Rubber filler, rubber composite material containing the same, method for producing the same, and use thereof

Abstract

The present invention discloses a rubber filler, a rubber composite material containing the same, a method for manufacturing the same, and uses thereof. The rubber filler includes polydivinylbenzene microspheres and polydopamine-modified white carbon black supported on the polydivinylbenzene microspheres, and the mass ratio of the polydivinylbenzene microspheres to the polydopamine-modified white carbon black is 1:0.5 to 20. The rubber composite material includes solution-polymerized raw rubber and the rubber filler, and the addition amount of the rubber filler is 10 to 60 wt% of the mass (dry weight basis) of the solution-polymerized raw rubber. The present invention solves the problems that white carbon black is prone to agglomeration and the bonding force between white carbon black and rubber is low by using polydivinylbenzene microspheres loaded with polydopamine-modified white carbon black as a filler. The rubber composite material obtained in the present invention is suitable for the manufacture of green tires.

Description

Cross - reference to related applications

[0001] This application claims the benefit of Chinese Patent Application No. 202310700409.3, filed on June 13, 2023, the content of which is incorporated herein by reference.

Technical Field

[0002] The present invention relates to the technical field of rubber materials, and specifically to rubber fillers, rubber composites containing the same, manufacturing methods thereof, and uses.

Background Art

[0003] Green tires (or fuel - saving tires) aim to save fuel and reduce exhaust gas emissions, and can significantly reduce energy consumption compared to ordinary radial tires. Solution - polymerized styrene - butadiene rubber is more environmentally friendly than general - purpose emulsion - polymerized styrene - butadiene rubber, can control and adjust a fine molecular structure as needed during the synthesis process, and can improve the rolling resistance coefficient and wet grip index of tires. It is predicted that the application of solution - polymerized styrene - butadiene rubber in the tire industry will surely progress rapidly in the next few years. Cis - butadiene rubber, isoprene rubber, and butyl rubber are also manufactured using the solution - polymerization process and are used in the tire industry.

[0004] Currently, the most widely used filler is carbon black. However, with the improvement of environmental protection requirements, white carbon black is gradually replacing carbon black as the most commonly used filler. The white carbon black / solution - polymerized styrene - butadiene rubber compounding system is a common compounding system for manufacturing high - performance green tire tread rubber. However, white carbon black has a small particle size, high surface polarity, and low compatibility with rubber, so it is prone to agglomeration and difficult to disperse. Therefore, white carbon black requires surface modification, and the filler surface modifiers commonly used in the prior art include titanate coupling agents and silane coupling agents.

[0005] CN101798473A discloses modifying white carbon black using a polysulfide silane coupling agent and then manufacturing a white carbon black / carbon black composite filler. However, increasing the usage amount of the silane coupling agent will reduce the vulcanization reaction kinetics, so it is necessary to supplement additional vulcanizing agent and vulcanization accelerator.

[0006] CN101220177A discloses a method for manufacturing a white carbon black / solution-polymerized styrene-butadiene rubber nanocomposite using amino-based silane coupling agent-modified white carbon black. The nano white carbon black and the silane coupling agent are dispersed in ethanol and subjected to a condensation reaction at high temperature. Then, the modified nano white carbon black powder is added to the solution-polymerized styrene-butadiene rubber solution, stirred and dispersed, the solvent is removed, dried, and a white carbon black / solution-polymerized styrene-butadiene rubber nanocomposite manufactured by the co-precipitation method is obtained. However, low molecular weight surface modifiers have disadvantages such as poor processing performance, generation of low molecular weight substances during the modification process, low storage stability, and affecting the service life of tires, and cannot solve the problem of low bonding strength between white carbon black and rubber.

Summary of the Invention

Problems to be Solved by the Invention

[0007] The object of the present invention is to provide a rubber composite material, a manufacturing method thereof, and a use thereof in order to solve the problems of the prior art such as the easy aggregation of white carbon black and the low bonding strength between white carbon black and rubber. The rubber composite material of the present invention uses polydopamine-modified white carbon black supported on polydivinylbenzene microspheres as a filler and polydivinylbenzene microspheres as a carrier, thereby further effectively improving the dispersibility of white carbon black. In addition, the polydivinylbenzene microspheres also play a role in physically intertwining cross-linking points and acting with the blend rubber through vulcanization cross-linking, thereby improving the physical and mechanical properties of the material. The rubber composite material can be used in the manufacture of green tires.

Means for Solving the Problems

[0008] In order to achieve the above object, a first aspect of the present invention provides a rubber filler including polydivinylbenzene microspheres and polydopamine-modified white carbon black supported on the polydivinylbenzene microspheres, wherein the mass ratio of the polydivinylbenzene microspheres to the polydopamine-modified white carbon black is 1:0.5 to 20.

[0009] A second aspect of the present invention is Step (1) of performing a first reaction between white carbon black and dopamine in a first buffer solution to obtain polydopamine-modified white carbon black, and Step (2) of performing a second reaction between polydivinylbenzene microspheres and the polydopamine-modified white carbon black obtained in step (1) in a second buffer solution to obtain polydivinylbenzene microspheres supporting polydopamine-modified white carbon black, including A manufacturing method of a rubber filler, wherein the mass ratio of the polydivinylbenzene microspheres to the polydopamine-modified white carbon black is 1:0.5 to 20.

[0010] A third aspect of the present invention provides a rubber composite material including a solution-polymerized raw rubber, a first filler, and a second filler, wherein the first filler is a rubber filler produced by the rubber filler of the aforementioned first aspect and the production method of the aforementioned second aspect, the second filler is polydopamine-modified white carbon black, and the total addition amount of the first rubber filler and the second rubber filler is 10 to 60 wt% of the mass (dry weight basis) of the solution-polymerized raw rubber.

[0011] A fourth aspect of the present invention provides a method for manufacturing a rubber composite material, including the steps of kneading a solution-polymerized raw rubber with a first filler and a second filler, and then vulcanizing to obtain the rubber composite material, wherein the first filler is a rubber filler produced by the rubber filler of the aforementioned first aspect and the production method of the aforementioned second aspect, the second filler is polydopamine-modified white carbon black, and the total addition amount of the first rubber filler and the second rubber filler is 10 to 60 wt% of the mass (dry weight basis) of the solution-polymerized raw rubber.

[0012] A fifth aspect of the present invention provides the use of the aforementioned rubber composite material in a tire or a rubber composite material produced by the aforementioned production method.

Advantages of the Invention

[0013] The beneficial technical effects obtained by the present invention through the above technical solutions are as follows. (1) The rubber filler of the present invention is a polydivinylbenzene microsphere carrying polydopamine-modified white carbon black. By modifying white carbon black with polydopamine, the aggregation of white carbon black itself is prevented, and the dispersibility of white carbon black is improved. Further, by using polydivinylbenzene microspheres as a carrier, the dispersibility of white carbon black is more effectively improved. (2) The rubber filler of the present invention can be used in the production of rubber composites. The polydivinylbenzene microspheres also play a role in physically intertwining crosslinking points. When a vulcanizing agent is added for vulcanization, the microsphere filler can effectively improve the physical and mechanical properties of the material by acting with the blend rubber through vulcanization crosslinking. In addition, the catecholamine structure in polydopamine has high affinity and can closely combine with the rubber to improve the mechanical strength of white carbon black / rubber. The rubber composite obtained by the present invention is suitable for the production of green tires. (3) The production method of the present invention has few steps and simple operations, and solves the problems that white carbon black is prone to aggregation and the bonding force between white carbon black and rubber is low.

Brief Description of the Drawings

[0014]

Figure 1

Embodiments for Carrying out the Invention

[0015] The endpoints and any values within the ranges disclosed in this specification are not limited to precise ranges or values, and these ranges or values should be understood to include values close to these ranges or values. In the case of numerical ranges, new numerical ranges can be obtained by combining between the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values, and these numerical ranges should be regarded as specifically disclosed in this specification.

[0016] The first aspect of the present invention provides a rubber filler comprising polydivinylbenzene microspheres and polydopamine-modified white carbon black supported on the polydivinylbenzene microspheres, wherein the mass ratio of the polydivinylbenzene microspheres to the polydopamine-modified white carbon black is 1:0.5 to 20, for example, 1:0.5, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:12, 1:14, 1:16, 1:18, 1:20, and any value within the range consisting of any two of these values, preferably 1:1 to 10.

[0017] The polydivinylbenzene microspheres used in the present invention have strong adsorption power and mainly serve as a carrier. In the present invention, the polydopamine-modified white carbon black is not limited to a specific loading form as long as it can be supported on the polydivinylbenzene microspheres. When the polydopamine-modified white carbon black is supported on the polydivinylbenzene microspheres (DVB), it may be supported on the surface of the polydivinylbenzene microspheres, may be supported in the internal channels of the polydivinylbenzene microspheres, or both situations may exist. Studies have shown that the polydopamine-modified white carbon black mainly accumulates and adheres to the surface of the microspheres.

[0018] In the present invention, by modifying white carbon black with polydopamine, aggregation of the white carbon black itself is prevented, and the dispersibility of the white carbon black is improved. The catecholamine structure in polydopamine has high affinity and can be closely combined with rubber to improve the mechanical strength of the white carbon black / rubber. Further, by using polydivinylbenzene microspheres as a carrier, the dispersibility of the white carbon black can be more effectively improved. The microspheres have good compatibility with rubber and strong adsorption capacity, and are suitable as a supported filler. When the polydivinylbenzene microspheres are used in the manufacturing process of rubber composites, they also play a role in physically entangling crosslinking points and acting on the blend rubber through physical crosslinking, so that the physical and mechanical properties of the material can be effectively improved, and it is suitable for the manufacture of green tires.

[0019] In some embodiments of the present invention, in the polydopamine-modified white carbon black, the mass ratio of the white carbon black to the polydopamine is 1:0.05 to 1, for example, 1:0.05, 1:0.08, 1:0.1, 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, and any value within the range consisting of any two values, preferably 1:0.1 to 0.6.

[0020] In some embodiments of the present invention, the particle size of the polydivinylbenzene microspheres is 0.1 to 1 μm, for example, 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, and any value within the range consisting of any two values, preferably 0.2 to 0.5 μm.

[0021] In some embodiments of the present invention, the particle size of the white carbon black is 20 to 60 nm, for example, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, and any value within the range consisting of any two values, preferably 30 to 50 nm.

[0022] The second aspect of the present invention is performing a first reaction between white carbon black and dopamine in a first buffer solution to obtain polydopamine-modified white carbon black in step (1); performing a second reaction between polydivinylbenzene microspheres and the polydopamine-modified white carbon black obtained in step (1) in a second buffer solution to obtain polydivinylbenzene microspheres carrying polydopamine-modified white carbon black in step (2), wherein the mass ratio of the polydivinylbenzene microspheres to the polydopamine-modified white carbon black is 1:0.5 to 20, for example, 1:0.5, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:12, 1:14, 1:16, 1:18, 1:20, and any value within the range consisting of any two values, preferably 1:1 to 10, and providing a method for producing a rubber filler.

[0023] As shown in FIG. 1, curve a is the infrared spectrum of white carbon black, curve b is the infrared spectrum of polydopamine-modified white carbon black, and curve c is the infrared spectrum of divinylbenzene microspheres carrying polydopamine-modified white carbon black. Here, in curve a, an asymmetric stretching vibration absorption peak of Si-O-Si appears at a wave number of 1099 cm -1 and a symmetric stretching vibration absorption peak of Si-O-Si appears at a wave number of 804 cm -1 and a bending vibration absorption peak of Si-O-Si appears at a wave number of 465 cm -1 . In curve b, a weak absorption peak of the benzene ring (1600 - 1450 cm -1 ) appears, which is considered to be attributed to the absorption of the benzene ring of polydopamine. In curve c, due to the phenolic hydroxyl group and N-H bond of polydopamine after loading, the absorption peak around 3450 cm -1 becomes broad and large, indicating that the polydopamine-modified white carbon black is well supported on the polydivinylbenzene microspheres.

[0024] In some embodiments of the present invention, step (1) specifically includes: adding an inorganic acid or an inorganic alkali to a weakly alkaline buffer solution to obtain a first buffer solution with a buffer concentration of 3 to 15 mmol / L and a pH of 7.5 to 10.5; adding white carbon black and dopamine to the first buffer solution, reacting at room temperature for 0.5 to 2 h, then filtering, washing and drying to obtain polydopamine-modified white carbon black.

[0025] In the present invention, in the modification process using white carbon black, dry white carbon black is used. As the dry white carbon black, drying by general techniques in the art may be used. For example, white carbon black is baked at 100 to 120 °C in a vacuum.

[0026] Furthermore, the mass ratio of white carbon black to dopamine is 1:0.05 to 1, for example, 1:0.05, 1:0.08, 1:0.1, 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, and any value within the range consisting of any two values, preferably 1:0.1 to 0.6.

[0027] Furthermore, the mass ratio of white carbon black to the first buffer solution is 1:5 to 50, for example, 1:5, 1:10, 1:15, 1:20, 1:25, 1:30, 1:40, 1:45, 1:50, and any value within the range consisting of any two values, preferably 1:10 to 40.

[0028] Furthermore, the weakly alkaline buffer is selected from one or more of tris(hydroxymethyl)aminomethane, barbital, barbital-sodium chloride composite buffer, boric acid-potassium chloride composite buffer, borax-calcium chloride composite buffer, disodium hydrogen phosphate, and potassium hydrogen phosphate-potassium dihydrogen phosphate composite buffer, preferably tris(hydroxymethyl)aminomethane or barbital.

[0029] Furthermore, the inorganic acid is one or more of hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid.

[0030] Furthermore, the inorganic alkali is potassium hydroxide and / or sodium hydroxide.

[0031] In some embodiments of the present invention, step (2) specifically comprises: adding an inorganic acid or an inorganic alkali to a weakly alkaline buffer solution to obtain a second buffer solution with a buffer concentration of 3 to 15 mmol / L and a pH of 7.5 to 10.5; and adding the polydivinylbenzene microspheres and the polydopamine-modified white carbon black obtained in step (1) to the second buffer solution, magnetically stirring at room temperature for 1 to 4 h for reaction, then filtering, washing, and drying to obtain polydivinylbenzene microspheres supporting polydopamine-modified white carbon black.

[0032] Furthermore, the mass ratio of the polydivinylbenzene microspheres to the second buffer solution is 1:50 to 500, such as 1:50, 1:100, 1:150, 1:200, 1:250, 1:300, 1:400, 1:450, 1:500, and any value within the range consisting of any two values, preferably 1:100 to 400.

[0033] Furthermore, the weakly alkaline buffer is selected from one or more of tris(hydroxymethyl)aminomethane, barbital, barbital-sodium chloride composite buffer, boric acid-potassium chloride composite buffer, borax-calcium chloride composite buffer, disodium hydrogen phosphate, and dipotassium hydrogen phosphate-potassium dihydrogen phosphate composite buffer, preferably tris(hydroxymethyl)aminomethane or barbital.

[0034] Furthermore, the inorganic acid is one or more of hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid.

[0035] Furthermore, the inorganic alkali is potassium hydroxide and / or sodium hydroxide.

[0036] The third aspect of the present invention provides a rubber composite material including a solution-polymerized raw rubber, a first filler, and a second filler, wherein the first filler is a rubber filler of the first aspect described above and a rubber filler manufactured by the manufacturing method of the second aspect described above, the second filler is polydopamine-modified white carbon black, and the total addition amount of the first rubber filler and the second rubber filler is 10 to 60 wt% of the mass (dry weight basis) of the solution-polymerized raw rubber, for example, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, and any value within the range composed of any two values, preferably 20 to 40 wt%.

[0037] In some embodiments of the present invention, the mass ratio of the first filler to the second filler is 1:0.5 to 20, for example, 1:0.5, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:12, 1:14, 1:16, 1:18, 1:20, and any value within the range composed of any two values, preferably 1:1 to 10.

[0038] In some embodiments of the present invention, the addition amount of the second rubber filler is 10 to 40 wt% of the mass (dry weight basis) of the solution-polymerized raw rubber, for example, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, and any value within the range composed of any two values, preferably 20 to 30 wt%.

[0039] In some embodiments of the present invention, the rubber composite material further includes an auxiliary agent.

[0040] Furthermore, the auxiliary agent is one or more selected from a vulcanizing agent, an antioxidant, an accelerator, and an activator.

[0041] In the present invention, the types, functions, and addition amounts of the auxiliaries are well-known to those skilled in the art. For example, there are descriptions related to "Practical Rubber Compounding Technology", so they will not be described in detail here.

[0042] In some embodiments of the present invention, the solution-polymerized raw rubber is one or more selected from solution-polymerized styrene-butadiene rubber, isoprene rubber, cis-butadiene rubber, and butyl rubber.

[0043] Furthermore, the solution-polymerized styrene-butadiene rubber has a number-average molecular weight Mn of 100,000 to 400,000 g / mol and a vinyl content of 30 to 70 wt% before coupling.

[0044] Furthermore, the isoprene rubber has a weight-average molecular weight Mw of 150,000 to 300,000 g / mol.

[0045] Furthermore, the cis-butadiene rubber has a weight-average molecular weight Mw of 200,000 to 300,000 g / mol.

[0046] Furthermore, the butyl rubber has a weight-average molecular weight Mw of 100,000 to 500,000 g / mol.

[0047] The fourth aspect of the present invention is A step of kneading a solution-polymerized raw rubber with a first filler and a second filler, and then vulcanizing to obtain a rubber composite material. The first filler is the rubber filler of the aforementioned first aspect and the rubber filler manufactured by the manufacturing method of the aforementioned second aspect. The second filler is polydopamine-modified white carbon black. The total addition amount of the first rubber filler and the second rubber filler is 10 to 60 wt% of the mass (dry weight basis) of the solution-polymerized raw rubber, for example, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, and any value within the range composed of any two values, preferably 20 to 40 wt%. A manufacturing method of a rubber composite material is provided.

[0048] In the present invention, by using polydivinylbenzene microspheres carrying polydopamine-modified white carbon black as the first rubber filler, aggregation of the white carbon black itself is prevented, the dispersibility and stability of the white carbon black are improved, and by modifying the white carbon black with polydopamine, aggregation of the white carbon black itself is also prevented, the dispersibility of the white carbon black is improved, and the mechanical strength of the white carbon black / rubber can also be improved. In the production process of the rubber composite material, the polydivinylbenzene microspheres also play a role in physically entangling the crosslinking points and acting with the blend rubber through physical crosslinking, thereby effectively improving the physical and mechanical properties of the material, mainly improving the strength, hardness, and wear resistance of the rubber material. There is a synergistic effect between these two rubber fillers. By using the polydivinylbenzene microspheres as a carrier, the dopamine-modified white carbon black can be more effectively dispersed and the stability can be improved, effectively improving the overall performance of the material compared to a single filler, and the resulting rubber composite material is suitable for the production of green tires.

[0049] In the present invention, for rubber kneading, ordinary kneading methods, such as kneading by an open roll and kneading by a closed kneader, may be used.

[0050] In some embodiments of the present invention, the mass ratio of the first filler to the second filler is 1:0.5 to 20, for example, 1:0.5, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:12, 1:14, 1:16, 1:18, 1:20, and any value within the range consisting of any two values, preferably 1:1 to 10.

[0051] In some embodiments of the present invention, the addition amount of the second rubber filler is 10 to 40 wt%, for example, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, and any value within the range consisting of any two values, preferably 20 to 30 wt%, based on the mass (dry weight basis) of the solution-polymerized raw rubber.

[0052] In some embodiments of the present invention, in the kneading step, an auxiliary agent is further added.

[0053] Furthermore, the auxiliary agent is one or more selected from vulcanizing agents, antioxidants, accelerators, and activators.

[0054] During the rubber mixing process, one or more of a vulcanizing agent, an antioxidant, an accelerator, and an activator may be added. The addition amounts and functions of these auxiliary agents are well known to those skilled in the art. For example, there are descriptions related to "Practical Rubber Compound Technology", so they will not be described in detail here.

[0055] In some embodiments of the present invention, the solution-polymerized raw rubber is one or more selected from solution-polymerized styrene-butadiene rubber, isoprene rubber, cis-butadiene rubber, and butyl rubber.

[0056] Furthermore, the solution-polymerized styrene-butadiene rubber has a number average molecular weight Mn of 100,000 to 400,000 g / mol and a vinyl content of 30 to 70 wt% before coupling.

[0057] Furthermore, the isoprene rubber has a weight average molecular weight Mw of 150,000 to 300,000 g / mol.

[0058] Furthermore, the cis-butadiene rubber has a weight average molecular weight Mw of 200,000 to 300,000 g / mol.

[0059] Furthermore, the butyl rubber has a weight average molecular weight Mw of 100,000 to 500,000 g / mol.

[0060] The fifth aspect of the present invention provides the use of the rubber composite material in a tire or the rubber composite material manufactured by the aforementioned manufacturing method.

[0061] The rubber composite material of the present invention solves the problems of poor dispersibility of white carbon black and low bonding strength between white carbon black and rubber, and improves the overall usage characteristics of the tire.

[0062] Furthermore, the aforementioned rubber composite material is used in green tires.

[0063] The present invention solves the problems that white carbon black is prone to agglomeration and the bonding strength between white carbon black and rubber is low. Also, by using polydivinylbenzene microspheres as a carrier, the dispersibility of white carbon black can be more effectively improved. The polydivinylbenzene microspheres also play a role in physically intertwining crosslinking points and act with the blend rubber through physical crosslinking to improve the physical and mechanical properties of the material, and can be used in the manufacture of green tires. Moreover, the manufacturing method of the present invention has few reaction steps and is easy to operate.

[0064] In the present invention, unless otherwise specified, % refers to mass percentage.

[0065] Hereinafter, the technical solutions in the present invention will be clearly and completely described by way of examples. It is obvious that the described examples are only a part of the examples of the present invention and not all of them. Based on the examples of the present invention, all other examples obtained by those skilled in the art without creative labor belong to the protection scope of the present invention.

[0066] When specific conditions are not described in the following examples and comparative examples, they are carried out according to conventional conditions or the conditions proposed by the manufacturer. When the reagents or equipment used are not specified by the manufacturer, they are all ordinary products that can be obtained commercially.

[0067] In the following examples, (1) Source of raw materials: White carbon black, purchased from Yifang Wanli Auxiliary Co., Ltd. Dopamine, tris(hydroxymethyl)aminomethane, 99.5%, purchased from Acros Organics Barbital, sodium chloride, borax, calcium chloride, boric acid, potassium chloride, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate, 99%, purchased from Sinopharm Chemical Reagent Co., Ltd. Polydivinylbenzene microspheres, particle size 0.2 - 0.5 μm, purchased from Suzhou Zhiwei Nano Technology Co., Ltd. Solution polymerization styrene-butadiene rubber slurry, purchased from Lanzhou Chemical Research Center and Dushanzi Petrochemical Company Isoprene rubber, purchased from Jilin Petrochemical Company of PetroChina and Lanzhou Chemical Research Center Butyl rubber, purchased from Bayer of Germany

[0068] (2) Analytical test methods: Infrared spectrum analysis of samples: Using an infrared spectrometer from Bruker Spectral Instruments of Germany, perform functional group analysis on samples before and after the modification of nano white carbon black. Put the samples into a vacuum oven and bake at 100 °C, compress them into tablets using potassium bromide, and collect data in the wavenumber range of 400 - 4000. Differential thermal analysis of polymer deposition amount: Analyze the deposition amount of polydopamine using a synchronous thermal analyzer (TG / DSC, STA449C) from NETZSCH of Germany. Put the samples into a vacuum oven and bake at 100 °C, and collect the weight loss data of the samples in the range of 20 - 600 °C. Glass transition temperature analysis: Measure the glass transition temperature using a synchronous thermal analyzer (TG / DSC, STA449C) from NETZSCH of Germany. Analysis of mechanical and mechanical properties: Use a 5567 universal material testing machine manufactured by Instron of the United States to test the mechanical properties of the test pieces. Tensile strength, elongation at break: Conform to standard GB / T528 - 2009. Shore A type hardness: Conform to standard GB / T531.1 - 2008. Example 1

[0069] (1) Modification of white carbon black: White carbon black was baked in a vacuum at 100 °C. Dry white carbon black and dopamine were added to the prepared Tris (hydroxymethyl) aminomethane buffer solution with a pH of 8.5 (the concentration of Tris (hydroxymethyl) aminomethane was 9 mmol / L), and after reacting at room temperature for 1.5 h, it was filtered, washed and dried to obtain polydopamine-modified white carbon black, designated as polydopamine-modified white carbon black-1. In the above process, the mass ratio of white carbon black to dopamine was 1:0.1, and the mass ratio of white carbon black to the buffer solution was 1:20. (2) Preparation of polydopamine-modified white carbon black-supported polydivinylbenzene microspheres (DVB): The polydopamine-modified white carbon black-1 prepared in step (1) was baked in a vacuum at 100 °C. 0.2 μm polydivinylbenzene microspheres, dry polydopamine-modified white carbon black-1, and the prepared Tris (hydroxymethyl) aminomethane buffer solution with a pH of 8.5 (the concentration of Tris (hydroxymethyl) aminomethane was 9 mmol / L) were added to a round-bottom flask, magnetically stirred at room temperature for 3 h, then filtered, washed and dried to obtain polydivinylbenzene microspheres-1 supported with polydopamine-modified white carbon black. In the above process, the mass ratio of polydivinylbenzene microspheres to polydopamine-modified white carbon black-1 was 1:5, and the mass ratio of polydivinylbenzene microspheres to the buffer solution was 1:300. (3) Manufacture of rubber composite material: Solution-polymerized styrene-butadiene rubber-1 (parameters refer to Table 1), polydopamine-modified white carbon black-1 obtained in step (1), polydopamine-modified white carbon black-supported polydivinylbenzene microspheres-1 obtained in step (2), and other auxiliaries were kneaded. The formulations of the solution-polymerized raw rubber and other auxiliaries are shown in Table 2. The addition amount of polydopamine-modified white carbon black-1 accounts for 17 wt% of the solution-polymerized styrene-butadiene rubber-1, and the addition amount of polydopamine-modified white carbon black-supported polydivinylbenzene microspheres-1 accounts for 3 wt% of the solution-polymerized styrene-butadiene rubber-1. Next, it was vulcanized to obtain a rubber composite material, that is, a polydivinylbenzene microsphere filler / solution-polymerized styrene-butadiene rubber composite material supporting polydopamine-modified white carbon black, designated as A-1, and the test results are shown in Table 7.

[0070]

Table 1

[0071]

Table 2

[0072] (1) Modification of white carbon black: White carbon black was baked in vacuum at 110 °C. Dry white carbon black and dopamine were added to the prepared tris(hydroxymethyl)aminomethane buffer solution with a pH of 9 (the concentration of tris(hydroxymethyl)aminomethane was 6 mmol / L), reacted at room temperature for 2 h, then filtered, washed and dried to obtain polydopamine-modified nano white carbon black, designated as polydopamine-modified white carbon black-2. In the above process, the mass ratio of white carbon black to dopamine was 1:0.2, and the mass ratio of white carbon black to the buffer solution was 1:30. (2) Preparation of Polydopamine-Modified White Carbon Black-Supported Polydivinylbenzene Microspheres (DVB): The polydopamine-modified white carbon black-2 produced in step (1) was baked in a vacuum at 110 °C. 0.4-μm polydivinylbenzene microspheres, dried polydopamine-modified white carbon black-2, and a prepared pH 9 tris(hydroxymethyl)aminomethane buffer solution (the concentration of tris(hydroxymethyl)aminomethane was 6 mmol / L) were added to a round-bottom flask, magnetically stirred at room temperature for 4 h for reaction, then filtered, washed, and dried to obtain polydopamine-modified white carbon black-supported polydivinylbenzene microspheres-2. In the above process, the mass ratio of polydivinylbenzene microspheres to polydopamine-modified white carbon black-2 was 1:7, and the mass ratio of polydivinylbenzene microspheres to the buffer solution was 1:400. (3) Preparation of Rubber Composite: The polydopamine-modified white carbon black-2 obtained in step (1), the polydopamine-modified white carbon black-supported polydivinylbenzene microspheres-2 obtained in step (2), solution-polymerized styrene-butadiene rubber-2 (parameters are shown in Table 3), and other auxiliaries were kneaded. The formulations of the solution-polymerized raw rubber and other auxiliaries are shown in Table 2. The addition amount of polydopamine-modified white carbon black-2 in step (1) accounted for 20 wt% of the solution-polymerized styrene-butadiene rubber-2, and the addition amount of the polydopamine-modified white carbon black-supported polydivinylbenzene microspheres-2 in step (2) accounted for 5 wt% of the solution-polymerized styrene-butadiene rubber-2. Next, it was vulcanized to obtain a rubber composite, that is, a polydopamine-modified white carbon black-supported polydivinylbenzene microsphere filler / solution-polymerized styrene-butadiene rubber composite, designated as A-2, and its test results are shown in Table 7.

[0073]

Table 3

[0074] (1) Modification of white carbon black: The white carbon black was baked in a vacuum at 110 °C. Dry white carbon black and dopamine were added to the prepared tris(hydroxymethyl)aminomethane buffer solution with a pH of 9 (the concentration of tris(hydroxymethyl)aminomethane was 10 mmol / L), reacted at room temperature for 2 h, then filtered, washed and dried to obtain polydopamine-modified nano white carbon black, designated as polydopamine-modified white carbon black-3. In the above process, the mass ratio of white carbon black to dopamine was 1:0.3, and the mass ratio of white carbon black to buffer solution was 1:30. (2) Preparation of polydopamine-modified white carbon black-supported polydivinylbenzene microspheres (DVB): The polydopamine-modified white carbon black-3 prepared in step (1) was baked in a vacuum at 110 °C. 0.3 μm polydivinylbenzene microspheres, dry polydopamine-modified white carbon black-3, and the prepared tris(hydroxymethyl)aminomethane buffer solution with a pH of 9 (the concentration of tris(hydroxymethyl)aminomethane was 10 mmol / L) were added to a round-bottom flask, magnetically stirred at room temperature for 4 h, then filtered, washed and dried to obtain polydivinylbenzene microspheres-3 supported with polydopamine-modified white carbon black. In the above process, the mass ratio of polydivinylbenzene microspheres to polydopamine-modified white carbon black-3 was 1:8, and the mass ratio of polydivinylbenzene microspheres to buffer solution was 1:400. (3) Manufacture of rubber composite material: The polydopamine-modified white carbon black-3 obtained in step (1), the polydopamine-modified white carbon black-supported polydivinylbenzene microspheres-3 obtained in step (2), solution-polymerized styrene-butadiene rubber-3 (parameters refer to Table 4), and other auxiliaries were kneaded. The formulations of the solution-polymerized raw rubber and other auxiliaries are shown in Table 2. The addition amount of the polydopamine-modified white carbon black-3 in step (1) accounts for 25 wt% of the solution-polymerized styrene-butadiene rubber-3, and the addition amount of the polydopamine-modified white carbon black-supported polydivinylbenzene microspheres-3 in step (2) accounts for 5 wt% of the solution-polymerized styrene-butadiene rubber-3. Next, it was vulcanized to obtain a rubber composite material, that is, a polydivinylbenzene microsphere filler / solution-polymerized styrene-butadiene rubber composite material supporting polydopamine-modified white carbon black, designated as A-3, and the test results are shown in Table 7.

[0075]

Table 4

[0076] (1) Modification of white carbon black: The white carbon black was baked in a vacuum at 110 °C. Dry white carbon black and dopamine were added to the prepared barbital / sodium chloride buffer solution with a pH of 8.5 (the concentrations of barbital / sodium chloride are 6 mmol / L), reacted at room temperature for 2 h, then filtered, washed and dried to obtain polydopamine-modified nano white carbon black, designated as polydopamine-modified white carbon black-4. In the above process, the mass ratio of white carbon black to dopamine is 1:0.1, and the mass ratio of white carbon black to buffer solution is 1:20. (2) Preparation of Polydopamine-Modified White Carbon Black-Loaded Polydivinylbenzene Microspheres (DVB): The polydopamine-modified white carbon black-4 prepared in step (1) was baked under vacuum at 110 °C. 0.3 μm polydivinylbenzene microspheres, dried polydopamine-modified white carbon black-4, and the prepared barbital / sodium chloride buffer solution with a pH of 8.5 (the concentration of barbital / sodium chloride was 6 mmol / L) were added to a round-bottom flask, magnetically stirred at room temperature for 4 h for reaction, then filtered, washed, and dried to obtain polydopamine-modified white carbon black-loaded polydivinylbenzene microspheres-4. In the above process, the mass ratio of polydivinylbenzene microspheres to polydopamine-modified white carbon black-4 was 1:5, and the mass ratio of polydivinylbenzene microspheres to the buffer solution was 1:300. (3) Preparation of Rubber Composite: The polydopamine-modified white carbon black-4 obtained in step (1), the polydopamine-modified white carbon black-loaded polydivinylbenzene microspheres-4 obtained in step (2), raw rubber of polyisoprene rubber-1, and other auxiliaries were kneaded. The formulations of solution-polymerized raw rubber and other auxiliaries are shown in Table 2, the parameters of polyisoprene rubber-1 are referred to Table 5, the addition amount of polydopamine-modified white carbon black-4 in step (1) accounted for 17 wt% of polyisoprene rubber, and the addition amount of polydopamine-modified white carbon black-loaded polydivinylbenzene microspheres-4 in step (2) accounted for 3 wt% of polyisoprene rubber. Next, it was vulcanized to obtain a rubber composite, that is, a polydopamine-modified white carbon black-loaded polydivinylbenzene microsphere filler / polyisoprene rubber composite, designated as A-4, and its test results are shown in Table 7.

[0077]

Table 5

[0078] (1) Modification of white carbon black: White carbon black was baked in a vacuum at 110 °C. Dry white carbon black and dopamine were added to the prepared barbital / sodium chloride buffer solution with a pH of 8 (the concentration of barbital / sodium chloride was 9 mmol / L), reacted at room temperature for 2 h, then filtered, washed and dried to obtain polydopamine-modified nano white carbon black, designated as polydopamine-modified white carbon black-5. In the above process, the mass ratio of white carbon black to dopamine was 1:0.3, and the mass ratio of white carbon black to the buffer solution was 1:25. (2) Preparation of polydopamine-modified white carbon black-supported polydivinylbenzene microspheres (DVB): The polydopamine-modified white carbon black-5 prepared in step (1) was baked in a vacuum at 110 °C. 0.4 μm polydivinylbenzene microspheres, dry polydopamine-modified white carbon black-5, and the prepared barbital / sodium chloride buffer solution with a pH of 8 (the concentration of barbital / sodium chloride was 9 mmol / L) were added to a round-bottom flask, magnetically stirred at room temperature for 4 h, then filtered, washed and dried to obtain polydivinylbenzene microspheres-5 supported with polydopamine-modified white carbon black. In the above process, the mass ratio of polydivinylbenzene microspheres to polydopamine-modified white carbon black-5 was 1:8, and the mass ratio of polydivinylbenzene microspheres to the buffer solution was 1:400. (3) Manufacture of rubber composite material: The polydopamine-modified white carbon black-5 obtained in step (1), the polydopamine-modified white carbon black-supported polydivinylbenzene microspheres-5 obtained in step (2), the raw rubber of polyisoprene rubber-2, and other auxiliaries were kneaded. The formulations of the solution-polymerized raw rubber and other auxiliaries are shown in Table 2, the parameters of the raw rubber of polyisoprene rubber-2 are shown in Table 6, the addition amount of the polydopamine-modified white carbon black-5 in step (1) is 24 wt% of the polyisoprene rubber, and the addition amount of the polydopamine-modified white carbon black-supported polydivinylbenzene microspheres-5 in step (2) accounts for 6 wt% of the polyisoprene rubber. Next, it was vulcanized to obtain a rubber composite material, that is, a polydivinylbenzene microsphere filler / polyisoprene rubber composite material supported with polydopamine-modified white carbon black, designated as A-5, and the test results are shown in Table 7.

[0079]

Table 6

[0080] (1) Modification of white carbon black: The white carbon black was baked in a vacuum at 110 °C. Dry white carbon black and dopamine were added to the prepared barbital / sodium chloride buffer solution with a pH of 8.5 (the concentration of barbital / sodium chloride was 8 mmol / L), reacted at room temperature for 2 h, then filtered, washed and dried to obtain polydopamine-modified nano white carbon black, designated as polydopamine-modified white carbon black-6. In the above process, the mass ratio of white carbon black to dopamine was 1:0.1, and the mass ratio of white carbon black to buffer solution was 1:20. (2) Preparation of Polydopamine-Modified White Carbon Black-Loaded Polystyrene Microspheres (DVB): The polydopamine-modified white carbon black-6 produced in step (1) was baked at 110 °C under vacuum. 0.2 μm polystyrene microspheres, dried polydopamine-modified white carbon black-6, and the prepared barbital / sodium chloride buffer solution with a pH of 8.5 (the concentrations of barbital / sodium chloride were 8 mmol / L) were added to a round-bottom flask, magnetically stirred at room temperature for 4 h for reaction, then filtered, washed, and dried to obtain polydopamine-modified white carbon black-loaded polystyrene microspheres-6. In the above process, the mass ratio of polystyrene microspheres to polydopamine-modified white carbon black-6 was 1:5, and the mass ratio of polystyrene microspheres to the buffer solution was 1:300. (3) Preparation of Rubber Composite: The polydopamine-modified white carbon black-6 obtained in step (1), the polydopamine-modified white carbon black-loaded polystyrene microspheres-6 obtained in step (2), raw butyl rubber, and other auxiliaries were kneaded. The formulations of solution-polymerized raw rubber and other auxiliaries are shown in Table 2. The addition amount of polydopamine-modified white carbon black-6 in step (1) accounted for 20 wt% of butyl rubber, and the addition amount of polydopamine-modified white carbon black-loaded polystyrene microspheres-6 in step (2) accounted for 5 wt% of butyl rubber. Next, it was vulcanized to obtain a rubber composite, that is, a polydopamine-modified white carbon black-loaded polystyrene microsphere filler / butyl rubber composite, designated as A-6, and the test results are shown in Table 7. Example 7

[0081] (1) Modification of white carbon black: White carbon black was baked in a vacuum at 110 °C. Dry white carbon black and dopamine were added to a prepared barbital / sodium chloride buffer solution with a pH of 7.8 (the concentration of barbital / sodium chloride was 9 mmol / L), and after reacting at room temperature for 2 h, it was filtered, washed, and dried to obtain polydopamine-modified nano-white carbon black, designated as polydopamine-modified white carbon black-7. In the above process, the mass ratio of white carbon black to dopamine was 1:0.2, and the mass ratio of white carbon black to the buffer solution was 1:25. (2) Preparation of polydopamine-modified white carbon black-supported polydivinylbenzene microspheres (DVB): The polydopamine-modified white carbon black-7 prepared in step (1) was baked in a vacuum at 110 °C. 0.4-μm polydivinylbenzene microspheres, dry polydopamine-modified white carbon black-7, and a prepared barbital / sodium chloride buffer solution with a pH of 7.8 (the concentration of barbital / sodium chloride was 9 mmol / L) were added to a round-bottom flask, magnetically stirred at room temperature for 4 h, then filtered, washed, and dried to obtain polydivinylbenzene microspheres-7 supported with polydopamine-modified white carbon black. In the above process, the mass ratio of polydivinylbenzene microspheres to polydopamine-modified white carbon black-7 was 1:8, and the mass ratio of polydivinylbenzene microspheres to the buffer solution was 1:400. (3) Manufacture of rubber composite material: The polydopamine-modified white carbon black-7 obtained in step (1), the polydopamine-modified white carbon black-supported polydivinylbenzene microspheres-7 obtained in step (2), raw butyl rubber, and other auxiliaries were kneaded. The formulations of the solution-polymerized raw rubber and other auxiliaries are shown in Table 2. The addition amount of the polydopamine-modified white carbon black-7 in step (1) accounts for 30 wt% of the butyl rubber, and the addition amount of the polydopamine-modified white carbon black-supported polydivinylbenzene microspheres-7 in step (2) accounts for 10 wt% of the butyl rubber. Next, it was vulcanized to obtain a rubber composite material, that is, a polydivinylbenzene microsphere filler / butyl rubber composite material supporting polydopamine-modified white carbon black, designated as A-7, and the test results are shown in Table 7. Example 8

[0082] In step (2), a rubber composite material was manufactured according to the method of Example 7 except that the mass ratio of the polydivinylbenzene microspheres to the polydopamine-modified white carbon black-7 was 1:1, and a rubber composite material was obtained and designated as A-8. The test results are shown in Table 7. Example 9

[0083] In step (2), a rubber composite material was manufactured according to the method of Example 7 except that the mass ratio of the medium polydivinylbenzene microspheres to the polydopamine-modified white carbon black-7 was 1:0.5, and a rubber composite material was obtained and designated as A-9. The test results are shown in Table 7. Example 10

[0084] In step (2), a rubber composite material was manufactured according to the method of Example 7 except that the mass ratio of the polydivinylbenzene microspheres to the polydopamine-modified white carbon black-7 was 1:10, and a rubber composite material was obtained and designated as A-10. The test results are shown in Table 7. Example 11

[0085] In step (2), a rubber composite was produced according to the method of Example 7, except that the mass ratio of polydivinylbenzene microspheres to polydopamine-modified white carbon black-7 was 1:15, to obtain a rubber composite, designated as A-1. The test results are shown in Table 7. Example 12

[0086] In the production of the rubber composite in step (3), a rubber composite was produced according to the method of Example 7, except that the addition amount of polydopamine-modified white carbon black-7 in step (1) accounted for 20 wt% of butyl rubber, and the addition amount of polydivinylbenzene microspheres-7 carrying polydopamine-modified white carbon black in step (2) accounted for 40 wt% of butyl rubber, to obtain a rubber composite, designated as A-12. The test results are shown in Table 7. Example 13

[0087] In the production of the rubber composite in step (3), a rubber composite was produced according to the method of Example 7, except that the addition amount of polydopamine-modified white carbon black-7 in step (1) accounted for 40 wt% of butyl rubber, and the addition amount of polydivinylbenzene microspheres-7 carrying polydopamine-modified white carbon black in step (2) accounted for 20 wt% of butyl rubber, to obtain a rubber composite, designated as A-13. The test results are shown in Table 7. Comparative Example 1

[0088] Step (2) was not performed. In the production of the rubber composite in step (3), a rubber composite was produced according to the method of Example 1, except that white carbon black accounting for 17 wt% of solution-polymerized styrene-butadiene rubber-1, polydopamine-modified white carbon black-1 accounting for 3 wt% of solution-polymerized styrene-butadiene rubber-1, the solution-polymerized raw rubber shown in Table 2, and other auxiliaries were kneaded and then vulcanized, to obtain a white carbon black / solution-polymerized styrene-butadiene rubber composite sample, designated as D-1. The test results are shown in Table 7. Comparative Example 2

[0089] In the production of the rubber composite material in step (3), poly-dopamine modified white carbon black-1 in step (1) was not added, and the addition amount of polydivinylbenzene microspheres-1 carrying poly-dopamine modified white carbon black in step (2) accounted for 10 wt% of solution-polymerized styrene-butadiene rubber-1. Except for this, a rubber composite material was produced according to the method of Example 1 to obtain a rubber composite material, designated as D-2, and the test results are shown in Table 7. Comparative Example 3

[0090] In the production of the rubber composite material in step (3), polydivinylbenzene microspheres-1 carrying poly-dopamine modified white carbon black in step (2) was not added, and the addition amount of poly-dopamine modified white carbon black-1 in step (1) accounted for 40 wt% of solution-polymerized styrene-butadiene rubber-1. Except for this, a rubber composite material was produced according to the method of Example 1 to obtain a rubber composite material, designated as D-3. The test results are shown in Table 7. Comparative Example 4

[0091] Step (2) was not performed. In the production of the rubber composite material in step (3), white carbon black accounting for 25 wt% of solution-polymerized styrene-butadiene rubber-3, poly-dopamine modified white carbon black-3 obtained in step (1) accounting for 5 wt% of solution-polymerized styrene-butadiene rubber-3, the solution-polymerized raw rubber shown in Table 2, and other auxiliaries were kneaded, and then a rubber composite material was produced according to the method of Example 3 except for vulcanization to obtain a white carbon black / solution-polymerized styrene-butadiene rubber composite material sample, designated as D-4. The test results are shown in Table 7.

[0092]

Table 7

[0093] From the results in Table 7, it was found that the examples had significantly better effects than the comparative examples. In the present invention, as a substitute for a part of the polydopamine-modified white carbon black, a polydopamine-modified white carbon black-supported polydivinylbenzene microsphere is used as a filler, and by using the polydivinylbenzene microsphere as a carrier, the aggregation of the modified white carbon black is less likely to occur, the dispersion degree of the modified white carbon black is improved, the dispersibility and stability of the white carbon black are more effectively improved, and the modified polydivinylbenzene microsphere also plays a role in entangling cross-linking points. Since there are polar functional groups on its surface, an interaction force with the white carbon black can be generated. Furthermore, the modified polydivinylbenzene microsphere can improve the physical and mechanical properties of the material by vulcanization cross-linking.

[0094] As described above, the preferred embodiments of the present invention have been described in detail, but the present invention is not limited thereto. Within the scope of the technical concept of the present invention, a plurality of simple modifications can be made to the technical solution of the present invention, including combining each technical feature in any other appropriate way. These simple modifications and combinations should also be regarded as the disclosure content of the present invention and all belong to the protection scope of the present invention.

Claims

1. A rubber filler comprising polydivinylbenzene microspheres and polydopamine-modified white carbon black supported on the polydivinylbenzene microspheres, wherein the mass ratio of the polydivinylbenzene microspheres to the polydopamine-modified white carbon black is 1:0.5 to 20.

2. The mass ratio of the polydivinylbenzene microspheres to the polydopamine-modified white carbon black is 1:1 to 10, and / or, in the polydopamine-modified white carbon black, the mass ratio of white carbon black to polydopamine is 1:0.05 to 1. The rubber filler according to claim 1.

3. The rubber filler according to claim 1 or 2, wherein the particle size of the polydivinylbenzene microspheres is 0.1 to 1 μm.

4. The rubber filler according to claim 1 or 2, wherein the particle size of the white carbon black is 20 to 60 nm.

5. Performing a first reaction between white carbon black and dopamine in a first buffer solution to obtain polydopamine-modified white carbon black (step (1)); Performing a second reaction between polydivinylbenzene microspheres and the polydopamine-modified white carbon black obtained in step (1) in a second buffer solution to obtain polydivinylbenzene microspheres supporting polydopamine-modified white carbon black (step (2)), wherein the mass ratio of the polydivinylbenzene microspheres to the polydopamine-modified white carbon black is 1:0.5 to 20. A method for producing a rubber filler, characterized by the above.

6. Step (1) specifically includes: Adding an inorganic acid or an inorganic alkali to a weakly alkaline buffer solution to obtain a first buffer solution with a buffer concentration of 3 to 15 mmol / L and a pH of 7.5 to 10.5; Adding white carbon black and dopamine to the first buffer solution, reacting at room temperature for 0.5 to 2 h, then filtering, washing, and drying to obtain polydopamine-modified white carbon black. The production method according to claim 5.

7. The mass ratio of white carbon black to dopamine is 1:0.05 to 1, and / or, the mass ratio of white carbon black to the first buffer solution is 1:5 to 50. And / or, the weak alkaline buffer is one or more selected from tris(hydroxymethyl)aminomethane, barbital, barbital-sodium chloride complex buffer, boric acid-potassium chloride complex buffer, borax-calcium chloride complex buffer, disodium hydrogen phosphate, and dipotassium hydrogen phosphate-potassium dihydrogen phosphate complex buffer, And / or, the inorganic acid is one or more of hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid, And / or, the inorganic alkali is potassium hydroxide and / or sodium hydroxide, The production method according to claim 6.

8. Step (2) specifically is, Adding an inorganic acid or an inorganic alkali to a weak alkaline buffer solution to obtain a second buffer solution with a buffer concentration of 3 to 15 mmol / L and a pH of 7.5 to 10.5, Adding the polydivinylbenzene microspheres and the polydopamine-modified white carbon black obtained in step (1) to the second buffer solution, magnetically stirring at room temperature for 1 to 4 h for reaction, then filtering, washing, and drying to obtain polydopamine-modified white carbon black-supported polydivinylbenzene microspheres, The production method according to claim 5 or 6, comprising:

9. The mass ratio of the polydivinylbenzene microspheres to the polydopamine-modified white carbon black is 1:1 to 10, And / or, the mass ratio of the polydivinylbenzene microspheres to the second buffer solution is 1:50 to 500, And / or, the weak alkaline buffer is one or more selected from tris(hydroxymethyl)aminomethane, barbital, barbital-sodium chloride complex buffer, boric acid-potassium chloride complex buffer, borax-calcium chloride complex buffer, disodium hydrogen phosphate, and dipotassium hydrogen phosphate-potassium dihydrogen phosphate complex buffer, And / or, the inorganic acid is one or more of hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid, And / or, the inorganic alkali is potassium hydroxide and / or sodium hydroxide, The production method according to claim 8.

10. A rubber composite material comprising a solution-polymerized raw rubber, a first filler, and a second filler, wherein the first filler is a rubber filler according to any one of claims 1 to 4 or a rubber filler produced by the production method according to any one of claims 5 to 9, the second filler is polydopamine-modified white carbon black, and the total addition amount of the first rubber filler and the second rubber filler is 10 to 60 wt% of the mass (dry weight basis) of the solution-polymerized raw rubber.

11. The rubber composite material according to claim 10, wherein the mass ratio of the first filler to the second filler is 1:0.5 to 20.

12. The rubber composite material according to claim 10 or 11, wherein the addition amount of the second rubber filler is 10 to 40 wt% of the mass (dry weight basis) of the solution-polymerized raw rubber.

13. The rubber composite material according to claim 10 or 11, further comprising an auxiliary agent.

14. The rubber composite material according to claim 13, wherein the auxiliary agent is one or more selected from a vulcanizing agent, an antioxidant, an accelerator, and an activator.

15. The rubber composite material according to claim 10 or 11, wherein the solution-polymerized raw rubber is one or more selected from solution-polymerized styrene-butadiene rubber, isoprene rubber, cis-butadiene rubber, and butyl rubber.

16. A method for producing a rubber composite material, comprising the steps of kneading a solution-polymerized raw rubber with a first filler and a second filler, and then vulcanizing to obtain the rubber composite material, wherein the first filler is a rubber filler according to any one of claims 1 to 4 or a rubber filler produced by the production method according to any one of claims 5 to 9, the second filler is polydopamine-modified white carbon black, and the total addition amount of the first rubber filler and the second rubber filler is 10 to 60 wt% of the mass (dry weight basis) of the solution-polymerized raw rubber.

17. The production method according to claim 16, wherein the mass ratio of the first filler to the second filler is 1:0.5 to 20.

18. The production method according to claim 16 or 17, wherein the addition amount of the second rubber filler is 10 to 40 wt% of the mass (dry weight basis) of the solution-polymerized raw rubber.

19. The production method according to claim 16 or 17, wherein an auxiliary agent is further added in the kneading step.

20. The manufacturing method according to claim 19, wherein the auxiliary agent is one or more selected from a vulcanizing agent, an antioxidant, an accelerator, and an activator.

21. The manufacturing method according to claim 16 or 17, wherein the solution-polymerized raw rubber is one or more selected from solution-polymerized styrene-butadiene rubber, isoprene rubber, cis-butadiene rubber, and butyl rubber.

22. Use of the rubber composite according to any one of claims 10 to 15 in a tire or the rubber composite produced by the manufacturing method according to claims 16 to 21 above.

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