A low-resistance high-wear-resistance tire rubber composition, and a preparation method and application thereof

Abstract

The application discloses a low-resistance high-wear-resistance tire rubber material composition and a preparation method and application thereof, and belongs to the technical field of rubber materials. The tire rubber material composition comprises the following raw materials in parts by weight: natural rubber NR 50-70 parts, solution polymerized styrene-butadiene rubber SSBR 30-50 parts, modified white carbon black 40-60 parts, zinc oxide 3-5 parts, stearic acid 1-2 parts, antioxidant 6PPD 1-3 parts, and a vulcanization system 2.5-3.5 parts. The prepared tire rubber material not only significantly reduces rolling resistance, improves wear resistance and effectively reduces energy consumption, but also meets the demand of new energy vehicles for high-performance tires. Through three-step modification treatment, the white carbon black is uniformly dispersed in the rubber matrix, the interface is firmly combined, and the prepared tire can reduce the rolling resistance of the tire applied with the tread rubber, and the tread rubber has high wear resistance, tensile strength and elongation at break, and meets the development direction of future new energy vehicles.

Description

Technical Field

[0001] This invention belongs to the field of rubber material technology, specifically relating to a low-resistance, high-wear-resistant tire rubber compound composition, its preparation method, and its application. Background Technology

[0002] With the rapid development of China's highways and heavy industry, the requirements for tire quality are increasing. New energy vehicles place even higher demands on tire performance, including low rolling resistance (improving range), high wet grip (ensuring safety), and wear resistance (extending lifespan). New energy vehicle tires need to meet requirements for high inflation pressure, low noise, and lightweight design. However, existing traditional tires suffer from insufficient sidewall strength, high rolling resistance, and increased vehicle weight accelerates tire wear.

[0003] The matrix material of tire rubber is rubber, but rubber has a large free volume, weak intermolecular forces, a low glass transition temperature, and an amorphous, highly elastic state. Therefore, most rubbers cannot be used without reinforcement with fillers. Silica, as a reinforcing filler, can improve the tire's anti-skid performance and effectively reduce its rolling resistance. However, silica is prone to agglomeration, and the interfacial interaction between silica and the rubber matrix is ​​weak, resulting in a less than ideal reinforcing effect.

[0004] In the prior art, in order to improve the dispersibility of silica and enhance its compatibility with the matrix material, the added silica is often modified with silane coupling agents or surfactants, or silane coupling agents and silica dispersants are added at the same time as silica during the rubber compounding process.

[0005] CN113929978B discloses a solid aircraft tire tread compound and its preparation method. The raw material components include natural rubber, silica, silane coupling agent, silica dispersant, N660 carbon black, etc. In this invention, silica, silane coupling agent, and silica dispersant are directly added during the mixing step. Silane coupling agent and silica dispersant can improve the dispersibility of silica in the rubber matrix. However, the dispersion effect of the directly added silane coupling agent is not ideal, resulting in poor dispersion stability of silica and easy re-agglomeration. It cannot effectively improve the wet skid resistance of the tire using this tread compound, nor can it effectively reduce its rolling resistance.

[0006] CN113502135B discloses a self-healing rubber composition for tires and its preparation method, which uses a combination of materials such as anti-vulcanizing rubber prepolymer, liquid isoprene, modified silica, and tackifying resin. In this invention, the modified silica is hydrated silica with the following groups grafted onto its surface: vinyl-triethoxysilane, dimethyldichlorosilane, and polyethylene glycol-6000. This invention uses silane coupling agents or surfactants to modify the silica. Although this method improves the compatibility of silica with the rubber matrix, it leads to delayed vulcanization of the rubber material, causing a decrease in the tensile strength, elongation at break, and abrasion resistance of the tread rubber.

[0007] Therefore, how to achieve effective dispersion of fillers in rubber matrix is ​​a technical problem that urgently needs to be solved. Summary of the Invention

[0008] This invention addresses the problems existing in the prior art by providing a novel tire rubber formulation and its preparation method. By optimizing the silica modification process and dispersion technology, the uniform distribution of fillers in the rubber matrix is ​​significantly improved, effectively reducing rolling resistance while maintaining excellent wear resistance and mechanical properties, thus solving the problems of uneven dispersion and performance degradation in the prior art.

[0009] To achieve the above-mentioned technical objectives, the technical solution adopted by the present invention is as follows:

[0010] A low-resistance, high-wear-resistant tire compound composition comprises the following raw materials in parts by weight: 50-70 parts of natural rubber NR, 30-50 parts of solution-polymerized styrene-butadiene rubber SSBR, 40-60 parts of modified silica, 3-5 parts of zinc oxide, 1-2 parts of stearic acid, 1-3 parts of antioxidant 6PPD, and 2.5-3.5 parts of vulcanization system.

[0011] Furthermore, the vulcanization system comprises 2.0-2.8 parts of sulfur and 0.5-0.7 parts of accelerator; the accelerator is one or more of tetramethylthiuram disulfide (TMTD) or N-cyclohexyl-2-benzothiazole sulfenamide (CBS).

[0012] Furthermore, the preparation method of the modified silica is as follows:

[0013] (1) Add silica to anhydrous ethanol at a solid-liquid ratio of 1:5, sonicate for 60 minutes, transfer to a vacuum drying oven, dehydrate at 60°C until the moisture content is <0.3%, and obtain pretreated silica.

[0014] (2) Mix the aluminate coupling agent with anhydrous ethanol at a mass ratio of 1:4 and stir at 50°C for 30 minutes to obtain the aluminate coupling agent hydrolysate; mix the silane coupling agent Si75 with a 90% ethanol solution at a mass ratio of 1:9, adjust the pH to 4.5, and hydrolyze at 40°C for 1 hour to obtain the silane coupling agent Si75 hydrolysate.

[0015] (3) One-stage modification: Pretreated silica is added to a stirred reactor, heated to 80°C, and 1-butyl-3-methylimidazolium tetrafluoroborate is added at 10% of the mass of silica. The mixture is stirred at 2000 rpm for 30 minutes.

[0016] (4) Two-stage modification: Maintain the temperature at 80℃, slowly add aluminate coupling agent hydrolysate, the amount of aluminate coupling agent hydrolysate is 10% of the mass of silica, and continue stirring for 1 hour.

[0017] (5) Three-stage modification: Heat to 100℃, add silane coupling agent Si75 hydrolysate, the amount of silane coupling agent Si75 hydrolysate is 10% of the mass of white carbon black, stir at 1500 rpm for 45 minutes to complete the condensation reaction;

[0018] (6) Post-treatment and drying: The three-stage modified slurry is processed by spray dryer and ground to obtain modified silica.

[0019] Furthermore, in step (1), the ultrasonic treatment power is 800 W and the frequency is 40 kHz.

[0020] Furthermore, nitrogen gas is introduced during steps (3-5) for protection to prevent moisture interference.

[0021] Furthermore, in step (6), the spray drying temperature does not exceed 150°C.

[0022] Furthermore, the aluminate coupling agent, model DL-411, was purchased from Dinghai Plastics & Chemicals Co., Ltd.

[0023] A method for preparing a low-resistance, high-wear-resistant tire rubber compound composition includes the following preparation steps:

[0024] A. Preparation of modified silica;

[0025] B. Premixing stage: Natural rubber (NR) and solution-polymerized styrene-butadiene rubber (SSBR) are added to an internal mixer according to the specified ratio. The initial temperature is controlled at 80-90℃, and the mixture is plasticized for 4-6 minutes until it wraps around the rollers. Modified silica, zinc oxide, stearic acid, and antioxidant 6PPD are added sequentially. The cooling water system of the internal mixer is turned on, and the mixing temperature is controlled at 110-120℃. The mixture is mixed for 8-10 minutes to form a homogeneous rubber compound. When the torque curve fluctuation is ≤5%, the material is discharged and allowed to stand for 24 hours to release internal stress.

[0026] C. Final mixing stage: Put the stationary rubber compound back into the internal mixer, lower the temperature to 60-70℃, add sulfur and accelerator, mix for 3-4 minutes to ensure that the vulcanizing agent is evenly dispersed.

[0027] D. Vulcanization molding: Place the mixed rubber compound into a mold, heat it to 150-160℃, maintain the pressure for 1 hour to complete the vulcanization reaction, remove it and cool it to room temperature to obtain the finished tire rubber compound.

[0028] A low-resistance, high-wear-resistant tire compound composition is disclosed, suitable for use in tires for new energy vehicles. This composition significantly improves rolling resistance and wear resistance, extends tire service life, and reduces energy consumption by optimizing filler dispersion and interfacial bonding, meeting the demands of new energy vehicles for high-performance tires.

[0029] Currently, existing technologies suffer from poor dispersion and weak interfacial bonding of silica in the rubber matrix, making it difficult to simultaneously achieve high rolling resistance and good wear resistance. Therefore, finding ways to modify traditional modification methods to achieve efficient dispersion and strong interfacial bonding of silica has become crucial for improving tire performance.

[0030] Therefore, this invention achieves gradient functionalization through a three-step, phased process (ionic liquid physical coating → aluminate coupling agent chemical bonding → silane reinforcing crosslinking), meeting the performance requirements of tire rubber compounds for silica.

[0031] First, this invention disperses silica in anhydrous ethanol to break down hard silica agglomerates and expose surface hydroxyl groups. The aluminate coupling agent is pre-hydrolyzed, partially hydrolyzing to generate active Al-OH groups, enhancing its reactivity with silica. The silane coupling agent Si75 generates silanols (-Si-OH), preparing for the condensation reaction.

[0032] Secondly, the silica was modified in three stages. The first stage involved adding an ionic liquid (1-butyl-3-methylimidazolium tetrafluoroborate) for intercalation modification. The imidazolium cation intercalated between the silica layers, while the anion BF4... - Adsorption on the surface inhibits agglomeration. The second stage introduces an aluminate coupling agent, where Al-OH bonds with the hydroxyl groups on the silica surface, forming a strong interfacial bond. The third stage introduces a silane coupling agent, Si75, where silanol condenses with silica to form a three-dimensional cross-linked network, significantly improving filler dispersibility and interfacial bonding. The synergistic effect of ionic liquid physical coating → aluminate coupling agent chemical bonding → silane reinforcing cross-linking ensures uniform dispersion of silica in the rubber matrix, strong interfacial bonding, effectively reducing rolling resistance, improving wear resistance, extending tire life, meeting the stringent requirements of new energy vehicles for high-performance tires, and contributing to green travel.

[0033] Beneficial effects:

[0034] The tire compound prepared by this invention not only significantly reduces rolling resistance and improves wear resistance, but also effectively reduces energy consumption, meeting the demand for high-performance tires in new energy vehicles. Through a three-step modification process, silica is uniformly dispersed in the rubber matrix with strong interfacial bonding. The resulting tire can reduce the rolling resistance of tires using this tread compound and gives the tread compound high wear resistance, tensile strength, and elongation at break, aligning with the future development direction of new energy vehicles. Attached Figure Description

[0035] Figure 1 AFM photograph of the rubber compound in Example 1 of this invention;

[0036] Figure 2 Comparison images of AFM photographs of Comparative Examples 1-5 and Example 1. Detailed Implementation

[0037] The technical solution of the present invention will be further described below with reference to specific embodiments, but it is not limited thereto.

[0038] Example 1

[0039] A low-resistance, high-wear-resistant tire compound composition comprises the following raw materials in parts by weight: 50 parts of natural rubber NR, 50 parts of solution-polymerized styrene-butadiene rubber SSBR, 40 parts of modified silica, 3 parts of zinc oxide, 1 part of stearic acid, 1 part of antioxidant 6PPD, and 2.5 parts of vulcanization system.

[0040] The vulcanization system comprises 2.0 parts sulfur and 0.5 parts accelerator; the accelerator is tetramethylthiuram disulfide TMTD.

[0041] The modified silica is prepared by:

[0042] (1) Add silica to anhydrous ethanol at a solid-liquid ratio of 1:5, sonicate for 60 minutes, transfer to a vacuum drying oven, dehydrate at 60°C until the moisture content is <0.3%, and obtain pretreated silica.

[0043] (2) Mix the aluminate coupling agent with anhydrous ethanol at a mass ratio of 1:4 and stir at 50°C for 30 minutes to obtain the aluminate coupling agent hydrolysate; mix the silane coupling agent Si75 with a 90% ethanol solution at a mass ratio of 1:9, adjust the pH to 4.5, and hydrolyze at 40°C for 1 hour to obtain the silane coupling agent Si75 hydrolysate.

[0044] (3) One-stage modification: Pretreated silica is added to a stirred reactor, heated to 80°C, and 1-butyl-3-methylimidazolium tetrafluoroborate is added at 10% of the mass of silica. The mixture is stirred at 2000 rpm for 30 minutes.

[0045] (4) Two-stage modification: Maintain the temperature at 80℃, slowly add aluminate coupling agent hydrolysate, the amount of aluminate coupling agent hydrolysate is 10% of the mass of silica, and continue stirring for 1 hour.

[0046] (5) Three-stage modification: Heat to 100℃, add silane coupling agent Si75 hydrolysate, the amount of silane coupling agent Si75 hydrolysate is 10% of the mass of white carbon black, stir at 1500 rpm for 45 minutes to complete the condensation reaction;

[0047] (6) Post-treatment and drying: The three-stage modified slurry is processed by spray dryer and ground to obtain modified silica.

[0048] Step (1) Ultrasonic processing power 800 W, frequency 40 kHz.

[0049] Nitrogen gas is introduced during steps (3-5) for protection to prevent moisture interference.

[0050] Step (6) The spray drying temperature shall not exceed 150°C.

[0051] A method for preparing a low-resistance, high-wear-resistant tire rubber compound composition includes the following preparation steps:

[0052] A. Preparation of modified silica;

[0053] B. Premixing stage: Natural rubber (NR) and solution-polymerized styrene-butadiene rubber (SSBR) are added to an internal mixer according to the specified ratio. The initial temperature is controlled at 80-90℃, and the mixture is plasticized for 4-6 minutes until it wraps around the rollers. Modified silica, zinc oxide, stearic acid, and antioxidant 6PPD are added sequentially. The cooling water system of the internal mixer is turned on, and the mixing temperature is controlled at 110-120℃. The mixture is mixed for 8-10 minutes to form a homogeneous rubber compound. When the torque curve fluctuation is ≤5%, the material is discharged and allowed to stand for 24 hours to release internal stress.

[0054] C. Final mixing stage: Put the stationary rubber compound back into the internal mixer, lower the temperature to 60-70℃, add sulfur and accelerator, mix for 3-4 minutes to ensure that the vulcanizing agent is evenly dispersed.

[0055] D. Vulcanization molding: Place the mixed rubber compound into a mold, heat it to 150-160℃, maintain the pressure for 1 hour to complete the vulcanization reaction, remove it and cool it to room temperature to obtain the finished tire rubber compound.

[0056] Example 2

[0057] A low-resistance, high-wear-resistant tire compound composition comprises the following raw materials in parts by weight: 60 parts of natural rubber NR, 35 parts of solution-polymerized styrene-butadiene rubber SSBR, 50 parts of modified silica, 3 parts of zinc oxide, 1 part of stearic acid, 2 parts of antioxidant 6PPD, and 2.5 parts of vulcanization system.

[0058] The vulcanization system comprises 2.0 parts sulfur and 0.5 parts accelerator; the accelerator is N-cyclohexyl-2-benzothiazole sulfenamide (CBS).

[0059] The modified silica is prepared by:

[0060] (1) Add silica to anhydrous ethanol at a solid-liquid ratio of 1:5, sonicate for 60 minutes, transfer to a vacuum drying oven, dehydrate at 60°C until the moisture content is <0.3%, and obtain pretreated silica.

[0061] (2) Mix the aluminate coupling agent with anhydrous ethanol at a mass ratio of 1:4 and stir at 50°C for 30 minutes to obtain the aluminate coupling agent hydrolysate; mix the silane coupling agent Si75 with a 90% ethanol solution at a mass ratio of 1:9, adjust the pH to 4.5, and hydrolyze at 40°C for 1 hour to obtain the silane coupling agent Si75 hydrolysate.

[0062] (3) One-stage modification: Pretreated silica is added to a stirred reactor, heated to 80°C, and 1-butyl-3-methylimidazolium tetrafluoroborate is added at 10% of the mass of silica. The mixture is stirred at 2000 rpm for 30 minutes.

[0063] (4) Two-stage modification: Maintain the temperature at 80℃, slowly add aluminate coupling agent hydrolysate, the amount of aluminate coupling agent hydrolysate is 10% of the mass of silica, and continue stirring for 1 hour.

[0064] (5) Three-stage modification: Heat to 100℃, add silane coupling agent Si75 hydrolysate, the amount of silane coupling agent Si75 hydrolysate is 10% of the mass of white carbon black, stir at 1500 rpm for 45 minutes to complete the condensation reaction;

[0065] (6) Post-treatment and drying: The three-stage modified slurry is processed by spray dryer and ground to obtain modified silica.

[0066] Step (1) Ultrasonic processing power 800 W, frequency 40 kHz.

[0067] Nitrogen gas is introduced during steps (3-5) for protection to prevent moisture interference.

[0068] Step (6) The spray drying temperature shall not exceed 150°C.

[0069] A method for preparing a low-resistance, high-wear-resistant tire rubber compound composition includes the following preparation steps:

[0070] A. Preparation of modified silica;

[0071] B. Premixing stage: Natural rubber (NR) and solution-polymerized styrene-butadiene rubber (SSBR) are added to an internal mixer according to the specified ratio. The initial temperature is controlled at 80-90℃, and the mixture is plasticized for 4-6 minutes until it wraps around the rollers. Modified silica, zinc oxide, stearic acid, and antioxidant 6PPD are added sequentially. The cooling water system of the internal mixer is turned on, and the mixing temperature is controlled at 110-120℃. The mixture is mixed for 8-10 minutes to form a homogeneous rubber compound. When the torque curve fluctuation is ≤5%, the material is discharged and allowed to stand for 24 hours to release internal stress.

[0072] C. Final mixing stage: Put the stationary rubber compound back into the internal mixer, lower the temperature to 60-70℃, add sulfur and accelerator, mix for 3-4 minutes to ensure that the vulcanizing agent is evenly dispersed.

[0073] D. Vulcanization molding: Place the mixed rubber compound into a mold, heat it to 150-160℃, maintain the pressure for 1 hour to complete the vulcanization reaction, remove it and cool it to room temperature to obtain the finished tire rubber compound.

[0074] Example 3

[0075] A low-resistance, high-wear-resistant tire compound composition comprises the following raw materials in parts by weight: 65 parts of natural rubber NR, 45 parts of solution-polymerized styrene-butadiene rubber SSBR, 45 parts of modified silica, 5 parts of zinc oxide, 2 parts of stearic acid, 1 part of antioxidant 6PPD, and 3 parts of vulcanization system.

[0076] The vulcanization system comprises 2.5 parts sulfur and 0.5 parts accelerator; the accelerator is obtained by mixing tetramethylthiuram disulfide (TMTD) or N-cyclohexyl-2-benzothiazole sulfenamide (CBS) in a mass ratio of 1:1.

[0077] The modified silica is prepared by:

[0078] (1) Add silica to anhydrous ethanol at a solid-liquid ratio of 1:5, sonicate for 60 minutes, transfer to a vacuum drying oven, dehydrate at 60°C until the moisture content is <0.3%, and obtain pretreated silica.

[0079] (2) Mix the aluminate coupling agent with anhydrous ethanol at a mass ratio of 1:4 and stir at 50°C for 30 minutes to obtain the aluminate coupling agent hydrolysate; mix the silane coupling agent Si75 with a 90% ethanol solution at a mass ratio of 1:9, adjust the pH to 4.5, and hydrolyze at 40°C for 1 hour to obtain the silane coupling agent Si75 hydrolysate.

[0080] (3) One-stage modification: Pretreated silica is added to a stirred reactor, heated to 80°C, and 1-butyl-3-methylimidazolium tetrafluoroborate is added at 10% of the mass of silica. The mixture is stirred at 2000 rpm for 30 minutes.

[0081] (4) Two-stage modification: Maintain the temperature at 80℃, slowly add aluminate coupling agent hydrolysate, the amount of aluminate coupling agent hydrolysate is 10% of the mass of silica, and continue stirring for 1 hour.

[0082] (5) Three-stage modification: Heat to 100℃, add silane coupling agent Si75 hydrolysate, the amount of silane coupling agent Si75 hydrolysate is 10% of the mass of white carbon black, stir at 1500 rpm for 45 minutes to complete the condensation reaction;

[0083] (6) Post-treatment and drying: The three-stage modified slurry is processed by spray dryer and ground to obtain modified silica.

[0084] Step (1) Ultrasonic processing power 800 W, frequency 40 kHz.

[0085] Nitrogen gas is introduced during steps (3-5) for protection to prevent moisture interference.

[0086] Step (6) The spray drying temperature shall not exceed 150°C.

[0087] A method for preparing a low-resistance, high-wear-resistant tire rubber compound composition includes the following preparation steps:

[0088] A. Preparation of modified silica;

[0089] B. Premixing stage: Natural rubber (NR) and solution-polymerized styrene-butadiene rubber (SSBR) are added to an internal mixer according to the specified ratio. The initial temperature is controlled at 80-90℃, and the mixture is plasticized for 4-6 minutes until it wraps around the rollers. Modified silica, zinc oxide, stearic acid, and antioxidant 6PPD are added sequentially. The cooling water system of the internal mixer is turned on, and the mixing temperature is controlled at 110-120℃. The mixture is mixed for 8-10 minutes to form a homogeneous rubber compound. When the torque curve fluctuation is ≤5%, the material is discharged and allowed to stand for 24 hours to release internal stress.

[0090] C. Final mixing stage: Put the stationary rubber compound back into the internal mixer, lower the temperature to 60-70℃, add sulfur and accelerator, mix for 3-4 minutes to ensure that the vulcanizing agent is evenly dispersed.

[0091] D. Vulcanization molding: Place the mixed rubber compound into a mold, heat it to 150-160℃, maintain the pressure for 1 hour to complete the vulcanization reaction, remove it and cool it to room temperature to obtain the finished tire rubber compound.

[0092] Example 4

[0093] A low-resistance, high-wear-resistant tire compound composition comprises the following raw materials in parts by weight: 55 parts of natural rubber NR, 40 parts of solution-polymerized styrene-butadiene rubber SSBR, 55 parts of modified silica, 4 parts of zinc oxide, 1 part of stearic acid, 2 parts of antioxidant 6PPD, and 3 parts of vulcanization system.

[0094] The vulcanization system comprises 2.4 parts sulfur and 0.6 parts accelerator; the accelerator is obtained by mixing tetramethylthiuram disulfide (TMTD) or N-cyclohexyl-2-benzothiazole sulfenamide (CBS) at a mass ratio of 1:2.

[0095] The modified silica is prepared by:

[0096] (1) Add silica to anhydrous ethanol at a solid-liquid ratio of 1:5, sonicate for 60 minutes, transfer to a vacuum drying oven, dehydrate at 60°C until the moisture content is <0.3%, and obtain pretreated silica.

[0097] (2) Mix the aluminate coupling agent with anhydrous ethanol at a mass ratio of 1:4 and stir at 50°C for 30 minutes to obtain the aluminate coupling agent hydrolysate; mix the silane coupling agent Si75 with a 90% ethanol solution at a mass ratio of 1:9, adjust the pH to 4.5, and hydrolyze at 40°C for 1 hour to obtain the silane coupling agent Si75 hydrolysate.

[0098] (3) One-stage modification: Pretreated silica is added to a stirred reactor, heated to 80°C, and 1-butyl-3-methylimidazolium tetrafluoroborate is added at 10% of the mass of silica. The mixture is stirred at 2000 rpm for 30 minutes.

[0099] (4) Two-stage modification: Maintain the temperature at 80℃, slowly add aluminate coupling agent hydrolysate, the amount of aluminate coupling agent hydrolysate is 10% of the mass of silica, and continue stirring for 1 hour.

[0100] (5) Three-stage modification: Heat to 100℃, add silane coupling agent Si75 hydrolysate, the amount of silane coupling agent Si75 hydrolysate is 10% of the mass of white carbon black, stir at 1500 rpm for 45 minutes to complete the condensation reaction;

[0101] (6) Post-treatment and drying: The three-stage modified slurry is processed by spray dryer and ground to obtain modified silica.

[0102] Step (1) Ultrasonic processing power 800 W, frequency 40 kHz.

[0103] Nitrogen gas is introduced during steps (3-5) for protection to prevent moisture interference.

[0104] Step (6) The spray drying temperature shall not exceed 150°C.

[0105] A method for preparing a low-resistance, high-wear-resistant tire rubber compound composition includes the following preparation steps:

[0106] A. Preparation of modified silica;

[0107] B. Premixing stage: Natural rubber (NR) and solution-polymerized styrene-butadiene rubber (SSBR) are added to an internal mixer according to the specified ratio. The initial temperature is controlled at 80-90℃, and the mixture is plasticized for 4-6 minutes until it wraps around the rollers. Modified silica, zinc oxide, stearic acid, and antioxidant 6PPD are added sequentially. The cooling water system of the internal mixer is turned on, and the mixing temperature is controlled at 110-120℃. The mixture is mixed for 8-10 minutes to form a homogeneous rubber compound. When the torque curve fluctuation is ≤5%, the material is discharged and allowed to stand for 24 hours to release internal stress.

[0108] C. Final mixing stage: Put the stationary rubber compound back into the internal mixer, lower the temperature to 60-70℃, add sulfur and accelerator, mix for 3-4 minutes to ensure that the vulcanizing agent is evenly dispersed.

[0109] D. Vulcanization molding: Place the mixed rubber compound into a mold, heat it to 150-160℃, maintain the pressure for 1 hour to complete the vulcanization reaction, remove it and cool it to room temperature to obtain the finished tire rubber compound.

[0110] Example 5

[0111] A low-resistance, high-wear-resistant tire compound composition comprises the following raw materials in parts by weight: 70 parts of natural rubber NR, 30 parts of solution-polymerized styrene-butadiene rubber SSBR, 60 parts of modified silica, 5 parts of zinc oxide, 2 parts of stearic acid, 3 parts of antioxidant 6PPD, and 3.5 parts of vulcanization system.

[0112] The vulcanization system comprises 2.8 parts sulfur and 0.7 parts accelerator; the accelerator is tetramethylthiuram disulfide TMTD.

[0113] The modified silica is prepared by:

[0114] (1) Add silica to anhydrous ethanol at a solid-liquid ratio of 1:5, sonicate for 60 minutes, transfer to a vacuum drying oven, dehydrate at 60°C until the moisture content is <0.3%, and obtain pretreated silica.

[0115] (2) Mix the aluminate coupling agent with anhydrous ethanol at a mass ratio of 1:4 and stir at 50°C for 30 minutes to obtain the aluminate coupling agent hydrolysate; mix the silane coupling agent Si75 with a 90% ethanol solution at a mass ratio of 1:9, adjust the pH to 4.5, and hydrolyze at 40°C for 1 hour to obtain the silane coupling agent Si75 hydrolysate.

[0116] (3) One-stage modification: Pretreated silica is added to a stirred reactor, heated to 80°C, and 1-butyl-3-methylimidazolium tetrafluoroborate is added at 10% of the mass of silica. The mixture is stirred at 2000 rpm for 30 minutes.

[0117] (4) Two-stage modification: Maintain the temperature at 80℃, slowly add aluminate coupling agent hydrolysate, the amount of aluminate coupling agent hydrolysate is 10% of the mass of silica, and continue stirring for 1 hour.

[0118] (5) Three-stage modification: Heat to 100℃, add silane coupling agent Si75 hydrolysate, the amount of silane coupling agent Si75 hydrolysate is 10% of the mass of white carbon black, stir at 1500 rpm for 45 minutes to complete the condensation reaction;

[0119] (6) Post-treatment and drying: The three-stage modified slurry is processed by spray dryer and ground to obtain modified silica.

[0120] Step (1) Ultrasonic processing power 800 W, frequency 40 kHz.

[0121] Nitrogen gas is introduced during steps (3-5) for protection to prevent moisture interference.

[0122] Step (6) The spray drying temperature shall not exceed 150°C.

[0123] A method for preparing a low-resistance, high-wear-resistant tire rubber compound composition includes the following preparation steps:

[0124] A. Preparation of modified silica;

[0125] B. Premixing stage: Natural rubber (NR) and solution-polymerized styrene-butadiene rubber (SSBR) are added to an internal mixer according to the specified ratio. The initial temperature is controlled at 80-90℃, and the mixture is plasticized for 4-6 minutes until it wraps around the rollers. Modified silica, zinc oxide, stearic acid, and antioxidant 6PPD are added sequentially. The cooling water system of the internal mixer is turned on, and the mixing temperature is controlled at 110-120℃. The mixture is mixed for 8-10 minutes to form a homogeneous rubber compound. When the torque curve fluctuation is ≤5%, the material is discharged and allowed to stand for 24 hours to release internal stress.

[0126] C. Final mixing stage: Put the stationary rubber compound back into the internal mixer, lower the temperature to 60-70℃, add sulfur and accelerator, mix for 3-4 minutes to ensure that the vulcanizing agent is evenly dispersed.

[0127] D. Vulcanization molding: Place the mixed rubber compound into a mold, heat it to 150-160℃, maintain the pressure for 1 hour to complete the vulcanization reaction, remove it and cool it to room temperature to obtain the finished tire rubber compound.

[0128] Comparative Example 1

[0129] In this comparative example, except that the silica was not modified with an ionic liquid (1-butyl-3-methylimidazolium tetrafluoroborate), the raw materials and preparation process were the same as in Example 1. That is:

[0130] A low-resistance, high-wear-resistant tire compound composition comprises the following raw materials in parts by weight: 50 parts of natural rubber NR, 50 parts of solution-polymerized styrene-butadiene rubber SSBR, 40 parts of modified silica, 3 parts of zinc oxide, 1 part of stearic acid, 1 part of antioxidant 6PPD, and 2.5 parts of vulcanization system.

[0131] The modified silica is prepared by:

[0132] (1) Add silica to anhydrous ethanol at a solid-liquid ratio of 1:5, sonicate for 60 minutes, transfer to a vacuum drying oven, dehydrate at 60°C until the moisture content is <0.3%, and obtain pretreated silica.

[0133] (2) Mix the aluminate coupling agent with anhydrous ethanol at a mass ratio of 1:4 and stir at 50°C for 30 minutes to obtain the aluminate coupling agent hydrolysate; mix the silane coupling agent Si75 with a 90% ethanol solution at a mass ratio of 1:9, adjust the pH to 4.5, and hydrolyze at 40°C for 1 hour to obtain the silane coupling agent Si75 hydrolysate.

[0134] (3) First stage treatment: The pretreated silica is put into the stirred reactor, heated to 80°C, and stirred at 2000 rpm for 30 minutes.

[0135] (4) Two-stage modification: Maintain the temperature at 80℃, slowly add aluminate coupling agent hydrolysate, the amount of aluminate coupling agent hydrolysate is 10% of the mass of silica, and continue stirring for 1 hour.

[0136] (5) Three-stage modification: Heat to 100℃, add silane coupling agent Si75 hydrolysate, the amount of silane coupling agent Si75 hydrolysate is 10% of the mass of white carbon black, stir at 1500 rpm for 45 minutes to complete the condensation reaction;

[0137] (6) Post-treatment and drying: The three-stage modified slurry is processed by spray dryer and ground to obtain modified silica.

[0138] Comparative Example 2

[0139] In this comparative example, except that the silica was not modified with an aluminate coupling agent, the raw materials and preparation process were the same as in Example 1. That is:

[0140] A low-resistance, high-wear-resistant tire compound composition comprises the following raw materials in parts by weight: 50 parts of natural rubber NR, 50 parts of solution-polymerized styrene-butadiene rubber SSBR, 40 parts of modified silica, 3 parts of zinc oxide, 1 part of stearic acid, 1 part of antioxidant 6PPD, and 2.5 parts of vulcanization system.

[0141] The modified silica is prepared by:

[0142] (1) Add silica to anhydrous ethanol at a solid-liquid ratio of 1:5, sonicate for 60 minutes, transfer to a vacuum drying oven, dehydrate at 60°C until the moisture content is <0.3%, and obtain pretreated silica.

[0143] (2) Mix silane coupling agent Si75 with 90% ethanol solution at a mass ratio of 1:9, adjust the pH to 4.5, and hydrolyze at 40°C for 1 hour to obtain silane coupling agent Si75 hydrolysate.

[0144] (3) One-stage modification: Pretreated silica is added to a stirred reactor, heated to 80°C, and 1-butyl-3-methylimidazolium tetrafluoroborate is added at 10% of the mass of silica. The mixture is stirred at 2000 rpm for 30 minutes.

[0145] (4) Two-stage modification: Heat to 100℃, add silane coupling agent Si75 hydrolysate, the amount of silane coupling agent Si75 hydrolysate is 10% of the mass of silica, stir at 1500 rpm for 45 minutes to complete the condensation reaction;

[0146] (5) Post-treatment and drying: The slurry is treated by spray drying and ground to obtain modified silica.

[0147] Comparative Example 3

[0148] In this comparative example, except that the silica was not modified with the silane coupling agent Si75, the raw materials and preparation process were the same as in Example 1. That is:

[0149] A low-resistance, high-wear-resistant tire compound composition comprises the following raw materials in parts by weight: 50 parts of natural rubber NR, 50 parts of solution-polymerized styrene-butadiene rubber SSBR, 40 parts of modified silica, 3 parts of zinc oxide, 1 part of stearic acid, 1 part of antioxidant 6PPD, and 2.5 parts of vulcanization system.

[0150] The modified silica is prepared by:

[0151] (1) Add silica to anhydrous ethanol at a solid-liquid ratio of 1:5, sonicate for 60 minutes, transfer to a vacuum drying oven, dehydrate at 60°C until the moisture content is <0.3%, and obtain pretreated silica.

[0152] (2) Mix the aluminate coupling agent with anhydrous ethanol at a mass ratio of 1:4 and stir at 50°C for 30 minutes to obtain the aluminate coupling agent hydrolysate.

[0153] (3) One-stage modification: Pretreated silica is added to a stirred reactor, heated to 80°C, and 1-butyl-3-methylimidazolium tetrafluoroborate is added at 10% of the mass of silica. The mixture is stirred at 2000 rpm for 30 minutes.

[0154] (4) Two-stage modification: Maintain the temperature at 80℃, slowly add the hydrolysate of aluminate coupling agent, the amount of hydrolysate of aluminate coupling agent is 10% of the mass of silica, and continue stirring for 1 hour.

[0155] (5) Post-treatment and drying: The slurry is treated by spray drying and ground to obtain modified silica.

[0156] Comparative Example 4

[0157] In this comparative example, the modification steps of the modified silica are changed, i.e., no step-by-step modification is used, but a blending modification method is employed, namely:

[0158] The modified silica is prepared by:

[0159] (1) Add silica to anhydrous ethanol at a solid-liquid ratio of 1:5, sonicate for 60 minutes, transfer to a vacuum drying oven, dehydrate at 60°C until the moisture content is <0.3%, and obtain pretreated silica.

[0160] (2) Mix the aluminate coupling agent with anhydrous ethanol at a mass ratio of 1:4 and stir at 50°C for 30 minutes to obtain the aluminate coupling agent hydrolysate; mix the silane coupling agent Si75 with a 90% ethanol solution at a mass ratio of 1:9, adjust the pH to 4.5, and hydrolyze at 40°C for 1 hour to obtain the silane coupling agent Si75 hydrolysate.

[0161] (3) Modification treatment: The pretreated silica was put into a stirred reactor and heated to 80-100℃. 1-Butyl-3-methylimidazolium tetrafluoroborate, aluminate coupling agent hydrolysate and silane coupling agent Si75 hydrolysate were added at 10% of the silica mass. The mixture was stirred at 2000 rpm for 135 minutes.

[0162] (4) Post-treatment and drying: The slurry is treated by spray drying and ground to obtain modified silica.

[0163] Comparative Example 5

[0164] Tire adhesive is prepared according to existing technology CN113929978B.

[0165] Performance testing

[0166] The performance of the rubber compounds obtained in Examples 1-5 and Comparative Examples 1-5 of the present invention was tested. Five samples were set up for each group of experiments, and the average value of the results was taken.

[0167] Tear strength: Tested in accordance with GB / T 529-2008.

[0168] Abrasion resistance: GB / T1689-2014 Determination of abrasion resistance of vulcanized rubber (Akron abrasion test).

[0169] The dispersion of silica in the compound was tested using a carbon black dispersant according to GB / T18251-2000 (where the X value represents the degree of carbon black dispersion and the Y value represents the dispersion index of large carbon black aggregates in the compound; the larger the X and Y values, the better the carbon black dispersion).

[0170] AFM analysis: The dispersion of silica in tire rubber was analyzed by measuring the flat surface of the tire rubber sample under tapping mode (repulsion) and using phase diagrams.

[0171] Shore A hardness is tested according to GB / T531-2008.

[0172] The dynamic mechanical properties of the tread compound were tested using dynamic thermal mechanical analysis (DMTA) with a temperature scan range of -10℃ to 70℃, a heating rate of 5℃ / min, a frequency of 10Hz, and a strain of 0.20%.

[0173] Table 1 Performance Test Results

[0174]

[0175] From the data in the table, we can see that the tire tread compounds in the examples exhibit better overall performance compared to the comparative examples and existing technologies. Examples 1 to 5 show moderate Shore A hardness, while exhibiting excellent tensile strength and elongation at break, demonstrating good mechanical properties. The carbon black dispersibility in the examples is higher than in the comparative examples; the increased X and Y values ​​prove that the carbon black is more uniformly dispersed in the compound. Akron abrasion data also shows that the abrasion resistance of the examples is significantly better than that of the comparative examples, which is of great significance for extending tire life. Comparative examples 1-4, which changed the carbon black modification method, weakened the three-stage modification effect of ionic liquid physical coating → aluminate coupling agent chemical bonding → silane reinforcing crosslinking, thus reducing the dispersion effect of silica and resulting in a decrease in the overall performance of the tire compound. From the AFM phase diagram ( Figure 1 This also shows that different colors indicate differences in modulus. The dispersibility of silica can be determined based on the differences in modulus of raw materials such as silica and rubber. Figure 1 It can be seen that the carbon black dispersion in the embodiments of the present invention is more uniform, exhibiting excellent dispersion performance, and showing a significant improvement in dispersion effect compared to the comparative example. In summary, the optimized tire tread compound formulation in the embodiments brings about significant performance improvements, which are not only reflected in mechanical properties but also include a reduction in rolling resistance. This is highly beneficial to the needs of new energy vehicle tires and has broad market application prospects.

[0176] It should be noted that the above embodiments are merely some preferred embodiments of the present invention, and not all embodiments. Obviously, based on the above embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort should fall within the scope of protection of the present invention.

Claims

1. A low rolling resistance, high abrasion tire compound composition characterized in that, The raw materials include the following parts by weight: 50-70 parts natural rubber NR, 30-50 parts solution-polymerized styrene-butadiene rubber SSBR, 40-60 parts modified silica, 3-5 parts zinc oxide, 1-2 parts stearic acid, 1-3 parts antioxidant 6PPD, and 2.5-3.5 parts vulcanization system; the preparation method of the modified silica is as follows: (1) Add silica to anhydrous ethanol at a solid-liquid ratio of 1:5, sonicate for 60 minutes, transfer to a vacuum drying oven, dehydrate at 60°C until the moisture content is <0.3%, and obtain pretreated silica. (2) Mix the aluminate coupling agent with anhydrous ethanol at a mass ratio of 1:4 and stir at 50°C for 30 minutes to obtain the aluminate coupling agent hydrolysate; mix the silane coupling agent Si75 with a 90% ethanol solution at a mass ratio of 1:9, adjust the pH to 4.5, and hydrolyze at 40°C for 1 hour to obtain the silane coupling agent Si75 hydrolysate. (3) One-stage modification: Pretreated silica is added to a stirred reactor, heated to 80°C, and 1-butyl-3-methylimidazolium tetrafluoroborate is added at 10% of the mass of silica. The mixture is stirred at 2000 rpm for 30 minutes. (4) Two-stage modification: Maintain the temperature at 80℃, slowly add aluminate coupling agent hydrolysate, the amount of aluminate coupling agent hydrolysate is 10% of the mass of silica, and continue stirring for 1 hour. (5) Three-stage modification: Heat to 100℃, add silane coupling agent Si75 hydrolysate, the amount of silane coupling agent Si75 hydrolysate is 10% of the mass of silica, stir at 1500rpm for 45 minutes to complete the condensation reaction. (6) Post-treatment and drying: The three-stage modified slurry is processed by spray dryer and ground to obtain modified silica.

2. The low rolling resistance, high abrasion resistance tire compound composition of claim 1, wherein, The vulcanization system comprises 2.0-2.8 parts sulfur and 0.5-0.7 parts accelerator; the accelerator is one or more of tetramethylthiuram disulfide (TMTD) or N-cyclohexyl-2-benzothiazole sulfenamide (CBS).

3. The low rolling resistance, high abrasion resistance tire compound composition of claim 1, wherein, Step (1) Ultrasonic processing power 800W, frequency 40 kHz.

4. The low rolling resistance, high abrasion resistance tire mix composition of claim 1, wherein, Step (6) The spray drying temperature shall not exceed 150℃.

5. A process for the preparation of the low rolling resistance high wear resistant tire compound composition as claimed in any one of claims 1 to 4, characterized in that, The preparation steps include the following: A. Preparation of modified silica; B. Premixing stage: Natural rubber (NR) and solution-polymerized styrene-butadiene rubber (SSBR) are added to an internal mixer according to the specified ratio. The initial temperature is controlled at 80-90℃, and the mixture is plasticized for 4-6 minutes until it wraps around the rollers. Modified silica, zinc oxide, stearic acid, and antioxidant 6PPD are added sequentially. The cooling water system of the internal mixer is turned on, and the mixing temperature is controlled at 110-120℃. The mixture is mixed for 8-10 minutes to form a homogeneous rubber compound. When the torque curve fluctuation is ≤5%, the material is discharged and allowed to stand for 24 hours to release internal stress. C. Final mixing stage: Put the settled rubber compound back into the internal mixer, lower the temperature to 60-70℃, add sulfur and accelerator, mix for 3-4 minutes to ensure that the vulcanizing agent is evenly dispersed. D. Vulcanization molding: Place the mixed rubber compound into a mold, heat it to 150-160℃, maintain the pressure for 1 hour to complete the vulcanization reaction, remove it and cool it to room temperature to obtain the finished tire rubber compound.

6. A low rolling resistance high wear resistance tire mix composition as claimed in any one of claims 1 to 4, characterized in that, This composition is suitable for tires used in new energy vehicles.

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