Corrosion-resistant low-rolling-resistance tire rubber material and preparation method thereof

Abstract

The invention discloses a corrosion-resistant and low-rolling-resistance tire rubber material and a preparation method thereof, and belongs to the technical field of rubber materials. The tire rubber material comprises the following raw materials in parts by weight: 40-60 parts of natural rubber, 20-40 parts of solution polymerized styrene-butadiene rubber, 55-65 parts of modified white carbon black, 2-4 parts of zinc oxide, 3-5 parts of a microcapsule anti-aging agent, 3-6 parts of a silane coupling agent, 8-12 parts of environment-friendly aromatic oil, 1-3 parts of an accelerant and 2-4 parts of sulfur. Through material component innovation and process collaborative design, the corrosion resistance, low rolling resistance and comprehensive mechanical properties of the tire rubber material are remarkably improved, the problem of contradiction between corrosion resistance and low rolling resistance existing in the tire field for a long time is solved, and the tire rubber material is particularly suitable for high-end scenes such as new energy vehicle tires and port special vehicle tires.

Description

Technical Field

[0001] The invention belongs to the technical field of rubber materials, and in particular relates to a corrosion-resistant and low-rolling-resistance tire rubber material and a preparation method thereof. Background Art

[0002] In recent years, with the rapid development of my country's economy, the use of automobiles has increased rapidly, and environmental pollution has become increasingly serious. How to reduce carbon emissions and reduce energy consumption is a common challenge faced by all countries. For example, in the development of automobile tires, it is necessary to develop green tires with low hysteresis loss and wear resistance to achieve energy saving and carbon reduction requirements.

[0003] The corrosion resistance and low rolling resistance of tire rubber are key indicators for improving tire performance. Traditional sidewall rubber formulas mostly use a blend of natural rubber (NR) and butadiene rubber (BR), and rely on carbon black as a reinforcing filler. Although it can balance flexibility and crack growth resistance, it has the following technical bottlenecks: 1. High rolling resistance and high heat generation problems: Traditional formulas require the addition of operating oil to improve the processability and elongation of the rubber, but the operating oil will increase the hysteresis loss and significantly increase the rolling resistance and fuel consumption of the tire. Limitations of reinforcing materials: 2. Although high specific surface area carbon black (such as N330) can strengthen the rubber, it will increase the hardness and increase the rolling resistance; and although white carbon black can reduce rolling resistance, it is easy to cause ultraviolet aging problems when used alone, and the extruded surface is rough, and the corrosion resistance of the tire is reduced.

[0004] Existing technologies attempt to optimize performance by compounding silica with carbon black, such as using low specific surface area carbon black (N550 / N660) to balance reinforcement and hardness, or using a wet mixing process to prepare silica / natural rubber masterbatch to reduce hysteresis loss.

[0005] For example, the patent with application number CN200710050386.7 provides a high wear-resistant aviation tire tread rubber formula. The tread rubber is made of natural rubber as the main material, with new process high-structure and high-wear-resistant carbon black, high-dispersion white carbon black, silane coupling agent, and heat stabilizer as the main auxiliary materials, and then with zinc oxide, stearic acid, p-phenylenediamine antioxidants, ketamine antioxidants, protective wax, insoluble sulfur, sulfonamide accelerators and other raw materials, and mixed in an internal mixer.

[0006] However, these solutions still face the following contradictions: 1. Conflict between corrosion resistance and dynamic performance: High filling of silica may reduce the rubber's resistance to ozone aging; 2. Process complexity: Wet mixing has high requirements on equipment and the reaction conditions of silane coupling agent need to be strictly controlled, otherwise the dispersion effect will be affected.

[0007] In summary, it is urgent to develop a new type of rubber formula, which can significantly reduce rolling resistance while ensuring corrosion resistance and flexural fatigue performance through coordinated design of material components and process innovation. Summary of the invention

[0008] The present invention aims at the problems existing in the prior art. By effectively modifying white carbon black and compounding different types of silane coupling agents, a high content of white carbon black is effectively dispersed. Meanwhile, a microcapsule antioxidant is prepared to avoid the migration loss problem of traditional antioxidants, extend the protection period, and exhibit the characteristics of high wear resistance, corrosion resistance and low rolling resistance as a whole. The tire is suitable for tires in high humidity, coastal or rainy areas.

[0009] In order to achieve the above technical objectives, the technical solution adopted by the present invention is: A corrosion-resistant and low-rolling-resistance tire rubber material comprises the following raw materials in parts by weight: 40-60 parts of natural rubber, 20-40 parts of solution-polymerized styrene-butadiene rubber, 55-65 parts of modified white carbon black, 2-4 parts of zinc oxide, 3-5 parts of microcapsule antioxidant, 3-6 parts of silane coupling agent, 8-12 parts of environmentally friendly aromatic oil, 1-3 parts of accelerator, and 2-4 parts of sulfur.

[0010] Furthermore, the silane coupling agent is an acyloxysilane coupling agent and a fluorosilane coupling agent, and the mass ratio of the two is 1:1.

[0011] Furthermore, the acyloxysilane coupling agent is γ-methacryloxypropyltrimethoxysilane, and the fluorosilane coupling agent is tridecafluorooctyltriethoxysilane and / or ‌3,3,3-trifluoropropyltriethoxysilane.

[0012] Furthermore, the preparation method of the modified silica is: (1) Grinding the raw material white carbon black by air flow to control the average particle size to ≤20nm; (2) Add 1-butyl-3-methylimidazolium chloride and titanate to the white carbon black obtained in step (1), mix well, add bis-[3-(triethoxysilyl)propyl]tetrasulfide (silane coupling agent Si-69), react in a high-speed mixer at 120-150° C. for 20-30 minutes, and dry after completion.

[0013] Furthermore, in step (2), the mass ratio of white carbon black, 1-butyl-3-methylimidazolium chloride, titanate, and bis-[3-(triethoxysilyl)propyl]tetrasulfide is 10:1:0.5:0.3.

[0014] Furthermore, the accelerator is N-tert-butyl-2-benzothiazole sulfenamide.

[0015] Furthermore, the preparation method of the microcapsule antioxidant is: (1) Preparation of core material: The antioxidant composition was dissolved in ethyl acetate with a mass concentration of 20%, and then 5% of the mass of nano-silicon dioxide was added as a nucleating agent at the antioxidant composition, and shear emulsified at 40° C. for 30 minutes to form a uniformly dispersed suspension, and 0.5% of the mass of silane coupling agent KH-550 was added to the suspension, and reacted for 1 hour under nitrogen protection to form active groups on the surface of the antioxidant, thereby obtaining a core material suspension; (2) Preparation of wall material: polyurethane prepolymer (IPDI type, purchased from Dow Chemical) and amino-terminated polyether (ZD-1200, purchased from Guangzhou Ye Zeng Chemical Co., Ltd.) were mixed in a mass ratio of 1:1 as wall material, and nano-silicon carbide (10% by mass of the total mass of polyurethane prepolymer and amino-terminated polyether) was added as reinforcing filler, dissolved in anhydrous xylene, and prepared into an oil phase wall material solution with a solid content of 10%; (3) The core material suspension and the wall material solution were mixed in a mass ratio of 1:5 to obtain an oil phase mixture, which was slowly added into an aqueous phase containing 0.5% polyvinyl alcohol in a volume ratio of 1:3, and a high-pressure homogenizer was used at 25,000 psi for 3 cycles to prepare a W / O type emulsion, and the temperature was controlled not to exceed 40° C. (4) adding a 0.1% aqueous solution of dibutyltin dilaurate dropwise to the emulsion of step (3) at a volume ratio of 20:1, raising the temperature to 75° C., and stirring the mixture under nitrogen protection for 6 hours to allow the polyurethane-urea wall material to crosslink and solidify at the interface; (5) adding 2% of the mass of the emulsion epoxy resin (EPON 828) as a secondary crosslinking agent; adjusting the pH to 8.5, reacting at 90°C for 2 hours to form an epoxy-polyurethane interpenetrating network; centrifuging to obtain a solid, washing it three times with acetone and deionized water in sequence, and freeze-drying it; (6) Finally, the product was heat treated in a vacuum oven at 120°C for 1 hour and then cooled naturally to obtain a microcapsule antioxidant.

[0016] Furthermore, the antioxidant composition is a mixture of antioxidant 4020 and antioxidant RD in a mass ratio of 3:1.

[0017] A method for preparing a corrosion-resistant and low rolling resistance tire rubber material comprises the following preparation steps: (1) Preparation of modified silica and microcapsule antioxidant; (2) One-stage mixing: natural rubber and solution polymerized styrene-butadiene rubber are put into an internal mixer and mixed for 40-50 seconds. Zinc oxide and 1 / 3 of modified white carbon black are added and mixed for 120-150 seconds. The rubber discharge temperature is 130-140°C. The rubber is discharged and cooled to form a one-stage mixed rubber. The rubber is stored for 8 hours before use. (3) Second stage mixing: Add the first stage mixed rubber, the remaining modified silica, the silane coupling agent and the environmentally friendly aromatic oil into an internal mixer for mixing for 150-160 seconds, with the discharge temperature of 140-150°C, and then sheet out and cool to make the second stage mixed rubber, which is then placed for 8 hours before use; (4) Three-stage mixing: The second-stage mixed rubber, sulfur, accelerator, and microcapsule antioxidant are put into an internal mixer and mixed for 100-120 seconds at a mixing temperature of 120-130°C and a rubber discharge temperature of 90-100°C. The mixed rubber is discharged and cooled to obtain a three-stage mixed rubber, which is a corrosion-resistant and low rolling resistance tire rubber.

[0018] All raw materials of the present invention are commercially available.

[0019] Beneficial effects: (1) The solution-polymerized styrene-butadiene rubber (SSBR) and natural rubber (NR) are compounded. The high segment flexibility (low glass transition temperature) of SSBR complements the high strength of NR, optimizing the dynamic viscoelasticity of the rubber, reducing energy dissipation during tire driving, and reducing rolling resistance. (2) The present invention effectively modifies the traditional silica raw material, wherein the ionic liquid pretreatment reduces filler agglomeration and improves dispersion uniformity through the hydrogen bonding between 1-butyl-3-methylimidazolium chloride ionic liquid and the surface hydroxyl group of silica; the titanate and bis-[3-(triethoxysilyl)propyl] tetrasulfide composite modification enhances the interface bonding between silica and rubber, reduces filler-filler interaction (Payne effect), reduces dynamic hysteresis loss, and thus reduces rolling resistance; (3) Use a bifunctional silane coupling agent system. The acyloxysilane coupling agent and the fluorosilane coupling agent work synergistically to achieve effective and uniform dispersion of modified silica and reduce rolling resistance. Acyloxysilane hydrolyzes to generate silanol (Si-OH), which condenses with the hydroxyl group (Si-OH) on the surface of silica to form a stable Si-O-Si bond, thereby anchoring the inorganic filler on the surface and providing basic dispersibility and interface bonding. At the same time, organic functional groups such as methacryloxy react with the rubber matrix (such as SBR, NR) through free radical reactions or physical entanglement, enhancing the filler-rubber interface bonding and reducing interface slip. The fluoroalkyl chain in fluorosilane has extremely low surface energy, significantly reducing the van der Waals force and hydrogen bond interaction between silica particles and inhibiting filler agglomeration. In addition, in terms of improving corrosion resistance, fluorosilane introduces fluorocarbon chains to give the rubber surface hydrophobic and oleophobic properties, reducing the adsorption and diffusion of corrosive liquids (such as salt water and oil stains). Acyloxysilane coupling agent and fluorosilane coupling agent, the two are compounded in a 1:1 ratio to form a dual protection mechanism of "chemical bonding + physical shielding", which significantly improves the dispersibility of silica and the corrosion resistance of the rubber; (4) Preparation of microcapsule antioxidants. Antioxidant 4020 (long-term anti-ozone) and RD (anti-thermal oxidative aging) are compounded in a ratio of 3:1. The release rate is controlled by polyurethane-epoxy interpenetrating network (IPN) wall material to avoid the migration loss problem of traditional antioxidants and extend the protection period. Nano-silicon carbide fillers improve the density of the wall material and block the damage of external corrosion factors to the core material. At the same time, its own high temperature resistance (>2000°C) ensures the structural stability of the microcapsules during mixing and vulcanization. The prepared microcapsule antioxidant can slowly release the antioxidant in the rubber compound, continuously protect the rubber compound, reduce the performance degradation caused by aging, thereby extending the service life of the tire and enhancing the wear resistance. At the same time, it can effectively resist the erosion of environmental factors such as oxidation and ozone, delay the aging of the rubber compound, and thus improve the corrosion resistance. (5) The present invention adopts a three-stage mixing process, in which zinc oxide and part of white carbon black are pre-dispersed in the first stage, silane coupling agent and environmentally friendly aromatic oil are introduced in the second stage, and microcapsule antioxidant is added in the third stage to avoid high temperature shearing causing microcapsule rupture or premature release of antioxidant; (6) The present invention achieves significant improvements in the corrosion resistance, low rolling resistance and comprehensive mechanical properties of tire rubber through innovation of material components and coordinated process design, solving the long-standing contradiction between corrosion resistance and low rolling resistance in the tire field. It is particularly suitable for high-end scenarios such as new energy vehicle tires and port special vehicle tires. DETAILED DESCRIPTION

[0020] The technical solution of the present invention is further described below in conjunction with specific embodiments, but is not limited thereto.

[0021] Example 1 A corrosion-resistant and low-rolling-resistance tire rubber material comprises the following raw materials in parts by weight: 40 parts of natural rubber, 40 parts of solution-polymerized styrene-butadiene rubber, 55 parts of modified white carbon black, 4 parts of zinc oxide, 3 parts of microcapsule antioxidant, 6 parts of silane coupling agent, 12 parts of environmentally friendly aromatic oil, 1 part of accelerator, and 2 parts of sulfur.

[0022] The silane coupling agent is an acyloxysilane coupling agent and a fluorosilane coupling agent, and the mass ratio of the two is 1:1.

[0023] The acyloxysilane coupling agent is γ-methacryloxypropyltrimethoxysilane, and the fluorosilane coupling agent is tridecafluorooctyltriethoxysilane.

[0024] The preparation method of the modified white carbon black is: (1) Grinding the raw material white carbon black by air flow to control the average particle size to ≤20nm; (2) Add 1-butyl-3-methylimidazolium chloride and titanate to the white carbon black obtained in step (1), mix well, add bis-[3-(triethoxysilyl)propyl]tetrasulfide, react in a high-speed mixer at 120° C. for 20 minutes, and dry after completion.

[0025] In step (2), the mass ratio of white carbon black, 1-butyl-3-methylimidazolium chloride, titanate, and bis-[3-(triethoxysilyl)propyl]tetrasulfide is 10:1:0.5:0.3.

[0026] The accelerator is N-tert-butyl-2-benzothiazole sulfenamide.

[0027] The preparation method of the microcapsule antioxidant is: (1) Preparation of core material: The antioxidant composition was dissolved in ethyl acetate with a mass concentration of 20%, and then 5% of the mass of nano-silicon dioxide was added as a nucleating agent at the antioxidant composition, and shear emulsified at 40° C. for 30 minutes to form a uniformly dispersed suspension, and 0.5% of the mass of silane coupling agent KH-550 was added to the suspension, and reacted for 1 hour under nitrogen protection to form active groups on the surface of the antioxidant, thereby obtaining a core material suspension; (2) Preparation of wall material: polyurethane prepolymer (IPDI type, purchased from Dow Chemical) and amino-terminated polyether (ZD-1200, purchased from Guangzhou Ye Zeng Chemical Co., Ltd.) were mixed in a mass ratio of 1:1 as wall material, and nano-silicon carbide (10% by mass of the total mass of polyurethane prepolymer and amino-terminated polyether) was added as reinforcing filler, dissolved in anhydrous xylene, and prepared into an oil phase wall material solution with a solid content of 10%; (3) The core material suspension and the wall material solution were mixed in a mass ratio of 1:5 to obtain an oil phase mixture, which was slowly added into an aqueous phase containing 0.5% polyvinyl alcohol in a volume ratio of 1:3, and a high-pressure homogenizer was used at 25,000 psi for 3 cycles to prepare a W / O type emulsion, and the temperature was controlled not to exceed 40° C. (4) adding a 0.1% aqueous solution of dibutyltin dilaurate dropwise to the emulsion of step (3) at a volume ratio of 20:1, raising the temperature to 75° C., and stirring the mixture under nitrogen protection for 6 hours to allow the polyurethane-urea wall material to crosslink and solidify at the interface; (5) adding 2% of the mass of the emulsion epoxy resin (EPON 828) as a secondary crosslinking agent; adjusting the pH to 8.5, reacting at 90°C for 2 hours to form an epoxy-polyurethane interpenetrating network; centrifuging to obtain a solid, washing it three times with acetone and deionized water in sequence, and freeze-drying it; (6) Finally, the product was heat treated in a vacuum oven at 120°C for 1 hour and then cooled naturally to obtain a microcapsule antioxidant.

[0028] The antioxidant composition is a mixture of antioxidant 4020 and antioxidant RD in a mass ratio of 3:1.

[0029] A method for preparing a corrosion-resistant and low rolling resistance tire rubber material comprises the following preparation steps: (1) Preparation of modified silica and microcapsule antioxidant; (2) One-stage mixing: natural rubber and solution polymerized styrene-butadiene rubber are put into an internal mixer and mixed for 40 seconds. Zinc oxide and 1 / 3 of modified silica are added and mixed for another 120 seconds. The rubber discharge temperature is 130-140°C. The rubber is discharged and cooled to form a one-stage mixed rubber. The rubber is stored for 8 hours before use. (3) Second stage mixing: Add the first stage mixed rubber, the remaining modified silica, the silane coupling agent and the environmentally friendly aromatic oil into an internal mixer for mixing for 150 seconds, with the discharge temperature of 140-150°C, and then sheet out and cool to make the second stage mixed rubber. It is then placed for 8 hours before use. (4) Three-stage mixing: The second-stage mixed rubber, sulfur, accelerator, and microcapsule antioxidant are put into an internal mixer and mixed for 100 seconds at a mixing temperature of 120-130°C and a rubber discharge temperature of 90-100°C. The mixed rubber is discharged and cooled to obtain a three-stage mixed rubber, which is a corrosion-resistant and low rolling resistance tire rubber.

[0030] Example 2 A corrosion-resistant and low-rolling-resistance tire rubber material comprises the following raw materials in parts by weight: 50 parts of natural rubber, 30 parts of solution-polymerized styrene-butadiene rubber, 60 parts of modified white carbon black, 3 parts of zinc oxide, 4 parts of microcapsule antioxidant, 4 parts of silane coupling agent, 10 parts of environmentally friendly aromatic oil, 2 parts of accelerator, and 3 parts of sulfur.

[0031] The silane coupling agent is an acyloxysilane coupling agent and a fluorosilane coupling agent, and the mass ratio of the two is 1:1.

[0032] The acyloxysilane coupling agent is γ-methacryloxypropyltrimethoxysilane, and the fluorosilane coupling agent is ‌3,3,3-trifluoropropyltriethoxysilane.

[0033] The preparation method of the modified white carbon black is: (1) Grinding the raw material white carbon black by air flow to control the average particle size to ≤20nm; (2) Add 1-butyl-3-methylimidazolium chloride and titanate to the white carbon black obtained in step (1), mix well, add bis-[3-(triethoxysilyl)propyl]tetrasulfide, react in a high-speed mixer at 120° C. for 25 minutes, and dry after completion.

[0034] In step (2), the mass ratio of white carbon black, 1-butyl-3-methylimidazolium chloride, titanate, and bis-[3-(triethoxysilyl)propyl]tetrasulfide is 10:1:0.5:0.3.

[0035] The accelerator is N-tert-butyl-2-benzothiazole sulfenamide.

[0036] The preparation method of the microcapsule antioxidant is: (1) Preparation of core material: The antioxidant composition was dissolved in ethyl acetate with a mass concentration of 20%, and then 5% of the mass of nano-silicon dioxide was added as a nucleating agent at the antioxidant composition, and shear emulsified at 40° C. for 30 minutes to form a uniformly dispersed suspension, and 0.5% of the mass of silane coupling agent KH-550 was added to the suspension, and reacted for 1 hour under nitrogen protection to form active groups on the surface of the antioxidant, thereby obtaining a core material suspension; (2) Preparation of wall material: polyurethane prepolymer (IPDI type, purchased from Dow Chemical) and amino-terminated polyether (ZD-1200, purchased from Guangzhou Ye Zeng Chemical Co., Ltd.) were mixed in a mass ratio of 1:1 as wall material, and nano-silicon carbide (10% by mass of the total mass of polyurethane prepolymer and amino-terminated polyether) was added as reinforcing filler, dissolved in anhydrous xylene, and prepared into an oil phase wall material solution with a solid content of 10%; (3) The core material suspension and the wall material solution were mixed in a mass ratio of 1:5 to obtain an oil phase mixture, which was slowly added into an aqueous phase containing 0.5% polyvinyl alcohol in a volume ratio of 1:3, and a high-pressure homogenizer was used at 25,000 psi for 3 cycles to prepare a W / O type emulsion, and the temperature was controlled not to exceed 40° C. (4) adding a 0.1% aqueous solution of dibutyltin dilaurate dropwise to the emulsion of step (3) at a volume ratio of 20:1, raising the temperature to 75° C., and stirring the mixture under nitrogen protection for 6 hours to allow the polyurethane-urea wall material to crosslink and solidify at the interface; (5) adding 2% of the mass of the emulsion epoxy resin (EPON 828) as a secondary crosslinking agent; adjusting the pH to 8.5, reacting at 90°C for 2 hours to form an epoxy-polyurethane interpenetrating network; centrifuging to obtain a solid, washing it three times with acetone and deionized water in sequence, and freeze-drying it; (6) Finally, the product was heat treated in a vacuum oven at 120°C for 1 hour and then cooled naturally to obtain a microcapsule antioxidant.

[0037] The antioxidant composition is a mixture of antioxidant 4020 and antioxidant RD in a mass ratio of 3:1.

[0038] A method for preparing a corrosion-resistant and low rolling resistance tire rubber material comprises the following preparation steps: (1) Preparation of modified silica and microcapsule antioxidant; (2) One-stage mixing: natural rubber and solution polymerized styrene-butadiene rubber are put into an internal mixer and mixed for 40 seconds. Zinc oxide and 1 / 3 of modified silica are added and mixed for 140 seconds. The rubber discharge temperature is 130-140°C. The sheet is produced and cooled to make a one-stage mixed rubber. The mixed rubber is stored for 8 hours before use. (3) Second stage mixing: Add the first stage mixed rubber, the remaining modified silica, the silane coupling agent, and the environmentally friendly aromatic oil into an internal mixer for mixing for 160 seconds, with the discharge temperature at 140-150°C, and then sheet out and cool to make the second stage mixed rubber, which is then placed for 8 hours before use; (4) Three-stage mixing: Put the second-stage mixed rubber, sulfur, accelerator, and microcapsule antioxidant into an internal mixer and mix for 110 seconds at a mixing temperature of 120-130°C and a rubber discharge temperature of 90-100°C. Discard the sheet and cool it to obtain the three-stage mixed rubber, which is the corrosion-resistant and low rolling resistance tire rubber. Example 3 A corrosion-resistant and low-rolling-resistance tire rubber material comprises the following raw materials in parts by weight: 55 parts of natural rubber, 25 parts of solution-polymerized styrene-butadiene rubber, 58 parts of modified white carbon black, 2 parts of zinc oxide, 3 parts of microcapsule antioxidant, 5 parts of silane coupling agent, 11 parts of environmentally friendly aromatic oil, 2 parts of accelerator, and 3 parts of sulfur.

[0039] The silane coupling agent is an acyloxysilane coupling agent and a fluorosilane coupling agent, and the mass ratio of the two is 1:1.

[0040] The acyloxysilane coupling agent is γ-methacryloxypropyltrimethoxysilane, and the fluorosilane coupling agent is tridecafluorooctyltriethoxysilane.

[0041] The preparation method of the modified white carbon black is: (1) Grinding the raw material white carbon black by air flow to control the average particle size to ≤20nm; (2) Add 1-butyl-3-methylimidazolium chloride and titanate to the white carbon black obtained in step (1), mix well, add bis-[3-(triethoxysilyl)propyl]tetrasulfide, react in a high-speed mixer at 150° C. for 25 minutes, and dry after completion.

[0042] In step (2), the mass ratio of white carbon black, 1-butyl-3-methylimidazolium chloride, titanate, and bis-[3-(triethoxysilyl)propyl]tetrasulfide is 10:1:0.5:0.3.

[0043] The accelerator is N-tert-butyl-2-benzothiazole sulfenamide.

[0044] The preparation method of the microcapsule antioxidant is: (1) Preparation of core material: The antioxidant composition was dissolved in ethyl acetate with a mass concentration of 20%, and then 5% of the mass of nano-silicon dioxide was added as a nucleating agent at the antioxidant composition, and shear emulsified at 40° C. for 30 minutes to form a uniformly dispersed suspension, and 0.5% of the mass of silane coupling agent KH-550 was added to the suspension, and reacted for 1 hour under nitrogen protection to form active groups on the surface of the antioxidant, thereby obtaining a core material suspension; (2) Preparation of wall material: polyurethane prepolymer (IPDI type, purchased from Dow Chemical) and amino-terminated polyether (ZD-1200, purchased from Guangzhou Ye Zeng Chemical Co., Ltd.) were mixed in a mass ratio of 1:1 as wall material, and nano-silicon carbide (10% by mass of the total mass of polyurethane prepolymer and amino-terminated polyether) was added as reinforcing filler, dissolved in anhydrous xylene, and prepared into an oil phase wall material solution with a solid content of 10%; (3) The core material suspension and the wall material solution were mixed in a mass ratio of 1:5 to obtain an oil phase mixture, which was slowly added into an aqueous phase containing 0.5% polyvinyl alcohol in a volume ratio of 1:3, and a high-pressure homogenizer was used at 25,000 psi for 3 cycles to prepare a W / O type emulsion, and the temperature was controlled not to exceed 40° C. (4) adding a 0.1% aqueous solution of dibutyltin dilaurate dropwise to the emulsion of step (3) at a volume ratio of 20:1, raising the temperature to 75° C., and stirring the mixture under nitrogen protection for 6 hours to allow the polyurethane-urea wall material to crosslink and solidify at the interface; (5) adding 2% of the mass of the emulsion epoxy resin (EPON 828) as a secondary crosslinking agent; adjusting the pH to 8.5, reacting at 90°C for 2 hours to form an epoxy-polyurethane interpenetrating network; centrifuging to obtain a solid, washing it three times with acetone and deionized water in sequence, and freeze-drying it; (6) Finally, the product was heat treated in a vacuum oven at 120°C for 1 hour and then cooled naturally to obtain a microcapsule antioxidant.

[0045] The antioxidant composition is a mixture of antioxidant 4020 and antioxidant RD in a mass ratio of 3:1.

[0046] A method for preparing a corrosion-resistant and low rolling resistance tire rubber material comprises the following preparation steps: (1) Preparation of modified silica and microcapsule antioxidant; (2) One-stage mixing: natural rubber and solution polymerized styrene-butadiene rubber are put into an internal mixer and mixed for 50 seconds. Zinc oxide and 1 / 3 of modified silica are added and mixed for 150 seconds. The rubber discharge temperature is 130-140°C. The rubber is discharged and cooled to form a one-stage mixed rubber. The rubber is stored for 8 hours before use. (3) Second stage mixing: Add the first stage mixed rubber, the remaining modified silica, the silane coupling agent, and the environmentally friendly aromatic oil into an internal mixer for mixing for 160 seconds, with the discharge temperature at 140-150°C, and then sheet out and cool to make the second stage mixed rubber, which is then placed for 8 hours before use; (4) Three-stage mixing: The second-stage mixed rubber, sulfur, accelerator, and microcapsule antioxidant are put into an internal mixer and mixed for 120 seconds at a mixing temperature of 120-130°C and a rubber discharge temperature of 90-100°C. The mixed rubber is discharged into sheets and cooled to obtain a three-stage mixed rubber, which is a corrosion-resistant and low rolling resistance tire rubber.

[0047] Example 4 A corrosion-resistant and low-rolling-resistance tire rubber material comprises the following raw materials in parts by weight: 60 parts of natural rubber, 20 parts of solution-polymerized styrene-butadiene rubber, 65 parts of modified white carbon black, 2 parts of zinc oxide, 5 parts of microcapsule antioxidant, 3 parts of silane coupling agent, 8 parts of environmentally friendly aromatic oil, 3 parts of accelerator, and 4 parts of sulfur.

[0048] The silane coupling agent is an acyloxysilane coupling agent and a fluorosilane coupling agent, and the mass ratio of the two is 1:1.

[0049] The acyloxysilane coupling agent is γ-methacryloxypropyltrimethoxysilane, and the fluorosilane coupling agent is tridecafluorooctyltriethoxysilane and ‌3,3,3-trifluoropropyltriethoxysilane, and the mass ratio of the two is 1:2.

[0050] The preparation method of the modified white carbon black is: (1) Grinding the raw material white carbon black by air flow to control the average particle size to ≤20nm; (2) Add 1-butyl-3-methylimidazolium chloride and titanate to the white carbon black obtained in step (1), mix well, add bis-[3-(triethoxysilyl)propyl]tetrasulfide, react in a high-speed mixer at 150° C. for 30 minutes, and dry after completion.

[0051] In step (2), the mass ratio of white carbon black, 1-butyl-3-methylimidazolium chloride, titanate, and bis-[3-(triethoxysilyl)propyl]tetrasulfide is 10:1:0.5:0.3.

[0052] The accelerator is N-tert-butyl-2-benzothiazole sulfenamide.

[0053] The preparation method of the microcapsule antioxidant is: (1) Preparation of core material: The antioxidant composition was dissolved in ethyl acetate with a mass concentration of 20%, and then 5% of the mass of nano-silicon dioxide was added as a nucleating agent at the antioxidant composition, and shear emulsified at 40° C. for 30 minutes to form a uniformly dispersed suspension, and 0.5% of the mass of silane coupling agent KH-550 was added to the suspension, and reacted for 1 hour under nitrogen protection to form active groups on the surface of the antioxidant, thereby obtaining a core material suspension; (2) Preparation of wall material: polyurethane prepolymer (IPDI type, purchased from Dow Chemical) and amino-terminated polyether (ZD-1200, purchased from Guangzhou Ye Zeng Chemical Co., Ltd.) were mixed in a mass ratio of 1:1 as wall material, and nano-silicon carbide (10% by mass of the total mass of polyurethane prepolymer and amino-terminated polyether) was added as reinforcing filler, dissolved in anhydrous xylene, and prepared into an oil phase wall material solution with a solid content of 10%; (3) The core material suspension and the wall material solution were mixed in a mass ratio of 1:5 to obtain an oil phase mixture, which was slowly added into an aqueous phase containing 0.5% polyvinyl alcohol in a volume ratio of 1:3, and a high-pressure homogenizer was used at 25,000 psi for 3 cycles to prepare a W / O type emulsion, and the temperature was controlled not to exceed 40° C. (4) adding a 0.1% aqueous solution of dibutyltin dilaurate dropwise to the emulsion of step (3) at a volume ratio of 20:1, raising the temperature to 75° C., and stirring the mixture under nitrogen protection for 6 hours to allow the polyurethane-urea wall material to crosslink and solidify at the interface; (5) adding 2% of the mass of the emulsion epoxy resin (EPON 828) as a secondary crosslinking agent; adjusting the pH to 8.5, reacting at 90°C for 2 hours to form an epoxy-polyurethane interpenetrating network; centrifuging to obtain a solid, washing it three times with acetone and deionized water in sequence, and freeze-drying it; (6) Finally, the product was heat treated in a vacuum oven at 120°C for 1 hour and then cooled naturally to obtain a microcapsule antioxidant.

[0054] The antioxidant composition is a mixture of antioxidant 4020 and antioxidant RD in a mass ratio of 3:1.

[0055] A method for preparing a corrosion-resistant and low rolling resistance tire rubber material comprises the following preparation steps: (1) Preparation of modified silica and microcapsule antioxidant; (2) One-stage mixing: natural rubber and solution polymerized styrene-butadiene rubber are put into an internal mixer and mixed for 50 seconds. Zinc oxide and 1 / 3 of modified silica are added and mixed for 150 seconds. The rubber discharge temperature is 130-140°C. The rubber is discharged and cooled to form a one-stage mixed rubber. The rubber is stored for 8 hours before use. (3) Second stage mixing: Add the first stage mixed rubber, the remaining modified silica, the silane coupling agent, and the environmentally friendly aromatic oil into an internal mixer for mixing for 160 seconds, with the discharge temperature at 140-150°C, and then sheet out and cool to make the second stage mixed rubber, which is then placed for 8 hours before use; (4) Three-stage mixing: The second-stage mixed rubber, sulfur, accelerator, and microcapsule antioxidant are put into an internal mixer and mixed for 120 seconds at a mixing temperature of 120-130°C and a rubber discharge temperature of 90-100°C. The mixed rubber is discharged into sheets and cooled to obtain a three-stage mixed rubber, which is a corrosion-resistant and low rolling resistance tire rubber.

[0056] Comparative Example 1 In this comparative example, except that only the traditional silane coupling agent is used for modification of white carbon black, the other raw materials and preparation process are the same as those of Example 4.

[0057] Right now: A corrosion-resistant and low-rolling-resistance tire rubber material comprises the following raw materials in parts by weight: 60 parts of natural rubber, 20 parts of solution-polymerized styrene-butadiene rubber, 65 parts of modified white carbon black, 2 parts of zinc oxide, 5 parts of microcapsule antioxidant, 3 parts of silane coupling agent, 8 parts of environmentally friendly aromatic oil, 3 parts of accelerator, and 4 parts of sulfur.

[0058] The preparation method of the modified white carbon black is: (1) Grinding the raw material white carbon black by air flow to control the average particle size to ≤20nm; (2) Add the white carbon black obtained in step (1) to bis-[3-(triethoxysilyl)propyl]tetrasulfide, react in a high-speed mixer at 150° C. for 30 minutes, and dry after completion. In step (2), the mass ratio of white carbon black to bis-[3-(triethoxysilyl)propyl]tetrasulfide is 10:0.3.

[0059] Comparative Example 2 In this comparative example, except that only acyloxysilane coupling agent is used in the silane coupling agent, the other raw materials and preparation process are the same as those in Example 4. That is: A corrosion-resistant and low-rolling-resistance tire rubber material comprises the following raw materials in parts by weight: 60 parts of natural rubber, 20 parts of solution-polymerized styrene-butadiene rubber, 65 parts of modified white carbon black, 2 parts of zinc oxide, 5 parts of microcapsule antioxidant, 3 parts of silane coupling agent, 8 parts of environmentally friendly aromatic oil, 3 parts of accelerator, and 4 parts of sulfur.

[0060] The silane coupling agent is an acyloxysilane coupling agent.

[0061] The acyloxysilane coupling agent is γ-methacryloxypropyltrimethoxysilane.

[0062] Comparative Example 3 In this comparative example, except that only fluorosilane coupling agent is used in the silane coupling agent, the other raw materials and preparation process are the same as those in Example 4. That is: A corrosion-resistant and low-rolling-resistance tire rubber material comprises the following raw materials in parts by weight: 60 parts of natural rubber, 20 parts of solution-polymerized styrene-butadiene rubber, 65 parts of modified white carbon black, 2 parts of zinc oxide, 5 parts of microcapsule antioxidant, 3 parts of silane coupling agent, 8 parts of environmentally friendly aromatic oil, 3 parts of accelerator, and 4 parts of sulfur.

[0063] The silane coupling agent is a fluorosilane coupling agent.

[0064] The fluorosilane coupling agent is tridecafluorooctyl triethoxysilane and 3,3,3-trifluoropropyl triethoxysilane, with a mass ratio of 1:2. Comparative Example 4 In this comparative example, except for using only the traditional antioxidant, the other raw materials and preparation process are the same as those in Example 4. That is: A corrosion-resistant and low-rolling-resistance tire rubber material comprises the following raw materials in parts by weight: 60 parts of natural rubber, 20 parts of solution-polymerized styrene-butadiene rubber, 65 parts of modified white carbon black, 2 parts of zinc oxide, 5 parts of antioxidant, 3 parts of silane coupling agent, 8 parts of environmentally friendly aromatic oil, 3 parts of accelerator, and 4 parts of sulfur.

[0065] The antioxidant is a mixture of antioxidant 4020 and antioxidant RD in a mass ratio of 3:1.

[0066] Comparative Example 5 Prior art tire rubber is prepared by referring to the method of CN200710050386.7.

[0067] Composition testing: The composition of the embodiment and the comparative example was vulcanized at 160°C for 15 minutes using a flat vulcanizer to obtain a 2 mm thick property sheet. Its basic physical properties were tested and the results are listed in Tables 1-3. Five samples were set for each group of experiments and the results were averaged.

[0068] Performance Testing Hardness is carried out in accordance with GB / T 531.1-2008; The tensile properties are carried out in accordance with GB / T528-2009; Tear strength is carried out according to GB / T 529-2008; Carbon black dispersion is carried out in accordance with GB / T 6030-2006; 60℃ acid etching weight loss rate: HG / T 2413.2 "Rubber chemical resistance test method immersion method"; Salt spray corrosion resistance time: GB / T 10125-2021 "Artificial atmosphere corrosion test salt spray test"; Aging resistance: After aging at 100°C for 72 hours, the retention rate of tensile strength and elongation at break were measured; Wear resistance: GB / T1689-2014 Determination of wear resistance of vulcanized rubber (Akron abrasion machine test).

[0069] The rubber formulations of the embodiment and the comparative example were used to produce 205 / 55R16 passenger car tires. The finished tires were vulcanized to obtain finished tires. After vulcanization, the finished tires were subjected to hair cutting, edge removal, appearance, dynamic balancing, and X-ray inspection. After passing the inspection, they were used for rolling resistance test. Rolling resistance test: The rolling resistance test standard is GB / T18861-2002. The force measurement method is used. The rolling resistance coefficient and grade are shown in Table 2 (the EU tire labeling law stipulates that C3 tires, RRC≤4.0 is grade A). Conventional durability tests are carried out according to GB / T4501-2023.

[0070] Table 1 Physical properties test results Table 2 Corrosion resistance test results Table 2 Rolling resistance of finished tires From the data in the table, we can see that the tire rubber compound of the present invention exhibits good mechanical properties, low rolling resistance and corrosion resistance, and excellent acid and salt resistance, and is suitable for use in various complex environments. However, in Comparative Example 1 in which the modification method of white carbon black is changed, Comparative Examples 2-3 in which the composition of the silane coupling agent is changed, and Comparative Example 4 in which the composition of the antioxidant is changed, the modification effect of white carbon black is reduced and the synergistic effect between the raw materials is reduced, thereby resulting in a reduction in the overall comprehensive performance of the rubber compound.

[0071] It should be noted that the above embodiments are only partial embodiments of the preferred methods of implementing the present invention, rather than all embodiments. Obviously, based on the above embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work should fall within the scope of protection of the present invention.

Claims

1. A corrosion-resistant and low rolling resistance tire rubber compound, characterized in that: The invention comprises the following raw materials in parts by weight: 40-60 parts of natural rubber, 20-40 parts of solution-polymerized styrene-butadiene rubber, 55-65 parts of modified white carbon black, 2-4 parts of zinc oxide, 3-5 parts of microcapsule antioxidant, 3-6 parts of silane coupling agent, 8-12 parts of environmentally friendly aromatic oil, 1-3 parts of accelerator and 2-4 parts of sulfur.

2. The corrosion-resistant and low rolling resistance tire rubber material according to claim 1, characterized in that: The silane coupling agent is an acyloxysilane coupling agent and a fluorosilane coupling agent, and the mass ratio of the two is 1:

1.

3. The corrosion-resistant and low rolling resistance tire rubber material according to claim 2, characterized in that: The acyloxysilane coupling agent is γ-methacryloxypropyltrimethoxysilane, and the fluorosilane coupling agent is tridecafluorooctyltriethoxysilane and / or ‌3,3,3-trifluoropropyltriethoxysilane.

4. The corrosion-resistant and low rolling resistance tire rubber material according to claim 1, characterized in that: The preparation method of the modified white carbon black is: (1) Grinding the raw material white carbon black by air flow to control the average particle size to ≤20nm; (2) Add 1-butyl-3-methylimidazolium chloride and titanate to the white carbon black obtained in step (1), mix well, add bis-[3-(triethoxysilyl)propyl]tetrasulfide, react in a high-speed mixer at 120-150° C. for 20-30 minutes, and dry after completion.

5. The corrosion-resistant and low rolling resistance tire rubber material according to claim 4, characterized in that: In step (2), the mass ratio of white carbon black, 1-butyl-3-methylimidazolium chloride, titanate, and bis-[3-(triethoxysilyl)propyl]tetrasulfide is 10:1:0.5:0.

3.

6. The corrosion-resistant and low rolling resistance tire rubber material according to claim 1, characterized in that: The accelerator is N-tert-butyl-2-benzothiazole sulfenamide.

7. The corrosion-resistant and low rolling resistance tire rubber material according to claim 1, characterized in that: The preparation method of the microcapsule antioxidant is: (1) Preparation of core material: The antioxidant composition was dissolved in ethyl acetate with a mass concentration of 20%, and then 5% of the mass of nano-silicon dioxide was added as a nucleating agent at the antioxidant composition, and shear emulsified at 40° C. for 30 minutes to form a uniformly dispersed suspension, and 0.5% of the mass of silane coupling agent KH-550 was added to the suspension, and reacted for 1 hour under nitrogen protection to form active groups on the surface of the antioxidant, thereby obtaining a core material suspension; (2) Preparation of wall material: polyurethane prepolymer and amino-terminated polyether are mixed in a mass ratio of 1:1 as wall material, and nano-silicon carbide is added as reinforcing filler at 10% of the total mass of polyurethane prepolymer and amino-terminated polyether, and dissolved in anhydrous xylene to prepare an oil phase wall material solution with a solid content of 10%; (3) The core material suspension and the wall material solution were mixed in a mass ratio of 1:5 to obtain an oil phase mixture, which was slowly added into an aqueous phase containing 0.5% polyvinyl alcohol in a volume ratio of 1:3, and a high-pressure homogenizer was used at 25,000 psi for 3 cycles to prepare a W / O type emulsion, and the temperature was controlled not to exceed 40° C. (4) adding a 0.1% aqueous solution of dibutyltin dilaurate dropwise to the emulsion of step (3) at a volume ratio of 20:1, raising the temperature to 75° C., and stirring the mixture under nitrogen protection for 6 hours to allow the polyurethane-urea wall material to crosslink and solidify at the interface; (5) adding 2% epoxy resin by weight of the emulsion as a secondary crosslinking agent; adjusting the pH to 8.5, reacting at 90° C. for 2 hours to form an epoxy-polyurethane interpenetrating network; centrifuging to obtain a solid, washing it three times with acetone and deionized water in sequence, and freeze-drying it; (6) Finally, the product was heat treated in a vacuum oven at 120°C for 1 hour and then cooled naturally to obtain a microcapsule antioxidant.

8. The corrosion-resistant and low rolling resistance tire rubber material according to claim 7, characterized in that: The antioxidant composition is a mixture of antioxidant 4020 and antioxidant RD in a mass ratio of 3:

1.

9. A method for preparing the corrosion-resistant and low rolling resistance tire rubber compound according to claims 1-8, characterized in that: The method comprises the following preparation steps: (1) Preparation of modified silica and microcapsule antioxidant; (2) One-stage mixing: natural rubber and solution polymerized styrene-butadiene rubber are put into an internal mixer and mixed for 40-50 seconds. Zinc oxide and 1 / 3 of modified white carbon black are added and mixed for 120-150 seconds. The rubber discharge temperature is 130-140°C. The rubber is discharged and cooled to form a one-stage mixed rubber. The rubber is stored for 8 hours before use. (3) Second stage mixing: Add the first stage mixed rubber, the remaining modified silica, the silane coupling agent and the environmentally friendly aromatic oil into an internal mixer for mixing for 150-160 seconds, with the discharge temperature of 140-150°C, and then sheet out and cool to make the second stage mixed rubber, which is then placed for 8 hours before use; (4) Three-stage mixing: The second-stage mixed rubber, sulfur, accelerator, and microcapsule antioxidant are put into an internal mixer and mixed for 100-120 seconds at a mixing temperature of 120-130°C and a rubber discharge temperature of 90-100°C. The mixed rubber is discharged and cooled to obtain a three-stage mixed rubber, which is a corrosion-resistant and low rolling resistance tire rubber.

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