CN111748193A - High-thermal-conductivity graphene-carbon nanotube modified polyurethane elastomer and preparation method thereof - Google Patents
High-thermal-conductivity graphene-carbon nanotube modified polyurethane elastomer and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of polyurethane, and discloses a high-thermal-conductivity graphene-carbon nanotube modified polyurethane elastomer, which is prepared by taking graphene oxide as a raw material, performing ultrasonic dispersion, then taking azobisisobutyronitrile as an initiator to obtain cyano-group modified graphene oxide, hydrolyzing the cyano-group modified graphene oxide under an alkaline condition to obtain carboxylated graphene with rich carboxyl content, wherein a large amount of carboxyl can promote amidation reaction with amino of 4,4' -diaminobiphenyl, and the high-thermal-conductivity graphene-carbon nanotube modified polyurethane elastomer has the advantages that the chemical grafting structure of carbon nano-tubes and graphene is favorable for dispersion of the carbon nano-tubes and the graphene, the carbon nano-tubes have a support effect on the graphene, the special structures of the carbon nano-tubes and the graphene greatly enhance the mechanical property of a polyurethane material, and the graphene and the carbon nano-tubes both have good thermal conductivity, the heat-conducting property of the polyurethane material can be further improved.
Description
Technical Field
The invention relates to the technical field of polyurethane, in particular to a graphene-carbon nanotube modified polyurethane elastomer with high thermal conductivity and a preparation method thereof.
Background
The graphene is a two-dimensional honeycomb network structure consisting of carbon atoms, belongs to a compound hexagonal crystal structure, is very stable, the connection between the atoms is very flexible, when force is applied, the carbon atom surface can be bent and deformed, a good buffering effect is achieved, and the stable structure endows the graphene with good mechanical property and heat conductivity.
The carbon nanotube is a novel carbon material, and the special structure of the carbon nanotube determines the excellent properties of the carbon nanotube in the fields of mechanics, electricity, thermology and the like, such as high thermal stability and high Young modulus, and the carbon nanotube has wide application prospects in interdisciplines of material science, chemistry and the like.
The polyurethane material is an organic high polymer material containing a plurality of urethane chain segments and obtained by reacting polyisocyanate and polyol, has excellent acoustic, electrical and chemical medium resistance, can be made into materials such as plastics, rubber, adhesives and the like, and is widely applied to a plurality of fields such as buildings, clothes, furniture, medical treatment and the like, but the mechanical properties such as toughness, stretching and the like of the polyurethane material are not high, and the heat conductivity is general, so that the application of the polyurethane material in certain aspects is greatly limited, and therefore, the polyurethane material is necessary to be modified by one or more substances.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a high-thermal-conductivity graphene-carbon nanotube modified polyurethane elastomer and a preparation method thereof, and solves the problem of poor thermal conductivity of polyurethane.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of a high-thermal-conductivity graphene-carbon nanotube modified polyurethane elastomer comprises the following steps:
(1) adding graphene oxide into a toluene solvent in a nitrogen atmosphere, performing ultrasonic dispersion for 0.5-1.5h by using an ultrasonic device, reacting for 5-10h at the temperature of 60-80 ℃ by using azobisisobutyronitrile as an initiator in a mass ratio of 1:20-50 with the graphene oxide, filtering and washing a product, and drying to obtain cyano-modified graphene oxide;
(2) adding sodium hydroxide and cyano-modified graphene oxide into an ethanol solvent according to the mass ratio of 10:10-30, stirring and reacting for 35-45h at 70-90 ℃, adjusting the pH of the solution to 2-3, filtering, washing a filtrate with distilled water, and drying to obtain carboxylated graphene;
(3) adding carboxylated graphene into a distilled aqueous solvent, adding 4,4 '-diaminobiphenyl and concentrated ammonia water after ultrasonic dispersion, stirring and refluxing for 5-10h at 90-110 ℃, filtering a product, ultrasonically cleaning with ethanol, removing unreacted 4,4' -diaminobiphenyl, and drying for 20-30h at 50-80 ℃ to prepare the arylamino graphene;
(4) oxidizing and filtering a multiwall carbon nanotube in a mixture of concentrated sulfuric acid and concentrated nitric acid with a volume ratio of 100:25-40, washing with dilute hydrochloric acid and ammonia water to remove impurities to obtain an acidified multiwall carbon nanotube, then dropwise adding concentrated hydrochloric acid into the mixture of aromatic aminated graphene and sodium nitrite, adding the acidified multiwall carbon nanotube, heating under reflux at 60-90 ℃ for 3-6h, washing a product with hydrochloric acid and distilled water, filtering and drying to prepare carbon nanotube modified graphene;
(5) dispersing carbon nano tube modified graphene in tetrahydrofuran, carrying out ultrasonic treatment for 20-50min, adding a thermoplastic polyurethane elastomer, mixing for 3-6h, carrying out ultrasonic treatment for 0.5-2h, then pouring into a polytetrafluoroethylene mold, drying and curing to prepare the graphene-carbon nano tube modified polyurethane elastomer.
Preferably, the supersound device in step (1) includes the control box, the outer wall fixedly connected with computer control ware of control box, computer control ware's right side fixedly connected with switch, the right side fixedly connected with wire of control box, the right side fixedly connected with ultrasonic emitter of wire, ultrasonic emitter's bottom fixedly connected with puddler, the outer wall fixedly connected with experiment box of puddler, the bottom fixedly connected with backup pad of experiment box, the last fixed surface of backup pad is connected with the lifter, the board is placed to the top fixedly connected with of lifter, the right side of lifter is rotated and is connected with adjusting nut.
Preferably, the mass ratio of the carboxylated graphene, the 4,4' -diaminobiphenyl and the ammonia water in the step (3) is 10:180-230: 50-70.
Preferably, the mass ratio of the carboxylated graphene, the sodium nitrite, the concentrated hydrochloric acid and the acidified multi-wall carbon nanotube in the step (4) is 10:400-800:1000-3000: 15-40.
Preferably, the mass ratio of the carbon nanotube modified graphene to the thermoplastic polyurethane elastomer is 1-4: 100.
(III) advantageous technical effects
Compared with the prior art, the invention has the following experimental principle and beneficial technical effects:
according to the high-thermal-conductivity graphene-carbon nanotube modified polyurethane elastomer, firstly, graphene oxide is used as a raw material, azodiisobutyronitrile is used as an initiator after ultrasonic dispersion, cyano-modified graphene oxide is obtained, the cyano-modified graphene oxide is hydrolyzed under an alkaline condition to obtain carboxylated graphene with rich carboxyl content, a large number of carboxyl groups can promote amidation reaction with amino groups of 4,4' -diaminobiphenyl to obtain arylamino graphene, the arylamino groups react with sodium nitrite in a hydrochloric acid atmosphere to generate diazonium salt, the diazonium salt and oxygen-containing groups of acidified carbon nanotubes are subjected to diazotization to obtain carbon nanotube modified graphene, and the carbon nanotube modified graphene and polyurethane thermoplastic elastomer are prepared through a liquid phase blending method to obtain the graphene-carbon nanotube modified polyurethane elastomer.
According to the high-thermal-conductivity graphene-carbon nanotube modified polyurethane elastomer, the chemical grafting structures of carbon nanotubes and graphene are beneficial to the dispersion of the carbon nanotubes and the graphene, the carbon nanotubes have a support effect on the graphene, the graphene sheet layers are prevented from being stacked again, the special structures of the carbon nanotubes and the graphene greatly enhance the mechanical property of a polyurethane material, the graphene and the carbon nanotubes have good thermal conductivity, and the thermal conductivity of the polyurethane material can be further improved.
Drawings
FIG. 1 is a schematic front view of an ultrasound device;
fig. 2 is an enlarged view of a part of the lifter.
1-a control box; 2-a computer controller; 3, switching; 4-a wire; 5-an ultrasonic transmitter; 6-a stirring rod; 7-an experimental box; 8-a support plate; 9-a lifting rod; 10-placing a plate; 11-adjusting the nut.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: a preparation method of a high-thermal-conductivity graphene-carbon nanotube modified polyurethane elastomer comprises the following steps:
(1) adding graphene oxide into a toluene solvent in a nitrogen atmosphere, passing through an ultrasonic device, wherein the ultrasonic device comprises a control box, the outer wall of the control box is fixedly connected with a computer controller, the right side of the computer controller is fixedly connected with a switch, the right side of the control box is fixedly connected with a lead, the right side of the lead is fixedly connected with an ultrasonic emitter, the bottom of the ultrasonic emitter is fixedly connected with a stirring rod, the outer wall of the stirring rod is fixedly connected with an experimental box, the bottom of the experimental box is fixedly connected with a supporting plate, the upper surface of the supporting plate is fixedly connected with a lifting rod, the top of the lifting rod is fixedly connected with a placing plate, the right side of the lifting rod is rotatably connected with an adjusting nut, carrying out ultrasonic dispersion for 0.5-1.5h, then taking azodiisobutyronitrile as an initiator, enabling the mass ratio of the azodiisobutyronitrile to the graphene oxide, filtering and washing the product, and drying to obtain cyano modified graphene oxide;
(2) adding sodium hydroxide and cyano-modified graphene oxide into an ethanol solvent according to the mass ratio of 10:10-30, stirring and reacting for 35-45h at 70-90 ℃, adjusting the pH of the solution to 2-3, filtering, washing a filtrate with distilled water, and drying to obtain carboxylated graphene;
(3) adding carboxylated graphene into a distilled aqueous solvent, adding 4,4' -diaminobiphenyl and concentrated ammonia water after ultrasonic dispersion, wherein the mass ratio of the carboxylated graphene to the 4,4' -diaminobiphenyl to the ammonia water is 10:180-230:50-70, stirring and refluxing for 5-10h at the temperature of 90-110 ℃, filtering the product, ultrasonically cleaning the product with ethanol, removing unreacted 4,4' -diaminobiphenyl, and drying for 20-30h at the temperature of 50-80 ℃ to prepare the arylamino graphene;
(4) oxidizing and filtering a multiwall carbon nanotube in a mixture of concentrated sulfuric acid and concentrated nitric acid with a volume ratio of 100:25-40, washing with dilute hydrochloric acid and ammonia water to remove impurities to obtain an acidified multiwall carbon nanotube, then dropwise adding concentrated hydrochloric acid into the mixture of aromatic aminated graphene and sodium nitrite, adding the acidified multiwall carbon nanotube, wherein the mass ratio of carboxylated graphene, sodium nitrite, concentrated hydrochloric acid and acidified multiwall carbon nanotube is 10: 400-;
(5) dispersing carbon nanotube modified graphene in tetrahydrofuran, carrying out ultrasonic treatment for 20-50min, adding a thermoplastic polyurethane elastomer, wherein the mass ratio of the carbon nanotube modified graphene to the thermoplastic polyurethane elastomer is 1-4:100, mixing for 3-6h, carrying out ultrasonic treatment for 0.5-2h, then pouring into a polytetrafluoroethylene mold, drying and curing to prepare the graphene-carbon nanotube modified polyurethane elastomer.
Example 1
(1) In the nitrogen atmosphere, adding graphene oxide into a toluene solvent, passing through an ultrasonic device, wherein the ultrasonic device comprises a control box, the outer wall of the control box is fixedly connected with a computer controller, the right side of the computer controller is fixedly connected with a switch, the right side of the control box is fixedly connected with a lead, the right side of the lead is fixedly connected with an ultrasonic emitter, the bottom of the ultrasonic emitter is fixedly connected with a stirring rod, the outer wall of the stirring rod is fixedly connected with an experimental box, the bottom of the experimental box is fixedly connected with a supporting plate, the upper surface of the supporting plate is fixedly connected with a lifting rod, the top of the lifting rod is fixedly connected with a placing plate, the right side of the lifting rod is rotatably connected with an adjusting, then azodiisobutyronitrile is used as an initiator, the mass ratio of azodiisobutyronitrile to graphene oxide is 1:20, reacting for 5 hours at the temperature of 60 ℃, filtering and washing a product, and drying to prepare cyano-modified graphene oxide;
(2) adding sodium hydroxide and cyano-modified graphene oxide into an ethanol solvent according to the mass ratio of 10:10, stirring and reacting for 35 hours at 70 ℃, adjusting the pH of the solution to 2, filtering, washing the filtrate with distilled water, and drying to obtain carboxylated graphene;
(3) adding carboxylated graphene into a distilled aqueous solvent, adding 4,4' -diaminobiphenyl and concentrated ammonia water after ultrasonic dispersion, wherein the mass ratio of the carboxylated graphene to the 4,4' -diaminobiphenyl to the ammonia water is 10:180:50, stirring and refluxing for 5 hours at 90 ℃, filtering the product, ultrasonically cleaning the product with ethanol, removing unreacted 4,4' -diaminobiphenyl, and drying for 20 hours at 50 ℃ to obtain the arylamino graphene;
(4) oxidizing and filtering multiwall carbon nanotubes in a mixture of concentrated sulfuric acid and concentrated nitric acid with a volume ratio of 100:25, washing with dilute hydrochloric acid and ammonia water to remove impurities to obtain acidified multiwall carbon nanotubes, then dropwise adding concentrated hydrochloric acid into the mixture of aromatic aminated graphene and sodium nitrite, adding the acidified multiwall carbon nanotubes, wherein the mass ratio of carboxylated graphene to sodium nitrite to concentrated hydrochloric acid to the acidified multiwall carbon nanotubes is 10:400:1000:15, carrying out reflux heating at 60 ℃ for 3 hours, washing the product with hydrochloric acid and distilled water, filtering and drying to obtain carbon nanotube modified graphene;
(5) dispersing carbon nanotube modified graphene in tetrahydrofuran, carrying out ultrasonic treatment for 20min, adding a thermoplastic polyurethane elastomer, wherein the mass ratio of the carbon nanotube modified graphene to the thermoplastic polyurethane elastomer is 1:100, mixing for 3h, carrying out ultrasonic treatment for 0.5h, pouring into a polytetrafluoroethylene mold, drying and curing to prepare the graphene-carbon nanotube modified polyurethane elastomer.
Example 2
(1) In the nitrogen atmosphere, adding graphene oxide into a toluene solvent, passing through an ultrasonic device, wherein the ultrasonic device comprises a control box, the outer wall of the control box is fixedly connected with a computer controller, the right side of the computer controller is fixedly connected with a switch, the right side of the control box is fixedly connected with a lead, the right side of the lead is fixedly connected with an ultrasonic emitter, the bottom of the ultrasonic emitter is fixedly connected with a stirring rod, the outer wall of the stirring rod is fixedly connected with an experimental box, the bottom of the experimental box is fixedly connected with a supporting plate, the upper surface of the supporting plate is fixedly connected with a lifting rod, the top of the lifting rod is fixedly connected with a placing plate, the right side of the lifting rod is rotatably connected with an adjusting, then azodiisobutyronitrile is used as an initiator, the mass ratio of azodiisobutyronitrile to graphene oxide is 1:50, reacting for 10 hours at 80 ℃, filtering and washing a product, and drying to prepare cyano-modified graphene oxide;
(2) adding sodium hydroxide and cyano-modified graphene oxide into an ethanol solvent according to the mass ratio of 10:30, stirring and reacting for 45 hours at 90 ℃, adjusting the pH of the solution to 3, filtering, washing the filtrate with distilled water, and drying to obtain carboxylated graphene;
(3) adding carboxylated graphene into a distilled water solvent, adding 4,4' -diaminobiphenyl and concentrated ammonia water after ultrasonic dispersion, wherein the mass ratio of the carboxylated graphene to the 4,4' -diaminobiphenyl to the ammonia water is 10:230:70, stirring and refluxing for 10 hours at the temperature of 110 ℃, filtering the product, ultrasonically cleaning the product with ethanol, removing unreacted 4,4' -diaminobiphenyl, and drying for 30 hours at the temperature of 80 ℃ to obtain the arylamino graphene;
(4) oxidizing and filtering multiwall carbon nanotubes in a mixture of concentrated sulfuric acid and concentrated nitric acid with a volume ratio of 100:40, washing with dilute hydrochloric acid and ammonia water to remove impurities to obtain acidified multiwall carbon nanotubes, then dropwise adding concentrated hydrochloric acid into the mixture of aromatic aminated graphene and sodium nitrite, adding the acidified multiwall carbon nanotubes, wherein the mass ratio of carboxylated graphene to sodium nitrite to concentrated hydrochloric acid to the acidified multiwall carbon nanotubes is 10:800:3000:40, refluxing and heating at 90 ℃ for 6 hours, washing the product with hydrochloric acid and distilled water, filtering and drying to obtain carbon nanotube modified graphene;
(5) dispersing carbon nanotube modified graphene in tetrahydrofuran, carrying out ultrasonic treatment for 50min, adding a thermoplastic polyurethane elastomer, wherein the mass ratio of the carbon nanotube modified graphene to the thermoplastic polyurethane elastomer is 4:100, mixing for 6h, carrying out ultrasonic treatment for 2h, then pouring into a polytetrafluoroethylene mold, drying and curing to prepare the graphene-carbon nanotube modified polyurethane elastomer.
Example 3
(1) In the nitrogen atmosphere, adding graphene oxide into a toluene solvent, passing through an ultrasonic device, wherein the ultrasonic device comprises a control box, the outer wall of the control box is fixedly connected with a computer controller, the right side of the computer controller is fixedly connected with a switch, the right side of the control box is fixedly connected with a lead, the right side of the lead is fixedly connected with an ultrasonic emitter, the bottom of the ultrasonic emitter is fixedly connected with a stirring rod, the outer wall of the stirring rod is fixedly connected with an experimental box, the bottom of the experimental box is fixedly connected with a supporting plate, the upper surface of the supporting plate is fixedly connected with a lifting rod, the top of the lifting rod is fixedly connected with a placing plate, the right side of the lifting rod is rotatably connected with, then azodiisobutyronitrile is used as an initiator, the mass ratio of azodiisobutyronitrile to graphene oxide is 1:35, reacting for 7 hours at 70 ℃, filtering and washing a product, and drying to obtain cyano-modified graphene oxide;
(2) adding sodium hydroxide and cyano-modified graphene oxide into an ethanol solvent according to the mass ratio of 10:20, stirring and reacting for 40 hours at 85 ℃, adjusting the pH of the solution to 2, filtering, washing the filtrate with distilled water, and drying to obtain carboxylated graphene;
(3) adding carboxylated graphene into a distilled aqueous solvent, adding 4,4' -diaminobiphenyl and concentrated ammonia water after ultrasonic dispersion, wherein the mass ratio of the carboxylated graphene to the 4,4' -diaminobiphenyl to the ammonia water is 10:200:60, stirring and refluxing for 7 hours at 100 ℃, filtering the product, ultrasonically cleaning the product with ethanol, removing unreacted 4,4' -diaminobiphenyl, and drying for 25 hours at 70 ℃ to obtain the arylamino graphene;
(4) oxidizing and filtering multiwall carbon nanotubes in a mixture of concentrated sulfuric acid and concentrated nitric acid with a volume ratio of 100:30, washing with dilute hydrochloric acid and ammonia water to remove impurities to obtain acidified multiwall carbon nanotubes, then dropwise adding concentrated hydrochloric acid into the mixture of aromatic aminated graphene and sodium nitrite, adding the acidified multiwall carbon nanotubes, wherein the mass ratio of carboxylated graphene to sodium nitrite to concentrated hydrochloric acid to the acidified multiwall carbon nanotubes is 10:500:2000:30, carrying out reflux heating at 80 ℃ for 5 hours, washing the product with hydrochloric acid and distilled water, filtering and drying to obtain carbon nanotube modified graphene;
(5) dispersing carbon nanotube modified graphene in tetrahydrofuran, carrying out ultrasonic treatment for 40min, adding a thermoplastic polyurethane elastomer, wherein the mass ratio of the carbon nanotube modified graphene to the thermoplastic polyurethane elastomer is 3:100, mixing for 5h, carrying out ultrasonic treatment for 1.5h, pouring into a polytetrafluoroethylene mold, drying and curing to prepare the graphene-carbon nanotube modified polyurethane elastomer.
Example 4
(1) In the nitrogen atmosphere, adding graphene oxide into a toluene solvent, passing through an ultrasonic device, wherein the ultrasonic device comprises a control box, the outer wall of the control box is fixedly connected with a computer controller, the right side of the computer controller is fixedly connected with a switch, the right side of the control box is fixedly connected with a lead, the right side of the lead is fixedly connected with an ultrasonic emitter, the bottom of the ultrasonic emitter is fixedly connected with a stirring rod, the outer wall of the stirring rod is fixedly connected with an experimental box, the bottom of the experimental box is fixedly connected with a supporting plate, the upper surface of the supporting plate is fixedly connected with a lifting rod, the top of the lifting rod is fixedly connected with a placing plate, the right side of the lifting rod is rotatably connected with an adjusting, then azodiisobutyronitrile is used as an initiator, the mass ratio of azodiisobutyronitrile to graphene oxide is 1:20, reacting for 5 hours at 70 ℃, filtering and washing a product, and drying to obtain cyano-modified graphene oxide;
(2) adding sodium hydroxide and cyano-modified graphene oxide into an ethanol solvent according to the mass ratio of 10:20, stirring and reacting for 35 hours at 70 ℃, adjusting the pH of the solution to 3, filtering, washing the filtrate with distilled water, and drying to obtain carboxylated graphene;
(3) adding carboxylated graphene into a distilled aqueous solvent, adding 4,4' -diaminobiphenyl and concentrated ammonia water after ultrasonic dispersion, wherein the mass ratio of the carboxylated graphene to the 4,4' -diaminobiphenyl to the ammonia water is 10:180:60, stirring and refluxing for 7 hours at 90 ℃, filtering the product, ultrasonically cleaning the product with ethanol, removing unreacted 4,4' -diaminobiphenyl, and drying for 20 hours at 60 ℃ to obtain the arylamino graphene;
(4) oxidizing multi-walled carbon nanotubes in a mixture of concentrated sulfuric acid and concentrated nitric acid with a volume ratio of 100:30, filtering, washing with dilute hydrochloric acid and ammonia water to remove impurities to obtain acidified multi-walled carbon nanotubes, then dropwise adding concentrated hydrochloric acid into the mixture of arylamino graphene and sodium nitrite, adding the acidified multi-walled carbon nanotubes, wherein the mass ratio of carboxylated graphene, sodium nitrite, concentrated hydrochloric acid and acidified multi-walled carbon nanotubes is 10:400:2500:15, refluxing and heating at 70 ℃ for 3 hours, washing a product with hydrochloric acid and distilled water, filtering and drying to prepare carbon nanotube modified graphene;
(5) dispersing carbon nanotube modified graphene in tetrahydrofuran, carrying out ultrasonic treatment for 30min, adding a thermoplastic polyurethane elastomer, wherein the mass ratio of the carbon nanotube modified graphene to the thermoplastic polyurethane elastomer is 2:100, mixing for 4h, carrying out ultrasonic treatment for 0.5h, pouring into a polytetrafluoroethylene mold, drying and curing to prepare the graphene-carbon nanotube modified polyurethane elastomer.
Comparative example 1
(1) In the nitrogen atmosphere, adding graphene oxide into a toluene solvent, passing through an ultrasonic device, wherein the ultrasonic device comprises a control box, the outer wall of the control box is fixedly connected with a computer controller, the right side of the computer controller is fixedly connected with a switch, the right side of the control box is fixedly connected with a lead, the right side of the lead is fixedly connected with an ultrasonic emitter, the bottom of the ultrasonic emitter is fixedly connected with a stirring rod, the outer wall of the stirring rod is fixedly connected with an experimental box, the bottom of the experimental box is fixedly connected with a supporting plate, the upper surface of the supporting plate is fixedly connected with a lifting rod, the top of the lifting rod is fixedly connected with a placing plate, the right side of the lifting rod is rotatably connected with, then azodiisobutyronitrile is used as an initiator, the mass ratio of azodiisobutyronitrile to graphene oxide is 1:10, reacting for 3 hours at 100 ℃, filtering and washing a product, and drying to prepare cyano-modified graphene oxide;
(2) adding sodium hydroxide and cyano-modified graphene oxide into an ethanol solvent in a mass ratio of 10:50, stirring and reacting for 60 hours at 50 ℃, adjusting the pH of the solution to 1, filtering, washing the filtrate with distilled water, and drying to obtain carboxylated graphene;
(3) adding carboxylated graphene into a distilled aqueous solvent, adding 4,4' -diaminobiphenyl and concentrated ammonia water after ultrasonic dispersion, wherein the mass ratio of the carboxylated graphene to the 4,4' -diaminobiphenyl to the ammonia water is 10:150:30, stirring and refluxing for 2 hours at 70 ℃, filtering the product, ultrasonically cleaning the product with ethanol, removing unreacted 4,4' -diaminobiphenyl, and drying for 10 hours at 40 ℃ to obtain the arylamino graphene;
(4) oxidizing and filtering multiwall carbon nanotubes in a mixture of concentrated sulfuric acid and concentrated nitric acid with a volume ratio of 100:10, washing with dilute hydrochloric acid and ammonia water to remove impurities to obtain acidified multiwall carbon nanotubes, then dropwise adding concentrated hydrochloric acid into the mixture of aromatic aminated graphene and sodium nitrite, adding the acidified multiwall carbon nanotubes, wherein the mass ratio of carboxylated graphene to sodium nitrite to concentrated hydrochloric acid to acidified multiwall carbon nanotubes is 10:1000:500:10, refluxing and heating at 50 ℃ for 1h, washing the product with hydrochloric acid and distilled water, filtering and drying to obtain carbon nanotube modified graphene;
(5) dispersing carbon nanotube modified graphene in tetrahydrofuran, carrying out ultrasonic treatment for 10min, adding a thermoplastic polyurethane elastomer, wherein the mass ratio of the carbon nanotube modified graphene to the thermoplastic polyurethane elastomer is 6:100, mixing for 1h, carrying out ultrasonic treatment for 5h, pouring into a polytetrafluoroethylene mold, drying and curing to prepare the graphene-carbon nanotube modified polyurethane elastomer.
The polyurethane materials in the examples and comparative examples were tested for Young's modulus using a WN-WP02 type high and low temperature universal tester, test Standard GB/T32104-.
The polyurethane materials in the examples and comparative examples were tested for thermal conductivity and thermal conductivity in the in-plane direction using a DRE-2C type thermal conductivity tester, test Standard GB/T3399-.
Claims (5)
1. A high-thermal-conductivity graphene-carbon nanotube modified polyurethane elastomer is characterized in that: the preparation method of the high-thermal-conductivity graphene-carbon nanotube modified polyurethane elastomer comprises the following steps:
(1) adding graphene oxide into a toluene solvent in a nitrogen atmosphere, performing ultrasonic dispersion for 0.5-1.5h by using an ultrasonic device, reacting for 5-10h at the temperature of 60-80 ℃ by using azobisisobutyronitrile as an initiator in a mass ratio of 1:20-50 with the graphene oxide, filtering and washing a product, and drying to obtain cyano-modified graphene oxide;
(2) adding sodium hydroxide and cyano-modified graphene oxide into an ethanol solvent according to the mass ratio of 10:10-30, stirring and reacting for 35-45h at 70-90 ℃, adjusting the pH of the solution to 2-3, filtering, washing a filtrate with distilled water, and drying to obtain carboxylated graphene;
(3) adding carboxylated graphene into a distilled aqueous solvent, adding 4,4 '-diaminobiphenyl and concentrated ammonia water after ultrasonic dispersion, stirring and refluxing for 5-10h at 90-110 ℃, filtering a product, ultrasonically cleaning with ethanol, removing unreacted 4,4' -diaminobiphenyl, and drying for 20-30h at 50-80 ℃ to prepare the arylamino graphene;
(4) oxidizing and filtering a multiwall carbon nanotube in a mixture of concentrated sulfuric acid and concentrated nitric acid with a volume ratio of 100:25-40, washing with dilute hydrochloric acid and ammonia water to remove impurities to obtain an acidified multiwall carbon nanotube, then dropwise adding concentrated hydrochloric acid into the mixture of aromatic aminated graphene and sodium nitrite, adding the acidified multiwall carbon nanotube, heating under reflux at 60-90 ℃ for 3-6h, washing a product with hydrochloric acid and distilled water, filtering and drying to prepare carbon nanotube modified graphene;
(5) dispersing carbon nano tube modified graphene in tetrahydrofuran, carrying out ultrasonic treatment for 20-50min, adding a thermoplastic polyurethane elastomer, mixing for 3-6h, carrying out ultrasonic treatment for 0.5-2h, then pouring into a polytetrafluoroethylene mold, drying and curing to prepare the graphene-carbon nano tube modified polyurethane elastomer.
2. The high thermal conductivity graphene-carbon nanotube modified polyurethane elastomer according to claim 1, wherein: the ultrasonic device in step (1) includes the control box, the outer wall fixedly connected with computer control ware of control box, computer control ware's right side fixedly connected with switch, the right side fixedly connected with wire of control box, the right side fixedly connected with ultrasonic emitter of wire, ultrasonic emitter's bottom fixedly connected with puddler, the outer wall fixedly connected with experiment box of puddler, the bottom fixedly connected with backup pad of experiment box, the last fixed surface of backup pad is connected with the lifter, the board is placed to the top fixedly connected with of lifter, the right side of lifter rotates and is connected with adjusting nut.
3. The high thermal conductivity graphene-carbon nanotube modified polyurethane elastomer according to claim 1, wherein: the mass ratio of the carboxylated graphene, the 4,4' -diaminobiphenyl and the ammonia water in the step (3) is 10:180-230: 50-70.
4. The high thermal conductivity graphene-carbon nanotube modified polyurethane elastomer according to claim 1, wherein: the mass ratio of the carboxylated graphene, the sodium nitrite, the concentrated hydrochloric acid and the acidified multi-wall carbon nano tube in the step (4) is 10: 400-.
5. The high thermal conductivity graphene-carbon nanotube modified polyurethane elastomer according to claim 1, wherein: the mass ratio of the carbon nanotube modified graphene to the thermoplastic polyurethane elastomer is 1-4: 100.
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