CN115960394A - Graphene-supported white carbon black composite material and its preparation method and application - Google Patents

Abstract

The invention provides a graphene supported white carbon black composite material and a preparation method and application thereof. The preparation method comprises the following steps: s1, preparing a sodium silicate solution; s2, preparing a graphene oxide dispersion liquid; s3, forming a mixed solution of graphene oxide and sodium silicate; s4, dropwise adding the mixed solution of graphene oxide and sodium silicate into the ammonium bicarbonate solution; s5, adding a reducing agent into the mixed solution obtained in the step S4; s6, filtering to obtain a solid mixture, and washing and drying the solid mixture; and S7, carrying out high-temperature treatment on the dried solid mixture. The white carbon black in the composite material prepared by the method is attached to the surface of the graphene, so that the low heat generation performance of the white carbon black can be exerted, and the secondary agglomeration of the graphene in the rubber can be prevented. The composite material is used as a rubber filler, has more excellent processing performance, obviously improves the fluidization mechanical property, and can improve the compression heat generation and mechanical property of rubber.

Description

Graphene-supported white carbon black composite material and its preparation method and application

technical field

The invention belongs to the technical field of graphene nanomaterials, and in particular relates to a graphene-loaded white carbon black composite material and a preparation method and application thereof.

Background technique

Graphene is a new material with a single-layer sheet structure composed of carbon atoms. It is a planar film composed of carbon atoms with sp ² hybrid orbitals forming a hexagonal honeycomb lattice, a two-dimensional material with a thickness of only one carbon atom. Because graphene has many excellent physical and chemical properties, it is widely used in energy storage materials, environmental engineering, and sensitive sensing. It is called "black gold" or "king of new materials", and has broad potential application prospects. At present, it has become the focus of attention and research hotspot all over the world, especially the excellent performance of graphene has realized great prospects for the development of high-performance, multifunctional polymer nanocomposites. However, it is precisely because of the sheet structure of graphene that it is easy to agglomerate in polymers such as rubber, and the agglomerated graphene will form stress concentration points and affect the performance of composite materials.

Silica, commonly known as white carbon black, is a white, non-toxic, amorphous white powder with a size of 10-40nm, a very large specific surface area, and a large number of hydroxyl functional groups, which can greatly reduce the compression heat generation of rubber , is an important filler in rubber composites. However, due to the poor strength of silica, the strength of the prepared rubber composite is also poor.

All the existing studies and literatures have reported that graphene and white carbon black are used as technical solutions for rubber fillers. The dispersion of graphene in rubber is the key to the preparation of high-performance rubber composites. If the dispersion of the filler is poor, it is difficult to have a good use value. Therefore, solving the dispersion of graphene and silica in the rubber matrix has become the key to both being good rubber fillers.

Therefore, how to obtain a method that can better evenly disperse graphene and silica in the rubber matrix, and give full play to the enhancement of graphene and the low heat generation performance of silica is currently the focus of many R&D personnel and institutions. focus.

Contents of the invention

The present invention aims to provide a graphene-loaded white carbon black material, a preparation method thereof and an application as a rubber filler.

The invention provides a method for preparing a graphene-loaded white carbon black composite material, comprising: S1, dissolving sodium silicate in water to prepare a sodium silicate solution; S2, dispersing graphene oxide in water to prepare graphite oxide ene dispersion; S3, the graphene oxide dispersion is added to the sodium silicate solution, and then dispersed to form a mixed solution of graphene oxide and sodium silicate; S4, the graphene oxide and silicon Add the mixed solution of sodium bicarbonate dropwise to the ammonium bicarbonate solution, and continuously stir during the dropping process; S5, add the reducing agent to the mixed solution obtained in the S4 step; S6, add the reducing agent to the mixed solution obtained in the S5 step. The reacted mixed solution is filtered to obtain a solid mixture, and the solid mixture is washed and dried; and S7, the dried solid mixture is subjected to high-temperature treatment, and the temperature of the high-temperature treatment is 200-800° C., preferably 260° C. °C, the time for the high temperature treatment is 1 to 6 hours, preferably 2 hours.

According to an embodiment of the present invention, the concentration of the sodium silicate solution in the step S1 is 1-10 wt%, preferably 5 wt%.

According to another embodiment of the present invention, the concentration of the graphene oxide dispersion in the step S2 is 0.1 to 2 wt%, preferably 1 wt%; preferably, the graphene oxide has a sheet diameter of 2 to 15 microns , the sheet thickness of the graphene oxide is 0.7-10 nanometers; preferably, the oxygen content of the graphene oxide is 20-60 wt%.

According to another embodiment of the present invention, in the step S3, the mass ratio of the graphene oxide to the sodium silicate is 0.1˜10:100.

According to another embodiment of the present invention, the concentration of the ammonium bicarbonate in the step S4 is 1-10 wt %; the molar ratio of the ammonium bicarbonate to the sodium silicate is 2.0-3.0:1.

According to another embodiment of the present invention, in the S5 step, the reducing agent is selected from vitamin C, hydrazine hydrate, sodium borohydride, hydrogen, ammonia, vitamin C, potassium hydroxide, sodium oxide, dimethylhydrazine , p-diphenone, hydroiodic acid, phenylhydrazine or one or more.

According to another embodiment of the present invention, the reducing agent is vitamin C, and the mass ratio of the vitamin C to the graphene oxide is 0.5-3:1; the temperature at which the vitamin C reduces graphene oxide is 50-50 90°C, preferably 80°C; the time for the vitamin C to reduce graphene oxide is 0.5-4h, preferably 1h.

According to another embodiment of the present invention, the pH value of the solid-liquid mixture during the filtering and washing in the step S6 is 5-7.

The present invention also provides a graphene-loaded white carbon black composite material prepared by the above method.

The present invention further provides the application of a graphene-loaded white carbon black composite material as a rubber filler.

In the composite material prepared by the method of the invention, the white carbon black is attached to the surface of the graphene, so that the low heat generation performance of the white carbon black can be exerted, and the sheet-like graphene can be separated to prevent secondary agglomeration in the rubber. Compared with the rubber compound prepared by directly adding graphene and white carbon black to rubber, the composite material has better processing performance and significantly improved fluidization mechanical properties, which can improve the compression heat generation and Mechanical properties, especially for tire rubber. Moreover, in the method of the present invention, the production route for preparing white carbon black by the existing precipitation method is basically not changed, the equipment modification is small, the production cost will not increase, and the process is simple and the economic value is high.

Description of drawings

Fig. 1 is a schematic diagram of the structure of graphene-supported silica of the present invention.

2 is a scanning electron micrograph of graphene-loaded silica prepared in Example 1.

Detailed ways

The technical solutions of the present invention will be further described below through specific examples. It should be clear to those skilled in the art that the embodiments are only for helping to understand the present invention, and should not be regarded as specific limitations on the present invention.

The preparation method of the graphene-supported silica composite material of the present invention comprises: S1, dissolving sodium silicate in water to prepare a sodium silicate solution; S2, dispersing graphene oxide in water to prepare graphene oxide dispersion solution; S3, the graphene oxide dispersion was added to the sodium silicate solution, and then dispersed to form a mixed solution of graphene oxide and sodium silicate; S4, the mixed solution of graphene oxide and sodium silicate was added dropwise In the ammonium bicarbonate solution, continuously stir during the dropping process; S5, adding the reducing agent to the mixed solution obtained in the S4 step; S6, filter the reacted mixed solution in the S5 step to obtain a solid mixture, and Washing and drying the solid mixture; and S7, subjecting the dried solid mixture to high-temperature treatment, the temperature of the high-temperature treatment is 200-800°C, preferably 260°C, and the time of high-temperature treatment is 1-6h, preferably 2h.

In step S1, the concentration of the sodium silicate solution is 1-10 wt%. If the concentration of sodium silicate solution is too low (less than 1wt%), then the efficiency of the follow-up reaction is lower; if the concentration is too high (higher than 10wt%), sodium silicate can not react completely in the follow-up reaction, resulting in unnecessary waste. An appropriate concentration range can be selected according to specific conditions, such as but not limited to 1wt%, 3wt%, 5wt%, 7wt%, 9wt%, 10wt%, etc. The preferred concentration of sodium silicate is 5 wt%.

In step S2, the concentration of the graphene oxide dispersion liquid is 0.1-2 wt%. If the concentration of graphene oxide in the dispersion is lower than 0.1wt%, the subsequent reaction efficiency will be low; if the concentration is higher than 2wt%, the graphene oxide will not completely react in the subsequent reaction, resulting in unnecessary waste. Preferably, the concentration of graphene oxide in the dispersion is 1 wt%. The sheet diameter of the graphene oxide in the dispersion liquid is 2-15 microns. The sheet diameter of graphene oxide is greater than 15 microns thick, and the dispersion effect is not good; but the sheet diameter of graphene oxide can be lower, but based on cost considerations, the sheet diameter of graphene oxide in the dispersion is selected to be more than 2 microns. The sheet thickness of the graphene oxide in the dispersion liquid is 0.7-10 nanometers. If the thickness of the sheet is greater than 10 nanometers, the number of layers of graphene oxide will be more, so the strengthening effect will not be achieved. Graphene oxide below 0.7 nanometers can still achieve the purpose of the present invention, but the cost is too high. Based on cost considerations, the sheet thickness of graphene oxide is preferably more than 0.7 nanometers. Those skilled in the art can choose any value in the above range according to actual needs, such as but not limited to 1 nanometer, 2 nanometers, 3 nanometers, 4 nanometers, 5nm, 6nm, 7nm, 8nm, 9nm, 10nm, etc. Also can choose the graphene of specific sheet, for example 2 layers, 3 layers, 4 layers, 5 layers, 6 layers, 7 layers, 8 layers, 9 layers, 10 layers, 11 layers, 12 layers, 13 layers, 14 layers, 15th floor, 16th floor, 17th floor, 18th floor, 19th floor, 20th floor, etc. The oxygen content of the graphene oxide in the dispersion liquid is 20-60 wt%. When the oxygen content in graphene oxide is lower than 20wt%, its dispersibility in the dispersion liquid is not good; if the oxygen content in graphene oxide is too high, the price is higher, and it cannot be realized technically, so graphite oxide is preferred The amount of olefin oxidation is between 20wt% and 60wt%. Those skilled in the art can select any value within the above range according to actual needs, such as but not limited to 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt% and so on.

In step S3, the mass ratio of graphene oxide to sodium silicate is 0.1-10:100. When the mass ratio of graphene oxide to sodium silicate is lower than 0.1:100, the content of graphene in the composite material is too low, and the strengthening effect of graphene is not obvious; if the mass ratio of graphene oxide to sodium silicate is higher than 1: When the value is 100, the graphene cannot be fully dispersed in the process of forming the composite material, and the performance of the composite material will also be reduced. Those skilled in the art can choose any value within the above range according to actual needs, such as but not limited to 0.1:100, 0.2:100, 0.3:100, 0.4:100, 0.5:100, 0.6:100, 0.7:100, 0.8 :100, 0.9:100, 1:100, 1.5:100, 2:100, 2.5:100, 3:100, 3.5:100, 4:100, 4.5:100, 5:100, 5.5:100, 6:100 , 6.5:100, 7:100, 7.5:100, 8:100, 8.5:100, 9:100, 9.5:100, 10:100, etc.

The concentration of ammonium bicarbonate in step S4 is 1-10wt%. When the concentration of ammonium bicarbonate is lower than 1wt%, the follow-up reaction will be incomplete; when the concentration of ammonium bicarbonate in the solution is higher than 10wt%, the graphene oxide in the solution will be agglomerated. Therefore, the concentration of ammonium bicarbonate can be selected from any value in the above range, such as but not limited to 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt% wait. The quality of the ammonium bicarbonate solution is calculated based on the molar mass of sodium silicate contained in the sodium silicate solution, and the molar ratio of ammonium bicarbonate to sodium silicate is 2.0-3.0:1. When the molar ratio of ammonium bicarbonate to sodium silicate is lower than 2.0:1, the reaction is incomplete; when the molar ratio of ammonium bicarbonate to sodium silicate is higher than 3.0:1, excess ammonium bisilicate leads to waste.

Graphene oxide is initially reduced in step S5. The reducing agent is selected from one or more of vitamin C, hydrazine hydrate, sodium borohydride, hydrogen, ammonia, vitamin C, potassium hydroxide, sodium oxide, dimethylhydrazine, p-diphenone, hydroiodic acid, and phenylhydrazine. Several kinds. When the reducing agent is vitamin C, the mass ratio of vitamin C to graphene oxide is 0.5-3:1. The temperature at which vitamin C reduces graphene oxide is 50-90°C, preferably 80°C. The time for vitamin C to reduce graphene oxide is 0.5-4 hours, preferably 1 hour. The above reaction conditions are the preferred parameters for the reaction between vitamin C and graphene oxide. When selecting other reducing agents, those skilled in the art can select an appropriate mass ratio, reaction temperature, time, etc. according to the type of reducing agent.

The pH value of the solid-liquid mixture when filtering and washing in step S6 is 5-7. Filtration can be suction filtration. The suction filtration process may be that the mixed solution after the reaction in step S5 is processed to obtain a solid mixture, and the filter cake is added to excess water again, and while stirring, dilute hydrochloric acid is added dropwise to adjust the pH value to 5-7. Excess water is 5 to 20 times the quality of the filter cake. The molar mass of dilute hydrochloric acid is 0.1-2 mol/L. Dilute hydrochloric acid can use one or more of dilute sulfuric acid, dilute nitric acid, and acetic acid. The purpose of the above steps is to clean the solid mixture, and dry the solid mixture after cleaning. The drying process can be one or more of blast drying, vacuum drying and freeze drying. When blast drying is used, the drying temperature is 60-120°C, preferably 80°C. The drying time is 2h-10h, preferably 6h. It can also be spray-dried. During spray-drying, the pH value of the solution containing the solid mixture can be adjusted between 5 and 7, and then the mixed solution can be directly spray-dried. The drying temperature of the spray drying is 100 to 200°C, preferably 150°C.

In step S7, the dried solid mixture is subjected to high temperature treatment. Graphene oxide will be further reduced during high temperature treatment. The temperature of the high temperature treatment is 200-800°C. Graphene will be decomposed if the temperature of high temperature treatment is higher than 800°C, and the temperature below 200°C cannot completely remove moisture from silica. Preferably it is 260°C. The high-temperature treatment time is 1-6 hours. If the treatment time is too long, the graphene is easy to decompose, and if the treatment time is too short, the moisture in the white carbon black cannot be completely removed.

The invention also discloses a graphene-loaded white carbon black composite material prepared by the method. The microscopic schematic diagram of the graphene-supported silica composite material prepared by the method of the present invention is shown in FIG. 1 , that is, the silica particles 2 are supported on the surface of the graphene sheet 1 . Therefore, in addition to the low heat generation performance of silica, it can also separate the sheet-shaped graphene and prevent its secondary agglomeration in rubber. The graphene-loaded silica composite material prepared by the above method can be used as a rubber filler. Compared with the rubber compound prepared by directly adding graphene and white carbon black to rubber, the composite material has better processing performance and significantly improved fluidization mechanical properties, which can improve the compression heat generation and Mechanical properties, especially for tire rubber. Moreover, in the method of the present invention, the production route for preparing white carbon black by the existing precipitation method is basically not changed, the equipment modification is small, the production cost will not increase, and the process is simple and the economic value is high.

Example 1

(1) Add water in the reactor, use oil bath heating to control the temperature of water to be 80°C, add powdered instant sodium silicate, and prepare the concentration of sodium silicate solution to be 5wt%, wherein, configure the sodium silicate solution Throughout the process, the temperature was maintained at 80°C.

(2) Take 2% graphene oxide of the mass of sodium silicate, add it into deionized water, and stir at high speed for 2 hours. Among them, the graphene oxide has 10 layers, the sheet diameter is 2 microns, and the oxygen content is 30wt%.

(3) The treated graphene oxide is dispersed into the sodium silicate solution, and the mixed solution is homogenized using a high-pressure homogenizer, the homogenization pressure is 800 bar, and the homogenization time is 1 h.

(4) Add ammonium bicarbonate into water and heat to 30°C to prepare a 2.4mol/L ammonium bicarbonate solution.

(5) Add the prepared mixed solution of graphene oxide and sodium silicate dropwise into the ammonium bicarbonate solution using a peristaltic pump, and keep stirring.

(6) Add 1 wt% vitamin C aqueous solution to the reactant in step (5), heat the oil bath to 80° C., and react for 1 h.

(7) Suction filter the product of step (6), add excess water to the filter cake, stir until completely dispersed, and adjust the pH value to 7 with 1 mol/L dilute hydrochloric acid.

(8) Suction filter the mixture with adjusted pH value, and dry the filter cake at 80° C. for 6 hours in a blast drying oven.

(9) Treat the dried solid at a high temperature of 260°C for 2 hours to obtain a graphene-supported silica material.

Example 2

Except that the quality of the graphene oxide of step (2) is 4wt% of sodium silicate quality, other steps are identical with embodiment 1.

Example 3

(1) Add water in the reactor, use oil bath heating to control the temperature of water to be 80°C, add powdered instant sodium silicate, and prepare the concentration of sodium silicate solution to be 5wt%, wherein, configure the sodium silicate solution Throughout the process, the temperature was maintained at 80°C.

(2) Take 2 wt% graphene oxide based on the mass of sodium silicate, add it into deionized water, and stir at high speed for 2 hours. Among them, the graphene oxide has 10 layers, the sheet diameter is 2 microns, and the oxygen content is 30wt%.

(3) Dispersing the treated graphene oxide into the sodium silicate solution, and stirring the mixed solution for 2 hours at a speed of 3000 r/min.

(4) Add ammonium bicarbonate into water and heat to 30°C to prepare a 2.4mol/L ammonium bicarbonate solution.

(5) Add the prepared mixed solution of graphene oxide and sodium silicate dropwise into the ammonium bicarbonate solution using a peristaltic pump, and keep stirring.

(6) Add 1 wt% vitamin C aqueous solution to the reactant in step (5), heat the oil bath to 60° C., react for 3 hours, and then adjust the pH value to 7 with dilute hydrochloric acid.

(7) Spray-dry the mixture with adjusted pH value, and the drying temperature is 120°C.

(8) Treat the dried solid at 400° C. for 2 hours at a high temperature to obtain a graphene-loaded silica material.

Example 4

Except that the quality of the graphene oxide of step (2) is 4wt% of sodium silicate quality, other steps are identical with embodiment 3.

Comparative example 1

This comparative example refers to Example 1, the difference is that there are no steps (2) and (3).

Comparative example 2

This comparative example refers to Example 1, and the difference is: without steps (2) and (3), step (8) is carried out after getting 2wt% graphene oxide of sodium silicate quality and the solid obtained in step (7) directly mixed.

Comparative example 3

This comparative example refers to Example 3, the difference is that there are no steps (2) and (3).

Comparative example 4

This comparative example refers to Example 3, the difference is: without steps (2) and (3), step (8) is carried out after getting 2wt% graphene oxide of sodium silicate quality and the solid obtained in step (7) directly mixed.

The composite material prepared in Example 1 was scanned by an electron microscope, and the photo is shown in FIG. 2 . It can be seen from Figure 2 that silica is supported on the surface of graphene sheets. It can thus be proved that the method of the present invention can indeed support the silica on the surface of the graphene sheet, so as to fully utilize the low heat generation performance of the silica and prevent the agglomeration of graphene.

The composite materials prepared in Examples 1-4 and Comparative Examples 1-4 were used to prepare rubber mixes, and the prepared rubber mixes were tested.

The preparation method is as follows:

The formula is: smoked sheet rubber (3#), 70g; butadiene rubber (BR9000), 30g, graphene-loaded silica, 100g; silicon 69, 1g; zinc oxide, 5g; stearic acid, 2g; RD), 3.5g; antioxidant (4020), 2g; microcrystalline wax, 1g; accelerator (D), 2.1g; accelerator (CZ) 2g; sulfur, 4g.

The recipe is prepared as follows:

(1) Adjust the roller distance to 1mm, add smoked sheet rubber and butadiene rubber, then wrap the rubber on the roller without wrapping the roller to break the rubber once, and then wrap the rubber on the roller.

(2) Add sulfur evenly and slowly. When the sulfur is mixed, alternately make 3/4 cutting knives from both ends of the roller every 20s, and cut 6 knives (alternating knives are regarded as one knife). The operation time is 4min.

(3) Add zinc oxide evenly, make a 3/4 cutter alternately from both ends of the roller every 20s, and cut 2 knives. The operation time is 1.5min.

(4) Add stearic acid evenly, make 3/4 cutters alternately from both ends of the roller every 20s, and cut 2 knives. The operation time is 1.5min.

(5) Add 1/3 white carbon black, make a 3/4 cutting knife alternately from both ends of the roller every 20s, and cut 4 knives. The operation time is 5 minutes.

(6) Add 1/3 white carbon black, make a 3/4 cutting knife alternately from both ends of the roller every 20s, and cut 4 knives. The operation time is 5 minutes.

(7) After adding 1/3 white carbon black, add the active agent PEG4000, make 3/4 cutting knife alternately from both ends of the roller every 20s, and cut 6 knives. The operation time is 8.5min.

(8) Slowly cover the accelerator evenly on the rubber and add. When all the materials are mixed in, make a 3/4 cutter alternately from both ends of the roller every 20s, cut 4 times, and the operation time is 3.5 minutes.

(9) Cut off the film from the rubber mixing machine, and wrap it in 3 triangular bags. The operation time is 1.5min.

(10) Cut the film from the rubber mixing machine, adjust the roller distance to 2mm, and pass the rubber material through the roller 3 times for 1 minute without wrapping the roller.

(11) Cut off the rubber material from the film, the total operation time: 31.5min.

(12) Take off the film and mark it according to the film output direction.

After the rubber is placed at room temperature for 24 hours, relevant processing performance and mechanical performance tests can be carried out. The test results are shown in Table 1:

Table 1 Changes in processability and mechanical properties of graphene-loaded silica rubber with reaction conditions

The vulcanization time T90 means: the time required for the rubber material to rise to 90% of the maximum torque from the beginning of heating, and m:s represents the time in minutes and seconds.

Based on the results of the above examples and comparative examples, it can be seen that the silica obtained by the method of the present invention has excellent processing performance in tire rubber, and the mechanical properties of the vulcanized rubber are also significantly improved. The method provided by the invention is simple in technique, does not need to increase the use of silane coupling agent or other additives, does not increase the production cost, and has good technical economy. Comparative example does not adopt the scheme of the present invention, thereby can't obtain the excellent effect of the present invention.

The applicant declares that the present invention illustrates the detailed methods of the present invention through the above-mentioned examples, but the present invention is not limited to the above-mentioned detailed methods, that is, it does not mean that the present invention must rely on the above-mentioned detailed methods to be implemented. Those skilled in the art should understand that any improvement of the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the scope of protection and disclosure of the present invention. The present invention is further described below by specific examples. However, these examples are only exemplary and do not constitute any limitation to the protection scope of the present invention.

Claims (10)

1. a preparation method of graphene-loaded white carbon black composite material, is characterized in that, comprises: S1, dissolving sodium silicate in water to prepare a sodium silicate solution; S2, dispersing graphene oxide in water to prepare a graphene oxide dispersion; S3, adding the graphene oxide dispersion into the sodium silicate solution, and then performing dispersion treatment to form a mixed solution of graphene oxide and sodium silicate; S4, adding the mixed solution of the graphene oxide and sodium silicate dropwise into the ammonium bicarbonate solution, and continuously stirring during the dropping process; S5, adding a reducing agent to the mixed solution obtained in the step S4; S6, filtering the mixed solution after the reaction in the step S5 to obtain a solid mixture, and washing and drying the solid mixture; and S7, subjecting the dried solid mixture to high-temperature treatment, the temperature of the high-temperature treatment is 200-800° C., preferably 260° C., and the time of the high-temperature treatment is 1-6 hours, preferably 2 hours. 2. The preparation method according to claim 1, characterized in that, in the step S1, the concentration of the sodium silicate solution is 1 to 10 wt%, preferably 5 wt%. 3. preparation method according to claim 1, is characterized in that, the concentration of described graphene oxide dispersion liquid in described S2 step is 0.1～2wt%, is preferably 1wt%; Preferably, the concentration of described graphene oxide The sheet diameter is 2-15 microns, and the sheet thickness of the graphene oxide is 0.7-10 nm; preferably, the oxygen content of the graphene oxide is 20-60 wt%. 4. The preparation method according to claim 1, characterized in that, in the step S3, the mass ratio of the graphene oxide to the sodium silicate is 0.1-10:100. 5. preparation method according to claim 1, is characterized in that, the concentration of described ammonium bicarbonate in described S4 step is 1～10wt%; The mol ratio of described ammonium bicarbonate and described sodium silicate is 2.0～3.0:1. 6. The preparation method according to claim 1, wherein, in the S5 step, the reducing agent is selected from vitamin C, hydrazine hydrate, sodium borohydride, hydrogen, ammonia, vitamin C, potassium hydroxide, One or more of sodium oxide, dimethylhydrazine, p-diphenone, hydroiodic acid, and phenylhydrazine. 7. The preparation method according to claim 6, wherein the reducing agent is vitamin C, and the mass ratio of the vitamin C to the graphene oxide is 0.5 to 3:1; the vitamin C reduces and oxidizes The temperature of the graphene is 50-90°C, preferably 80°C; the time for the vitamin C to reduce the graphene oxide is 0.5-4h, preferably 1h. 8. The preparation method according to claim 1, characterized in that, in the step S6, the pH value of the solid-liquid mixture during the filtering and the washing is 5-7. 9. A graphene-loaded white carbon black composite material, characterized in that, said composite material is prepared by any one of claims 1-8. 10. the application of the graphene-loaded silica composite material as claimed in claim 9 as a rubber filler.

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