Rubber composite material for high-performance tire and preparation method of rubber composite material

Abstract

The invention discloses a rubber composite material for a high-performance tire and a preparation method of the rubber composite material. The rubber composite material is prepared from the following raw materials in parts by weight: 30-50 parts of natural rubber, 10-15 parts of butadiene rubber, 25-40 parts of butadiene styrene rubber, 10-20 parts of carbon black, 10-30 parts of composite filler, 2-8 parts of aromatic hydrocarbon oil, 2-5 parts of an anti-aging agent, 1-5 parts of a vulcanizing agent, 1-5 parts of a vulcanization accelerator and 1-3 parts of stearic acid. The prepared rubber composite material has excellent mechanical properties, enhanced tear resistance and overall strength, the outstanding wear resistance enables a tire to adapt to various road conditions, the heat dissipation performance is optimized, thermo-oxidative aging is reduced, the service life is prolonged, the hardness and rigidity are improved, the wear resistance is enhanced, the rolling resistance is reduced, and the fuel efficiency is improved; the improved dynamic balance performance and anti-flowability improve the driving safety, are suitable for wear-resistant tires used for a long time and vehicles with special road conditions, and provide high-quality choices for severe environments.

Description

Technical Field

[0001] The invention relates to the field of rubber technology, and in particular to a rubber composite material for high-performance tires and a preparation method thereof. Background Art

[0002] With the rapid development of the automobile industry, people have higher and higher requirements on the performance of tires. High-performance tires are not only required to have excellent anti-skid, wear resistance and tear resistance, but also need to have low rolling resistance to reduce fuel consumption. Therefore, the development of new high-performance tire rubber composite materials has become a hot topic in current research.

[0003] Traditional tire rubber formulas are mainly composed of the following parts: base rubber, reinforcing fillers, softeners, vulcanization systems, antioxidants and other additives. Base rubbers usually include natural rubber (NR), styrene-butadiene rubber (SBR) and butadiene rubber (BR). NR has excellent mechanical and dynamic properties, SBR provides good wear resistance and wet skid resistance, and BR improves the wear resistance and low temperature performance of tires. Reinforcing fillers mainly include carbon black and white carbon black (precipitated silica). Carbon black can significantly improve the strength, modulus and wear resistance of rubber, while white carbon black improves the wet skid resistance and rolling resistance of tires. Softeners such as aromatic oils and cycloalkane oils are used to improve the processing properties, low temperature flexibility and aging resistance of rubber. The vulcanization system includes sulfur (the main cross-linking agent), accelerators (such as CBS, TBBS) and activators (such as zinc oxide and stearic acid). Sulfur realizes cross-linking between rubber molecules, accelerators accelerate the vulcanization reaction, and activators activate accelerators and participate in the cross-linking reaction. Antioxidants include phenols (such as BHT) and amines (such as 6PPD), which are used to prevent rubber oxidation and ozone aging and extend the service life of tires. Other additives such as coupling agents improve the interface bonding between fillers and rubber, resins improve the adhesion of rubber, and wax prevents the rubber surface from cracking. These additives work together to optimize the comprehensive performance of rubber.

[0004] Chinese patent document CN106633449A discloses a composite butyl rubber tire material, wherein the raw materials include, by weight: 15-25 parts of natural rubber, 30-50 parts of chlorosulfonated polyethylene, 10-20 parts of butyl rubber, 4-12 parts of polyurethane rubber, 15-25 parts of 320 type chloroprene rubber, 0.2-0.8 parts of antioxidant MBZ, 0.1-0.8 parts of antioxidant SP, 0.15-0.65 parts of antioxidant 4010NA, 1-2 parts of white oil, 0.5-1.5 parts of pine tar, 30-50 parts of modified vermiculite powder, 4-10 parts of barium sulfate, 2-10 parts of calcium carbonate, 3-12 parts of limestone, 4-12 parts of silicon dioxide, 2-8 parts of soot, 2-6 parts of magnesium hydroxide, 1-3 parts of sulfur, 1-2 parts of vulcanizing agent HTDM, and vulcanization accelerator CZ. 0.25-0.65 parts, vulcanization accelerator TMTD 0.15-0.45 parts.

[0005] However, this traditional formula is difficult to meet multiple performance requirements of tires at the same time. It has limitations such as difficulty in balancing rolling resistance and grip, some additives facing environmental pressure, limited performance under extreme conditions, and large impact from fluctuations in raw material costs.

[0006] To overcome these problems, researchers have tried to improve the performance of tire rubber in recent years by developing new functional rubbers, using new nanofillers, optimizing filler dispersion technology, developing new coupling agents and plasticizers, and using new vulcanization systems. Although some progress has been made, there are still challenges such as performance balance, cost control, environmental protection requirements, durability issues, and process adaptability.

[0007] Therefore, developing a tire rubber composite material that can simultaneously meet the requirements of high performance, low cost, environmental protection and easy processing is of great significance for promoting the technological progress and sustainable development of the tire industry. The present invention aims to address the above problems and propose a new high-performance tire rubber composite material and a preparation method thereof, in order to achieve breakthroughs in tire performance, cost and environmental protection. Summary of the invention

[0008] In order to address the deficiencies in the prior art, the object of the present invention is to provide a high-performance rubber composite material for tires and a preparation method thereof. The prepared rubber composite material has excellent mechanical properties, including enhanced tear resistance and overall strength. Its outstanding wear resistance enables the tire to maintain a good condition under various road conditions. The optimized heat dissipation performance effectively reduces the thermal oxygen aging of the rubber and extends the life of the tire. The improvement in material hardness and rigidity not only enhances wear resistance, but also reduces the rolling resistance of the tire and improves fuel efficiency. Improved dynamic balance performance and anti-fluidity enhance driving safety. This multifunctional material is particularly suitable for wear-resistant tires used for a long time and vehicles under special road conditions, providing a high-quality choice for harsh use environments.

[0009] In order to achieve the above object, the present invention adopts the following technical solution:

[0010] A high-performance tire rubber composite material is prepared from the following components by weight: 30-50 parts of natural rubber, 10-15 parts of butadiene rubber, 25-40 parts of styrene-butadiene rubber, 10-20 parts of carbon black, 10-30 parts of composite filler, 2-8 parts of aromatic hydrocarbon oil, 2-5 parts of antioxidant, 1-5 parts of vulcanizing agent, 1-5 parts of vulcanization accelerator and 1-3 parts of stearic acid.

[0011] Preferably, it is made of the following components, by weight: 40 parts of natural rubber, 12 parts of butadiene rubber, 30 parts of styrene-butadiene rubber, 15 parts of carbon black, 20 parts of composite filler, 5 parts of aromatic hydrocarbon oil, 4 parts of antioxidant, 3 parts of vulcanizing agent, 3 parts of vulcanization accelerator, and 2 parts of stearic acid.

[0012] Preferably, the method for preparing the composite filler comprises the following steps:

[0013] Synthesis of double-arm silane coupling agent: In the first step, 3-[3-carboxyallylamide]propyltriethoxysilane and 4,4'-diaminodiphenylamine are condensed in anhydrous DMF to form an amide bond under nitrogen protection and p-toluenesulfonic acid catalysis. After the reaction is completed, the product is obtained by hexane precipitation, filtration, washing and drying. The reaction equation can be simplified as: R-COOH+H2N-R'-NH2+HOOC-R→R-CONH-R'-NH-CO-R+2H2O, where R represents the remaining part of 3-[3-allylamide]propyltriethoxysilane and R' represents the diphenyl part.

[0014] (1) adding 3-[3-carboxyallylamide]propyltriethoxysilane and 4,4'-diaminodiphenylamine to anhydrous DMF, continuously introducing nitrogen, adding p-toluenesulfonic acid, heating and stirring to react, cooling the product, pouring it into hexane and stirring to precipitate, filtering, washing with hexane, and drying to obtain a double-arm silane coupling agent;

[0015] Preferably, in step (1), the molar ratio of 3-[3-carboxyallylamide]propyltriethoxysilane to 4,4'-diaminodiphenylamine is 2-2.2:1, and the amount of p-toluenesulfonic acid used is 1-5 wt% of 4,4'-diaminodiphenylamine.

[0016] Preferably, in step (1), the reaction conditions are heating to 110-120° C. and stirring the reaction for 8-12 hours.

[0017] Specifically, in step (1), the temperature can be raised to 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, or 120° C., and the stirring reaction time can be 8, 9, 10, 11, or 12 h.

[0018] Preferably, in step (1), after the reaction is completed, the reaction product is poured into hexane and stirred for precipitation for 20 to 60 minutes; and washed with hexane 2 to 3 times.

[0019] Specifically, in step (1), the stirring and precipitation time can be 20, 25, 30, 35, 40, 45, 50, 55, or 60 min.

[0020] Preparation of composite filler: First, nano zinc oxide and carbon fiber are ultrasonically dispersed in an isopropanol aqueous solution, and then the synthesized double-arm silane coupling agent and coconut oil fatty acid diethanolamide dispersant are added. During the heating and stirring process, the two ends of the double-arm silane coupling agent react with the hydroxyl groups on the surface of nano zinc oxide and carbon fiber to form Si-O-Zn and Si-OC bonds, and establish a bridge structure of nano zinc oxide-silane coupling agent-carbon fiber. This method tightly connects the inorganic filler and organic fiber through chemical bonds. At the same time, coconut oil fatty acid diethanolamide enhances the dispersibility of nano zinc oxide and carbon fiber, stabilizes the suspension through steric hindrance and electrostatic repulsion, improves the interfacial compatibility, and thus assists the occurrence of the coupling process. The final composite filler has a structure in which nano zinc oxide and carbon fiber are tightly combined, which can significantly improve the mechanical strength, thermal conductivity and flame retardancy of rubber materials.

[0021] (2) Adding nano zinc oxide and carbon fiber to an isopropanol aqueous solution, ultrasonically treating the solution, then adding a double-arm silane coupling agent and coconut oil fatty acid diethanolamide, heating and stirring, filtering, washing and drying the product to obtain the composite filler.

[0022] Preferably, in step (2), the particle size of the nano zinc oxide is 50 to 100 nm.

[0023] Specifically, in step (2), the particle size of the nano zinc oxide can be 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100 nm.

[0024] Preferably, in step (2), the carbon fiber is polyacrylonitrile-based carbon fiber, and the fiber length is 30 to 80 μm; the concentration of the isopropanol aqueous solution is 50 to 70 wt%, and the ultrasonic treatment is performed for 20 to 50 min.

[0025] Specifically, in step (2), the carbon fiber length can be 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80 μm; the concentration of the isopropanol aqueous solution can be 50, 55, 60, 65, 70 wt %; and the ultrasonic treatment time can be 20, 25, 30, 35, 40, 45, 50 min.

[0026] Preferably, in step (2), the usage ratio of nano zinc oxide, carbon fiber, double-arm silane coupling agent, and coconut oil fatty acid diethanolamide is 2-6 g: 10 g: 1-3 mL: 0.1-1 g.

[0027] Preferably, in step (2), the heating and stirring reaction conditions are 60-70° C. and stirring the reaction for 6-9 hours.

[0028] Specifically, in step (2), the stirring reaction temperature can be 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, or 70° C., and the stirring reaction time can be 6, 7, 8, or 9 h.

[0029] The present invention also claims protection for a method for preparing the rubber composite material, comprising the following steps: placing natural rubber, butadiene rubber, styrene-butadiene rubber, and half the weight of carbon black into an internal mixer for first-stage mixing, and removing the rubber to obtain a first-stage mixed rubber; placing the first-stage mixed rubber, the remaining carbon black, a composite filler, an aromatic hydrocarbon oil, an antioxidant, and stearic acid into an internal mixer for second-stage mixing, and removing the rubber to obtain a second-stage mixed rubber; placing the second-stage mixed rubber, a vulcanizing agent, and a vulcanization accelerator into an internal mixer for third-stage mixing, and removing the rubber to obtain the rubber composite material for high-performance tires.

[0030] Preferably, the first stage mixing temperature is 140-165° C., and the mixing is for 3-5 min; the second stage mixing temperature is 140-165° C., and the mixing is for 3-5 min; the third stage mixing temperature is 90-110° C., and the mixing is for 2-3 min.

[0031] Specifically, the mixing temperature of the first stage can be 140, 145, 150, 155, 160, 165°C, and the mixing time can be 3, 4, 5 min; the mixing temperature of the second stage can be 140, 145, 150, 155, 160, 165°C, and the mixing time can be 3, 4, 5 min; the mixing temperature of the third stage can be 90, 95, 100, 105, 110°C, and the mixing time can be 2, 3 min.

[0032] Compared with the prior art, the present invention has the following beneficial effects:

[0033] 1) The present invention provides a high-performance rubber composite material for tires, which achieves a significant improvement in comprehensive performance through the careful proportioning of multiple components. Natural rubber provides excellent elasticity and tear resistance; cis-1,4-butadiene rubber enhances the wear resistance and elasticity of the material; styrene-butadiene rubber improves the heat resistance and anti-aging performance of the material; carbon black, as a traditional reinforcing filler, enhances the mechanical strength and wear resistance of the material; aromatic hydrocarbon oil, as a softener, improves the processing performance of the material; antioxidants extend the service life of rubber; vulcanizers and vulcanization accelerators control the vulcanization process and optimize the cross-linking structure of rubber; stearic acid, as a dispersant, improves the dispersibility of each component. Innovative composite fillers, including nano zinc oxide, carbon fiber and double-arm silane coupling agent, further enhance the mechanical properties, wear resistance and heat dissipation of the material; among them, nano zinc oxide improves the anti-aging performance and flame retardancy, fills the rubber pores to increase the density, carbon fiber enhances the mechanical strength and provides a good heat dissipation channel, and the double-arm silane coupling agent connects the components through chemical bonds to improve the interface bonding force. Its structure also ensures that the composite filler is evenly dispersed in the rubber.

[0034] 2) The present invention provides a high-performance rubber composite material for tires, and the synergistic effect of multiple components makes the final tire rubber composite material present a comprehensive performance improvement. The material exhibits excellent tear resistance, which greatly extends the service life of the tire. The significantly improved wear resistance enables the tire to adapt to various complex road conditions and maintain a long-term use state. The optimized heat dissipation performance effectively reduces heat accumulation and slows down the thermal oxidation aging process of rubber. The enhanced anti-aging performance ensures that the tire maintains stable performance during long-term use. The improved dynamic performance improves the stability and safety of the tire when driving at high speeds. In addition, the improvement of the hardness and rigidity of the material not only further enhances the wear resistance, but also effectively reduces the rolling resistance of the tire, thereby improving the fuel efficiency of the vehicle. The optimized dynamic balance performance and anti-flowability significantly improve the handling and driving safety of the tire under various road conditions.

[0035] 3) The present invention provides a method for preparing a composite filler. First, 3-[3-carboxyallylamide]propyltriethoxysilane and 4,4'-diaminodiphenylamine are subjected to a condensation reaction in anhydrous DMF to form an amide bond under nitrogen protection and p-toluenesulfonic acid catalysis to synthesize a double-arm silane coupling agent. Subsequently, nano zinc oxide and carbon fiber are ultrasonically dispersed in an isopropanol aqueous solution, and a double-arm silane coupling agent and coconut oil fatty acid diethanolamide are added. During the heating and stirring process, the double-arm silane coupling agent reacts with the hydroxyl groups on the surface of the nano zinc oxide and carbon fiber to form Si-O-Zn and Si-OC bonds, thereby establishing a bridge structure of nano zinc oxide-silane coupling agent-carbon fiber to achieve chemical bond connection between the inorganic filler and the organic fiber.

[0036] 4) The present invention provides a composite filler, wherein the double-arm silane coupling agent is used as a bridging agent, which not only closely connects the nano zinc oxide and the carbon fiber through chemical bonds, but also forms a cross-linked structure with the rubber molecular chain, significantly enhancing the interfacial bonding force and compatibility between the filler and the rubber matrix. The diphenylamine structure in the coupling agent has a certain rotation characteristic, which makes the nano zinc oxide produce a "ball" effect on the surface of the carbon fiber, greatly enhancing the wear resistance of the rubber. Nano zinc oxide enhances the anti-aging performance, thermal conductivity and flame retardancy of the material, while filling the rubber pores and improving the density. The carbon fiber not only enhances the mechanical strength and electrical conductivity of the material, but also provides a good heat dissipation channel for the tire with its excellent thermal conductivity, and at the same time inhibits the flow of the rubber as a skeleton material. The structures such as the benzene ring and alkyl chain introduced by the double-arm silane coupling agent help to improve the compatibility of the composite filler with the rubber, and ensure the uniform dispersion of the filler in the rubber matrix. The synergistic effect of this multifunctional composite filler makes the final tire rubber composite material comprehensively improved in terms of mechanical strength, wear resistance, thermal conductivity, flame retardancy and environmental protection. DETAILED DESCRIPTION

[0037] In order to make the purpose, technical solution and advantages of the present invention clearer, the present invention is further described in detail below in conjunction with embodiments. Of course, the specific embodiments described here are only used to explain the present invention and are not used to limit the present invention.

[0038] Unless otherwise specified, the chemical reagents and materials in the present invention are purchased from commercial sources or synthesized from raw materials purchased from commercial sources.

[0039] Natural rubber: 20# standard rubber, ash content <1.0%; impurities <0.16%; volatile matter <0.8%; basic rubber for the composition of the present invention;

[0040] Styrene butadiene rubber: SBR1739 or SBR1723, provided by Sinopec Qilu Petrochemical Company;

[0041] Butadiene rubber: high cis-butadiene rubber, ash content <0.2%; volatile matter <0.8%; basic rubber of the composition of the present invention, a product of Lanxess Chemical, corresponding to the grade CB24;

[0042] Carbon black: Granular; Heating loss at 105°C <1.5%; 325 mesh sieve residue <0.05%; Used as rubber reinforcing agent.

[0043] Aromatic hydrocarbon oil, VIVATEC500 from H&R GROUP, kinematic viscosity 15.0-25.0 mm 2 / s (100℃); flash point 210℃; can improve the plasticity of the rubber, reduce the viscosity of the rubber, and at the same time improve the tensile strength and flexural properties of the rubber.

[0044] Paraphenylenediamine antioxidant: granular; crystallization point>45℃; heating loss<0.5%; provides anti-aging properties for the rubber.

[0045] Quinoline antioxidant: granular; softening point 90.0±5.0℃; heating loss <0.5%, providing anti-aging properties for the rubber.

[0046] The vulcanizing agent is sulfur: powdered; total sulfur content>98%; 200 mesh sieve residue<0.5%; 80°C, heating loss for 3 hours<0.5%, used as rubber vulcanization crosslinking agent.

[0047] The vulcanization accelerator is one or more of accelerator DM, accelerator TMTD, accelerator NOBS, accelerator M and accelerator Z.

[0048] Stearic acid: granular; iodine value <8g I2 / 100g; freezing point 57.0±5.0℃; acid value 200.0±12.0mgKOH / g; used as rubber vulcanization activator.

[0049] A method for preparing a high-performance tire rubber composite material comprises the following steps:

[0050] (1) adding 0.2-0.22 mol 3-[3-carboxyallylamide]propyltriethoxysilane and 0.1 mol 4,4'-diaminodiphenylamine to 100 mL anhydrous DMF, continuously introducing nitrogen, adding p-toluenesulfonic acid (1-5 wt% of 4,4'-diaminodiphenylamine), heating to 110-120° C., stirring for reaction for 8-12 h, cooling the product, pouring it into hexane, stirring and precipitating for 20-60 min, filtering, washing with hexane 2-3 times, and drying to obtain a double-arm silane coupling agent;

[0051] (2) adding 2 to 6 g of nano zinc oxide and 10 g of carbon fiber to a 50 to 70 wt % isopropanol aqueous solution, ultrasonically treating for 20 to 50 min, then adding 1 to 3 mL of a double-arm silane coupling agent and 0.1 to 1 g of coconut oil fatty acid diethanolamide, stirring and reacting at 60 to 70° C. for 6 to 9 h, filtering, washing, and drying the product to obtain the composite filler;

[0052] (3) 30 to 50 parts of natural rubber, 10 to 15 parts of cis-1,4-dibutyl rubber, 25 to 40 parts of styrene-butadiene rubber, and 5 to 10 parts of carbon black are put into an internal mixer and mixed at 140 to 165° C. for 3 to 5 minutes, and the rubber is discharged to obtain a first-stage mixed rubber; the first-stage mixed rubber, 5 to 10 parts of carbon black, 10 to 30 parts of composite fillers, 2 to 8 parts of aromatic hydrocarbon oil, 2 to 5 parts of antioxidant, and 1 to 3 parts of stearic acid are put into an internal mixer and mixed at 140 to 165° C. for 3 to 5 minutes, and the rubber is discharged to obtain a second-stage mixed rubber; the second-stage mixed rubber, 1 to 5 parts of sulfur, and 1 to 5 parts of vulcanization accelerator are put into an internal mixer and mixed at 90 to 110° C. for 2 to 3 minutes, and the rubber is discharged to obtain the rubber composite material for high-performance tires.

[0053] The present invention will be further described below through specific embodiments.

[0054] Example 1

[0055] A method for preparing a high-performance tire rubber composite material comprises the following steps:

[0056] (1) Add 0.22 mol 3-[3-carboxyallylamide]propyltriethoxysilane and 0.1 mol 4,4'-diaminodiphenylamine to 100 mL anhydrous DMF, continue to introduce nitrogen, add 1 g p-toluenesulfonic acid, raise the temperature to 120° C., stir and react for 8 h, cool the product, pour it into hexane and stir and precipitate for 60 min, filter, wash with hexane 3 times, and dry to obtain a double-arm silane coupling agent;

[0057] (2) adding 6 g of nano zinc oxide and 10 g of carbon fiber to a 70 wt % isopropanol aqueous solution, ultrasonically treating for 50 min, then adding 3 mL of a double-arm silane coupling agent and 1 g of coconut oil fatty acid diethanolamide, stirring and reacting at 70° C. for 6 h, filtering, washing, and drying the product to obtain the composite filler;

[0058] (3) 50 g of natural rubber, 15 g of cis-1,40 g of styrene-butadiene rubber, and 10 g of carbon black were put into an internal mixer and mixed at 160° C. for 4 min, and the rubber was discharged to obtain a first-stage mixed rubber; the first-stage mixed rubber, 10 g of carbon black, 30 g of composite filler, 8 g of aromatic hydrocarbon oil, 5 g of quinoline antioxidant, and 3 g of stearic acid were put into an internal mixer and mixed at 155° C. for 4 min, and the rubber was discharged to obtain a second-stage mixed rubber; the second-stage mixed rubber, 5 g of sulfur, and 5 g of vulcanization accelerator DM were put into an internal mixer and mixed at 100° C. for 3 min, and the rubber was discharged to obtain the rubber composite material for high-performance tires.

[0059] Example 2

[0060] A method for preparing a high-performance tire rubber composite material comprises the following steps:

[0061] (1) Add 0.21 mol 3-[3-carboxyallylamide]propyltriethoxysilane and 0.1 mol 4,4'-diaminodiphenylamine to 100 mL anhydrous DMF, continue to introduce nitrogen, add 0.8 g p-toluenesulfonic acid, raise the temperature to 126° C., stir and react for 10 h, cool the product, pour it into hexane and stir and precipitate for 50 min, filter, wash with hexane 3 times, and dry to obtain a double-arm silane coupling agent;

[0062] (2) adding 5 g of nano zinc oxide and 10 g of carbon fiber to a 60 wt % isopropanol aqueous solution, ultrasonically treating for 40 min, then adding 2 mL of a double-arm silane coupling agent and 0.8 g of coconut oil fatty acid diethanolamide, stirring and reacting at 66° C. for 7 h, filtering, washing, and drying the product to obtain the composite filler;

[0063] (3) 44 g of natural rubber, 14 g of cis-1,4-dibutyl rubber, 35 g of styrene-butadiene rubber, and 8 g of carbon black were put into an internal mixer and mixed at 160° C. for 4 min, and the rubber was discharged to obtain a first-stage mixed rubber; the first-stage mixed rubber, 8 g of carbon black, 25 g of composite filler, 6 g of aromatic hydrocarbon oil, 4 g of quinoline antioxidant, and 2 g of stearic acid were put into an internal mixer and mixed at 155° C. for 4 min, and the rubber was discharged to obtain a second-stage mixed rubber; the second-stage mixed rubber, 4 g of sulfur, and 4 g of vulcanization accelerator DM were put into an internal mixer and mixed at 100° C. for 3 min, and the rubber was discharged to obtain the rubber composite material for high-performance tires.

[0064] Example 3

[0065] A method for preparing a high-performance tire rubber composite material comprises the following steps:

[0066] (1) Add 0.2 mol 3-[3-carboxyallylamide]propyltriethoxysilane and 0.1 mol 4,4'-diaminodiphenylamine to 100 mL anhydrous DMF, continue to introduce nitrogen, add 0.6 g p-toluenesulfonic acid, raise the temperature to 114° C., stir and react for 10 h, cool the product, pour it into hexane and stir and precipitate for 30 min, filter, wash with hexane 3 times, and dry to obtain a double-arm silane coupling agent;

[0067] (2) adding 4 g of nano zinc oxide and 10 g of carbon fiber to a 60 wt % isopropanol aqueous solution, ultrasonically treating for 30 min, then adding 2 mL of a double-arm silane coupling agent and 0.4 g of coconut oil fatty acid diethanolamide, stirring and reacting at 64° C. for 8 h, filtering, washing, and drying the product to obtain the composite filler;

[0068] (3) 36 g of natural rubber, 12 g of cis-1,4-dibutyl rubber, 30 g of styrene-butadiene rubber, and 6 g of carbon black were put into an internal mixer and mixed at 160° C. for 4 min, and the rubber was discharged to obtain a first-stage mixed rubber; the first-stage mixed rubber, 6 g of carbon black, 20 g of composite filler, 4 g of aromatic hydrocarbon oil, 3 g of quinoline antioxidant, and 2 g of stearic acid were put into an internal mixer and mixed at 155° C. for 4 min, and the rubber was discharged to obtain a second-stage mixed rubber; the second-stage mixed rubber, 2 g of sulfur, and 2 g of vulcanization accelerator DM were put into an internal mixer and mixed at 100° C. for 3 min, and the rubber was discharged to obtain the rubber composite material for high-performance tires.

[0069] Example 4

[0070] A method for preparing a high-performance tire rubber composite material comprises the following steps:

[0071] (1) Add 0.2 mol 3-[3-carboxyallylamide]propyltriethoxysilane and 0.1 mol 4,4'-diaminodiphenylamine to 100 mL anhydrous DMF, continue to introduce nitrogen, add 0.6 g p-toluenesulfonic acid, raise the temperature to 110° C., stir and react for 12 h, cool the product, pour it into hexane and stir and precipitate for 20 min, filter, wash with hexane 3 times, and dry to obtain a double-arm silane coupling agent;

[0072] (2) adding 2 g of nano zinc oxide and 10 g of carbon fiber to a 60 wt % isopropanol aqueous solution, ultrasonically treating for 20 min, then adding 1 mL of a double-arm silane coupling agent and 0.1 g of coconut oil fatty acid diethanolamide, stirring and reacting at 60° C. for 9 h, filtering, washing, and drying the product to obtain the composite filler;

[0073] (3) 30 g of natural rubber, 10 g of cis-1,4-dibutyl rubber, 25 g of styrene-butadiene rubber, and 5 g of carbon black were put into an internal mixer and mixed at 160° C. for 4 min, and the rubber was discharged to obtain a first-stage mixed rubber; the first-stage mixed rubber, 5 g of carbon black, 15 g of composite filler, 2 g of aromatic hydrocarbon oil, 2 g of quinoline antioxidant, and 1 g of stearic acid were put into an internal mixer and mixed at 155° C. for 4 min, and the rubber was discharged to obtain a second-stage mixed rubber; the second-stage mixed rubber, 1 g of sulfur, and 1 g of vulcanization accelerator DM were put into an internal mixer and mixed at 100° C. for 3 min, and the rubber was discharged to obtain the rubber composite material for high-performance tires.

[0074] Comparative Example 1

[0075] A method for preparing a rubber composite material for a tire comprises the following steps:

[0076] (1) adding 10 g of nano zinc oxide to a 70 wt % isopropanol aqueous solution, ultrasonically treating for 50 min, then adding 3 mL of 3-[3-carboxyallylamide]propyltriethoxysilane and 1 g of coconut oil fatty acid diethanolamide, stirring and reacting at 70° C. for 6 h, filtering, washing, and drying the product to obtain modified nano zinc oxide;

[0077] (2) 10 g of carbon fiber was added to a 70 wt % isopropanol aqueous solution, and ultrasonic treatment was performed for 50 min. Then, 3 mL of 3-[3-carboxyallylamide]propyltriethoxysilane and 1 g of coconut oil fatty acid diethanolamide were added, and the mixture was stirred at 70 ° C for 6 h. The product was filtered, washed, and dried to obtain modified carbon fiber;

[0078] (3) 50 g of natural rubber, 15 g of cis-1,40 g of styrene-butadiene rubber, and 10 g of carbon black were put into an internal mixer and mixed at 160° C. for 4 min, and the rubber was discharged to obtain a first-stage mixed rubber; the first-stage mixed rubber, 10 g of carbon black, 20 g of modified carbon fiber, 10 g of modified nano zinc oxide, 8 g of aromatic hydrocarbon oil, 5 g of quinoline antioxidant, and 3 g of stearic acid were put into an internal mixer and mixed at 155° C. for 4 min, and the rubber was discharged to obtain a second-stage mixed rubber; the second-stage mixed rubber, 5 g of sulfur, and 5 g of vulcanization accelerator DM were put into an internal mixer and mixed at 100° C. for 3 min, and the rubber was discharged to obtain the rubber composite material for tires.

[0079] Comparative Example 2

[0080] A method for preparing a rubber composite material for a tire comprises the following steps:

[0081] (1) adding 10 g of nano zinc oxide to a 70 wt % isopropanol aqueous solution, ultrasonically treating for 50 min, then adding 3 mL of 3-[3-carboxyallylamide]propyltriethoxysilane and 1 g of coconut oil fatty acid diethanolamide, stirring and reacting at 70° C. for 6 h, filtering, washing, and drying the product to obtain modified nano zinc oxide;

[0082] (2) 50 g of natural rubber, 15 g of cis-1,40 g of styrene-butadiene rubber, and 10 g of carbon black were put into an internal mixer and mixed at 160° C. for 4 min, and the rubber was discharged to obtain a first-stage mixed rubber; the first-stage mixed rubber, 10 g of carbon black, 20 g of modified nano zinc oxide, 8 g of aromatic hydrocarbon oil, 5 g of quinoline antioxidant, and 3 g of stearic acid were put into an internal mixer and mixed at 155° C. for 4 min, and the rubber was discharged to obtain a second-stage mixed rubber; the second-stage mixed rubber, 5 g of sulfur, and 5 g of vulcanization accelerator DM were put into an internal mixer and mixed at 100° C. for 3 min, and the rubber was discharged to obtain the rubber composite material for tires.

[0083] Comparative Example 3

[0084] A method for preparing a rubber composite material for a tire comprises the following steps:

[0085] (1) 10 g of carbon fiber was added to a 70 wt % isopropanol aqueous solution, and ultrasonic treatment was performed for 50 min. Then, 3 mL of 3-[3-carboxyallylamide]propyltriethoxysilane and 1 g of coconut oil fatty acid diethanolamide were added, and the mixture was stirred at 70 ° C for 6 h. The product was filtered, washed, and dried to obtain modified carbon fiber;

[0086] (2) 50 g of natural rubber, 15 g of cis-1,40 g of styrene-butadiene rubber, and 10 g of carbon black were put into an internal mixer and mixed at 160° C. for 4 min, and the rubber was discharged to obtain a first-stage mixed rubber; the first-stage mixed rubber, 10 g of carbon black, 20 g of modified carbon fiber, 8 g of aromatic hydrocarbon oil, 5 g of quinoline antioxidant, and 3 g of stearic acid were put into an internal mixer and mixed at 155° C. for 4 min, and the rubber was discharged to obtain a second-stage mixed rubber; the second-stage mixed rubber, 5 g of sulfur, and 5 g of vulcanization accelerator DM were put into an internal mixer and mixed at 100° C. for 3 min, and the rubber was discharged to obtain the rubber composite material for tires.

[0087] Comparative Example 4

[0088] A method for preparing a rubber composite material for a tire comprises the following steps:

[0089] 50g of natural rubber, 15g of butadiene rubber, 40g of styrene-butadiene rubber and 10g of carbon black were put into an internal mixer and mixed at 160°C for 4min, and the rubber was discharged to obtain a first-stage mixed rubber; the first-stage mixed rubber, 10g of carbon black, 20g of carbon fiber, 10g of nano zinc oxide, 8g of aromatic hydrocarbon oil, 5g of quinoline antioxidant and 3g of stearic acid were put into an internal mixer and mixed at 155°C for 4min, and the rubber was discharged to obtain a second-stage mixed rubber; the second-stage mixed rubber, 5g of sulfur and 5g of vulcanization accelerator DM were put into an internal mixer and mixed at 100°C for 3min, and the rubber was discharged to obtain the rubber composite material for tire.

[0090] The rubber composite materials prepared in Examples 1 to 4 and Comparative Examples 1 to 4 were subjected to performance tests. The hardness was tested at room temperature using a hardness tester with reference to GB / T531.1-2008 "Test method for indentation hardness of vulcanized rubber or thermoplastic rubber Part 1: Shore hardness method (Shore hardness)"; the tensile strength, 100% tensile stress, 300% tensile stress, and elongation at break were tested using an electronic tensile testing machine with reference to GB / T 528-2009 "Determination of tensile stress-strain properties of vulcanized rubber or thermoplastic rubber" (tensile speed 500 mm / min, temperature 23±2°C, type 2 dumbbell-shaped specimen); the tear strength was tested using an electronic tensile testing machine with reference to GB / T 529-2008 "Determination of tear strength of vulcanized rubber or thermoplastic rubber (trouser-shaped, right-angled and crescent-shaped specimens)" (tensile speed 500 mm / min, temperature 23±2°C, right-angled specimen); the tear strength was tested using an electronic tensile testing machine with reference to GB / T 1687.1-2016 "Determination of temperature rise and fatigue resistance of vulcanized rubber in flexure tests Part 1: Basic principles" tests temperature rise and fatigue resistance (compression heating temperature rise, compression heating permanent deformation); refer to GB / T 1689-2014 "Determination of wear resistance of vulcanized rubber (using Akron abrasion tester)" to test wear resistance; specific data are shown in Table 1.

[0091] Table 1 Rubber composite material performance test results

[0092]

[0093] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. A rubber composite material for high-performance tires, characterized in that: The invention is made of the following components in parts by weight: 30-50 parts of natural rubber, 10-15 parts of butadiene rubber, 25-40 parts of styrene-butadiene rubber, 10-20 parts of carbon black, 10-30 parts of composite filler, 2-8 parts of aromatic hydrocarbon oil, 2-5 parts of antioxidant, 1-5 parts of vulcanizing agent, 1-5 parts of vulcanization accelerator and 1-3 parts of stearic acid.

2. The rubber composite material according to claim 1, characterized in that: The preparation method of the composite filler comprises the following steps: (1) adding 3-[3-carboxyallylamide]propyltriethoxysilane and 4,4'-diaminodiphenylamine to anhydrous DMF, continuously introducing nitrogen, adding p-toluenesulfonic acid, heating and stirring to react, cooling the product, pouring it into hexane and stirring to precipitate, filtering, washing with hexane, and drying to obtain a double-arm silane coupling agent; (2) Adding nano zinc oxide and carbon fiber to an isopropanol aqueous solution, ultrasonically treating the solution, then adding a double-arm silane coupling agent and coconut oil fatty acid diethanolamide, heating and stirring, filtering, washing and drying the product to obtain the composite filler.

3. The rubber composite material according to claim 2, characterized in that: In step (1), the molar ratio of 3-[3-carboxyallylamide]propyltriethoxysilane to 4,4'-diaminodiphenylamine is 2-2.2:1, and the amount of p-toluenesulfonic acid used is 1-5 wt% of 4,4'-diaminodiphenylamine.

4. The rubber composite material according to claim 2, characterized in that: In step (1), the reaction conditions are heating to 110-120° C. and stirring the reaction for 8-12 hours.

5. The rubber composite material according to claim 2, characterized in that: In step (1), after the reaction is completed, the reaction product is poured into hexane and stirred for precipitation for 20 to 60 minutes; and washed with hexane 2 to 3 times.

6. The rubber composite material according to claim 2, characterized in that: In step (2), the carbon fiber is polyacrylonitrile-based carbon fiber, and the fiber length is 30 to 80 μm; the concentration of the isopropanol aqueous solution is 50 to 70 wt%, and the ultrasonic treatment is performed for 20 to 50 minutes.

7. The rubber composite material according to claim 2, characterized in that: In step (2), the usage ratio of nano zinc oxide, carbon fiber, double-arm silane coupling agent and coconut oil fatty acid diethanolamide is 2-6 g: 10 g: 1-3 mL: 0.1-1 g.

8. The rubber composite material according to claim 2, characterized in that: In step (2), the heating and stirring reaction conditions are 60-70° C. and stirring the reaction for 6-9 hours.

9. A method for preparing the rubber composite material according to any one of claims 1 to 8, characterized in that: The method comprises the following steps: putting natural rubber, butadiene rubber, styrene-butadiene rubber and half the weight of carbon black into an internal mixer for first-stage mixing, and removing the rubber to obtain a first-stage mixed rubber; putting the first-stage mixed rubber, the remaining carbon black, the composite filler, the aromatic hydrocarbon oil, the antioxidant and the stearic acid into an internal mixer for second-stage mixing, and removing the rubber to obtain a second-stage mixed rubber; putting the second-stage mixed rubber, the vulcanizing agent and the vulcanization accelerator into an internal mixer for third-stage mixing, and removing the rubber to obtain the rubber composite material for high-performance tires.

10. The preparation method according to claim 9, characterized in that: The first stage mixing temperature is 140-165°C, and the mixing is for 3-5 minutes; the second stage mixing temperature is 140-165°C, and the mixing is for 3-5 minutes; the third stage mixing temperature is 90-110°C, and the mixing is for 2-3 minutes.

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