Simplified preparation process of long-life graphene / natural rubber for improving migration resistance of antioxidant based on bonding effect

Abstract

The invention relates to the field of preparation of graphene and functional natural rubber composite materials, in particular to a simple preparation process of long-life graphene / natural rubber for improving the migration resistance of an antioxidant based on a bonding effect. The preparation method comprises the following steps: carrying out an amidation reaction between a water-soluble polymer and graphene oxide to obtain graphene oxide loaded with an antioxidant based on a bonding effect, and then preparing the graphene / natural rubber masterbatch loaded with the antioxidant. And finally preparing the long-service-life graphene / natural rubber capable of improving the migration resistance of the antioxidant based on the bonding effect through internal mixing, open mixing and vulcanization processes. The water-soluble polymer is introduced, and based on the covalent bond bonding effect of the water-soluble polymer and the GO and the hydrogen bond interaction of the water-soluble polymer and the antioxidant, the physical loading capacity of the antioxidant on the surface of the GO can be remarkably improved, so that the subsequent migration of the antioxidant and the formation of a protective film are facilitated.

Description

Technical Field

[0001] This invention relates to the field of graphene and functional natural rubber composite material preparation, and particularly to a simplified preparation process for long-life graphene / natural rubber based on bonding to enhance the antioxidant migration resistance. Background Technology

[0002] As a strategic resource, natural rubber (NR) is a polymer material with high elasticity and viscoelasticity, and its typical self-reinforcing properties make it an indispensable matrix material. However, during storage and use, the combined effects of internal and external factors can cause changes in the molecular network structure and chemical composition of NR products, leading to a decline in mechanical properties and a reduction in product lifespan, or even rendering them unusable—a process known as aging. Among the various forms of NR aging, thermo-oxidative aging is the most common and destructive. Thermo-oxidative aging is the aging process that occurs under the combined influence of heat and oxygen, causing severe damage to all properties of rubber materials.

[0003] Graphene and its derivatives possess exceptional physicochemical properties, which can significantly enhance various properties of polymer matrices. The numerous oxygen-containing functional groups on the surface of graphene oxide (GO) can interact with many other functional groups, allowing it to be easily compounded with other functional particles, thereby improving the performance of natural graphene oxide (NR).

[0004] Currently, the aging resistance of rubber is commonly improved by adding antioxidants. Antioxidants are uniformly dispersed in the rubber compound system using a mixing process. Finally, they migrate to the surface of the product to form a protective film against heat, oxidation, and aging, thereby extending the service life of the rubber product. However, commonly used antioxidants are prone to migration due to their small molecular weight. While this is beneficial for protecting the rubber matrix to some extent, it also leads to rapid antioxidant depletion, significantly reducing their protective ability. Some researchers are dedicated to developing novel environmentally friendly antioxidants, but their application in industrial production is difficult due to complex reaction conditions and high costs. Furthermore, some studies have shown that modifying GO (polyoxochemical oxide) and directly loading antioxidants onto its surface can effectively improve the antioxidant's migration resistance, thus improving the heat and oxidation aging resistance of rubber composites. However, while these methods improve the aging resistance of rubber to some extent, they cannot simultaneously maintain or enhance other properties of rubber. Mechanical properties and heat and oxidation aging resistance directly determine the application areas and effectiveness of NR (reactive rubber). Summary of the Invention

[0005] To address the problem that modified GO cannot simultaneously maintain or improve the mechanical properties and heat and oxygen aging resistance of rubber, this invention provides a simplified preparation process for long-life graphene / natural rubber based on bonding to enhance the antioxidant migration resistance.

[0006] This invention is achieved through the following technical solution: a simplified preparation process for long-life graphene / natural rubber based on bonding to enhance the migration resistance of antioxidants, wherein the long-life graphene / natural rubber is prepared from the following materials in parts by weight: Natural rubber 100; Based on the bonding effect, the antioxidant graphene oxide is loaded with a value of 0-1, and not 0; Rubber additives 10-20; The reinforcing filler is 0-90, and not 0; The simplified preparation process for the long-life graphene / natural rubber includes the following steps: (1) The aqueous solution of the water-soluble polymer is slowly added to the ethanol solution of the antioxidant and homogenized to obtain an antioxidant / water-soluble polymer solution; an activator is added to the graphene oxide aqueous dispersion, and the obtained activator / graphene oxide aqueous dispersion is added to the antioxidant / water-soluble polymer solution. The reaction is carried out at a certain temperature for a certain time. During the reaction, the water-soluble polymer is grafted onto the surface of graphene oxide through an amidation reaction. At the same time, it uses the hydrogen bond interaction between the polymer and the antioxidant molecules to load the antioxidant onto the surface of graphene oxide, thus obtaining a graphene oxide dispersion loaded with antioxidant based on bonding. The water-soluble polymer is selected from at least one of polyethyleneimine, polyacrylamide, polyacrylic acid, polyvinylpyrrolidone, polyvinyl alcohol, polymaleic anhydride, and polyethylene glycol; the concentration of the aqueous solution of the water-soluble polymer is 0-50 mg / mL and is not 0. The concentration of the antioxidant in ethanol solution is 0-50 mg / mL, and not 0; The activator is a mixture of 1-ethyl-(3-dimethylaminopropyl)carbodiimide and N-hydroxysuccinimide; the mass ratio of the activator to graphene oxide is 0-0.02:1, and the activator content is not zero; The reaction temperature is 0 - 30 °C; (2) The graphene oxide dispersion based on bonding effect loaded with antioxidant obtained in step (1) is filtered, and deionized water is added to the obtained graphene oxide slurry loaded with antioxidant, and ultrasonic treatment is performed for a certain time to obtain an aqueous dispersion of graphene oxide based on bonding effect loaded with antioxidant; the ultrasonic treatment power is 50-200 W and the time is 5-20 min. (3) Add the graphene oxide aqueous dispersion with bonded antioxidant obtained in step (2) to natural rubber latex and stir thoroughly to obtain a uniformly dispersed mixed emulsion. In this emulsion, the graphene oxide with bonded antioxidant will form bound particles with the rubber particles due to the positive ionic electrostatic attraction of the protein-phospholipid film on the surface of the rubber particles and remain stable. When a flocculant is added, the repulsive force between the particles that keep the emulsion stable is reduced, so flocculation occurs. The bound particles and natural rubber latex particles are orderly aggregated in the aqueous phase and precipitated out together. The obtained raw rubber is washed, dehydrated, and dried to obtain graphene oxide / natural rubber masterbatch with bonded antioxidant. (4) Add the bond-supported antioxidant graphene oxide / natural rubber masterbatch obtained in step (3) to a mixer and mix it at a certain temperature for a certain time. During this time, rubber additives and reinforcing fillers are added in sequence. After the mixture is evenly dispersed, the rubber compound is discharged and cooled to room temperature. Then, the rubber compound is mixed on a two-roll mill at a certain temperature for a certain time. During this time, vulcanizing agent is added and the mixture is evenly mixed. The mixture is then passed through a thin stream until there are no bubbles in the rubber compound to obtain the compound. (5) The compound obtained in step (4) is left to stand for a certain period of time, and then vulcanized at a certain temperature and pressure for a certain period of time to obtain long-life graphene / natural rubber with improved antioxidant migration resistance based on bonding effect.

[0007] As a further improvement to the technical solution of the present invention, the antioxidant is selected from at least one of N-cyclohexyl-N'-phenyl-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, diphenyl-p-phenylenediamine, N,N'-disec-butyl-p-phenylenediamine, N-(1,4-dimethylpentyl)-N'-phenyl-p-phenylenediamine and N,N'-di(β-naphthyl)-p-phenylenediamine.

[0008] As a further improvement to the technical solution of the present invention, the mass ratio of the water-soluble polymer to graphene oxide is 0-1:1, and the mass ratio of the water-soluble polymer is not 0.

[0009] As a further improvement to the technical solution of the present invention, in step (1), the reaction time is 4-12 h.

[0010] As a further improvement to the technical solution of the present invention, the rubber additives include antioxidants, activators, softeners, vulcanization accelerators and vulcanizing agents.

[0011] As a further improvement to the technical solution of the present invention, the mass ratio of the antioxidant to the activator, softener, vulcanization accelerator and vulcanizing agent is 2:5:2:2:2.

[0012] As a further improvement to the technical solution of the present invention, the reinforcing filler is selected from at least one of carbon black N110, N220, N234, N330, N550, N660 and N774.

[0013] As a further improvement to the technical solution of the present invention, in step (4), the mixing temperature is 105-120 °C and the mixing time is 10-20 min; the initial mixing temperature is 50-70 °C and the initial mixing time is 8-12 min.

[0014] As a further improvement to the technical solution of the present invention, in step (5), the glue stopping time is 18-36 h.

[0015] As a further improvement to the technical solution of the present invention, in step (5), the vulcanization temperature is 135-170 °C, the vulcanization pressure is 13-17 MPa, and the vulcanization time is 5-20 min.

[0016] This invention provides a simplified preparation process for long-life graphene / natural rubber based on bonding to enhance the migration resistance of antioxidants, which has the following advantages compared with existing technologies: ① This invention utilizes an activator to enhance the activity of -COOH groups on the GO surface. Therefore, the reaction between these groups and -NH2 groups in the water-soluble polymer molecules, forming covalent bonds through amidation, is further promoted and enhanced. Furthermore, the water-soluble polymer also possesses physical adsorption and structural regulation functions. Firstly, the water-soluble polymer can act as a high-molecular-weight surfactant to encapsulate GO sheets or insert into the interlayer, improving dispersibility and reducing agglomeration. Secondly, the long-chain structure of the water-soluble polymer can also bridge GO sheets, forming a denser physical barrier and optimizing the mechanical properties of the final NR composite material.

[0017] ② The water-soluble polymer introduced in this invention, based on its covalent bonding with GO and its hydrogen bonding interaction with antioxidants, can not only significantly increase the physical loading of antioxidants on the GO surface, thus facilitating the subsequent migration of antioxidants and the formation of a protective film, but also ensure the maintenance of the antioxidant state on the GO surface (i.e., the loading is not affected) during the mixing and open milling of the rubber compound. This lays the foundation for improving and maintaining the heat and oxygen aging resistance of NR.

[0018] ③ This invention achieves antioxidant loading in a physical manner. Compared with traditional chemical loading, it can not only increase the loading rate without consuming the functional groups on the surface of antioxidants, but also improve the dispersibility of antioxidants while enhancing their migration resistance. Therefore, it can further improve the aging resistance and service life of the obtained NR products.

[0019] ④ This invention utilizes water-soluble polymers to modify the surface of GO, which can improve the crosslinking degree of NR composite materials, thereby enhancing the interfacial interaction between GO filler and the NR matrix, and ultimately effectively improving the mechanical properties of NR products, especially tensile strength. Attached Figure Description

[0020] The accompanying drawings, which are incorporated in and form part of this specification, illustrate embodiments consistent with the invention and, together with the description, serve to explain the principles of the invention.

[0021] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, for those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0022] Figure 1 XPS spectra of GO (4020 / PEI@GO) and GO raw materials (i.e. GO in Comparative Example 1), 4020@GO in Comparative Example 2, and PEI@GO in Comparative Example 3, obtained in Example 1 based on the bonding loading 4020.

[0023] Figure 2 The infrared (FT-IR) spectra of GO (4020 / PEI@GO) and GO raw material (i.e. GO in Comparative Example 1), 4020@GO in Comparative Example 2, PEI@GO in Comparative Example 3, pure PEI and pure 4020 obtained in Example 1.

[0024] Figure 3 Scanning electron micrographs of GO (4020 / PEI@GO), GO raw material (i.e. GO in Comparative Example 1), and antioxidant 4020 raw material based on bonding loading 4020 obtained in Example 1.

[0025] Figure 4 A comparison chart of the antioxidant 4020 loading rates in GO (4020 / PEI@GO) based on bonding loading 4020 obtained in Example 1 and 4020@GO obtained in Comparative Example 2.

[0026] Figure 5 The tensile strength of long-life graphene / natural rubber prepared in Examples 1 and 2 with enhanced antioxidant migration resistance based on bonding effect and graphene / natural rubber prepared in Comparative Example 1 after aging at 100°C for 0-7 days. Detailed Implementation

[0027] To better understand the above-mentioned objectives, features, and advantages of the present invention, the solutions of the present invention will be further described below. It should be noted that, unless otherwise specified, the embodiments of the present invention and the features thereof can be combined with each other.

[0028] Many specific details are set forth in the following description in order to provide a full understanding of the invention, but the invention may also be practiced in other ways different from those described herein; obviously, the embodiments in the specification are only some embodiments of the invention, and not all embodiments.

[0029] The specific embodiments of the present invention will be described in detail below. Example 1

[0030] A simplified preparation process for long-life graphene / natural rubber based on bonding to enhance the antioxidant migration resistance includes the following steps: (I) 50 mL of an aqueous solution of the water-soluble polymer polyethyleneimine (PEI) with a concentration of 10 mg / mL was slowly added to 100 mL of an ethanolic solution of the antioxidant N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (i.e., antioxidant 4020) with a concentration of 20 mg / mL. After mixing evenly, a 4020 / PEI solution was obtained. Activators (0.005 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide and 0.005 g of N-hydroxysuccinimide) were added to 50 mL of an aqueous dispersion of GO with a concentration of 10 mg / mL. Then, the obtained 4020 / PEI solution was slowly added. The reaction was carried out at 10°C for 12 h. During this period, PEI was grafted onto the GO surface through an amidation reaction. At the same time, it utilized the hydrogen bond interaction between PEI and antioxidant 4020 molecules to load 4020 onto the GO surface, resulting in a GO dispersion based on bond-loaded 4020. (II) The GO dispersion based on bonded loading 4020 obtained in step (I) was filtered, and then the obtained GO slurry with 4020 antioxidant was added to deionized water and ultrasonically dispersed at 50W for 15 min to obtain an aqueous dispersion of GO based on bonded loading 4020, wherein the mass of GO based on bonded loading 4020 was 0.5 g. (III) The GO aqueous dispersion based on bonding effect loading 4020 obtained in step (II) was added to 166.7g of natural rubber latex with a solid content of 60wt.% and stirred thoroughly to obtain a uniformly dispersed mixed emulsion. The GO loaded with 4020 antioxidant formed bound particles with the rubber particles due to the positive ionic electrostatic attraction of the protein-phospholipid film on the surface of the rubber particles and remained stable. Subsequently, a flocculant (60g of 10 mg / mL calcium chloride solution) was added. Due to the reduction of the interparticle repulsion that kept the emulsion stable, flocculation occurred. The bound particles and natural rubber latex particles aggregated in an orderly manner in the aqueous phase and precipitated out together. The obtained raw rubber was washed with water, dehydrated, and dried at 60°C for 16h to obtain GO / NR masterbatch based on bonding effect loading 4020 antioxidant. (IV) The bond-loaded 4020 antioxidant GO / NR masterbatch obtained in step (III) was added to a mixer and mixed at 110°C for 16 min. During this period, 2 g of antioxidant 2,2,4-trimethyl-1,2-dihydroquinoline polymer, 5 g of activator ZnO, 2 g of softener stearic acid, 2 g of accelerator N-cyclohexyl-2-benzothiazole sulfenamide and 35 g of reinforcing filler carbon black N330 were added sequentially. After being evenly dispersed, the rubber compound was discharged and cooled to room temperature. Then the rubber compound was placed in the two rolls of a two-roll mill and milled at 60°C with 2 g of sulfur added. After milling for a total of 8 min, the mixture was passed through a thin tube until there were no bubbles in the rubber compound, and the compound was obtained. (V) The compound obtained in step (IV) is left to stand for 24 hours and then vulcanized at 150°C and 15MPa for 12 minutes on a flat vulcanizing machine to obtain long-life graphene / natural rubber with improved antioxidant migration resistance based on bonding. Example 2

[0031] It is exactly the same as Example 1, except that the amount of water-soluble polymer PEI aqueous solution added in step (I) is 25 mL. Example 3

[0032] It is exactly the same as Example 1, except that the water-soluble polymer is polyacrylamide. Example 4

[0033] It is exactly the same as Example 1, except that the water-soluble polymer is polyvinylpyrrolidone. Comparative Example 1

[0034] A process for preparing GO / NR includes the following steps: (I) Same as step (III) of Example 1, except that the GO aqueous dispersion loaded with 4020 in Example 1 is replaced with pure GO aqueous dispersion. Therefore, GO / NR masterbatch is obtained.

[0035] (II) Same as step (IV) of Example 1, except that the GO / NR masterbatch loaded with 4020 antioxidant in Example 1 is replaced with GO / NR masterbatch.

[0036] (III) Same as step (V) in Example 1, except that GO / NR is obtained. Comparative Example 2

[0037] A preparation process for GO (i.e., 4020@GO) / NR with a physical load of 4020 is exactly the same as in Example 1, except that PEI is not added. The specific steps are as follows: (I) Same as step (I) in Example 1, except without PEI. Specifically: Activator (0.005 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide and 0.005 g of N-hydroxysuccinimide) was added to 50 mL of GO aqueous dispersion with a concentration of 10 mg / mL. Then, 100 mL of ethanol solution of antioxidant 4020 with a concentration of 20 mg / mL was slowly added. The reaction was carried out at 10°C for 12 h to obtain 4020@GO dispersion.

[0038] (II) Same as step (II) of Example 1, except that the GO dispersion based on the bonding loading 4020 in Example 1 is replaced with 4020@GO dispersion. Therefore, the 4020@GO aqueous dispersion is obtained.

[0039] (III) Same as step (III) of Example 1, except that the GO aqueous dispersion based on bonding loading 4020 in Example 1 is replaced with 4020@GO aqueous dispersion. Therefore, the obtained product is 4020@GO / NR masterbatch.

[0040] (IV) Same as step (IV) of Example 1, except that the GO / NR masterbatch based on bonding loading 4020 in Example 1 is replaced with 4020@GO / NR masterbatch.

[0041] (V) is the same as step (V) in Example 1, except that the result is 4020@GO / NR. Comparative Example 3

[0042] A preparation process for chemically loaded PEI-based GO (i.e., PEI@GO) is the same as step (I) in Example 1, except that antioxidant 4020 is not added. The specific steps are as follows: An activator (0.005 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide and 0.005 g of N-hydroxysuccinimide) was added to 50 mL of GO aqueous dispersion with a concentration of 10 mg / mL. Then, 50 mL of PEI aqueous solution with a concentration of 10 mg / mL was slowly added. The reaction was carried out at 10°C for 12 h. During this period, PEI was grafted onto the GO surface through an amidation reaction. The resulting PEI@GO dispersion was dried to obtain PEI@GO powder.

[0043] Depend on Figure 1 It can be seen that in the C1s spectrum of pure GO (i.e., GO in Comparative Example 1), there are a large number of oxygen-containing functional groups, with 284.8 eV, 286.8 eV, 288.2 eV, and 288.9 eV corresponding to CC, CO, C=O, and OC=O bonds, respectively. In the C1s spectrum of 4020@GO in Comparative Example 2, there are obvious peaks of GO oxygen-containing functional groups, and no obvious CN peak appears; the situation is the opposite for PEI@GO in Comparative Example 3, with a significant reduction in oxygen-containing functional groups and the presence of a CN peak; indicating that PEI and GO form a bond, while 4020 is mainly physically loaded on the GO surface. In the C1s spectrum of 4020 / PEI@GO in Example 1, CO and OC=O bonds were also found to be reduced, and CN chemical bonds appeared at 285.9 eV. The binding energy of C=O bonds shifted from 288.2 eV to 287.9 ​​eV, indicating that there is chemical bonding or electron transfer between GO and 4020 / PEI.

[0044] Depend on Figure 2 It can be seen that in the FT-IR spectrum of pure GO (i.e., GO in Comparative Example 1), the 3600-3200 cm⁻¹... -1 and 1734cm -1 The stretching vibration peaks belong to the -OH and C=O bonds; while the stretching vibration peaks of the CO bonds in the carboxyl, epoxy, and alkoxy groups are located at 1396 cm⁻¹. -1 1249 cm -1 and 1047 cm -1 For pure PEI, 3726-3326 cm. -1 The broad peak belongs to the active amine group -NH2, 1075 cm⁻¹ -1 This corresponds to the stretching vibration of the CN bond. For 4020, the stretching vibration peak of the antioxidant group -NH is located at 3390 cm⁻¹. -1However, in the spectrum of 4020@GO in Comparative Example 2, the characteristic peak of 4020 appeared and a blue shift occurred, indicating the presence of hydrogen bonds and that 4020 does not exist on the GO surface through a chemical reaction. Compared to GO, in both PEI@GO in Comparative Example 3 and 4020 / PEI@GO in Example 1, a large amount of oxygen-containing functional groups on the GO surface were consumed, which is consistent with... Figure 1 The results are consistent. 1627 cm -1 and 1386 cm -1 The characteristic peak of O=C-NH at the O=C-NH indicates that the carboxyl group on the GO surface and the amino group in the PEI molecule underwent an amidation reaction, meaning that there is a chemical bond between GO and PEI.

[0045] Depend on Figure 3 It can be seen that, compared with pure GO (i.e., GO in Comparative Example 1), the 4020 / PEI@GO in Example 1 has obvious wrinkles and stacking, and the surface structure is rougher, indicating that 4020 / PEI was successfully loaded onto the GO surface. In addition, comparing the 4020 / PEI@GO and the antioxidant 4020 raw material in Example 1, it can be found that, due to the mechanical action and grafting reaction during the stirring process, the 4020 in 4020 / PEI@GO is transformed into smaller particles that adhere to the GO surface, and the particle size distribution is more uniform. This is beneficial to improving the dispersibility of 4020 in the matrix and enhancing its migration resistance.

[0046] Depend on Figure 4 It can be seen that the loading rate of antioxidant 4020 in Comparative Example 2 (4020@GO) is approximately 6%, while the loading rate of antioxidant 4020 in Example 1 (4020 / PEI@GO) is approximately 34%, and the loading rate of antioxidant 4020 in Example 2 (4020 / PEI@GO) is approximately 16%. This indicates that the present invention can indeed significantly increase the physical loading of antioxidants on the GO surface. The significant increase in antioxidant loading rate will improve the antioxidant migration resistance, thereby enhancing the aging resistance and service life of the obtained NR product.

[0047] Depend on Figure 5 It can be seen that, compared with the GO / NR obtained in Comparative Example 1, the tensile strength of the long-life graphene / natural rubber obtained in Example 1 and Example 2 is increased by 12% and 7%, respectively; the tensile strength retention rate after 3 days of aging is increased by 18% and 10%, respectively; and the tensile strength retention rate after 7 days of aging is increased by 7% and 5%, respectively. That is, both mechanical properties and aging resistance are significantly improved.

[0048] The above description is merely a specific embodiment of the present invention, enabling those skilled in the art to understand or implement the present invention. Although detailed descriptions have been provided with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments, and they should all be covered within the protection scope of the claims.

Claims

1. A simplified preparation process for long-life graphene / natural rubber based on bonding to enhance the migration resistance of antioxidants, characterized in that, The long-life graphene / natural rubber is prepared from the following materials in parts by weight: Natural rubber 100; Based on the bonding effect, the antioxidant graphene oxide is loaded with a value of 0-1, and not 0; Rubber additives 10-20; The reinforcing filler is 0-90, and not 0; The simplified preparation process for the long-life graphene / natural rubber includes the following steps: (1) The aqueous solution of the water-soluble polymer is slowly added to the ethanol solution of the antioxidant and homogenized to obtain an antioxidant / water-soluble polymer solution; an activator is added to the graphene oxide aqueous dispersion, and the obtained activator / graphene oxide aqueous dispersion is added to the antioxidant / water-soluble polymer solution. The reaction is carried out at a certain temperature for a certain time. During the reaction, the water-soluble polymer is grafted onto the surface of graphene oxide through an amidation reaction. At the same time, it uses the hydrogen bond interaction between the polymer and the antioxidant molecules to load the antioxidant onto the surface of graphene oxide, thus obtaining a graphene oxide dispersion loaded with antioxidant based on bonding. The water-soluble polymer is selected from at least one of polyethyleneimine, polyacrylamide, polyacrylic acid, polyvinylpyrrolidone, polyvinyl alcohol, polymaleic anhydride, and polyethylene glycol; the concentration of the aqueous solution of the water-soluble polymer is 0-50 mg / mL and is not 0. The concentration of the antioxidant in ethanol solution is 0-50 mg / mL, and not 0; The activator is a mixture of 1-ethyl-(3-dimethylaminopropyl)carbodiimide and N-hydroxysuccinimide; the mass ratio of the activator to graphene oxide is 0-0.02:1, and the activator content is not zero; The reaction temperature is 0 - 30 °C; (2) The graphene oxide dispersion based on bonding effect loaded with antioxidant obtained in step (1) is filtered, and deionized water is added to the obtained graphene oxide slurry loaded with antioxidant. The mixture is ultrasonically treated for a certain time to obtain an aqueous dispersion of graphene oxide based on bonding effect loaded with antioxidant. The ultrasonic treatment power is 50-200 W and the time is 5-20 min. (3) Add the graphene oxide aqueous dispersion with bonded antioxidant obtained in step (2) to natural rubber latex and stir thoroughly to obtain a uniformly dispersed mixed emulsion. In this emulsion, the graphene oxide with bonded antioxidant will form bound particles with the rubber particles due to the positive ionic electrostatic attraction of the protein-phospholipid film on the surface of the rubber particles and remain stable. When a flocculant is added, the repulsive force between the particles that keep the emulsion stable is reduced, so flocculation occurs. The bound particles and natural rubber latex particles are orderly aggregated in the aqueous phase and precipitated out together. The obtained raw rubber is washed, dehydrated, and dried to obtain graphene oxide / natural rubber masterbatch with bonded antioxidant. (4) Add the bond-supported antioxidant graphene oxide / natural rubber masterbatch obtained in step (3) to a mixer and mix it at a certain temperature for a certain time. During this time, rubber additives and reinforcing fillers are added in sequence. After the mixture is evenly dispersed, the rubber compound is discharged and cooled to room temperature. Then, the rubber compound is mixed on a two-roll mill at a certain temperature for a certain time. During this time, vulcanizing agent is added and the mixture is evenly mixed. The mixture is then passed through a thin stream until there are no bubbles in the rubber compound to obtain the compound. (5) The compound obtained in step (4) is left to stand for a certain period of time, and then vulcanized at a certain temperature and pressure for a certain period of time to obtain long-life graphene / natural rubber with improved antioxidant migration resistance based on bonding effect.

2. The simplified preparation process for long-life graphene / natural rubber based on bonding to enhance the antioxidant migration resistance, as described in claim 1, is characterized in that... The antioxidant is selected from at least one of N-cyclohexyl-N'-phenyl-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, diphenyl-p-phenylenediamine, N,N'-disec-butyl-p-phenylenediamine, N-(1,4-dimethylpentyl)-N'-phenyl-p-phenylenediamine and N,N'-di(β-naphthyl)-p-phenylenediamine.

3. The simplified preparation process for long-life graphene / natural rubber based on bonding to enhance the antioxidant migration resistance according to claim 1, characterized in that, The mass ratio of the water-soluble polymer to graphene oxide is 0-1:1, and the mass of the water-soluble polymer is not 0.

4. The simplified preparation process for long-life graphene / natural rubber based on bonding to enhance the antioxidant migration resistance, as described in claim 1, is characterized in that... In step (1), the reaction time is 4-12 h.

5. The simplified preparation process for long-life graphene / natural rubber based on bonding to enhance the antioxidant migration resistance according to claim 1, characterized in that, The rubber additives include antioxidants, activators, softeners, vulcanization accelerators, and vulcanizing agents.

6. The simplified preparation process for long-life graphene / natural rubber based on bonding to enhance the antioxidant migration resistance according to claim 5, characterized in that, The mass ratio of the antioxidant to the activator, softener, vulcanization accelerator, and vulcanizing agent is 2:5:2:2:

2.

7. The simplified preparation process for long-life graphene / natural rubber based on bonding to enhance the antioxidant migration resistance according to claim 1, characterized in that, The reinforcing filler is selected from at least one of carbon black N110, N220, N234, N330, N550, N660 and N774.

8. The simplified preparation process for long-life graphene / natural rubber based on bonding to enhance the antioxidant migration resistance according to claim 1, characterized in that, In step (4), the internal mixing temperature is 105-120 °C and the internal mixing time is 10-20 min; the initial mixing temperature is 50-70 °C and the initial mixing time is 8-12 min.

9. The simplified preparation process for long-life graphene / natural rubber based on bonding to enhance the antioxidant migration resistance according to claim 1, characterized in that, In step (5), the glue stopping time is 18-36 hours.

10. The simplified preparation process for long-life graphene / natural rubber based on bonding to enhance the antioxidant migration resistance according to claim 1, characterized in that, In step (5), the vulcanization temperature is 135-170 °C, the vulcanization pressure is 13-17 MPa, and the vulcanization time is 5-20 min.

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