High-wear-resistance rubber and preparation process thereof

Abstract

The invention relates to the technical field of rubber materials, and particularly discloses high-wear-resistance rubber and a preparation technology thereof.The high-wear-resistance rubber is prepared from, by weight, 71-115 parts of rubber matrix, 40-48 parts of modified filler, 5-7 parts of zinc carbonate, 1-3 parts of stearic acid, 4-6 parts of composite vulcanizing agent and 0.6-1 part of anti-aging agent; the functional monomer solution is used for modifying the high-styrene rubber, the mechanical property of the high-styrene rubber and the interface bonding force between rubber matrixes are remarkably enhanced, the modified diatomite is used as the raw material, the modified filler is prepared by introducing the titanate coupling agent and tyrosine, the dispersity and compatibility of the filler are improved, and the service life of the filler is prolonged. The mechanical property of the rubber material is further enhanced, and the service life of the rubber can be effectively prolonged; according to the high-wear-resistance rubber provided by the invention, the wear resistance and the tear resistance are enhanced, and meanwhile, the burden of the environment and energy is reduced.

Description

Technical Field

[0001] The present application relates to the technical field of rubber materials, and more specifically, to a highly wear-resistant rubber and a preparation process thereof. Background Art

[0002] Rubber refers to a highly elastic polymer material with reversible deformation. It is elastic at room temperature, can produce large deformation under very small external forces, and can return to its original state after the external force is removed. Rubber is divided into two types: natural rubber and synthetic rubber. Natural rubber has excellent processing properties, resilience, insulation, and plasticity, etc., and has been widely used in daily life, medical and health, transportation, industry, agriculture and other fields. However, the wear resistance of natural rubber products is not good, which affects the service life and safety of products. With the continuous development of modern science and technology and modern industry, the requirements for the application environment of rubber products are becoming more and more stringent. Improving the wear resistance of rubber to extend the service life of rubber products (especially high-wear components such as tires) has become a research hotspot in the field of materials science at home and abroad in recent years.

[0003] To improve the wear resistance of rubber materials, in the prior art, the method of changing the raw material formula has a very limited improvement in the wear resistance of rubber materials. Blending modification is also a commonly used method to enhance the performance in the rubber industry. However, due to the incompatibility between rubbers, phase separation and poor interfacial adhesion often occur, resulting in insufficient mechanical properties of rubber composites. Adding a large amount of fillers and chemical additives during the preparation of rubber will also cause serious environmental pollution. For example, carbon black, as a commonly used filler in rubber preparation, its large-scale use will cause a burden on the environment and energy; compared with carbon black, diatomite is a green and environmentally friendly material with strong adsorption performance and high chemical stability, but the dispersibility and compatibility of diatomite in the rubber matrix are poor, which will cause uneven distribution or agglomeration of fillers. Therefore, the present application proposes a highly wear-resistant rubber that can enhance the wear resistance of natural rubber and has little environmental pollution and a preparation process thereof. Summary of the Invention

[0004] In order to solve the problems of poor wear resistance, insufficient mechanical properties, and non-environmental protection of raw materials in related technologies, the present application provides a highly wear-resistant rubber and a preparation process thereof.

[0005] In the first aspect, the present application provides a highly wear-resistant rubber, adopting the following technical solution:

[0006] A highly wear-resistant rubber, comprising the following components in parts by weight: 71 - 115 parts of rubber matrix, 40 - 48 parts of modified filler, 5 - 7 parts of zinc carbonate, 1 - 3 parts of stearic acid, 4 - 6 parts of composite vulcanizing agent, and 0.6 - 1 part of antioxidant.

[0007] Preferably, the rubber matrix comprises the following components in parts by weight: 30-50 parts of natural rubber, 16-20 parts of cis-butadiene rubber, and 25-45 parts of modified high styrene rubber.

[0008] Preferably, the modified high styrene rubber is prepared by the following method:

[0009] 1) Add styrene, butadiene, and cyclohexane to a reaction kettle, and stir and mix to obtain a mixture;

[0010] 2) Stir and mix the composite acid and polyethylene glycol, heat up, add a palladium-carbon catalyst, and stir and mix to obtain a functional monomer solution;

[0011] 3) Add the functional monomer solution to the mixture, heat up, add an initiator, stir and react, and dry to obtain the modified high styrene rubber.

[0012] Preferably, in step 1), the mass ratio of styrene, butadiene, and cyclohexane is 22-30:10-12:100.

[0013] Preferably, in step 2), the mass ratio of the composite acid, polyethylene glycol, and palladium-carbon catalyst is 18-22:100:1-3.

[0014] Preferably, in step 2), the composite acid is composed of rosin acid, cinnamic acid, and maleic acid mixed in a mass ratio of 3-5:1:1-3.

[0015] Preferably, in step 3), the mass ratio of the mixture, the functional monomer solution, and the initiator is 5-7:1:0.1-0.3.

[0016] Preferably, the initiator in step 3) is benzoyl peroxide.

[0017] Preferably, the modified filler is prepared by the following method:

[0018] (1) Dissolve dopamine in Tris-HCl, add polyethylene glycol and stir evenly, carry out grafting reaction, add diatomite, ultrasonically disperse at room temperature for 1-3 h, then under nitrogen protection, react for 1-1.8 h, and centrifuge to obtain a modified diatomite solution;

[0019] (2) Stir and mix the modified diatomite solution and a titanate coupling agent, ultrasonically disperse, then add tyrosine and a photoinitiator, react under ultraviolet lamp irradiation, then stir and react, and then centrifuge and dry to obtain the modified filler.

[0020] Preferably, in step (1), the mass ratio of dopamine, polyethylene glycol, diatomite, and Tris-HCl is 5-7:10-12:20-22:100.

[0021] Preferably, in the step (2), the mass ratio of the modified diatomite solution, titanate coupling agent, tyrosine and photoinitiator is 50:8-10:1-3:0.5-0.9.

[0022] Preferably, the photoinitiator in the step (2) is benzophenone.

[0023] Preferably, the composite vulcanizing agent is composed of tetraethylthiuram disulfide, sulfur and triethylenetetramine in a mass ratio of 1-3:1:4-6.

[0024] Preferably, the anti-aging agent is composed of anti-aging agent AW, anti-aging agent DNP and anti-aging agent RD in a mass ratio of 1.5:1:2.

[0025] In a second aspect, the present application provides a preparation process for high wear-resistant rubber, which specifically includes the following steps:

[0026] S1. Knead the rubber matrix in a kneader for 3-5 min, and control the temperature at 60-80 °C;

[0027] S2. Add the modified filler, zinc carbonate, stearic acid and anti-aging agent to the above kneader, and continue to knead for 6-8 min, and control the temperature at 80-100 °C to obtain a kneaded material;

[0028] S3. Add the composite vulcanizing agent to the kneaded material, and continue to knead evenly to obtain a premixed rubber;

[0029] S4. Add the premixed rubber to a vulcanizer for vulcanization, and discharge the material to obtain high wear-resistant rubber.

[0030] In summary, the present application has the following beneficial effects:

[0031] 1. In the present application, natural rubber, cis-butadiene rubber and modified high styrene rubber are mixed as the rubber matrix, and a modified filler, zinc carbonate, stearic acid, a composite vulcanizing agent and an anti-aging agent are added. By controlling the preparation process and parameters, the prepared rubber material has high wear resistance and strong tear resistance, and at the same time has good environmental protection.

[0032] 2. The functional monomer solution prepared by further reacting the composite acid composed of rosin acid, cinnamic acid, and maleic acid is used in this application to modify high styrene rubber. Rosin acid can enhance the weather resistance and chemical corrosion resistance of rubber. Cinnamic acid can improve the antibacterial properties of rubber. Maleic acid can enhance the strength and wear resistance of rubber. Adding rosin acid, cinnamic acid, and maleic acid simultaneously can significantly improve the mechanical properties such as tensile strength and tear strength of rubber. Modifying high styrene rubber with the functional monomer solution, on the one hand, forms stronger intermolecular forces between rubber molecular chains, improving the compatibility between rubber matrices; on the other hand, it can significantly improve the heat resistance and chemical corrosion resistance of rubber, thus extending the service life of rubber. Natural rubber has good mechanical properties and elasticity, but relatively weak wear resistance. cis-1,4-Polybutadiene rubber has excellent cold resistance, wear resistance, and elasticity, but relatively low tensile strength and tear strength. The modified high styrene rubber has strong wear resistance and high tensile strength and tear strength. The blending of the three enables the rubber material to not only maintain excellent elasticity but also significantly improve the mechanical properties such as wear resistance and tear resistance. During the processing, they can blend with each other to form a uniform and dense material structure, thereby improving the overall quality of the rubber material.

[0033] 3. In this application, diatomite is first modified with polyethylene glycol grafted polydopamine, significantly improving the stability and dispersibility of diatomite. Then, the modified diatomite is secondarily modified with titanate coupling agent and tyrosine. The titanate coupling agent can improve the adhesion of diatomite and enhance the interaction between diatomite and rubber matrix, so that the mechanical properties such as tensile strength and tear strength of the rubber material are improved; tyrosine can significantly improve the compatibility between diatomite and rubber matrix, making diatomite more easily dispersed in the rubber matrix, thereby enhancing the overall performance of the rubber material. In addition, diatomite is a green and environmentally friendly material with good biodegradability. Using the modified filler of this application to replace traditional carbon black as a rubber material reinforcing agent can not only enhance the mechanical properties of the rubber material but also effectively reduce the burden on the environment and energy. Detailed implementation manners

[0034] The following further elaborates on this application in conjunction with examples.

[0035] In this example and the comparative example, the natural rubber (product number: 56469, purchased from Guangxi Wusen New Materials Technology Co., Ltd.), cis-butadiene rubber (model: KBR01, purchased from Guangzhou Liben Rubber Raw Material Trading Co., Ltd.), styrene-butadiene rubber (CAS number: 9003-55-8, purchased from Hubei Watson Chemical Technology Co., Ltd.), zinc carbonate (effective ingredient content 99%, purchased from Hebei Jianshuo Chemical Technology Co., Ltd.), stearic acid (CAS number: 6565-66-1, purchased from Hebei Bangtai Chemical Co., Ltd.), diatomite (model: SD-3004A, purchased from Dongguan Senda Diatomite Materials Co., Ltd.), titanate coupling agent (model: RT-224, purchased from Nanjing Tengchuan Technology Co., Ltd.), tetraethylthiuram disulfide (product number: R12021957-100g, purchased from Shanghai Ruichu Biotechnology Co., Ltd.), sulfur (sulfur content: >99.95%, purchased from Qingdao Luchuan Chemical Co., Ltd.), triethylenetetramine (model: 112-24-3, purchased from Tianjin Shengxinyuan Chemical), antioxidant AW (CAS number: 91-53-2, purchased from Jiangsu Pulesi Biotechnology Co., Ltd.), antioxidant DNP (CAS number: 93-46-9, purchased from Hubei Shineng Chemical Technology Co., Ltd.), antioxidant RD (CAS number: 26780-96-1, purchased from Changzhou Xince High Polymer Materials Co., Ltd.) were used.

[0036] Example 1

[0037] A highly wear-resistant rubber comprises the following components in parts by weight: 30 parts of natural rubber, 16 parts of cis-butadiene rubber, 25 parts of modified high styrene rubber, 40 parts of modified filler, 5 parts of zinc carbonate, 1 part of stearic acid, 4 parts of compound vulcanizing agent, and 0.6 part of antioxidant.

[0038] The antioxidant is composed of antioxidant AW, antioxidant DNP, and antioxidant RD mixed in a mass ratio of 1.5:1:2; the compound vulcanizing agent is composed of tetraethylthiuram disulfide, sulfur, and triethylenetetramine mixed in a mass ratio of 1:1:4.

[0039] The modified high styrene rubber is prepared by the following method:

[0040] 1) According to the mass ratio of styrene, butadiene, and cyclohexane being 22:10:100, styrene, butadiene, and cyclohexane are added to a reaction kettle and stirred at 600 r / min for 30 min to obtain a mixture;

[0041] 2) According to the mass ratio of the composite acid (composed of rosin acid, cinnamic acid, and maleic acid mixed in a mass ratio of 3:1:1), polyethylene glycol, and palladium-carbon catalyst being 18:100:1, the composite acid and polyethylene glycol are mixed, heated to 150 °C, the palladium-carbon catalyst is added, and stirred at 400 r / min for 30 min to obtain a functional monomer solution;

[0042] 3) Add the functional monomer solution to the mixture according to the mass ratio of the mixture, the functional monomer solution, and benzoyl peroxide being 1:1:0.1. Heat the mixture to 100 °C, add benzoyl peroxide, stir at 500 r / min for 1 h, and then dry at 52 °C for 1 h to obtain the modified high styrene rubber.

[0043] The modified filler is prepared by the following method:

[0044] (1) According to the mass ratio of dopamine, polyethylene glycol, diatomite, and Tris-HCl being 5:10:20:100, dissolve dopamine in 0.1 mol / L Tris-HCl, add polyethylene glycol and stir evenly, carry out grafting reaction, react at room temperature for 30 min, add diatomite, ultrasonically disperse at room temperature for 1 h, control the ultrasonic power to be 400 W, the ultrasonic frequency to be 20 KHz, then under nitrogen protection, stand and react at room temperature for 1 h, centrifuge at 10000 r / min for 10 min to obtain the modified diatomite solution;

[0045] (2) According to the mass ratio of the modified diatomite solution, titanate coupling agent, tyrosine, and benzophenone being 50:8:1:0.5, stir the modified diatomite solution and the titanate coupling agent at 600 r / min for 30 min, ultrasonically disperse for 40 min, control the ultrasonic power to be 600 W, the ultrasonic frequency to be 26 KHz, then add tyrosine and benzophenone, react at room temperature for 1 h under the irradiation of an ultraviolet lamp with a light irradiance of 15 mW / cm 2 , then stir and react at a rotation speed of 500 r / min for 50 min, then centrifuge at 10000 r / min for 10 min, and dry at 58 °C for 1 h to obtain the modified filler.

[0046] A preparation process of a highly wear-resistant rubber specifically includes the following steps:

[0047] S1. Mix natural rubber, cis-butadiene rubber, and modified high styrene rubber, knead in a kneader for 3 min, control the temperature to be 60 °C, and the kneading rotation speed to be 20 r / min;

[0048] S2. Add the modified filler, zinc carbonate, stearic acid, and antioxidant to the above kneader, continue to knead for 6 min, control the temperature to be 80 °C, and the kneading rotation speed to be 30 r / min to obtain a kneaded material;

[0049] S3. Add the kneaded material to a compound vulcanizing agent, knead for 5 min, control the temperature to be 50 °C, and the kneading rotation speed to be 30 r / min to obtain a premixed rubber;

[0050] S4. Add the premixed rubber to a vulcanizer for vulcanization, control the vulcanization temperature to be 140 °C, the time to be 10 min, and the pressure to be 15 MPa, and discharge to obtain the highly wear-resistant rubber.

[0051] Example 2

[0052] A highly wear-resistant rubber, comprising the following components in parts by weight: 35 parts of natural rubber, 17 parts of cis-butadiene rubber, 30 parts of modified high styrene rubber, 42 parts of modified filler, 5.5 parts of zinc carbonate, 1.5 parts of stearic acid, 4.5 parts of compound vulcanizing agent, and 0.7 part of antioxidant.

[0053] The antioxidant is composed of antioxidant AW, antioxidant DNP, and antioxidant RD mixed in a mass ratio of 1.5:1:2; in step S3, the compound vulcanizing agent is composed of tetraethylthiuram disulfide, sulfur, and triethylenetetramine mixed in a mass ratio of 1.5:1:4.5.

[0054] The modified high styrene rubber is prepared by the following method:

[0055] 1) According to the mass ratio of styrene, butadiene, and cyclohexane being 24:10.5:100, add styrene, butadiene, and cyclohexane to a reaction kettle, stir at 600 r / min for 30 min to obtain a mixture;

[0056] 2) According to the mass ratio of composite acid (composed of rosin acid, cinnamic acid, and maleic acid mixed in a mass ratio of 3.5:1:1.5), polyethylene glycol, and palladium-carbon catalyst being 19:100:1.5, mix the composite acid and polyethylene glycol, heat up to 155 °C, add the palladium-carbon catalyst, stir at 400 r / min for 35 min to obtain a functional monomer solution;

[0057] 3) According to the mass ratio of the mixture, the functional monomer solution, and benzoyl peroxide being 1.5:1:0.15, add the functional monomer solution to the mixture, heat up to 105 °C, add benzoyl peroxide, stir at 500 r / min for 1.1 h, and then dry at 54 °C for 1.5 h to obtain the modified high styrene rubber.

[0058] The modified filler is prepared by the following method:

[0059] (1) According to the mass ratio of dopamine, polyethylene glycol, diatomite, and Tris-HCl being 5.5:10.5:20.5:100, dissolve dopamine in 0.1 mol / L Tris-HCl, add polyethylene glycol and stir evenly, carry out a grafting reaction, react at room temperature for 30 min, add diatomite, ultrasonically disperse at room temperature for 1.5 h, control the ultrasonic power to be 450 W and the ultrasonic frequency to be 25 KHz, then under nitrogen protection, stand and react at room temperature for 1.2 h, centrifuge at 10500 r / min for 15 min to obtain a modified diatomite solution;

[0060] (2) According to the mass ratio of the modified diatomite solution, titanate coupling agent, tyrosine, and benzophenone being 50:8.5:1.5:0.6, the modified diatomite solution and the titanate coupling agent are stirred at 650 r / min for 30 min, then ultrasonically dispersed for 40 min, with the ultrasonic power controlled at 650 W and the ultrasonic frequency at 27 KHz. Then tyrosine and benzophenone are added, and the reaction is carried out at room temperature for 1 h under the irradiation of a UV lamp with a light irradiance of 16 mW / cm 2 and then stirred at a rotation speed of 500 r / min for 50 min, and then centrifuged at 10500 r / min for 15 min and dried at 59 °C for 1.5 h to obtain the modified filler.

[0061] A preparation process of a highly wear-resistant rubber specifically includes the following steps:

[0062] S1. Mix natural rubber, cis-butadiene rubber, and modified high styrene rubber, and carry out kneading in a kneader for 3.5 min, controlling the temperature at 65 °C and the kneading rotation speed at 25 r / min;

[0063] S2. Add the modified filler, zinc carbonate, stearic acid, and antioxidant to the above kneader, and continue kneading for 6.5 min, controlling the temperature at 85 °C and the kneading rotation speed at 15 r / min to obtain a kneaded material;

[0064] S3. Add the kneaded material to a compound vulcanizing agent and knead for 5.5 min, controlling the temperature at 50 °C and the kneading rotation speed at 35 r / min to obtain a premixed rubber;

[0065] S4. Add the premixed rubber to a vulcanizer for vulcanization, controlling the vulcanization temperature at 145 °C, the time at 15 min, and the pressure at 15.5 MPa, and discharging to obtain the highly wear-resistant rubber.

[0066] Example 3

[0067] A highly wear-resistant rubber comprises the following components in parts by weight: 40 parts of natural rubber, 18 parts of cis-butadiene rubber, 35 parts of modified high styrene rubber, 44 parts of modified filler, 6 parts of zinc carbonate, 2 parts of stearic acid, 5 parts of compound vulcanizing agent, and 0.8 part of antioxidant.

[0068] The antioxidant is composed of antioxidant AW, antioxidant DNP, and antioxidant RD mixed in a mass ratio of 1.5:1:2; in step S3, the compound vulcanizing agent is composed of tetraethylthiuram disulfide, sulfur, and triethylenetetramine mixed in a mass ratio of 2:1:5.

[0069] The modified high styrene rubber is prepared by the following method:

[0070] 1) Add styrene, butadiene, and cyclohexane to a reaction kettle according to the mass ratio of 26:11:100, stir at 600 r / min for 30 min to obtain a mixture;

[0071] 2) Mix the composite acid (composed of rosin acid, cinnamic acid, and maleic acid mixed according to the mass ratio of 4:1:2), polyethylene glycol, and palladium-carbon catalyst according to the mass ratio of 20:100:2. Mix the composite acid and polyethylene glycol, heat up to 160 °C, add the palladium-carbon catalyst, stir at 400 r / min for 40 min to obtain a functional monomer solution;

[0072] 3) Add the functional monomer solution to the mixture according to the mass ratio of the mixture, the functional monomer solution, and benzoyl peroxide of 2:1:0.2. Heat up to 110 °C, add benzoyl peroxide, stir at 500 r / min for 1.2 h, and then dry at 56 °C for 2 h to obtain modified high styrene rubber.

[0073] The modified filler is prepared by the following method:

[0074] (1) Dissolve dopamine in 0.1 mol / L Tris-HCl according to the mass ratio of dopamine, polyethylene glycol, diatomite, and Tris-HCl of 6:11:21:100. Add polyethylene glycol and stir evenly, carry out grafting reaction, react at room temperature for 30 min, add diatomite, ultrasonically disperse at room temperature for 2 h, control the ultrasonic power at 500 W, the ultrasonic frequency at 30 KHz, then under nitrogen protection, let it stand and react at room temperature for 1.4 h, centrifuge at 11000 r / min for 20 min to obtain a modified diatomite solution;

[0075] (2) According to the mass ratio of the modified diatomite solution, titanate coupling agent, tyrosine, and benzophenone of 50:9:2:0.7, stir the modified diatomite solution and the titanate coupling agent at 700 r / min for 30 min, ultrasonically disperse for 40 min, control the ultrasonic power at 700 W, the ultrasonic frequency at 28 KHz, then add tyrosine and benzophenone, react at room temperature for 1 h under the irradiation of an ultraviolet lamp with a light irradiance of 17 mW / cm 2 Then stir and react at a rotation speed of 500 r / min for 50 min, then centrifuge at 11000 r / min for 20 min, and dry at 60 °C for 2 h to obtain the modified filler.

[0076] A preparation process of a highly wear-resistant rubber specifically includes the following steps:

[0077] S1. Mix natural rubber, cis-butadiene rubber, and modified high styrene rubber, knead in a kneader for 4 min, control the temperature at 70 °C, and the kneading speed at 30 r / min;

[0078] S2. Add modified filler, zinc carbonate, stearic acid, and antioxidant to the above internal mixer, and continue mixing for 7 min, controlling the temperature at 90 °C and the mixing speed at 20 r / min to obtain a mixed material.

[0079] S3. Add compound vulcanizing agent to the mixed material, mix for 6 min, control the temperature at 50 °C and the mixing speed at 40 r / min to obtain a premixed rubber.

[0080] S4. Add the premixed rubber to a vulcanizer for vulcanization, control the vulcanization temperature at 150 °C, the time at 20 min, and the pressure at 16 MPa, and discharge the material to obtain high wear-resistant rubber.

[0081] Example 4

[0082] A high wear-resistant rubber, comprising the following components in parts by weight: 45 parts of natural rubber, 19 parts of cis-butadiene rubber, 40 parts of modified high styrene rubber, 46 parts of modified filler, 6.5 parts of zinc carbonate, 2.5 parts of stearic acid, 5.5 parts of compound vulcanizing agent, and 0.9 part of antioxidant.

[0083] The antioxidant is composed of antioxidant AW, antioxidant DNP, and antioxidant RD mixed in a mass ratio of 1.5:1:2; in step S3, the compound vulcanizing agent is composed of tetraethylthiuram disulfide, sulfur, and triethylenetetramine mixed in a mass ratio of 2.5:1:5.5.

[0084] The modified high styrene rubber is prepared by the following method:

[0085] 1) According to the mass ratio of styrene:butadiene:cyclohexane of 28:11.5:100, add styrene, butadiene, and cyclohexane to a reaction kettle, and stir at 600 r / min for 30 min to obtain a mixture.

[0086] 2) According to the mass ratio of composite acid (composed of rosin acid, cinnamic acid, and maleic acid mixed in a mass ratio of 4.5:1:2.5), polyethylene glycol, and palladium-carbon catalyst of 21:100:2.5, mix the composite acid and polyethylene glycol, heat up to 165 °C, add the palladium-carbon catalyst, and stir at 400 r / min for 45 min to obtain a functional monomer solution.

[0087] 3) According to the mass ratio of the mixture:functional monomer solution:benzoyl peroxide of 2.5:1:0.25, add the functional monomer solution to the mixture, heat up to 115 °C, add benzoyl peroxide, stir at 500 r / min for 1.3 h, and then dry at 58 °C for 2.5 h to obtain the modified high styrene rubber.

[0088] The modified filler is prepared by the following method:

[0089] (1) Dissolve dopamine in 0.1 mol / L Tris-HCl according to the mass ratio of dopamine, polyethylene glycol, diatomite and Tris-HCl being 6.5:11.5:21.5:100. Add polyethylene glycol and stir evenly, then carry out grafting reaction at room temperature for 30 min. Add diatomite and ultrasonically disperse for 2.5 h at room temperature, controlling the ultrasonic power at 550 W and the ultrasonic frequency at 35 KHz. Then, under nitrogen protection, let it stand and react at room temperature for 1.6 h, and centrifuge at 11500 r / min for 25 min to obtain the modified diatomite solution;

[0090] (2) According to the mass ratio of the modified diatomite solution, titanate coupling agent, tyrosine and benzophenone being 50:9.5:2.5:0.8, stir the modified diatomite solution and the titanate coupling agent at 750 r / min for 30 min, then ultrasonically disperse for 40 min, controlling the ultrasonic power at 750 W and the ultrasonic frequency at 29 KHz. Then add tyrosine and benzophenone, and react at room temperature for 1 h under the irradiation of an ultraviolet lamp with a light irradiance of 18 mW / cm 2 . Then stir and react at a rotation speed of 500 r / min for 50 min, then centrifuge at 11500 r / min for 25 min, and dry at 61 °C for 2.5 h to obtain the modified filler.

[0091] A preparation process of high wear-resistant rubber specifically includes the following steps:

[0092] S1. Mix natural rubber, cis-butadiene rubber and modified high styrene rubber, and carry out kneading in a kneader for 4.5 min, controlling the temperature at 75 °C and the kneading rotation speed at 35 r / min;

[0093] S2. Add the modified filler, zinc carbonate, stearic acid and antioxidant to the above kneader, and continue to knead for 7.5 min, controlling the temperature at 95 °C and the kneading rotation speed at 25 r / min to obtain the kneaded material;

[0094] S3. Add the kneaded material to the compound vulcanizing agent and knead for 6.5 min, controlling the temperature at 50 °C and the kneading rotation speed at 45 r / min to obtain the premixed rubber;

[0095] S4. Add the premixed rubber to a vulcanizer for vulcanization, controlling the vulcanization temperature at 155 °C, the time at 25 min, and the pressure at 16.5 MPa. The high wear-resistant rubber is obtained after discharging.

[0096] Example 5

[0097] A high wear-resistant rubber includes the following components in parts by weight: 50 parts of natural rubber, 20 parts of cis-butadiene rubber, 45 parts of modified high styrene rubber, 48 parts of modified filler, 7 parts of zinc carbonate, 3 parts of stearic acid, 6 parts of compound vulcanizing agent, and 1 part of antioxidant.

[0098] The antioxidant is composed of antioxidant AW, antioxidant DNP, and antioxidant RD mixed in a mass ratio of 1.5:1:2; in step S3, the compound vulcanizing agent is composed of tetraethylthiuram disulfide, sulfur, and triethylenetetramine mixed in a mass ratio of 3:1:6.

[0099] The modified high styrene rubber is prepared by the following method:

[0100] 1) Styrene, butadiene, and cyclohexane are added to a reaction kettle according to a mass ratio of 30:12:100, and stirred at 600 r / min for 30 min to obtain a mixture;

[0101] 2) The compound acid (composed of rosin acid, cinnamic acid, and maleic acid mixed in a mass ratio of 5:1:3), polyethylene glycol, and palladium-carbon catalyst are mixed according to a mass ratio of 22:100:3. The compound acid and polyethylene glycol are mixed and heated to 170 °C, then the palladium-carbon catalyst is added, and stirred at 400 r / min for 50 min to obtain a functional monomer solution;

[0102] 3) The functional monomer solution is added to the mixture according to a mass ratio of the mixture, the functional monomer solution, and benzoyl peroxide of 3:1:0.3. The temperature is raised to 120 °C, benzoyl peroxide is added to the reaction kettle, and stirred at 500 r / min for 1.4 h, and then dried at 60 °C for 3 h to obtain the modified high styrene rubber.

[0103] The modified filler is prepared by the following method:

[0104] (1) Dopamine, polyethylene glycol, diatomite, and Tris-HCl are mixed according to a mass ratio of 7:12:22:100. Dopamine is dissolved in 0.1 mol / L Tris-HCl, polyethylene glycol is added and stirred evenly, and grafting reaction is carried out. The reaction is carried out at room temperature for 30 min, diatomite is added, and ultrasonic dispersion is carried out at room temperature for 3 h. The ultrasonic power is controlled at 600 W, and the ultrasonic frequency is 40 KHz. Then, under nitrogen protection, the reaction is allowed to stand at room temperature for 1.8 h and centrifuged at 12000 r / min for 30 min to obtain a modified diatomite solution;

[0105] (2) The modified diatomite solution, titanate coupling agent, tyrosine, and benzophenone are mixed according to a mass ratio of 50:10:3:0.9. The modified diatomite solution and the titanate coupling agent are stirred at 800 r / min for 30 min and ultrasonically dispersed for 40 min. The ultrasonic power is controlled at 800 W, and the ultrasonic frequency is 30 KHz. Then tyrosine and benzophenone are added, and the reaction is carried out at room temperature for 1 h under the irradiation of an ultraviolet lamp with a light irradiance of 19 mW / cm 2 Then, the reaction is stirred at a rotation speed of 500 r / min for 50 min, and then centrifuged at 12000 r / min for 30 min and dried at 63 °C for 3 h to obtain the modified filler.

[0106] A preparation process of a highly wear-resistant rubber, specifically including the following steps:

[0107] S1. Mix natural rubber, cis-butadiene rubber and modified high styrene rubber, and carry out internal mixing in an internal mixer for 5 min, control the temperature at 80 °C, and the internal mixing speed at 40 r / min;

[0108] S2. Add modified filler, zinc carbonate, stearic acid and antioxidant to the above internal mixer, and continue mixing for 8 min, control the temperature at 100 °C, and the mixing speed at 30 r / min to obtain a mixed material;

[0109] S3. Add compound vulcanizing agent to the mixed material, and mix for 7 min, control the temperature at 50 °C, and the mixing speed at 50 r / min to obtain a premixed rubber;

[0110] S4. Add the premixed rubber to a vulcanizer for vulcanization, control the vulcanization temperature at 160 °C, the time at 30 min, and the pressure at 17 MPa, and discharge to obtain the highly wear-resistant rubber.

[0111] Comparative Example 1

[0112] A highly wear-resistant rubber, comprising the following components in parts by weight: 55 parts of natural rubber, 16 parts of cis-butadiene rubber, 40 parts of modified filler, 5 parts of zinc carbonate, 1 part of stearic acid, 4 parts of compound vulcanizing agent, and 0.6 part of antioxidant.

[0113] The antioxidant is composed of antioxidant AW, antioxidant DNP and antioxidant RD mixed in a mass ratio of 1.5:1:2; the compound vulcanizing agent is composed of tetraethylthiuram disulfide, sulfur and triethylenetetramine mixed in a mass ratio of 1:1:4.

[0114] The modified filler is prepared by the following method:

[0115] (1) According to the mass ratio of dopamine, polyethylene glycol, diatomite and Tris-HCl being 5:10:20:100, dissolve dopamine in 0.1 mol / L Tris-HCl, add polyethylene glycol and stir evenly, carry out grafting reaction, react at room temperature for 30 min, add diatomite, carry out ultrasonic dispersion at room temperature for 1 h, control the ultrasonic power at 400 W and the ultrasonic frequency at 20 KHz, then under nitrogen protection, stand and react at room temperature for 1 h, centrifuge at 10000 r / min for 10 min to obtain a modified diatomite solution;

[0116] (2) According to the mass ratio of the modified diatomite solution, titanate coupling agent, tyrosine and benzophenone being 50:8:1:0.5, the modified diatomite solution and the titanate coupling agent are stirred at 600 r / min for 30 min, ultrasonically dispersed for 40 min, with the ultrasonic power controlled at 600 W and the ultrasonic frequency at 26 KHz. Then tyrosine and benzophenone are added, and the reaction is carried out at room temperature for 1 h under the irradiation of an ultraviolet lamp with a light irradiance of 15 mW / cm 2 and then stirred at a rotation speed of 500 r / min for 50 min, and then centrifuged at 10000 r / min for 10 min and dried at 58 °C for 1 h to obtain the modified filler.

[0117] A preparation process of a highly wear-resistant rubber specifically includes the following steps:

[0118] S1. Mix natural rubber and cis-butadiene rubber, and carry out internal mixing in an internal mixer for 3 min, with the temperature controlled at 60 °C and the internal mixing rotation speed at 20 r / min;

[0119] S2. Add the modified filler, zinc carbonate, stearic acid, and antioxidant to the above internal mixer, and continue mixing for 6 min, with the temperature controlled at 80 °C and the mixing rotation speed at 30 r / min to obtain a mixed material;

[0120] S3. Add the compound vulcanizing agent to the mixed material and mix for 5 min, with the temperature controlled at 50 °C and the mixing rotation speed at 30 r / min to obtain a premixed rubber;

[0121] S4. Add the premixed rubber to a vulcanizer for vulcanization, with the vulcanization temperature controlled at 140 °C, the time at 10 min, and the pressure at 15 MPa, and the high wear-resistant rubber is obtained after discharging.

[0122] Comparative Example 2

[0123] A highly wear-resistant rubber includes the following components in parts by weight: 30 parts of natural rubber, 16 parts of cis-butadiene rubber, 25 parts of high styrene rubber, 40 parts of modified filler, 5 parts of zinc carbonate, 1 part of stearic acid, 4 parts of compound vulcanizing agent, and 0.6 part of antioxidant.

[0124] The antioxidant is composed of antioxidant AW, antioxidant DNP, and antioxidant RD mixed in a mass ratio of 1.5:1:2; the compound vulcanizing agent is composed of tetraethylthiuram disulfide, sulfur, and triethylenetetramine mixed in a mass ratio of 1:1:4.

[0125] The high styrene rubber is prepared by the following method:

[0126] 1) According to the mass ratio of styrene, butadiene, and cyclohexane being 22:10:100, add styrene, butadiene, and cyclohexane to a reaction kettle, and stir at 600 r / min for 30 min to obtain a mixture;

[0127] 2) Add benzoyl peroxide to the mixture at a mass ratio of the mixture to benzoyl peroxide of 1:0.1, stir at 500 r / min for 1 h, and then dry at 52 °C for 1 h to obtain high styrene rubber.

[0128] The modified filler is prepared by the following method:

[0129] (1) Dissolve dopamine in 0.1 mol / L Tris-HCl according to the mass ratio of dopamine, polyethylene glycol, diatomite and Tris-HCl of 5:10:20:100, add polyethylene glycol and stir evenly, carry out grafting reaction, react at room temperature for 30 min, add diatomite, ultrasonically disperse at room temperature for 1 h, control the ultrasonic power to be 400 W and the ultrasonic frequency to be 20 KHz, then under nitrogen protection, let it stand and react at room temperature for 1 h, centrifuge at 10000 r / min for 10 min to obtain a modified diatomite solution;

[0130] (2) According to the mass ratio of the modified diatomite solution, titanate coupling agent, tyrosine and benzophenone of 50:8:1:0.5, stir the modified diatomite solution and the titanate coupling agent at 600 r / min for 30 min, ultrasonically disperse for 40 min, control the ultrasonic power to be 600 W and the ultrasonic frequency to be 26 KHz, then add tyrosine and benzophenone, and react at room temperature for 1 h under the irradiation of an ultraviolet lamp with a light irradiance of 15 mW / cm 2 , then stir and react at a rotation speed of 500 r / min for 50 min, then centrifuge at 10000 r / min for 10 min, and dry at 58 °C for 1 h to obtain the modified filler.

[0131] A preparation process of a highly wear-resistant rubber specifically includes the following steps:

[0132] S1. Mix natural rubber, cis-butadiene rubber and high styrene rubber, carry out internal mixing in an internal mixer for 3 min, control the temperature to be 60 °C, and the internal mixing rotation speed to be 20 r / min;

[0133] S2. Add the modified filler, zinc carbonate, stearic acid, and antioxidant to the above internal mixer, continue to mix for 6 min, control the temperature to be 80 °C, and the mixing rotation speed to be 30 r / min to obtain a mixed material;

[0134] S3. Add a compound vulcanizing agent to the mixed material, mix for 5 min, control the temperature to be 50 °C, and the mixing rotation speed to be 30 r / min to obtain a premixed rubber;

[0135] S4. Add the premixed rubber to a vulcanizer for vulcanization, control the vulcanization temperature to be 140 °C, the time to be 10 min, and the pressure to be 15 MPa, and discharge to obtain the highly wear-resistant rubber.

[0136] Comparative Example 3

[0137] A highly wear-resistant rubber, comprising the following components in parts by weight: 30 parts of natural rubber, 16 parts of cis-butadiene rubber, 25 parts of modified high styrene rubber, 40 parts of modified filler, 5 parts of zinc carbonate, 1 part of stearic acid, 4 parts of compound vulcanizing agent, and 0.6 part of antioxidant.

[0138] The antioxidant is composed of antioxidant AW, antioxidant DNP, and antioxidant RD mixed in a mass ratio of 1.5:1:2; the compound vulcanizing agent is composed of tetraethylthiuram disulfide, sulfur, and triethylenetetramine mixed in a mass ratio of 1:1:4.

[0139] The modified high styrene rubber is prepared by the following method:

[0140] 1) According to the mass ratio of styrene, butadiene, and cyclohexane being 22:10:100, add styrene, butadiene, and cyclohexane to a reaction kettle, stir at 600 r / min for 30 min to obtain a mixture;

[0141] 2) According to the mass ratio of compound acid (composed of rosin acid and cinnamic acid mixed in a mass ratio of 3:1), polyethylene glycol, and palladium-carbon catalyst being 18:100:1, mix the compound acid and polyethylene glycol, heat up to 150 °C, add the palladium-carbon catalyst, stir at 400 r / min for 30 min to obtain a functional monomer solution;

[0142] 3) According to the mass ratio of the mixture, the functional monomer solution, and benzoyl peroxide being 1:1:0.1, add the functional monomer solution to the mixture, heat up to 100 °C, add benzoyl peroxide, stir at 500 r / min for 1 h, and then dry at 52 °C for 1 h to obtain the modified high styrene rubber.

[0143] The modified filler is prepared by the following method:

[0144] (1) According to the mass ratio of dopamine, polyethylene glycol, diatomite, and Tris-HCl being 5:10:20:100, dissolve dopamine in 0.1 mol / L Tris-HCl, add polyethylene glycol and stir evenly, carry out a grafting reaction, react at room temperature for 30 min, add diatomite, ultrasonically disperse at room temperature for 1 h, control the ultrasonic power to be 400 W, the ultrasonic frequency to be 20 KHz, then under nitrogen protection, stand and react at room temperature for 1 h, centrifuge at 10000 r / min for 10 min to obtain a modified diatomite solution;

[0145] (2) According to the mass ratio of the modified diatomite solution, titanate coupling agent, tyrosine and benzophenone being 50:8:1:0.5, the modified diatomite solution and the titanate coupling agent are stirred at 600 r / min for 30 min, ultrasonically dispersed for 40 min, with the ultrasonic power controlled at 600 W and the ultrasonic frequency at 26 KHz. Then tyrosine and benzophenone are added, and the reaction is carried out at room temperature for 1 h under the irradiation of an ultraviolet lamp with a light irradiance of 15 mW / cm 2 Then, the reaction is stirred at 500 r / min for 50 min, and then centrifuged at 10000 r / min for 10 min, and dried at 58 °C for 1 h to obtain the modified filler.

[0146] A preparation process of a highly wear-resistant rubber specifically includes the following steps:

[0147] S1. Mix natural rubber, cis-butadiene rubber and modified high styrene rubber, and carry out kneading in a kneader for 3 min, controlling the temperature at 60 °C and the kneading speed at 20 r / min;

[0148] S2. Add the modified filler, zinc carbonate, stearic acid and antioxidant to the above kneader, and continue to knead for 6 min, controlling the temperature at 80 °C and the kneading speed at 30 r / min to obtain a kneaded material;

[0149] S3. Add the compound vulcanizing agent to the kneaded material and knead for 5 min, controlling the temperature at 50 °C and the kneading speed at 30 r / min to obtain a premixed rubber;

[0150] S4. Add the premixed rubber to a vulcanizer for vulcanization, controlling the vulcanization temperature at 140 °C, the time at 10 min and the pressure at 15 MPa, and discharging to obtain the highly wear-resistant rubber.

[0151] Comparative Example 4

[0152] A highly wear-resistant rubber includes the following components in parts by weight: 30 parts of natural rubber, 16 parts of cis-butadiene rubber, 25 parts of modified high styrene rubber, 40 parts of modified filler, 5 parts of zinc carbonate, 1 part of stearic acid, 4 parts of compound vulcanizing agent, and 0.6 part of antioxidant.

[0153] The antioxidant is composed of antioxidant AW, antioxidant DNP and antioxidant RD mixed in a mass ratio of 1.5:1:2; the compound vulcanizing agent is composed of tetraethylthiuram disulfide, sulfur and triethylenetetramine mixed in a mass ratio of 1:1:4.

[0154] The modified high styrene rubber is prepared by the following method:

[0155] 1) According to the mass ratio of styrene, butadiene and cyclohexane being 22:10:100, add styrene, butadiene and cyclohexane to a reaction kettle, and stir at 600 r / min for 30 min to obtain a mixture;

[0156] 2) Mix the composite acid (composed of rosin acid, cinnamic acid, and maleic acid mixed in a mass ratio of 3:1:1) and polyethylene glycol in a mass ratio of 18:100 to obtain a functional monomer solution.

[0157] 3) Add the functional monomer solution to the mixture in a mass ratio of 1:1:0.1 for the mixture, functional monomer solution, and benzoyl peroxide. Heat the mixture to 100 °C, add benzoyl peroxide, stir at 500 r / min for 1 h, and then dry at 52 °C for 1 h to obtain the modified high styrene rubber.

[0158] The modified filler is prepared by the following method:

[0159] (1) Dissolve dopamine in 0.1 mol / L Tris-HCl according to a mass ratio of 5:10:20:100 for dopamine, polyethylene glycol, diatomite, and Tris-HCl. Add polyethylene glycol and stir evenly, then carry out a grafting reaction. React at room temperature for 30 min, add diatomite, and ultrasonically disperse at room temperature for 1 h. Control the ultrasonic power at 400 W and the ultrasonic frequency at 20 KHz. Then, under nitrogen protection, let it stand and react at room temperature for 1 h, and centrifuge at 10000 r / min for 10 min to obtain a modified diatomite solution.

[0160] (2) According to a mass ratio of 50:8:1:0.5 for the modified diatomite solution, titanate coupling agent, tyrosine, and benzophenone, stir the modified diatomite solution and the titanate coupling agent at 600 r / min for 30 min, ultrasonically disperse for 40 min. Control the ultrasonic power at 600 W and the ultrasonic frequency at 26 KHz. Then add tyrosine and benzophenone, and react at room temperature for 1 h under the irradiation of an ultraviolet lamp with a light irradiance of 15 mW / cm 2 . Then stir and react at a rotation speed of 500 r / min for 50 min, then centrifuge at 10000 r / min for 10 min, and dry at 58 °C for 1 h to obtain the modified filler.

[0161] A preparation process of a highly wear-resistant rubber specifically includes the following steps:

[0162] S1. Mix natural rubber, cis-butadiene rubber, and modified high styrene rubber, and carry out internal mixing in an internal mixer for 3 min. Control the temperature at 60 °C and the internal mixing rotation speed at 20 r / min.

[0163] S2. Add the modified filler, zinc carbonate, stearic acid, and antioxidant to the above internal mixer, and continue internal mixing for 6 min. Control the temperature at 80 °C and the internal mixing rotation speed at 30 r / min to obtain a mixed material.

[0164] S3. Add a composite vulcanizing agent to the mixed material and mix for 5 min. Control the temperature at 50 °C and the mixing rotation speed at 30 r / min to obtain a pre-mixed rubber.

[0165] S4. Add the premixed glue into a vulcanizer for vulcanization, control the vulcanization temperature at 140 °C, the time at 10 min, and the pressure at 15 MPa. After discharging, high wear-resistant rubber is obtained.

[0166] Comparative Example 5

[0167] A kind of high wear-resistant rubber, comprising the following components in parts by weight: 30 parts of natural rubber, 16 parts of cis-butadiene rubber, 25 parts of modified high styrene rubber, 40 parts of modified filler, 5 parts of zinc carbonate, 1 part of stearic acid, 4 parts of compound vulcanizing agent, and 0.6 part of antioxidant.

[0168] The antioxidant is composed of antioxidant AW, antioxidant DNP, and antioxidant RD mixed in a mass ratio of 1.5:1:2; the compound vulcanizing agent is composed of tetraethylthiuram disulfide, sulfur, and triethylenetetramine mixed in a mass ratio of 1:1:4.

[0169] The modified high styrene rubber is prepared by the following method:

[0170] 1) According to the mass ratio of styrene, butadiene, and cyclohexane being 22:10:100, add styrene, butadiene, and cyclohexane into a reaction kettle, stir at 600 r / min for 30 min to obtain a mixture;

[0171] 2) According to the mass ratio of the composite acid (composed of rosin acid, cinnamic acid, and maleic acid mixed in a mass ratio of 3:1:1), polyethylene glycol, and palladium-carbon catalyst being 18:100:1, mix the composite acid and polyethylene glycol, heat up to 150 °C, add the palladium-carbon catalyst, stir at 400 r / min for 30 min to obtain a functional monomer solution;

[0172] 3) According to the mass ratio of the mixture, the functional monomer solution, and benzoyl peroxide being 1:1:0.1, add the functional monomer solution to the mixture, heat up to 100 °C, add benzoyl peroxide, stir at 500 r / min for 1 h, and then dry at 52 °C for 1 h to obtain the modified high styrene rubber.

[0173] The modified filler is prepared by the following method:

[0174] (1) According to the mass ratio of diatomite and polyethylene glycol being 1:5, mix diatomite and polyethylene glycol, perform ultrasonic dispersion at room temperature for 1 h, control the ultrasonic power at 400 W and the ultrasonic frequency at 20 KHz, and then centrifuge at 10000 r / min for 10 min to obtain a modified diatomite solution;

[0175] (2) According to the mass ratio of the modified diatomite solution, titanate coupling agent, tyrosine and benzophenone being 50:8:1:0.5, the modified diatomite solution and the titanate coupling agent are stirred at 600 r / min for 30 min, ultrasonically dispersed for 40 min, with the ultrasonic power controlled at 600 W and the ultrasonic frequency at 26 KHz. Then tyrosine and benzophenone are added, and the reaction is carried out at room temperature for 1 h under the irradiation of an ultraviolet lamp with a light irradiance of 15 mW / cm 2 , followed by stirring the reaction at 500 r / min for 50 min, then centrifuging at 10000 r / min for 10 min, and drying at 58 °C for 1 h to obtain the modified filler.

[0176] A preparation process of a highly wear-resistant rubber specifically includes the following steps:

[0177] S1. Mix natural rubber, cis-butadiene rubber and modified high styrene rubber, and carry out internal mixing in an internal mixer for 3 min, controlling the temperature at 60 °C and the internal mixing speed at 20 r / min;

[0178] S2. Add the modified filler, zinc carbonate, stearic acid, and antioxidant to the above internal mixer, and continue internal mixing for 6 min, controlling the temperature at 80 °C and the internal mixing speed at 30 r / min to obtain a mixed material;

[0179] S3. Add a composite vulcanizing agent to the mixed material, and carry out internal mixing for 5 min, controlling the temperature at 50 °C and the internal mixing speed at 30 r / min to obtain a premixed rubber;

[0180] S4. Add the premixed rubber to a vulcanizer for vulcanization, controlling the vulcanization temperature at 140 °C, the time at 10 min, and the pressure at 15 MPa, and discharging to obtain the highly wear-resistant rubber.

[0181] Comparative Example 6

[0182] A highly wear-resistant rubber includes the following components in parts by weight: 30 parts of natural rubber, 16 parts of cis-butadiene rubber, 25 parts of modified high styrene rubber, 40 parts of modified filler, 5 parts of zinc carbonate, 1 part of stearic acid, 4 parts of composite vulcanizing agent, and 0.6 part of antioxidant.

[0183] The antioxidant is composed of antioxidant AW, antioxidant DNP, and antioxidant RD mixed in a mass ratio of 1.5:1:2; the composite vulcanizing agent is composed of tetraethylthiuram disulfide, sulfur, and triethylenetetramine mixed in a mass ratio of 1:1:4.

[0184] The modified high styrene rubber is prepared by the following method:

[0185] 1) According to the mass ratio of styrene, butadiene, and cyclohexane being 22:10:100, add styrene, butadiene, and cyclohexane to a reaction kettle, and stir at 600 r / min for 30 min to obtain a mixture;

[0186] 2) Mix the composite acid (composed of rosin acid, cinnamic acid, and maleic acid mixed in a mass ratio of 3:1:1), polyethylene glycol, and palladium-carbon catalyst at a mass ratio of 18:100:1. Mix the composite acid and polyethylene glycol, heat up to 150 °C, add the palladium-carbon catalyst, stir at 400 r / min for 30 min to obtain the functional monomer solution;

[0187] 3) Add the functional monomer solution to the mixture at a mass ratio of the mixture, functional monomer solution, and benzoyl peroxide of 1:1:0.1. Heat up to 100 °C, add benzoyl peroxide, stir at 500 r / min for 1 h, and then dry at 52 °C for 1 h to obtain the modified high styrene rubber.

[0188] The modified filler is prepared by the following method:

[0189] (1) Dissolve dopamine in 0.1 mol / L Tris-HCl at a mass ratio of dopamine, polyethylene glycol, diatomite, and Tris-HCl of 5:10:20:100. Add polyethylene glycol and stir evenly, carry out the grafting reaction, react at room temperature for 30 min, add diatomite, ultrasonically disperse at room temperature for 1 h, control the ultrasonic power at 400 W and the ultrasonic frequency at 20 KHz, then under nitrogen protection, stand and react at room temperature for 1 h, centrifuge at 10000 r / min for 10 min to obtain the modified diatomite solution;

[0190] (2) Mix the modified diatomite solution and titanate coupling agent at a mass ratio of the modified diatomite solution to titanate coupling agent of 50:8, stir at 600 r / min for 30 min, ultrasonically disperse for 40 min, control the ultrasonic power at 600 W and the ultrasonic frequency at 26 KHz, then centrifuge at 10000 r / min for 10 min, and dry at 58 °C for 1 h to obtain the modified filler.

[0191] A preparation process of a highly wear-resistant rubber specifically includes the following steps:

[0192] S1. Mix natural rubber, cis-butadiene rubber, and modified high styrene rubber, and carry out kneading in a kneader for 3 min, control the temperature at 60 °C, and the kneading speed at 20 r / min;

[0193] S2. Add the modified filler, zinc carbonate, stearic acid, and antioxidant to the above kneader, continue kneading for 6 min, control the temperature at 80 °C, and the kneading speed at 30 r / min to obtain the kneaded material;

[0194] S3. Add the composite vulcanizing agent to the kneaded material, knead for 5 min, control the temperature at 50 °C, and the kneading speed at 30 r / min to obtain the premixed rubber;

[0195] S4. Add the premixed rubber into a vulcanizer for vulcanization, control the vulcanization temperature at 140 °C, the time at 10 min, and the pressure at 15 MPa. The high wear-resistant rubber can be obtained after discharging.

[0196] I. Performance Testing

[0197] Perform hardness, mechanical property, and abrasion tests on the high wear-resistant rubbers obtained in Examples 1-5 and Comparative Examples 1-6.

[0198] 1. Hardness Test

[0199] Using an LX-A type Shore hardness tester, according to the GB / T 531.1-2008 standard, stack the high wear-resistant rubbers obtained in Examples 1-5 and Comparative Examples 1-6 into a spline with a thickness of 6 mm for Shore hardness testing. The test results are shown in Table 1.

[0200] 2. Tensile Strength Test

[0201] Using an HZ-1003B type rubber tensile testing machine, according to the GB / T 528-2009 standard, conduct tensile strength testing and elongation at break testing on the high wear-resistant rubbers obtained in Examples 1-5 and Comparative Examples 1-6. The tensile rate of the testing machine is 500 mm / min. The test results are shown in Table 1.

[0202] 3. Tear Resistance

[0203] According to the method in the standard GB / T 529-2008, conduct tear resistance testing on the high wear-resistant rubbers obtained in Examples 1-5 and Comparative Examples 1-6. The tensile rate is 50 mm / min, the test temperature is room temperature, and the force value per unit thickness records the tear strength. The test results are shown in Table 1.

[0204] 4. Akron Abrasion Test

[0205] Using a JMH-76 type Akron abrasion testing machine, prepare the high wear-resistant rubbers obtained in Examples 1-5 and Comparative Examples 1-6 into long strip-shaped specimens with a thickness of 5.0 mm and a width of 12 mm, stick them to the rubber roller, and after standing for 24 h, fix the rubber wheel on the Akron abrasion machine to travel 1.61 km. The test load is 26.7 N, the rotational speed of the rubber wheel is 76 r / min, and the rotational speed of the grinding wheel is 34 r / min. Conduct Akron abrasion testing according to the GB / T1689-2014 standard. The test results are shown in Table 1.

[0206] Table 1 Test results of various properties of the high wear-resistant rubbers in Examples 1-5 and Comparative Examples 1-6

[0207]

[0208]

[0209] According to Table 1, by comparing Comparative Examples 1-4 with Examples 1-5, it can be seen that for the rubber materials prepared without adding high styrene rubber or with unmodified high styrene rubber or by changing the modification method of high styrene rubber, the hardness, tear resistance and wear resistance are all significantly reduced, indicating that the limitation of the preparation raw materials and the preparation process can effectively improve the comprehensive performance of the rubber material; by comparing Comparative Examples 5-6 with Examples 1-5, it can be seen that the change in the preparation method of the modified filler will also significantly reduce the comprehensive performance of the rubber material. The hardness, tear resistance and wear resistance of the high wear-resistant rubber prepared in Examples 1-5 of this application are significantly better than those of the high wear-resistant rubber prepared in Comparative Examples 1-6, indicating that the high wear-resistant rubber prepared in this application can significantly enhance the wear resistance and tear resistance of the rubber, and the raw materials used in this application are more environmentally friendly and friendly to the environment.

[0210] This specific embodiment is only an explanation of this application and does not limit this application. After reading this specification, those skilled in the art can make modifications to this embodiment without creative contributions as needed, but as long as it is within the scope of the claims of this application, it is protected by the patent law.

Claims

1. A highly wear-resistant rubber, characterized in that: The invention comprises the following components in parts by weight: 71-115 parts of rubber matrix, 40-48 parts of modified filler, 5-7 parts of zinc carbonate, 1-3 parts of stearic acid, 4-6 parts of composite vulcanizing agent and 0.6-1 part of antioxidant.

2. The high wear-resistant rubber according to claim 1, characterized in that: The rubber matrix comprises the following components in parts by weight: 30-50 parts of natural rubber, 16-20 parts of butadiene rubber, and 25-45 parts of modified high styrene rubber.

3. The high wear-resistant rubber according to claim 2, characterized in that: The modified high styrene rubber is prepared by the following method: 1) Add styrene, butadiene and cyclohexane into a reaction kettle, and stir to obtain a mixture; 2) The composite acid and polyethylene glycol are stirred and mixed, the temperature is increased, a palladium-carbon catalyst is added, and the mixture is stirred and mixed to obtain a functional monomer solution; 3) Add the functional monomer solution to the mixture, increase the temperature, add the initiator, stir to react, and dry to obtain the modified high styrene rubber.

4. The highly wear-resistant rubber according to claim 3, characterized in that: In the step 1), the mass ratio of styrene, butadiene and cyclohexane is 22-30:10-12:

100.

5. The highly wear-resistant rubber according to claim 3, characterized in that: In the step 2), the mass ratio of the composite acid, polyethylene glycol and palladium-carbon catalyst is 18-22:100:1-3.

6. The highly wear-resistant rubber according to claim 3, characterized in that: In the step 2), the composite acid is composed of rosin acid, cinnamic acid and maleic acid mixed in a mass ratio of 3-5:1:1-3.

7. The highly wear-resistant rubber according to claim 1, characterized in that: The modified filler is prepared by the following method: (1) dissolving dopamine in Tris-HCl, adding polyethylene glycol and stirring evenly to carry out grafting reaction, adding diatomaceous earth, ultrasonically dispersing at room temperature for 1-3 hours, and then reacting for 1-1.8 hours under nitrogen protection, centrifuging to obtain a modified diatomaceous earth solution; (2) The modified diatomite solution and the titanate coupling agent are stirred and mixed, ultrasonically dispersed, and then tyrosine and a photoinitiator are added to react under ultraviolet light, followed by stirring the reaction, and then centrifuged and dried to obtain a modified filler.

8. The highly wear-resistant rubber according to claim 7, characterized in that: In the step (1), the mass ratio of dopamine, polyethylene glycol, diatomaceous earth and Tris-HCl is 5-7:10-12:20-22:

100.

9. The highly wear-resistant rubber according to claim 7, characterized in that: In the step (2), the mass ratio of the modified diatomite solution, the titanate coupling agent, the tyrosine and the photoinitiator is 50:8-10:1-3:0.5-0.

9.

10. A process for preparing the highly wear-resistant rubber according to any one of claims 1 to 9, characterized in that: The specific steps include: S1. Mix the rubber matrix in an internal mixer for 3-5 minutes at a temperature of 60-80°C; S2, adding modified filler, zinc carbonate, stearic acid and antioxidant to the above internal mixer, continuing mixing for 6-8 minutes, controlling the temperature to 80-100° C., to obtain a mixed material; S3, adding the compound vulcanizing agent to the mixed material, and continuing to mix evenly to obtain a premixed rubber; S4. Add the premixed rubber into a vulcanizer for vulcanization, and discharge the material to obtain a highly wear-resistant rubber.

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