubber mixture, plasticating for 5min at 65 ℃, cooling to room temperature, washing with deionized water, and drying to obtain maleic anhydride modified styrene butadiene rubber;
(2) adding a deionized water-ethanol mixed solvent and oleic acid in a volume ratio of 1:1 into a three-necked bottle, placing the three-necked bottle in a water bath stirring device for uniform dispersion, adding boron nitride nanosheets, wherein the mass ratio of the oleic acid to the boron nitride nanosheets is 2:100, uniformly dispersing, transferring the mixture into a reaction kettle, reacting for 9 hours at 160 ℃, performing centrifugal separation, washing with ethanol, and drying to obtain oleic acid modified boron nitride nanosheets;
(3) adding a dichloromethane-cyclohexane mixed solvent, an oleic acid modified boron nitride nanosheet and m-chloroperoxybenzoic acid in a volume ratio of 1:1 into a three-necked bottle, wherein the mass ratio of the dichloromethane-cyclohexane mixed solvent to the oleic acid modified boron nitride nanosheet to the m-chloroperoxybenzoic acid is 0.4:100, uniformly dispersing in a water bath stirring device, carrying out reflux reaction at 50 ℃ for 2.5h, centrifuging, washing with ethanol, and drying to obtain an epoxidized boron nitride nanosheet;
(4) adding a trichloromethane solvent and maleic anhydride modified styrene-butadiene rubber into a three-necked bottle, placing the three-necked bottle in a water bath stirring device, stirring the three-necked bottle at 75 ℃ for 2.5 hours, adding an epoxidized boron nitride nanosheet and a catalyst 2-methylimidazole, wherein the mass ratio of the maleic anhydride modified styrene-butadiene rubber to the epoxidized boron nitride nanosheet to the 2-methylimidazole is 100:9:1, uniformly dispersing, reacting at 80 ℃ for 1.5 hours, precipitating a product with methanol, centrifuging, washing the product with ethanol, and drying to obtain boron nitride grafted styrene-butadiene rubber;
(5) adding boron nitride grafted styrene-butadiene rubber into a low-temperature double-roller open type rubber mixing mill, adding an activating agent zinc oxide, a peptizer stearic acid, an antioxidant tetra (3, 5-di-tert-butyl-4-hydroxyhydrocinnamic acid) pentaerythritol ester and an accelerator N-cyclohexyl-2-benzothiazole sulfonamide after roller wrapping, wherein the mass ratio of the boron nitride grafted styrene butadiene rubber, the zinc oxide, the stearic acid, the tetra (3, 5-di-tert-butyl-4-hydroxyhydrocinnamic acid) pentaerythritol ester and the N-cyclohexyl-2-benzothiazole sulfonamide is 100:5:1:0.8:0.6, the mixed rubber is obtained after even mixing, plasticating for 10min at 70 ℃, placing the product on a flat vulcanizing machine, and pressing for 20min at 140 ℃ and 13MPa to obtain the high-heat-conductivity boron nitride modified styrene-butadiene rubber.
Example 2
(1) Adding styrene butadiene rubber into a low-temperature double-roller open type rubber mixing mill, wrapping rollers, adding maleic anhydride and an initiator cumene hydroperoxide, wherein the mass ratio of the styrene butadiene rubber to the maleic anhydride to the cumene hydroperoxide is 100:8:0.7, uniformly mixing to obtain a rubber mixture, plasticating for 10min at 70 ℃, cooling to room temperature, washing with deionized water, and drying to obtain maleic anhydride modified styrene butadiene rubber;
(2) adding a deionized water-ethanol mixed solvent and oleic acid in a volume ratio of 1:1.5 into a three-necked bottle, placing the three-necked bottle in a water bath stirring device for uniform dispersion, adding boron nitride nanosheets, wherein the mass ratio of the oleic acid to the boron nitride nanosheets is 3:100, the uniform dispersion is carried out, transferring the mixture into a reaction kettle, reacting for 10 hours at 170 ℃, carrying out centrifugal separation, washing with ethanol, and drying to obtain oleic acid modified boron nitride nanosheets;
(3) adding a dichloromethane-cyclohexane mixed solvent, an oleic acid modified boron nitride nanosheet and m-chloroperoxybenzoic acid in a volume ratio of 1:1.5 into a three-necked bottle, wherein the mass ratio of the dichloromethane-cyclohexane mixed solvent to the oleic acid modified boron nitride nanosheet to the m-chloroperoxybenzoic acid is 0.5:100, uniformly dispersing in a water bath stirring device, carrying out reflux reaction at 55 ℃ for 3h, centrifuging, washing with ethanol, and drying to obtain an epoxidized boron nitride nanosheet;
(4) adding a trichloromethane solvent and maleic anhydride modified styrene-butadiene rubber into a three-necked bottle, placing the three-necked bottle in a water bath stirring device, stirring for 3h at 80 ℃, adding epoxidized boron nitride nanosheets and a catalyst 2-methylimidazole, wherein the mass ratio of the maleic anhydride modified styrene-butadiene rubber to the epoxidized boron nitride nanosheets to the 2-methylimidazole is 100:10:1.5, uniformly dispersing, reacting for 2h at 85 ℃, precipitating a product with methanol, centrifuging, washing with ethanol, and drying to obtain boron nitride grafted styrene-butadiene rubber;
(5) adding boron nitride grafted styrene-butadiene rubber into a low-temperature double-roller open type rubber mixing mill, adding an activating agent zinc oxide, a peptizer stearic acid, an antioxidant tetra (3, 5-di-tert-butyl-4-hydroxyhydrocinnamic acid) pentaerythritol ester and an accelerator N-cyclohexyl-2-benzothiazole sulfonamide after roller wrapping, wherein the mass ratio of the boron nitride grafted styrene butadiene rubber, the zinc oxide, the stearic acid, the tetra (3, 5-di-tert-butyl-4-hydroxyhydrocinnamic acid) pentaerythritol ester and the N-cyclohexyl-2-benzothiazole sulfonamide is 100:6:1.3:1:0.8, the mixed rubber is obtained after even mixing, plasticating for 15min at 75 ℃, placing the product on a flat vulcanizing machine, and carrying out mould pressing for 25min at 150 ℃ and 14MPa to obtain the high-thermal-conductivity boron nitride modified styrene-butadiene rubber.
Example 3
(1) Adding styrene butadiene rubber into a low-temperature double-roller open type rubber mixing mill, wrapping rollers, adding maleic anhydride and an initiator cumene hydroperoxide, wherein the mass ratio of the styrene butadiene rubber to the maleic anhydride to the cumene hydroperoxide is 100:10:0.9, uniformly mixing to obtain a rubber mixture, plasticating for 15min at 75 ℃, cooling to room temperature, washing with deionized water, and drying to obtain maleic anhydride modified styrene butadiene rubber;
(2) adding a deionized water-ethanol mixed solvent and oleic acid in a volume ratio of 1:2 into a three-necked bottle, placing the three-necked bottle in a water bath stirring device for uniform dispersion, adding boron nitride nanosheets, wherein the mass ratio of the oleic acid to the boron nitride nanosheets is 4:100, uniformly dispersing, transferring the mixture into a reaction kettle, reacting for 11 hours at 180 ℃, performing centrifugal separation, washing with ethanol, and drying to obtain oleic acid modified boron nitride nanosheets;
(3) adding a dichloromethane-cyclohexane mixed solvent, an oleic acid modified boron nitride nanosheet and m-chloroperoxybenzoic acid in a volume ratio of 1:2 into a three-necked bottle, wherein the mass ratio of the dichloromethane-cyclohexane mixed solvent to the oleic acid modified boron nitride nanosheet to the m-chloroperoxybenzoic acid is 0.6:100, placing the three-necked bottle into a water bath stirring device for uniform dispersion, carrying out reflux reaction for 3.5 hours at 60 ℃, centrifuging, washing with ethanol, and drying to obtain an epoxidized boron nitride nanosheet;
(4) adding a trichloromethane solvent and maleic anhydride modified styrene-butadiene rubber into a three-necked bottle, placing the three-necked bottle in a water bath stirring device, stirring the three-necked bottle at 85 ℃ for 3.5 hours, adding epoxidized boron nitride nanosheets and a catalyst 2-methylimidazole, wherein the mass ratio of the maleic anhydride modified styrene-butadiene rubber to the epoxidized boron nitride nanosheets to the 2-methylimidazole is 100:11:2, uniformly dispersing, reacting at 90 ℃ for 2.5 hours, precipitating a product with methanol, centrifuging, washing the product with ethanol, and drying to obtain boron nitride grafted styrene-butadiene rubber;
(5) adding boron nitride grafted styrene-butadiene rubber into a low-temperature double-roller open type rubber mixing mill, adding an activating agent zinc oxide, a peptizer stearic acid, an antioxidant tetra (3, 5-di-tert-butyl-4-hydroxyhydrocinnamic acid) pentaerythritol ester and an accelerator N-cyclohexyl-2-benzothiazole sulfonamide after roller wrapping, wherein the mass ratio of the boron nitride grafted styrene butadiene rubber, the zinc oxide, the stearic acid, the tetra (3, 5-di-tert-butyl-4-hydroxyhydrocinnamic acid) pentaerythritol ester and the N-cyclohexyl-2-benzothiazole sulfonamide is 100:7:1.6:1.2:1, the mixed rubber is obtained after uniform mixing, plasticating for 20min at the temperature of 80 ℃, placing the product on a flat vulcanizing machine, and pressing for 30min at the temperature of 160 ℃ and the pressure of 15MPa to obtain the high-heat-conductivity boron nitride modified styrene-butadiene rubber.
Example 4
(1) Adding styrene butadiene rubber into a low-temperature double-roller open type rubber mixing mill, wrapping rollers, adding maleic anhydride and an initiator cumene hydroperoxide, wherein the mass ratio of the styrene butadiene rubber to the maleic anhydride to the cumene hydroperoxide is 100:12:1.1, uniformly mixing to obtain a rubber mixture, plasticating for 20min at 80 ℃, cooling to room temperature, washing with deionized water, and drying to obtain maleic anhydride modified styrene butadiene rubber;
(2) adding a deionized water-ethanol mixed solvent and oleic acid in a volume ratio of 1:3 into a three-necked bottle, placing the three-necked bottle in a water bath stirring device for uniform dispersion, adding boron nitride nanosheets, wherein the mass ratio of the oleic acid to the boron nitride nanosheets is 5:100, uniformly dispersing, transferring the mixture into a reaction kettle, reacting for 12 hours at 190 ℃, performing centrifugal separation, washing with ethanol, and drying to obtain oleic acid modified boron nitride nanosheets;
(3) adding a dichloromethane-cyclohexane mixed solvent, an oleic acid modified boron nitride nanosheet and m-chloroperoxybenzoic acid in a volume ratio of 1:3 into a three-necked bottle, wherein the mass ratio of the dichloromethane-cyclohexane mixed solvent to the oleic acid modified boron nitride nanosheet to the m-chloroperoxybenzoic acid is 0.7:100, placing the three-necked bottle into a water bath stirring device for uniform dispersion, carrying out reflux reaction for 4 hours at 65 ℃, centrifuging, washing with ethanol, and drying to obtain an epoxidized boron nitride nanosheet;
(4) adding a trichloromethane solvent and maleic anhydride modified styrene-butadiene rubber into a three-necked bottle, placing the three-necked bottle in a water bath stirring device, stirring for 4 hours at 90 ℃, adding epoxidized boron nitride nanosheets and a catalyst 2-methylimidazole, wherein the mass ratio of the maleic anhydride modified styrene-butadiene rubber to the epoxidized boron nitride nanosheets to the 2-methylimidazole is 100:12:2.5, uniformly dispersing, reacting for 3 hours at 95 ℃, precipitating a product with methanol, centrifuging, washing with ethanol, and drying to obtain boron nitride grafted styrene-butadiene rubber;
(5) adding boron nitride grafted styrene-butadiene rubber into a low-temperature double-roller open type rubber mixing mill, adding an activating agent zinc oxide, a peptizer stearic acid, an antioxidant tetra (3, 5-di-tert-butyl-4-hydroxyhydrocinnamic acid) pentaerythritol ester and an accelerator N-cyclohexyl-2-benzothiazole sulfonamide after roller wrapping, wherein the mass ratio of the boron nitride grafted styrene butadiene rubber, the zinc oxide, the stearic acid, the tetra (3, 5-di-tert-butyl-4-hydroxyhydrocinnamic acid) pentaerythritol ester and the N-cyclohexyl-2-benzothiazole sulfonamide is 100:8:2:1.4:1.2, the mixed rubber is obtained after uniform mixing, plasticating for 25min at 85 ℃, placing the product on a flat vulcanizing machine, and carrying out mould pressing for 35min at 170 ℃ and 6MPa to obtain the high-thermal-conductivity boron nitride modified styrene-butadiene rubber.
Comparative example 1
(1) Adding styrene butadiene rubber into a low-temperature double-roller open type rubber mixing mill, wrapping rollers, adding maleic anhydride and an initiator cumene hydroperoxide, wherein the mass ratio of the styrene butadiene rubber to the maleic anhydride to the cumene hydroperoxide is 100:3:0.2, uniformly mixing to obtain a rubber mixture, plasticating for 5min at 65 ℃, cooling to room temperature, washing with deionized water, and drying to obtain maleic anhydride modified styrene butadiene rubber;
(2) adding a deionized water-ethanol mixed solvent and oleic acid in a volume ratio of 1:1 into a three-necked bottle, placing the three-necked bottle in a water bath stirring device for uniform dispersion, adding boron nitride nanosheets, wherein the mass ratio of the oleic acid to the boron nitride nanosheets is 1:100, uniformly dispersing, transferring the mixture into a reaction kettle, reacting for 9 hours at 160 ℃, performing centrifugal separation, washing with ethanol, and drying to obtain oleic acid modified boron nitride nanosheets;
(3) adding a dichloromethane-cyclohexane mixed solvent, an oleic acid modified boron nitride nanosheet and m-chloroperoxybenzoic acid in a volume ratio of 1:1 into a three-necked bottle, wherein the mass ratio of the dichloromethane-cyclohexane mixed solvent to the oleic acid modified boron nitride nanosheet to the m-chloroperoxybenzoic acid is 0.2:100, uniformly dispersing in a water bath stirring device, carrying out reflux reaction at 50 ℃ for 2.5h, centrifuging, washing with ethanol, and drying to obtain an epoxidized boron nitride nanosheet;
(4) adding a trichloromethane solvent and maleic anhydride modified styrene-butadiene rubber into a three-necked bottle, placing the three-necked bottle in a water bath stirring device, stirring the three-necked bottle at 75 ℃ for 2.5 hours, adding epoxidized boron nitride nanosheets and a catalyst 2-methylimidazole, wherein the mass ratio of the maleic anhydride modified styrene-butadiene rubber to the epoxidized boron nitride nanosheets to the 2-methylimidazole is 100:4.5:0.5, uniformly dispersing, reacting at 80 ℃ for 1.5 hours, precipitating a product with methanol, centrifuging, washing the product with ethanol, and drying to obtain boron nitride grafted styrene-butadiene rubber;
(5) adding boron nitride grafted styrene-butadiene rubber into a low-temperature double-roller open type rubber mixing mill, adding an activating agent zinc oxide, a peptizer stearic acid, an antioxidant tetra (3, 5-di-tert-butyl-4-hydroxyhydrocinnamic acid) pentaerythritol ester and an accelerator N-cyclohexyl-2-benzothiazole sulfonamide after roller wrapping, wherein the mass ratio of the boron nitride grafted styrene butadiene rubber, the zinc oxide, the stearic acid, the tetra (3, 5-di-tert-butyl-4-hydroxyhydrocinnamic acid) pentaerythritol ester and the N-cyclohexyl-2-benzothiazole sulfonamide is 100:2.5:0.5:0.4:0.3, the mixed rubber is obtained after even mixing, plasticating for 10min at 70 ℃, placing the product on a flat vulcanizing machine, and pressing for 20min at 140 ℃ and 13MPa to obtain the high-heat-conductivity boron nitride modified styrene-butadiene rubber.
Comparative example 2
(1) Adding styrene butadiene rubber into a low-temperature double-roller open type rubber mixing mill, wrapping rollers, adding maleic anhydride and an initiator cumene hydroperoxide, wherein the mass ratio of the styrene butadiene rubber to the maleic anhydride to the cumene hydroperoxide is 100:18:1.6, uniformly mixing to obtain a rubber mixture, plasticating for 20min at 80 ℃, cooling to room temperature, washing with deionized water, and drying to obtain maleic anhydride modified styrene butadiene rubber;
(2) adding a deionized water-ethanol mixed solvent and oleic acid in a volume ratio of 1:3 into a three-necked bottle, placing the three-necked bottle in a water bath stirring device for uniform dispersion, adding boron nitride nanosheets, wherein the mass ratio of the oleic acid to the boron nitride nanosheets is 7:100, uniformly dispersing, transferring the mixture into a reaction kettle, reacting for 12 hours at 190 ℃, performing centrifugal separation, washing with ethanol, and drying to obtain oleic acid modified boron nitride nanosheets;
(3) adding a dichloromethane-cyclohexane mixed solvent, an oleic acid modified boron nitride nanosheet and m-chloroperoxybenzoic acid in a volume ratio of 1:3 into a three-necked bottle, wherein the mass ratio of the dichloromethane-cyclohexane mixed solvent to the oleic acid modified boron nitride nanosheet to the m-chloroperoxybenzoic acid is 1.1:100, uniformly dispersing in a water bath stirring device, carrying out reflux reaction for 4 hours at 65 ℃, centrifuging, washing with ethanol, and drying to obtain an epoxidized boron nitride nanosheet;
(4) adding a trichloromethane solvent and maleic anhydride modified styrene-butadiene rubber into a three-necked bottle, placing the three-necked bottle in a water bath stirring device, stirring for 4 hours at 90 ℃, adding epoxidized boron nitride nanosheets and a catalyst 2-methylimidazole, wherein the mass ratio of the maleic anhydride modified styrene-butadiene rubber to the epoxidized boron nitride nanosheets to the 2-methylimidazole is 100:21:3.5, uniformly dispersing, reacting for 3 hours at 95 ℃, precipitating a product with methanol, centrifuging, washing with ethanol, and drying to obtain boron nitride grafted styrene-butadiene rubber;
(5) adding boron nitride grafted styrene-butadiene rubber into a low-temperature double-roller open type rubber mixing mill, adding an activating agent zinc oxide, a peptizer stearic acid, an antioxidant tetra (3, 5-di-tert-butyl-4-hydroxyhydrocinnamic acid) pentaerythritol ester and an accelerator N-cyclohexyl-2-benzothiazole sulfonamide after roller wrapping, wherein the mass ratio of the boron nitride grafted styrene butadiene rubber, the zinc oxide, the stearic acid, the tetra (3, 5-di-tert-butyl-4-hydroxyhydrocinnamic acid) pentaerythritol ester and the N-cyclohexyl-2-benzothiazole sulfonamide is 100:13:3:2.2:1.8, the mixed rubber is obtained after uniform mixing, plasticating for 25min at 85 ℃, placing the product on a flat vulcanizing machine, and carrying out mould pressing for 35min at 170 ℃ and 16MPa to obtain the high-thermal-conductivity boron nitride modified styrene-butadiene rubber.
The tensile strength and elongation at break of the high thermal conductive boron nitride modified styrene-butadiene rubber obtained in the examples and comparative examples were tested using a WBE-9000B type universal tester with the test standard GB/T7762-.
The DRPL-III type high-precision material thermal conductivity tester is used for testing the thermal conductivity of the high-thermal conductivity boron nitride modified styrene-butadiene rubber obtained in the examples and the comparative examples at room temperature, and the test standard is GB/T11205-2009.
Claims (9)
1. The high-thermal-conductivity boron nitride modified styrene butadiene rubber is characterized in that: the preparation method of the high-thermal-conductivity boron nitride modified styrene butadiene rubber comprises the following steps:
(1) adding maleic anhydride and an initiator cumene hydroperoxide into the styrene butadiene rubber coated with the roll, uniformly mixing to obtain a rubber compound, plasticating for 5-20min at 65-80 ℃, cooling to room temperature, washing and drying to obtain maleic anhydride modified styrene butadiene rubber;
(2) adding oleic acid into a deionized water-ethanol mixed solvent with a volume ratio of 1:1-3, placing the mixture into a water bath stirring device for uniform dispersion, adding boron nitride nanosheets, uniformly dispersing, transferring the mixture into a reaction kettle for reaction, performing centrifugal separation, washing and drying to obtain oleic acid modified boron nitride nanosheets;
(3) adding an oleic acid modified boron nitride nanosheet and m-chloroperoxybenzoic acid into a dichloromethane-cyclohexane mixed solvent with a volume ratio of 1:1-3, placing the mixture into a water bath stirring device for uniform dispersion, reacting, centrifuging, washing and drying to obtain an epoxidized boron nitride nanosheet;
(4) adding maleic anhydride modified styrene-butadiene rubber into a trichloromethane solvent, placing the mixture into a water bath stirring device, stirring the mixture for 2.5 to 4 hours at the temperature of between 75 and 90 ℃, adding an epoxidized boron nitride nanosheet and a catalyst 2-methylimidazole, uniformly dispersing the mixture, carrying out reaction, precipitating a product with methanol, centrifuging, washing and drying the product to obtain boron nitride grafted styrene-butadiene rubber;
(5) adding an activating agent zinc oxide, a peptizer stearic acid, an antioxidant pentaerythritol tetrakis (3, 5-di-tert-butyl-4-hydroxyhydrocinnamate) and an accelerator N-cyclohexyl-2-benzothiazole sulfenamide into the boron nitride grafted styrene butadiene rubber coated with the roller, uniformly mixing to obtain a mixed rubber, plastifying at 70-85 ℃ for 10-25min, placing the product on a flat vulcanizing machine, and pressing at 140-170 ℃ and 13-16MPa for 20-35min to obtain the boron nitride modified styrene butadiene rubber with high thermal conductivity.
2. The high thermal conductivity boron nitride modified styrene-butadiene rubber according to claim 1, wherein: in the step (1), the mass ratio of the styrene-butadiene rubber, the maleic anhydride and the cumene hydroperoxide is 100:6-12: 0.5-1.1.
3. The high thermal conductivity boron nitride modified styrene-butadiene rubber according to claim 1, wherein: in the step (2), the mass ratio of the oleic acid to the boron nitride nanosheet is 2-5: 100.
4. The high thermal conductivity boron nitride modified styrene-butadiene rubber according to claim 1, wherein: the reaction condition in the step (2) is that the reaction is carried out for 9-12h at the temperature of 160-190 ℃.
5. The high thermal conductivity boron nitride modified styrene-butadiene rubber according to claim 1, wherein: the mass ratio of the oleic acid modified boron nitride nanosheet to the m-chloroperoxybenzoic acid in the step (3) is 0.4-0.7: 100.
6. The high thermal conductivity boron nitride modified styrene-butadiene rubber according to claim 1, wherein: the reaction condition in the step (3) is reflux reaction at 50-65 ℃ for 2.5-4 h.
7. The high thermal conductivity boron nitride modified styrene-butadiene rubber according to claim 1, wherein: in the step (4), the mass ratio of the maleic anhydride modified styrene-butadiene rubber, the epoxidized boron nitride nanosheet and the 2-methylimidazole is 100:9-12: 1-2.5.
8. The high thermal conductivity boron nitride modified styrene-butadiene rubber according to claim 1, wherein: the reaction condition in the step (4) is that the reaction is carried out for 1.5 to 3 hours at the temperature of between 80 and 95 ℃.
9. The high thermal conductivity boron nitride modified styrene-butadiene rubber according to claim 1, wherein: in the step (5), the mass ratio of the boron nitride grafted styrene-butadiene rubber, the zinc oxide, the stearic acid, the pentaerythritol tetrakis (3, 5-di-tert-butyl-4-hydroxyhydrocinnamate) and the N-cyclohexyl-2-benzothiazole sulfonamide is 100:5-8:1-2:0.8-1.4: 0.6-1.2.
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