Rubber filler, rubber composite material containing same, preparation method therefor, and use thereof

Abstract

Disclosed in the present invention are a rubber filler, a rubber composite material containing same, a preparation method therefor, and the use thereof. The rubber filler comprises polydivinylbenzene microspheres and polydopamine-modified white carbon black loaded onto the polydivinylbenzene microspheres, the mass ratio of the polydivinylbenzene microspheres to the polydopamine-modified white carbon black being 1:(0.5-20). The rubber composite material comprises raw rubber of a solution-polymerized rubber and the rubber filler, the dosage of the rubber filler being 10-60 wt% of the dry-basis mass of the raw rubber of the solution-polymerized rubber. The present invention uses as the filler the polydivinylbenzene microspheres onto which the polydopamine-modified white carbon black is loaded, thereby solving the problems that white carbon black is prone to agglomeration and the binding force between white carbon black and rubber is poor. The rubber composite material obtained by the present invention is suitable for manufacturing green tires.

Description

Rubber filler, rubber composite material containing same, and preparation method and application thereof

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of Chinese patent application No. 202310700409.3 filed on June 13, 2023, the contents of which are incorporated herein by reference. Technical Field

[0003] The present invention relates to the technical field of rubber materials, and in particular to a rubber filler, a rubber composite material containing the same, and a preparation method and application thereof. Background Art

[0004] Green tires (or fuel-efficient tires) are designed to save fuel and reduce exhaust emissions. Compared to conventional radial tires, green tires significantly reduce energy consumption. Solution-polymerized styrene-butadiene rubber (SBR) is more environmentally friendly than general-purpose emulsion-polymerized styrene-butadiene rubber (ESBR). Furthermore, the micromolecular structure can be controlled and adjusted as needed during the synthesis process, improving both the tire's rolling resistance coefficient and wet grip index. The application of SBR in the tire industry is expected to make rapid progress in the coming years. Butadiene rubber, isoprene rubber, and butyl rubber are also produced using the solution polymerization process and are all used in the tire industry.

[0005] Currently, carbon black is the most widely used filler, but as environmental protection requirements increase, silica will gradually replace carbon black as the most widely used filler. A silica / solution-polymerized styrene-butadiene rubber (SPBR) system is a common formulation for high-performance, green tire treads. However, silica's small particle size and high surface polarity result in poor compatibility with rubber, making it prone to agglomeration and difficult to disperse. Therefore, silica requires surface modification. Common filler surface modifiers used in the prior art include titanate coupling agents and silane coupling agents.

[0006] CN101798473A discloses the use of a polysulfide silane coupling agent to modify silica and then prepare a silica / carbon black composite filler. However, increasing the amount of the silane coupling agent will cause a decrease in the vulcanization kinetics, requiring the addition of a vulcanizing agent and a vulcanization accelerator.

[0007] CN101220177A discloses a method for preparing a silica / solution-polymerized styrene-butadiene rubber nanocomposite material by modifying silica with an amino-based silane coupling agent. Nano-silica and a silane coupling agent are dispersed in ethanol, subjected to a condensation reaction at high temperature, and the modified nano-silica powder is then added to a solution-polymerized styrene-butadiene rubber solution. After stirring and dispersion, the solvent is removed and dried to obtain a silica / solution-polymerized styrene-butadiene rubber nanocomposite material prepared by a co-coagulation method. However, small-molecule surface modifiers have drawbacks such as poor processing performance, the generation of small molecules during the modification process, poor storage stability, and a reduced tire lifespan. Furthermore, they fail to address the problem of poor silica-rubber bonding.

[0008] Summary of the Invention

[0009] The present invention aims to overcome the problems of prior art, such as the tendency of silica to agglomerate and poor silica-rubber bonding, by providing a rubber composite material, its preparation method, and its application. The rubber composite material of the present invention uses polydivinylbenzene microspheres loaded with dopamine-modified silica as a filler. The polydivinylbenzene microspheres serve as a carrier, effectively improving the dispersibility of silica. The polydivinylbenzene microspheres also act as physical entanglement crosslinking points, enhancing the physical and mechanical properties of the material through vulcanization crosslinking with the blended rubber. The rubber composite material can be used to manufacture green tires.

[0010] In order to achieve the above-mentioned object, the first aspect of the present invention provides a rubber filler, which comprises: polydivinylbenzene microspheres and polydopamine-modified silica attached to the polydivinylbenzene microspheres; wherein the mass ratio of the polydivinylbenzene microspheres to the polydopamine-modified silica is 1:0.5-20.

[0011] A second aspect of the present invention provides a method for preparing a rubber filler, the method comprising:

[0012] (1) in a first buffer solution, reacting silica with dopamine to obtain polydopamine-modified silica;

[0013] (2) in a second buffer solution, subjecting the polydivinylbenzene microspheres to a second reaction with the polydopamine-modified silica obtained in step (1) to obtain polydivinylbenzene microspheres loaded with polydopamine-modified silica; wherein the mass ratio of the polydivinylbenzene microspheres to the polydopamine-modified silica is 1:0.5-20.

[0014] A third aspect of the present invention provides a rubber composite material, comprising: a solution-polymerized raw rubber, a first filler, and a second filler, wherein the first filler is the rubber filler of the first aspect and the rubber filler prepared by the preparation method of the second aspect, and the second filler is polydopamine-modified silica; wherein the total addition amount of the first rubber filler and the second rubber filler is 10-60wt% of the dry basis mass of the solution-polymerized raw rubber.

[0015] A fourth aspect of the present invention provides a method for preparing a rubber composite material, the preparation method comprising: mixing a solution-polymerized rubber raw rubber with a first filler and a second filler, and then vulcanizing the mixture to obtain a rubber composite material; wherein the first filler is the rubber filler of the first aspect and the rubber filler obtained by the preparation method of the second aspect, and the second filler is polydopamine-modified silica; and the total amount of the first rubber filler and the second rubber filler added is 10-60 wt% of the dry basis mass of the solution-polymerized rubber raw rubber.

[0016] A fifth aspect of the present invention provides use of the aforementioned rubber composite material or the rubber composite material prepared by the aforementioned preparation method in a tire.

[0017] Through the above technical solution, the beneficial technical effects achieved by the present invention are as follows:

[0018] (1) The rubber filler of the present invention is polydivinylbenzene microspheres loaded with polydopamine-modified silica. The use of polydopamine to modify silica can prevent silica from agglomerating itself and improve the dispersibility of silica. At the same time, using polydivinylbenzene microspheres as a carrier can more effectively improve the dispersibility of silica.

[0019] (2) The rubber filler of the present invention can be used to prepare a rubber composite material. The polydivinylbenzene microspheres can also serve as physical entanglement crosslinking points. When a vulcanizing agent is added for vulcanization, the microsphere filler and the blended rubber can effectively enhance the physical and mechanical properties of the material through vulcanization crosslinking. At the same time, the catecholamine structure in the polydopamine has a high affinity and can be tightly bonded to the rubber, thereby improving the mechanical strength of the silica / rubber. The rubber composite material obtained by the present invention is suitable for manufacturing green tires.

[0020] (3) The preparation method of the present invention has few steps and is simple to operate, which solves the problem that white carbon black is easy to agglomerate and has poor bonding strength between white carbon black and rubber. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 is the infrared spectra of silica, polydopamine-modified silica and polydivinylbenzene microspheres loaded with polydopamine-modified silica, respectively; wherein, curve a is the infrared spectra of silica; curve b is the infrared spectra of polydopamine-modified silica; curve c is the infrared spectra of divinylbenzene microspheres loaded with polydopamine-modified silica. DETAILED DESCRIPTION

[0022] The endpoints of the ranges and any values ​​disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoints of each range, the endpoints of each range and individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered to be specifically disclosed herein.

[0023] A first aspect of the present invention provides a rubber filler, comprising: polydivinylbenzene microspheres and polydopamine-modified silica supported on the polydivinylbenzene microspheres; wherein the mass ratio of the polydivinylbenzene microspheres to the polydopamine-modified silica is 1:0.5-20, 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 in a range consisting of any two values, preferably 1:1-10.

[0024] The polydivinylbenzene microspheres used in this invention have strong adsorption properties, primarily through loading. The specific loading method of the polydopamine-modified silica is not limited in this invention, as long as it can be loaded onto the polydivinylbenzene microspheres. The polydopamine-modified silica can be loaded onto the polydivinylbenzene microspheres (DVB) on their surfaces, within their internal pores, or both. Research has found that the polydopamine-modified silica primarily deposits and adheres to the microsphere surfaces.

[0025] The present invention uses polydopamine to modify silica to prevent silica from agglomerating and improve its dispersibility. The catecholamine structure in polydopamine has a high affinity and can tightly bind to rubber, thereby improving the mechanical strength of the silica / rubber composite. Furthermore, using polydivinylbenzene microspheres as a carrier can more effectively improve the dispersibility of silica. Furthermore, the microspheres have good compatibility with rubber and strong adsorption capacity, making them suitable for use as attached fillers. In the process of preparing rubber composite materials, the polydivinylbenzene microspheres can also act as physical entanglement crosslinking points, effectively enhancing the physical and mechanical properties of the material through physical crosslinking with the blended rubber, making them suitable for manufacturing green tires.

[0026] In some embodiments of the present invention, in the polydopamine-modified silica, the mass ratio of silica to polydopamine is 1:0.05-1, 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 in the range of any two values, preferably 1:0.1-0.6.

[0027] In some embodiments of the present invention, the particle size of the polydivinylbenzene microspheres is 0.1-1 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 in the range consisting of any two values, preferably 0.2-0.5 μm.

[0028] In some embodiments of the present invention, the particle size of the white carbon black is 20-60 nm, for example, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, and any value in a range consisting of any two values, preferably 30-50 nm.

[0029] A second aspect of the present invention provides a method for preparing a rubber filler, the method comprising:

[0030] (1) in a first buffer solution, reacting silica with dopamine to obtain polydopamine-modified silica;

[0031] (2) in a second buffer solution, subjecting the polydivinylbenzene microspheres to a second reaction with the polydopamine-modified silica obtained in step (1) to obtain polydivinylbenzene microspheres loaded with polydopamine-modified silica; wherein the mass ratio of the polydivinylbenzene microspheres to the polydopamine-modified silica is 1:0.5-20, 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 in a range consisting of any two values, preferably 1:1-10.

[0032] As shown in Figure 1, curve a is the infrared spectrum of white carbon black; curve b is the infrared spectrum of polydopamine-modified white carbon black; curve c is the infrared spectrum of divinylbenzene microspheres loaded with polydopamine-modified white carbon black, wherein in curve a, at a wave number of 1099 cm -1 The asymmetric stretching vibration absorption peak of Si-O-Si appears at the wave number 804 cm -1 The symmetrical stretching vibration absorption peak of Si-O-Si appears at the wave number of 465cm -1 The bending vibration absorption peak of Si-O-Si appears at the curve b. In curve b, the benzene ring (1600-1450cm -1 ) can be attributed to the absorption of the benzene ring in polydopamine. In curve c, 3450cm -1 The broadening and enlargement of the absorption peak near is due to the phenolic hydroxyl group and NH bond of polydopamine after loading, indicating that polydopamine-modified silica is successfully loaded on polydivinylbenzene microspheres.

[0033] In some embodiments of the present invention, step (1) specifically includes the following steps:

[0034] Adding an inorganic acid or an inorganic base to a weakly alkaline buffer solution to obtain a first buffer solution with a pH of 7.5-10.5, wherein the concentration of the buffer in the first buffer solution is 3-15 mmol / L;

[0035] Adding silica and dopamine into the first buffer solution, reacting at room temperature for 0.5-2 hours, and then filtering, washing and drying to obtain polydopamine-modified silica.

[0036] In the present invention, dried silica is used in the modification process. The dried silica can be dried using common techniques in the art, for example, by drying the silica at 100-120° C. in a vacuum oven.

[0037] Furthermore, the mass ratio of silica to dopamine is 1:0.05-1, 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 in the range of any two values, preferably 1:0.1-0.6.

[0038] Furthermore, the mass ratio of white carbon black to the first buffer solution is 1:5-50, for example, 1:5, 1:10, 1:15, 1:20, 1:25, 1:30, 1:40, 1:45, 1:50, and any value in the range consisting of any two values, preferably 1:10-40.

[0039] Furthermore, the weak 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.

[0040] Furthermore, the inorganic acid is one or more of hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid.

[0041] Furthermore, the inorganic base is potassium hydroxide and / or sodium hydroxide.

[0042] In some embodiments of the present invention, step (2) specifically includes the following steps:

[0043] Adding an inorganic acid or an inorganic base to the weakly alkaline buffer solution to obtain a second buffer solution with a pH of 7.5-10.5, wherein the concentration of the buffer in the second buffer solution is 3-15 mmol / L;

[0044] The polydivinylbenzene microspheres and the polydopamine-modified silica obtained in step (1) are added to the second buffer solution, and reacted under magnetic stirring at room temperature for 1-4 hours, and then filtered, washed and dried to obtain polydivinylbenzene microspheres loaded with polydopamine-modified silica.

[0045] Furthermore, the mass ratio of the polydivinylbenzene microspheres to the second buffer solution is 1:50-500, for example, 1:50, 1:100, 1:150, 1:200, 1:250, 1:300, 1:400, 1:450, 1:500, and any value in the range consisting of any two values, preferably 1:100-400.

[0046] Furthermore, the weak 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.

[0047] Furthermore, the inorganic acid is one or more of hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid.

[0048] Furthermore, the inorganic base is potassium hydroxide and / or sodium hydroxide.

[0049] A third aspect of the present invention provides a rubber composite material, comprising: a solution-polymerized raw rubber, a first filler and a second filler, wherein the first filler is the rubber filler of the first aspect and the rubber filler prepared by the preparation method of the second aspect, and the second filler is polydopamine-modified silica; wherein the total addition amount of the first rubber filler and the second rubber filler is 10-60wt% of the dry basis mass of the solution-polymerized raw rubber, for example, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, and any value in the range consisting of any two values, preferably 20-40wt%.

[0050] In some embodiments of the present invention, the mass ratio of the first filler to the second filler is 1:0.5-20, 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 in the range consisting of any two values, preferably 1:1-10.

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

[0052] In some embodiments of the present invention, the rubber composite material further comprises an additive.

[0053] Furthermore, the auxiliary agent is selected from one or more of a vulcanizing agent, an antioxidant, an accelerator and an activator.

[0054] In the present invention, the types, functions and addition amounts of the additives are well known to those skilled in the art. For example, relevant descriptions thereof are given in "Practical Rubber Formulation Technology" and will not be repeated here.

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

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

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

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

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

[0060] A fourth aspect of the present invention provides a method for preparing a rubber composite material, the method comprising the following steps:

[0061] The solution-polymerized raw rubber is mixed with a first filler and a second filler, and then vulcanized to obtain a rubber composite material; wherein the first filler is the rubber filler of the first aspect and the rubber filler prepared by the preparation method of the second aspect, and the second filler is polydopamine-modified white carbon black; the total addition amount of the first rubber filler and the second rubber filler is 10-60wt% of the dry basis mass of the solution-polymerized raw rubber, for example, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, and any value in the range consisting of any two values, preferably 20-40wt%.

[0062] The present invention adopts polydivinylbenzene microspheres loaded with polydopamine-modified silica as the first rubber filler, which can prevent silica from agglomerating itself and improve the dispersibility and stability of silica. At the same time, polydopamine-modified silica can also prevent silica from agglomerating itself, improve the dispersibility of silica, and improve the mechanical strength of silica / rubber. In the preparation process of the rubber composite material, the polydivinylbenzene microspheres can also serve as physical entanglement crosslinking points, and can effectively enhance the physical and mechanical properties of the material through physical crosslinking with the blended rubber, mainly improving the strength, hardness and wear resistance of the rubber material. There is a synergistic effect between the two rubber fillers. Using the polydivinylbenzene microspheres as a carrier can make the dopamine-modified silica more effectively dispersed and improve the stability, and more effectively improve the comprehensive performance of the material than a single filler. The obtained rubber composite material is suitable for manufacturing green tires.

[0063] In the present invention, conventional mixing methods may be used in the rubber mixing process, such as mixing in an open mill and mixing in an internal mixer.

[0064] In some embodiments of the present invention, the mass ratio of the first filler to the second filler is 1:0.5-20, 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 in the range consisting of any two values, preferably 1:1-10.

[0065] In some embodiments of the present invention, the amount of the second rubber filler added is 10-40wt% of the dry basis mass of the solution-polymerized rubber raw rubber, for example, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, and any value in the range consisting of any two values, preferably 20-30wt%.

[0066] In some embodiments of the present invention, an auxiliary agent is further added during the mixing step.

[0067] Furthermore, the auxiliary agent is selected from one or more of a vulcanizing agent, an antioxidant, an accelerator and an activator.

[0068] During the rubber mixing process, one or more additives such as vulcanizers, antioxidants, accelerators, and activators may be added. These additives, their addition amounts, and their effects are well known to those skilled in the art. For example, relevant descriptions thereof are given in "Practical Rubber Formulation Technology" and will not be repeated here.

[0069] In some embodiments of the present invention, the solution polymerized rubber is selected from one or more of solution polymerized styrene-butadiene rubber, isoprene rubber, butadiene rubber and butyl rubber.

[0070] Furthermore, the number average molecular weight Mn of the solution-polymerized styrene-butadiene rubber before coupling is 100,000-400,000 g / mol, and the vinyl content is 30-70 wt%.

[0071] Furthermore, the weight average molecular weight Mw of the isoprene rubber is 150,000-300,000 g / mol.

[0072] Furthermore, the weight average molecular weight Mw of the butadiene rubber is 200,000-300,000 g / mol.

[0073] Furthermore, the weight average molecular weight Mw of the butyl rubber is 100,000-500,000 g / mol.

[0074] A fifth aspect of the present invention provides use of the aforementioned rubber composite material or the rubber composite material prepared by the aforementioned preparation method in a tire.

[0075] The rubber composite material of the present invention solves the dispersibility problem of white carbon black and simultaneously solves the problem of poor bonding between white carbon black and rubber, thereby improving the comprehensive performance of the tire.

[0076] Furthermore, the aforementioned rubber composite material is used in green tires.

[0077] The present invention addresses the problems of silica's easy agglomeration and poor bonding between silica and rubber. Furthermore, the use of polydivinylbenzene microspheres as a carrier effectively improves silica's dispersibility. The polydivinylbenzene microspheres also serve as physical crosslinking points, enhancing the physical and mechanical properties of the material through physical crosslinking with the blended rubber, making it suitable for use in the manufacture of green tires. Furthermore, the preparation method of the present invention has few reaction steps and is simple to operate.

[0078] In the present invention, unless otherwise specified, % refers to mass percentage.

[0079] The following examples clearly and completely describe the technical solutions of the present invention. Obviously, the described examples are only some of the examples of the present invention, not all of them. Based on the examples of the present invention, all other examples obtained by persons of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0080] In the following examples and comparative examples, if no specific conditions are specified, the experiments were carried out under conventional conditions or those recommended by the manufacturer. All reagents and instruments used, if no manufacturer is specified, are commercially available conventional products.

[0081] In the following examples,

[0082] (1) Source of raw materials:

[0083] Silica was purchased from Weifang Wanli Additive Co., Ltd.

[0084] Dopamine, tris(hydroxymethyl)aminomethane, 99.5%, purchased from Acros Organics;

[0085] Barbiturate, sodium chloride, borax, calcium chloride, boric acid, potassium chloride, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate, 99%, were purchased from Sinopharm Chemical Reagent Co., Ltd.;

[0086] Polydivinylbenzene microspheres, with a particle size of 0.2–0.5 μm, were purchased from Suzhou Zhiwei Nanotechnology Co., Ltd.

[0087] Solution polymerized styrene butadiene rubber (SBR) was purchased from Lanzhou Chemical Research Center and Dushanzi Petrochemical Company.

[0088] Isoprene rubber was purchased from PetroChina Jilin Petrochemical Company and Lanzhou Chemical Research Center;

[0089] Butyl rubber was purchased from Bayer, Germany.

[0090] (2) Analytical testing methods:

[0091] Infrared spectroscopy analysis of samples: Functional group analysis was performed on samples before and after modification using an infrared spectrometer from Bruker Spectroscopy Instruments of Germany. The samples were dried in a vacuum oven at 100°C and pressed into pellets using potassium bromide. The wavenumber range was 400-4000.

[0092] Polymer deposition differential thermal analysis: The deposition of polydopamine was analyzed using a simultaneous thermal analyzer (TG / DSC, STA449C) from NETZSCH, Germany. The samples were dried in a vacuum oven at 100°C, and weight loss data was collected over a temperature range of 20-600°C.

[0093] Glass transition temperature analysis: The glass transition temperature was determined using a synchronous thermal analyzer (TG / DSC, STA449C) from NETZSCH, Germany.

[0094] Mechanical properties analysis: The mechanical properties of the samples were tested using a 5567 universal material testing machine produced by Instron, USA.

[0095] Tensile strength, elongation at break: Implementation standard GB / T528-2009;

[0096] Shore A hardness: Implementation standard GB / T531.1-2008.

[0097] Example 1

[0098] (1) Modification of silica: silica was dried at 100°C under vacuum; dried silica and dopamine were added to a tris(hydroxymethylaminomethane) buffer solution (the concentration of tris(hydroxymethylaminomethane) was 9 mmol / L) with a pH of 8.5, and reacted at room temperature for 1.5 h. The mixture was then filtered, washed, and dried to obtain polydopamine-modified silica, designated as polydopamine-modified silica-1; wherein the mass ratio of silica to dopamine was 1:0.1, and the mass ratio of silica to buffer solution was 1:20;

[0099] (2) Preparation of polydivinylbenzene microspheres (DVB) loaded with polydopamine-modified silica: The polydopamine-modified silica-1 prepared in step (1) was dried under vacuum at 100°C; 0.2 μm polydivinylbenzene microspheres, dried polydopamine-modified silica-1, and a tris(hydroxymethylaminomethane) buffer solution (the concentration of tris(hydroxymethylaminomethane) was 9 mmol / L) were added to a round-bottom flask, and the mixture was stirred under magnetic stirring for 3 h at room temperature. The mixture was then filtered, washed, and dried to obtain polydivinylbenzene microspheres loaded with polydopamine-modified silica-1; wherein the mass ratio of the polydivinylbenzene microspheres to the polydopamine-modified silica-1 was 1:5; and the mass ratio of the polydivinylbenzene microspheres to the buffer solution was 1:300;

[0100] (3) Preparation of rubber composite material: Solution-polymerized styrene-butadiene rubber-1 (parameters are shown in Table 1), polydopamine-modified silica-1 obtained in step (1), polydivinylbenzene microspheres loaded with polydopamine-modified silica-1 obtained in step (2), and other additives are mixed, wherein the formula of the solution-polymerized rubber raw rubber and other additives is shown in Table 2, the amount of polydopamine-modified silica-1 added accounts for 17wt% of the solution-polymerized styrene-butadiene rubber-1, and the amount of polydivinylbenzene microspheres loaded with polydopamine-modified silica-1 added accounts for 3wt% of the solution-polymerized styrene-butadiene rubber-1; then, after vulcanization, a rubber composite material is obtained, i.e., polydivinylbenzene microspheres loaded with polydopamine-modified silica filler / solution-polymerized styrene-butadiene rubber composite material, denoted as A-1, and its test results are shown in Table 7.

[0101] Table 1 Parameters of solution polymerized styrene-butadiene rubber-1

[0102] Table 2 Rubber compound formula

[0103] Example 2

[0104] (1) Modification of silica: silica was dried at 110°C under vacuum; dried silica and dopamine were added to a tris(hydroxymethylaminomethane) buffer solution (the concentration of tris(hydroxymethylaminomethane) was 6 mmol / L) with a pH of 9, and reacted at room temperature for 2 h. After filtration, washing and drying, polydopamine-modified nano-silica was obtained, which was designated as polydopamine-modified silica-2; wherein the mass ratio of silica to dopamine was 1:0.2, and the mass ratio of silica to buffer solution was 1:30;

[0105] (2) Preparation of polydivinylbenzene microspheres (DVB) loaded with polydopamine-modified silica: The polydopamine-modified silica-2 prepared in step (1) was dried under vacuum at 110°C; 0.4 μm polydivinylbenzene microspheres, dried polydopamine-modified silica-2, and a tris(hydroxymethylaminomethane) buffer solution (the concentration of tris(hydroxymethylaminomethane) was 6 mmol / L) were added to a round-bottom flask, and the mixture was stirred under magnetic stirring for 4 h at room temperature. After filtration, washing, and drying, polydivinylbenzene microspheres loaded with polydopamine-modified silica-2 were obtained; wherein the mass ratio of the polydivinylbenzene microspheres to the polydopamine-modified silica-2 was 1:7; and the mass ratio of the polydivinylbenzene microspheres to the buffer solution was 1:400;

[0106] (3) Preparation of rubber composite material: The polydopamine-modified silica-2 obtained in step (1) and the polydivinylbenzene microspheres-2 loaded with polydopamine-modified silica obtained in step (2), solution-polymerized styrene-butadiene rubber-2 (parameters are shown in Table 3) and other additives are mixed. The formula of the solution-polymerized rubber raw rubber and other additives is shown in Table 2, wherein the amount of polydopamine-modified silica-2 added in step (1) accounts for 20wt% of the solution-polymerized styrene-butadiene rubber-2, and the amount of polydivinylbenzene microspheres-2 loaded with polydopamine-modified silica added in step (2) accounts for 5wt% of the solution-polymerized styrene-butadiene rubber-2; then, the mixture is vulcanized to obtain a rubber composite material, i.e., a polydivinylbenzene microsphere filler loaded with polydopamine-modified silica / solution-polymerized styrene-butadiene rubber composite material, denoted as A-2. The test results are shown in Table 7.

[0107] Table 3 Parameters of solution-polymerized styrene-butadiene rubber-2

[0108] Example 3

[0109] (1) Modification of silica: silica was dried at 110°C in a vacuum oven; dried silica and dopamine were added to a tris(hydroxymethylaminomethane) buffer solution (the concentration of tris(hydroxymethylaminomethane) was 10 mmol / L) at pH 9, and the mixture was reacted at room temperature for 2 h. The mixture was then filtered, washed, and dried to obtain polydopamine-modified nano-silica, designated as polydopamine-modified silica-3; wherein the mass ratio of silica to dopamine was 1:0.3, and the mass ratio of silica to buffer solution was 1:30;

[0110] (2) Preparation of polydivinylbenzene microspheres (DVB) loaded with polydopamine-modified silica: The polydopamine-modified silica-3 prepared in step (1) was dried under vacuum at 110°C; 0.3 μm polydivinylbenzene microspheres, dried polydopamine-modified silica-3, and a tris(hydroxymethylaminomethane) buffer solution (the concentration of tris(hydroxymethylaminomethane) was 10 mmol / L) were added to a round-bottom flask, and the mixture was stirred under magnetic stirring for 4 h at room temperature. After filtration, washing, and drying, polydivinylbenzene microspheres loaded with polydopamine-modified silica-3 were obtained; wherein the mass ratio of the polydivinylbenzene microspheres to the polydopamine-modified silica-3 was 1:8; and the mass ratio of the polydivinylbenzene microspheres to the buffer solution was 1:400;

[0111] (3) Preparation of rubber composite material: The polydopamine-modified silica-3 obtained in step (1) and the polydivinylbenzene microspheres-3 loaded with polydopamine-modified silica obtained in step (2), solution-polymerized styrene-butadiene rubber-3 (parameters are shown in Table 4) and other additives are mixed. The formula of the solution-polymerized rubber raw rubber and other additives is shown in Table 2, wherein the amount of polydopamine-modified silica-3 added in step (1) accounts for 25wt% of the solution-polymerized styrene-butadiene rubber-3, and the amount of polydivinylbenzene microspheres-3 loaded with polydopamine-modified silica added in step (2) accounts for 5wt% of the solution-polymerized styrene-butadiene rubber-3; then, the mixture is vulcanized to obtain a rubber composite material, i.e., a polydivinylbenzene microsphere filler loaded with polydopamine-modified silica / solution-polymerized styrene-butadiene rubber composite material, which is denoted as A-3. The test results are shown in Table 7.

[0112] Table 4 Parameters of solution polymerized styrene-butadiene rubber-3

[0113] Example 4

[0114] (1) Modification of silica: silica was dried at 110°C under vacuum; dried silica and dopamine were added to a prepared barbital / sodium chloride buffer solution with a pH of 8.5 (barbital / sodium chloride concentration was 6 mmol / L), reacted at room temperature for 2 h, filtered, washed, and dried to obtain polydopamine-modified nano-silica, designated as polydopamine-modified silica-4; wherein the mass ratio of silica to dopamine was 1:0.1, and the mass ratio of silica to buffer solution was 1:20;

[0115] (2) Preparation of polydivinylbenzene microspheres (DVB) loaded with polydopamine-modified silica: The polydopamine-modified silica-4 prepared in step (1) was dried under vacuum at 110°C; 0.3 μm polydivinylbenzene microspheres, dried polydopamine-modified silica-4, and a barbital / sodium chloride buffer solution (barbital / sodium chloride concentration was 6 mmol / L) with a pH of 8.5 were added to a round-bottom flask, and the mixture was stirred under magnetic stirring for 4 h at room temperature. After filtration, washing, and drying, polydivinylbenzene microspheres loaded with polydopamine-modified silica-4 were obtained; wherein the mass ratio of the polydivinylbenzene microspheres to the polydopamine-modified silica-4 was 1:5; and the mass ratio of the polydivinylbenzene microspheres to the buffer solution was 1:300.

[0116] (3) Preparation of rubber composite material: The polydopamine-modified silica-4 obtained in step (1) and the polydivinylbenzene microspheres-4 loaded with polydopamine-modified silica obtained in step (2), polyisoprene rubber-1 raw rubber and other additives are mixed. The formula of the solution-polymerized rubber raw rubber and other additives is shown in Table 2, and the polyisoprene rubber-1 (parameters are shown in Table 5); wherein, the amount of polydopamine-modified silica-4 added in step (1) accounts for 17wt% of the polyisoprene rubber, and the amount of polydivinylbenzene microspheres-4 loaded with polydopamine-modified silica added in step (2) accounts for 3wt% of the polyisoprene rubber; then, after vulcanization, a rubber composite material is obtained, i.e., a polydivinylbenzene microsphere filler loaded with polydopamine-modified silica / polyisoprene rubber composite material, denoted as A-4, and its test results are shown in Table 7.

[0117] Table 5 Parameters of polyisoprene rubber-1

[0118] Example 5

[0119] (1) Modification of silica: silica was dried at 110°C under vacuum; dried silica and dopamine were added to a prepared barbital / sodium chloride buffer solution with a pH of 8 (barbital / sodium chloride concentration was 9 mmol / L), reacted at room temperature for 2 h, filtered, washed, and dried to obtain polydopamine-modified nano-silica, designated as polydopamine-modified silica-5; wherein the mass ratio of silica to dopamine was 1:0.3, and the mass ratio of silica to buffer solution was 1:25;

[0120] (2) Preparation of polydivinylbenzene microspheres (DVB) loaded with polydopamine-modified silica: The polydopamine-modified silica-5 prepared in step (1) was dried under vacuum at 110°C; 0.4 μm polydivinylbenzene microspheres, dried polydopamine-modified silica-5, and a pH 8 barbital / sodium chloride buffer solution (barbital / sodium chloride concentration was 9 mmol / L) were added to a round-bottom flask, and the mixture was stirred under magnetic stirring for 4 h at room temperature. After filtration, washing, and drying, polydivinylbenzene microspheres loaded with polydopamine-modified silica-5 were obtained; wherein the mass ratio of polydivinylbenzene microspheres to polydopamine-modified silica-5 was 1:8; and the mass ratio of polydivinylbenzene microspheres to buffer solution was 1:400;

[0121] (3) Preparation of rubber composite material: The polydopamine-modified silica-5 obtained in step (1) and the polydivinylbenzene microspheres-5 loaded with polydopamine-modified silica obtained in step (2), polyisoprene rubber-2 raw rubber and other additives are mixed. The formula of the solution-polymerized rubber raw rubber and other additives is shown in Table 2, and the parameters of the polyisoprene rubber-2 raw rubber are shown in Table 6; wherein, the amount of polydopamine-modified silica-5 added in step (1) accounts for 24wt% of the polyisoprene rubber, and the amount of polydivinylbenzene microspheres-5 loaded with polydopamine-modified silica added in step (2) accounts for 6wt% of the polyisoprene rubber; then, after vulcanization, a rubber composite material is obtained, i.e., a polydivinylbenzene microsphere filler loaded with polydopamine-modified silica / polyisoprene rubber composite material, denoted as A-5, and its test results are shown in Table 7.

[0122] Table 6 Parameters of polyisoprene rubber-2

[0123] Example 6

[0124] (1) Modification of silica: silica was dried at 110°C under vacuum; dried silica and dopamine were added to a barbital / sodium chloride buffer solution (barbital / sodium chloride concentration was 8 mmol / L) with a pH of 8.5, and reacted at room temperature for 2 h. After filtration, washing, and drying, polydopamine-modified nano-silica was obtained, which was designated as polydopamine-modified silica-6; wherein the mass ratio of silica to dopamine was 1:0.1, and the mass ratio of silica to buffer solution was 1:20;

[0125] (2) Preparation of polydivinylbenzene microspheres (DVB) loaded with polydopamine-modified silica: The polydopamine-modified silica-6 prepared in step (1) was dried under vacuum at 110°C; 0.2 μm polydivinylbenzene microspheres, dried polydopamine-modified silica-6, and a barbital / sodium chloride buffer solution (barbital / sodium chloride concentration was 8 mmol / L) with a pH of 8.5 were added to a round-bottom flask, and the mixture was stirred under magnetic stirring for 4 h at room temperature. After filtration, washing, and drying, polydivinylbenzene microspheres loaded with polydopamine-modified silica-6 were obtained; wherein the mass ratio of the polydivinylbenzene microspheres to the polydopamine-modified silica-6 was 1:5; and the mass ratio of the polydivinylbenzene microspheres to the buffer solution was 1:300;

[0126] (3) Preparation of rubber composite material: The polydopamine-modified silica-6 obtained in step (1) and the polydivinylbenzene microspheres-6 loaded with polydopamine-modified silica obtained in step (2), butyl rubber and other additives are mixed. The formula of the solution-polymerized rubber and other additives is shown in Table 2, wherein the amount of polydopamine-modified silica-6 added in step (1) accounts for 20wt% of the butyl rubber, and the amount of polydivinylbenzene microspheres-6 loaded with polydopamine-modified silica added in step (2) accounts for 5wt% of the butyl rubber; then, the mixture is vulcanized to obtain a rubber composite material, i.e., a polydivinylbenzene microsphere filler loaded with polydopamine-modified silica / butyl rubber composite material, denoted as A-6. The test results are shown in Table 7.

[0127] Example 7

[0128] (1) Modification of silica: silica was dried at 110°C under vacuum; dried silica and dopamine were added to a prepared barbital / sodium chloride buffer solution with a pH of 7.8 (barbital / sodium chloride concentration was 9 mmol / L), reacted at room temperature for 2 h, filtered, washed, and dried to obtain polydopamine-modified nano-silica, designated as polydopamine-modified silica-7; wherein the mass ratio of silica to dopamine was 1:0.2, and the mass ratio of silica to buffer solution was 1:25;

[0129] (2) Preparation of polydivinylbenzene microspheres (DVB) loaded with polydopamine-modified silica: The polydopamine-modified silica-7 prepared in step (1) was dried under vacuum at 110°C; 0.4 μm polydivinylbenzene microspheres, dried polydopamine-modified silica-7, and a barbital / sodium chloride buffer solution (barbital / sodium chloride concentration was 9 mmol / L) with a pH of 7.8 were added to a round-bottom flask, and the mixture was stirred under magnetic stirring for 4 h at room temperature. After filtration, washing, and drying, polydivinylbenzene microspheres loaded with polydopamine-modified silica-7 were obtained; wherein the mass ratio of the polydivinylbenzene microspheres to the polydopamine-modified silica-7 was 1:8; and the mass ratio of the polydivinylbenzene microspheres to the buffer solution was 1:400;

[0130] (3) Preparation of rubber composite material: The polydopamine-modified silica-7 obtained in step (1) and the polydivinylbenzene microspheres-7 loaded with polydopamine-modified silica obtained in step (2), butyl rubber and other additives are mixed. The formula of the solution-polymerized rubber and other additives is shown in Table 2, wherein the amount of polydopamine-modified silica-7 added in step (1) accounts for 30wt% of the butyl rubber, and the amount of polydivinylbenzene microspheres-7 loaded with polydopamine-modified silica added in step (2) accounts for 10wt% of the butyl rubber; then, the mixture is vulcanized to obtain a rubber composite material, i.e., a polydivinylbenzene microsphere filler loaded with polydopamine-modified silica / butyl rubber composite material, denoted as A-7. The test results are shown in Table 7.

[0131] Example 8

[0132] A rubber composite material was prepared according to the method of Example 7, except that the mass ratio of polydivinylbenzene microspheres to polydopamine-modified silica-7 in step (2) was 1:1; the obtained rubber composite material was designated A-8, and the test results are shown in Table 7.

[0133] Example 9

[0134] A rubber composite material was prepared according to the method of Example 7, except that the mass ratio of polydivinylbenzene microspheres to polydopamine-modified silica-7 in step (2) was 1:0.5; the obtained rubber composite material was designated A-9, and the test results are shown in Table 7.

[0135] Example 10

[0136] A rubber composite material was prepared according to the method of Example 7, except that the mass ratio of polydivinylbenzene microspheres to polydopamine-modified silica-7 in step (2) was 1:10. The obtained rubber composite material was designated as A-10, and the test results are shown in Table 7.

[0137] Example 11

[0138] A rubber composite material was prepared according to the method of Example 7, except that the mass ratio of polydivinylbenzene microspheres to polydopamine-modified silica-7 in step (2) was 1:15. The obtained rubber composite material was designated as A-11, and the test results are shown in Table 7.

[0139] Example 12

[0140] A rubber composite material was prepared according to the method of Example 7, except that in the preparation of the rubber composite material in step (3), the amount of polydopamine-modified silica-7 added in step (1) accounted for 20 wt% of the butyl rubber, and the amount of polydivinylbenzene microspheres-7 loaded with polydopamine-modified silica added in step (2) accounted for 40 wt% of the butyl rubber; the obtained rubber composite material was designated A-12, and the test results are shown in Table 7.

[0141] Example 13

[0142] A rubber composite material was prepared according to the method of Example 7, except that in the preparation of the rubber composite material in step (3), the amount of polydopamine-modified silica-7 added in step (1) accounted for 40 wt% of the butyl rubber, and the amount of polydivinylbenzene microspheres-7 loaded with polydopamine-modified silica added in step (2) accounted for 20 wt% of the butyl rubber; the obtained rubber composite material was designated A-13, and the test results are shown in Table 7.

[0143] Comparative Example 1

[0144] A rubber composite material was prepared according to the method of Example 1, except that step (2) was not performed. In step (3), the rubber composite material was prepared by mixing 17 wt% of silica with respect to the solution-polymerized styrene-butadiene rubber-1, 3 wt% of polydopamine-modified silica-1 with respect to the solution-polymerized styrene-butadiene rubber-1, the solution-polymerized rubber raw rubber shown in Table 2, and other additives; and then vulcanizing to obtain a silica / solution-polymerized styrene-butadiene rubber composite sample, designated D-1. The test results are shown in Table 7.

[0145] Comparative Example 2

[0146] A rubber composite material was prepared according to the method of Example 1, except that, in the preparation of the rubber composite material in step (3), the polydopamine-modified silica-1 in step (1) was not added, and the amount of polydivinylbenzene microspheres-1 loaded with polydopamine-modified silica in step (2) was 10 wt% of the solution-polymerized styrene-butadiene rubber-1; the obtained rubber composite material was designated as D-2, and the test results are shown in Table 7.

[0147] Comparative Example 3

[0148] A rubber composite material was prepared according to the method of Example 1, except that, in the preparation of the rubber composite material in step (3), the polydivinylbenzene microspheres-1 loaded with polydopamine-modified silica in step (2) were not added, and the amount of polydopamine-modified silica-1 added in step (1) accounted for 40 wt% of the solution-polymerized styrene-butadiene rubber-1; a rubber composite material was obtained, designated D-3, and its test results are shown in Table 7.

[0149] Comparative Example 4

[0150] A rubber composite material was prepared according to the method of Example 3, except that step (2) was not performed. In step (3), the rubber composite material was prepared by mixing 25 wt% of silica in the solution-polymerized styrene-butadiene rubber-3, 5 wt% of the polydopamine-modified silica-3 obtained in step (1) in the solution-polymerized rubber-3, the solution-polymerized rubber raw rubber shown in Table 2, and other additives, and then vulcanizing to obtain a silica / solution-polymerized styrene-butadiene rubber composite sample, recorded as D-4. The test results are shown in Table 7.

[0151] Table 7 Test results of rubber composite materials

[0152] The results in Table 7 show that the examples have significantly better results than the comparative examples. The present invention uses polydivinylbenzene microspheres loaded with polydopamine-modified silica as a filler to replace a portion of the polydopamine-modified silica. The use of the polydivinylbenzene microspheres as a carrier reduces agglomeration of the modified silica, improves the dispersion of the modified silica, and more effectively enhances the dispersibility and stability of the silica. Furthermore, the modified polydivinylbenzene microspheres also serve as entanglement crosslinking points. Due to the polar functional groups on their surfaces, they can generate interaction forces with silica. Furthermore, the modified polydivinylbenzene microspheres enhance the physical and mechanical properties of the material through vulcanization crosslinking.

[0153] The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, various simple variations of the technical solution of the present invention may be made, including combining the various technical features in any other appropriate manner. These simple variations and combinations should also be regarded as disclosed in the present invention and fall within the scope of protection of the present invention.

Claims

1. A rubber filler, characterized in that: The rubber filler comprises: 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 1:0.5-20.

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

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

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

5. A method for preparing a rubber filler, characterized in that: The preparation method comprises: (1) in a first buffer solution, reacting white carbon black with dopamine to obtain polydopamine-modified white carbon black; (2) In a second buffer solution, subjecting the polydivinylbenzene microspheres to a second reaction with the polydopamine-modified silica obtained in step (1) to obtain polydivinylbenzene microspheres loaded with polydopamine-modified silica; wherein the mass ratio of the polydivinylbenzene microspheres to the polydopamine-modified silica is 1:0.5-20.

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

7. The preparation method according to claim 6, wherein: The mass ratio of white carbon black to dopamine is 1:0.05-1; and / or the mass ratio of white carbon black to the first buffer solution is 1:5-50; And / or, the weak 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; And / or, the inorganic acid is one or more of hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid; And / or, the inorganic base is potassium hydroxide and / or sodium hydroxide.

8. The preparation method according to claim 5 or 6, wherein: Step (2) specifically includes the following steps: Adding an inorganic acid or an inorganic base to a weakly alkaline buffer solution to obtain a second buffer solution having a pH of 7.5-10.5, wherein the concentration of the buffer in the second buffer solution is 3-15 mmol / L; The polydivinylbenzene microspheres and the polydopamine-modified silica obtained in step (1) are added to the second buffer solution, and reacted under magnetic stirring at room temperature for 1-4 hours, and then filtered, washed and dried to obtain polydivinylbenzene microspheres loaded with polydopamine-modified silica.

9. The preparation method according to claim 8, wherein: The mass ratio of the polydivinylbenzene microspheres to the polydopamine-modified white carbon black is 1:1-10; and / or, the mass ratio of the polydivinylbenzene microspheres to the second buffer solution is 1:50-500; And / or, the weak 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; And / or, the inorganic acid is one or more of hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid; And / or, the inorganic base is potassium hydroxide and / or sodium hydroxide.

10. A rubber composite material, characterized in that: The rubber composite material comprises: a solution-polymerized rubber, a first filler and a second filler, wherein the first filler is the rubber filler described in any one of claims 1 to 4 or the rubber filler prepared by the preparation method described in any one of claims 5 to 9, and the second filler is polydopamine-modified silica; the total addition amount of the first rubber filler and the second rubber filler is 10-60wt% of the dry basis mass of the solution-polymerized rubber.

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

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

13. The rubber composite material according to claim 10 or 11, wherein: The rubber composite material further includes an additive.

14. The rubber composite material according to claim 13, wherein The auxiliary agent is selected from one or more of 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 rubber raw rubber is selected from one or more of solution polymerized styrene-butadiene rubber, isoprene rubber, butadiene rubber and butyl rubber.

16. A method for preparing a rubber composite material, characterized in that: The preparation method comprises: The solution-polymerized rubber raw rubber is kneaded with a first filler and a second filler, and then vulcanized to obtain a rubber composite material; wherein the first filler is a rubber filler according to any one of claims 1 to 4 or a rubber filler prepared by the preparation method according to any one of claims 5 to 9, and 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 10-60wt% of the dry basis mass of the solution-polymerized rubber raw rubber.

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

18. The preparation method according to claim 16 or 17, wherein: The added amount of the second rubber filler is 10-40wt% of the dry basis mass of the solution-polymerized raw rubber.

19. The preparation method according to claim 16 or 17, wherein: In the mixing step, an auxiliary agent is also added.

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

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

22. Use of the rubber composite material according to any one of claims 10 to 15 or the rubber composite material prepared by the preparation method according to claims 16 to 21 in tires.

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