Tire material with high-temperature-resistant and wear-resistant functions and preparation method thereof

Abstract

The invention provides a tire material with high-temperature-resistant and wear-resistant functions and a preparation method thereof. The tire material with the high-temperature-resistant and wear-resistant functions is prepared from the following components in parts by mass: 30 to 50 parts of natural rubber, 10 to 30 parts of butadiene styrene rubber, 10 to 20 parts of isoprene rubber, 20 to 30 parts of carbon black, 15 to 30 parts of modified white carbon black, 2 to 5 parts of zinc oxide, 1 to 3 parts of stearic acid, 1 to 3 parts of sulfur and 1 to 2 parts of accelerant, wherein the modified white carbon black is obtained by reacting white carbon black with an amino silane coupling agent and then reacting with epoxy group star-shaped polybutadiene. Toughening modification and compatibility improvement of the white carbon black are achieved, the mechanical property, wear resistance and heat resistance of the tire can be improved, the technical problems in current tire materials are solved, and the material has important significance in promoting technical upgrading and high-quality development of the tire industry.

Description

Technical Field

[0001] This invention relates to the field of tire material technology, and in particular to a tire material with high temperature resistance and wear resistance and its preparation method. Background Technology

[0002] With the rapid development of the automotive industry, the market has placed increasingly higher demands on the comprehensive performance of tires. Tires not only need to have excellent mechanical properties to ensure structural stability and load-bearing capacity during driving, but also need to have good wear resistance and heat resistance to extend service life, reduce replacement frequency, and improve safety under high-temperature driving conditions.

[0003] In tire compounding systems, reinforcing fillers are a key component determining tire performance. Silica, due to its large specific surface area, excellent reinforcing effect, and ability to effectively reduce rolling resistance, is widely used in the production of green and energy-saving tires. However, the presence of numerous hydroxyl groups on the surface of silica results in its high polarity, leading to poor compatibility with the non-polar rubber matrix. This makes it prone to agglomeration in rubber, hindering its reinforcing effect and consequently affecting the tire's mechanical properties. Furthermore, unmodified silica exhibits weak interfacial bonding with rubber, making it susceptible to separation under long-term friction and high-temperature conditions. This results in tires failing to meet the wear resistance and heat resistance requirements of high-end tires.

[0004] To improve the compatibility of silica and rubber, existing technologies often employ silane coupling agents for surface modification, enhancing the interfacial bonding between silica and rubber through the bridging effect of the coupling agent. However, traditional silane coupling agent modification methods have significant shortcomings: firstly, the modified silica only offers limited improvement in compatibility, with limited enhancement of tire mechanical properties, particularly in toughening; secondly, the modified structure exhibits poor thermal stability, easily decomposing at high temperatures and failing to effectively guarantee the long-term heat resistance of tires. Furthermore, some modification methods suffer from complex processes, high costs, and poor environmental performance, hindering large-scale industrial application.

[0005] Therefore, there is an urgent need to develop a new technical solution to address the problems existing in the current technology. Summary of the Invention

[0006] To address the problems existing in the prior art, this invention develops a tire material with high-temperature resistance and wear resistance, as well as its preparation method. Grafting epoxy-based star-shaped polybutadiene with silica improves the toughening modification and compatibility of silica. The synergistic effect of multiple components enhances the tire's mechanical properties, wear resistance, and heat resistance, solving a current technical challenge in tire materials and playing a significant role in promoting technological upgrading and high-quality development in the tire industry.

[0007] One object of the present invention is to provide a tire material with high temperature resistance and wear resistance, wherein the tire material with high temperature resistance and wear resistance comprises the following components in parts by weight: 30-50 parts natural rubber 10-30 parts of styrene-butadiene rubber 10-20 parts of isoprene rubber 20-30 parts carbon black 15-30 parts modified silica 2-5 parts zinc oxide 1-3 parts stearic acid 1-3 parts sulfur Accelerator 1-2 parts; The modified silica is obtained by reacting silica with an aminosilane coupling agent and then with epoxy star-shaped polybutadiene.

[0008] Furthermore, the carbon black undergoes surface activation treatment.

[0009] Furthermore, the tire material with high temperature resistance and wear resistance also includes 1-5 parts of additives.

[0010] Furthermore, the additive is selected from one or more of antioxidants, initiators, catalysts, dispersants, plasticizers, toughening agents, and anti-scorching agents.

[0011] Another object of the present invention is to provide a method for preparing the above-mentioned tire material with high temperature resistance and wear resistance, wherein the method for preparing the tire material with high temperature resistance and wear resistance includes the following steps: S1. Butadiene and initiator are mixed and heated to react. Then silicon tetrachloride is added and the reaction continues. Formic acid and hydrogen peroxide are then added and the reaction is stirred to obtain epoxy star-shaped polybutadiene. S2. Mix silica and aminosilane coupling agent, heat and react to obtain intermediate product, then mix the intermediate product, epoxy star polybutadiene and catalyst, heat and react to obtain modified silica; S3. Mix and masticate natural rubber, styrene-butadiene rubber, and isoprene rubber; S4. Add carbon black, modified silica, zinc oxide and stearic acid and mix. S5. Add sulfur and accelerators, mix and vulcanize to obtain tire material with high temperature resistance and wear resistance.

[0012] Further, in step S1, the molar ratio of butadiene, initiator and silicon tetrachloride is (350-400):1:(0.1-1).

[0013] Further, in step S2, the mass ratio of the intermediate product to the epoxy star-shaped polybutadiene is 10:(0.5-2).

[0014] Furthermore, in step S1, the temperature of the heating reaction is 40-60°C.

[0015] Furthermore, in step S2, the temperature of the heating reaction is 70-100℃.

[0016] The present invention has the following beneficial effects: This invention provides a tire material with high-temperature and wear-resistant properties, which is a compound of modified silica, natural rubber, styrene-butadiene rubber, isoprene rubber, and carbon black. The modified silica is obtained by reacting branched epoxy star-shaped polybutadiene with amino-modified silica. The modified silica exhibits better dispersibility and enhanced affinity with the matrix rubber, thus improving the wear resistance provided by silica. Simultaneously, the branched star-shaped polybutadiene segments can form physical entanglement with the rubber, while the epoxy groups chemically crosslink with the rubber matrix during vulcanization, allowing the various components to fully combine and obtain a more stable and complex three-dimensional network structure, further improving the material's strength and toughness.

[0017] The present invention also performs surface activation treatment on carbon black, introducing a large number of carboxyl functional groups, which can react with active groups such as epoxy, hydroxyl, and amino groups in modified silica and rubber and generate intermolecular forces, so that carbon black and other components form an integrated structure. This not only prevents carbon black from falling off and improves wear resistance, but also promotes the formation of a heat-resistant skeleton, effectively improving the overall performance of the tire. Detailed Implementation

[0018] To more clearly illustrate the technical solution of the present invention, the following embodiments are provided. Unless otherwise stated, the raw materials, reactions, and post-processing methods appearing in the embodiments are all commercially available raw materials and technical methods well known to those skilled in the art.

[0019] The terms "preferred," "more preferably," and "more suitable" used in this invention refer to embodiments of the invention that provide certain beneficial effects under certain circumstances. However, other embodiments may also be preferred under the same or other circumstances. Furthermore, the description of one or more preferred embodiments does not imply that other embodiments are unavailable, nor is it intended to exclude other embodiments from the scope of this invention.

[0020] It should be understood that, except in any operational instance or otherwise indicated, all figures representing the amounts of ingredients used, for example, in the specification and claims, should be understood to be modified in all cases by the term "about". Therefore, unless otherwise stated, the numerical parameters set forth in the following specification and appended claims are approximations varying with the desired performance to be obtained according to the invention.

[0021] The carbon black in this embodiment of the invention undergoes surface activation treatment, including the following steps: N330 carbon black and concentrated nitric acid (68 wt%) were mixed at a mass ratio of 1:10 and refluxed for 3 h. After the reaction was completed, the upper acid layer was discarded, and the mixture was washed with deionized water until neutral. After filtration, the mixture was dried at 110 °C to obtain the product. Example 1

[0022] A tire material with high temperature resistance and wear resistance, wherein the tire material with high temperature resistance and wear resistance comprises the following components in parts by weight: 40 parts natural rubber 20 parts of styrene-butadiene rubber 10 parts of isoprene rubber 20 parts carbon black 15 parts modified silica 3 parts zinc oxide 2 parts stearic acid 2 parts sulfur Accelerator CBS 1 part Accelerator TMTD 0.5 parts Anti-aging agent 4010NA 2 parts; The method for preparing the tire material with high temperature resistance and wear resistance includes the following steps: S1. Using cyclohexane as solvent, under a nitrogen atmosphere, butadiene, tetrahydrofuran as regulator and n-butyllithium as initiator are mixed and reacted at 50°C for 3 h. Then, silicon tetrachloride is added and a coupling reaction is carried out at 50°C for 3 h. Finally, sufficient isopropanol is added to terminate the reaction. After removing the solvent by vacuum distillation, star-shaped polybutadiene is obtained. The molar ratio of butadiene, tetrahydrofuran, n-butyllithium, and silicon tetrachloride is 370:0.1:1:0.3. Using toluene as a solvent, the star-shaped polybutadiene, formic acid aqueous solution (concentration 88 wt%) and hydrogen peroxide (concentration 30 wt%) were mixed and reacted at 50°C for 2 h. The mixture was washed until neutral, and then the solvent was removed by vacuum distillation and dried to obtain epoxy star-shaped polybutadiene. The mass ratio of star-shaped polybutadiene, formic acid, and hydrogen peroxide is 1000:23:13.6. S2. Mix KH-550, water and ethanol in a mass ratio of 2:10:88, then add silica (KH-550 and silica in a mass ratio of 2:10), sonicate for 30 min, then react at 80℃ for 10 h, filter, wash and dry to obtain intermediate product. Using toluene as solvent, the intermediate product, epoxy star-shaped polybutadiene, and catalyst 4-dimethylaminopyridine were mixed in a mass ratio of 10:2:0.1 and reacted at 95°C for 5 h. After filtration and drying, modified silica was obtained. S3. According to the above mass proportions, natural rubber, styrene-butadiene rubber and isoprene rubber are mixed and added to an internal mixer, and plasticized at 120°C for 3 min to obtain plasticized rubber; S4. Add the plasticized rubber, carbon black, modified silica, zinc oxide, stearic acid and antioxidant to a mixer and mix at 150°C for 5 min to obtain the plasticized rubber. S5. Add the intensively mixed rubber, sulfur and accelerator to a two-roll mill, mix at 55°C for 5 min, cool for 24 h, and vulcanize at 150°C for 25 min to obtain a tire material with high temperature resistance and wear resistance. Example 2

[0023] A tire material with high temperature resistance and wear resistance, wherein the tire material with high temperature resistance and wear resistance comprises the following components in parts by weight: 45 parts natural rubber 22 parts of styrene-butadiene rubber 11 parts of isoprene rubber 22 parts carbon black 18 parts modified silica 3.5 parts zinc oxide Stearic acid 2.4 parts 2.4 parts sulfur Accelerator CBS 1.2 parts Accelerator TMTD 0.5 parts Anti-aging agent 4010NA 2 parts; The method for preparing the tire material with high temperature resistance and wear resistance includes the following steps: S1. Using cyclohexane as solvent, under a nitrogen atmosphere, butadiene, tetrahydrofuran as regulator and n-butyllithium as initiator are mixed and reacted at 50°C for 3 h. Then, silicon tetrachloride is added and a coupling reaction is carried out at 50°C for 3 h. Finally, sufficient isopropanol is added to terminate the reaction. After removing the solvent by vacuum distillation, star-shaped polybutadiene is obtained. The molar ratio of butadiene, tetrahydrofuran, n-butyllithium, and silicon tetrachloride is 370:0.1:1:0.3. Using toluene as a solvent, the star-shaped polybutadiene, formic acid aqueous solution (concentration 88 wt%) and hydrogen peroxide (concentration 30 wt%) were mixed and reacted at 50°C for 2 h. The mixture was washed until neutral, and then the solvent was removed by vacuum distillation and dried to obtain epoxy star-shaped polybutadiene. The mass ratio of star-shaped polybutadiene, formic acid, and hydrogen peroxide is 1000:23:13.6. S2. Mix KH-550, water and ethanol in a mass ratio of 2:10:88, then add silica (KH-550 and silica in a mass ratio of 2:10), sonicate for 30 min, then react at 80℃ for 10 h, filter, wash and dry to obtain intermediate product. Using toluene as solvent, the intermediate product, epoxy star-shaped polybutadiene, and catalyst 4-dimethylaminopyridine were mixed in a mass ratio of 10:2:0.1 and reacted at 95°C for 5 h. After filtration and drying, modified silica was obtained. S3. According to the above mass proportions, natural rubber, styrene-butadiene rubber and isoprene rubber are mixed and added to an internal mixer, and plasticized at 120°C for 3 min to obtain plasticized rubber; S4. Add the plasticized rubber, carbon black, modified silica, zinc oxide, stearic acid and antioxidant to a mixer and mix at 150°C for 5 min to obtain the plasticized rubber. S5. Add the intensively mixed rubber, sulfur and accelerator to a two-roll mill, mix at 55°C for 5 min, cool for 24 h, and vulcanize at 150°C for 25 min to obtain a tire material with high temperature resistance and wear resistance. Example 3

[0024] A tire material with high temperature resistance and wear resistance, wherein the tire material with high temperature resistance and wear resistance comprises the following components in parts by weight: 50 parts natural rubber 25 parts of styrene-butadiene rubber 12 parts of isoprene rubber 25 parts carbon black 25 parts modified silica 3.6 parts zinc oxide 2.5 parts stearic acid Sulfur 2.6 parts Accelerator CBS 1.5 parts Accelerator TMTD 0.5 parts Antioxidant 4010NA 2.5 parts; The method for preparing the tire material with high temperature resistance and wear resistance includes the following steps: S1. Using cyclohexane as solvent, under a nitrogen atmosphere, butadiene, tetrahydrofuran as regulator and n-butyllithium as initiator are mixed and reacted at 50°C for 3 h. Then, silicon tetrachloride is added and a coupling reaction is carried out at 50°C for 3 h. Finally, sufficient isopropanol is added to terminate the reaction. After removing the solvent by vacuum distillation, star-shaped polybutadiene is obtained. The molar ratio of butadiene, tetrahydrofuran, n-butyllithium, and silicon tetrachloride is 370:0.1:1:0.3. Using toluene as a solvent, the star-shaped polybutadiene, formic acid aqueous solution (concentration 88 wt%) and hydrogen peroxide (concentration 30 wt%) were mixed and reacted at 50°C for 2 h. The mixture was washed until neutral, and then the solvent was removed by vacuum distillation and dried to obtain epoxy star-shaped polybutadiene. The mass ratio of star-shaped polybutadiene, formic acid, and hydrogen peroxide is 1000:23:13.6. S2. Mix KH-550, water and ethanol in a mass ratio of 2:10:88, then add silica (KH-550 and silica in a mass ratio of 2:10), sonicate for 30 min, then react at 80℃ for 10 h, filter, wash and dry to obtain intermediate product. Using toluene as solvent, the intermediate product, epoxy star-shaped polybutadiene, and catalyst 4-dimethylaminopyridine were mixed in a mass ratio of 10:2:0.1 and reacted at 95°C for 5 h. After filtration and drying, modified silica was obtained. S3. According to the above mass proportions, natural rubber, styrene-butadiene rubber and isoprene rubber are mixed and added to an internal mixer, and plasticized at 120°C for 3 min to obtain plasticized rubber; S4. Add the plasticized rubber, carbon black, modified silica, zinc oxide, stearic acid and antioxidant to a mixer and mix at 150°C for 5 min to obtain the plasticized rubber. S5. Add the intensively mixed rubber, sulfur and accelerator to a two-roll mill, mix at 55°C for 5 min, cool for 24 h, and vulcanize at 150°C for 25 min to obtain a tire material with high temperature resistance and wear resistance.

[0025] Comparative Example 1 A tire material, the difference between this comparative example and Example 1 is that the carbon black was not surface activated, while the other components and preparation methods are the same as in Example 1.

[0026] Comparative Example 2 A tire material, the difference between this comparative example and Example 1 is that step S1 is deleted, step S2 only prepares the intermediate product, the intermediate product is used as modified silica, and the other components and preparation methods are the same as in Example 1.

[0027] Test case Test methods: Mechanical properties and abrasion resistance were tested according to GB / T 528-2009 and GB / T 1689-2014.

[0028] After aging the sample at 100℃ for 72 h, the tensile strength was retested.

[0029] The test results are shown in Table 1.

[0030] Table 1 Performance Test Results

[0031] Table 1 shows that the tire material with high-temperature and wear-resistant properties prepared in the embodiments of the present invention has high tensile strength and elongation at break, minimal performance degradation after aging, and excellent wear resistance. In contrast, the carbon black in Comparative Example 1, without activation treatment, exhibited agglomeration and uneven dispersion, significantly impacting the material's mechanical properties, heat resistance, and wear resistance. The silica in Comparative Example 2, lacking treatment with silane coupling agents, struggled to form sufficient crosslinks and synergistic effects with other components, also affecting its strength, heat resistance, and wear resistance. In summary, the tire material with high-temperature and wear-resistant properties provided by the present invention overcomes the problems existing in the prior art and has promising application prospects.

[0032] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.

[0033] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A tire material with high temperature resistance and wear resistance, characterized in that, The tire material with high temperature resistance and wear resistance comprises the following components in parts by weight: 30-50 parts natural rubber 10-30 parts of styrene-butadiene rubber 10-20 parts of isoprene rubber 20-30 parts carbon black 15-30 parts modified silica 2-5 parts zinc oxide 1-3 parts stearic acid 1-3 parts sulfur Accelerator 1-2 parts; The modified silica is obtained by reacting silica with an aminosilane coupling agent and then with epoxy star-shaped polybutadiene.

2. The tire material with high temperature resistance and wear resistance according to claim 1, characterized in that, The carbon black undergoes surface activation treatment.

3. The tire material with high temperature resistance and wear resistance according to claim 1, characterized in that, The tire material with high temperature resistance and wear resistance also includes 1-5 parts of additives.

4. The tire material with high temperature resistance and wear resistance according to claim 3, characterized in that, The additives are selected from one or more of the following: antioxidants, initiators, catalysts, dispersants, plasticizers, toughening agents, and anti-scorching agents.

5. A method for preparing the tire material with high-temperature resistance and wear resistance as described in any one of claims 1-4, characterized in that, The method for preparing the tire material with high temperature resistance and wear resistance includes the following steps: S1. Butadiene and initiator are mixed and heated to react. Then silicon tetrachloride is added and the reaction continues. Formic acid and hydrogen peroxide are then added and the reaction is stirred to obtain epoxy star-shaped polybutadiene. S2. Mix silica and aminosilane coupling agent, heat and react to obtain intermediate product, then mix the intermediate product, epoxy star polybutadiene and catalyst, heat and react to obtain modified silica; S3. Mix and masticate natural rubber, styrene-butadiene rubber, and isoprene rubber; S4. Add carbon black, modified silica, zinc oxide and stearic acid and mix. S5. Add sulfur and accelerators, mix and vulcanize to obtain tire material with high temperature resistance and wear resistance.

6. The method for preparing the tire material with high temperature resistance and wear resistance according to claim 5, characterized in that, In step S1, the molar ratio of butadiene, initiator and silicon tetrachloride is (350-400):1:(0.1-1).

7. The method for preparing the tire material with high temperature resistance and wear resistance according to claim 5, characterized in that, In step S2, the mass ratio of the intermediate product to the epoxy star-shaped polybutadiene is 10:(0.5-2).

8. The method for preparing the tire material with high temperature resistance and wear resistance according to claim 5, characterized in that, In step S1, the temperature of the heating reaction is 40-60℃.

9. The method for preparing the tire material with high temperature resistance and wear resistance according to claim 6, characterized in that, In step S2, the temperature of the heating reaction is 70-100℃.

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