High-wear-resistance solid rubber tire and preparation method thereof

Abstract

The invention relates to the technical field of solid tires, and provides a high-wear-resistance solid rubber tire and a preparation method of the high-wear-resistance solid rubber tire. The rubber material is prepared from 90-100 parts of natural rubber, 60-70 parts of butadiene styrene rubber, 10-20 parts of epoxidized natural rubber, 2-3 parts of zinc oxide, 40-50 parts of carbon black, 1-2 parts of stearic acid, 10-12 parts of modified carbon fibers, 1-2 parts of an antioxidant, 1-2 parts of a vulcanizing material and 0.8-1.5 parts of an accelerant. Through the technical scheme, the problems of stress concentration caused by poor dispersibility of carbon black, easy agglomeration due to weak interface bonding force between the filler and the rubber matrix, insufficient stability of a vulcanization cross-linked network and the like of a solid tire in related technologies are solved, the wear resistance, mechanical strength and thermal stability of the tire are remarkably improved, and the service life is prolonged.

Description

Technical Field

[0001] This invention relates to the field of solid tire technology, specifically to a high wear-resistant solid rubber tire and its preparation method. Background Technology

[0002] Currently, solid rubber tires are widely used in industrial vehicles, construction machinery and other fields. However, due to the friction caused by long-term high loads and complex road conditions, they generally suffer from insufficient wear resistance and short service life.

[0003] Traditional tires often use a blend of natural rubber and styrene-butadiene rubber (SBR), with carbon black added as a reinforcing agent. While this improves some mechanical properties, carbon black has poor dispersion in the rubber matrix, easily leading to stress concentration and accelerating tire wear. Furthermore, existing technologies often add ordinary carbon fiber to improve wear resistance, but due to the inertness of the carbon fiber surface, the interfacial bonding with the rubber matrix is ​​weak, making it prone to agglomeration, which reduces material uniformity and mechanical properties. Regarding vulcanization processes, conventional vulcanization systems are mainly sulfur-based, resulting in low crosslinking efficiency and insufficient stability of the formed network structure. This makes them susceptible to aging and degradation at high temperatures or during long-term use, further affecting tire durability. Although some studies have attempted to improve the bond between fibers and the matrix by adding silane coupling agents or introducing antioxidants to delay aging, these methods often only address one aspect of the problem and cannot simultaneously address wear resistance, mechanical strength, and thermal stability.

[0004] Therefore, developing a solid rubber tire with high wear resistance, excellent mechanical properties and long-term stability remains a difficult problem that urgently needs to be solved in the current technological field. Summary of the Invention

[0005] This invention proposes a high wear-resistant solid rubber tire and its preparation method, which solves the problems in related technologies such as stress concentration due to poor carbon black dispersion, weak interfacial bonding between filler and rubber matrix and easy agglomeration, and insufficient stability of vulcanization crosslinking network in solid tires. It significantly improves the wear resistance, mechanical strength and thermal stability of the tire and extends its service life.

[0006] The technical solution of the present invention is as follows: A high wear-resistant solid rubber tire comprises the following components: by weight, 90-100 parts natural rubber, 60-70 parts styrene-butadiene rubber, 10-20 parts epoxidized natural rubber, 2-3 parts zinc oxide, 40-50 parts carbon black, 1-2 parts stearic acid, 10-12 parts modified carbon fiber, 1-2 parts antioxidant, 1-2 parts vulcanizing material, and 0.8-1.5 parts accelerator.

[0007] In a more optimized manner, the preparation process of the modified carbon fiber is as follows: A1: The cleaned carbon fibers are placed in a nitric acid solution and soaked at 50-60℃ for 4-5 hours. After removal, they are washed and dried to obtain pretreated carbon fibers. Subsequently, they are transferred to an aqueous solution of γ-aminopropyltriethoxysilane, ultrasonically dispersed for 30-40 minutes, and the temperature is raised to 60-70℃ for 5-6 hours. After the reaction is completed, they are washed and dried to obtain aminated carbon fibers. A2: Add the modified copolymer to N,N-dimethylformamide and stir for 10-12 hours. Then add the aminated carbon fiber, ultrasonically disperse for 30-40 minutes, raise the temperature to 60-70℃, react for 6-7 hours, and dry to obtain the modified carbon fiber.

[0008] In this method, carbon fibers are pretreated with nitric acid solution to oxidize their surface and introduce active groups. Subsequently, they are modified by amination with γ-aminopropyltriethoxysilane. The silanols obtained from the hydrolysis of the silane condense with the hydroxyl groups on the carbon fiber surface to form covalent bonds, giving the fiber surface an amino group. Next, an epoxy-containing modified copolymer is dissolved in DMF. The epoxy groups react with the amino groups on the amination surface of the carbon fibers through a ring-opening reaction, forming stable covalent bonds, thereby grafting polymer chains onto the fiber surface.

[0009] In a more optimized manner, the raw materials for preparing the aminated carbon fiber include the following components: by weight, 10-12 parts carbon fiber, 50-60 parts nitric acid solution, and 10-12 parts aqueous solution of γ-aminopropyltriethoxysilane; wherein, the concentration of the nitric acid solution is 35 wt%; and the concentration of the aqueous solution of γ-aminopropyltriethoxysilane is 2.5 wt%.

[0010] In a more optimized manner, the raw materials for preparing the modified carbon fiber include the following components: by weight, 2-3 parts of modified copolymer, 10-30 parts of N,N-dimethylformamide, and 10-12 parts of aminated carbon fiber.

[0011] In a more optimized manner, the preparation process of the modified copolymer is as follows: S1: Mix 3,5-diamino-1,2,4-triazole, 3,4-dihydroxybenzaldehyde, and anhydrous ethanol, raise the temperature to 85°C, reflux and stir for 3-4 hours, then add 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, continue the reaction at 85°C for 3-4 hours, then add 1,4-phenylenediboric acid, stir for 30-40 minutes, the reaction is complete, filter, wash, and dry to obtain intermediate A; S2: Mix intermediate A, triethylamine, and anhydrous tetrahydrofuran, stir evenly, keep the temperature at 0-5℃, slowly add acryloyl chloride solution, after the addition is complete, raise the temperature to room temperature, continue stirring for 2-3 hours, after the reaction is complete, perform post-processing to obtain the modified monomer. S3: Under a protective atmosphere, the modified monomer, glycidyl methacrylate, and vinyl acetate were added to N,N-dimethylformamide and stirred for 20-30 min. Then, azobisisobutyronitrile solution was slowly added, the temperature was raised to 70-80℃, and the reaction was carried out for 6-7 h. After the reaction was completed, the mixture was cooled to room temperature and post-treated to obtain the modified copolymer.

[0012] In the scheme, the amino group of 3,5-diamino-1,2,4-triazole condenses with the aldehyde group of 3,4-dihydroxybenzaldehyde to form an imine. The pH bond of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) undergoes nucleophilic addition with the imine to form a phosphorus-containing flame-retardant structure. Finally, 1,4-phenylenediboronic acid reacts with the ortho-diphenol hydroxyl group in the system to form a borate ester bond, yielding intermediate A. In a more optimized manner, the raw materials for preparing intermediate A include the following components: by weight, 8-9 parts of 3,5-diamino-1,2,4-triazole, 13-14 parts of 3,4-dihydroxybenzaldehyde, 60-80 parts of anhydrous ethanol, 21-22 parts of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and 8-10 parts of 1,4-phenylenediboronic acid.

[0013] In the proposed method, at low temperature (0-5℃), the remaining amino group of intermediate A nucleophilically attacks the acyl chloride group of acryloyl chloride to obtain the modified monomer.

[0014] In a more optimized manner, the raw materials for preparing the modified monomer include the following components: by weight, 20-22 parts of intermediate A, 7-8 parts of triethylamine, 150-200 parts of anhydrous tetrahydrofuran, and 10-15 parts of acryloyl chloride solution; wherein the concentration of the acryloyl chloride solution is 12 wt%.

[0015] The preparation process of the modified copolymer is shown below:

[0016] In this scheme, under the action of a free radical initiator (AIBN), the modified monomer, glycidyl methacrylate (GMA), and vinyl acetate undergo free radical copolymerization to obtain a modified copolymer.

[0017] In a more optimized manner, the raw materials for preparing the modified copolymer include the following components: by weight, 20-25 parts of modified monomer, 15-20 parts of glycidyl methacrylate, 10-15 parts of vinyl acetate, 120-150 parts of N,N-dimethylformamide, and 3-5 parts of azobisisobutyronitrile solution; wherein the concentration of the azobisisobutyronitrile solution is 10 wt%.

[0018] A method for preparing a high wear-resistant solid rubber tire includes the following steps: Step 1: Mix natural rubber, styrene-butadiene rubber, and epoxidized natural rubber at 50-70℃ for 4-5 minutes. Add zinc oxide and stearic acid and mix at 70-90℃ for 3-4 minutes. Then add carbon black, antioxidant, and modified carbon fiber and mix at 100-120℃ for 5-7 minutes. Then cool down to 90-100℃ and add vulcanizing materials and accelerators in sequence. Mix quickly for 2-3 minutes until uniform. Quickly discharge the rubber, cool, and transfer it to a mold to make tire blanks. Step 2: Place the tire blank in the vulcanizing machine, introduce low-pressure saturated steam, and pre-vulcanize at 120-130℃ for 5-8 minutes. Then increase the steam pressure and vulcanize at 150-160℃ for 20-30 minutes. After vulcanization, turn off the steam, cool, demold, and obtain the finished product.

[0019] Ideally, the vulcanizing material is sulfur.

[0020] The advantages of this invention compared to existing technologies are as follows: Firstly, in this scheme, 1,4-phenylenediboric acid is introduced during the preparation of the modified monomer. While forming borate ester bonds, some boron hydroxyl groups remain. The epoxy groups (three-membered ring structure) on the epoxidized natural rubber molecular chain have high reactivity and can specifically interact with the boron hydroxyl groups: on the one hand, the hydroxyl groups of the boron hydroxyl groups can form hydrogen bonds with the epoxy groups, achieving preliminary physical adsorption; on the other hand, under the temperature and pressure conditions of the vulcanization process, the boron hydroxyl groups can initiate ring opening of the epoxy groups, forming stable covalent bonds. Simultaneously, the double bonds retained in the modified copolymer grafted onto the surface of the modified carbon fiber can also synergistically participate in the crosslinking reaction initiated by the vulcanizing material (sulfur) with the double bonds in natural rubber and styrene-butadiene rubber, thus forming a three-dimensional network structure. When the tire rubs against the ground, the network structure can quickly disperse frictional stress, reduce rubber wear and detachment caused by excessive local deformation, and extend service life.

[0021] Secondly, the modified copolymer (containing glycidyl methacrylate and vinyl acetate segments) grafted onto the surface of the modified carbon fiber exhibits good chemical compatibility with the rubber matrix, thus preventing carbon fiber agglomeration and ensuring uniform dispersion within the rubber matrix. Simultaneously, the DOPO phosphaphenanthrene structure and borate ester bonds contained in the modified copolymer possess excellent thermal stability, inhibiting thermal aging during friction and reducing performance degradation caused by high-temperature degradation of the rubber. This improves the overall performance of the tire. Detailed Implementation

[0022] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0023] Example 1: A method for preparing a high wear-resistant solid rubber tire, comprising the following steps: Step 1: Mix 90 parts natural rubber, 60 parts styrene-butadiene rubber, and 10 parts epoxidized natural rubber at 50°C for 4 minutes. Add 2 parts zinc oxide and 1 part stearic acid and mix at 70°C for 3 minutes. Then add 40 parts carbon black, 1 part antioxidant (antioxidant 1010), and 10 parts modified carbon fiber and mix at 100°C for 5 minutes. Then cool down to 90°C and add 1 part vulcanizing material (sulfur) and 0.8 parts accelerator (accelerator CZ) in sequence. Mix quickly for 2 minutes until uniform. Quickly discharge the rubber, cool, and transfer to a mold to make a tire blank. Step 2: Place the tire blank in the vulcanizing machine, introduce low-pressure saturated steam, pre-vulcanize at 120℃ for 5 minutes, then increase the steam pressure and vulcanize at 150℃ for 20 minutes. After vulcanization, turn off the steam, cool, demold, and obtain the finished product. The preparation process of modified carbon fiber is as follows: A1: Ten parts of cleaned carbon fiber were placed in 50 parts of nitric acid solution (concentration 35wt%) and soaked at 50℃ for 4h. After removal, washing and drying were performed to obtain pretreated carbon fiber. Subsequently, it was transferred to 10 parts of γ-aminopropyltriethoxysilane aqueous solution (concentration 2.5wt%), ultrasonically dispersed for 30min, and the temperature was raised to 60℃ for 5h. After the reaction was completed, it was washed and dried to obtain aminated carbon fiber. A2: Add 2 parts of the modified copolymer to 10 parts of N,N-dimethylformamide, stir for 10 h, then add 10 parts of aminated carbon fiber, ultrasonically disperse for 30 min, raise the temperature to 60℃, react for 6 h, and dry to obtain modified carbon fiber; The preparation process of the modified copolymer is as follows: S1: Mix 8 parts of 3,5-diamino-1,2,4-triazole, 13 parts of 3,4-dihydroxybenzaldehyde, and 60 parts of anhydrous ethanol, raise the temperature to 85°C, reflux and stir for 3 hours, then add 21 parts of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, continue the reaction at 85°C for 3 hours, then add 8 parts of 1,4-phenylenediboric acid, stir for 30 minutes, the reaction is complete, filter, wash, and dry to obtain intermediate A; S2: Mix 20 parts of intermediate A, 7 parts of triethylamine, and 150 parts of anhydrous tetrahydrofuran, stir evenly, keep the temperature at 0-5℃, slowly add 10 parts of acryloyl chloride solution, after the addition is complete, raise the temperature to room temperature, continue stirring for 2 hours, after the reaction is completed, perform post-processing to obtain the modified monomer. S3: Under a protective atmosphere, 20 parts of modified monomer, 15 parts of glycidyl methacrylate, and 10 parts of vinyl acetate were added to 120 parts of N,N-dimethylformamide and stirred for 20 min. Then, 3 parts of azobisisobutyronitrile solution (concentration of 10 wt%) were slowly added, the temperature was raised to 70 °C, and the reaction was carried out for 6 h. After the reaction was completed, the mixture was cooled to room temperature and post-treated to obtain the modified copolymer.

[0024] Example 2: A method for preparing a high wear-resistant solid rubber tire, comprising the following steps: Step 1: Mix 100 parts natural rubber, 70 parts styrene-butadiene rubber, and 20 parts epoxidized natural rubber at 70°C for 5 minutes. Add 3 parts zinc oxide and 2 parts stearic acid and mix at 90°C for 4 minutes. Then add 50 parts carbon black, 2 parts antioxidant (antioxidant 1010), and 12 parts modified carbon fiber and mix at 120°C for 7 minutes. Then cool down to 100°C and add 2 parts vulcanizing material (sulfur) and 1.5 parts accelerator (accelerator CZ) in sequence. Mix quickly for 3 minutes until uniform. Quickly discharge the rubber, cool, and transfer to a mold to make a tire blank. Step 2: Place the tire blank in the vulcanizing machine, introduce low-pressure saturated steam, pre-vulcanize at 130℃ for 8 minutes, then increase the steam pressure and vulcanize at 160℃ for 30 minutes. After vulcanization, turn off the steam, cool, demold, and obtain the finished product. The preparation process of modified carbon fiber is as follows: A1: 12 parts of cleaned carbon fiber were placed in 60 parts of nitric acid solution (concentration of 35 wt%) and soaked at 60℃ for 5 h. After removal, washing and drying were performed to obtain pretreated carbon fiber. Subsequently, it was transferred to 12 parts of γ-aminopropyltriethoxysilane aqueous solution (concentration of 2.5 wt%), ultrasonically dispersed for 40 min, and the temperature was raised to 70℃ for 6 h. After the reaction was completed, it was washed and dried to obtain aminated carbon fiber. A2: Add 3 parts of the modified copolymer to 30 parts of N,N-dimethylformamide, stir for 12 hours, then add 12 parts of aminated carbon fiber, ultrasonically disperse for 40 minutes, raise the temperature to 70°C, react for 7 hours, and dry to obtain the modified carbon fiber. The preparation process of the modified copolymer is as follows: S1: Mix 9 parts of 3,5-diamino-1,2,4-triazole, 14 parts of 3,4-dihydroxybenzaldehyde, and 80 parts of anhydrous ethanol, raise the temperature to 85°C, reflux and stir for 4 hours, then add 22 parts of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, continue the reaction at 85°C for 4 hours, then add 10 parts of 1,4-phenylenediboric acid, stir for 40 minutes, the reaction is complete, filter, wash, and dry to obtain intermediate A; S2: Mix 22 parts of intermediate A, 8 parts of triethylamine, and 200 parts of anhydrous tetrahydrofuran, stir evenly, keep the temperature at 5°C, slowly add 15 parts of acryloyl chloride solution, after the addition is complete, raise the temperature to room temperature, continue stirring for 3 hours, after the reaction is completed, perform post-processing to obtain the modified monomer. S3: Under a protective atmosphere, 25 parts of modified monomer, 20 parts of glycidyl methacrylate, and 15 parts of vinyl acetate were added to 150 parts of N,N-dimethylformamide and stirred for 30 min. Then, 5 parts of azobisisobutyronitrile solution (concentration of 10 wt%) were slowly added, the temperature was raised to 80 °C, and the reaction was carried out for 7 h. After the reaction was completed, the mixture was cooled to room temperature and post-treated to obtain the modified copolymer.

[0025] Example 3: A method for preparing a high wear-resistant solid rubber tire, comprising the following steps: Step 1: Mix 95 parts natural rubber, 65 parts styrene-butadiene rubber, and 15 parts epoxidized natural rubber at 60°C for 4.5 minutes. Add 2.5 parts zinc oxide and 1.5 parts stearic acid and mix at 80°C for 3.5 minutes. Then add 45 parts carbon black, 1.5 parts antioxidant (antioxidant 1010), and 11 parts modified carbon fiber and mix at 110°C for 6 minutes. Then cool down to 95°C and add 1.5 parts vulcanizing material (sulfur) and 1.15 parts accelerator (accelerator CZ) in sequence. Mix quickly for 2.5 minutes until uniform. Quickly discharge the rubber, cool, and transfer to a mold to make a tire blank. Step 2: Place the tire blank in the vulcanizing machine, introduce low-pressure saturated steam, pre-vulcanize at 125℃ for 6.5 minutes, then increase the steam pressure and vulcanize at 155℃ for 25 minutes. After vulcanization, turn off the steam, cool, demold, and obtain the finished product. The preparation process of modified carbon fiber is as follows: A1: 11 parts of cleaned carbon fiber were placed in 55 parts of nitric acid solution (concentration 35wt%) and soaked at 55℃ for 4.5h. After removal, washing and drying were performed to obtain pretreated carbon fiber. Subsequently, it was transferred to 11 parts of γ-aminopropyltriethoxysilane aqueous solution (concentration 2.5wt%), ultrasonically dispersed for 35min, and the temperature was raised to 65℃ for 5.5h. After the reaction was completed, it was washed and dried to obtain aminated carbon fiber. A2: Add 2.5 parts of the modified copolymer to 20 parts of N,N-dimethylformamide, stir for 11 h, then add 11 parts of aminated carbon fiber, ultrasonically disperse for 35 min, raise the temperature to 65℃, react for 6.5 h, and dry to obtain modified carbon fiber; The preparation process of the modified copolymer is as follows: S1: Mix 8.5 parts of 3,5-diamino-1,2,4-triazole, 13.5 parts of 3,4-dihydroxybenzaldehyde, and 70 parts of anhydrous ethanol, raise the temperature to 85°C, and reflux and stir for 3.5 h. Then add 21.5 parts of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and continue the reaction at 85°C for 3.5 h. Then add 9 parts of 1,4-phenylenediboric acid, stir for 35 min, and the reaction is complete. Filter, wash, and dry to obtain intermediate A. S2: Mix 21 parts of intermediate A, 7.5 parts of triethylamine, and 175 parts of anhydrous tetrahydrofuran, stir evenly, keep the temperature at 2.5℃, slowly add 12.5 parts of acryloyl chloride solution, after the addition is complete, raise the temperature to room temperature, continue stirring for 2.5h, after the reaction is completed, perform post-processing to obtain the modified monomer. S3: Under a protective atmosphere, 22.5 parts of modified monomer, 17.5 parts of glycidyl methacrylate, and 12.5 parts of vinyl acetate were added to 135 parts of N,N-dimethylformamide and stirred for 25 min. Then, 4 parts of azobisisobutyronitrile solution (concentration of 10 wt%) were slowly added, the temperature was raised to 75 °C, and the reaction was carried out for 6.5 h. After the reaction was completed, the mixture was cooled to room temperature and post-treated to obtain the modified copolymer.

[0026] Comparative Example 1: No modified carbon fiber was added, as follows: Step 1: Mix 95 parts natural rubber, 65 parts styrene-butadiene rubber, and 15 parts epoxidized natural rubber at 60°C for 4.5 minutes. Add 2.5 parts zinc oxide and 1.5 parts stearic acid and mix at 80°C for 3.5 minutes. Then add 45 parts carbon black and 1.5 parts antioxidant (antioxidant 1010) and mix at 110°C for 6 minutes. Then cool down to 95°C and add 1.5 parts vulcanizing material (sulfur) and 1.15 parts accelerator (accelerator CZ) in sequence. Mix quickly for 2.5 minutes until uniform. Quickly discharge the rubber, cool, and transfer it to a mold to make a tire blank. Step 2: Place the tire blank in the vulcanizing machine, introduce low-pressure saturated steam, pre-vulcanize at 125℃ for 6.5 minutes, then increase the steam pressure and vulcanize at 155℃ for 25 minutes. After vulcanization, turn off the steam, cool, demold, and obtain the finished product.

[0027] Comparative Example 2: Further modification of carbon fibers without the use of modified copolymers, as detailed below: Step 1: Mix 95 parts natural rubber, 65 parts styrene-butadiene rubber, and 15 parts epoxidized natural rubber at 60°C for 4.5 minutes. Add 2.5 parts zinc oxide and 1.5 parts stearic acid and mix at 80°C for 3.5 minutes. Then add 45 parts carbon black, 1.5 parts antioxidant (antioxidant 1010), and 11 parts modified carbon fiber and mix at 110°C for 6 minutes. Then cool down to 95°C and add 1.5 parts vulcanizing material (sulfur) and 1.15 parts accelerator (accelerator CZ) in sequence. Mix quickly for 2.5 minutes until uniform. Quickly discharge the rubber, cool, and transfer to a mold to make a tire blank. Step 2: Place the tire blank in the vulcanizing machine, introduce low-pressure saturated steam, pre-vulcanize at 125℃ for 6.5 minutes, then increase the steam pressure and vulcanize at 155℃ for 25 minutes. After vulcanization, turn off the steam, cool, demold, and obtain the finished product. The preparation process of modified carbon fiber is as follows: A1: 11 parts of cleaned carbon fiber were placed in 55 parts of nitric acid solution (concentration 35wt%) and soaked at 55℃ for 4.5h. After removal, washing and drying were performed to obtain pretreated carbon fiber. Subsequently, it was transferred to 11 parts of γ-aminopropyltriethoxysilane aqueous solution (concentration 2.5wt%), ultrasonically dispersed for 35min, and the temperature was raised to 65℃ for 5.5h. After the reaction was completed, it was washed and dried to obtain modified carbon fiber. Testing experiment: (1) The wear resistance of the finished tires obtained in the examples and comparative examples was tested in accordance with the standard GB / T22391-2017; (2) The tensile strength of the finished tires obtained in the examples and comparative examples was tested in accordance with standard GB / T10824-2008; (3) After aging in an oven at 150℃ for 72 hours, the tensile strength retention rate was tested; The obtained data is shown in the table below:

[0028] Conclusion: This invention successfully prepared a high-wear-resistant solid rubber tire by optimizing the formula and process, and its performance is significantly superior to traditional products. According to experimental data, the wear resistance indices of Examples 1-3 reached 488, 479, and 492, respectively, and the tensile strengths were 27.8 MPa, 26.7 MPa, and 27.9 MPa, respectively. The tensile strength retention rate after aging was over 92%, and all indicators were significantly better than those of Comparative Example 1 (wear resistance index 320, tensile strength 21.5 MPa, retention rate 75.6%) without modified carbon fiber and Comparative Example 2 (wear resistance index 405, tensile strength 24.2 MPa, retention rate 85.2%) using only aminated carbon fiber.

[0029] Specifically, the introduction of modified carbon fibers, through surface-grafted modified copolymers, forms stable covalent bonds and a three-dimensional network structure with the rubber matrix. This not only significantly improves the tire's wear resistance and mechanical strength but also enhances thermal stability through the DOPO phosphaphenanthrene structure and borate ester bonds, effectively inhibiting high-temperature aging. Among these, Example 3 exhibits the best overall performance, indicating that its formulation and process parameters are more reasonable.

[0030] In summary, this invention achieves a comprehensive improvement in tire performance through innovative material modification and process design, especially in terms of wear resistance, mechanical strength, and thermal stability, demonstrating significant technical advantages and practical value.

[0031] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A high-wear-resistant solid rubber tire, characterized in that, It includes the following components by weight: 90-100 parts natural rubber, 60-70 parts styrene-butadiene rubber, 10-20 parts epoxidized natural rubber, 2-3 parts zinc oxide, 40-50 parts carbon black, 1-2 parts stearic acid, 10-12 parts modified carbon fiber, 1-2 parts antioxidant, 1-2 parts vulcanizing material, and 0.8-1.5 parts accelerator.

2. The high wear-resistant solid rubber tire according to claim 1, characterized in that, The preparation process of the modified carbon fiber is as follows: A1: The cleaned carbon fibers are placed in a nitric acid solution and soaked at 50-60℃ for 4-5 hours. After removal, they are washed and dried to obtain pretreated carbon fibers. Subsequently, they are transferred to an aqueous solution of γ-aminopropyltriethoxysilane, ultrasonically dispersed for 30-40 minutes, and the temperature is raised to 60-70℃ for 5-6 hours. After the reaction is completed, they are washed and dried to obtain aminated carbon fibers. A2: Add the modified copolymer to N,N-dimethylformamide and stir for 10-12 hours. Then add the aminated carbon fiber, ultrasonically disperse for 30-40 minutes, raise the temperature to 60-70℃, react for 6-7 hours, and dry to obtain the modified carbon fiber.

3. A high wear-resistant solid rubber tire according to claim 2, characterized in that, The raw materials for preparing the aminated carbon fiber include the following components: by weight, 10-12 parts carbon fiber, 50-60 parts nitric acid solution, and 10-12 parts aqueous solution of γ-aminopropyltriethoxysilane; wherein, the concentration of the nitric acid solution is 35 wt%; and the concentration of the aqueous solution of γ-aminopropyltriethoxysilane is 2.5 wt%.

4. A high wear-resistant solid rubber tire according to claim 2, characterized in that, The raw materials for preparing the modified carbon fiber include the following components: by weight, 2-3 parts of modified copolymer, 10-30 parts of N,N-dimethylformamide, and 10-12 parts of aminated carbon fiber.

5. A high wear-resistant solid rubber tire according to claim 2, characterized in that, The preparation process of the modified copolymer is as follows: S1: Mix 3,5-diamino-1,2,4-triazole, 3,4-dihydroxybenzaldehyde, and anhydrous ethanol, raise the temperature to 85°C, reflux and stir for 3-4 hours, then add 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, continue the reaction at 85°C for 3-4 hours, then add 1,4-phenylenediboric acid, stir for 30-40 minutes, the reaction is complete, filter, wash, and dry to obtain intermediate A; S2: Mix intermediate A, triethylamine, and anhydrous tetrahydrofuran, stir evenly, keep the temperature at 0-5℃, slowly add acryloyl chloride solution, after the addition is complete, raise the temperature to room temperature, continue stirring for 2-3 hours, after the reaction is complete, perform post-processing to obtain the modified monomer. S3: Under a protective atmosphere, the modified monomer, glycidyl methacrylate, and vinyl acetate were added to N,N-dimethylformamide and stirred for 20-30 min. Then, azobisisobutyronitrile solution was slowly added, the temperature was raised to 70-80℃, and the reaction was carried out for 6-7 h. After the reaction was completed, the mixture was cooled to room temperature and post-treated to obtain the modified copolymer.

6. A high wear-resistant solid rubber tire according to claim 5, characterized in that, The raw materials for preparing intermediate A include the following components: by weight, 8-9 parts of 3,5-diamino-1,2,4-triazole, 13-14 parts of 3,4-dihydroxybenzaldehyde, 60-80 parts of anhydrous ethanol, 21-22 parts of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and 8-10 parts of 1,4-phenylenediboronic acid.

7. A high wear-resistant solid rubber tire according to claim 5, characterized in that, The raw materials for preparing the modified monomer include the following components: by weight, 20-22 parts intermediate A, 7-8 parts triethylamine, 150-200 parts anhydrous tetrahydrofuran, and 10-15 parts acryloyl chloride solution; wherein the concentration of the acryloyl chloride solution is 12 wt%.

8. A high wear-resistant solid rubber tire according to claim 5, characterized in that, The raw materials for preparing the modified copolymer include the following components: by weight, 20-25 parts of modified monomer, 15-20 parts of glycidyl methacrylate, 10-15 parts of vinyl acetate, 120-150 parts of N,N-dimethylformamide, and 3-5 parts of azobisisobutyronitrile solution; wherein the concentration of the azobisisobutyronitrile solution is 10 wt%.

9. A method for preparing a high wear-resistant solid rubber tire, used to prepare the high wear-resistant solid rubber tire according to any one of claims 1-8, characterized in that, Includes the following steps: Step 1: Mix natural rubber, styrene-butadiene rubber, and epoxidized natural rubber at 50-70℃ for 4-5 minutes. Add zinc oxide and stearic acid and mix at 70-90℃ for 3-4 minutes. Then add carbon black, antioxidant, and modified carbon fiber and mix at 100-120℃ for 5-7 minutes. Then cool down to 90-100℃ and add vulcanizing materials and accelerators in sequence. Mix quickly for 2-3 minutes until uniform. Quickly discharge the rubber, cool, and transfer it to a mold to make tire blanks. Step 2: Place the tire blank in the vulcanizing machine, introduce low-pressure saturated steam, and pre-vulcanize at 120-130℃ for 5-8 minutes. Then increase the steam pressure and vulcanize at 150-160℃ for 20-30 minutes. After vulcanization, turn off the steam, cool, demold, and obtain the finished product.

10. The method for preparing a high wear-resistant solid rubber tire according to claim 9, characterized in that, The vulcanizing material is sulfur.

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