Near-nanoscale whisker carbon tube in-situ loaded inorganic nanoparticle hybrid filler and rubber composite material

Abstract

The invention discloses a near-nano-scale whisker carbon tube in-situ loaded inorganic nanoparticle hybrid filler, a preparation method thereof and a rubber composite material. The hybrid filler comprises a modified whisker carbon tube and inorganic nanoparticles loaded on the modified whisker carbon tube, and the modified whisker carbon tube is obtained by modifying a whisker carbon tube through polyamide epichlorohydrin. The rubber composite material comprises a rubber matrix, a hybrid filler and other processing aids. The rubber composite material is small in dynamic heat generation, good in heat conduction, excellent in mechanical property, good in comprehensive performance, simple in processing technology, environment-friendly in process and suitable for heat conduction tires and the like.

Description

Technical Field

[0001] This invention relates to the field of rubber nanocomposite materials, specifically to a near-nanoscale carbon nanotube in-situ supported inorganic nanoparticle hybrid filler, its preparation method, and a rubber composite material. Background Technology

[0002] Rubber's high elasticity and large deformation capacity make it an extremely important strategic material. However, due to its hysteresis and low thermal conductivity, rubber products generate a lot of heat under dynamic operating conditions, which is difficult to dissipate. Localized high temperatures caused by heat accumulation degrade product performance and reduce its service life. While heat accumulation can be addressed by reducing heat generation or improving thermal conductivity, reducing dynamic heat generation cannot solve the problem of heat accumulation under prolonged operating conditions. Only by improving the thermal conductivity of rubber composites can the dynamic temperature rise problem be fundamentally solved. Adding fillers with high thermal conductivity to the rubber matrix is ​​the simplest and most effective way to improve the thermal conductivity of rubber composites.

[0003] Carbon nanotubes possess a perfect hexagonal graphite lattice structure and extremely high theoretical thermal conductivity, making them widely used in the field of thermally conductive polymer composites. Adding carbon nanotubes to a rubber matrix can provide good reinforcement and low rolling resistance, but it is difficult to achieve the desired improvement in thermal conductivity. Increasing the amount of carbon nanotubes can improve thermal conductivity to some extent, but it will significantly increase the dynamic heat generation of the rubber composite.

[0004] The above problems arise for two main reasons. First, the high specific surface area of ​​carbon nanotubes leads to a large amount of interfacial and internal friction when carbon nanotubes are filled into rubber. This results in severe phonon scattering at the interface between carbon nanotubes and rubber, high interfacial thermal resistance, poor thermal conductivity, and a large amount of heat generated by internal friction, leading to a significant temperature rise. Second, the inertness of the carbon nanotube surface makes surface modification difficult and interfacial interactions poor. Traditional modification methods can damage the lattice structure of the carbon nanotube surface, resulting in a decrease in thermal conductivity.

[0005] Therefore, a new method for preparing rubber composite materials is needed to solve the problem of dynamic temperature rise in rubber composite materials. Summary of the Invention

[0006] To address the problems existing in the prior art, this invention designs a hybrid filler with near-nanoscale carbon nanotubes in situ loaded with inorganic nanoparticles, and applies it to rubber products under dynamic working conditions such as tires, so as to achieve the purpose of high thermal conductivity, low heat generation, and reduced heat accumulation.

[0007] To address the current technical challenges in thermally conductive rubber composite materials, this invention has the following main objectives:

[0008] (1) A method for preparing near-nanoscale carbon nanotube in-situ supported inorganic nanoparticle hybrid filler is provided;

[0009] (2) A rubber composite material containing near-nanoscale carbon nanotubes in situ supported inorganic nanoparticle composite fillers obtained by the above preparation method is provided.

[0010] One objective of this invention is to provide a near-nanoscale carbon nanotube in-situ supported inorganic nanoparticle hybrid filler, comprising modified carbon nanotubes and inorganic nanoparticles supported thereon, wherein the modified carbon nanotubes are obtained by modifying the carbon nanotubes with polyamide epichlorohydrin.

[0011] In the hybrid filler of the present invention, inorganic nanoparticles are grown in situ on the surface of modified carbon whisker tubes, wherein polyamide epichlorohydrin is adsorbed onto the carbon whisker tubes through cation-π interaction, and inorganic nanoparticles are grown on polyamide epichlorohydrin to form a hybrid filler.

[0012] The diameter of the carbon whisker tube is 50–200 nm.

[0013] The inorganic nanoparticles are at least one of nano-alumina or nano-silicon oxide.

[0014] The second objective of this invention is to provide a method for preparing a near-nanoscale carbon nanotube in-situ supported inorganic nanoparticle hybrid filler, preferably used for preparing the hybrid filler described in the first objective of this invention, comprising the following steps:

[0015] (1) Modified carbon whisker tubes were obtained by modifying carbon whisker tubes with polyamide epichlorohydrin.

[0016] (2) Add the modified carbon whisker to the solvent, adjust the pH to 8-12, add the inorganic nanoparticle precursor, and obtain the hybrid filler after reaction.

[0017] In step (1), carbon whisker tubes are ultrasonically dispersed in a polyamide epichlorohydrin solution, the pH of the dispersion is adjusted to 5-12, and modified carbon whisker tubes are obtained by centrifugation, filtration and drying.

[0018] The near-nanoscale carbon whisker refers to carbon whisker nanotubes with a diameter of about 100 nm, wherein the preferred carbon whisker has a diameter of 50 to 200 nm.

[0019] The mass ratio of polyamide epichlorohydrin to carbon nanotube whiskers is (1-100):1, preferably (5-20):1, and can be, for example, 1:1, 5:1, 10:1, 15:1, 20:1, 30:1, 40:1, 50:1, 60:1, 70:1, 80:1, 90:1, 100:1, etc.

[0020] The polyamide epichlorohydrin solution has a mass fraction of 2-15 wt%, preferably 2-12.5 wt%.

[0021] The ultrasonic power is 50–1500W, the ultrasonic temperature is 0–60℃, and the ultrasonic dispersion time is 0.5–5 hours.

[0022] In step (2), the solvent is a mixture of deionized water and ethanol. Preferably, the mass ratio of deionized water to ethanol is 1:1 to 1:20.

[0023] The aluminum nitrate described in this invention is a precursor for loading inorganic nanoparticles. Other inorganic nanoparticle precursors, such as tetraethyl orthosilicate, can also be used.

[0024] The mass ratio of inorganic nanoparticle precursor to carbon whisker is (5-20):1, preferably (5-10):1, and can be, for example, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 12:1, 15:1, 18:1, 20:1, etc.

[0025] The reaction temperature is 20–60℃, and the reaction time is 6–48 h.

[0026] The reaction may also include steps such as filtration and drying.

[0027] According to a preferred embodiment of the present invention, the preparation method includes:

[0028] (1) Near-nanoscale carbon nanotubes (NNCT) were dispersed in a polyamide epichlorohydrin (PAE) solution, the pH of the dispersion was adjusted to 5-12, and ultrasonic dispersion was carried out for 0.5-5 hours. Then, PAE-NNCT powder was collected by centrifugation, filtration and drying.

[0029] (2) Add the PAE-NNCT powder obtained in step (1) to a mixed solution of ethanol / deionized water, add ammonia to adjust the pH to 8-12, add inorganic nanoparticle precursor, stir the reaction for 6-48 h, the reaction temperature is 20-60℃, and after the reaction is completed, filter and dry to obtain hybrid filler.

[0030] The third objective of this invention is to provide near-nanoscale carbon nanotubes in situ supported inorganic nanoparticle hybrid fillers obtained by the preparation method described in the second objective of this invention.

[0031] The fourth objective of this invention is to provide a rubber composite material comprising near-nanoscale carbon nanotubes in situ supported inorganic nanoparticles as described in one or three of the objectives of this invention and a rubber matrix.

[0032] The rubber matrix used in this invention is one or more of natural rubber, styrene-butadiene rubber, cis-butadiene rubber, nitrile rubber, polyurethane rubber, and silicone rubber.

[0033] The obtained hybrid filler is dispersed into the rubber matrix through a mixing technique to obtain a rubber composite material with high thermal conductivity.

[0034] The rubber composite material includes,

[0035] 100 parts by weight of rubber matrix;

[0036] The hybrid filler is 5 to 100 parts by weight; preferably 20 to 70 parts by weight.

[0037] The mixing technology used in this invention is a common technology in rubber processing, specifically one or more of the following: internal mixer mixing, silane in-situ modified dispersion internal mixer mixing, open mill mixing, planetary mixing, screw extrusion mixing, etc.

[0038] Other processing aids that can be used in the rubber nanocomposite material of the present invention include various vulcanizing agents such as sulfur, various accelerators or catalysts, various antioxidants, commonly used reinforcing agents such as carbon black and silica, and various plasticizers. The dosage of these agents is conventional or may be adjusted according to the actual requirements.

[0039] The basic principle of this invention is to improve the high interfacial thermal resistance caused by the high specific surface area of ​​small-diameter carbon nanotubes by using near-nanoscale carbon whisker nanotubes. Modification is achieved through cation-π interactions between the π-delocalized system on the surface of the carbon whisker nanotubes and the cationic resin polyamide epichlorohydrin. Simultaneously, the active groups on the surface of the polyamide epichlorohydrin provide sites for the growth of inorganic nanoparticles, forming a hybrid filler. Adding this hybrid filler to the rubber matrix achieves good interfacial bonding, reduces interfacial thermal resistance, improves filler dispersion, and gives the rubber composite material high thermal conductivity, low heat generation, and excellent mechanical properties.

[0040] The rubber nanocomposite material of this invention possesses high mechanical properties, along with low rolling resistance, low heat generation, and high thermal conductivity, exhibiting excellent overall performance. A key feature is the significant improvement in the thermal conductivity of the rubber compound while maintaining its original performance, thereby enhancing the material's heat dissipation and improving tire safety during dynamic driving.

[0041] This invention has the following characteristics:

[0042] 1. This invention uses near-nanoscale carbon nanotube whiskers to improve the problem of excessive interfacial and internal friction when carbon nanotubes are filled into rubber, so that the rubber nanocomposite material has good reinforcement, low heat generation and high thermal conductivity.

[0043] 2. This invention uses polyamide epichlorohydrin as a modifier, and utilizes cation-π interaction to achieve modification without destroying the lattice structure of the carbon nanotube surface, thus maintaining its high thermal conductivity. At the same time, the active groups on the modifier provide growth sites for inorganic nanoparticles, realizing the compounding of thermally conductive fillers.

[0044] 3. Modification and loading are carried out in the aqueous or ethanol phase, without involving any toxic solvents.

[0045] 4. The mixing process of this invention is compatible with actual factory processing equipment and can be directly put into production. Attached Figure Description

[0046] Figure 1 This is a SEM image of near-nanometer-sized carbon nanotube whiskers.

[0047] Figure 2 This is a SEM image of the composite material from Example 1.

[0048] Figure 3 This is a SEM image of the composite material from Example 4. Detailed Implementation

[0049] The present invention will now be described in detail with reference to specific embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention are still within the scope of protection of the present invention.

[0050] Furthermore, various embodiments of the present invention can be combined in any way, as long as they do not violate the spirit of the present invention. The resulting technical solutions are part of the original disclosure of this specification and also fall within the protection scope of the present invention.

[0051] Unless otherwise specified, the raw materials used in the examples and comparative examples are all disclosed in the prior art, such as those that can be directly purchased or prepared according to the preparation methods disclosed in the prior art.

[0052] Comparative Example 1

[0053] 50g of silica (VN3), 70g of solution-polymerized styrene-butadiene rubber (2506), 30g of rare earth butadiene rubber (CB24), 5g of zinc oxide, 2g of stearic acid, 2g of antioxidant 4020, 1.2g of sulfur, 2.3g of accelerator NS, and 0.5g of Si69 were mixed in an internal mixer for 8 minutes, followed by an additional 5 minutes of mixing in a two-roll mill before sheeting. High-performance rubber nanocomposite materials were obtained by vulcanization at 150℃ according to the optimal vulcanization time T90.

[0054] Comparative Example 2

[0055] 10g of carbon nanotubes (average diameter 10nm), 40g of carbon black, 100g of natural rubber, 5g of zinc oxide, 2g of stearic acid, 2g of antioxidant 4020, 1.2g of sulfur, 2.3g of accelerator NS, and 0.5g of Si69 were mixed in an internal mixer for 8 minutes, followed by an additional 5 minutes of mixing in a two-roll mill before sheeting. The high-performance rubber nanocomposite material was obtained by vulcanization at 150℃ according to the optimal vulcanization time T90.

[0056] Comparative Example 3

[0057] 20g of carbon nanotube whiskers (approximately 100nm in diameter) were mixed with 100g of natural rubber, 5g of zinc oxide, 2g of stearic acid, 2g of antioxidant 4020, 1.5g of sulfur, 1.5g of accelerator CZ, and 6g of Si69 in an internal mixer for 8 minutes, followed by an additional 5 minutes of mixing in a two-roll mill before sheeting. High-performance rubber nanocomposite materials were obtained by vulcanization at 150℃ according to the optimal vulcanization time T90.

[0058] Example 1

[0059] Carbon nanotubes (approximately 50 nm in diameter) were added to 500 ml of a 2.5 wt% PAE solution. The mass ratio of carbon nanotubes to polyamide epichlorohydrin was 1:5. The pH of the dispersion was adjusted to 11, and the mixture was further ultrasonically dispersed for 0.5 hours at room temperature and an ultrasonic power of 100 W. Finally, the carbon nanotube dispersion was filtered, washed, and dried to obtain PAE-NNCT powder. This powder was dispersed in a water / ethanol co-solvent (water / ethanol ratio of 1:9), and then ammonia (1 wt%) was added to adjust the pH of the solution to 11. Aluminum nitrate (5 times the mass of the carbon nanotubes) was then added, and the mixture was stirred and reacted for 12 hours at room temperature. Finally, the product was filtered and dried to obtain the hybrid material.

[0060] 5g of the obtained hybrid filler was mixed with 100g of natural rubber, 5g of zinc oxide, 2g of stearic acid, 2g of antioxidant 4020, 1.2g of sulfur, 2.3g of accelerator NS, and 0.5g of Si69 in an internal mixer for 8 minutes, followed by an additional 5 minutes of mixing in a two-roll mill before sheeting. High-performance rubber nanocomposite materials were obtained by vulcanization at 150℃ according to the optimal vulcanization time T90.

[0061] Example 2

[0062] Carbon nanotubes (approximately 100 nm in diameter) were added to 500 ml of a 5 wt% PAE solution. The mass ratio of carbon nanotubes to polyamide epichlorohydrin was 1:10. The pH of the dispersion was adjusted to 11, and the mixture was further ultrasonically dispersed for 1 hour at room temperature and an ultrasonic power of 100 W. Finally, the carbon nanotube dispersion was filtered, washed, and dried to obtain PAE-NNCT powder. This powder was dispersed in a water / ethanol co-solvent (water / ethanol ratio of 1:9), and then ammonia (1 wt%) was added to adjust the pH of the solution to 11. Aluminum nitrate (10 times the mass of the carbon nanotubes) was then added, and the mixture was stirred and reacted for 12 hours at room temperature. Finally, the product was filtered and dried to obtain the hybrid material.

[0063] 20g of the obtained hybrid filler was mixed with 70g of solution-polymerized styrene-butadiene rubber (2506), 30g of butadiene rubber (CB24), 5g of zinc oxide, 2g of stearic acid, 2g of antioxidant 4020, and 2g of Si69 in an internal mixer for 8 minutes. After the rubber compound cooled, 1.2g of sulfur and 2.3g of accelerator NS were added to a two-roll mill and mixed evenly. The mixture was then sheeted and further mixed in a two-roll mill for 5 minutes before sheeting. High-performance rubber nanocomposite materials were obtained by vulcanization at 150℃ according to the optimal vulcanization time T90.

[0064] Example 3

[0065] Carbon nanotubes (approximately 100 nm in diameter) were added to 500 ml of a 2.5 wt% PAE solution. The mass ratio of carbon nanotubes to polyamide epichlorohydrin was 1:5. The pH of the dispersion was adjusted to 11, and the mixture was further ultrasonically dispersed for 0.5 hours at room temperature and an ultrasonic power of 100 W. Finally, the carbon nanotube dispersion was filtered, washed, and dried to obtain PAE-NNCT powder. This powder was dispersed in a water / ethanol co-solvent (water / ethanol ratio of 1:9), and then ammonia (1 wt%) was added to adjust the pH of the solution to 11. Aluminum nitrate (5 times the mass of the carbon nanotubes) was then added, and the mixture was stirred and reacted for 12 hours at room temperature. Finally, the product was filtered and dried to obtain the hybrid material.

[0066] 20g of the obtained hybrid filler was mixed with 100g of natural rubber, 5g of zinc oxide, 2g of stearic acid, 2g of antioxidant 4020, 1.2g of sulfur, 2.3g of accelerator NS, and 2g of Si69 in an internal mixer for 8 minutes, followed by an additional 5 minutes of mixing in a two-roll mill before sheeting. High-performance rubber nanocomposite materials were obtained by vulcanization at 150℃ according to the optimal vulcanization time T90.

[0067] Example 4

[0068] Carbon nanotubes (approximately 150 nm in diameter) were added to 500 ml of a 7.5 wt% PAE solution. The mass ratio of carbon nanotubes to polyamide epichlorohydrin was 1:15. The pH of the dispersion was adjusted to 11, and the mixture was further ultrasonically dispersed for 1 hour at room temperature and an ultrasonic power of 100 W. Finally, the carbon nanotube dispersion was filtered, washed, and dried to obtain PAE-NNCT powder. This powder was dispersed in a water / ethanol co-solvent (water / ethanol ratio of 1:9), and then ammonia (1 wt%) was added to adjust the pH of the solution to 11. Aluminum nitrate (20 times the mass of the carbon nanotubes) was then added, and the mixture was stirred and reacted for 12 hours at room temperature. Finally, the product was filtered and dried to obtain the hybrid material.

[0069] First, 100g of raw polyurethane rubber was plasticized on a two-roll mill, then added to a Banbury mixer along with 30g of whisker-carbon nanotube hybrid filler, 5g of zinc oxide, 2g of stearic acid, 2g of antioxidant 4020, 3g of Si69, and 2.3g of accelerator NS. The temperature of the Banbury mixer was controlled below 75℃. After uniform mixing, 2g of sulfur was added, and the mixture was further mixed thoroughly before being discharged. The compound was then sheeted on the two-roll mill. High-performance rubber nanocomposite materials were obtained by vulcanization at 150℃ according to the optimal vulcanization time T90.

[0070] Example 5

[0071] Carbon nanotubes (approximately 200 nm in diameter) were added to 500 ml of a 10 wt% PAE solution. The mass ratio of carbon nanotubes to polyamide epichlorohydrin was 1:20. The pH of the dispersion was adjusted to 11, and the mixture was further ultrasonically dispersed for 1 hour at room temperature and an ultrasonic power of 100 W. Finally, the carbon nanotube dispersion was filtered, washed, and dried to obtain PAE-NNCT powder. This powder was dispersed in a water / ethanol co-solvent (water / ethanol ratio of 1:9), and then ammonia (1 wt%) was added to adjust the pH of the solution to 11. Next, tetraethyl orthosilicate (5 times the mass of the carbon nanotubes) was added, and the mixture was stirred and reacted for 12 hours at room temperature. Finally, the product was filtered and dried to obtain the hybrid material.

[0072] 50g of the obtained hybrid filler was mixed with 100g of nitrile rubber, 5g of zinc oxide, 2g of stearic acid, 2g of antioxidant 4020, 1.2g of sulfur, 2.3g of accelerator NS, and 5g of Si69 in an internal mixer for 8 minutes, followed by an additional 5 minutes of mixing in a two-roll mill before sheeting. High-performance rubber nanocomposite materials were obtained by vulcanization at 150℃ according to the optimal vulcanization time T90.

[0073] Example 6

[0074] Carbon nanotubes (approximately 100 nm in diameter) were added to 500 ml of a 12.5 wt% PAE solution. The mass ratio of carbon nanotubes to polyamide epichlorohydrin was 1:5. The pH of the dispersion was adjusted to 11, and the mixture was further ultrasonically dispersed for 1 hour at room temperature and an ultrasonic power of 100 W. Finally, the carbon nanotube dispersion was filtered, washed, and dried to obtain PAE-NNCT powder. This powder was dispersed in a water / ethanol co-solvent (water / ethanol ratio of 1:9), and then ammonia (1 wt%) was added to adjust the pH of the solution to 11. Next, tetraethyl orthosilicate (10 times the mass of the carbon nanotubes) was added, and the mixture was stirred and reacted for 12 hours at room temperature. Finally, the product was filtered and dried to obtain the hybrid material.

[0075] 70g of the obtained hybrid filler was mixed with 100g of natural rubber, 5g of zinc oxide, 2g of stearic acid, 2g of antioxidant 4020, 1.2g of sulfur, 2.3g of accelerator NS, and 7g of Si69 in an internal mixer for 8 minutes, followed by an additional 5 minutes of mixing in a two-roll mill before sheeting. High-performance rubber nanocomposite materials were obtained by vulcanization at 150℃ according to the optimal vulcanization time T90.

[0076] Example 7

[0077] Carbon nanotubes (approximately 100 nm in diameter) were added to 500 ml of a 15 wt% PAE solution. The mass ratio of carbon nanotubes to polyamide epichlorohydrin was 1:5. The pH of the dispersion was adjusted to 11, and the mixture was further ultrasonically dispersed for 1 hour at room temperature and an ultrasonic power of 100 W. Finally, the carbon nanotube dispersion was filtered, washed, and dried to obtain PAE-NNCT powder. This powder was dispersed in a water / ethanol co-solvent (water / ethanol ratio of 1:9), and then ammonia (1 wt%) was added to adjust the pH of the solution to 11. Next, tetraethyl orthosilicate (20 times the mass of the carbon nanotubes) was added, and the mixture was stirred and reacted for 12 hours at room temperature. Finally, the product was filtered and dried to obtain the hybrid material.

[0078] 100g of the obtained hybrid filler was mixed with 100g of natural rubber, 5g of zinc oxide, 2g of stearic acid, 2g of antioxidant 4020, 1.2g of sulfur, 2.3g of accelerator NS, and 10g of Si69 in an internal mixer for 8 minutes, followed by an additional 5 minutes of mixing in a two-roll mill before sheeting. High-performance rubber nanocomposite materials were obtained by vulcanization at 150℃ according to the optimal vulcanization time T90.

[0079] The tensile properties of the composite material were tested according to national standard GB / T 528-2009, the dynamic compression heat generation of the composite material was tested according to national standard GB1687-2016, and the thermal conductivity of the composite material was tested according to national standard GB / T 10297-2015. The loss factor tanδ at 60℃ was tested using a rubber processing analyzer (RPA). The performance of the comparative examples and embodiments was tested, and the results are recorded in Table 1.

[0080] Table 1: Mechanical, Dynamic and Thermal Conductivity Properties of Comparative Examples and Embodiments

[0081]

[0082] As shown in Table 1, the rubber composites using whisker-carbon nanotube hybrid fillers (Examples 1-7) exhibit superior tensile strength compared to the green tire material using silica and the rubber composites with added carbon nanotubes. Comparing the loss factors at 60°C, the rubber composites using whisker-carbon nanotube hybrid fillers are generally lower than the comparative examples, indicating reduced heat generation in the rubber composites obtained in these examples. The compression heat generation value shows a trend similar to rolling resistance, further demonstrating that whisker-carbon nanotube hybrid fillers can significantly reduce dynamic heat generation and increase tire driving safety. Comparing the thermal conductivity reveals a significant improvement in the thermal conductivity of the rubber compounds with added whisker-carbon nanotube hybrid fillers. Hybrid fillers modified and compounded with whisker-carbon nanotubes further enhance thermal conductivity, allowing the heat generated by the rubber composite to be dissipated promptly, preventing heat accumulation that could lead to decreased tire performance and blowouts. The more whisker-carbon nanotube hybrid fillers added, the stronger the thermal conductivity, but the loss factor at 60°C also increases, leading to increased heat generation.

[0083] The above examples provide a detailed description of the present invention, but the present invention is not limited to the embodiments described. Equivalent substitutions can be made for the modifiers and compounding examples, and other processing aids in the rubber composite material can also be changed. For example, when compounding with traditional reinforcing fillers such as carbon black and silica, other processing techniques can be used to process the raw materials described in the present invention. These equivalent modifications and substitutions are all within the scope of protection claimed in this application.

[0084] The endpoints and any values ​​of the ranges disclosed in this application are not limited to the precise ranges or values; such ranges or values ​​should be understood to include values ​​close to them. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein. In principle, various technical solutions can be combined with each other to obtain new technical solutions, which should also be considered as specifically disclosed herein.

Claims

1. A near-nanoscale carbon nanotube in-situ supported inorganic nanoparticle hybrid filler, comprising modified carbon nanotubes and inorganic nanoparticles supported thereon, wherein the modified carbon nanotubes are obtained by modifying the carbon nanotubes with polyamide epichlorohydrin.

2. The near-nanoscale carbon nanotube in-situ supported inorganic nanoparticle hybrid filler according to claim 1, characterized in that: The diameter of the carbon whisker tube is 50–200 nm; The inorganic nanoparticles are at least one of nano-alumina or nano-silicon oxide.

3. A method for preparing a near-nanoscale carbon nanotube in-situ supported inorganic nanoparticle hybrid filler, preferably used for preparing the hybrid filler of claim 1 or 2, comprising the following steps: (1) Modified carbon whisker tubes were obtained by modifying carbon whisker tubes with polyamide epichlorohydrin. (2) Add the modified carbon whisker to the solvent, adjust the pH to 8-12, add the inorganic nanoparticle precursor, and obtain the hybrid filler after reaction.

4. The preparation method according to claim 3, characterized in that: In step (1), carbon whisker tubes are ultrasonically dispersed in a polyamide epichlorohydrin solution, and modified carbon whisker tubes are obtained by centrifugation, filtration and drying.

5. The preparation method according to claim 4, characterized in that: The mass ratio of polyamide epichlorohydrin to carbon nanotube whiskers is (1-100):1, preferably (5-20):1; The polyamide epichlorohydrin solution has a mass fraction of 2–15 wt%, preferably 2–12.5 wt%. The ultrasonic power is 50–1500W, the ultrasonic temperature is 0–60℃, and the ultrasonic dispersion time is 0.5–5 hours.

6. The preparation method according to claim 3, characterized in that... In step (2): The inorganic nanoparticle precursor is selected from at least one of aluminum nitrate and tetraethyl orthosilicate. The mass ratio of inorganic nanoparticle precursor to carbon whisker is (5-20):1, preferably (5-10):1; The reaction temperature is 20–60℃, and the reaction time is 6–48 h.

7. The near-nanoscale carbon nanotube in-situ supported inorganic nanoparticle hybrid filler obtained by the preparation method according to any one of claims 3 to 6.

8. A rubber composite material comprising a hybrid filler as described in claim 1, 2 or 7 and a rubber matrix.

9. The rubber composite material according to claim 8, characterized in that: The rubber matrix is ​​selected from at least one of natural rubber, styrene-butadiene rubber, cis-butadiene rubber, polyurethane rubber, nitrile rubber, and silicone rubber.

10. The rubber composite material according to claim 8 or 9, characterized in that... Based on 100 parts by weight of the rubber matrix, the hybrid filler is 5 to 100 parts by weight, preferably 20 to 70 parts by weight.

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