Preparation method and application of functionalized boron nitride hybrid filler

Abstract

The invention discloses a functionalized boron nitride-cerium dioxide hybrid filler as well as a preparation method and application thereof, and belongs to the technical field of hybrid fillers. The boron nitride-cerium dioxide hybrid filler is constructed by a hydrothermal method, and is functionally modified by using N-(4-anilinophenyl) maleimide, so that the prepared filler has good mechanical reinforcing and anti-aging effects, is uniformly dispersed when being applied to a rubber matrix, can form a good heat-conducting passage and barrier effect, and has a good anti-aging effect. The thermo-oxidative aging of a rubber material can be relieved fundamentally, and the rubber composite material is endowed with good mechanical properties. Besides, small molecular N-(4-anilinophenyl) maleimide is combined with the hybrid filler, so that migration and emigration of N-(4-anilinophenyl) maleimide in a rubber matrix are avoided, physical loss of the anti-aging agent and pollution to the environment are reduced, and the N-(4-anilinophenyl) maleimide has high environmental friendliness and practicability, has an important application prospect in high-performance anti-aging rubber composite materials, and has wide application prospects. The method is especially suitable for light-color rubber products in various severe environments.

Description

Technical Field

[0001] The invention relates to the field of hybrid filler preparation, and in particular to a preparation method and application of a functionalized boron nitride hybrid filler. Background Art

[0002] Rubber is an indispensable strategic key material for the country and has been widely used in many fields such as tires, seals, medical products, electronic equipment, aerospace, etc. However, the strength of raw rubber is low, and reinforcing fillers such as carbon black and white carbon black must be added; on the other hand, the main chain of diene rubber contains unsaturated double bonds, which are particularly prone to aging during storage and use, resulting in deterioration of appearance, hardness and physical / mechanical properties, causing serious waste of rubber resources.

[0003] At present, adding antioxidants to the rubber matrix is ​​a common method to delay the aging of rubber products. However, due to the low molecular weight of rubber antioxidants, small molecule antioxidants are easy to migrate from the rubber matrix over time under low pressure, liquid, high temperature and other conditions, resulting in physical loss of antioxidants, affecting the appearance of rubber products, and even causing pollution to the surrounding environment, threatening people's health and life safety. In recent years, although researchers have developed a variety of new antioxidants that are resistant to migration, the key factors such as heat and oxygen that cause rubber aging have not been solved. Two-dimensional boron nitride has excellent intrinsic thermal conductivity and good barrier properties, and is expected to improve the aging properties of rubber composites from the aspects of thermal conductivity and oxygen barrier. However, it is worth noting that the improvement effect of a single boron nitride filler on the aging properties of rubber materials is limited, and hexagonal boron nitride has extremely high chemical inertness and is difficult to be evenly dispersed in the rubber matrix, resulting in poor mechanical reinforcement of rubber composites. Summary of the invention

[0004] In order to overcome the deficiencies of the prior art, the present invention constructs a boron nitride-cerium dioxide hybrid filler by a hydrothermal method, and utilizes N-(4-anilinophenyl) maleimide to functionally modify it, and prepares a hybrid filler with mechanical reinforcement and anti-aging functions. Compared with ordinary boron nitride, the boron nitride-cerium dioxide hybrid filler has abundant active reaction sites, which lays a foundation for its further functional modification, and the special rare earth 4f electronic structure on the surface of cerium dioxide can inhibit the formation of free radicals, and form a good synergistic anti-aging effect with N-(4-anilinophenyl) maleimide; on the other hand, this functionalized hybrid filler is evenly dispersed in the rubber matrix, can form a good heat conduction path and barrier effect, can fundamentally alleviate the thermal oxidation aging of rubber materials, and give the rubber composite material good mechanical properties, in addition, the combination of small molecule N-(4-anilinophenyl) maleimide and hybrid filler avoids its migration and migration out of the rubber matrix, and reduces the physical loss of antioxidants and pollution to the environment. This functionalized boron nitride-cerium dioxide hybrid filler has important application prospects in the mechanical reinforcement and aging resistance of rubber composites.

[0005] The purpose of the present invention is achieved through the following technical solutions:

[0006] A method for preparing a functionalized boron nitride-cerium dioxide hybrid filler comprises the following steps:

[0007] S1. Add boron nitride and cerium salt in a mass ratio of 9:1 to 6:4 to water, add 0.01 to 0.03 M surfactant, and evenly disperse by ultrasonication. Adjust the pH value to 8 to 11 with ammonia water, stir at room temperature for 1 h to 5 h, pour the dispersion into a polytetrafluoroethylene-lined reactor, react at 150° C. to 190° C. for 5 h to 24 h, centrifuge, wash, and dry the dispersion to obtain a boron nitride-cerium dioxide hybrid filler;

[0008] S2. Add an aminosilane coupling agent and N-(4-anilinophenyl)maleimide in an equal molar ratio to an organic solvent, add 0.5wt% to 2wt% of a catalyst, stir and react at 50°C to 80°C for 5h to 10h, remove the solvent, disperse the resulting product and a boron nitride-cerium dioxide hybrid filler in an 80% to 98% ethanol aqueous solution, add ammonia water to adjust the pH value to 8 to 10, stir at 60°C to 90°C for 5h to 12h, centrifuge, wash and dry to obtain a functionalized boron nitride-cerium dioxide hybrid filler modified with N-(4-anilinophenyl)maleimide.

[0009] Furthermore, the boron nitride in step S1 is one or both of hexagonal boron nitride and boron nitride nanosheets of different sizes.

[0010] Furthermore, the cerium source in step S1 is at least one of cerium nitrate, cerium sulfate, cerium acetate, and cerium chloride.

[0011] Furthermore, the surfactant in step S1 is at least one of polyvinyl pyrrolidone, fatty alcohol polyoxyethylene ether, sodium lauryl sulfate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, and polyethylene glycol sorbitan monostearate.

[0012] Furthermore, the aminosilane coupling agent in step S2 is at least one of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-aminoethyl-3-aminopropylmethyldimethoxysilane, N-aminoethyl-3-aminopropylmethyldiethoxysilane, and (4-aminophenyl)triethoxysilane.

[0013] Furthermore, the catalyst in step S2 is at least one of triethylamine, tributylamine, N,N-diisopropylethylamine, 4-dimethylaminopyridine, and 1,4-diazabicyclo[2.2.2]octane.

[0014] Furthermore, the organic solvent in step S2 is at least one of tetrahydrofuran, acetone, ethanol, methanol, toluene, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, ethyl acetate, and carbon tetrachloride.

[0015] Furthermore, the centrifugal washing and drying conditions are: centrifugal washing at a rotation speed of 3000r / min to 8000r / min, the number of washing times is 3 to 6 times, and the drying temperature is 60°C to 120°C.

[0016] In addition, the present invention also provides an application of a functionalized boron nitride-cerium dioxide hybrid filler, and the application is an application of the functionalized boron nitride-cerium dioxide hybrid filler in a rubber composite material.

[0017] Compared with the prior art, the present invention has the following advantages:

[0018] The present invention utilizes the special rare earth 4f electronic structure on the surface of cerium dioxide in combination with the small molecule antioxidant N-(4-anilinophenyl)maleimide from multiple dimensions such as thermal conductivity, oxygen barrier and antioxidant loading to construct a functionalized boron nitride-cerium dioxide hybrid filler with good mechanical reinforcement and anti-aging effects. This functionalized hybrid filler has excellent comprehensive performance, an environmentally friendly preparation method and strong practicality. It has important application prospects in high-performance anti-aging rubber composite materials, and is particularly suitable for light-colored rubber products in various harsh environments. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 TEM image of the boron nitride-cerium dioxide hybrid filler prepared in Example 1;

[0020] Figure 2 XPS spectra of the boron nitride-cerium dioxide hybrid filler and boron nitride prepared in Example 1;

[0021] Figure 3 Schematic diagram of the structure of the functionalized boron nitride-cerium dioxide hybrid filler modified by N-(4-anilinophenyl)maleimide in Example 1;

[0022] Figure 4 This is the oxidation induction period curve of the rubber composite material prepared in Example 1 before and after extraction. DETAILED DESCRIPTION

[0023] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with its embodiments. It should be understood that the specific implementation methods described herein are only used to explain the present invention and do not limit the protection scope of the present invention.

[0024] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used herein in the specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention. The term "and / or" used herein includes any and all combinations of one or more related listed items.

[0025] A method for preparing a functionalized boron nitride-cerium dioxide hybrid filler in one embodiment of the present invention comprises the following steps:

[0026] S1. Add boron nitride and cerium salt in a mass ratio of 9:1 to 6:4 to water, add 0.01 to 0.03 M surfactant, and evenly disperse by ultrasonication. Adjust the pH value to 8 to 11 with ammonia water, stir at room temperature for 1 h to 5 h, pour the dispersion into a polytetrafluoroethylene-lined reactor, react at 150° C. to 190° C. for 5 h to 24 h, centrifuge, wash, and dry the dispersion to obtain a boron nitride-cerium dioxide hybrid filler;

[0027] S2. Add an aminosilane coupling agent and N-(4-anilinophenyl)maleimide in an equal molar ratio to an organic solvent, add 0.5wt% to 2wt% of a catalyst, stir and react at 50°C to 80°C for 5h to 10h, remove the solvent, disperse the resulting product and a boron nitride-cerium dioxide hybrid filler in an 80% to 98% ethanol aqueous solution, add ammonia water to adjust the pH value to 8 to 10, stir at 60°C to 90°C for 5h to 12h, centrifuge, wash and dry to obtain a functionalized boron nitride-cerium dioxide hybrid filler modified with N-(4-anilinophenyl)maleimide.

[0028] In one embodiment, the boron nitride in step S1 is one or both of hexagonal boron nitride and boron nitride nanosheets of different sizes.

[0029] In one embodiment, the cerium source in step S1 is at least one of cerium nitrate, cerium sulfate, cerium acetate, and cerium chloride.

[0030] In one embodiment, the surfactant in step S1 is at least one of polyvinyl pyrrolidone, fatty alcohol polyoxyethylene ether, sodium lauryl sulfate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, and polyethylene glycol sorbitan monostearate.

[0031] In one embodiment, the aminosilane coupling agent in step S2 is at least one of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-aminoethyl-3-aminopropylmethyldimethoxysilane, N-aminoethyl-3-aminopropylmethyldiethoxysilane, and (4-aminophenyl)triethoxysilane.

[0032] In one embodiment, the catalyst in step S2 is at least one of triethylamine, tributylamine, N,N-diisopropylethylamine, 4-dimethylaminopyridine, and 1,4-diazabicyclo[2.2.2]octane.

[0033] In one embodiment, the organic solvent in step S2 is at least one of tetrahydrofuran, acetone, ethanol, methanol, toluene, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, ethyl acetate, and carbon tetrachloride.

[0034] In one of the embodiments, the centrifugal washing and drying conditions are: centrifugal washing at a rotation speed of 3000r / min to 8000r / min, the number of washing times is 3 to 6 times, and the drying temperature is 60°C to 120°C.

[0035] In addition, the present invention also provides an application of a functionalized boron nitride-cerium dioxide hybrid filler, and the application is an application of the functionalized boron nitride-cerium dioxide hybrid filler in a rubber composite material.

[0036] The above scheme utilizes the special rare earth 4f electronic structure on the surface of cerium dioxide and combines it with the small molecule antioxidant N-(4-anilinophenyl)maleimide to construct a functionalized boron nitride-cerium dioxide hybrid filler with good mechanical reinforcement and anti-aging effects. This functionalized hybrid filler has excellent comprehensive performance, environmentally friendly preparation method, and strong practicality. It has important application prospects in high-performance aging-resistant rubber composite materials, and is particularly suitable for light-colored rubber products in various harsh environments.

[0037] The embodiments of the present invention will be described in detail below with reference to specific examples.

[0038] Embodiment 1:

[0039] A method for preparing a functionalized boron nitride-cerium dioxide hybrid filler comprises the following steps:

[0040] 90 mg of boron nitride nanosheets and 30 mg of cerium nitrate hexahydrate were dispersed in 40 mL of deionized water and ultrasonically treated for 2 h. 0.01 M polyvinyl pyrrolidone was added. After ultrasonic dispersion, the pH value was adjusted to 10 with ammonia water. After stirring at room temperature for 3 h, the dispersion was poured into a polytetrafluoroethylene-lined reactor. After reacting at 180 ° C for 10 h, the dispersion was centrifuged and washed 5 times at 3000 r / min. After drying in a vacuum oven at 60 ° C, a boron nitride-cerium dioxide hybrid filler (TEM as shown in the attached figure) was obtained. Figure 1 , Attached Figure 2 The XPS spectra in further prove the existence of ceria nanoparticles;

[0041] The 3-aminopropyl triethoxysilane coupling agent and N-(4-anilinophenyl) maleimide in an equal molar ratio were added to a mixed solvent of 80 mL tetrahydrofuran and 20 mL methanol, and 0.5 wt % triethylamine was added. The mixture was stirred at 50° C. for 10 h. After removing the solvent, the obtained product and the boron nitride-cerium dioxide hybrid filler were dispersed in an ethanol aqueous solution with a mass percentage concentration of 95%, and ammonia water was added to adjust the pH value to 9. The mixture was stirred at 80° C. for 10 h, and the mixture was centrifuged, washed, and dried to obtain a functionalized boron nitride-cerium dioxide hybrid filler modified with N-(4-anilinophenyl) maleimide (the structural schematic diagram is shown in the attached figure). Figure 3 shown).

[0042] By weight, 40 parts of the functionalized boron nitride-cerium dioxide hybrid filler prepared in this example were blended with 100 parts of natural rubber, 5 parts of zinc oxide, 2 parts of stearic acid, 2 parts of a vulcanization accelerator and 1.8 parts of sulfur, and then the mixed rubber was vulcanized at high temperature to obtain a rubber composite material.

[0043] The rubber composite material prepared in this embodiment was made into a test sample, and the mechanical properties, aging performance retention rate, oxidation induction period and thermal conductivity of the composite material of this embodiment were measured using a universal material testing machine, a thermal oxygen aging box, a differential scanning calorimeter, an LFA laser thermal conductivity meter, etc. (the specific detection method is in accordance with conventional operations in the field and is not described in detail in this embodiment). It was measured that the tensile strength of the composite material prepared in this embodiment reached 26.74MPa, the oxidation induction period reached 123.6min, and the thermal conductivity was 1.46W / mK. After 10 days of thermal oxygen aging, the tensile performance retention rate was 90.16%; in addition, in order to prove that the antioxidant in this embodiment has good migration resistance, after the rubber composite material was extracted at high temperature with an organic solvent for 7 days, its oxidation induction period still reached 69.5min (the oxidation induction period curve before and after extraction is shown in the attached figure Figure 4 It has good migration resistance.

[0044] Embodiment 2:

[0045] A method for preparing a functionalized boron nitride-cerium dioxide hybrid filler comprises the following steps:

[0046] 60 mg of hexagonal boron nitride and 40 mg of cerium sulfate were dispersed in 40 mL of deionized water and ultrasonically treated for 2 h, 0.02 M of fatty alcohol polyoxyethylene ether was added, and after ultrasonic dispersion was uniform, the pH value was adjusted to 8 with ammonia water, and after stirring at room temperature for 5 h, the dispersion was poured into a polytetrafluoroethylene-lined reactor, reacted at 190 ° C for 5 h, and then the dispersion was centrifuged and washed 3 times at 8000 r / min, and dried in a vacuum drying oven at 100 ° C to obtain a boron nitride-cerium dioxide hybrid filler;

[0047] An equal molar ratio of 3-aminopropyltrimethoxysilane coupling agent and N-(4-anilinophenyl)maleimide is added to a mixed solvent of 90 mL of tetrahydrofuran and 10 mL of ethanol, 1 wt % of triethylamine is added, and the reaction is stirred at 60° C. for 8 h. After removing the solvent, the resulting product and a boron nitride-cerium dioxide hybrid filler are dispersed in a 98% ethanol aqueous solution, ammonia water is added to adjust the pH value to 10, and the mixture is stirred at 90° C. for 5 h. The mixture is centrifuged, washed, and dried to obtain a functionalized boron nitride-cerium dioxide hybrid filler modified with N-(4-anilinophenyl)maleimide.

[0048] In parts by weight, 30 parts of the functionalized boron nitride-cerium dioxide hybrid filler prepared in this embodiment are blended with 100 parts of styrene-butadiene rubber, 5 parts of zinc oxide, 2 parts by weight of stearic acid, 2 parts of a vulcanization accelerator and 1.8 parts of sulfur, and then the mixed rubber is vulcanized at high temperature to obtain a rubber composite material.

[0049] Tests show that the prepared styrene-butadiene rubber composite material has a tensile strength of 12.39 MPa, an oxidation induction period of 112.4 min, a thermal conductivity of 1.04 W / mK, and after 10 days of thermal oxidation aging, the tensile property retention rate is 89.23%.

[0050] Embodiment 3:

[0051] A method for preparing a functionalized boron nitride-cerium dioxide hybrid filler comprises the following steps:

[0052] 90 mg of boron nitride nanosheets and 10 mg of cerium acetate were dispersed in 40 mL of deionized water and ultrasonically treated for 3 h. 0.03 M sodium dodecyl sulfate was added. After ultrasonic dispersion, the pH value was adjusted to 11 with ammonia water. After stirring at room temperature for 1 h, the dispersion was poured into a polytetrafluoroethylene-lined reactor. After reacting at 150 ° C for 24 h, the dispersion was centrifuged and washed 6 times at 5000 r / min. After drying in a vacuum drying oven at 120 ° C, a boron nitride-cerium dioxide hybrid filler was obtained.

[0053] Equal molar ratios of N-(2-aminoethyl)-3-aminopropyltrimethoxysilane coupling agent and N-(4-anilinophenyl)maleimide are added to a mixed solvent of 80 mL N,N-dimethylformamide and 20 mL ethanol, 2 wt % of 4-dimethylaminopyridine is added, and the reaction is stirred at 80° C. for 5 h. After removing the solvent, the resulting product and boron nitride-cerium dioxide hybrid filler are dispersed in 80% ethanol aqueous solution, ammonia water is added to adjust the pH value to 8, and the mixture is stirred at 60° C. for 12 h. The mixture is centrifuged, washed, and dried to obtain a functionalized boron nitride-cerium dioxide hybrid filler modified with N-(4-anilinophenyl)maleimide.

[0054] In parts by weight, 30 parts of the functionalized boron nitride-cerium dioxide hybrid filler prepared in this example are blended with 100 parts of styrene-butadiene rubber, 5 parts of zinc oxide, 2 parts of stearic acid, 2 parts of a vulcanization accelerator and 1.8 parts of sulfur, and then the mixed rubber is vulcanized at high temperature to obtain a rubber composite material.

[0055] Tests show that the prepared styrene-butadiene rubber composite material has a tensile strength of 13.43 MPa, an oxidation induction period of 104.6 min, a thermal conductivity of 1.21 W / mK, and after 10 days of thermal oxidation aging, the tensile property retention rate is 83.27%.

[0056] Comparative Example 1:

[0057] In order to prove the advantages of functionalized boron nitride-cerium dioxide hybrid filler in aging resistance and mechanical reinforcement of rubber composite materials, the difference between this comparative example and Example 1 is that N-(4-anilinophenyl) maleimide-modified boron nitride nanosheets are prepared instead of N-(4-anilinophenyl) maleimide-modified boron nitride-cerium dioxide hybrid fillers. 40 parts by weight of N-(4-anilinophenyl) maleimide-modified boron nitride nanosheets prepared in this comparative example are blended with 100 parts by weight of natural rubber, 5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 2 parts by weight of vulcanization accelerator and 1.8 parts by weight of sulfur, and then the mixed rubber is vulcanized at high temperature to obtain a rubber composite material. It can be seen from the test that the tensile strength of the composite material prepared in this example reaches 21.35MPa, the oxidation induction period reaches 101.3min, the thermal conductivity is 1.12W / mK, and after 10 days of thermal oxidation aging, the tensile property retention rate is 84.35%.

[0058] By comparing Example 1 and Comparative Example 1, it can be seen that compared with the modified boron nitride nanosheets, under the bridging effect of cerium dioxide nanoparticles, the functionalized boron nitride-cerium dioxide hybrid filler is easier to form a good thermal conductivity path, and the interface bonding with the rubber matrix is ​​significantly enhanced, showing good thermal conductivity and mechanical properties; in addition, thanks to the special rare earth 4f electronic structure on the surface of cerium dioxide, the formation of free radicals can be inhibited, thereby forming a good synergistic anti-aging effect with N-(4-anilinophenyl)maleimide, so that the rubber composite material in Example 1 shows a better anti-aging effect than Comparative Example 1.

[0059] Comparative Example 2:

[0060] In order to demonstrate the functional modification effect of N-(4-anilinophenyl)maleimide on the boron nitride-cerium dioxide hybrid filler, the difference between this comparative example and Example 1 is that N-(4-anilinophenyl)maleimide and the boron nitride-cerium dioxide hybrid filler are directly added and not combined together by reaction. 40 parts by weight of the prepared unmodified boron nitride-cerium dioxide hybrid filler are blended with an equal amount of N-(4-anilinophenyl)maleimide in Example 1, 100 parts by weight of natural rubber, 5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 2 parts by weight of a vulcanization accelerator and 1.8 parts by weight of sulfur, and then the mixed rubber is vulcanized at high temperature to obtain a rubber composite material. Tests show that the composite material prepared in this embodiment has a tensile strength of 22.14 MPa, an oxidation induction period of 104.9 min, a thermal conductivity of 1.21 W / mK, and a tensile property retention rate of only 83.1% after 10 days of thermal oxidation aging. After further high-temperature extraction of the prepared composite material using a solvent for 7 days, its oxidation induction period is only 41.2 min.

[0061] By comparing Example 1 and Comparative Example 2, it can be seen that the boron nitride-cerium dioxide hybrid filler that has not been modified with N-(4-anilinophenyl)maleimide has a poor reinforcing effect on rubber and low aging performance. In particular, the extraction experiment shows that the functional modification of the hybrid filler with small molecule N-(4-anilinophenyl)maleimide can effectively enhance the migration and outflow of small molecule antioxidants.

[0062] In summary, in combination with the embodiments and comparative examples, it can be seen that the boron nitride-cerium dioxide hybrid filler modified with N-(4-anilinophenyl)maleimide in the present invention can effectively improve the thermal conductivity, anti-aging and mechanical properties of the rubber composite material, and improve the migration and migration of small molecule antioxidants in the rubber matrix, reduce the physical loss of the antioxidants and pollution to the environment, and has important application prospects in the new generation of high-performance aging-resistant rubber composite materials.

[0063] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0064] The above-mentioned embodiments only express several implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A method for preparing a functionalized boron nitride-cerium dioxide hybrid filler, characterized in that: The following steps are involved: S1. Add boron nitride and cerium salt in a mass ratio of 9:1 to 6:4 to water, add 0.01 to 0.03 M surfactant, and evenly disperse by ultrasonication. Adjust the pH value to 8 to 11 with ammonia water, stir at room temperature for 1 h to 5 h, pour the dispersion into a polytetrafluoroethylene-lined reactor, react at 150° C. to 190° C. for 5 h to 24 h, centrifuge, wash, and dry the dispersion to obtain a boron nitride-cerium dioxide hybrid filler; S2. Add an aminosilane coupling agent and N-(4-anilinophenyl)maleimide in an equal molar ratio to an organic solvent, add 0.5wt% to 2wt% of a catalyst, stir and react at 50°C to 80°C for 5h to 10h, remove the solvent, disperse the resulting product and a boron nitride-cerium dioxide hybrid filler in an 80% to 98% ethanol aqueous solution, add ammonia water to adjust the pH value to 8 to 10, stir at 60°C to 90°C for 5h to 12h, centrifuge, wash and dry to obtain a functionalized boron nitride-cerium dioxide hybrid filler modified with N-(4-anilinophenyl)maleimide.

2. The preparation method according to claim 1, characterized in that: The boron nitride in step S1 is one or both of hexagonal boron nitride and boron nitride nanosheets of different sizes.

3. The preparation method according to claim 1, characterized in that: The cerium source in step S1 is at least one of cerium nitrate, cerium sulfate, cerium acetate, and cerium chloride.

4. The preparation method according to claim 1, characterized in that: The surfactant in step S1 is at least one of polyvinyl pyrrolidone, fatty alcohol polyoxyethylene ether, sodium lauryl sulfate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, and polyethylene glycol sorbitan monostearate.

5. The preparation method according to claim 1, characterized in that: The aminosilane coupling agent in step S2 is at least one of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-aminoethyl-3-aminopropylmethyldimethoxysilane, N-aminoethyl-3-aminopropylmethyldiethoxysilane, and (4-aminophenyl)triethoxysilane.

6. The preparation method according to claim 1, characterized in that: The catalyst in step S2 is at least one of triethylamine, tributylamine, N,N-diisopropylethylamine, 4-dimethylaminopyridine, and 1,4-diazabicyclo[2.2.2]octane.

7. The preparation method according to claim 1, characterized in that: The organic solvent in step S2 is at least one of tetrahydrofuran, acetone, ethanol, methanol, toluene, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, ethyl acetate, and carbon tetrachloride.

8. The preparation method according to claim 1, characterized in that: The centrifugal washing and drying conditions are: centrifugal washing at a rotation speed of 3000r / min to 8000r / min, washing times of 3 to 6 times, and drying temperature of 60°C to 120°C.

9. Application of a functionalized boron nitride-cerium dioxide hybrid filler, characterized in that: The application is the application of the functionalized boron nitride-cerium dioxide hybrid filler prepared by the preparation method according to claims 1 to 8 in rubber composite materials.

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