Rubber auxiliary-graphene compound material, preparation method thereof and rubber composite material

Abstract

The invention provides a rubber auxiliary agent-graphene compound material and a preparation method thereof and a rubber composite material, the rubber auxiliary agent-graphene compound material comprises a rubber auxiliary agent and graphene, the graphene is uniformly dispersed in the rubber auxiliary agent, the addition amount of the graphene is 0.1%-50% of the mass of the rubber auxiliary agent, and the melting point or softening point of the rubber auxiliary agent is 40-120 DEG C. The rubber additive-graphene compound material provided by the invention is in a solid state at normal temperature, and is finally added into rubber in an additive form, so that automatic metering and feeding can be realized, and an original formula and an original production process do not need to be changed; the preparation process is simple, does not involve any organic solvent, is green and environment-friendly, and can be perfectly linked with an additive granulation process for batch production.

Description

Technical Field

[0001] The invention belongs to the technical field of preparation and application of nano composite materials, and relates to a rubber additive-graphene compound material and a preparation method thereof, and a rubber composite material. Background Art

[0002] As the only highly elastic material, rubber has an irreplaceable position in many fields such as tire industry, sealing industry, and damping and shock absorption industry. Rubber industrial products are multiphase systems composed of raw rubber and many additives in softening and plasticizing systems, filling and reinforcing systems, vulcanization systems, and anti-aging systems. Their macroscopic properties not only depend on the properties of rubber molecules and various additives themselves, but are also closely related to the mixing uniformity of various additives in rubber.

[0003] Graphene, with a theoretical specific surface area of ​​up to 2630m 2 / g, Young's modulus up to 1TPa, thermal conductivity up to 5300W / m·K, is a new type of rubber reinforcing filler. However, due to the high specific surface area and strong π-π interaction between layers, when directly added in the form of powder in the traditional rubber preparation process, it is easy to fly and cause dust pollution, and tends to π-π stacking, agglomerate in rubber, form stress concentration points, and weaken the reinforcement effect on rubber. Therefore, how to achieve uniform dispersion of graphene in rubber has always been a research hotspot in the industry.

[0004] CN108329535A discloses a highly dispersed graphene-rubber masterbatch and a preparation method thereof, wherein graphene powder is rapidly dispersed in an aqueous latex in which a composite dispersion system of alcohol ether phosphate, alcohol ether glucoside, and fatty acid methyl ester ethoxylate is dissolved, and graphene rubber blocks are obtained by flocculation. Then, the graphene is mixed with zinc sorbate and naphthenic oil in an internal mixer, and the mixture is discharged, extruded, and granulated to obtain a highly dispersed graphene-rubber masterbatch. Although the preparation method can improve the interfacial force between graphene and rubber, so that graphene can be uniformly dispersed in the rubber matrix, and the purpose of pre-dispersing graphene is achieved, it is still essentially an emulsion composite process, involving processes such as flocculation and drying, and the process is complicated.

[0005] CN109666198A discloses a graphene oxide reinforced rubber composite material and a preparation method thereof, which utilizes graphene oxide and zinc stearate as a rubber filler to improve the compatibility of graphene oxide in a rubber matrix and promote good dispersion of graphene oxide. However, the preparation method of the graphene oxide zinc stearate composite material in this method is complicated, and the reaction involves an organic solvent, which is not conducive to environmental protection.

[0006] Therefore, achieving uniform dispersion of graphene in rubber with simple process and green environmental protection is an urgent problem to be solved in this field. Summary of the invention

[0007] In view of the deficiencies in the prior art, the present invention provides a rubber additive-graphene compound material and a preparation method thereof and a rubber composite material, aiming to provide a method for preparing highly dispersed graphene / rubber composite materials that is simple and efficient, adaptable to existing production processes, and can realize automatic weighing and feeding, break through the limitations of the use of graphene reinforcing fillers, achieve effective enhancement of graphene, and meet the use requirements of graphene rubber products in high-performance fields.

[0008] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

[0009] In a first aspect, the present invention provides a rubber additive-graphene composite material, wherein the rubber additive-graphene composite material comprises a rubber additive and graphene, wherein the graphene is uniformly dispersed in the rubber additive, and the addition amount of the graphene is 0.1% to 50% (for example, 0.1%, 0.5%, 0.8%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 20%, 30%, 40%, 50%, etc.) of the mass of the rubber additive, and the melting point or softening point of the rubber additive is 40 to 120°C (for example, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, etc.).

[0010] The rubber additive-graphene compound material provided by the present invention is in a solid state at room temperature, and is finally added to the rubber in the form of an additive, and can realize automatic metering and feeding without changing the original formula and the original production process.

[0011] In the present invention, in order to adapt to the original production process, the amount of graphene added in the rubber additive-graphene compound material depends on the original basic formula.

[0012] In the present invention, in order to adapt the rubber additive-graphene compound material to the production process of different types of rubber without introducing foreign dispersed substances, the rubber additive can be adjusted according to the existing production formula or rubber type.

[0013] Preferably, the rubber additive includes any one or a combination of at least two of an antioxidant, stearic acid, a peptizer, an organic cobalt salt series of an adhesive system, a protective wax or a tackifying resin.

[0014] Preferably, the antioxidant includes any one of antioxidant RD, antioxidant 4010NA, antioxidant 4020 or antioxidant DTPD, or a combination of at least two thereof.

[0015] Preferably, the protective wax includes any one of microcrystalline wax, paraffin wax or PE wax, or a combination of at least two of them.

[0016] Preferably, the tackifying resin includes any one of phenolic resin, rosin resin, petroleum resin, coumarone resin or tackifier TKO-80, or a combination of at least two of them.

[0017] Preferably, the rubber additive contains a benzene ring in its chemical structure, for example, the rubber additive includes antioxidant 4020, coumarone resin, tackifier TKO-80, etc. The agglomeration of graphene mainly comes from the strong π-π interaction between the sheets, and the rubber additive containing a benzene ring in the chemical structure can also form a π-π conjugated interaction with graphene, thereby being adsorbed on the graphene surface as a stabilizer, preventing the accumulation of graphene sheets, and ensuring that the graphene has a high dispersion.

[0018] Preferably, the added amount of the graphene is 4% to 10% of the mass of the rubber additive.

[0019] In a second aspect, the present invention provides a method for preparing the rubber additive-graphene composite material as described in the first aspect, the preparation method comprising the following steps:

[0020] (1) heating the rubber additive to a molten state;

[0021] (2) maintaining the above state unchanged, adding graphene powder and dispersing;

[0022] (3) Cooling and solidifying to obtain the rubber additive-graphene composite material.

[0023] The preparation process of the rubber additive-graphene composite material provided by the invention is simple, does not involve any organic solvent, is green and environmentally friendly, and can be perfectly connected with the additive granulation process for batch production.

[0024] In the present invention, the use of rubber additives to compound graphene is, on the one hand, to improve the dispersibility of graphene in the rubber matrix, and on the other hand, to adapt to the general trend of clean refining production and realize automatic metering and feeding. In order to meet the above requirements, the rubber additive preferably uses a low melting point rubber additive, whose melting point or softening point is 40 to 120°C, has fluidity in the molten state, can meet the dispersion of the liquid phase system of graphene, is in a solid state at room temperature, and can realize automatic metering and feeding.

[0025] In the present invention, for the low melting point rubber additive which is solid at room temperature, in order to ensure the rapid infiltration and good dispersion of graphene powder, the rubber additive is heated before adding the graphene powder to transform it into a liquid phase molten state. On the other hand, in order to adapt the formula of graphene / rubber composite materials with different addition amounts, the kinematic viscosity in the molten state is selected to be ≤20mm 2 / s low melting point rubber additives. This is because when the kinematic viscosity of the molten rubber additive is too high, it is not conducive to the large-scale addition and dispersion of graphene, and will affect the granulation molding of the compound material.

[0026] Preferably, the heating temperature in step (1) is a temperature above the melting point or softening point of the rubber additive, and at this heating temperature, the rubber additive maintains a low kinematic viscosity of ≤20 mm in a molten state. 2 / s, for example 20mm 2 / s, 18mm 2 / s, 15mm 2 / s, 12mm 2 / s, 10mm 2 / s, 8mm 2 / s, 6mm 2 / s, 5mm 2 / s、3mm 2 / s, etc. For example, the heating temperature of antioxidant 4020, coumarone resin and tackifier TKO-80 are all 100℃, and their kinematic viscosities are 5mm 2 / s, 11mm 2 / s and 8mm 2 / s.

[0027] Preferably, in order to satisfy the reinforcing effect of low filling and high lifting of graphene, a new type of reinforcing filler, when selecting graphene raw materials, the preparation method, specific surface area and sheet diameter of graphene are limited.

[0028] Preferably, the graphene powder includes any one of graphene, graphene oxide or reduced graphene oxide, or a combination of at least two thereof, preferably graphene.

[0029] Preferably, the specific surface area of ​​the graphene powder is 20 to 500 m 2 / g, for example 20m 2 / g, 50m 2 / g, 80m 2 / g、100m 2 / g, 150m 2 / g, 200m 2 / g, 250m 2 / g、300m 2 / g, 350m 2 / g, 400m 2 / g, 450m 2 / g、500m 2 / g, etc., preferably 100 to 500 m 2 / g.

[0030] Preferably, the flake diameter of the graphene powder is 0.01 to 100 μm, for example, 0.01 μm, 0.03 μm, 0.05 μm, 0.08 μm, 0.1 μm, 0.2 μm, 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, 1 μm, 5 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, etc., preferably 0.01 to 1 μm.

[0031] Preferably, the dispersing method in step (2) includes any one of high-speed stirring, high-speed shear emulsification, ultrasound, ball milling or homogenization, or a combination of at least two of them.

[0032] Preferably, the rotation speed of the high-speed stirring is 800-1200 rpm, for example, 800 rpm, 900 rpm, 1000 rpm, 1100 rpm, 1200 rpm, etc.

[0033] Preferably, the shear rate of the high-speed shear emulsification is 16000-20000 rpm, for example, 16000 rpm, 17000 rpm, 18000 rpm, 19000 rpm, 20000 rpm, etc.

[0034] Preferably, the power of the ultrasound is 1400-1800w, for example, 1400w, 1500w, 1600w, 1700w, 1800w, etc., and the frequency of the ultrasound is 15-25kHz, for example, 15kHz, 18kHz, 20kHz, 23kHz, 25kHz, etc.

[0035] Preferably, the rotation speed of the ball mill is 450-550rpm, for example 450rpm, 480rpm, 500rpm, 530rpm, 550rpm, etc., and the bead-to-material ratio is (3-8):1, for example 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, etc.

[0036] Preferably, the homogenization pressure is 800-1200 bar, for example, 800 bar, 900 bar, 1000 bar, 1100 bar, 1200 bar, etc.

[0037] Preferably, the dispersion in step (2) is performed by first high-speed shear emulsification and then ultrasound.

[0038] In a third aspect, the present invention provides a rubber composite material, which is prepared using the rubber additive-graphene compound material as described in the first aspect or the rubber additive-graphene compound material prepared by the preparation method described in the second aspect.

[0039] Compared with the prior art, the present invention has the following beneficial effects:

[0040] (1) The rubber additive provided by the present invention is a low-melting-point rubber additive. The rubber additive-graphene composite material prepared by the present invention also has a low melting point, that is, it is in a solid state at room temperature. It is finally added to the rubber in the form of an additive, and automatic metering and feeding can be achieved without changing the original formula and the original production process, and has great industrial potential.

[0041] (2) The present invention disperses graphene powder in a molten rubber additive, thereby reducing dust pollution, improving the production environment of the graphene / rubber composite material, and increasing the uniform dispersion of graphene in the rubber matrix.

[0042] (3) The preparation process of the rubber additive-graphene composite material provided by the present invention is simple, does not involve any organic solvent, is green and environmentally friendly, and can be perfectly connected with the additive granulation process for mass production. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] Figure 1 This is a finished product picture of the stearic acid-graphene composite material provided in Example 1 of the present invention.

[0044] Figure 2 This is a finished product picture of the plasticizer A-graphene composite material provided in Example 4 of the present invention.

[0045] Figure 3 This is a cross-sectional SEM image of the stearic acid-graphene composite material / rubber composite material provided in Application Example 1 of the present invention. DETAILED DESCRIPTION

[0046] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0047] Example 1

[0048] In this embodiment, a rubber additive-graphene composite material is provided, and the preparation method comprises the following steps:

[0049] 1) Heat 20 g of stearic acid in an oil bath at 70°C to make it molten, at which point the kinematic viscosity is 6 mm2 / s;

[0050] 2) Keep the oil bath heated at 70°C, add 1g of graphene powder (graphene, with a specific surface area of ​​189m 2 / g, flake diameter 0.43μm), ultrasonically dispersed at 1600w, 20kHz for 60min to obtain a liquid mixture;

[0051] 3) dropping the liquid mixture onto a glass plate and cooling it to room temperature to obtain a stearic acid-graphene composite material.

[0052] The finished product of the stearic acid-graphene composite material provided in this embodiment is shown in FIG. Figure 1 As shown in the figure, it can be seen that the granulation condition of the finished product of stearic acid-graphene composite material is good, the particles are relatively complete, there is no obvious debris, the color is uniform, and the graphene is evenly distributed in the stearic acid.

[0053] Example 2

[0054] In this embodiment, a rubber additive-graphene composite material is provided, and the preparation method comprises the following steps:

[0055] 1) Heat 10g of microcrystalline wax in an oil bath at 90°C to make it molten. The kinematic viscosity is 5mm 2 / s;

[0056] 2) Keep the oil bath heated at 90°C, add 1g of graphene powder (graphene, with a specific surface area of ​​189m 2 / g, flake diameter 0.43μm), ultrasonically dispersed at 1600w, 20kHz for 60min to obtain a liquid mixture;

[0057] 3) dropping the liquid mixture onto a glass plate and cooling it to room temperature to obtain a microcrystalline wax-graphene composite material.

[0058] Example 3

[0059] In this embodiment, a rubber additive-graphene composite material is provided, and the preparation method comprises the following steps:

[0060] 1) Heat 25g antioxidant 4020 in an oil bath at 100℃ to make it molten. The kinematic viscosity is 5mm 2 / s;

[0061] 2) Keep the oil bath heated at 100°C, add 1g of graphene powder (graphene, specific surface area of ​​189m 2 / g, flake diameter 0.43μm), ultrasonically dispersed at 1600w, 20kHz for 60min to obtain a liquid mixture;

[0062] 3) dropping the liquid mixture onto a glass plate and cooling it to room temperature to obtain an antioxidant 4020-graphene composite material.

[0063] Example 4

[0064] In this embodiment, a rubber additive-graphene composite material is provided, and the preparation method comprises the following steps:

[0065] 1) Heat 30g of plasticizer A in an oil bath at 108℃ to make it molten. The kinematic viscosity is 25mm 2 / s;

[0066] 2) Keep the oil bath heated at 108°C, add 0.6g of graphene powder (graphene, specific surface area of ​​189m 2 / g, flake diameter 0.43μm), ultrasonically dispersed at 1600w, 20kHz for 60min to obtain a liquid mixture;

[0067] 3) dropping the liquid mixture onto a glass plate and cooling it to room temperature to obtain a plasticizer A-graphene composite material.

[0068] The finished product of the plasticizer A-graphene composite material provided in this embodiment is shown in FIG. Figure 2 As shown in the figure, it can be seen that the finished granulation of the plasticizer A-graphene compound material is almost impossible to form, the whole is in a crushed state, and the surface of a small amount of formed particles is loose.

[0069] Application Examples 1-3

[0070] In Application Examples 1-3, a rubber composite material is provided respectively. The specific selection and dosage (weight parts) of the raw materials for preparing the rubber composite material are shown in Table 1.

[0071] The preparation method comprises the following steps:

[0072] (1) Adding natural rubber and carbon black into an internal mixer according to the formula, and when the mixing temperature reaches 110° C., adding zinc oxide, stearic acid or stearic acid-graphene compound material, antioxidant 4020 or antioxidant 4020-graphene compound material, and microcrystalline wax or microcrystalline wax-graphene compound material, and when the mixing temperature reaches 150° C., the rubber is discharged to obtain a masterbatch.

[0073] (2) mixing the masterbatch after internal mixing on a two-roll open mill, controlling the roll temperature at 50±5° C., adding sulfur, accelerator, anti-vulcanization reversion agent and anti-scorch agent after roll packing, mixing evenly by two-sided three-knife, triangle packing, rolling and other methods, and then rolling down to obtain the final mixed rubber, that is, obtaining the rubber composite material.

[0074] Comparative application example 1

[0075] In this comparative application example, a rubber composite material is provided. The specific selection and dosage (weight parts) of the raw materials for preparing the rubber composite material are shown in Table 1.

[0076] The preparation method comprises the following steps:

[0077] (1) Add natural rubber, carbon black and graphene into an internal mixer according to the formula. When the mixing temperature reaches 110°C, add zinc oxide, stearic acid, antioxidant 4020 and microcrystalline wax. When the mixing temperature reaches 150°C, discharge the rubber to obtain a masterbatch.

[0078] (2) mixing the masterbatch after internal mixing on a two-roll open mill, controlling the roll temperature at 50±5° C., adding sulfur, accelerator, anti-vulcanization reversion agent and anti-scorch agent after roll packing, mixing evenly by two-sided three-knife, triangle packing, rolling and other methods, and then rolling down to obtain the final mixed rubber, that is, obtaining the rubber composite material.

[0079] Table 1

[0080]

[0081]

[0082] The accelerator in Table 1 is NS, the anti-reversion agents are PK900 and KA9188 (the mass ratio of the two is 1:1), and the anti-scorch agent is CTP.

[0083] The performance test of the rubber composite materials provided in the corresponding use cases and comparative application examples is carried out in the following manner:

[0084] (1) Tensile strength: The test standard is GB / T528-2009, and the equipment used is Instron 3365;

[0085] (2) Tear strength: The test standard is GB / T529-2008, and the equipment used is Instron 3365;

[0086] (3) Compression heat generation: The test standard is ASTM D623-07 (2014), and the equipment used is Alpha Model II;

[0087] (4) Akron wear: The test standard is GB / T1689-2014 and the equipment used is Taiwan High Speed ​​Rail GT-7012-A.

[0088] The performance test results are shown in Table 2.

[0089] Table 2

[0090]

[0091] As can be seen from Table 2, the tensile strength of the rubber composite material provided by the application example of the present invention is 28.8-29.8 MPa, the tear strength is 127.4-131.5 kN / m, the compression heat generation is 23.3-24.6 ° C, and the Akron abrasion is 0.130-0.142 cm 3 / 1.61km, and its performance is better than that of the comparative application examples. Compared with direct dry mixing and addition, the graphene is pre-dispersed in stearic acid, microcrystalline wax or antioxidant 4020 and then added. Even at a filling amount of 0.1 parts, the tensile strength of the composite material is increased to 28.8MPa, 29.4MPa and 29.8MPa, respectively, with an increase of ≥3%, and the tear strength is also increased. This fully proves that adding graphene after compounding with low-melting point rubber additives can effectively improve the dispersion of graphene in the rubber matrix, promote further optimization of the filler network structure, achieve regular arrangement and crystallization of natural rubber molecular chains under lower strain, and give full play to the reinforcement effect of graphene, a new type of reinforcing filler. In addition, the evenly dispersed graphene can prevent crack growth in time, so the tear strength of the application examples is better than that of the comparative application examples.

[0092] The compression heat generation of the composite material comes from the friction heat between the rubber polymer chains, between the fillers, and between the polymer chains and the fillers. The friction heat generation between the fillers is particularly prominent. By characterizing the compression heat generation performance of the composite material, the dispersion state of the filler can be indirectly explained. As shown in Table 2, in the application example where graphene is compounded with a low-melting-point rubber additive and then added, the compression heat generation decreases, which means that the friction heat generation between the fillers is reduced, indicating that the dispersion of graphene in the application example is improved.

[0093] Studies have shown that the wear resistance of composite materials is mainly related to the particle size of the reinforcing filler and the hardness of the composite material. The smaller the size of the reinforcing filler, the smaller the impurity effect of itself. When the addition amount is the same, the larger the specific surface area, the stronger the restriction on the rubber molecular chain, and the better the wear resistance of the material. The greater the hardness of the composite material, the stronger the ability to resist deformation, the less contact with the rough surface, and the better the wear resistance. In the present invention, the application example and the comparative application example use the same formula, only the graphene addition method is different. As can be seen from Table 2, under the same formula, the Akron wear of the application example is significantly reduced, which shows that the dispersion of graphene is improved and the cross-linking density is increased, which in turn leads to an increase in the hardness and modulus of the material and an improvement in wear resistance.

[0094] In addition, by comparing the performance results of the rubber composite materials of the three application examples, it can be seen that the rubber composite material prepared by the antioxidant 4020-graphene compound material provided in Example 3 has the best comprehensive performance. This is because the antioxidant 4020 contains a benzene ring in its structure, which can form a π-π conjugated interaction with graphene, thereby being adsorbed on the graphene surface as a stabilizer, preventing the accumulation of graphene sheets and ensuring that the graphene has better dispersibility.

[0095] The cross-sectional SEM image of the stearic acid-graphene composite material / rubber composite material provided in Application Example 1 of the present invention is as follows: Figure 3 As shown in the figure, it can be seen that the filler is evenly dispersed without obvious agglomeration, and the graphene has good compatibility with the rubber matrix.

[0096] The applicant declares that the present invention illustrates the rubber additive-graphene compound material and its preparation method and the rubber composite material of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned embodiments, that is, it does not mean that the present invention must rely on the above-mentioned embodiments to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of the raw materials selected by the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A rubber additive-graphene composite material, characterized in that: The rubber additive-graphene compound material comprises a rubber additive and graphene, wherein the graphene is uniformly dispersed in the rubber additive, the added amount of the graphene is 0.1% to 50% of the mass of the rubber additive, and the melting point or softening point of the rubber additive is 40 to 120°C.

2. The rubber additive-graphene composite material according to claim 1, characterized in that: The rubber additives include any one or a combination of at least two of an antioxidant, stearic acid, a peptizer, an organic cobalt salt series of an adhesive system, a protective wax or a tackifying resin; Preferably, the antioxidant includes any one of antioxidant RD, antioxidant 4010NA, antioxidant 4020 or antioxidant DTPD, or a combination of at least two thereof; Preferably, the protective wax includes any one of microcrystalline wax, paraffin wax or PE wax, or a combination of at least two thereof; Preferably, the tackifying resin includes any one of phenolic resin, rosin resin, petroleum resin, coumarone resin or tackifier TKO-80, or a combination of at least two of them.

3. The rubber additive-graphene composite material according to claim 1 or 2, characterized in that: The rubber additive contains a benzene ring in its chemical structure.

4. The rubber additive-graphene composite material according to any one of claims 1 to 3, characterized in that: The added amount of the graphene is 4% to 10% of the mass of the rubber additive.

5. A method for preparing a rubber additive-graphene composite material as claimed in any one of claims 1 to 4, characterized in that: The preparation method comprises the following steps: (1) heating the rubber additive to a molten state; (2) maintaining the above state unchanged, adding graphene powder and dispersing; (3) Cooling and solidifying to obtain the rubber additive-graphene composite material.

6. The preparation method according to claim 5, characterized in that: The kinematic viscosity of the rubber additive in the molten state is ≤20 mm 2 / s.

7. The preparation method according to claim 5 or 6, characterized in that: The graphene powder includes any one of graphene, graphene oxide or reduced graphene oxide, or a combination of at least two of them, preferably graphene.

8. The preparation method according to any one of claims 5 to 7, characterized in that: The specific surface area of ​​the graphene powder is 20 to 500 m 2 / g, preferably 100 to 500 m 2 / g; Preferably, the flake diameter of the graphene powder is 0.01 to 100 μm, preferably 0.01 to 1 μm.

9. The preparation method according to any one of claims 5 to 8, characterized in that: The dispersion method in step (2) includes any one of high-speed stirring, high-speed shear emulsification, ultrasound, ball milling or homogenization, or a combination of at least two thereof; Preferably, the dispersion method in step (2) is first high-speed shear emulsification and then ultrasound.

10. A rubber composite material, characterized in that: The rubber composite material is prepared using the rubber additive-graphene compound material according to any one of claims 1 to 4 or the rubber additive-graphene compound material prepared using the preparation method according to any one of claims 5 to 9.

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