Rubber material for wear-resistant tire and preparation method of rubber material

Abstract

The invention relates to the technical field of rubber materials, and discloses a rubber material for a wear-resistant tire and a preparation method thereof.The preparation method comprises the following steps that butadiene rubber is placed on an open mill and plastified at 50-60 DEG C, the plastifying time is 10-15 min, the plastified butadiene rubber is put into an internal mixer, the internal mixer is started, the rotating speed is controlled to be 20-30 r / min, the temperature is controlled to be 80-100 DEG C, and the rubber material for the wear-resistant tire is obtained; the preparation method comprises the following steps: sequentially adding modified nano silicon dioxide, white carbon black and a vanillin flame retardant, mixing for 5-10 minutes, finally adding sulfur and a coupling agent KH-570, continuously mixing for 2-3 minutes, standing the mixed rubber material for 8-12 hours, vulcanizing for 10-20 minutes at the temperature of 140-160 DEG C and the pressure of 10-15 MPa, and demolding to obtain the rubber material for the wear-resistant tire. The rubber material disclosed by the invention has good wear resistance and flame retardance.

Description

Technical Field

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

[0002] Rubber, as a fundamental material for national strategy, plays an irreplaceable role in numerous fields. Automobiles, airplanes, trains, and ships all rely on rubber tires. They not only provide cushioning and shock absorption, ensuring smooth driving and passenger comfort, but also possess excellent anti-skid and grip properties, ensuring driving safety. However, the global waste of resources and the problem of waste disposal caused by tire wear each year are severe, leading to a higher frequency of tire replacements, which is inconsistent with sustainable development goals. Therefore, avoiding this phenomenon is key to solving the problem. For example, patent CN114716744A discloses an environmentally friendly bio-based L-cysteine ​​tire rubber. Its preparation method is as follows: first, hydroxylated carbon nanotubes are prepared; then, environmentally friendly bio-based L-cysteine ​​is added to the dispersed hydroxylated carbon nanotube solution, and a coupling oligomer is obtained through a solvothermal reaction; compressed air at 2-5 MPa is introduced into the raw rubber at 60-70℃ to obtain plasticized raw rubber; paraffin wax and plasticized raw rubber are mixed at 120-180℃ to obtain a rubber compound, which is then extruded through a rubber extrusion mechanism to obtain a molded rubber compound; finally, the molded rubber compound is mixed with the coupling oligomer and solvent, and vulcanized to obtain the environmentally friendly bio-based L-cysteine ​​tire rubber material. This invention's rubber material has good mechanical properties and biodegradability, but its wear resistance and flame retardancy need improvement. Summary of the Invention

[0003] (a) Technical problems to be solved

[0004] To address the shortcomings of existing technologies, this invention provides a wear-resistant tire rubber material and its preparation method. The rubber material of this invention has good wear resistance and flame retardancy.

[0005] (II) Technical Solution

[0006] To achieve the above objectives, the present invention provides the following technical solution: a rubber material for wear-resistant tires, comprising the following weight components: 60-80 parts by weight of butadiene rubber, 1-2 parts by weight of vanillin flame retardant, 1-1.5 parts by weight of modified nano-silica, 12-16 parts by weight of silica, 0.6-0.8 parts by weight of sulfur, and 1-2 parts by weight of coupling agent KH-570.

[0007] Furthermore, the preparation method of the vanillin flame retardant is as follows:

[0008] Step 1: Under inert gas protection, vanillin and glycidyl methacrylate were added to a tetrahydrofuran solution and stirred. Then, triethylamine catalyst and hydroquinone polymerization inhibitor were added. The mixture was stirred continuously for 6-8 hours in an oil bath at 70-75℃. After the reaction was completed, the pH was adjusted to neutral with dilute hydrochloric acid, and the mixture was purified by rotary evaporation, column chromatography, and drying to obtain intermediate 1.

[0009] Step 2: Add sulfaguanidine to a reactor containing anhydrous ethanol. After it is completely dissolved, add intermediate 1 and stir the reaction at 75-85℃ for 8-10 hours. Then add 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and react at 70-80℃ for 16-20 hours. After the reaction is completed, cool, filter and dry to obtain intermediate 2.

[0010] Step 3: Add intermediate 2,3-(methacryloyloxy)propyltrimethoxysilane to N,N-dimethylformamide solvent for dissolution. After dissolution, add azobisisobutyronitrile initiator and react at 65-75℃ for 3-5 hours. After reaction, remove the solvent by vacuum distillation, filter, wash and dry to obtain intermediate 3.

[0011] Step 4: Add intermediate 3 and natural fibrous mineral sepiolite to anhydrous ethanol, stir well, then add ammonia catalyst, and react at 70-80℃ for 6-8 hours. After the reaction is complete, centrifuge, wash and dry to obtain vanillin flame retardant.

[0012] Furthermore, in step one, the ratio of tetrahydrofuran, vanillin, glycidyl methacrylate, triethylamine, and hydroquinone is 28-30 mL: 1.52-1.55 g: 1.41-1.44 g: 0.03-0.05 g: 0.01-0.02 g.

[0013] Furthermore, in step two, the ratio of sulfaguanidine, anhydrous ethanol, intermediate 1, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 4.14-4.18 g: 45-50 mL: 3.05-3.08 g: 2.48-2.51 g.

[0014] Furthermore, in step three, the ratio of N,N-dimethylformamide, intermediate 2,3-(methacryloyloxy)propyltrimethoxysilane, and azobisisobutyronitrile is 30-35 mL: 3.49-3.54 g: 3.76-3.78 mL: 0.21-0.24 g.

[0015] Furthermore, in step four, the ratio of anhydrous ethanol, intermediate 3, natural fibrous mineral sepiolite, and ammonia is 90-100mL:2.53-2.58g:4.02-4.06g:0.1-0.12mL.

[0016] Furthermore, the preparation method of the modified nano silica is as follows: nano silica is added to deionized water, the pH value is adjusted to 3-4 with dilute hydrochloric acid, stirred evenly, and then phenyltrimethoxysilane is added. The reaction is carried out at 75-80℃ for 2-4 hours. After the reaction is completed, the mixture is filtered, washed and dried to obtain modified nano silica.

[0017] Furthermore, the ratio of the nano-silica, deionized water, and phenyltrimethoxysilane used is 4.65-4.68g:15-20mL:16.2-16.5g.

[0018] Further, the preparation method of the wear-resistant tire rubber material is as follows: Butadiene rubber is placed on a two-roll mill and plasticized at 50-60℃ for 10-15 minutes. The plasticized butadiene rubber is then fed into an internal mixer. The internal mixer is started, and the speed is controlled at 20-30 r / min and the temperature at 80-100℃. Modified nano-silica, silica, and vanillin flame retardant are added sequentially, and the mixing time is 5-10 minutes. Finally, sulfur and coupling agent KH-570 are added, and the mixing continues for 2-3 minutes. The mixed rubber compound is allowed to stand for 8-12 hours and vulcanized at 140-160℃ and 10-15 MPa for 10-20 minutes. The rubber material is then demolded to obtain the wear-resistant tire rubber material.

[0019] (III) Beneficial Technical Effects

[0020] This invention modifies nano-silica with phenyltrimethoxysilane. The methoxy group of phenyltrimethoxysilane can be hydrolyzed to silanol groups, which condense with the hydroxyl groups on the surface of nano-silica to form Si-O-Si covalent bonds, thus enhancing the interfacial chemical bonding. Furthermore, phenyltrimethoxysilane, nano-silica, and the sulfur crosslinking network in rubber interpenetrate to form a "rigid island-flexible sea" structure. During wear, the surface low-crosslinked regions are preferentially sacrificed to protect the main material, further improving the wear resistance of the material. The fibrous structure of sepiolite can form a dense network during combustion, delaying the diffusion of pyrolysis gases. The Mg it contains... 2+ It can promote the cross-linking of rubber molecular chains into carbon, forming a heat-insulating carbon layer. Vanillin condenses at around 300℃ to form a polyphenol structure, which, together with sepiolite, enhances the stability of the carbon layer. The two can work together to play a flame-retardant role. When heated, the phosphorus element in vanillin flame retardant produces acidic substances such as phosphoric acid and metaphosphoric acid, which can promote the dehydration of materials into carbon. Furthermore, these acidic substances can also further polyphosphoric acid cover the surface of the material, achieving a flame-retardant effect. Attached Figure Description

[0021] Figure 1 This is the 1H NMR spectrum of intermediate 1 in Example 1.

[0022] Figure 2 This is the 1H NMR spectrum of intermediate 2 in Example 1. Detailed Implementation

[0023] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are described clearly and completely. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0024] To better understand the above technical solutions, the following will provide a detailed explanation of the technical solutions in conjunction with the accompanying drawings and specific embodiments.

[0025] Example 1

[0026] (1) Under nitrogen protection, 1.52 g of vanillin and 1.41 g of glycidyl methacrylate were added to 28 mL of tetrahydrofuran solution and stirred. Then, 0.03 g of triethylamine catalyst and 0.01 g of hydroquinone polymerization inhibitor were added. The mixture was stirred continuously for 6 h in an oil bath at 70 °C. After the reaction was completed, the pH was adjusted to neutral with dilute hydrochloric acid, and the mixture was purified by rotary evaporation, column chromatography, and drying to obtain intermediate 1. The reaction process is as follows:

[0027]

[0028] (2) 4.14 g of sulfanilamide guanidine was added to a reactor containing 45 mL of anhydrous ethanol. After complete dissolution, 3.05 g of intermediate 1 was added, and the mixture was stirred at 75 °C for 8 h. Then, 2.48 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was added, and the mixture was reacted at 70 °C for 16 h. After the reaction was completed, the mixture was cooled, filtered, and dried to obtain intermediate 2. The reaction process is as follows:

[0029]

[0030] (3) Add 3.49 g of intermediate 2 and 3.76 mL of 3-(methacryloyloxy)propyltrimethoxysilane to 30 mL of N,N-dimethylformamide solvent for dissolution. After dissolution, add 0.21 g of azobisisobutyronitrile initiator and react at 65 °C for 3 h. After the reaction, remove the solvent by vacuum distillation, filter, wash and dry to obtain intermediate 3.

[0031] (4) Add 2.53g of intermediate 3 and 4.02g of natural fibrous mineral sepiolite to 90mL of anhydrous ethanol, stir evenly, then add 0.1mL of ammonia catalyst, and react at 70℃ for 6h. After the reaction is completed, centrifuge, wash and dry to obtain vanillin flame retardant.

[0032] (5) Add 4.65g of nano silica to 15mL of deionized water, adjust the pH value to 3 with dilute hydrochloric acid, stir evenly, then add 16.2g of phenyltrimethoxysilane, react at 75℃ for 2h, after the reaction is completed, filter, wash and dry to obtain modified nano silica.

[0033] (6) Place 60 parts by weight of butadiene rubber on a two-roll mill and plasticize it at 50°C for 10 minutes. Put the plasticized butadiene rubber into a mixer, turn on the mixer, control the speed at 20 r / min and the temperature at 80°C, add 1 part by weight of modified nano silica, 12 parts by weight of silica, and 1 part by weight of vanillin flame retardant in sequence, mix for 5 minutes, and finally add 0.6 parts by weight of sulfur and 1 part by weight of coupling agent KH-570, continue mixing for 2 minutes, let the mixed rubber compound stand for 8 hours, and vulcanize it at 140°C and 10 MPa for 10 minutes. Demold to obtain the rubber material for wear-resistant tires.

[0034] Example 2

[0035] (1) Under nitrogen protection, 1.55 g of vanillin and 1.44 g of glycidyl methacrylate were added to 30 mL of tetrahydrofuran solution and stirred. Then, 0.05 g of triethylamine catalyst and 0.02 g of hydroquinone polymerization inhibitor were added. The mixture was stirred continuously for 8 h in an oil bath at 75 °C. After the reaction was completed, the pH was adjusted to neutral with dilute hydrochloric acid, and the mixture was purified by rotary evaporation, column chromatography, and drying to obtain intermediate 1.

[0036] (2) Add 4.18 g of sulfanilamide to a reactor containing 50 mL of anhydrous ethanol. After it is completely dissolved, add 3.08 g of intermediate 1 and stir at 85 °C for 10 h. Then add 2.51 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and react at 80 °C for 20 h. After the reaction is completed, cool, filter and dry to obtain intermediate 2.

[0037] (3) Add 3.54 g of intermediate 2 and 3.78 mL of 3-(methacryloyloxy)propyltrimethoxysilane to 35 mL of N,N-dimethylformamide solvent for dissolution. After dissolution, add 0.24 g of azobisisobutyronitrile initiator and react at 75 °C for 5 h. After the reaction, remove the solvent by vacuum distillation, filter, wash and dry to obtain intermediate 3.

[0038] (4) Add 2.58g of intermediate 3 and 4.06g of natural fibrous mineral sepiolite to 100mL of anhydrous ethanol, stir evenly, then add 0.12mL of ammonia catalyst, and react at 80℃ for 8h. After the reaction is completed, centrifuge, wash and dry to obtain vanillin flame retardant.

[0039] (5) Add 4.68g of nano silica to 20mL of deionized water, adjust the pH value to 4 with dilute hydrochloric acid, stir evenly, then add 16.5g of phenyltrimethoxysilane, react at 80℃ for 4h, after the reaction is completed, filter, wash and dry to obtain modified nano silica.

[0040] (6) Place 80 parts by weight of butadiene rubber on a two-roll mill and plasticize it at 60°C for 15 minutes. Put the plasticized butadiene rubber into a mixer, turn on the mixer, control the speed at 30 r / min and the temperature at 100°C, and add 1.5 parts by weight of modified nano silica, 16 parts by weight of silica, and 2 parts by weight of vanillin flame retardant in sequence. Mix for 10 minutes. Finally, add 0.8 parts by weight of sulfur and 2 parts by weight of coupling agent KH-570, and continue mixing for 3 minutes. Let the mixed rubber compound stand for 12 hours, and vulcanize it at 160°C and 15 MPa for 20 minutes. Demold to obtain the rubber material for wear-resistant tires.

[0041] Example 3

[0042] (1) Under nitrogen protection, 1.53 g of vanillin and 1.42 g of glycidyl methacrylate were added to 29 mL of tetrahydrofuran solution and stirred. Then, 0.04 g of triethylamine catalyst and 0.01 g of hydroquinone polymerization inhibitor were added. The mixture was stirred continuously for 7 h in an oil bath at 72 °C. After the reaction was completed, the pH was adjusted to neutral with dilute hydrochloric acid, and the mixture was purified by rotary evaporation, column chromatography, and drying to obtain intermediate 1.

[0043] (2) Add 4.16 g of sulfaguanidine to a reactor containing 48 mL of anhydrous ethanol. After it is completely dissolved, add 3.06 g of intermediate 1 and stir at 80 °C for 9 h. Then add 2.5 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and react at 75 °C for 18 h. After the reaction is completed, cool, filter and dry to obtain intermediate 2.

[0044] (3) Add 3.52 g of intermediate 2 and 3.77 mL of 3-(methacryloyloxy)propyltrimethoxysilane to 32 mL of N,N-dimethylformamide solvent for dissolution. After dissolution, add 0.22 g of azobisisobutyronitrile initiator and react at 70 °C for 4 h. After the reaction, remove the solvent by vacuum distillation, filter, wash and dry to obtain intermediate 3.

[0045] (4) Add 2.55g of intermediate 3 and 4.04g of natural fibrous mineral sepiolite to 95mL of anhydrous ethanol, stir evenly, then add 0.11mL of ammonia catalyst, and react at 75℃ for 7h. After the reaction is completed, centrifuge, wash and dry to obtain vanillin flame retardant.

[0046] (5) Add 4.66g of nano silica to 18mL of deionized water, adjust the pH value to 3 with dilute hydrochloric acid, stir evenly, then add 16.3g of phenyltrimethoxysilane, react at 78℃ for 3h, after the reaction is completed, filter, wash and dry to obtain modified nano silica.

[0047] (6) Place 70 parts by weight of butadiene rubber on a two-roll mill and plasticize it at 55°C for 12 minutes. Put the plasticized butadiene rubber into a mixer, turn on the mixer, control the speed at 25 r / min and the temperature at 90°C, and add 1.2 parts by weight of modified nano silica, 14 parts by weight of silica, and 1 part by weight of vanillin flame retardant in sequence. Mix for 8 minutes. Finally, add 0.7 parts by weight of sulfur and 1 part by weight of coupling agent KH-570, and continue mixing for 2 minutes. Let the mixed rubber compound stand for 10 hours, and vulcanize it at 150°C and 12 MPa for 15 minutes. Demold to obtain the rubber material for wear-resistant tires.

[0048] Example 4

[0049] (1) Under nitrogen protection, 1.54 g of vanillin and 1.43 g of glycidyl methacrylate were added to 28 mL of tetrahydrofuran solution and stirred. Then, 0.03 g of triethylamine catalyst and 0.01 g of hydroquinone polymerization inhibitor were added. The mixture was stirred continuously for 6 h in an oil bath at 72 °C. After the reaction was completed, the pH was adjusted to neutral with dilute hydrochloric acid, and the mixture was purified by rotary evaporation, column chromatography, and drying to obtain intermediate 1.

[0050] (2) Add 4.15 g of sulfaguanidine to a reactor containing 46 mL of anhydrous ethanol. After it is completely dissolved, add 3.05 g of intermediate 1 and stir at 78 °C for 8 h. Then add 2.48 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and react at 72 °C for 17 h. After the reaction is completed, cool, filter and dry to obtain intermediate 2.

[0051] (3) Add 3.52 g of intermediate 2 and 3.76 mL of 3-(methacryloyloxy)propyltrimethoxysilane to 32 mL of N,N-dimethylformamide solvent for dissolution. After dissolution, add 0.22 g of azobisisobutyronitrile initiator and react at 68 °C for 4 h. After the reaction, remove the solvent by vacuum distillation, filter, wash and dry to obtain intermediate 3.

[0052] (4) Add 2.56g of intermediate 3 and 4.04g of natural fibrous mineral sepiolite to 93mL of anhydrous ethanol, stir evenly, then add 0.11mL of ammonia catalyst, and react at 72℃ for 6h. After the reaction is completed, centrifuge, wash and dry to obtain vanillin flame retardant.

[0053] (5) Add 4.65g of nano silica to 18mL of deionized water, adjust the pH value to 3 with dilute hydrochloric acid, stir evenly, then add 16.3g of phenyltrimethoxysilane, react at 76℃ for 3h, after the reaction is completed, filter, wash and dry to obtain modified nano silica.

[0054] (6) Place 65 parts by weight of butadiene rubber on a two-roll mill and plasticize it at 55°C for 12 minutes. Put the plasticized butadiene rubber into a mixer, turn on the mixer, control the speed at 25 r / min and the temperature at 85°C, and add 1.1 parts by weight of modified nano silica, 13 parts by weight of silica, and 1 part by weight of vanillin flame retardant in sequence. Mix for 6 minutes. Finally, add 0.6 parts by weight of sulfur and 1 part by weight of coupling agent KH-570, and continue mixing for 2 minutes. Let the mixed rubber compound stand for 9 hours, and vulcanize it at 145°C and 10 MPa for 12 minutes. Demold to obtain the rubber material for wear-resistant tires.

[0055] Example 5

[0056] (1) Under nitrogen protection, 1.55 g of vanillin and 1.42 g of glycidyl methacrylate were added to 30 mL of tetrahydrofuran solution and stirred. Then, 0.04 g of triethylamine catalyst and 0.02 g of hydroquinone polymerization inhibitor were added. The mixture was stirred continuously for 8 h in an oil bath at 72 °C. After the reaction was completed, the pH was adjusted to neutral with dilute hydrochloric acid, and the mixture was purified by rotary evaporation, column chromatography, and drying to obtain intermediate 1.

[0057] (2) Add 4.18 g of sulfaguanidine to a reactor containing 48 mL of anhydrous ethanol. After it is completely dissolved, add 3.07 g of intermediate 1 and stir at 82 °C for 10 h. Then add 2.51 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and react at 78 °C for 20 h. After the reaction is completed, cool, filter and dry to obtain intermediate 2.

[0058] (3) Add 3.52 g of intermediate 2 and 3.78 mL of 3-(methacryloyloxy)propyltrimethoxysilane to 35 mL of N,N-dimethylformamide solvent for dissolution. After dissolution, add 0.24 g of azobisisobutyronitrile initiator and react at 72 °C for 5 h. After the reaction, remove the solvent by vacuum distillation, filter, wash and dry to obtain intermediate 3.

[0059] (4) Add 2.56g of intermediate 3 and 4.06g of natural fibrous mineral sepiolite to 100mL of anhydrous ethanol, stir evenly, then add 0.12mL of ammonia water catalyst, and react at 80℃ for 7h. After the reaction is completed, centrifuge, wash and dry to obtain vanillin flame retardant.

[0060] (5) Add 4.68g of nano silica to 18mL of deionized water, adjust the pH value to 4 with dilute hydrochloric acid, stir evenly, then add 16.5g of phenyltrimethoxysilane, react at 78℃ for 4h, after the reaction is completed, filter, wash and dry to obtain modified nano silica.

[0061] (6) Place 75 parts by weight of butadiene rubber on a two-roll mill and plasticize it at 60°C for 15 minutes. Put the plasticized butadiene rubber into a mixer, turn on the mixer, control the speed at 25 r / min and the temperature at 95°C, and add 1.3 parts by weight of modified nano silica, 15 parts by weight of silica, and 2 parts by weight of vanillin flame retardant in sequence. Mix for 10 minutes. Finally, add 0.8 parts by weight of sulfur and 2 parts by weight of coupling agent KH-570, and continue mixing for 2 minutes. Let the mixed rubber compound stand for 12 hours, and vulcanize it at 155°C and 12 MPa for 18 minutes. Demold to obtain the rubber material for wear-resistant tires.

[0062] Comparative Example 1

[0063] The difference between this comparative example and Example 5 is that vanillin flame retardant was not added.

[0064] Comparative Example 2

[0065] The difference between this comparative example and Example 5 is that no modified nano-silica was added.

[0066] Performance testing:

[0067] The rubber materials obtained in Examples 1-5 and Comparative Examples 1-2 were subjected to performance tests.

[0068] The abrasion resistance test method is as follows: Abrasion resistance test is conducted according to ISO 4649 "Determination of abrasion resistance of vulcanized rubber or thermoplastic rubber".

[0069] The flame retardant performance testing methods are as follows: The oxygen index of the rubber material is tested using an oxygen index meter, and the flammability rating of the rubber material is tested using a horizontal and vertical burning tester. The test results are shown in Table 1.

[0070] Table 1: Test table for wear resistance and flame retardancy.

[0071] Group <![CDATA[DIN wear amount (mm 3 )]]> Oxygen index (%) UL-94 Example 1 72 30 V-0 Example 2 69 33 V-0 Example 3 70 32 V-0 Example 4 71 31 V-0 Example 5 71 31 V-0 Comparative Example 1 84 23 V-1 Comparative Example 2 93 28 V-0

[0072] As can be seen from Table 1, the rubber materials prepared in Examples 1-5 have low wear and high oxygen index, which means that the materials can only burn under higher oxygen concentrations, indicating that the rubber materials of the present invention have good wear resistance and flame retardancy.

[0073] The tensile properties of the material were tested using an electronic universal testing machine. The test results are shown in Table 2.

[0074] Table 2: Tensile property test table.

[0075] Group Tensile properties (MPa) Example 1 22.43 Example 2 22.76 Example 3 22.51 Example 4 22.32 Example 5 22.41 Comparative Example 1 19.31 Comparative Example 2 16.54

[0076] As shown in Table 2, the tensile properties of the rubber material of the present invention reach 22.76 MPa, indicating that it has good tensile properties and therefore good mechanical properties.

[0077] It should be noted that, in this document, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Unless otherwise specified, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.

[0078] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

[0079] Those skilled in the art should understand that the above descriptions are merely several specific embodiments of the present invention, and not all embodiments. It should be noted that many modifications and improvements can be made by those skilled in the art, and all modifications or improvements not exceeding the scope of the claims should be considered within the protection scope of the present invention.

Claims

1. A rubber material for wear-resistant tires, characterized in that, It includes the following components by weight: 60-80 parts by weight of butadiene rubber, 1-2 parts by weight of vanillin flame retardant, 1-1.5 parts by weight of modified nano silica, 12-16 parts by weight of silica, 0.6-0.8 parts by weight of sulfur, and 1-2 parts by weight of coupling agent KH-570.

2. The wear-resistant tire rubber material according to claim 1, characterized in that, The preparation method of the vanillin flame retardant is as follows: Step 1: Under inert gas protection, vanillin and glycidyl methacrylate were added to a tetrahydrofuran solution and stirred. Then, triethylamine catalyst and hydroquinone polymerization inhibitor were added. The mixture was stirred continuously for 6-8 hours in an oil bath at 70-75℃. After the reaction was completed, the pH was adjusted to neutral with dilute hydrochloric acid, and the mixture was purified by rotary evaporation, column chromatography, and drying to obtain intermediate 1. Step 2: Add sulfaguanidine to a reactor containing anhydrous ethanol. After it is completely dissolved, add intermediate 1 and stir the reaction at 75-85℃ for 8-10 hours. Then add 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and react at 70-80℃ for 16-20 hours. After the reaction is completed, cool, filter and dry to obtain intermediate 2. Step 3: Add intermediate 2,3-(methacryloyloxy)propyltrimethoxysilane to N,N-dimethylformamide solvent for dissolution. After dissolution, add azobisisobutyronitrile initiator and react at 65-75℃ for 3-5 hours. After reaction, remove the solvent by vacuum distillation, filter, wash and dry to obtain intermediate 3. Step 4: Add intermediate 3 and natural fibrous mineral sepiolite to anhydrous ethanol, stir well, then add ammonia catalyst, and react at 70-80℃ for 6-8 hours. After the reaction is complete, centrifuge, wash and dry to obtain vanillin flame retardant.

3. The wear-resistant tire rubber material according to claim 2, characterized in that, In step one, the ratio of tetrahydrofuran, vanillin, glycidyl methacrylate, triethylamine, and hydroquinone is 28-30 mL: 1.52-1.55 g: 1.41-1.44 g: 0.03-0.05 g: 0.01-0.02 g.

4. The wear-resistant tire rubber material according to claim 2, characterized in that, In step two, the ratio of sulfaguanidine, anhydrous ethanol, intermediate 1, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 4.14-4.18 g: 45-50 mL: 3.05-3.08 g: 2.48-2.51 g.

5. The wear-resistant tire rubber material according to claim 2, characterized in that, In step three, the ratio of N,N-dimethylformamide, intermediate 2,3-(methacryloyloxy)propyltrimethoxysilane, and azobisisobutyronitrile is 30-35 mL: 3.49-3.54 g: 3.76-3.78 mL: 0.21-0.24 g.

6. The wear-resistant tire rubber material according to claim 2, characterized in that, In step four, the ratio of anhydrous ethanol, intermediate 3, natural fibrous mineral sepiolite, and ammonia is 90-100mL: 2.53-2.58g: 4.02-4.06g: 0.1-0.12mL.

7. The wear-resistant tire rubber material according to claim 1, characterized in that, The modified nano-silica is prepared by adding nano-silica to deionized water, adjusting the pH value to 3-4 with dilute hydrochloric acid, stirring evenly, then adding phenyltrimethoxysilane, reacting at 75-80℃ for 2-4 hours, filtering, washing and drying after the reaction is completed to obtain modified nano-silica.

8. The wear-resistant tire rubber material according to claim 7, characterized in that, The ratio of nano-silica, deionized water, and phenyltrimethoxysilane is 4.65-4.68g:15-20mL:16.2-16.5g.

9. A rubber material for wear-resistant tires as described in any one of claims 1-8, characterized in that, The preparation method of the wear-resistant tire rubber material is as follows: Butadiene rubber is placed on a two-roll mill and plasticized at 50-60℃ for 10-15 minutes. The plasticized butadiene rubber is then fed into an internal mixer. The internal mixer is started, and the speed is controlled at 20-30 r / min and the temperature at 80-100℃. Modified nano-silica, silica, and vanillin flame retardant are added sequentially, and the mixing time is 5-10 minutes. Finally, sulfur and coupling agent KH-570 are added, and the mixing continues for 2-3 minutes. The mixed rubber compound is allowed to stand for 8-12 hours and vulcanized at 140-160℃ and 10-15 MPa for 10-20 minutes. The rubber material is then demolded to obtain the wear-resistant tire rubber material.

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