Rubber filler, rubber composite material containing same as well as preparation method and application of rubber filler

Abstract

The invention discloses a rubber filler, a rubber composite material containing the same, and a preparation method and application of the rubber filler. The rubber filler disclosed by the invention is prepared from polydivinylbenzene microspheres and polydopamine modified white carbon black loaded on the polydivinylbenzene microspheres, wherein the mass ratio of the polydivinylbenzene microspheres to the polydopamine modified white carbon black is 1: (0.5-20). The rubber composite material provided by the invention comprises solution polymerized raw rubber and the rubber filler, wherein the addition amount of the rubber filler is 10-60wt% of the dry basis mass of the solution polymerized raw rubber. According to the invention, the polydopamine modified white carbon black loaded polydivinylbenzene microspheres are used as a filler, so that the problems that white carbon black is easy to agglomerate and the binding force between the white carbon black and rubber is poor are solved. The obtained rubber composite material can be suitable for manufacturing green tires.

Description

Technical Field

[0001] The 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

[0002] Green tires (or fuel-saving tires) are designed to save fuel and reduce exhaust emissions. Compared with ordinary radial tires, green tires have significantly lower energy consumption. Solution-polymerized styrene butadiene rubber is more environmentally friendly than general-purpose emulsion-polymerized styrene butadiene rubber, and the microscopic molecular structure can be controlled and adjusted as needed during the synthesis process, which can simultaneously improve the rolling resistance coefficient and wet grip index of the tire. In the next few years, the application of solution-polymerized styrene butadiene rubber in the tire industry will surely make rapid progress. Butadiene rubber, isoprene rubber and butyl rubber are also produced using the solution polymerization process and are all used in the tire industry.

[0003] Currently, the most widely used filler is carbon black, but with the increasing environmental protection requirements, white carbon black will gradually replace carbon black and become the largest filler. White carbon black / solution polymerized styrene butadiene rubber compounding system is a commonly used compounding system for preparing high-performance green tire tread rubber, but white carbon black has a small particle size, high surface polarity and poor compatibility with rubber, so it is easy to agglomerate and difficult to disperse. Therefore, white carbon black needs surface modification, and the filler surface modifiers commonly used in the prior art include titanate coupling agents and silane coupling agents.

[0004] CN101798473A discloses the use of polysulfide silane coupling agent to modify white carbon black and then prepare white carbon black / carbon black composite filler. However, increasing the amount of silane coupling agent will cause the vulcanization kinetics to decrease, and the vulcanizer and vulcanization accelerator need to be added.

[0005] CN101220177A discloses a method for preparing a nanocomposite material of white carbon black / solution polymerized styrene butadiene rubber by modifying white carbon black with an amino-type silane coupling agent. Nano-white carbon black and a silane coupling agent are dispersed in ethanol, and a condensation reaction is carried out at a high temperature. The modified nano-white carbon black powder is then added to a solution polymerized styrene butadiene rubber solution, and the white carbon black / solution polymerized styrene butadiene rubber nanocomposite material prepared by a co-coagulation method is obtained after stirring and dispersing, removing the solvent, and drying. However, small-molecule surface modifiers have the disadvantages of poor processing performance, small molecules generated during the modification process, poor storage stability, and affecting the service life of tires, and the problem of poor bonding between white carbon black and rubber cannot be solved. Summary of the invention

[0006] The purpose of the present invention is to overcome the problems of the prior art that white carbon black is easy to agglomerate and the bonding strength between white carbon black and rubber is poor, and to provide a rubber composite material and a preparation method and application thereof. The rubber composite material of the present invention uses polydivinylbenzene microspheres loaded with dopamine-modified white carbon black as filler, and uses the polydivinylbenzene microspheres as carriers, which can more effectively improve the dispersibility of white carbon black. At the same time, the polydivinylbenzene microspheres can also play the role of physical entanglement crosslinking points, and the physical and mechanical properties of the material are improved by vulcanization crosslinking with the blended rubber. The rubber composite material can be used to manufacture green tires.

[0007] 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.

[0008] A second aspect of the present invention provides a method for preparing a rubber filler, the preparation method comprising:

[0009] (1) in a first buffer solution, reacting white carbon black with dopamine to obtain polydopamine-modified white carbon black;

[0010] (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.

[0011] The third aspect of the present invention provides a rubber composite material, which includes: a solution-polymerized rubber 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 rubber raw rubber.

[0012] The 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 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 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 rubber raw rubber.

[0013] 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.

[0014] Through the above technical solution, the beneficial technical effects achieved by the present invention are as follows:

[0015] (1) The rubber filler of the present invention is polydivinylbenzene microspheres loaded with polydopamine-modified white carbon black. The use of polydopamine to modify white carbon black can prevent the self-agglomeration of white carbon black and improve the dispersibility of white carbon black. At the same time, using polydivinylbenzene microspheres as a carrier can more effectively improve the dispersibility of white carbon black.

[0016] (2) The rubber filler of the present invention can be used to prepare a rubber composite material, and the polydivinylbenzene microspheres can also play the role of 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 closely combined with the rubber to improve the mechanical strength of white carbon black / rubber. The rubber composite material obtained by the present invention can be used to manufacture green tires.

[0017] (3) The preparation method of the present invention has few steps and is simple to operate, thereby solving the problem that white carbon black is easy to agglomerate and that the bonding strength between white carbon black and rubber is poor. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 They are 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

[0019] The endpoints and any values ​​of the ranges disclosed in this article 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 endpoint values ​​of each range, the endpoint values ​​of each range and the 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 as specifically disclosed in this article.

[0020] A first aspect of the present invention provides a rubber filler, comprising: 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, 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 of any two values, preferably 1:1-10.

[0021] The polydivinylbenzene microspheres used in the present invention have strong adsorption capacity, and are mainly loaded. The present invention does not limit the specific loading form of polydopamine-modified silica, as long as it can be loaded on the polydivinylbenzene microspheres. The polydopamine-modified silica is loaded on the polydivinylbenzene microspheres (DVB), and may be loaded on the surface of the polydivinylbenzene microspheres, may be loaded in the internal pores of the polydivinylbenzene microspheres, or may exist in both situations. It has been found through research that the polydopamine-modified silica is mainly deposited and adhered to the surface of the microspheres.

[0022] The present invention adopts polydopamine to modify white carbon black, prevents the self-agglomeration of white carbon black, and improves the dispersibility of white carbon black. The catecholamine structure in polydopamine has high affinity, can be closely combined with rubber, and improves the mechanical strength of white carbon black / rubber. At the same time, polydivinylbenzene microspheres are used as carriers to more effectively improve the dispersibility of white carbon black, and the microspheres have good compatibility with rubber. The microspheres have strong adsorption and can be well used as attached fillers. In the process of preparing rubber composite materials, the polydivinylbenzene microspheres can also play the role of physical entanglement crosslinking points, and can effectively enhance the physical and mechanical properties of the material through physical crosslinking with the blended rubber, and can be suitable for manufacturing green tires.

[0023] 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 composed of any two values, preferably 1:0.1-0.6.

[0024] 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.

[0025] 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.

[0026] A second aspect of the present invention provides a method for preparing a rubber filler, the preparation method comprising:

[0027] (1) in a first buffer solution, reacting white carbon black with dopamine to obtain polydopamine-modified white carbon black;

[0028] (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.

[0029] like Figure 1 As shown, 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 the wave number of 1099 cm -1 The asymmetric stretching vibration absorption peak of Si-O-Si appears at 804 cm -1 The symmetric 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. 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 nearby 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.

[0030] In some embodiments of the present invention, step (1) specifically comprises the following steps:

[0031] 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;

[0032] 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.

[0033] In the present invention, dried white carbon black is used in the modification process, and the dried white carbon black can be dried using a common technique in the art, for example, drying the white carbon black at 100-120° C. in a vacuum.

[0034] Further, the mass ratio of white carbon black 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 composed of any two values, preferably 1:0.1-0.6.

[0035] Further, 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.

[0036] 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.

[0037] Furthermore, the inorganic acid is one or more of hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid.

[0038] Furthermore, the inorganic base is potassium hydroxide and / or sodium hydroxide.

[0039] In some embodiments of the present invention, step (2) specifically comprises the following steps:

[0040] 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;

[0041] 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.

[0042] Further, 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 of any two values, preferably 1:100-400.

[0043] 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.

[0044] Furthermore, the inorganic acid is one or more of hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid.

[0045] Furthermore, the inorganic base is potassium hydroxide and / or sodium hydroxide.

[0046] The third aspect of the present invention provides a rubber composite material, which includes: a solution-polymerized rubber 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 white carbon black; 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 rubber raw rubber, for example, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, and any value in the range composed of any two numerical values, preferably 20-40wt%.

[0047] 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.

[0048] In some embodiments of the present invention, the added amount of the second rubber filler 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%.

[0049] In some embodiments of the present invention, the rubber composite material further includes an additive.

[0050] Furthermore, the auxiliary agent is selected from one or more of a vulcanizing agent, an antioxidant, a accelerator and an activator.

[0051] In the present invention, the types, functions and addition amounts of the additives are well known to those skilled in the art, for example, there are relevant descriptions thereof in "Practical Rubber Formulation Technology", which will not be repeated here.

[0052] In some embodiments of the present invention, 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.

[0053] 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%.

[0054] Furthermore, the weight average molecular weight Mw of the isoprene rubber is 150,000-300,000 g / mol.

[0055] Furthermore, the weight average molecular weight Mw of the butadiene rubber is 200,000-300,000 g / mol.

[0056] Furthermore, the weight average molecular weight Mw of the butyl rubber is 100,000-500,000 g / mol.

[0057] A fourth aspect of the present invention provides a method for preparing a rubber composite material, the preparation method comprising the following steps:

[0058] 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 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 rubber raw rubber, for example, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, and any value in the range composed of any two values, preferably 20-40wt%.

[0059] The present invention adopts polydivinylbenzene microspheres loaded with polydopamine-modified white carbon black as the first rubber filler, which can prevent the white carbon black from agglomerating itself and improve the dispersibility and stability of the white carbon black. At the same time, the polydopamine-modified white carbon black can also prevent the white carbon black from agglomerating itself, improve the dispersibility of the white carbon black, and improve the mechanical strength of the white carbon black / rubber. In the preparation process of the rubber composite material, the polydivinylbenzene microspheres can also play the role of 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 white carbon black 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 can be suitable for manufacturing green tires.

[0060] In the present invention, conventional mixing methods may be used in the rubber mixing process, such as mixing in an open mixer and mixing in an internal mixer.

[0061] 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.

[0062] In some embodiments of the present invention, the added amount of the second rubber filler 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%.

[0063] In some embodiments of the present invention, an auxiliary agent is also added in the mixing step.

[0064] Furthermore, the auxiliary agent is selected from one or more of a vulcanizing agent, an antioxidant, a accelerator and an activator.

[0065] During the mixing process of rubber, one or more additives such as vulcanizers, antioxidants, accelerators, and activators can be added. These additives, the amounts added, and their effects are well known to those skilled in the art. For example, there is a relevant description of them in "Practical Rubber Formulation Technology", which will not be repeated here.

[0066] In some embodiments of the present invention, 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.

[0067] 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%.

[0068] Furthermore, the weight average molecular weight Mw of the isoprene rubber is 150,000-300,000 g / mol.

[0069] Furthermore, the weight average molecular weight Mw of the butadiene rubber is 200,000-300,000 g / mol.

[0070] Furthermore, the weight average molecular weight Mw of the butyl rubber is 100,000-500,000 g / mol.

[0071] 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.

[0072] The rubber composite material of the 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.

[0073] Furthermore, the aforementioned rubber composite material is used in green tires.

[0074] The invention solves the problem that white carbon black is easy to agglomerate and the bonding strength between white carbon black and rubber is poor. Moreover, the polydivinylbenzene microspheres are used as carriers to more effectively improve the dispersibility of white carbon black. The polydivinylbenzene microspheres can also play the role of physical entanglement crosslinking points, and can improve the physical and mechanical properties of the material through physical crosslinking with the blended rubber, and can be used to manufacture green tires. At the same time, the preparation method of the invention has fewer reaction steps and is simple to operate.

[0075] In the present invention, unless otherwise specified, % refers to mass percentage.

[0076] The technical solutions in the present invention are described clearly and completely by way of embodiments below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments in the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0077] In the following examples and comparative examples, if no specific conditions are specified, the experiments were carried out under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used, if no manufacturer is specified, are all conventional products that can be obtained through commercial channels.

[0078] In the following embodiments,

[0079] (1) Source of raw materials:

[0080] White carbon black was purchased from Weifang Wanli Additive Co., Ltd.

[0081] Dopamine, tris(hydroxymethyl)aminomethane, 99.5%, purchased from Acros Organics;

[0082] 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.;

[0083] Polydivinylbenzene microspheres, with a particle size of 0.2-0.5 μm, were purchased from Suzhou Zhiwei Nanotechnology Co., Ltd.;

[0084] Solution polymerized styrene butadiene rubber was purchased from Lanzhou Chemical Research Center and Dushanzi Petrochemical Company;

[0085] Isoprene rubber was purchased from PetroChina Jilin Petrochemical Company and Lanzhou Chemical Research Center;

[0086] Butyl rubber was purchased from Bayer, Germany.

[0087] (2) Analytical testing methods:

[0088] Infrared spectrum analysis of samples: The functional group analysis of nano-silica before and after modification was performed using an infrared spectrometer from Bruker Spectroscopy Instruments of Germany. The samples were dried in a vacuum oven at 100°C, pressed into tablets using potassium bromide, and the wave number range was 400-4000.

[0089] Differential thermal analysis of polymer deposition: The deposition of polydopamine was analyzed using a synchronous thermal analyzer (TG / DSC, STA449C) from NETZSCH, Germany. The sample was dried in a vacuum oven at 100°C, and the weight loss data of the sample in the range of 20-600°C was collected.

[0090] Glass transition temperature analysis: The glass transition temperature was determined using a synchronous thermal analyzer (TG / DSC, STA449C) from NETZSCH, Germany.

[0091] Mechanical properties analysis: The mechanical properties of the samples were tested using a 5567 universal material testing machine produced by Instron, USA.

[0092] Tensile strength, elongation at break: Implementation standard GB / T528-2009;

[0093] Shore A hardness: Implementation standard GB / T531.1-2008.

[0094] Example 1

[0095] (1) Modification of silica: silica was dried at 100°C under vacuum; dried silica and dopamine were added to a tris(hydroxymethyl)aminomethane buffer solution (the concentration of tris(hydroxymethyl)aminomethane was 9 mmol / L) with a pH of 8.5, reacted at room temperature for 1.5 h, and then filtered, washed and dried to obtain polydopamine-modified silica, which was recorded 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;

[0096] (2) Preparation of polydivinylbenzene microspheres (DVB) loaded with polydopamine-modified silica: The polydopamine-modified silica-1 prepared in step (1) is 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) is 9 mmol / L) are added to a round-bottom flask, and the mixture is reacted under magnetic stirring for 3 h at room temperature, and then filtered, washed, and dried to obtain polydivinylbenzene microspheres-1 loaded with polydopamine-modified silica; wherein the mass ratio of the polydivinylbenzene microspheres to the polydopamine-modified silica-1 is 1:5; and the mass ratio of the polydivinylbenzene microspheres to the buffer solution is 1:300;

[0097] (3) Preparation of rubber composite material: Solution polymerized styrene butadiene rubber-1 (parameters see Table 1), polydopamine-modified silica-1 obtained in step (1), polydivinylbenzene microspheres-1 loaded with polydopamine-modified silica 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-1 loaded with polydopamine-modified silica is 3wt% of the solution polymerized styrene butadiene rubber-1; then, after vulcanization, a rubber composite material is obtained, i.e., polydivinylbenzene microspheres filler loaded with polydopamine-modified silica / solution polymerized styrene butadiene rubber composite material, denoted as A-1, and its test results are shown in Table 7.

[0098] Table 1 Parameters of solution polymerized styrene-butadiene rubber-1

[0099]

[0100]

[0101] Table 2 Rubber compound formula

[0102]

[0103] Example 2

[0104] (1) Modification of silica: The silica was dried at 110°C in a vacuum oven; the dried silica and dopamine were added to a tris(hydroxymethyl)aminomethane buffer solution (the concentration of tris(hydroxymethyl)aminomethane was 6 mmol / L) at a pH of 9, and the mixture was reacted at room temperature for 2 h. The mixture was filtered, washed and dried to obtain polydopamine-modified nano silica, 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) is 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) is 6 mmol / L) are added to a round-bottom flask, and the mixture is reacted under magnetic stirring at room temperature for 4 h. After filtering, washing, and drying, polydivinylbenzene microspheres-2 loaded with polydopamine-modified silica are obtained; wherein the mass ratio of the polydivinylbenzene microspheres to the polydopamine-modified silica-2 is 1:7; and the mass ratio of the polydivinylbenzene microspheres to the buffer solution is 1:400;

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

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

[0108] Sample name Styrene Vinyl Mn(before coupling) Tg Solution Polymerized Styrene Butadiene Rubber-2 25％ 65％ 260,000 g / mol -25℃

[0109] Example 3

[0110] (1) Modification of silica: The silica was dried at 110°C in a vacuum oven; the dried silica and dopamine were added to a tris(hydroxymethyl)aminomethane buffer solution (the concentration of tris(hydroxymethyl)aminomethane was 10 mmol / L) at a pH of 9, and reacted at room temperature for 2 h, and then filtered, washed and dried to obtain polydopamine-modified nano silica, which was recorded 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;

[0111] (2) Preparation of polydivinylbenzene microspheres (DVB) loaded with polydopamine-modified silica: The polydopamine-modified silica-3 prepared in step (1) is 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) is 10 mmol / L) are added to a round-bottom flask, and the mixture is reacted under magnetic stirring for 4 h at room temperature. After filtering, washing, and drying, polydivinylbenzene microspheres-3 loaded with polydopamine-modified silica are obtained; wherein the mass ratio of the polydivinylbenzene microspheres to the polydopamine-modified silica-3 is 1:8; and the mass ratio of the polydivinylbenzene microspheres to the buffer solution is 1:400;

[0112] (3) Preparation of rubber composite material: The polydopamine-modified silica-3 obtained in step (1), 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 the polydopamine-modified silica-3 added in step (1) accounts for 25wt% of the solution-polymerized styrene-butadiene rubber-3, and the amount of the polydivinylbenzene microspheres-3 loaded with polydopamine-modified silica in step (2) accounts for 5wt% of the solution-polymerized styrene-butadiene rubber-3; then, after vulcanization, a rubber composite material is obtained, namely, a polydivinylbenzene microsphere filler loaded with polydopamine-modified silica / solution-polymerized styrene-butadiene rubber composite material, denoted as A-3, and the test results are shown in Table 7.

[0113] Table 4 Parameters of solution polymerized styrene butadiene rubber-3

[0114] Sample name Styrene Vinyl Mn(before coupling) Tg Solution Polymerized Styrene Butadiene Rubber-3 25％ 70％ 230,000 g / mol -23℃

[0115] Example 4

[0116] (1) Modification of silica: The silica was dried at 110°C in a vacuum oven; the dried silica and dopamine were added to a barbital / sodium chloride buffer solution (barbital / sodium chloride concentration was 6 mmol / L) with a pH of 8.5, and reacted at room temperature for 2 h. After filtering, washing and drying, polydopamine-modified nano silica was obtained, which was recorded 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;

[0117] (2) Preparation of polydivinylbenzene microspheres (DVB) loaded with polydopamine-modified silica: The polydopamine-modified silica-4 prepared in step (1) is dried under vacuum at 110°C; 0.3 μm polydivinylbenzene microspheres, dried polydopamine-modified silica-4 and a barbiturate / sodium chloride buffer solution (barbiturate / sodium chloride concentration is 6 mmol / L) with a pH of 8.5 are added to a round-bottom flask, and the mixture is reacted under magnetic stirring at room temperature for 4 h. After filtering, washing and drying, polydivinylbenzene microspheres-4 loaded with polydopamine-modified silica are obtained; wherein the mass ratio of polydivinylbenzene microspheres to polydopamine-modified silica-4 is 1:5; and the mass ratio of polydivinylbenzene microspheres to buffer solution is 1:300.

[0118] (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 the polydopamine-modified silica-4 added in step (1) accounts for 17wt% of the polyisoprene rubber, and the amount of the polydivinylbenzene microspheres-4 loaded with polydopamine-modified silica in step (2) accounts for 3wt% of the polyisoprene rubber; and then vulcanization is performed to obtain a rubber composite material, 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.

[0119] Table 5 Parameters of polyisoprene rubber-1

[0120]

[0121] Example 5

[0122] (1) Modification of silica: The silica was dried at 110°C in a vacuum oven; the dried silica and dopamine were added to a barbital / sodium chloride buffer solution (barbital / sodium chloride concentration was 9 mmol / L) with a pH of 8, and reacted at room temperature for 2 h. After filtering, washing and drying, polydopamine-modified nano silica was obtained, which was recorded 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;

[0123] (2) Preparation of polydivinylbenzene microspheres (DVB) loaded with polydopamine-modified silica: The polydopamine-modified silica-5 prepared in step (1) is dried under vacuum at 110° C.; 0.4 μm polydivinylbenzene microspheres, dried polydopamine-modified silica-5, and a pH 8 barbiturate / sodium chloride buffer solution (barbiturate / sodium chloride concentration is 9 mmol / L) are added to a round-bottom flask, and the mixture is reacted under magnetic stirring at room temperature for 4 h. After filtering, washing, and drying, polydivinylbenzene microspheres-5 loaded with polydopamine-modified silica are obtained; wherein the mass ratio of the polydivinylbenzene microspheres to the polydopamine-modified silica-5 is 1:8; and the mass ratio of the polydivinylbenzene microspheres to the buffer solution is 1:400;

[0124] (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 the polydopamine-modified silica-5 added in step (1) accounts for 24 wt% of the polyisoprene rubber, and the amount of the polydivinylbenzene microspheres-5 loaded with polydopamine-modified silica in step (2) accounts for 6 wt% of the polyisoprene rubber; and then the rubber composite material is obtained by vulcanization, i.e., the polydivinylbenzene microspheres filler loaded with polydopamine-modified silica / polyisoprene rubber composite material, denoted as A-5, and the test results are shown in Table 7.

[0125] Table 6 Parameters of polyisoprene rubber-2

[0126]

[0127] Example 6

[0128] (1) Modification of silica: The silica was dried at 110°C in a vacuum oven; the 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 filtering, washing and drying, polydopamine-modified nano silica was obtained, which was recorded 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;

[0129] (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 is 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 filtering, 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;

[0130] (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 the polydopamine-modified silica-6 added in step (1) accounts for 20wt% of the butyl rubber, and the amount of the polydivinylbenzene microspheres-6 loaded with polydopamine-modified silica in step (2) accounts for 5wt% of the butyl rubber; then, after vulcanization, a rubber composite material is obtained, i.e., a polydivinylbenzene microsphere filler loaded with polydopamine-modified silica / butyl rubber composite material, denoted as A-6, and its test results are shown in Table 7.

[0131] Example 7

[0132] (1) Modification of silica: The silica was dried at 110°C in a vacuum oven; the dried silica and dopamine were added to a barbital / sodium chloride buffer solution (barbital / sodium chloride concentration was 9 mmol / L) with a pH of 7.8, and reacted at room temperature for 2 h. After filtering, washing and drying, polydopamine-modified nano silica was obtained, which was recorded 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;

[0133] (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 pH 7.8 barbiturate / sodium chloride buffer solution (barbiturate / 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 filtering, 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;

[0134] (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 the polydopamine-modified silica-7 added in step (1) accounts for 30wt% of the butyl rubber, and the amount of the polydivinylbenzene microspheres-7 loaded with polydopamine-modified silica in step (2) accounts for 10wt% of the butyl rubber; then, after vulcanization, a rubber composite material is obtained, i.e., a polydivinylbenzene microsphere filler loaded with polydopamine-modified silica / butyl rubber composite material, denoted as A-7, and the test results are shown in Table 7.

[0135] Example 8

[0136] A rubber composite material was prepared according to the method of Example 7, except that in step (2), the mass ratio of polydivinylbenzene microspheres to polydopamine-modified silica-7 was 1:1; the obtained rubber composite material was designated as A-8, and the test results thereof are shown in Table 7.

[0137] Example 9

[0138] A rubber composite material was prepared according to the method of Example 7, except that in step (2), the mass ratio of polydivinylbenzene microspheres to polydopamine-modified silica-7 was 1:0.5; the obtained rubber composite material was designated as A-9, and the test results thereof are shown in Table 7.

[0139] Example 10

[0140] A rubber composite material was prepared according to the method of Example 7, except that in step (2), the mass ratio of polydivinylbenzene microspheres to polydopamine-modified silica-7 was 1:10; the obtained rubber composite material was designated as A-10, and the test results thereof are shown in Table 7.

[0141] Embodiment 11

[0142] A rubber composite material was prepared according to the method of Example 7, except that in step (2), the mass ratio of polydivinylbenzene microspheres to polydopamine-modified silica-7 was 1:15; the obtained rubber composite material was designated as A-11, and the test results thereof are shown in Table 7.

[0143] Example 12

[0144] 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 20wt% of the butyl rubber, and the amount of polydivinylbenzene microspheres-7 loaded with polydopamine-modified silica added in step (2) accounted for 40wt% of the butyl rubber; the rubber composite material was obtained, denoted as A-12, and the test results thereof are shown in Table 7.

[0145] Embodiment 13

[0146] 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 40wt% of the butyl rubber, and the amount of polydivinylbenzene microspheres-7 loaded with polydopamine-modified silica added in step (2) accounted for 20wt% of the butyl rubber; the rubber composite material was obtained, recorded as A-13, and its test results are shown in Table 7.

[0147] Comparative Example 1

[0148] 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 white carbon black in solution polymerized butadiene styrene rubber-1, 3 wt% of polydopamine-modified white carbon black-1 in solution polymerized butadiene styrene rubber-1, the solution polymerized rubber raw rubber shown in Table 2, and other additives; then, the mixture was vulcanized to obtain a white carbon black / solution polymerized butadiene styrene rubber composite sample, which was designated as D-1. The test results are shown in Table 7.

[0149] Comparative Example 2

[0150] 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) accounted for 10wt% of the solution-polymerized styrene-butadiene rubber-1; a rubber composite material was obtained, denoted as D-2, and its test results are shown in Table 7.

[0151] Comparative Example 3

[0152] 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 40wt% of the solution-polymerized styrene-butadiene rubber-1; a rubber composite material was obtained, denoted as D-3, and its test results are shown in Table 7.

[0153] Comparative Example 4

[0154] A rubber composite material was prepared according to the method of Example 3, except that step (2) was not performed. Step (3) Preparation of the rubber composite material: 25 wt% of white carbon black accounting for 5 wt% of the solution polymerized styrene butadiene rubber-3, the polydopamine-modified white carbon black-3 obtained in step (1) accounting for 5 wt% of the solution polymerized styrene butadiene rubber-3, the solution polymerized rubber raw rubber shown in Table 2 and other additives were mixed, and then vulcanized to obtain a white carbon black / solution polymerized styrene butadiene rubber composite sample, recorded as D-4, and its test results are shown in Table 7.

[0155] Table 7 Test results of rubber composite materials

[0156]

[0157]

[0158] It can be seen from the results in Table 7 that the embodiment has a significantly better effect than the comparative example. The present invention uses polydivinylbenzene microspheres loaded with polydopamine-modified white carbon black as filler to replace part of the polydopamine-modified white carbon black. The polydivinylbenzene microspheres are used as carriers, so that the modified white carbon black is not easy to agglomerate, and the dispersion of the modified white carbon black is improved, and the dispersibility and stability of the white carbon black can be more effectively improved. At the same time, the modified polydivinylbenzene microspheres can also play the role of entanglement crosslinking points. Since the surface of the modified polydivinylbenzene microspheres has polar functional groups, they can generate interaction forces with white carbon black, and the modified polydivinylbenzene microspheres improve the physical and mechanical properties of the material through vulcanization crosslinking.

[0159] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope 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 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; 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, auxiliary agents are 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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