阅读说明：本技术 一种高导热的石墨烯原位接枝聚氨酯弹性体及其制法 (High-thermal-conductivity graphene in-situ grafted polyurethane elastomer and preparation method thereof ) 是由 黄卫兵 于 2020-12-15 设计创作，主要内容包括：本发明涉及聚氨酯技术领域,且公开了一种高导热的石墨烯原位接枝聚氨酯弹性体,氯丙基化石墨烯的氯原子与叠氮化钠反应,得到叠氮化石墨烯,以二炔基二醇衍生物作为二醇小分子扩链剂,成功引入到聚氨酯的支链中,得到侧链含炔基的聚氨酯,以抗坏血酸钠作为点击反应催化剂,使叠氮化石墨烯得叠氮基团与聚氨酯侧链的炔基进行点击化反应,生成三氮唑基团,使石墨烯通过三氮唑基团的侨联作用,有机结合到聚氨酯的侧链中,改善了石墨烯与聚氨酯的界面相容性,分散均匀的石墨烯在聚氨酯中形成三维导热网络,提高了其导热系数和导热性能,石墨烯作为侧链交联位点,提高了聚氨酯弹性体的交联度和拉伸强度等机械性能。(The invention relates to the technical field of polyurethane, and discloses a high-thermal-conductivity graphene in-situ grafted polyurethane elastomer, wherein chlorine atoms of chloropropylated graphene react with sodium azide to obtain azido graphene, a dialkynyl diol derivative is used as a diol micromolecule chain extender and successfully introduced into a branched chain of polyurethane to obtain polyurethane with a side chain containing alkynyl, sodium ascorbate is used as a click reaction catalyst to enable azido graphene to obtain an azido group and the alkynyl of a polyurethane side chain to carry out click reaction to generate a triazole group, the graphene is organically combined into the side chain of the polyurethane through the cross-linking effect of the triazole group, the interface compatibility of the graphene and the polyurethane is improved, the uniformly dispersed graphene forms a three-dimensional thermal-conductive network in the polyurethane, the thermal conductivity and the thermal conductivity of the polyurethane are improved, the graphene is used as a side chain cross-linking site, the cross-linking degree, the tensile strength and other mechanical properties of the polyurethane elastomer are improved.)

1. The high-thermal-conductivity graphene in-situ grafted polyurethane elastomer is characterized in that: the preparation method of the high-thermal-conductivity graphene in-situ grafted polyurethane elastomer comprises the following steps:

(1) in a nitrogen atmosphere, adding graphene oxide into an N, N-dimethyl polyamide solvent, placing the mixture into an ultrasonic treatment instrument, heating the mixture to 100 ℃ and 120 ℃ after uniform ultrasonic dispersion, adding 3-chloropropyltrimethoxysilane, reacting for 20-30h, centrifugally washing and drying to prepare chloropropylated graphene;

(2) in a nitrogen atmosphere, adding chloropropylated graphene into an N, N-dimethyl polyamide solvent, uniformly dispersing by ultrasonic, adding sodium azide, a catalyst and a cocatalyst, heating to 90-120 ℃, reacting for 24-36h, centrifugally washing and drying to prepare azidographene;

(3) adding toluene diisocyanate and polyester diol into a reaction system in a nitrogen atmosphere, heating to 75-85 ℃, reacting for 2-3h, cooling to 40-50 ℃, adding 1, 4-butanediol and dibutyltin dilaurate, reacting for 30-60min, adding acetone to adjust the viscosity of the solution, adding a dikynyl diol derivative, heating to 70-80 ℃, reacting for 2-4h, and preparing polyurethane with side chains containing alkynyl;

(4) adding azido graphene into an N, N-dimethyl polyamide solvent in a nitrogen atmosphere, adding polyurethane containing alkynyl on a side chain, a click reaction catalyst and an accelerator after uniform ultrasonic dispersion, reacting for 10-20h, centrifugally washing and drying, pouring a product into a mold, and carrying out pressure curing and high-temperature curing processes in a flat vulcanizing machine to prepare the high-thermal-conductivity graphene in-situ grafted polyurethane elastomer.

2. The high thermal conductivity graphene in-situ grafted polyurethane elastomer as claimed in claim 1, wherein: the ultrasonic treatment instrument in the step (1) comprises an ultrasonic device, a water bath is arranged in the ultrasonic treatment instrument, a heating plate is arranged below the inside of the water bath, a top cover is movably connected above the water bath, a supporting rod is fixedly connected below the top cover, a clamping plate is fixedly connected with the supporting rod, and a reaction bottle is movably connected with the clamping plate.

3. The high thermal conductivity graphene in-situ grafted polyurethane elastomer as claimed in claim 1, wherein: the mass ratio of the graphene oxide to the 3-chloropropyltrimethoxysilane in the step (1) is 10: 10-30.

4. The high thermal conductivity graphene in-situ grafted polyurethane elastomer as claimed in claim 1, wherein: the catalyst in the step (2) is potassium iodide, a cocatalyst of tetrabutylammonium bromide, chloropropylated graphene, sodium azide, potassium iodide and tetrabutylammonium bromide in a mass ratio of 100:25-40:6-10: 10-20.

5. The high thermal conductivity graphene in-situ grafted polyurethane elastomer as claimed in claim 1, wherein: the molecular formula of the dialkynyl glycol derivative in the step (3) is C₉H₁₂O₂The mass ratio of the toluene diisocyanate to the polyester diol to the 1, 4-butanediol to the dibutyltin dilaurate to the dialkynyl diol derivative is 60-70:100:4-10:3-5: 6-12.

6. The high thermal conductivity graphene in-situ grafted polyurethane elastomer as claimed in claim 1, wherein: the mass ratio of the click reaction catalyst in the step (4) to the sodium ascorbate, the accelerator to the copper sulfate, the azido graphene to the polyurethane with alkynyl group on the side chain, the sodium ascorbate and the copper sulfate is 100:0.5-3:0.15-0.25: 0.1-0.15.

7. The high thermal conductivity graphene in-situ grafted polyurethane elastomer as claimed in claim 1, wherein: the pressure curing pressure in the step (4) is 8-12MPa, the curing is performed for 30-60min, the high-temperature curing is performed at 90-110 ℃, and the curing is performed for 20-30 h.

Technical Field

The invention relates to the technical field of polyurethane, in particular to a high-thermal-conductivity graphene in-situ grafted polyurethane elastomer and a preparation method thereof.

Background

Polyurethane is a common polyurethane polymer material, has excellent mechanical property and chemical resistance, high hardness and good rebound resilience, and mainly comprises polyurethane plastics, polyurethane coating, polyurethane rubber elastomer and the like, wherein the polyurethane elastomer has a soft chain segment and a hard chain segment, so that the comprehensive properties of the material such as strength, toughness, wear resistance and the like can be improved by designing the chain segments, and the polyurethane elastomer has high elasticity of rubber and rigidity of plastics, has important application in the fields of the building industry, the automobile manufacturing industry, the aerospace industry and the like, and becomes a research hotspot for further improving the comprehensive properties of the polyurethane elastomer.

Graphene is a hexagonal honeycomb lattice two-dimensional carbon nanomaterial, has special optical, electrical and mechanical properties, is high in thermal conductivity, good in electrical conductivity and excellent in mechanical property, can be used as an inorganic nano filler, is combined with organic polymer materials such as epoxy resin and polyurethane, improves the overall properties of materials such as thermal property and mechanical property, but is poor in interface compatibility with polyurethane, and has strong van der waals force among graphene nanoparticles, so that the graphene nanoparticles are easy to agglomerate and accumulate in the polyurethane, the comprehensive properties and the service performance of the materials are affected, and the surface modification of the graphene becomes a research hotspot.

Technical problem to be solved

Aiming at the defects of the prior art, the invention provides a high-thermal-conductivity graphene in-situ grafted polyurethane elastomer and a preparation method thereof, so that the polyurethane elastomer has good thermal conductivity and mechanical strength.

(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 in-situ grafted polyurethane elastomer comprises the following steps:

(1) adding an N, N-dimethyl polyamide solvent and graphene oxide into a reaction bottle in a nitrogen atmosphere, placing the reaction bottle in an ultrasonic treatment instrument, performing ultrasonic dispersion uniformly, heating to 100-120 ℃, adding 3-chloropropyltrimethoxysilane, reacting for 20-30h, performing centrifugal washing by using distilled water and acetone, and drying to prepare the chloropropylated graphene.

(2) Adding an N, N-dimethyl polyamide solvent and chloropropylated graphene into a reaction bottle in a nitrogen atmosphere, adding sodium azide, a catalyst and a cocatalyst after uniformly dispersing by ultrasound, heating to 90-120 ℃, reacting for 24-36h, centrifugally washing and drying by using distilled water and acetone, and preparing the azido graphene.

(3) Adding toluene diisocyanate and polyester diol into a reaction bottle in a nitrogen atmosphere, heating to 75-85 ℃, reacting for 2-3h, cooling to 40-50 ℃, adding 1, 4-butanediol and dibutyltin dilaurate, reacting for 30-60min, adding acetone to adjust the viscosity of the solution, adding a dikynyl diol derivative, heating to 70-80 ℃, and reacting for 2-4h to prepare the polyurethane with the side chain containing alkynyl.

(4) Adding an N, N-dimethyl polyamide solvent and azido graphene into a reaction bottle in a nitrogen atmosphere, adding polyurethane containing alkynyl on a side chain, a click reaction catalyst and an accelerator after uniform ultrasonic dispersion, stirring at a constant speed for reaction for 10-20h, drying the solution in vacuum to remove the solvent, centrifugally washing and drying a solid product by using distilled water, pouring the product into a mold, and carrying out pressure curing and high-temperature curing processes in a flat-plate vulcanizing machine to prepare the high-thermal-conductivity graphene in-situ grafted polyurethane elastomer.

Preferably, the ultrasonic treatment instrument in the step (1) comprises an ultrasonic device, a water bath is arranged in the ultrasonic treatment instrument, a heating plate is arranged below the inside of the water bath, a top cover is movably connected above the water bath, a supporting rod is fixedly connected below the top cover, a clamping plate is fixedly connected with the supporting rod, and a reaction bottle is movably connected with the clamping plate.

Preferably, the mass ratio of the graphene oxide to the 3-chloropropyltrimethoxysilane in the step (1) is 10: 10-30.

Preferably, the catalyst in the step (2) is potassium iodide, the cocatalyst is tetrabutylammonium bromide, and the mass ratio of chloropropylated graphene, sodium azide, potassium iodide to tetrabutylammonium bromide is 100:25-40:6-10: 10-20.

It is preferable thatThe molecular formula of the dialkynyl glycol derivative in the step (3) is C₉H₁₂O₂The mass ratio of the toluene diisocyanate to the polyester diol to the 1, 4-butanediol to the dibutyltin dilaurate to the dialkynyl diol derivative is 60-70:100:4-10:3-5: 6-12.

Preferably, the click reaction catalyst in the step (4) is sodium ascorbate, the accelerator is copper sulfate, and the mass ratio of the azido graphene to the side chain alkynyl-containing polyurethane to the sodium ascorbate to the copper sulfate is 100:0.5-3:0.15-0.25: 0.1-0.15.

Preferably, the pressure curing pressure in the step (4) is 8-12MPa, the curing time is 30-60min, the high-temperature curing time is 90-110 ℃, and the curing time is 20-30 h.

(III) advantageous technical effects

Compared with the prior art, the invention has the following beneficial technical effects:

according to the high-thermal-conductivity graphene in-situ grafting polyurethane elastomer, 3-chloropropyltrimethoxysilane and graphene oxide are subjected to surface modification to obtain chloropropylated graphene, chlorine atoms react with sodium azide in a catalysis system of potassium iodide and tetrabutylammonium bromide to obtain azido graphene, the azido graphene contains abundant azido groups, and a dialkynyl diol derivative is used as a diol micromolecule chain extender and is successfully introduced into a branched chain of polyurethane to obtain polyurethane with a side chain containing alkynyl.

According to the high-thermal-conductivity graphene in-situ grafted polyurethane elastomer, sodium ascorbate is used as a click reaction catalyst, so that an azide group obtained by nitridizing graphene and an alkynyl group of a polyurethane side chain are subjected to click reaction to carry out a [3+2] cycloaddition reaction, the azide group and the alkynyl group are cyclized to generate a triazole group, so that the graphene is organically combined into the side chain of the polyurethane through the coupling effect of the triazole group, the interface compatibility and the dispersibility of the graphene and the polyurethane are obviously improved, the agglomeration of graphene nano particles is inhibited, the uniformly dispersed graphene forms a three-dimensional heat conduction network in the polyurethane, the heat conduction coefficient and the heat conduction performance of the polyurethane elastomer are obviously improved, and the graphene is used as a side chain crosslinking site, so that the crosslinking degree of the polyurethane elastomer is improved, and the mechanical properties such as tensile strength and the like of the material are improved.

Drawings

FIG. 1 is a schematic front view of an ultrasonic treatment apparatus;

FIG. 2 is a chemical structural formula of a dialkynediol derivative.

1-ultrasonic treatment instrument; 2-an ultrasonic device; 3-water bath; 4-heating plate; 5-a top cover; 6-supporting rods; 7-clamping plate; 8-reaction flask.

Detailed Description

To achieve the above object, the present invention provides the following embodiments and examples: a high-thermal-conductivity graphene in-situ grafted polyurethane elastomer is prepared by the following steps:

(1) adding an N, N-dimethyl polyamide solvent and graphene oxide into a reaction bottle in a nitrogen atmosphere, placing the reaction bottle in an ultrasonic treatment instrument, wherein the ultrasonic treatment instrument comprises an ultrasonic device, a water bath is arranged in the ultrasonic treatment instrument, a heating sheet is arranged below the water bath, a top cover is movably connected above the water bath, a support rod is fixedly connected below the top cover, a clamping plate is fixedly connected with the support rod, the clamping plate is movably connected with the reaction bottle, heating the reaction bottle to 100 ℃ and 120 ℃ after ultrasonic dispersion is uniform, adding 3-chloropropyltrimethoxysilane, performing reaction for 20-30h, performing centrifugal washing and drying by using distilled water and acetone, and preparing the chloropropylated graphene.

(2) Adding an N, N-dimethyl polyamide solvent and chloropropylated graphene into a reaction bottle in a nitrogen atmosphere, uniformly dispersing by ultrasonic waves, adding sodium azide, a catalyst potassium iodide and a cocatalyst tetrabutylammonium bromide in a mass ratio of 100:25-40:6-10:10-20, heating to 90-120 ℃, reacting for 24-36h, centrifugally washing and drying by using distilled water and acetone, and preparing the azidoated graphene.

(3) Adding toluene diisocyanate and polyester diol into a reaction bottle in a nitrogen atmosphere, heating to 75-85 ℃, reacting for 2-3h, cooling to 40-50 ℃, adding 1, 4-butanediol and dibutyltin dilaurate, reacting for 30-60min, adding acetone to adjust the viscosity of the solution, and then adding C₉H₁₂O₂(iii) dialkynyl groupAnd (2) diol derivatives, wherein the mass ratio of the toluene diisocyanate to the polyester diol to the 1, 4-butanediol to the dibutyltin dilaurate to the dialkynyl diol derivatives is 60-70:100:4-10:3-5:6-12, heating to 70-80 ℃, and reacting for 2-4h to prepare polyurethane containing alkynyl on the side chain.

(4) Adding N, N-dimethyl polyamide solvent and azido graphene into a reaction bottle in a nitrogen atmosphere, adding alkynyl polyurethane containing side chains, sodium ascorbate serving as a click reaction catalyst and copper sulfate serving as an accelerator into the reaction bottle after uniform ultrasonic dispersion, stirring the mixture at a constant speed for reaction for 10 to 20 hours, drying the solution in vacuum to remove the solvent, centrifugally washing and drying a solid product by using distilled water, pouring the product into a mold, carrying out a pressure curing process in a flat plate vulcanizing machine at 8 to 12MPa for 30 to 60 minutes, and carrying out a high-temperature curing process at 90 to 110 ℃ for 20 to 30 hours to prepare the high-thermal-conductivity graphene in-situ grafted polyurethane elastomer.

Example 1

(1) Adding an N, N-dimethyl polyamide solvent and graphene oxide into a reaction bottle in a nitrogen atmosphere, placing the reaction bottle into an ultrasonic treatment instrument, wherein the ultrasonic treatment instrument comprises an ultrasonic device, a water bath is arranged in the ultrasonic treatment instrument, a heating sheet is arranged below the water bath, a top cover is movably connected above the water bath, a support rod is fixedly connected below the top cover, a clamping plate is fixedly connected with the support rod, the clamping plate is movably connected with the reaction bottle, heating the reaction bottle to 100 ℃ after uniform ultrasonic dispersion, adding 3-chloropropyltrimethoxysilane, reacting the reaction bottle for 20 hours, performing centrifugal washing by using distilled water and acetone, and drying the reaction bottle to prepare the chloropropylated graphene.

(2) Adding an N, N-dimethyl polyamide solvent and chloropropylated graphene into a reaction bottle in a nitrogen atmosphere, uniformly dispersing by ultrasonic, adding sodium azide, a catalyst potassium iodide and a cocatalyst tetrabutylammonium bromide in a mass ratio of 100:25:6:10, heating to 90 ℃, reacting for 24 hours, centrifugally washing by using distilled water and acetone, and drying to prepare the azidoated graphene.

(3) Adding toluene diisocyanate and polyester diol into a reaction bottle in a nitrogen atmosphere, and heating to the temperatureReacting at 75 deg.C for 2h, cooling to 40 deg.C, adding 1, 4-butanediol and dibutyltin dilaurate, reacting for 30min, adding acetone to adjust solution viscosity, and adding C₉H₁₂O₂The mass ratio of the toluene diisocyanate to the polyester diol to the 1, 4-butanediol to the dibutyltin dilaurate to the dialkynyl diol derivative is 60:100:4:3:6, the temperature is raised to 70 ℃, and the reaction is carried out for 2 hours to prepare the polyurethane containing alkynyl on the side chain.

(4) Adding N, N-dimethyl polyamide solvent and azido graphene into a reaction bottle in a nitrogen atmosphere, adding side chain alkynyl-containing polyurethane, a click reaction catalyst sodium ascorbate and an accelerant copper sulfate after uniform ultrasonic dispersion, wherein the mass ratio of the four is 100:0.5:0.15:0.1, stirring at a constant speed for reaction for 10 hours, drying the solution in vacuum to remove the solvent, centrifugally washing and drying a solid product by using distilled water, pouring the product into a mold, carrying out a pressure curing process for 30 minutes in a flat plate vulcanizing machine at 8MPa, and carrying out a high-temperature curing process for 20 hours at 90 ℃ to prepare the high-thermal-conductivity graphene in-situ grafted polyurethane elastomer 1.

Example 2

(1) Adding an N, N-dimethyl polyamide solvent and graphene oxide into a reaction bottle in a nitrogen atmosphere, placing the reaction bottle into an ultrasonic treatment instrument, wherein the ultrasonic treatment instrument comprises an ultrasonic device, a water bath is arranged in the ultrasonic treatment instrument, a heating sheet is arranged below the water bath, a top cover is movably connected above the water bath, a support rod is fixedly connected below the top cover, a clamping plate is fixedly connected with the support rod, the clamping plate is movably connected with the reaction bottle, heating the reaction bottle to 120 ℃ after uniform ultrasonic dispersion, adding 3-chloropropyltrimethoxysilane, reacting the reaction bottle for 30 hours, performing centrifugal washing and drying by using distilled water and acetone, and preparing the chloropropylated graphene.

(2) Adding an N, N-dimethyl polyamide solvent and chloropropylated graphene into a reaction bottle in a nitrogen atmosphere, uniformly dispersing by ultrasonic waves, adding sodium azide, a catalyst potassium iodide and a cocatalyst tetrabutylammonium bromide in a mass ratio of 100:30:7:13, heating to 120 ℃, reacting for 36 hours, centrifugally washing by using distilled water and acetone, and drying to prepare the azidoated graphene.

(3) Adding toluene diisocyanate and polyester diol into a reaction bottle in a nitrogen atmosphere, heating to 85 ℃, reacting for 3h, cooling to 40 ℃, adding 1, 4-butanediol and dibutyltin dilaurate, reacting for 60min, adding acetone to adjust the solution viscosity, and adding a compound with a molecular formula of C₉H₁₂O₂The mass ratio of the toluene diisocyanate to the polyester diol to the 1, 4-butanediol to the dibutyltin dilaurate to the dialkynyl diol derivative is 65:100:6:3.5:8, the temperature is increased to 80 ℃, and the reaction is carried out for 4 hours to prepare the polyurethane containing alkynyl on the side chain.

(4) Adding N, N-dimethyl polyamide solvent and azido graphene into a reaction bottle in a nitrogen atmosphere, adding alkynyl polyurethane containing a side chain, a click reaction catalyst sodium ascorbate and an accelerant copper sulfate after uniform ultrasonic dispersion, wherein the mass ratio of the four is 100:1:0.18:0.11, stirring at a constant speed for reaction for 20 hours, drying the solution in vacuum to remove the solvent, centrifugally washing and drying a solid product by using distilled water, pouring the product into a mold, carrying out a pressure curing process in a flat vulcanizing machine at 10MPa for 60 minutes, and carrying out a high-temperature curing process at 90 ℃ for 30 hours to prepare the high-thermal-conductivity graphene in-situ grafted polyurethane elastomer 2.

Example 3

(1) Adding an N, N-dimethyl polyamide solvent and graphene oxide into a reaction bottle in a nitrogen atmosphere, placing the reaction bottle into an ultrasonic treatment instrument, wherein the ultrasonic treatment instrument comprises an ultrasonic device, a water bath is arranged in the ultrasonic treatment instrument, a heating sheet is arranged below the water bath, a top cover is movably connected above the water bath, a support rod is fixedly connected below the top cover, a clamping plate is fixedly connected with the support rod, the clamping plate is movably connected with the reaction bottle, heating the reaction bottle to 110 ℃ after uniform ultrasonic dispersion, adding 3-chloropropyltrimethoxysilane, reacting the reaction bottle for 24 hours, performing centrifugal washing and drying by using distilled water and acetone, and preparing the chloropropylated graphene.

(2) Adding an N, N-dimethyl polyamide solvent and chloropropylated graphene into a reaction bottle in a nitrogen atmosphere, uniformly dispersing by ultrasonic waves, adding sodium azide, a catalyst potassium iodide and a cocatalyst tetrabutylammonium bromide in a mass ratio of 100:35:8:16, heating to 110 ℃, reacting for 30 hours, centrifugally washing by using distilled water and acetone, and drying to prepare the azidoated graphene.

(3) Adding toluene diisocyanate and polyester diol into a reaction bottle in a nitrogen atmosphere, heating to 80 ℃, reacting for 2.5h, cooling to 45 ℃, adding 1, 4-butanediol and dibutyltin dilaurate, reacting for 45min, adding acetone to adjust the solution viscosity, and adding a compound with a molecular formula of C₉H₁₂O₂The mass ratio of the toluene diisocyanate to the polyester diol to the 1, 4-butanediol to the dibutyltin dilaurate to the dialkynyl diol derivative is 68:100:8:4.5:10, the temperature is raised to 75 ℃, and the reaction is carried out for 3 hours to prepare the polyurethane containing alkynyl on the side chain.

(4) Adding N, N-dimethyl polyamide solvent and azido graphene into a reaction bottle in a nitrogen atmosphere, adding alkynyl polyurethane containing a side chain, a click reaction catalyst sodium ascorbate and an accelerant copper sulfate after uniform ultrasonic dispersion, wherein the mass ratio of the four is 100:2:0.22:0.13, stirring at a constant speed for reaction for 15h, drying the solution in vacuum to remove the solvent, centrifugally washing and drying a solid product by using distilled water, pouring the product into a mold, carrying out a pressure curing process in a flat vulcanizing machine at 10MPa for 45min, and carrying out a high-temperature curing process at 100 ℃ for 25h to prepare the high-thermal-conductivity graphene in-situ grafted polyurethane elastomer 3.

Example 4

(1) Adding an N, N-dimethyl polyamide solvent and graphene oxide into a reaction bottle in a nitrogen atmosphere, placing the reaction bottle into an ultrasonic treatment instrument, wherein the ultrasonic treatment instrument comprises an ultrasonic device, a water bath is arranged in the ultrasonic treatment instrument, a heating sheet is arranged below the water bath, a top cover is movably connected above the water bath, a support rod is fixedly connected below the top cover, a clamping plate is fixedly connected with the support rod, the clamping plate is movably connected with the reaction bottle, heating the reaction bottle to 120 ℃ after uniform ultrasonic dispersion, adding 3-chloropropyltrimethoxysilane, reacting the reaction bottle for 30 hours, performing centrifugal washing and drying by using distilled water and acetone, and preparing the chloropropylated graphene.

(2) Adding an N, N-dimethyl polyamide solvent and chloropropylated graphene into a reaction bottle in a nitrogen atmosphere, uniformly dispersing by ultrasonic waves, adding sodium azide, a catalyst potassium iodide and a cocatalyst tetrabutylammonium bromide in a mass ratio of 100:40:10:20, heating to 120 ℃, reacting for 36 hours, centrifugally washing by using distilled water and acetone, and drying to prepare the azidoated graphene.

(3) Adding toluene diisocyanate and polyester diol into a reaction bottle in a nitrogen atmosphere, heating to 85 ℃, reacting for 3h, cooling to 50 ℃, adding 1, 4-butanediol and dibutyltin dilaurate, reacting for 60min, adding acetone to adjust the solution viscosity, and adding a compound with a molecular formula of C₉H₁₂O₂The mass ratio of the toluene diisocyanate to the polyester diol to the 1, 4-butanediol to the dibutyltin dilaurate to the dialkynyl diol derivative is 70:100:10:5:12, the temperature is increased to 80 ℃, and the reaction is carried out for 4 hours to prepare the polyurethane containing alkynyl on the side chain.

(4) Adding N, N-dimethyl polyamide solvent and azido graphene into a reaction bottle in a nitrogen atmosphere, adding alkynyl polyurethane containing a side chain, a click reaction catalyst sodium ascorbate and an accelerant copper sulfate after uniform ultrasonic dispersion, wherein the mass ratio of the four is 100:3:0.25:0.15, stirring at a constant speed for reaction for 20 hours, drying the solution in vacuum to remove the solvent, centrifugally washing and drying a solid product by using distilled water, pouring the product into a mold, carrying out a pressure curing process in a flat vulcanizing machine at 12MPa for 60 minutes, and carrying out a high-temperature curing process at 110 ℃ for 30 hours to prepare the high-thermal-conductivity graphene in-situ grafted polyurethane elastomer 4.

Comparative example 1

(1) Adding an N, N-dimethyl polyamide solvent and graphene oxide into a reaction bottle in a nitrogen atmosphere, placing the reaction bottle into an ultrasonic treatment instrument, wherein the ultrasonic treatment instrument comprises an ultrasonic device, a water bath is arranged in the ultrasonic treatment instrument, a heating sheet is arranged below the water bath, a top cover is movably connected above the water bath, a support rod is fixedly connected below the top cover, a clamping plate is fixedly connected with the support rod, the clamping plate is movably connected with the reaction bottle, heating the reaction bottle to 120 ℃ after uniform ultrasonic dispersion, adding 3-chloropropyltrimethoxysilane, reacting the reaction bottle for 30 hours, performing centrifugal washing and drying by using distilled water and acetone, and preparing the chloropropylated graphene.

(2) Adding an N, N-dimethyl polyamide solvent and chloropropylated graphene into a reaction bottle in a nitrogen atmosphere, uniformly dispersing by ultrasonic waves, adding sodium azide, a catalyst potassium iodide and a cocatalyst tetrabutylammonium bromide in a mass ratio of 100:20:4:8, heating to 120 ℃, reacting for 36 hours, centrifugally washing by using distilled water and acetone, and drying to prepare the azidoated graphene.

(3) Adding toluene diisocyanate and polyester diol into a reaction bottle in a nitrogen atmosphere, heating to 85 ℃, reacting for 2h, cooling to 50 ℃, adding 1, 4-butanediol and dibutyltin dilaurate, reacting for 60min, adding acetone to adjust the solution viscosity, and adding a compound with a molecular formula of C₉H₁₂O₂The mass ratio of the toluene diisocyanate to the polyester diol to the 1, 4-butanediol to the dibutyltin dilaurate to the dialkynyl diol derivative is 55:100:3:2:5, the temperature is increased to 80 ℃, and the reaction is carried out for 4 hours to prepare the polyurethane containing alkynyl on the side chain.

(4) Adding N, N-dimethyl polyamide solvent and azido graphene into a reaction bottle in a nitrogen atmosphere, adding side chain alkynyl-containing polyurethane, a click reaction catalyst sodium ascorbate and an accelerant copper sulfate after uniform ultrasonic dispersion, wherein the mass ratio of the four is 100:0.3:0.12:0.08, stirring at a constant speed for reaction for 20 hours, drying the solution in vacuum to remove the solvent, centrifugally washing and drying a solid product by using distilled water, pouring the product into a mold, carrying out a pressure curing process in a flat plate vulcanizing machine at 12MPa for 60 minutes, and carrying out a high-temperature curing process at 90 ℃ for 30 hours to prepare the high-thermal-conductivity graphene in-situ grafted polyurethane elastomer comparative 1.

The thermal conductivity coefficient of the high-thermal-conductivity graphene in-situ grafted polyurethane elastomer in the ultrasonic embodiment and the comparative example is tested by using a TC-1200RH thermal conductivity tester, and the test standard is GB/T3399-.

And testing the tensile strength of the high-thermal-conductivity graphene in-situ grafted polyurethane elastomer by using a T150 UTM tensile tester, wherein the test standard is GB/T1040.1-2006.