Rubber compositions and vulcanizates, and methods of making and using the same

Abstract

The application relates to the field of vulcanized rubber, and discloses a rubber composition and vulcanized rubber as well as a preparation method and application thereof. The composition comprises a rubber matrix, carbon black, hollow carbon spheres, a layered silicate, an activator, an antioxidant, a softener, tackifying resin, a vulcanizing agent and an accelerator, wherein the rubber matrix is a compound of styrene butadiene rubber and high-vinyl polybutadiene rubber, the styrene butadiene rubber has a styrene content of 30-55%, a Mooney viscosity ML (1+4) 100 centigrade is 40-80. The vulcanized rubber has excellent mechanical properties, a high damping factor and a sound absorption coefficient.

Description

Technical Field

[0001] This invention relates to the field of vulcanized rubber, and more specifically, to a rubber composition, a vulcanized rubber, a method for preparing the same, and its applications. Background Technology

[0002] Damping materials are materials that convert the mechanical kinetic energy of solids into internal energy and dissipate it, primarily used for vibration and sound control. Rubber, as one of the key materials in the preparation of damping materials, has a significant impact on the molecular motion of polymers due to its microscopic molecular structure and sequence structure (such as the saturation degree and polarity of the main chain, the length and content of side chains, and the distribution of monomers in the copolymer). This ultimately affects the damping value and damping temperature range of the polymer material.

[0003] Rubber materials meet two requirements: first, the characteristic acoustic impedance of rubber must match the acoustic impedance of the sound wave propagation medium (water); second, rubber must have high damping, ensuring that sound energy is fully absorbed when it enters the material layer due to high energy attenuation. Rubber's viscoelasticity is the main reason for its use as a water-absorbing material. When sound waves act on rubber, the material deforms, and the relaxation of the rubber molecular chains causes a hysteresis effect, where strain lags behind stress, resulting in energy loss. Butyl rubber, due to its high internal loss and excellent water and aging resistance, is suitable for use as a sound-absorbing rubber. However, butyl rubber has poor adhesion, necessitating the search for a replacement material. Furthermore, a higher loss factor leads to a higher reflection coefficient and poorer impedance matching with water, creating a contradiction between impedance matching requirements and high loss.

[0004] Therefore, it is of great significance to research and develop a vulcanized rubber suitable for preparing high-damping sound-absorbing materials or damping vibration-damping materials. Summary of the Invention

[0005] The purpose of this invention is to overcome the problem of poor damping and vibration reduction effect of styrene-butadiene vulcanized rubber in the prior art, and to provide a rubber composition, vulcanized rubber, preparation method and application thereof, wherein the vulcanized rubber has excellent mechanical properties, high damping factor and sound absorption coefficient.

[0006] To achieve the above objectives, a first aspect of the present invention provides a high-damping sound-absorbing rubber composition, wherein the composition comprises a rubber matrix, carbon black, hollow carbon spheres, layered silicate, activator, antioxidant, softener, tackifying resin, vulcanizing agent, and accelerator, wherein the rubber matrix is ​​a blend of styrene-butadiene rubber and high-vinyl polybutadiene rubber, wherein the styrene-butadiene rubber contains 30-55% styrene and has a Mooney viscosity of ML. (1+4) 100℃ corresponds to 40-80.

[0007] A second aspect of the present invention provides a method for preparing vulcanized rubber using the aforementioned composition, wherein the method comprises:

[0008] (1) The rubber matrix, activator, antioxidant and tackifying resin are first mixed to obtain a masterbatch;

[0009] (2) The first stage of masterbatch is mixed with carbon black, hollow carbon balls, layered silicates and softener for a second mixing to obtain the second stage of masterbatch;

[0010] (3) The second-stage masterbatch is mixed with vulcanizing agent and accelerator in a third mixing process to obtain the final compound;

[0011] (4) The final rubber compound is vulcanized to obtain vulcanized rubber.

[0012] A third aspect of the present invention provides a vulcanized rubber prepared by the method described above.

[0013] The fourth aspect of the present invention provides an application of the aforementioned vulcanized rubber in the preparation of high-damping sound-absorbing materials or damping vibration-damping materials.

[0014] By adopting the above technical solution, the styrene content in styrene-butadiene rubber is increased, and the hardness and elongation of the vulcanized rubber are improved to varying degrees. From the microscopic structure, the internal friction between molecules increases and the internal consumption is improved, so that the vulcanized rubber has different mechanical properties, high damping factor and sound absorption coefficient, and is also suitable for preparing sound-absorbing materials or damping vibration reduction materials. Detailed Implementation

[0015] The endpoints and any values ​​of the ranges 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 endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0016] As previously stated, the first aspect of this invention provides a high-damping sound-absorbing rubber composition, wherein the composition comprises a rubber matrix, carbon black, hollow carbon spheres, layered silicates, an activator, an antioxidant, a softener, a tackifying resin, a vulcanizing agent, and an accelerator, wherein the rubber matrix is ​​a blend of styrene-butadiene rubber and high-vinyl polybutadiene rubber, wherein the styrene-butadiene rubber contains 30-55% styrene and has a Mooney viscosity of ML. (1+4) 100℃ corresponds to 40-80.

[0017] The inventors of this invention discovered that although styrene-butadiene rubber (SBR) has a relatively low sound absorption coefficient and its damping properties are not as excellent as butyl rubber, this can be compensated for by adjusting the rubber formulation and product structure. The vulcanized rubber provided by this invention, with SBR as the main component, features large groups like benzene rings in its structure that can vibrate freely with significant vibrational energy, which helps increase the material's internal friction. When there is a phase difference between the frequency of the incident sound wave and the vibrational frequency of the benzene rings, the sound wave will inevitably consume some energy to impede the vibration of the benzene rings, thereby achieving sound absorption. The number of freely vibrating benzene rings in SBR is closely related to its sound absorption capacity; the more freely vibrating benzene rings, the better the sound absorption. That is, when butadiene and styrene copolymerize and reach complete random polymerization, the sound absorption performance of SBR is relatively high.

[0018] Furthermore, the inventors of this invention used a compound molybdenum-based catalyst to prepare a high-vinyl polybutadiene rubber, which increased the 1,2-vinyl structure content in the high-vinyl polybutadiene rubber. Under the action of external force at a certain frequency, the dense vinyl side groups can increase the relaxation resistance and internal friction of the chain segments. Its glass transition temperature is about -25°C, which is closer to room temperature than other commonly used rubber damping materials.

[0019] Furthermore, the inventors of this invention have achieved a balance between the sound absorption coefficient and damping performance of rubber to a certain extent by using high-vinyl polybutadiene rubber in combination with styrene-butadiene rubber.

[0020] According to the present invention, the outer diameter of the hollow carbon sphere is 0.1-10 μm, preferably 0.1-8 μm, and the ratio of the wall thickness to the outer diameter of the hollow carbon sphere is 1:(2-15), preferably 1:(2-13). In the present invention, the hollow carbon sphere is XFP13 and / or microspheres, wherein the XFP13 has an outer diameter of 100-200 nm and a wall thickness of about 35 nm, and is purchased from Jiangsu Xianfeng Nanomaterials Technology Co., Ltd.; the microspheres have an outer diameter of 2-8 μm and a wall thickness of about 0.6 μm, and are purchased from Hefei Kejing Materials Technology Co., Ltd. The introduction of hollow carbon spheres can ensure impedance matching with water while increasing the attenuation of incident sound waves, which is important for ensuring low-frequency sound absorption performance.

[0021] According to the present invention, in a preferred embodiment, the styrene-butadiene rubber contains 35-50% styrene and has a Mooney viscosity of ML. (1+4) The temperature at 100℃ is 45-80℃; more preferably, the styrene-butadiene rubber contains 40-46% styrene and has a Mooney viscosity of ML. (1+4) The temperature at 100℃ is 45-55℃; in this invention, the styrene content and Mooney viscosity of the styrene-butadiene rubber are limited to the aforementioned range, which can improve the mechanical properties, high damping factor and sound absorption coefficient of the vulcanized rubber.

[0022] According to the present invention, the styrene-butadiene rubber is preferably non-oil-extended styrene-butadiene rubber, and more preferably, the styrene-butadiene rubber includes solution-polymerized styrene-butadiene rubber and / or emulsion-polymerized styrene-butadiene rubber; in the present invention, solution-polymerized styrene-butadiene rubber: Asaprene TM 303, Mooney viscosity (ML) (1+4) 100℃) 45, styrene content is 46%, Asahi Kasei Corporation, Japan; 1013, Mooney viscosity (ML) (1+4) (100℃) 55, with a styrene content of 40%.

[0023] According to the present invention, the high vinyl polybutadiene rubber contains 70-90% 1,2-vinyl structure and has a Mooney viscosity of ML. (1+4) The temperature at 100℃ is 50-100℃; preferably, the high-vinyl polybutadiene rubber contains 75-90% 1,2-vinyl structure and has a Mooney viscosity of ML. (1+4) At 100℃, the viscosity is 60-95; in this invention, the high-vinyl polybutadiene rubber (HVBR) has a 1,2-vinyl structure content of 80% and a Mooney viscosity (ML). (1+4) 100℃) 95, Sinopec Qilu Rubber Plant.

[0024] According to the present invention, the content of styrene-butadiene rubber (SBR) is 75-95 parts by weight relative to 100 parts by weight of the rubber matrix, and the content of high-vinyl polybutadiene rubber (HPP) is 5-25 parts by weight; preferably, the content of SBR is 78-92 parts by weight relative to 100 parts by weight of the rubber matrix, and the content of HPP is 8-22 parts by weight. In the present invention, the mixing of SBR and HPP can improve the damping performance of SBR, while the processing performance of HPP can also be improved to some extent.

[0025] According to the present invention, relative to 100 parts by weight of the rubber matrix, the content of carbon black is 5-50 parts by weight, the content of hollow carbon spheres is 3-30 parts by weight, the content of layered silicate is 4-40 parts by weight, the content of activator is 0.5-10 parts by weight, the content of antioxidant is 0.1-5 parts by weight, the content of softener is 1-10 parts by weight, the content of tackifying resin is 1-20 parts by weight, the content of vulcanizing agent is 0.1-5 parts by weight, and the content of accelerator is 0.1-5 parts by weight.

[0026] Preferably, relative to 100 parts by weight of the rubber matrix, the content of carbon black is 10-50 parts by weight, the content of hollow carbon spheres is 6-30 parts by weight, the content of layered silicate is 5-35 parts by weight, the content of activator is 1-10 parts by weight, the content of antioxidant is 0.5-5 parts by weight, the content of softener is 1-10 parts by weight, the content of tackifying resin is 1.5-15 parts by weight, the content of vulcanizing agent is 1.5-2.5 parts by weight, and the content of accelerator is 1-1.5 parts by weight.

[0027] More preferably, relative to 100 parts by weight of the rubber matrix, the content of carbon black is 15-41 parts by weight, the content of hollow carbon spheres is 5-24 parts by weight, the content of layered silicate is 4-30 parts by weight, the content of activator is 3.6-6 parts by weight, the content of antioxidant is 1.5-2.2 parts by weight, the content of softener is 4-9 parts by weight, the content of tackifying resin is 1.5-9 parts by weight, the content of vulcanizing agent is 1.5-2.5 parts by weight, and the content of accelerator is 1-1.5 parts by weight.

[0028] According to the present invention, the CTAB adsorption specific surface area of ​​the carbon black is 10-100 m². 2 / g; the iodine adsorption value of the carbon black is 10-100 mg / kg; the iodine adsorption value of carbon black is the mass of iodine absorbed by 1 kg of carbon black, expressed in mg / kg, and is used to characterize the specific surface area of ​​the carbon black. More preferably, in this invention, the carbon black is furnace black. For example, the carbon black can be N330, and the carbon black is N330 (CTAB adsorption specific surface area is 73-85 m² / kg). 2 / g, iodine uptake value 76-89mg / kg), Jiangxi Black Cat Carbon Black Co., Ltd.

[0029] According to the present invention, the D of the layered silicate 50 The thickness is 1-5 μm, and the BET specific surface area is 5-50 m². 2 / g. In this invention, there is no particular limitation on the particle size of the layered silicate, as long as it can be combined with other components in the composition of this invention to achieve the aforementioned objectives. In this invention, the layered silicate is selected from at least one of silica, sericite, wollastonite, mica powder, diatomaceous earth, palygorskite, pyrophyllite powder, illite, chlorite, dickite, kaolin, montmorillonite, and talc; preferably, the layered silicate is silica; more preferably, the layered silicate is selected from silica GW-5, purchased from Fujian Changtai Wantai Mineral Products Co., Ltd., wherein the fineness D 50 Its thickness is 2 μm, and its BET specific surface area is 9.6 m². 2 / g; Silica GW-29, purchased from Fujian Changtai Wantai Mineral Products Co., Ltd., of which fineness D50 The thickness is 0.8 μm, and the BET specific surface area is 24 m². 2 / g; Using this silica, no surface modifier intercalation treatment is required; uniformly dispersed layered silicate particles can be obtained in rubber through direct mixing. Furthermore, the aforementioned layered silicate of this invention is an readily available clay mineral, inexpensive, and can be used directly without modification, which is beneficial for improving the damping and barrier properties of rubber materials.

[0030] According to the present invention, the activator is a mixture of metal oxide and fatty acid. For example, the activator may be zinc oxide and stearic acid; more preferably, the weight ratio of zinc oxide and stearic acid is (1-6):1; the zinc oxide and stearic acid are purchased from Weifang Hengfeng Chemical Co., Ltd.

[0031] According to the present invention, the antioxidant is at least one selected from amine antioxidants, quinoline antioxidants, hindered phenolic antioxidants, and benzimidazole antioxidants. For example, the antioxidant may be antioxidant RD, purchased from Shanghai Chengjin Chemical Co., Ltd.

[0032] According to the present invention, the softener is selected from at least one of naphthenic oil, aromatic oil, paraffin oil, microcrystalline wax, castor oil, and polyethylene wax; preferably, the softener is naphthenic oil (KN4010), with a molecular weight of 405 and a kinematic viscosity of 10.29 mm at 40°C. 2 / s, Hengshui Xihao Chemical Co., Ltd.

[0033] According to the present invention, the tackifying resin is selected from at least one of C5 petroleum resin, C9 petroleum resin, rosin resin, terpene resin, phenolic resin, coumarone-indene resin, styrene resin, and dicyclopentadiene resin; C5 petroleum resin, Escorez 1102, light-colored or colorless granules, softening point 96-104℃, ExxonMobil; C9 thermally polymerized petroleum resin PR-100-11, yellow or pale yellow granules, softening point 90-100℃, Henghe Materials Technology Co., Ltd.

[0034] According to the present invention, the vulcanizing agent is selected from at least one of sulfur donors, wherein the sulfur donor refers to a substance capable of providing sulfur. The sulfur includes at least one of insoluble sulfur, soluble sulfur, and oil-extended sulfur. For example, the vulcanizing agent is ordinary sulfur S, oil-extended insoluble sulfur IS, etc. In this invention, the sulfur is purchased from Weifang Zhongheng Chemical Co., Ltd.

[0035] According to the present invention, the accelerator is selected from at least one of diphenylguanidine, tetramethylthiuram disulfide, 2-thiol benzothiazole, ethylidene thiourea, N-cyclohexyl-2-benzothiazole sulfenamide, N-tert-butyl-2-benzothiazole sulfenamide, 2,2'-dibenzothiazole disulfide (DM), N-tert-butyl-bis(2-benzothiazole)sulfenimide, and N-cyclohexyl-2-benzothiazole sulfenamide. Specifically, N-tert-butyl-2-benzothiazole sulfenamide (TBBS) was purchased from Shandong Yanggu Huatai Chemical Co., Ltd.

[0036] This invention does not impose any particular limitation on the method for preparing vulcanized rubber using the aforementioned composition; various methods commonly used in the art for preparing vulcanized rubber can be employed. However, in order to make the composition of the obtained compound more uniform, and thus to give the vulcanized rubber obtained after subsequent vulcanization better mechanical properties and high damping sound absorption properties, a second aspect of this invention provides a method for preparing vulcanized rubber using the aforementioned composition, wherein the method includes:

[0037] (1) The rubber matrix, activator, antioxidant and tackifying resin are first mixed to obtain a masterbatch;

[0038] (2) The first stage of masterbatch is mixed with carbon black, hollow carbon balls, layered silicates and softener for a second mixing to obtain the second stage of masterbatch;

[0039] (3) The second-stage masterbatch is mixed with vulcanizing agent and accelerator in a third mixing process to obtain the final compound;

[0040] (4) The final rubber compound is vulcanized to obtain vulcanized rubber.

[0041] All components involved in the second aspect of the present invention have the same properties as the corresponding components in the first aspect of the present invention. In order to avoid repetition, the properties of the components, including the optional types of components, will not be described again in the second aspect of the present invention.

[0042] According to the present invention, the conditions for the first mixing include: a temperature of 80-130°C and a time of 3-12 min; preferably, the conditions for the first mixing include: a temperature of 90-120°C and a time of 4-12 min.

[0043] According to the present invention, the conditions for the second mixing include: a temperature of 90-130°C and a time of 3-12 min; preferably, the conditions for the second mixing include: a temperature of 100-130°C and a time of 3-7 min.

[0044] According to the present invention, the conditions for the third mixing include: temperature ≤130℃ and time 4-7 min.

[0045] According to the present invention, the vulcanization conditions include: a temperature of 150-170°C, a pressure of 10-20 MPa, and a time of 25-50 min.

[0046] According to the present invention, the initial mixing temperature in the first mixing process is 70-100℃, and the raw rubber plasticizing time is 0.3-2min.

[0047] According to the present invention, preferably, the first mixing and the second mixing are carried out in an internal mixer, and preferably the rotation speed of the internal mixer for the first mixing and the second mixing is independently 30-90 rpm.

[0048] According to the present invention, preferably, the mixed rubber compound obtained after the second mixing is first sheeted out in a two-roll mill and placed at 0-50°C for 3-12 hours to obtain the second-stage masterbatch.

[0049] It should be noted that in step (3) of the preferred embodiment described above, plasticizing is not necessary, but only for obtaining better processing results.

[0050] Unless otherwise specified, all pressures used in this invention are gauge pressures.

[0051] A third aspect of the present invention provides a vulcanized rubber prepared by the method described above.

[0052] The fourth aspect of the present invention provides an application of the aforementioned vulcanized rubber in the preparation of high-damping sound-absorbing materials or damping vibration-damping materials.

[0053] The present invention will be described in detail below through embodiments.

[0054] In the following examples, the 1,2-vinyl content and the bound styrene content were determined by 1H NMR spectroscopy, and the Mooney viscosity was determined by a disk shear viscometer.

[0055] 2466, Mooney viscosity (ML) (1+4) (100℃) 68, with a styrene content of 20% and a vinyl content of 69%, TSRC Corporation;

[0056] The equipment used to prepare the vulcanized rubber in the following examples and comparative examples is shown in Table 1.

[0057] The testing instruments for the vulcanized rubbers prepared in the following examples and comparative examples are shown in Table 2.

[0058] The test conditions for the vulcanized rubber prepared in the following examples and comparative examples are shown in Table 3.

[0059] In the following examples and comparative examples, the component amounts are all parts by weight (or parts), and the total amount of the rubber compositions involved is the same, which is 1200g.

[0060] Unless otherwise specified, the room temperature mentioned below refers to 25±3℃.

[0061] The sound absorption performance was tested in accordance with standard GB / T 14369-2011.

[0062] Table 1

[0063]

[0064] Table 2

[0065]

[0066] Table 3

[0067]

[0068] Example 1

[0069] The preparation process of vulcanized rubber:

[0070] (1) Styrene-butadiene rubber, high-vinyl polybutadiene rubber, activator, antioxidant and tackifying resin are first mixed to obtain a first-stage masterbatch; specifically, styrene-butadiene rubber and high-vinyl polybutadiene rubber are added to a mixer, the speed is set to 75 rpm, the initial mixing temperature is 90°C, and the raw rubber plasticizing time is 1 min; the activator, antioxidant and tackifying resin are added to the above mixer and mixed at a mixing temperature of 105°C for 7 min to obtain a first-stage masterbatch;

[0071] (2) The first stage of masterbatch is mixed with carbon black, hollow carbon balls, layered silicates and softener to obtain the second stage of masterbatch; specifically, the above ingredients are added into the internal mixer and mixed with the first stage of masterbatch for a second time of 5 minutes and a mixing temperature of 120°C. The mixture is then discharged and left to stand for 5 hours to obtain the second stage of masterbatch.

[0072] (3) The second-stage masterbatch is mixed with vulcanizing agent and accelerator for a third mixing to obtain the final compound; specifically, the speed of the internal mixer is set to 65 rpm, the initial mixing temperature is 45°C, the second-stage masterbatch is plasticized for 0.5 min, and then vulcanizing agent and accelerator are added for a third mixing, the mixing temperature is 105°C, the mixing time is 5 min, and the final compound is obtained by discharging.

[0073] (4) The final rubber is pressed into sheets by an open mill, cut into sheets, and then placed into a flat vulcanizing machine for vulcanization. The vulcanization temperature is 160℃, the vulcanization pressure is 15MPa, and the vulcanization time is 30min to obtain vulcanized rubber sample S1.

[0074] The formulations of the rubber compositions in the examples are shown in Table 4.

[0075] Examples 2-5

[0076] Vulcanized rubbers S2-S5 were prepared using the same method as in Example 1, except that the formulation and process parameters of the rubber compositions used were different, as detailed in Table 4.

[0077] Example 6

[0078] The rubber composition formulation in this embodiment is the same as that in Example 1, and the vulcanized rubber is prepared using a similar method as in Example 1. The difference is that:

[0079] During the preparation of the masterbatch, the temperature of the first mixing step was 125℃ and the time was 3.5 min.

[0080] During the preparation of the two-stage masterbatch, the temperature of the second mixing was 98℃ and the time was 10min;

[0081] During the preparation of the final rubber compound, the third mixing time is 5 minutes and the discharge temperature is 130℃.

[0082] Vulcanized rubber sample S6 was obtained.

[0083] The formulations of the rubber compositions in the examples are shown in Table 4.

[0084] Comparative Examples 1-4

[0085] Vulcanized rubber was prepared using the same method as in Example 1, except that the formulation and process parameters of the rubber composition were different, as detailed in Table 4.

[0086] Comparative Example 5

[0087] The vulcanized rubber was prepared using the same method as in Example 1, except that the "high vinyl polybutadiene rubber HVBR" in Example 1 was modified to "high cis-content polybutadiene rubber BR9000", wherein the high cis-content polybutadiene rubber has a 1,4-vinyl structure content of 97.8% and a Mooney viscosity of ML. (1+4) "100℃ is 45", see Table 4 for details.

[0088] Table 4

[0089]

[0090] Test case

[0091] The tensile strength and dynamic viscoelastic properties of the rubber products prepared in the examples and comparative examples were tested respectively, and the results are shown in Table 5.

[0092] Molding: The rubber compound is vulcanized into a cylinder with a diameter of 56.5 mm and a height of 50 mm. Given the sample size, the vulcanization time can be increased based on the original vulcanized sample to ensure complete vulcanization.

[0093] Test: First, the sample was immersed in water for more than 48 hours to ensure that there were no air bubbles on the surface of the rubber sample, and then tested in water. The acoustic tube testing system (φ57 pulse acoustic tube) of the Institute of Acoustics, Chinese Academy of Sciences was used, and the measurement was carried out according to the standard. The results are shown in Table 5.

[0094] Table 5

[0095]

[0096] As shown in Table 5, the SBR / HVBR rubber vulcanization composition provided by this invention, with its high-bonded styrene-structured rubber, hollow carbon spheres, and other components, results in a rubber material with good sound absorption properties, making it suitable for use as an underwater sound-absorbing material. Furthermore, smaller hollow carbon sphere sizes are more beneficial for improving sound absorption performance. HVBR and layered silicates ensure excellent damping properties in the rubber material. Simultaneously, thorough mixing of all components ensures that the vulcanized rubber exhibits superior mechanical properties.

[0097] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. The application of a vulcanized rubber prepared using a high-damping sound-absorbing rubber composition in the preparation of high-damping sound-absorbing materials or damping vibration-damping materials, characterized in that, Methods for preparing vulcanized rubber using compositions include: (1) The rubber matrix, activator, antioxidant and tackifying resin are first mixed to obtain a masterbatch; (2) Mix the first stage of masterbatch with carbon black, hollow carbon balls, layered silicates and softener for a second mixing process to obtain the second stage of masterbatch; (3) The second-stage masterbatch is mixed with vulcanizing agent and accelerator in a third mixing process to obtain the final rubber; (4) The final rubber compound is vulcanized to obtain vulcanized rubber; Relative to 100 parts by weight of rubber matrix, the amount of carbon black is 5-50 parts by weight, the amount of hollow carbon spheres is 3-30 parts by weight, the amount of layered silicate is 4-40 parts by weight, the amount of activator is 0.5-10 parts by weight, the amount of antioxidant is 0.1-5 parts by weight, the amount of softener is 1-10 parts by weight, the amount of tackifying resin is 1-20 parts by weight, the amount of vulcanizing agent is 0.1-5 parts by weight, and the amount of accelerator is 0.1-5 parts by weight. The rubber matrix is ​​a blend of styrene-butadiene rubber and high-vinyl polybutadiene rubber. The styrene content in the styrene-butadiene rubber is 35-50%, and the Mooney viscosity is ML. (1+4) 100℃ is 45-80; The content of styrene-butadiene rubber is 75-95 parts by weight relative to 100 parts by weight of the rubber matrix, and the content of high vinyl polybutadiene rubber is 5-25 parts by weight.

2. The application according to claim 1, wherein, High-vinyl polybutadiene rubber contains 75-90% 1,2-vinyl structure and has a Mooney viscosity of ML. (1+4) 100℃ corresponds to 60-95.

3. The application according to claim 1, wherein, The outer diameter of the hollow carbon sphere is 0.1-10 μm, and the ratio of the wall thickness of the hollow carbon sphere to its outer diameter is 1:(2-15).

4. The application according to claim 1, wherein, Styrene-butadiene rubber includes solution-polymerized styrene-butadiene rubber and / or emulsion-polymerized styrene-butadiene rubber.

5. The application according to claim 1, wherein, Relative to 100 parts by weight of the rubber matrix, the content of styrene-butadiene rubber is 78-92 parts by weight, and the content of high-vinyl polybutadiene rubber is 8-22 parts by weight.

6. The application according to claim 1, wherein, The CTAB adsorption specific surface area of ​​carbon black is 10-100 m². 2 / g; And / or, layered silicates D 50 The thickness is 1-5 μm, and the BET specific surface area is 5-50 m². 2 / g.

7. The application according to claim 1, wherein, The conditions for the first mixing process include: a temperature of 80-130℃ and a time of 3-12 minutes; And / or, the conditions for the second mixing include: a temperature of 90-130℃ and a time of 3-12 min; And / or, the conditions for the third mixing include: temperature ≤130℃, time 4-7min; And / or, the vulcanization conditions include: a temperature of 150-170℃, a pressure of 10-20MPa, and a time of 25-50min.

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