CN113025287B - Preparation method of graphene-based hybrid composite material and application of graphene-based hybrid composite material in preparation of heat-conducting automobile tires - Google Patents

Preparation method of graphene-based hybrid composite material and application of graphene-based hybrid composite material in preparation of heat-conducting automobile tires Download PDF

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CN113025287B
CN113025287B CN202110173202.6A CN202110173202A CN113025287B CN 113025287 B CN113025287 B CN 113025287B CN 202110173202 A CN202110173202 A CN 202110173202A CN 113025287 B CN113025287 B CN 113025287B
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CN113025287A (en
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戴李宗
王秀
曹和胜
陈国荣
罗伟昂
袁丛辉
曾碧榕
许一婷
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Xiamen University
Cheng Shin Petrel Tire Xiamen Co Ltd
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Abstract

本发明公开了一种石墨烯基杂化复合材料的制备方法及其在制备导热汽车轮胎中的应用，首先通过改进的水热法和金属‑酸辅助刻蚀法制备得到中空氨基‑锆有机框架材料，再通过Kabachnik‑Fields反应接枝有机膦DOPO，实现石墨烯基杂化复合材料的制备。本发明制得的石墨烯基杂化复合材料中的石墨烯具有导热作用，很好的提高了汽车轮胎的导热性，尤其对于载重轮胎具有优异的散热效果；金属、中空结构、有机膦和石墨烯之间的协同作用大大提高了橡胶材料的阻燃性能；存在有机配体，改善了添加剂与橡胶基体的相容性，具有良好的机械性能。

Figure 202110173202

The invention discloses a preparation method of a graphene-based hybrid composite material and its application in the preparation of thermally conductive automobile tires. First, a hollow amino-zirconium organic framework is prepared by an improved hydrothermal method and a metal-acid-assisted etching method. materials, and then grafted organic phosphine DOPO through the Kabachnik-Fields reaction to achieve the preparation of graphene-based hybrid composites. The graphene in the graphene-based hybrid composite material prepared by the invention has a thermal conductivity, which improves the thermal conductivity of automobile tires well, and especially has excellent heat dissipation effect for truck tires; metal, hollow structure, organic phosphine and graphite The synergistic effect between olefins greatly improves the flame retardant properties of rubber materials; the presence of organic ligands improves the compatibility of additives with rubber matrix, and has good mechanical properties.

Figure 202110173202

Description

Preparation method of graphene-based hybrid composite material and application of graphene-based hybrid composite material in preparation of heat-conducting automobile tires
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a preparation method of a graphene-based hybrid composite material and application of the graphene-based hybrid composite material in preparation of a heat-conducting automobile tire.
Background
With the continuous development of society, the living conditions of people are gradually improved, the utilization rate of automobiles is greatly improved, and the demand of automobile tires is also continuously expanded. But the tire is a flammable rubber material, which greatly limits its practical application, and heat dissipation of the tire is very important. Heavy duty tires (such as loader, truck and bus tires) are more prone to internal heat build-up too quickly under heavy loads than light duty tires due to poor thermal conduction, causing them to run at relatively high temperatures, which has an impact on the long term thermal durability of the tire. Through improving matrix material thermal conductivity, thereby can guarantee that the tire is in time released away the running temperature of tire with the heat that the tire warp and produce in the use, guaranteed the performance and the life-span of tire.
Graphene has outstanding electrical conductivity, thermal conductivity, and excellent mechanical properties, and thus is widely used. The graphene is applied to tire products, and the special reinforcing effect of the unique two-dimensional honeycomb structure on rubber can optimize the thermal conductivity and mechanical strength of the rubber. But in the practical application process, the defects that the compatibility of the graphene and the rubber is poor, the graphene is easy to aggregate and is difficult to disperse, and the like are found. Therefore, there is a need for a method to improve the compatibility between the filler and the base material, so as to improve the thermal conductivity, flame retardancy and mechanical properties of the tire rubber material.
The metal organic framework material is an organic-inorganic hybrid material formed by self-assembling organic ligands or clusters and metal ions through coordination bonds. The material has excellent catalytic performance, and the compatibility problem with rubber can be well solved due to the existence of the organic ligand.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a graphene-based hybrid composite material.
The invention also aims to provide application of the graphene-based hybrid composite material.
It is yet another object of the present invention to provide a thermally conductive heavy duty vehicle tire.
The technical scheme of the invention is as follows:
a preparation method of a graphene-based hybrid composite material comprises the following steps:
(1) stirring and mixing zirconium tetrachloride, 2-amino terephthalic acid, dimethylformamide and acetic acid at room temperature, reacting at 100-140 ℃ for 18-30h, sequentially washing with DMF (dimethyl formamide) and methanol, and then drying in vacuum to obtain a zirconium metal organic framework material;
(2) stirring and mixing sodium tungstate and water at room temperature, adjusting the pH to 2.0 by using hydrochloric acid, adding water, and adjusting the pH to 2.3 by using oxalic acid to obtain a sodium tungstate solution;
(3) adding the zirconium metal organic framework material obtained in the step (1) into the sodium tungstate solution obtained in the step (2), reacting for 3-9h at the temperature of 160-200 ℃ after ultrasonic treatment, fully washing with deionized water, and then drying in vacuum to obtain a hollow zirconium metal organic framework material;
(4) stirring and mixing the hollow zirconium metal organic framework material obtained in the step (3), tetrahydrofuran and polyformaldehyde at room temperature, adding DOPO and graphene oxide, carrying out condensation reflux reaction at 40-60 ℃ for 8-12h, then carrying out centrifugal washing with tetrahydrofuran and water, and then carrying out vacuum drying to obtain the graphene-based hybrid composite material.
In a preferred embodiment of the present invention, in said step (1), the ratio of zirconium tetrachloride, 2-aminoterephthalic acid, dimethylformamide and acetic acid is 0.17-0.19g: 0.12-0.13g: 38-42mL: 4-6 mL.
In a preferred embodiment of the present invention, in the step (2), the concentration of the sodium tungstate solution is 32 to 34 g/L.
In a preferred embodiment of the present invention, in the step (4), the ratio of the hollow zirconium metal organic framework material, polyoxymethylene, tetrahydrofuran, DOPO, graphene oxide is 0.8-1.2g: 0.08-0.12g: 90-110 mL: 0.2-0.5 g.
In a preferred embodiment of the present invention, the temperature of the vacuum drying is 50 to 100 ℃.
In a preferred embodiment of the present invention, in the step (1), the ratio of zirconium tetrachloride, 2-aminoterephthalic acid, dimethylformamide and acetic acid is 0.18g: 0.128g: 40mL: 5 mL; in the step (2), the concentration of the sodium tungstate solution is 33 g/L; in the step (4), the ratio of the hollow zirconium metal organic framework material to the polyformaldehyde to the tetrahydrofuran to the DOPO to the graphene oxide is 1g to 0.1g to 100mL to 0.25-0.5 g.
The other technical scheme of the invention is as follows:
the graphene-based hybrid composite material prepared by the preparation method is applied to preparation of heat-conducting automobile tires (particularly has an excellent heat dissipation effect on heavy duty tires).
The invention adopts another technical scheme as follows:
a heat-conducting heavy-load automobile tire comprises the graphene-based hybrid composite material prepared by the preparation method.
In a preferred embodiment of the present invention, the raw materials further include natural rubber, styrene-butadiene rubber, carbon black, zinc oxide, stearic acid, and paraffin wax.
Further preferably, the mass ratio of the graphene-based hybrid composite material to the natural rubber to the styrene butadiene rubber to the carbon black to the zinc oxide to the stearic acid to the paraffin wax is 2-3: 40-45: 18-20: 25-30: 2-4:1: 2-4.
The invention has the beneficial effects that:
1. graphene in the graphene-based hybrid composite material prepared by the invention has a heat conduction effect, so that the heat conductivity of the automobile tire is well improved;
2. the synergistic effect among metal, hollow structure, organic phosphine and graphene in the graphene-based hybrid composite material greatly improves the flame retardant property of the rubber material;
3. the graphene-based hybrid composite material prepared by the invention has organic ligands, improves the compatibility of the additive and the rubber matrix, and has good mechanical properties.
4. The heat-conducting heavy-duty automobile tire prepared by the invention has higher heat conductivity coefficient and mechanical strength, and meets the relevant use requirements of heavy-duty tires.
Drawings
Fig. 1 is a synthesis route diagram of the graphene-based hybrid composite material of the present invention.
Fig. 2 is an XRD spectrum of the graphene-based hybrid composite prepared in example 1 of the present invention.
Fig. 3 is an FTIR spectrum of the graphene-based hybrid composite prepared in example 1 of the present invention.
Detailed Description
The technical solution of the present invention will be further illustrated and described below with reference to the accompanying drawings by means of specific embodiments.
Example 1
1. Preparing the graphene-based hybrid composite material:
as shown in fig. 1, the preparation method of the graphene-based hybrid composite material comprises the following specific steps:
(1) adding 0.18g of zirconium tetrachloride, 0.128g of 2-aminoterephthalic acid, 40mL of dimethylformamide and 5mL of acetic acid into a reaction vessel, stirring for 20min at room temperature, pouring the reaction solution into a tetrafluoroethylene reaction kettle, reacting for 36h at 120 ℃, sequentially and respectively carrying out centrifugal washing for 5 times by using dimethylformamide and methanol, and carrying out vacuum drying at 80 ℃ to obtain the zirconium metal organic framework material (UiO 66-N)H2)。
(2) Adding 8.25g sodium tungstate and 25mL water into a reaction vessel, stirring at room temperature for 30min, and adding 2mol L-1Then water was added to obtain 250mL of a solution, and oxalic acid was added to adjust the pH of the solution to 2.3, to obtain a sodium tungstate solution. Adding 70mL of the sodium tungstate solution obtained in the step (2) into a reaction vessel, and adding 1g of UiO66-NH2Performing ultrasonic treatment on the powder for 10min, pouring the reaction solution into a tetrafluoroethylene reaction kettle, reacting for 6h at 180 ℃, centrifuging and washing for 5 times by using water, and performing vacuum drying at 80 ℃ to obtain the hollow zirconium metal organic framework material (W-UiO 66-NH)2)。
(3) Adding 1g W-Zr-MOF-NH into the reaction vessel2Stirring 0.1g of polyformaldehyde and 100mL of tetrahydrofuran for 10min at room temperature, adding 0.25g of DOPO and 0.25g of graphene oxide, carrying out condensation reflux reaction for 10h at 40-60 ℃, respectively carrying out centrifugal washing for 5 times by using tetrahydrofuran and water, and carrying out vacuum drying at 80 ℃ to obtain the graphene-based hybrid composite material (W-UiO 66-DOPO-GO).
The phase structure of the graphene-based hybrid composite material was measured by an X-ray diffractometer, and the measurement results are shown in fig. 2.
The functional groups of the graphene-based hybrid composite material were characterized by an infrared spectrometer, and the characterization results are shown in fig. 3.
2. Preparing a graphene-based hybrid composite material modified heat-conducting automobile tire rubber material:
mixing the graphene-based hybrid composite material prepared in the embodiment, natural rubber, styrene butadiene rubber, carbon black, zinc oxide, stearic acid and paraffin wax at a stirring speed of 285r/min for 20min at 140 ℃, then conveying the mixture to an internal mixer for fully mixing at a stirring speed of 700r/min at 160 ℃, finally conveying the mixture to a screw extruder for extrusion granulation and cooling at a rotating speed of 190r/min at 180 ℃ to obtain a heat-conducting automobile tire rubber material, and preparing the heat-conducting heavy-load automobile tire by using the heat-conducting automobile tire rubber material.
Example 2
1. Preparing the graphene-based hybrid composite material:
as shown in fig. 1, the preparation method of the graphene-based hybrid composite material comprises the following specific steps:
(1) adding 0.18g of zirconium tetrachloride, 0.128g of 2-aminoterephthalic acid, 40mL of dimethylformamide and 5mL of acetic acid into a reaction vessel, stirring for 20min at room temperature, pouring the reaction solution into a tetrafluoroethylene reaction kettle, reacting for 36h at 120 ℃, sequentially and respectively carrying out centrifugal washing for 5 times by using dimethylformamide and methanol, and carrying out vacuum drying at 80 ℃ to obtain the zirconium metal organic framework material (UiO 66-NH)2)。
(2) Adding 8.25g sodium tungstate and 25mL water into a reaction vessel, stirring at room temperature for 30min, and adding 2mol L-1Then water was added to obtain 250mL of a solution, and oxalic acid was added to adjust the pH of the solution to 2.3, to obtain a sodium tungstate solution. Adding 70mL of the sodium tungstate solution obtained in the step (2) into a reaction vessel, and adding 1g of UiO66-NH2Performing ultrasonic treatment on the powder for 10min, pouring the reaction solution into a tetrafluoroethylene reaction kettle, reacting for 6h at 180 ℃, centrifuging and washing for 5 times by using water, and performing vacuum drying at 80 ℃ to obtain the hollow zirconium metal organic framework material (W-UiO 66-NH)2)。
(3) Adding 1g W-Zr-MOF-NH into the reaction vessel2Stirring 0.1g of polyformaldehyde and 100mL of tetrahydrofuran at room temperature for 10min, adding 0.5g of DOPO and 0.5g of graphene oxide, carrying out condensation reflux reaction at 40-60 ℃ for 10h, respectively carrying out centrifugal washing for 5 times by using tetrahydrofuran and water, and carrying out vacuum drying at 80 ℃ to obtain the graphene-based hybrid composite material (W-UiO 66-DOPO-GO).
2. Preparing a graphene-based hybrid composite material modified heat-conducting automobile tire rubber material:
mixing the graphene-based hybrid composite material prepared in the embodiment, natural rubber, styrene butadiene rubber, carbon black, zinc oxide, stearic acid and paraffin wax at a stirring speed of 285r/min for 20min at 140 ℃, then conveying the mixture to an internal mixer for fully mixing at a stirring speed of 700r/min at 160 ℃, finally conveying the mixture to a screw extruder for extrusion granulation and cooling at a rotating speed of 190r/min at 180 ℃ to obtain a heat-conducting automobile tire rubber material, and preparing the heat-conducting heavy-load automobile tire by using the heat-conducting automobile tire rubber material.
Example 3
1. Preparing the graphene-based hybrid composite material:
as shown in fig. 1, the preparation method of the graphene-based hybrid composite material comprises the following specific steps:
(1) adding 0.18g of zirconium tetrachloride, 0.128g of 2-aminoterephthalic acid, 40mL of dimethylformamide and 5mL of acetic acid into a reaction vessel, stirring for 20min at room temperature, pouring the reaction solution into a tetrafluoroethylene reaction kettle, reacting for 36h at 120 ℃, sequentially and respectively carrying out centrifugal washing for 5 times by using dimethylformamide and methanol, and carrying out vacuum drying at 80 ℃ to obtain the zirconium metal organic framework material (UiO 66-NH)2)。
(2) Adding 8.25g sodium tungstate and 25mL water into a reaction vessel, stirring at room temperature for 30min, and adding 2mol L-1Then water was added to obtain 250mL of a solution, and oxalic acid was added to adjust the pH of the solution to 2.3, to obtain a sodium tungstate solution. Adding 70mL of the sodium tungstate solution obtained in the step (2) into a reaction vessel, and adding 1g of UiO66-NH2Performing ultrasonic treatment on the powder for 10min, pouring the reaction solution into a tetrafluoroethylene reaction kettle, reacting for 6h at 180 ℃, centrifuging and washing for 5 times by using water, and performing vacuum drying at 80 ℃ to obtain the hollow zirconium metal organic framework material (W-UiO 66-NH)2)。
(3) Adding 1g W-Zr-MOF-NH into the reaction vessel2Stirring 0.1g of polyformaldehyde and 100mL of tetrahydrofuran for 10min at room temperature, adding 0.25g of DOPO and 0.25g of graphene oxide, carrying out condensation reflux reaction for 10h at 40-60 ℃, respectively carrying out centrifugal washing for 5 times by using tetrahydrofuran and water, and carrying out vacuum drying at 80 ℃ to obtain the graphene-based hybrid composite material (W-UiO 66-DOPO-GO).
2. Preparing a graphene-based hybrid composite material modified heat-conducting automobile tire rubber material:
mixing the graphene-based hybrid composite material prepared in the embodiment, natural rubber, styrene butadiene rubber, carbon black, zinc oxide, stearic acid and paraffin wax at a stirring speed of 285r/min for 20min at 140 ℃, then conveying the mixture to an internal mixer for fully mixing at a stirring speed of 700r/min at 160 ℃, finally conveying the mixture to a screw extruder for extrusion granulation and cooling at a rotating speed of 190r/min at 180 ℃ to obtain a heat-conducting automobile tire rubber material, and preparing the heat-conducting heavy-load automobile tire by using the heat-conducting automobile tire rubber material.
Example 4
1. Preparing the graphene-based hybrid composite material:
as shown in fig. 1, the preparation method of the graphene-based hybrid composite material comprises the following specific steps:
(1) adding 0.18g of zirconium tetrachloride, 0.128g of 2-aminoterephthalic acid, 40mL of dimethylformamide and 5mL of acetic acid into a reaction vessel, stirring for 20min at room temperature, pouring the reaction solution into a tetrafluoroethylene reaction kettle, reacting for 36h at 120 ℃, sequentially and respectively carrying out centrifugal washing for 5 times by using dimethylformamide and methanol, and carrying out vacuum drying at 80 ℃ to obtain the zirconium metal organic framework material (UiO 66-NH)2)。
(2) Adding 8.25g sodium tungstate and 25mL water into a reaction vessel, stirring at room temperature for 30min, and adding 2mol L-1Then water was added to obtain 250mL of a solution, and oxalic acid was added to adjust the pH of the solution to 2.3, to obtain a sodium tungstate solution. Adding 70mL of the sodium tungstate solution obtained in the step (2) into a reaction vessel, and adding 1g of UiO66-NH2Performing ultrasonic treatment on the powder for 10min, pouring the reaction solution into a tetrafluoroethylene reaction kettle, reacting for 6h at 180 ℃, centrifuging and washing for 5 times by using water, and performing vacuum drying at 80 ℃ to obtain the hollow zirconium metal organic framework material (W-UiO 66-NH)2)。
(3) Adding 1g W-Zr-MOF-NH into the reaction vessel2Stirring 0.1g of polyformaldehyde and 100mL of tetrahydrofuran at room temperature for 10min, adding 0.5g of DOPO and 0.5g of graphene oxide, carrying out condensation reflux reaction at 40-60 ℃ for 10h, respectively carrying out centrifugal washing for 5 times by using tetrahydrofuran and water, and carrying out vacuum drying at 80 ℃ to obtain the graphene-based hybrid composite material (W-UiO 66-DOPO-GO).
2. Preparing a graphene-based hybrid composite material modified heat-conducting automobile tire rubber material:
mixing the graphene-based hybrid composite material prepared in the embodiment, natural rubber, styrene butadiene rubber, carbon black, zinc oxide, stearic acid and paraffin wax at a stirring speed of 285r/min for 20min at 140 ℃, then conveying the mixture to an internal mixer for fully mixing at a stirring speed of 700r/min at 160 ℃, finally conveying the mixture to a screw extruder for extrusion granulation and cooling at a rotating speed of 190r/min at 180 ℃ to obtain a heat-conducting automobile tire rubber material, and preparing the heat-conducting heavy-load automobile tire by using the heat-conducting automobile tire rubber material.
Comparative example 1
Compared with example 1, the preparation and addition of the graphene-based hybrid composite material are omitted in the present comparative example, and the method steps are the same except for this.
Comparative example 2
1. Preparation of UiO66-NH2: adding 0.18g of zirconium tetrachloride, 0.128g of 2-aminoterephthalic acid, 40mL of dimethylformamide and 5mL of acetic acid into a reaction vessel, stirring for 20min at room temperature, pouring the reaction solution into a tetrafluoroethylene reaction kettle, reacting for 36h at 120 ℃, sequentially and respectively carrying out centrifugal washing for 5 times by using dimethylformamide and methanol, and carrying out vacuum drying at 80 ℃ to obtain the zirconium metal organic framework material (UiO 66-NH)2)。
2. Preparation of UiO66-NH2Modified automobile tire rubber:
UiO66-NH prepared by the comparative example is mixed according to the mass ratio of 2: 45: 18: 25: 3: 1: 32Mixing natural rubber, styrene butadiene rubber, carbon black, zinc oxide, stearic acid and paraffin at 140 ℃ at a stirring speed of 285r/min for 20min, then conveying the mixture into an internal mixer for fully mixing at 160 ℃ at a stirring speed of 700r/min, finally conveying the mixture into a screw extruder for extruding, granulating and cooling at 180 ℃ at a rotating speed of 190r/min to obtain an automobile tire rubber material, and manufacturing the automobile tire by using the automobile tire rubber material.
Comparative example 3
1. Preparation of W-UiO66-NH2：
(1) Adding 0.18g of zirconium tetrachloride, 0.128g of 2-aminoterephthalic acid, 40mL of dimethylformamide and 5mL of acetic acid into a reaction vessel, stirring for 20min at room temperature, pouring the reaction solution into a tetrafluoroethylene reaction kettle, reacting for 36h at 120 ℃, sequentially and respectively carrying out centrifugal washing for 5 times by using dimethylformamide and methanol, and carrying out vacuum drying at 80 ℃ to obtain the zirconium metal organic framework material (UiO 66-NH)2)；
(2) ToAdding 8.25g sodium tungstate and 25mL water into a reaction container, stirring at room temperature for 30min, and adding 2mol L-1Then water was added to obtain 250mL of a solution, and oxalic acid was added to adjust the pH of the solution to 2.3, to obtain a sodium tungstate solution. Adding 70mL of the sodium tungstate solution obtained in the step (2) into a reaction vessel, and adding 1g of UiO66-NH2Performing ultrasonic treatment on the powder for 10min, pouring the reaction solution into a tetrafluoroethylene reaction kettle, reacting for 6h at 180 ℃, centrifuging and washing for 5 times by using water, and performing vacuum drying at 80 ℃ to obtain the hollow zirconium metal organic framework material (W-UiO 66-NH)2)。
2. Preparation of W-UiO66-NH2Modified automobile tire rubber:
W-UiO66-NH prepared by the comparative example is mixed according to the mass ratio of 2: 45: 18: 25: 3: 1: 32Mixing natural rubber, styrene butadiene rubber, carbon black, zinc oxide, stearic acid and paraffin at 140 ℃ at a stirring speed of 285r/min for 20min, then conveying the mixture into an internal mixer for fully mixing at 160 ℃ at a stirring speed of 700r/min, finally conveying the mixture into a screw extruder for extruding, granulating and cooling at 180 ℃ at a rotating speed of 190r/min to obtain an automobile tire rubber material, and manufacturing the automobile tire by using the automobile tire rubber material.
Comparative example 4
Preparing a GO modified automobile tire rubber material: GO, natural rubber, styrene butadiene rubber, carbon black, zinc oxide, stearic acid and paraffin are mixed for 20min at the stirring speed of 285r/min at the temperature of 140 ℃, then conveyed into an internal mixer to be fully mixed at the stirring speed of 700r/min at the temperature of 160 ℃, finally conveyed into a screw extruder to be extruded and granulated at the rotating speed of 190r/min at the temperature of 180 ℃ and cooled to obtain an automobile tire rubber material, and the automobile tire rubber material is used for manufacturing the automobile tire.
The automobile tire rubber materials obtained in the examples and the comparative examples are tested for heat conductivity, thermal diffusion coefficient, specific heat and heat storage coefficient, and the detection results are shown in table 1; the automobile tire rubber materials obtained in the examples and the comparative examples are tested for flame retardant property, tensile strength and tear strength, the oxygen index is generally considered to be less than 22 and belongs to flammable materials, the oxygen index is between 22 and 27 and belongs to flame-retardant materials, and the specific test results are shown in table 2.
TABLE 1
Figure BDA0002939128880000081
TABLE 2
Figure BDA0002939128880000082
Figure BDA0002939128880000091
As can be seen from tables 1 and 2, the heat-conductive automobile tire rubber materials prepared in examples 1 to 4 of the present invention are excellent in heat-conductive property, mechanical property and flame retardant property.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims.

Claims (6)

1.石墨烯基杂化复合材料在制备导热重载汽车轮胎中的应用，其特征在于：该导热重载汽车轮胎的原料包括质量比为2-3: 40-45: 18-20: 25-30: 2-4:1: 2-4的石墨烯基杂化复合材料、天然橡胶、丁苯橡胶、炭黑、氧化锌、硬脂酸和石蜡，其中，该石墨烯基杂化复合材料的制备方法包括如下步骤：1. the application of graphene-based hybrid composite material in preparing heat-conducting heavy-duty automobile tire, it is characterized in that: the raw material of this heat-conducting heavy-duty automobile tire comprising mass ratio is 2-3: 40-45: 18-20: 25- 30:2-4:1:2-4 graphene-based hybrid composite material, natural rubber, styrene-butadiene rubber, carbon black, zinc oxide, stearic acid and paraffin, wherein, the graphene-based hybrid composite material The preparation method includes the following steps: （1）将四氯化锆、2-氨基对苯二甲酸、二甲基甲酰胺和醋酸于室温下搅拌混合后于100-140 ℃反应18-30 h，接着依次用DMF和甲醇洗涤，然后经真空干燥后得到锆金属有机框架材料；四氯化锆、2-氨基对苯二甲酸、二甲基甲酰胺和醋酸的比例为0.17-0.19g: 0.12-0.13g: 38-42mL: 4-6mL；(1) Zirconium tetrachloride, 2-aminoterephthalic acid, dimethylformamide and acetic acid were stirred and mixed at room temperature, reacted at 100-140 °C for 18-30 h, then washed with DMF and methanol in turn, and then Zirconium metal organic framework material is obtained after vacuum drying; the ratio of zirconium tetrachloride, 2-aminoterephthalic acid, dimethylformamide and acetic acid is 0.17-0.19g: 0.12-0.13g: 38-42mL: 4- 6mL; （2）将钨酸钠和水于室温下搅拌混合后，用盐酸调节pH至2.0后加水，再用草酸调节pH至2.3，得到浓度为32-34g/L的钨酸钠溶液；(2) After stirring and mixing sodium tungstate and water at room temperature, adjust the pH to 2.0 with hydrochloric acid, add water, and then adjust the pH to 2.3 with oxalic acid to obtain a sodium tungstate solution with a concentration of 32-34g/L; （3）在步骤（2）所得的钨酸钠溶液中加入步骤（1）所得的锆金属有机框架材料，超声处理后于160-200 ℃下反应3-9 h，接着用去离子水充分洗涤，然后经真空干燥后得到中空锆金属有机框架材料；(3) Add the zirconium metal organic framework material obtained in step (1) to the sodium tungstate solution obtained in step (2), and after ultrasonic treatment, react at 160-200 °C for 3-9 h, and then fully wash with deionized water , and then vacuum-drying to obtain a hollow zirconium metal-organic framework material; （4）将步骤（3）所得的中空锆金属有机框架材料、四氢呋喃和聚甲醛于室温下搅拌混合后加入DOPO和氧化石墨烯，于40-60℃下冷凝回流反应8-12 h，接着用四氢呋喃和水离心洗涤，然后经真空干燥，得到所述石墨烯基杂化复合材料；中空锆金属有机框架材料、聚甲醛、四氢呋喃、DOPO、氧化石墨烯的比例为0.8-1.2g: 0.08-0.12g: 90-110mL：0.2-0.5g: 0.2-0.5g。(4) The hollow zirconium metal-organic framework material, tetrahydrofuran and polyoxymethylene obtained in step (3) were stirred and mixed at room temperature, DOPO and graphene oxide were added, and the reaction was condensed and refluxed at 40-60 °C for 8-12 h, and then used Tetrahydrofuran and water are centrifugally washed, and then vacuum-dried to obtain the graphene-based hybrid composite material; the ratio of hollow zirconium metal organic framework material, polyoxymethylene, tetrahydrofuran, DOPO, and graphene oxide is 0.8-1.2g: 0.08-0.12 g: 90-110mL: 0.2-0.5g: 0.2-0.5g. 2.如权利要求1所述的应用，其特征在于：所述真空干燥的温度为50-100℃。2 . The application according to claim 1 , wherein the temperature of the vacuum drying is 50-100° C. 3 . 3. 如权利要求1所述的应用，其特征在于：所述步骤（1）中，四氯化锆、2-氨基对苯二甲酸、二甲基甲酰胺和醋酸的比例为0.18g: 0.128g: 40mL: 5mL；所述步骤（2）中，所述钨酸钠溶液的浓度为33g/L；所述步骤（4）中，所述中空锆金属有机框架材料、聚甲醛、四氢呋喃、DOPO、氧化石墨烯的比例为1g: 0.1g: 100mL：0.25-0.5g: 0.25-0.5g。3. application as claimed in claim 1, is characterized in that: in described step (1), the ratio of zirconium tetrachloride, 2-amino terephthalic acid, dimethylformamide and acetic acid is 0.18g: 0.128 g: 40mL: 5mL; in the step (2), the concentration of the sodium tungstate solution is 33g/L; in the step (4), the hollow zirconium metal organic framework material, polyoxymethylene, tetrahydrofuran, DOPO , the ratio of graphene oxide is 1g: 0.1g: 100mL: 0.25-0.5g: 0.25-0.5g. 4. 一种导热重载汽车轮胎，其特征在于：其原料包括质量比为2-3: 40-45: 18-20:25-30: 2-4:1: 2-4的石墨烯基杂化复合材料、天然橡胶、丁苯橡胶、炭黑、氧化锌、硬脂酸和石蜡，其中，该石墨烯基杂化复合材料的制备方法包括如下步骤：4. a heat-conducting heavy-duty automobile tire, is characterized in that: its raw material comprises the graphene-based miscellaneous material whose mass ratio is 2-3: 40-45: 18-20: 25-30: 2-4: 1: 2-4 Chemical composite material, natural rubber, styrene-butadiene rubber, carbon black, zinc oxide, stearic acid and paraffin, wherein, the preparation method of the graphene-based hybrid composite material comprises the following steps: （1）将四氯化锆、2-氨基对苯二甲酸、二甲基甲酰胺和醋酸于室温下搅拌混合后于100-140 ℃反应18-30 h，接着依次用DMF和甲醇洗涤，然后经真空干燥后得到锆金属有机框架材料；四氯化锆、2-氨基对苯二甲酸、二甲基甲酰胺和醋酸的比例为0.17-0.19g: 0.12-0.13g: 38-42mL: 4-6mL；(1) Zirconium tetrachloride, 2-aminoterephthalic acid, dimethylformamide and acetic acid were stirred and mixed at room temperature, reacted at 100-140 °C for 18-30 h, then washed with DMF and methanol in turn, and then Zirconium metal organic framework material is obtained after vacuum drying; the ratio of zirconium tetrachloride, 2-aminoterephthalic acid, dimethylformamide and acetic acid is 0.17-0.19g: 0.12-0.13g: 38-42mL: 4- 6mL; （2）将钨酸钠和水于室温下搅拌混合后，用盐酸调节pH至2.0后加水，再用草酸调节pH至2.3，得到浓度为32-34g/L的钨酸钠溶液；(2) After stirring and mixing sodium tungstate and water at room temperature, adjust the pH to 2.0 with hydrochloric acid, add water, and then adjust the pH to 2.3 with oxalic acid to obtain a sodium tungstate solution with a concentration of 32-34g/L; （3）在步骤（2）所得的钨酸钠溶液中加入步骤（1）所得的锆金属有机框架材料，超声处理后于160-200 ℃下反应3-9 h，接着用去离子水充分洗涤，然后经真空干燥后得到中空锆金属有机框架材料；(3) Add the zirconium metal organic framework material obtained in step (1) to the sodium tungstate solution obtained in step (2), and after ultrasonic treatment, react at 160-200 °C for 3-9 h, and then fully wash with deionized water , and then vacuum-drying to obtain a hollow zirconium metal-organic framework material; （4）将步骤（3）所得的中空锆金属有机框架材料、四氢呋喃和聚甲醛于室温下搅拌混合后加入DOPO和氧化石墨烯，于40-60℃下冷凝回流反应8-12 h，接着用四氢呋喃和水离心洗涤，然后经真空干燥，得到所述石墨烯基杂化复合材料；中空锆金属有机框架材料、聚甲醛、四氢呋喃、DOPO、氧化石墨烯的比例为0.8-1.2g: 0.08-0.12g: 90-110mL：0.2-0.5g: 0.2-0.5g。(4) The hollow zirconium metal-organic framework material, tetrahydrofuran and polyoxymethylene obtained in step (3) were stirred and mixed at room temperature, DOPO and graphene oxide were added, and the reaction was condensed and refluxed at 40-60 °C for 8-12 h, and then used Tetrahydrofuran and water are centrifugally washed, and then vacuum-dried to obtain the graphene-based hybrid composite material; the ratio of hollow zirconium metal organic framework material, polyoxymethylene, tetrahydrofuran, DOPO, and graphene oxide is 0.8-1.2g: 0.08-0.12 g: 90-110mL: 0.2-0.5g: 0.2-0.5g. 5.如权利要求4所述的一种导热重载汽车轮胎，其特征在于：所述真空干燥的温度为50-100℃。5 . The thermally conductive heavy-duty automobile tire according to claim 4 , wherein the temperature of the vacuum drying is 50-100° C. 6 . 6.如权利要求4所述的一种导热重载汽车轮胎，其特征在于：所述步骤（1）中，四氯化锆、2-氨基对苯二甲酸、二甲基甲酰胺和醋酸的比例为0.18g: 0.128g: 40mL: 5mL；所述步骤（2）中，所述钨酸钠溶液的浓度为33g/L；所述步骤（4）中，所述中空锆金属有机框架材料、聚甲醛、四氢呋喃、DOPO、氧化石墨烯的比例为1g: 0.1g: 100mL：0.25-0.5g: 0.25-0.5g。6 . The heat-conducting heavy-duty automobile tire according to claim 4 , wherein in the step (1), zirconium tetrachloride, 2-aminoterephthalic acid, dimethylformamide and acetic acid are mixed with zirconium tetrachloride. 7 . The ratio is 0.18g: 0.128g: 40mL: 5mL; in the step (2), the concentration of the sodium tungstate solution is 33g/L; in the step (4), the hollow zirconium metal organic framework material, The ratio of polyoxymethylene, tetrahydrofuran, DOPO, and graphene oxide is 1 g: 0.1 g: 100 mL: 0.25-0.5 g: 0.25-0.5 g.
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