Rubber composition containing nano reinforced composite material and application of rubber composition in tire preparation

Abstract

The invention relates to the technical field of tire rubber manufacturing, in particular to a rubber composition containing a nano reinforced composite material and application of the rubber composition in tire preparation. The nano reinforced composite material is prepared by mixing the following raw materials in parts by weight: 20-40 parts of butadiene rubber or natural rubber, 1-10 parts of filler, 1-4 parts of organic sulfide and 0.4-2 parts of dihydrazide. The nano-reinforced composite material is applied to preparation of tire rubber and can absorb a large amount of energy in the stretching process through heterogeneous distribution of filler in the rubber, so that the damage resistance and the high-temperature performance of the rubber material are improved; and the dihydrazide enhances the chemical combination of the nano reinforced composite material and natural rubber, and reacts with aldehyde groups, carboxyl groups, carbonyl groups and other groups at the tail end of the rubber, so that the activity of the tail end of a free radical is reduced, and the heat generation is reduced.

Description

Technical Field

[0001] The invention relates to the technical field of tire rubber manufacturing, in particular to a rubber composition containing a nano-reinforced composite material and application thereof in tire preparation. Background Art

[0002] Tires are an important part of vehicles, and their performance directly affects driving safety and fuel efficiency. In the tire structure, tread rubber and base rubber are important parts that determine the overall performance of the tire. The design and performance of tread rubber and base rubber have an important impact on the service life, wear resistance, handling and stability of the tire in high temperature environments. However, in the prior art, the performance of tread rubber and base rubber still has many shortcomings, especially in high-speed and high-temperature environments, and it is difficult to meet the increasingly high performance requirements.

[0003] The tread rubber is located on the outermost layer of the tire and is in direct contact with the road surface, which is related to the driving safety and performance of the vehicle. The main function of the tread rubber is to provide good grip and wear resistance to ensure the safe driving of the vehicle under various road conditions. The design and material selection of the tread rubber are directly related to the vehicle's handling, braking performance and fuel efficiency. However, the tread rubber faces multiple challenges in actual use: 1. Degradation of high temperature performance: During the driving process of the vehicle, the tread temperature can rise to above 60°C, resulting in a decrease in the mechanical properties of the rubber material by more than 30%, such as a decrease in modulus and a decrease in tear strength, which directly affects the grip and safety of the tire; 2. Dynamic fatigue damage: When the tire is subjected to periodic deformation at high speed (the dynamic frequency can exceed 10Hz), the rubber material is prone to aging due to heat generation, causing fatigue damage; 3. Performance balance problem: In traditional formulas, improving wear resistance may sacrifice grip, and enhancing high temperature performance often leads to a decrease in dynamic performance. How to strike a balance between multiple performances is a technical difficulty.

[0004] The base rubber is the "skeleton" of the tire, providing basic structure and strength. The base rubber is located inside the tire and mainly plays the role of supporting and protecting the internal structure. It is usually closely combined with the internal structural layers of the tire (such as the carcass layer, belt layer, etc.), providing basic structural and strength support for the tire, and playing the role of buffering and transmitting stress. The quality and performance of the base rubber directly affect the overall durability and safety of the tire. High-strength and high-durability rubber materials are usually used to ensure the overall structural stability and durability of the tire. However, the base rubber also faces the following problems in use: 1. Heat generation problem: During the driving process of the tire, the temperature of the base rubber can reach 80°C, resulting in violent movement of the internal molecular chains of the rubber material, further aggravating aging and failure; 2. Insufficient fatigue resistance: Under long-term dynamic deformation conditions, the base rubber is prone to crack propagation and fatigue damage, affecting the life of the tire; 3. Deterioration of mechanical properties: Under high temperature conditions, the modulus and strength of the base rubber decrease significantly, and it cannot fully support the tread, resulting in overall performance degradation.

[0005] The Chinese invention patent applied by the applicant (publication number: CN115572416B, publication date: 2023-09-08) is a high-temperature resistant tire tread rubber composed of the following materials by weight: 40% to 60% natural rubber, 6% to 18% polybutadiene, 25% to 33% filler, 1% to 7% activator, 0.2% to 2% microcrystalline wax, 1% to 4% antioxidant, 0.3% to 1.2% vulcanizer, 0.3% to 2% accelerator, and 0% to 0.2% anti-scorch agent. The prepared tread rubber composition has a high storage modulus E' at low strain, and the modulus at high temperature is significantly improved, the wear resistance is improved, and the rolling resistance is reduced, thereby increasing the service life and mileage of the tire.

[0006] Although the existing technology has made many improvements in the design of tread rubber and base rubber, there are still the following deficiencies in practical applications: 1. High temperature dynamic performance: The dynamic performance and fatigue performance of tires under high temperature and high speed conditions still have a lot of room for improvement. 2. Mechanical properties: While improving wear resistance and fatigue resistance, it is necessary to maintain the balance of tensile strength and modulus of the rubber. 3. Process optimization: It is difficult for the existing process to fully achieve the uniform distribution of fillers and the efficient synergy of rubber components. Summary of the invention

[0007] In view of the deficiencies in the prior art, the present invention provides a rubber composition containing a nano-reinforced composite material. The rubber composition applies the nano-reinforced composite material to the preparation of tire rubber, and through the inhomogeneous distribution of fillers, the nano-reinforced wear-resistant composite material is used to improve the modulus and mechanical properties of the rubber composition at high temperatures, thereby further improving the wear resistance of the rubber composition.

[0008] In order to achieve the above-mentioned purpose, the present invention adopts the following technical solutions: A rubber composition containing a nano-reinforced composite material is prepared by mixing raw materials including a rubber component I, a filler I, an activator, an antioxidant and a vulcanizer. The mixed raw materials of the rubber composition also include a nano-reinforced composite material. The nano-reinforced composite material is prepared by pre-mixing raw materials including a rubber component II, a filler II, an organosilicon polysulfide and a dihydrazide compound; wherein, based on the total weight of the rubber component I + the rubber component II being 100 parts by weight, the rubber component I is 60-90 parts by weight, and the rubber component II is 10-40 parts by weight; the filler II is a nano-scale filler, the weight of the filler II is 5.0-20% of the weight of the rubber component II, the organosilicon polysulfide is 1.0-8.0%, and the dihydrazide compound is 2.0-10%.

[0009] Preferably, rubber component I is 65-75 parts by weight, and rubber component II is 25-35 parts by weight; specifically, rubber component I can be 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, or 75 parts by weight.

[0010] Preferably, the weight of filler II is 10.0-16.0% of the weight of rubber component II, silicone polysulfide is 4.0-8.0%, and dihydrazide compound is 3.0-6.0%; more preferably, the weight of filler II is 12.0-14.0% of the weight of rubber component II, silicone polysulfide is 5.0-7.0%, and dihydrazide compound is 4.5-5.5%.

[0011] Preferably, rubber component I is selected from one or more mixtures of natural rubber, styrene-butadiene rubber, butadiene rubber, nitrile rubber, chloroprene rubber, ethylene-propylene rubber, butyl rubber and silicone rubber; more preferably, rubber component I is a mixture of one or more mixtures of natural rubber, isoprene rubber, styrene-butadiene rubber, butadiene rubber, butyl rubber, EPDM rubber, acrylonitrile-butadiene rubber, styrene-isoprene-butadiene rubber and chloroprene rubber; more preferably, rubber component I is selected from one or more mixtures of natural rubber, butadiene rubber and styrene-butadiene rubber.

[0012] Preferably, the rubber component II is made of butadiene rubber and / or natural rubber.

[0013] Preferably, filler I is a mixture of one or more of carbon black, white carbon black, calcium carbonate, kaolin, talc, barium sulfate, mica powder, aluminum hydroxide and silicate fillers; more preferably, filler I is carbon black and / or white carbon black.

[0014] Preferably, the BET specific surface area of ​​the white carbon black is 50 to 250 m 2 / g, more preferably 80 to 210 m 2 / g, more preferably 100 to 190 m2 / g; the BET specific surface area of ​​the carbon black particles is preferably 20 to 160 m 2 / g, more preferably 40 to 130 m 2 / g, more preferably 50 to 120 m 2 / g; preferably, the amount of white carbon black is 20 to 120 parts by mass, more preferably 25 to 100 parts by mass, and further preferably 60 to 90 parts by mass; carbon black is preferably 5 to 60 parts by mass, more preferably 5 to 55 parts by mass, and further preferably 20 to 55 parts by mass.

[0015] From the viewpoint of further improving the processability, wet skid resistance and wear resistance of the obtained rubber composition, the average secondary particle size of silica is preferably 0.04 to 3 μm, more preferably 0.1 to 1 μm, and even more preferably 0.2 to 0.7 μm. The average secondary particle size of silica can be measured by laser diffraction and scattering method, which is the particle size at the cumulative basis accumulation of 50% in the particle size distribution measured by laser diffraction and scattering method (volume basis cumulative 50% particle size), that is, D50 (median diameter). The volume basis cumulative 50% particle size (D50) is the particle size distribution calculated on a volume basis. In the cumulative curve with the total volume set to 100%, the number of particles is measured from the side with the smaller particle size, and the particle size at the point where the cumulative value reaches 50%.

[0016] The BET specific surface area of ​​the carbon black particles is preferably 20 to 160 m 2 / g, more preferably 40 to 130 m 2 / g, more preferably 50 to 120 m 2 / g. The BET specific surface area of ​​carbon black particles can be measured in accordance with JIS Z8830. The so-called BET method is a method of adsorbing nitrogen gas with a known area on the surface of sample powder particles and calculating the specific surface area of ​​the sample powder particles based on the adsorption amount. The specific surface area calculated by this method is called "BET specific surface area".

[0017] The average secondary particle size of the carbon black particles is preferably 0.05 to 3 μm, more preferably 0.1 to 1.0 μm, and even more preferably 0.2 to 0.9 μm from the viewpoint of further improving dispersibility, mechanical strength, and hardness. The average secondary particle size of the carbon black particles can be measured by a laser diffraction scattering method, and is the particle size at the cumulative basis of 50% in the particle size distribution measured by the laser diffraction scattering method (volume basis cumulative 50% particle size), i.e., D50 (median diameter). The volume basis cumulative 50% particle size (D50) is the particle size distribution calculated on a volume basis, and in the cumulative curve with the total volume set to 100%, the number of particles is measured from the side with a smaller particle size, and the particle size at the point where the cumulative value reaches 50%.

[0018] More preferably, the carbon black is one or more of N134, N220, N234, N375 or N375, N330, N339, N347, and N326; More preferably, the carbon black is N234 or N330.

[0019] Preferably, filler II is a mixture of one or more of nano-carbon black, nano-white carbon black, nano-graphene, nano-calcium carbonate and carbon nanotubes. The carbon nanotubes are preferably array-type, the carbon black is preferably N134, N234 or N375, and the graphene is preferably 2-10 layers of graphene oxide.

[0020] Preferably, filler I is carbon black and white carbon black, and the mass ratio of carbon black to white carbon black is 2:1-8:1; more preferably, the mass ratio of carbon black to white carbon black is 4:1-6:1.

[0021] Preferably, filler II is selected from nano-scale carbon black and carbon nanotubes, and the mass ratio of nano-scale carbon black to carbon nanotubes is 1:1-5:1; more preferably, the mass ratio of nano-scale carbon black to carbon nanotubes is 2:1, 3:1, 4:1, 5:1.

[0022] Preferably, the dihydrazide compound is selected from one or more of sebacic acid dihydrazide, adipic acid dihydrazide and succinic acid dihydrazide; more preferably, the dihydrazide compound is selected from sebacic acid dihydrazide.

[0023] Preferably, the organosilicon polysulfide is selected from one or more of γ-mercaptopropyl triethoxysilane, γ-mercaptopropyl trimethoxysilane, bis(3-mercaptopropyl) tetrasulfide, bis(3-mercaptopropyl) disulfide, mercaptoethyl triethoxysilane, mercaptopropyl siloxane copolymer, methyl mercaptosilane, dimercaptoethylsilane, tetra(mercaptopropyl) silane and bis(γ-triethoxysilylpropyl) sulfide. More preferably, the organosilicon polysulfide is selected from bis(γ-triethoxysilylpropyl) sulfide; the organosilicon polysulfide is bis(γ-triethoxysilylpropyl) sulfide, and its structural formula is as follows: , Where x=2-4.

[0024] Preferably, the activator is 4.0-8.0 parts by weight, the antioxidant is 1.0-5.0 parts by weight, and the vulcanizing agent is 1.5-4.0 parts by weight; more preferably, the activator is 5.0-7.0 parts by weight, the antioxidant is 2.0-4.0 parts by weight, and the vulcanizing agent is 2.0-3.5 parts by weight.

[0025] Preferably, the activator is selected from one or more of zinc oxide, stearic acid, and zinc stearate; more preferably, the activator is selected from 1.0-4.0 parts by weight of zinc oxide and 1.5-4.0 parts by weight of stearic acid.

[0026] Preferably, the antioxidant is selected from one or more of antioxidant 4010, antioxidant 4020, antioxidant RD, 2-mercaptobenzothiazole, and antioxidant TMQ; more preferably, the antioxidant is selected from 1.0-2.0 parts by weight of antioxidant TMQ and 2.0-4.0 parts by weight of antioxidant 4010.

[0027] Preferably, the vulcanizing agent is selected from one or more of sulfur, dicumyl peroxide, vulcanization accelerator NS, vulcanization accelerator CZ, and tetramethylthiuram disulfide. More preferably, the vulcanizing agent is selected from sulfur and vulcanization accelerator NS or vulcanization accelerator CZ.

[0028] Preferably, the mixing raw materials of the rubber composition further include one or more of a silane coupling agent, an anti-tear resin, a microcrystalline wax, and an anti-scorch agent. The brand of the silane coupling agent includes at least one of TESPT, Si75, and Si747. The brand of the tear resin includes at least one of R-110, DCPD, and CSR200.

[0029] Preferably, the preparation method of the nano-reinforced composite material comprises the following steps: starting an internal mixer, setting the speed to 30-45 rpm, adding rubber component II, filler II and silicone polysulfide, mixing for 25-40 seconds, adding a dihydrazide compound, continuing to mix for 1-2.5 minutes, debonding, and obtaining a nano-reinforced composite material.

[0030] Furthermore, the present invention also provides a wear-resistant and high-temperature resistant tire, the components of which are prepared by vulcanizing the rubber composition. The components of the tire are sidewalls, base tread, bead apex, clinch apex, inner liner, under tread, breaker topping, ply topping, tread (single-layer tread, cap tread of multi-layer tread, etc.), and other components of the tire.

[0031] The present invention adopts the above technical solution to provide a rubber composition containing a nano-reinforced composite material and its application in tire preparation, and exhibits the following significant technical effects through unique material design and process optimization: 1. Significantly improved wear resistance: The present invention optimizes the distribution characteristics of fillers in the rubber matrix by introducing nano-reinforced composite materials. During the stretching process, the nano-fillers can effectively absorb strain energy and significantly improve the anti-destruction ability of the rubber material, thereby enhancing the wear resistance of the tread rubber and extending the service life of the tire.

[0032] 2. Optimized high-temperature performance: Nano-reinforced composite materials provide excellent modulus retention under high-temperature conditions, ensuring that the tread rubber and base rubber have good mechanical properties in an operating environment of 60-80°C. The drop in the material's tear strength and dynamic modulus at high temperatures is more than 30% less than that of traditional materials, greatly improving the high-temperature stability and safety of the tire.

[0033] 3. Enhanced dynamic fatigue performance: Through the inhomogeneous distribution design of fillers, the rubber composition of the present invention effectively reduces the heat generation during dynamic driving and significantly delays the aging process of rubber. The anti-fatigue performance of rubber under dynamic compression deformation (>10 Hz) is enhanced, which is particularly suitable for high-speed driving scenarios.

[0034] 4. Balance of mechanical properties: Through the chemical modification of dihydrazide compounds, the interfacial bonding force between the nanofiller and the rubber matrix is ​​enhanced, while the activity of the terminal groups of the rubber is optimized, further improving the strength and flexibility of the rubber, while taking into account the balance between tensile strength, wear resistance and dynamic properties.

[0035] 5. Significantly reduced heat generation: The dihydrazide compound can react chemically with the aldehyde, carboxyl and carbonyl groups at the end of the rubber, effectively reducing the activity of the free radical end, and reducing the internal friction and heat generation of the rubber during dynamic deformation. Compared with traditional rubber compositions, the temperature rise of the material of the present invention is reduced by 20%-30%, further improving the durability of the tire.

[0036] 6. Synergistic improvement of multiple performances: The present invention not only improves wear resistance and high temperature resistance, but also successfully solves the contradiction between grip and rolling resistance in traditional rubber formulas. The tire prepared using the rubber composition of the present invention not only has higher driving safety, but also significantly reduces rolling resistance and improves fuel efficiency.

[0037] 7. Wide application range: The rubber composition is suitable for tire tread rubber and base rubber, and can be widely used in passenger car tires, truck tires and other high-performance tires. It is also suitable for the manufacture of industrial rubber products, such as conveyor belts, shockproof materials, etc.

[0038] In summary, the present invention not only significantly improves the wear resistance, high temperature resistance and dynamic fatigue performance of the tire through material innovation and process optimization, but also achieves the synergistic improvement of multiple performances, providing a new solution for the preparation of tire rubber. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 This is a schematic diagram of a SEM scanning electron microscope of the rubber composition of Application Example 1, and the black part in the figure is a nano-reinforced composite material.

[0040] Figure 2This is a schematic diagram of the SEM scanning electron microscope of the rubber composition of Comparative Example 1. DETAILED DESCRIPTION

[0041] The following is a clear and complete description of the technical solutions in the embodiments of the present invention in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0042] The formulations of Example 1-2 and Comparative Example 1-2 are shown in Table 1.

[0043] Table 1 Example 1 Example 2 Comparative Example 1 Comparative Example 2 Natural rubber*1 75 75 75 75 N234 50 50 50 50 Zinc Oxide 3.0 3.0 3.0 3.0 Stearic acid 2.5 2.5 2.5 2.5 sulfur 1.3 1.3 1.3 1.3 Vulcanization accelerator CZ 1.0 1.0 1.0 1.0 Antioxidant 4020 2.5 2.5 2.5 2.5 Tear Resin CSR200 1 1 1 1 Microcrystalline wax 1 1 1 1 Butadiene rubber*2 / / 25 25 N234 / / 3.5 2.5 Multi-walled carbon nanotubes*3 / / / 1 Sebacic acid dihydrazide*4 / / 1 1 Silicone polysulfide*5 / / 1.5 1.5 Nano-reinforced composite materials A 31.0 / / / Nano-reinforced composite materials B / 31.0 / / The formula of nano-reinforced composite materials is shown in Table 2.

[0044] Table 2 Nano-reinforced composite materials A Nano-reinforced composite materials B Butadiene rubber*2 25 25 Packing B N234 3.5 2.5 Filler B Multi-walled carbon nanotubes*3 / 1 Sebacic acid dihydrazide compound*4 1 1 Silicone polysulfide*5 1.5 1.5 Note: 1. Natural rubber, Thailand No. 20 standard rubber; 2. Butadiene rubber, neodymium butadiene BR-544 NP from Nizhnekamsk, Russia; 3. Multi-walled carbon nanotubes, a product of Shandong Dazhan Nanomaterials Co., Ltd.; 4. Sebacic acid dihydrazide compound, provided by Harbin Quaker New Materials Co., Ltd.; 5. Organosilicon polysulfide, bis-[γ-(triethoxysilyl)propyl] tetrasulfide produced by Jiangxi Hongbai New Materials Co., Ltd.; 6. Other additives are commercially available products.

[0045] The preparation method of the nano-reinforced composite material is as follows: The internal mixer was started and the speed was set to 40 rpm. Butadiene rubber, filler B and organosilicon polysulfide were first added and mixed for 30 seconds. The dihydrazide compound was added and mixed for 1.5 minutes. The mixture was discharged to obtain a nano-reinforced composite material.

[0046] The preparation method of the embodiment is as follows: 1) First stage mixing: start the internal mixer, set the speed to 50 rpm, add natural rubber, filler A, activator, antioxidant, tear-resistant resin, microcrystalline wax, mix for 40 seconds, remove the plug and mix for 25 seconds, remove the plug and mix until the temperature reaches 160°C to discharge the rubber, and obtain masterbatch 1; 2) Second stage mixing: Start the internal mixer, set the speed to 30 rpm, add masterbatch 1 and nano-reinforced composite material, mix for 35 seconds, remove the plug and mix for 20 seconds, remove the plug and mix until the glue is discharged at 140°C to obtain masterbatch 2; 3) Adding vulcanization: start the internal mixer, set the speed to 25 rpm, add masterbatch 2 and vulcanizer, mix for 35 seconds, mix for 30 seconds with the bolt raised and the bolt pressed, mix until the temperature reaches 112°C for rubber discharge, and obtain a wear-resistant and high-temperature resistant rubber composition.

[0047] The preparation method of the comparative example is as follows: 1) First-stage mixing: start the internal mixer, set the speed to 50 rpm, add all materials except the vulcanizing agent, dihydrazide compound and organic vulcanizing agent, mix for 40 seconds, remove the plug and mix for 25 seconds, remove the plug and mix until the temperature reaches 160°C to discharge the glue, and obtain masterbatch 1; 2) Second stage mixing: Start the internal mixer, set the speed to 30 rpm, add masterbatch 1, dihydrazide compound and organic vulcanizing agent, mix for 35 seconds, mix for 20 seconds with the plug lifted, and mix until the temperature reaches 140°C to discharge the glue, to obtain masterbatch 2; 3) Vulcanization: start the internal mixer, set the speed to 25 rpm, add masterbatch 2 and vulcanizer, mix for 35 seconds, mix for 30 seconds with the bolt raised and the bolt pressed, mix until the temperature reaches 112°C for rubber discharge, and obtain a rubber composition.

[0048] The rubber compositions obtained in the examples and comparative examples were subjected to performance tests, and the test results are shown in Table 3.

[0049] Table 3 project Example 1 Example 2 Comparative Example 1 Comparative Example 2 M50 1.8 2.1 1.6 1.9 M300 19 20.5 18.5 19.6 TB 27 28 26.7 25.8 EB% 530 524 536 528 High temperature 100℃, M300 12.3 12.8 9.5 10.1 High temperature 100℃, TB 20.5 21.4 18.3 19.1 E’(60℃) 7.4 7.8 6.2 6.7 Akron Wear 0.105 0.085 0.178 0.162 From the above examples 1 and 2 and comparative examples 1 and 2, it can be seen that the use of nano-reinforced composite materials can significantly improve the high temperature resistance of the tread rubber composition. Under high temperature 100°C stretching, M300 is increased by 29.4% and 26.7%; E' at 60°C is increased by 19.3% and 16.4% respectively; and wear resistance is increased by 41% and 47.5% respectively. It can be seen that the tread rubber composition prepared by the present invention has wear resistance and high temperature resistance.

[0050] The formulations of Examples 3-4 and Comparative Examples 3-4 are shown in Table 1.

[0051] Table 1 Example 3 Example 4 Comparative Example 3 Comparative Example 4 Natural rubber*1 75 75 75 75 N330 34 34 34 34 White Carbon Black 175GR 6 6 6 6 Zinc Oxide 3.0 3.0 3.0 3.0 Stearic acid 2.5 2.5 2.5 2.5 sulfur 2.0 2.0 2.0 2.0 Vulcanization accelerator CZ 0.8 0.8 0.8 0.8 Antioxidant 4020 2.0 2.0 2.0 2.0 Antioxidant RD 0.5 0.5 0.5 0.5 Tear Resin CSR200 1 1 1 1 Microcrystalline wax 1 1 1 1 Anti-scorch agent CTP 0.2 0.2 0.2 0.2 Natural rubber*1 / / 25 25 N330 / / / 2.5 Multi-walled carbon nanotubes*2 / / / 1 Sebacic acid dihydrazide*3 / / / 1 Silicone polysulfide / / 1.5 1.5 Nano-reinforced wear-resistant composite material C 31.0 / / / Nano-enhanced wear-resistant composite materials / 31.0 / / The formula of nano-reinforced composite materials is shown in Table 2.

[0052] Table 2 Nano-reinforced composites C Nano-reinforced composites Natural rubber*1 25 25 Packing B N330 3.5 2.5 Filler B Multi-walled carbon nanotubes*2 / 1 Sebacic acid dihydrazide compound*3 1 1 Silicone polysulfide*4 1.5 1.5 Note: 1. Natural rubber, Thailand No. 20 standard rubber; 2. Multi-walled carbon nanotubes, a product of Shandong Dazhan Nanomaterials Co., Ltd.; 3. Sebacic acid dihydrazide compound, provided by Harbin Quaker New Materials Co., Ltd.; 4. Silicone polysulfide, bis-[γ-(triethoxysilyl)propyl] tetrasulfide produced by Jiangxi Hongbai New Materials Co., Ltd.; 5. Other additives are commercially available products.

[0053] The preparation method of the nano-reinforced composite material is as follows: The internal mixer was started and the speed was set to 40 rpm. Natural rubber, filler B and silicone polysulfide were first added and mixed for 30 seconds. The dihydrazide compound was added and mixed for 1.5 minutes. The mixture was discharged to obtain a nano-reinforced composite material.

[0054] The preparation method of the embodiment is as follows: 1) First stage mixing: start the internal mixer, set the speed to 50 rpm, add natural rubber, filler A, activator, antioxidant, tear-resistant resin, microcrystalline wax, mix for 40 seconds, remove the plug and mix for 25 seconds, remove the plug and mix until the temperature reaches 160°C to discharge the rubber, and obtain masterbatch 1; 2) Second stage mixing: Start the internal mixer, set the speed to 30 rpm, add masterbatch 1 and nano-reinforced composite material, mix for 35 seconds, remove the plug and mix for 20 seconds, remove the plug and mix until the glue is discharged at 140°C to obtain masterbatch 2; 3) Vulcanization: start the internal mixer, set the speed to 25 rpm, add masterbatch 2, anti-scorch agent CTP and vulcanizing agent, mix for 35 seconds, mix for 30 seconds with the bolt raised and the bolt pressed, mix until the temperature reaches 112°C for rubber discharge, and obtain the wear-resistant and high-temperature resistant rubber composition A or B.

[0055] The preparation method of the comparative example is as follows: 1) First-stage mixing: start the internal mixer, set the speed to 50 rpm, add all materials except the anti-scorch agent CTP, the vulcanizing agent, the dihydrazide compound and the organic vulcanizing agent, mix for 40 seconds, remove the plug and mix for 25 seconds, remove the plug and mix until the temperature reaches 160°C to discharge the glue, and obtain the masterbatch 1; 2) Second stage mixing: Start the internal mixer, set the speed to 30 rpm, first add masterbatch 1, dihydrazide compound and organic vulcanizing agent, mix for 35 seconds, remove the plug and mix for 20 seconds, remove the plug and mix until the temperature reaches 140°C to discharge the glue, and obtain masterbatch 2; 3) Vulcanization: start the internal mixer and set the speed to 25 rpm. First add the masterbatch 2, anti-scorch agent CTP and vulcanizing agent, mix for 35 seconds, mix for 30 seconds with the bolt raised and the bolt pressed, mix until the temperature reaches 112°C for rubber discharge to obtain the rubber composition.

[0056] The rubber compositions obtained in the examples and comparative examples were subjected to performance tests, and the test results are shown in Table 3.

[0057] Table 3 project Example 3 Example 4 Comparative Example 3 Comparative Example 4 M50 1.6 1.7 1.4 1.6 M300 16.5 17.2 15.5 16.6 TB 27.2 28 26.2 26.9 EB% 542 533 532 548 High temperature 100℃, M300 11.4 11.8 9.0 9.9 High temperature 100℃, TB 19.5 20.1 18.2 18.5 E’(60℃) 6.8 7.2 5.6 6.1 tanδ(60℃) 0.075 0.085 0.098 0.096 From the above examples 3 and 4 and comparative examples 3 and 4, it can be seen that the use of nano-reinforced composite materials can significantly improve the high temperature resistance of the tread rubber composition. Under high temperature 100°C stretching, M300 is increased by 26.7% and 19.2%; E' at 60°C is increased by 21.4% and 18% respectively; and hysteresis loss tanδ (60°C) is reduced by 23.5% and 11.5% respectively. It can be seen that the base rubber composition prepared by the present invention has low heat generation and high temperature resistance.

[0058] The above is a description of the application examples of the present invention. Through the above description of the disclosed application examples, professionals and technicians in the field can implement or use the present invention. Various modifications to these application examples will be obvious to professionals and technicians in the field. The general principles defined in this article can be implemented in other application examples without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to these embodiments shown in this article, but will conform to the widest range consistent with the principles and novel points disclosed in this article.

Claims

1. A rubber composition containing a nano-reinforced composite material, the rubber composition being prepared by mixing raw materials including a rubber component I, a filler I, an activator, an antioxidant and a vulcanizing agent, characterized in that: The rubber composition mixing raw materials also include a nano-reinforced composite material, and the nano-reinforced composite material is prepared by pre-mixing raw materials including rubber component II, filler II, organic sulfide and dihydrazide compound; Wherein, based on the total weight of rubber component I + rubber component II being 100 parts by weight, rubber component I is 60-90 parts by weight, and rubber component II is 10-40 parts by weight; Filler II is a nano-scale filler, and the weight of filler II is 5.0-20% of the weight of rubber component II, organic silicon polysulfide is 1.0-8.0%, and dihydrazide compound is 2.0-10%.

2. The rubber composition according to claim 1, characterized in that The rubber component I is 65-75 parts by weight, and the rubber component II is 25-35 parts by weight; And / or, the weight of filler II is 10.0-16.0% of the weight of rubber component II, the organic sulfide is 4.0-8.0%, and the dihydrazide compound is 3.0-6.0%.

3. The rubber composition according to claim 1 or 2, characterized in that: The rubber component I is selected from one or more of natural rubber, styrene-butadiene rubber, butadiene rubber, nitrile rubber, chloroprene rubber, ethylene-propylene rubber, butyl rubber and silicone rubber; And / or, the rubber component II is selected from butadiene rubber and / or natural rubber.

4. The rubber composition according to claim 1 or 2, characterized in that: Filler I is a mixture of one or more of carbon black, white carbon black, calcium carbonate, kaolin, talcum powder, barium sulfate, mica powder, aluminum hydroxide and silicate fillers; And / or, filler II is a mixture of one or more of nano-carbon black, nano-white carbon black, nano-graphene, nano-calcium carbonate and carbon nanotube.

5. The rubber composition according to claim 1, characterized in that Filler I uses carbon black and white carbon black, and the mass ratio of carbon black to white carbon black is 2:1-8:1; And / or, filler II is selected from nano-scale carbon black and carbon nanotubes, and the mass ratio of nano-scale carbon black to carbon nanotubes is 1:1-5:

1.

6. The rubber composition according to claim 1, characterized in that The dihydrazide compound is selected from one or more of sebacic acid dihydrazide, adipic acid dihydrazide, and succinic acid dihydrazide; And / or, the organosilicon polysulfide is selected from one or more of γ-mercaptopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, bis(3-mercaptopropyl)tetrasulfide, bis(3-mercaptopropyl)disulfide, mercaptoethyltriethoxysilane, mercaptopropylsiloxane copolymer, methylmercaptosilane, dimercaptoethylsilane, tetra(mercaptopropyl)silane and bis(γ-triethoxysilylpropyl)sulfide.

7. The rubber composition according to claim 1, characterized in that The activator is 4.0-8.0 parts by weight, the antioxidant is 1.0-5.0 parts by weight, and the vulcanizing agent is 1.5-4.0 parts by weight; and / or, the activator is selected from one or more of zinc oxide, stearic acid, and zinc stearate; and / or, the antioxidant is selected from one or more of antioxidant 4010, antioxidant 4020, antioxidant RD, 2-mercaptobenzothiazole, and antioxidant TMQ; And / or, the vulcanizing agent is selected from one or more of sulfur, dicumyl peroxide, vulcanization accelerator NS, vulcanization accelerator CZ, and tetramethylthiuram disulfide.

8. The rubber composition according to claim 1, characterized in that: The mixed raw materials of the rubber composition also include one or more of a silane coupling agent, an anti-tearing resin, a microcrystalline wax and a scorch retardant.

9. The rubber composition according to any one of claims 1 to 8, characterized in that: The preparation method of the nano-reinforced composite material comprises the following steps: starting an internal mixer, setting the speed to 30-45 revolutions, adding rubber component II, filler II and organosilicon polysulfide, mixing for 25-40 seconds, adding a dihydrazide compound, continuing mixing for 1-2.5 minutes, and removing the glue to obtain the nano-reinforced composite material.

10. A wear-resistant and high-temperature resistant tire, characterized in that: The tire components are prepared by vulcanizing the rubber composition described in any one of claims 1 to 9.

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