High-strength low-temperature-resistant aging-resistant polymer rubber material and preparation method thereof

Abstract

The invention discloses a high-strength, low-temperature-resistant and aging-resistant polymer rubber material and a preparation method thereof in the technical field of rubber materials. The high-strength, low-temperature-resistant and aging-resistant polymer rubber material comprises the following components in parts by weight: 100-120 parts of a rubber matrix, 44-62.5 parts of an interface auxiliary agent, 8-15 parts of a vulcanization system, 4-5 parts of a protection system and 8-12 parts of a toughening agent. According to the invention, a multi-component synergistic system is constructed by the multifunctional reinforcer, amino-terminated polysiloxane, amino-terminated polybutadiene and epoxidized soybean oil, and meanwhile, a carbon black / Si-69 interface assistant and a protection / vulcanization system are optimized, so that the synergistic improvement of mechanical properties, low temperature resistance and aging resistance is achieved; the technical problems that traditional rubber is single, excellent in performance and unbalanced in comprehensive performance are solved.

Description

Technical Field

[0001] This invention belongs to the field of rubber material technology, specifically referring to a high-strength, low-temperature resistant, and aging-resistant polymeric rubber material and its preparation method. Background Technology

[0002] Rubber, as a uniquely elastic polymer elastomer, possesses a large molecular weight (hundreds of thousands to millions) and a polydisperse structure, making it an indispensable basic material in engineering fields. Rubber materials have evolved from natural rubber to synthetic rubber, and now comprise two major systems: general-purpose rubber (natural rubber NR, styrene-butadiene rubber SBR, etc.) and specialty rubber (silicone rubber, fluororubber, ethylene propylene diene monomer (EPDM), etc.). These are widely used in core sectors of the national economy such as transportation, energy, aerospace, and construction, with tens of thousands of product types. However, as modern industry upgrades towards extreme environments, high-end manufacturing, and green low-carbon practices, the shortcomings of traditional rubber materials in the three core properties of strength, low-temperature resistance, and aging resistance are becoming increasingly prominent. Therefore, the development of multifunctional integrated high-performance rubber materials has become an urgent industry need.

[0003] While current mainstream rubber materials each possess unique characteristics, they all exhibit significant performance contradictions, making it difficult to meet diverse needs: General-purpose rubber systems: Natural rubber (NR) boasts excellent tensile strength (approximately 25 MPa), but its low-temperature resistance is limited (embrittlement temperature approximately -20°C), and it is prone to aging and cracking in oxygen and ozone environments. Furthermore, the self-sufficiency rate of natural rubber is only 15%, far below the international safety standard of 30%. Styrene-butadiene rubber (SBR) is inexpensive and has good processability, but it suffers from poor aging resistance, a low-temperature embrittlement temperature of approximately -30°C, and a tensile strength of less than 20 MPa, making it unsuitable for heavy-duty applications. Specialty rubber systems: Ethylene propylene diene monomer (EPDM) offers excellent weather resistance and ozone resistance. While polyisoprene rubber exhibits excellent low-temperature resistance (embrittlement temperature ≤ -77℃ to -69℃), its high-strength grade products typically have tensile strengths below 20MPa, and its resilience significantly decreases below -30℃, making it difficult to balance strength and ultra-low temperature elasticity. Silicone rubber boasts excellent low-temperature resistance (embrittlement temperature ≤ -70℃), but its mechanical strength is extremely low (tensile strength typically 3~8MPa), making it prone to tearing and wear, thus limiting its application in load-bearing scenarios. Fluororubber exhibits strong aging resistance and media resistance, but its embrittlement temperature is only -15~-20℃, and its high cost hinders large-scale application. Existing modified polyisoprene rubbers generally have tensile strengths below 26MPa and insufficient fatigue aging resistance, with a minimum of 5×10 cycles. 5 The dynamic stiffness retention rate after the second pass is less than 84%. Common technical bottlenecks: Existing materials generally suffer from performance imbalance. Materials with excellent low-temperature resistance (such as silicone rubber) often have insufficient strength, while materials with high strength (such as natural rubber) lack low-temperature resistance and aging resistance. At the same time, most rubber materials are prone to thermal-oxidative aging and ultraviolet aging during long-term use, resulting in loss of elasticity, strength reduction, and shortened service life. Summary of the Invention

[0004] To address the above issues and overcome the shortcomings of existing technologies, this invention provides a high-strength, low-temperature resistant, and aging-resistant polymeric rubber material and its preparation method. This invention constructs a multi-component synergistic system by combining a multifunctional reinforcing agent with amino-terminated polysiloxane, amino-terminated polybutadiene, and epoxidized soybean oil. Simultaneously, it optimizes the carbon black / Si-69 interface additive and the protection / vulcanization system, achieving a synergistic leap in mechanical properties, low-temperature resistance, and anti-aging properties. This overcomes the technical challenge of traditional rubbers having excellent single properties but unbalanced overall performance.

[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows: The present invention proposes a high-strength, low-temperature resistant, and aging-resistant polymer rubber material, wherein the polymer rubber material comprises the following components in parts by weight: 100-120 parts of rubber matrix, 44-62.5 parts of interface additives, 8-15 parts of vulcanization system, 4-5 parts of protective system, and 8-12 parts of toughening agent.

[0006] Preferably, the rubber matrix comprises the following components in parts by weight: 38-50 parts of natural rubber, 30-35 parts of styrene-butadiene rubber, and 30-40 parts of cis-butadiene rubber;

[0007] Preferably, the interface additive comprises the following components in parts by weight: 42-60 parts carbon black and 1.5-2.5 parts silane coupling agent Si-69;

[0008] Preferably, the vulcanization system comprises the following components in parts by weight: 1.2-1.8 parts sulfur, 1.8-2.4 parts accelerator CZ, 1.6-2.8 parts stearic acid, and 4.6-7.0 parts zinc oxide;

[0009] Preferably, the protective system comprises the following components in parts by weight: 1.5-2.5 parts paraffin wax and 2.0-3.0 parts antioxidant 4020;

[0010] Preferably, the raw materials for preparing the toughening agent include the following components in parts by weight: 3.8-4.2 parts of amino-terminated polybutadiene, 8-10 parts of reinforcing agent, 0.8-1.0 g of amino-terminated polysiloxane, and 0.5-0.8 g of epoxidized soybean oil;

[0011] Preferably, the preparation method of the amino-terminated polybutadiene specifically includes the following steps:

[0012] S1. Place a 1,3-butadiene / hexane solution in a dry flask, introduce flowing nitrogen gas, add pyridine and mix well. Dissolve CoCl2 and AlEt2Cl in anhydrous toluene and add it to the reaction system. Under sealed conditions, raise the reaction temperature to carry out the polymerization reaction. After the reaction is completed, cool to obtain polybutadiene reaction solution.

[0013] Preferably, in step S1, the volume fraction of pyridine in the 1,3-butadiene / hexane solution is 0.05%-0.1%;

[0014] Preferably, in step S1, the mass-to-volume ratio of CoCl2 to 1,3-butadiene is 0.25-0.5 mg / mL;

[0015] Preferably, in step S1, the mass-to-volume ratio of AlEt2Cl to 1,3-butadiene is 0.5-1.0 mg / mL.

[0016] Preferably, in step S1, the polymerization reaction temperature is 50-60℃ and the polymerization reaction time is 3-4 hours;

[0017] S2. Under a sealed, nitrogen atmosphere, hexamethylene diisocyanate / hexane solution is added to the polybutadiene reaction solution prepared in step S1. The reaction temperature is increased to carry out the functionalization reaction. After the reaction is completed, anhydrous ethanol is added to terminate the reaction and a precipitate is generated. The precipitate is filtered, collected, washed repeatedly, and dried to obtain amide-functionalized polybutadiene.

[0018] Preferably, in step S2, the hexamethylene diisocyanate has a mass fraction of 0.5%-1.0% in the 1,3-butadiene / hexane solution described in step S1;

[0019] Preferably, in step S2, the functionalization reaction temperature is 50-60℃, and the functionalization reaction time is 3-4h;

[0020] S3. Under a dry nitrogen atmosphere, the amide-functionalized polybutadiene prepared in step S2 was dissolved in anhydrous THF and transferred to an ice-water bath for cooling. Lithium aluminum hydride and titanium tetrachloride were slowly added, and the reduction reaction was carried out under ice-water bath conditions. After the reaction was completed, saturated ammonium chloride aqueous solution was added until no bubbles were generated. The mixture was allowed to stand, filtered, and the filtrate was collected. After standing and separating into layers, the upper reaction layer was collected. The lower reaction layer was extracted with anhydrous THF, and the THF phases were combined. After drying with anhydrous magnesium sulfate to remove water, anhydrous ethanol / n-hexane solution was added for precipitation. The precipitate was filtered, collected, washed, and dried to obtain amino-terminated polybutadiene.

[0021] Preferably, in step S3, the mass-to-volume ratio between the lithium aluminum hydride and the hexamethylene diisocyanate in step S2 is 0.5-0.95 g / mL;

[0022] Preferably, in step S3, the volume ratio between the titanium tetrachloride and the hexamethylene diisocyanate in step S2 is 0.11-0.22:1;

[0023] Preferably, in step S3, the stirring speed of the reduction reaction is 200-400 rpm, and the reduction reaction time is 3-5 h;

[0024] Preferably, the preparation method of the reinforcing agent specifically includes the following steps:

[0025] S4. Dissolve dibromoneopentyl glycol in anhydrous 1,4-dioxane. Under a nitrogen atmosphere, add bis(pinacolyl)diboron and anhydrous potassium acetate to the reaction system in sequence. Stir until the reactants are completely dissolved. Prepare a palladium acetate and triphenylphosphine catalytic system and slowly add it to the reaction system. Increase the temperature to carry out the activation reaction. After the reaction is completed, continue to increase the temperature to carry out the borylation reaction. After the reaction is completed, cool, add diatomaceous earth, filter, collect the filtrate, and distill under reduced pressure to obtain intermediate A.

[0026] Preferably, in step S4, the mass ratio between dibromoneopentyl glycol and bis(pinacol)diboron is 0.34-0.47:1;

[0027] Preferably, in step S4, the mass ratio between dibromoneopentyl glycol and anhydrous potassium acetate is 0.54-0.64:1;

[0028] Preferably, in step S4, the mass ratio of palladium acetate, triphenylphosphine, and dibromoneopentyl glycol is 0.05-0.75:0.27-0.35:2-4;

[0029] Preferably, in step S4, the activation reaction temperature is 60-65℃ and the activation reaction time is 20-30 min; the borylation reaction time is 80-90℃ and the borylation reaction temperature is 8-12 h.

[0030] S5. Dissolve 5-bromo-2-mercaptobenzothiazole in anhydrous THF, transfer to an ice-water bath for thorough cooling, add trimethylchlorosilane, and stir the reaction at room temperature for 2-4 hours. After the reaction is complete, distill under reduced pressure to obtain TSM-S-intermediate. Dissolve TSM-S-intermediate in anhydrous 1,4-dioxane / anhydrous ethanol mixed solvent, add intermediate A prepared in step S4 and anhydrous potassium carbonate, mix well, add tetra(triphenylphosphine)palladium to the reaction system, and reflux the reaction under a nitrogen atmosphere. After the reaction is complete, cool, filter, collect the filtrate, cool the filtrate thoroughly in an ice-water bath, add tetrabutylammonium fluoride, stir the reaction at room temperature for 3-5 hours, add saturated ammonium chloride aqueous solution and stir until no bubbles are generated, collect the organic phase, dry the organic phase with anhydrous magnesium sulfate, and distill under reduced pressure to obtain intermediate B.

[0031] Preferably, in step S5, the mass-to-volume ratio of 5-bromo-2-mercaptobenzothiazole to trimethylchlorosilane is 1.8-2.0 g / mL;

[0032] Preferably, in step S5, the mass ratio between the 5-bromo-2-mercaptobenzothiazole and the bis(pinacol)diboron described in step S4 is 0.78-0.88:1;

[0033] Preferably, in step S5, the mass ratio of anhydrous potassium carbonate to 5-bromo-2-mercaptobenzothiazole is 1:3.4-4.5;

[0034] Preferably, in step S5, the mass fraction of the tetra(triphenylphosphine)palladium in 5-bromo-2-mercaptobenzothiazole is 2.0%-2.2%;

[0035] Preferably, in step S5, the mass-to-volume ratio of the tetrabutylammonium fluoride to trimethylchlorosilane is 2.1-3.0 g / mL;

[0036] Preferably, in step S5, the reflux reaction temperature is 80-90℃ and the reflux reaction time is 12-16h;

[0037] S6. Dissolve intermediate B prepared in step S5 in anhydrous dichloromethane, transfer it to an ice-water bath for cooling under a nitrogen atmosphere, add boron trifluoride diethyl ether complex, mix well, add glycidyl ether through a constant pressure dropping funnel, and after the addition is complete, carry out an epoxidation reaction at room temperature. After the reaction is complete, wash with saturated sodium bicarbonate aqueous solution, collect the organic phase, dry it with anhydrous magnesium sulfate to remove water, and then distill under reduced pressure to obtain the fortifying agent.

[0038] Preferably, in step S6, the mass-to-volume ratio of dibromoneopentyl glycol to glycidyl ether in step S4 is 0.67-0.83 g / mL;

[0039] Preferably, in step S6, the boron trifluoride diethyl ether complex accounts for 8.3%-10.0% of the volume fraction of glycidyl ether.

[0040] Preferably, in step S6, the stirring speed of the epoxidation reaction is 300-500 rpm, and the reaction time of the epoxidation reaction is 8-12 h;

[0041] Preferably, the method for preparing the toughening agent specifically includes the following steps:

[0042] S7. Place amino-terminated polybutadiene, amino-terminated polysiloxane, epoxidized soybean oil and the fortifying agent in a flask, introduce flowing nitrogen gas, add anhydrous toluene, mix well, add acetic acid / anhydrous toluene solution, control the flow rate of nitrogen gas, increase the reaction temperature to carry out the first step reaction, after the reaction is completed, increase the flow rate of nitrogen gas, increase the reaction temperature to carry out the second step reaction, after the reaction is completed, cool, remove excess reaction solvent by vacuum distillation, vacuum dry, seal and store to obtain toughening agent;

[0043] Preferably, in step S7, the mass-volume ratio of the reinforcing agent to acetic acid is 3.2-4.5 g / mL;

[0044] Preferably, in step S7, the reaction temperature of the first reaction is 35-45℃, the nitrogen flow rate of the first reaction is 2-5 mL / min, and the reaction time of the first reaction is 6-8 h.

[0045] Preferably, in step S7, the reaction temperature of the second step reaction is 60-70℃, the nitrogen flow rate of the second step reaction is 20-25 mL / min, and the reaction time of the second step reaction is 4-6 h;

[0046] This invention also provides a method for preparing a high-strength, low-temperature resistant, and aging-resistant polymeric rubber material, specifically comprising the following steps:

[0047] ① Start the open mill, set the front roll temperature and rear roll temperature, adjust the roll gap, add natural rubber, and plasticize until the rubber surface is smooth and free of particles. Add styrene-butadiene rubber and cis-butadiene rubber, continue plasticizing for 3-5 minutes, mix evenly, and obtain the blended rubber base material.

[0048] ② Start the internal mixer, set the temperature, rotor speed, and filling factor, add the blended rubber base material prepared in step ①, and mix until completely melted. Add carbon black in batches, along with silane coupling agent Si-69, zinc oxide, stearic acid, paraffin wax, and antioxidant 4020. Raise the temperature to 135-145℃ and continue mixing for 4-6 minutes. Open the discharge door of the internal mixer to discharge the masterbatch. Sheet the masterbatch on the open mill, cool it to room temperature, and let it stand to obtain the masterbatch.

[0049] ③ Adjust the temperature and rotor speed of the internal mixer, add the masterbatch rubber prepared in step ②, mix until melted, add toughening agent, mix, and finally add sulfur and accelerator CZ, mix for 3-5 minutes, unload and sheet on the open mill, cut the triangular package with a cutter to ensure that each component is evenly dispersed to obtain the compound rubber.

[0050] ④ Cut the final compounded rubber into sheets and place them in a cool, ventilated place for curing for 4-8 hours. Turn on the flat vulcanizing machine, set the temperature and pressure, and preheat it. Take the compounded rubber prepared in step ③, place it in the mold, put it into the flat vulcanizing machine, and vulcanize it for 15-20 minutes. During this time, keep the pressure stable. After vulcanization, quickly turn on the flat vulcanizing machine, take out the product, and place it on a room temperature cooling rack to cool to 25°C to obtain the polymer rubber material.

[0051] The beneficial effects achieved by this invention are as follows:

[0052] This invention provides a high-strength, low-temperature resistant, and aging-resistant polymeric rubber material and its preparation method. This invention constructs a multi-component synergistic system by combining a multifunctional reinforcing agent with terminal amino polysiloxane, terminal amino polybutadiene, and epoxidized soybean oil. Simultaneously, it optimizes the carbon black / Si-69 interface additive and the protection / vulcanization system, achieving a synergistic leap in mechanical properties, low-temperature resistance, and anti-aging properties. This overcomes the technical challenge of traditional rubbers exhibiting excellent single properties but unbalanced overall performance. Specifically, the reinforcing agent is the core functional carrier. Its mechanism involves the simultaneous integration of sulfenamide dynamic bonds (-S-NH-), epoxy crosslinking sites, and benzothiazole groups, achieving a unified triple function of crosslinking reinforcement, dynamic toughening, and synergistic anti-aging. The epoxy groups undergo crosslinking reactions with the amino groups of terminal amino polybutadiene and terminal amino polysiloxane, forming a dense and stable chemical network that provides rigid support for the material. The sulfenamide dynamic bonds possess reversible breaking and recombination capabilities, which can alleviate stress concentration under stress and repair micro-damage during aging. The benzothiazole groups can form a synergistic free radical scavenging system with the antioxidant 4020, enhancing the anti-aging effect.

[0053] From the perspective of mechanical properties, the crystallinity of natural rubber provides basic strength, the benzene ring structure of styrene-butadiene rubber enhances intermolecular forces, and the high cis structure of cis-butadiene rubber imparts flexibility. These three factors help to balance rigidity and flexibility. The flexible segments of terminal amino polybutadiene and the cross-linking network of the reinforcing agent work synergistically, and the interface reinforcement of carbon black modified by the silane coupling reagent Si-69 improves the tensile strength and elongation at break of the material, achieving a unity of high strength and high toughness.

[0054] From the perspective of low-temperature resistance, the sulfenamide dynamic bond of the reinforcing agent is the core functional unit. Its bond energy and activation energy are low, allowing for rapid and reversible breakage and recombination even at -30℃. In low-temperature environments, when the rigidity of the rubber molecular chain increases, the sulfenamide bond can break under stress, releasing internal stress and preventing localized stress concentration that could lead to brittleness. After stress removal, the bonding sites recombine, restoring network integrity. Simultaneously, the reinforcing agent and the siloxane segments of the amino-terminated polysiloxane form an interfacial synergy. The hydrophobic structure of the benzothiazole group reduces interfacial tension, minimizing the risk of interfacial cracking at low temperatures. Combined with the appropriate crosslinking density formed by epoxy-amino crosslinking, this ensures network stability while providing space for molecular chain movement, enabling the material to maintain high elasticity even at -30℃.

[0055] In terms of anti-aging performance, the benzothiazole group of the reinforcing agent works synergistically with the antioxidant 4020 to efficiently capture the ·OOH and ·OH free radicals generated by thermo-oxidative aging, inhibiting the oxidative chain breaking of rubber molecules. The dense cross-linked network and the highly filled carbon black form a physical barrier layer, reducing the oxygen diffusion coefficient and delaying internal aging. The sulfenamide dynamic bond can repair the microcracks generated by aging, maintain the stability of the system structure, and enable the material to maintain high mechanical properties after thermal aging, significantly extending the service life of the material.

[0056] In terms of the overall solution, this technology achieves simultaneous breakthroughs in mechanical properties, low-temperature resistance, and anti-aging properties through multi-component synergistic design. Its high strength meets engineering load-bearing requirements, its high toughness and low-temperature resistance are suitable for low-temperature scenarios such as cold chain transportation and polar environments, and its excellent anti-aging properties are suitable for high-temperature working conditions and long-term outdoor use scenarios. It effectively solves the limitations of traditional rubber materials in dealing with complex and multi-environmental requirements, and provides high-performance material support for products such as automotive seals, engineering machinery rubber parts, and cold chain transportation seals. It has significant technological innovation value and broad application prospects. Attached Figure Description

[0057] Figure 1 The tensile strength results of the polymer rubber materials prepared in Examples 1-3 and Comparative Examples 1-3 of this invention are shown in the figure.

[0058] Figure 2 The graph shows the elongation at break of the polymer rubber materials prepared in Examples 1-3 and Comparative Examples 1-3 of this invention.

[0059] Figure 3 The graphs show the aging resistance results of the polymer rubber materials prepared in Examples 1-3 and Comparative Examples 1-3 of this invention.

[0060] The accompanying drawings are provided to further illustrate the invention and form part of the specification. They are used together with the embodiments of the invention to explain the invention and do not constitute a limitation thereof. Detailed Implementation

[0061] The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings of the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0062] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those familiar to those skilled in the art. Furthermore, any methods and materials similar to or equivalent to those described herein may be applied to this invention. The preferred embodiments and materials described herein are for illustrative purposes only and do not limit the scope of this application.

[0063] Unless otherwise specified, the experimental methods used in the following embodiments are conventional methods; unless otherwise specified, the experimental materials used in the following embodiments are all purchased from commercial channels.

[0064] Example 1

[0065] This embodiment proposes a high-strength, low-temperature resistant, and aging-resistant polymeric rubber material, which comprises the following components in parts by weight: 100 parts of rubber matrix, 53.5 parts of interface additives, 11 parts of vulcanization system, 4 parts of protective system, and 8.0 parts of toughening agent;

[0066] The rubber matrix comprises the following components in parts by weight: 40 parts natural rubber, 30 parts styrene-butadiene rubber, and 30 parts cis-butadiene rubber;

[0067] The interface additives include the following components in parts by weight: 52 parts carbon black and 1.5 parts silane coupling reagent Si-69;

[0068] The vulcanization system comprises the following components in parts by weight: 1.5 parts sulfur, 1.8 parts accelerator CZ, 1.6 parts stearic acid, and 6.3 parts zinc oxide;

[0069] The protective system comprises the following components in parts by weight: 2.0 parts paraffin wax and 2.0 parts antioxidant 4020;

[0070] The toughening agent is prepared from the following components in parts by weight: 3.8 parts of amino-terminated polybutadiene, 8 parts of reinforcing agent, 0.8 g of amino-terminated polysiloxane (poly(dimethylsiloxane) bis(3-aminopropyl) capped, PDMS, Aladdin P477941), and 0.5 g of epoxidized soybean oil.

[0071] The preparation method of amino-terminated polybutadiene specifically includes the following steps:

[0072] S1. Accurately weigh 20 mL of 1,3-butadiene / hexane solution (Innochem A93353, purity: 1.9M solution inhexane) and place it in a dry flask. Purge the air in the reaction system with flowing nitrogen. Add 0.01 mL of pyridine and mix thoroughly. Accurately weigh 0.1 g of CoCl2 and 0.2 g of AlEt2Cl and dissolve them in 100 mL of anhydrous toluene. Take 5 mL of this solution and add it to the reaction system. Mix at 200 rpm until homogeneous. Seal the reaction system and raise the reaction temperature to 50 °C to carry out the polymerization reaction for 4 h. After the reaction is completed, allow the reaction system to cool to room temperature to obtain the polybutadiene reaction solution.

[0073] S2. Under a sealed, nitrogen atmosphere, accurately weigh 10 mL of hexamethylene diisocyanate and dissolve it in 100 mL of hexane to obtain a hexamethylene diisocyanate / hexane solution. Add 1.0 mL of the hexamethylene diisocyanate / hexane solution to the polybutadiene reaction solution prepared in step S1. Stir and mix at 200 rpm, then raise the reaction temperature to 50 °C to carry out the functionalization reaction. After the reaction is completed, add anhydrous ethanol to terminate the reaction and a precipitate is formed. Filter, collect the precipitate, wash it repeatedly with anhydrous ethanol 5 times, and then dry it under vacuum at 50 °C to constant weight to obtain amide-functionalized polybutadiene.

[0074] S3. Under a dry nitrogen atmosphere, place the amide-functionalized polybutadiene prepared in step S2 into an anhydrous flask, add 20 mL of anhydrous THF to dissolve the reactants, and then transfer to an ice-water bath. Stir at 200 rpm for thorough cooling. Accurately weigh 5 g of lithium aluminum hydride and 1.1 mL of titanium tetrachloride, dissolve them in 100 mL of anhydrous THF, and slowly add 1 mL of the solution to the reaction system at a rate of 1 drop / s. Maintain the ice-water bath conditions and stir at 200 rpm for the reduction reaction. The reaction should last for 5 hours. After the reaction was complete, a saturated ammonium chloride aqueous solution was added while stirring at 500 rpm until no more bubbles were generated. The mixture was then allowed to stand, filtered to remove the aluminum hydroxide precipitate, and the filtrate was collected. The filtrate was allowed to separate into layers. Due to the large amount of ammonium chloride in the deionized water, the deionized water and THF separated into two phases: the upper layer was the THF phase, and the lower layer was the ammonium chloride aqueous solution phase. The upper reaction layer was collected, and the lower reaction layer was washed with anhydrous THF. The THF phases were combined, dried over anhydrous magnesium sulfate, and then anhydrous ethanol / n-hexane solution (V...) was added. 乙醇 :V 正己烷 The mixture was precipitated using a ratio of 1:3, filtered, the precipitate was collected, washed, and dried to obtain amino-terminated polybutadiene.

[0075] The preparation method of the reinforcing agent specifically includes the following steps:

[0076] S4. Accurately weigh 2.0 g of dibromoneopentyl glycol and place it in a dry flask. Purge with flowing nitrogen to keep the reaction system anhydrous and oxygen-free. Add 150 mL of anhydrous 1,4-dioxane to completely dissolve the dibromoneopentyl glycol. Then, add 5.8 g of bis(pinacol)diboron and 3.7 g of anhydrous potassium acetate to the reaction system in sequence. Stir at 300 rpm until the reactants are completely dissolved. Dissolve 50 mg of palladium acetate and 0.27 g of triphenylphosphine in 10 mL of anhydrous 1,4-dioxane and add them to the reaction system at a rate of 1 drop / s. Raise the reaction temperature to 60 °C for activation. After 30 min, continue to raise the temperature to 85 °C for borylation. React for 10 h. After the reaction is completed, let the reaction system cool to room temperature, add diatomaceous earth, filter, collect the filtrate, and wash the filter cake repeatedly with anhydrous 1,4-dioxane 3 times. Combine the washing liquid and filtrate, concentrate under reduced pressure to obtain intermediate A.

[0077] S5. Accurately weigh 4.5 g of 5-bromo-2-mercaptobenzothiazole and place it in a flask. Purge with flowing nitrogen to maintain anhydrous and oxygen-free reaction system. Add 50 mL of anhydrous THF and transfer to an ice-water bath for thorough cooling. Add 2.5 mL of trimethylchlorosilane and stir the reaction at room temperature for 2 h. After the reaction is complete, distill under reduced pressure to obtain the TSM-S-intermediate. Dissolve the TSM-S-intermediate in 100 mL of anhydrous 1,4-dioxane / anhydrous ethanol mixed solvent (V... 1,4-二氧六环 :V 乙醇 In a mixture of 6:1, intermediate A prepared in step S4 and 1.0 g of anhydrous potassium carbonate were added and mixed thoroughly. Then, 0.1 g of tetra(triphenylphosphine)palladium was added to the reaction system. Under a nitrogen atmosphere, the reaction temperature was raised to 85°C and refluxed for 14 h. After the reaction was completed, the reaction system was cooled to room temperature, filtered, and the filtrate was collected. The filtrate was cooled thoroughly in an ice-water bath. 7.5 g of tetrabutylammonium fluoride was dissolved in 30 mL of anhydrous ethanol. The mixture was stirred at room temperature for 3 h. Then, saturated ammonium chloride aqueous solution was added and stirred until no bubbles were generated. The organic phase was collected, dried with anhydrous magnesium sulfate, and distilled under reduced pressure to obtain intermediate B.

[0078] S6. Dissolve intermediate B prepared in step S5 in 80 mL of anhydrous dichloromethane. Purge the reaction system with flowing nitrogen to keep it anhydrous and oxygen-free. Transfer the system to an ice-water bath and stir at 400 rpm. After the reaction system is fully cooled, slowly add 30 μL of boron trifluoride diethyl ether complex. After mixing evenly, add 3.0 mL of glycidyl ether to the reaction system at a rate of 1 drop / s through a constant pressure dropping funnel. Stir at 300 rpm during the drop addition. After the drop addition is complete, stir for 30 min under ice-water bath conditions. After heating to room temperature, continue stirring at room temperature for 12 h to carry out the epoxidation reaction. After the reaction is completed, add saturated sodium bicarbonate aqueous solution and stir at 300 rpm for 10 min. Allow the mixture to stand and separate into layers. Collect the organic phase and wash it with saturated sodium bicarbonate aqueous solution. Combine the organic phases, dry them with anhydrous magnesium sulfate to remove water, and then concentrate the organic phase under reduced pressure to obtain the fortifying agent.

[0079] The preparation method of the toughening agent specifically includes the following steps:

[0080] S7. Place 3.8g of amino-terminated polybutadiene, 0.8g of amino-terminated polysiloxane, 0.5g of epoxidized soybean oil and 8.0g of reinforcing agent in a flask, purge with flowing nitrogen to keep the reaction system anhydrous and oxygen-free, add 10mL of anhydrous toluene, turn on mechanical stirring, adjust the speed to 400rpm, mix evenly until the system forms a uniform pale yellow viscous liquid, add 2.5mL of 0.1mol / L acetic acid / anhydrous toluene solution at a rate of 1 drop / s, control the nitrogen flow rate at 5mL / min, raise the reaction temperature to 40℃ to carry out the first step reaction, react for 7h. After the reaction is completed, increase the nitrogen flow rate to 25mL / min, raise the reaction temperature to 65℃ to carry out the second step reaction, react for 5h. After the reaction is completed, cool, remove excess reaction solvent by vacuum distillation, vacuum dry, seal and store to obtain toughening agent;

[0081] This embodiment also provides a method for preparing a high-strength, low-temperature resistant, and aging-resistant polymeric rubber material, which specifically includes the following steps:

[0082] ① Start the open mill, set the front roller temperature to 95℃ and the rear roller temperature to 90℃, adjust the roller gap to 1.0mm, add a portion of natural rubber, and plasticize for 5 minutes until the rubber surface is smooth and free of particles. Add styrene-butadiene rubber and cis-butadiene rubber, and continue plasticizing for 3 minutes to mix evenly to obtain a blended rubber base material.

[0083] ② Start the internal mixer, set the temperature to 135℃, the rotor speed to 60rpm, and the filling factor to 0.75. Add the blended rubber base material prepared in step ①, and mix for 1 minute until completely melted. Add carbon black in batches, along with silane coupling agent Si-69, zinc oxide, stearic acid, paraffin wax, and antioxidant 4020. Raise the temperature to 140℃ and continue mixing for 4 minutes. Open the discharge door of the internal mixer to discharge the masterbatch. Sheet the masterbatch on the open mill (roll gap 3mm), cool to room temperature, and let it stand for 2 hours to obtain the masterbatch.

[0084] ③ Adjust the internal mixer temperature to 85℃ and the rotor speed to 50rpm, add the masterbatch rubber prepared in step ②, internal mix for 1min until melted, add toughening agent, internal mix for 2min, finally add sulfur and accelerator CZ, internal mix for 3min, after unloading, sheet out on the open mill, cut the blade 3 times to make triangular wrapping to ensure that each component is evenly dispersed, and obtain the compound rubber.

[0085] ④ Cut the final compounded rubber into sheets and place them in a cool, ventilated place for curing for 4 hours. Turn on the flat vulcanizing machine, set the temperature to 150℃ and the pressure to 12MPa, and preheat for 30 minutes. Take the compounded rubber prepared in step ③, place it in the mold, put it into the flat vulcanizing machine, and vulcanize for 18 minutes. During this period, keep the pressure stable. After vulcanization, quickly turn on the flat vulcanizing machine, take out the product, and place it on a room temperature cooling rack to cool to 25℃ to obtain the polymer rubber material.

[0086] Example 2

[0087] This embodiment proposes a high-strength, low-temperature resistant, and aging-resistant polymer rubber material, which comprises the following components by weight: 110 parts of rubber matrix, 44 parts of interface additives, 8-15 parts of vulcanization system, 5 parts of protective system, and 12 parts of toughening agent.

[0088] The rubber matrix comprises the following components in parts by weight: 38 parts natural rubber, 32 parts styrene-butadiene rubber, and 40 parts cis-butadiene rubber;

[0089] The interface additives include the following components in parts by weight: 42 parts carbon black and 2.0 parts silane coupling reagent Si-69;

[0090] The vulcanization system comprises the following components in parts by weight: 1.2 parts sulfur, 2.0 parts accelerator CZ, 2.2 parts stearic acid, and 4.6 parts zinc oxide;

[0091] The protective system comprises the following components in parts by weight: 2.5 parts paraffin wax and 2.5 parts antioxidant 4020;

[0092] The toughening agent is prepared from the following components in parts by weight: 4.0 parts of amino-terminated polybutadiene, 9 parts of reinforcing agent, 0.9 g of amino-terminated polysiloxane (poly(dimethylsiloxane) bis(3-aminopropyl) capped, PDMS, Aladdin P477941), and 0.6 g of epoxidized soybean oil.

[0093] The preparation method of amino-terminated polybutadiene specifically includes the following steps:

[0094] S1. Accurately weigh 20 mL of 1,3-butadiene / hexane solution (Innochem A93353, purity: 1.9M solution inhexane) and place it in a dry flask. Purge the air in the reaction system with flowing nitrogen. Add 0.015 mL of pyridine and mix thoroughly. Accurately weigh 0.1 g of CoCl2 and 0.2 g of AlEt2Cl and dissolve them in 100 mL of anhydrous toluene. Take 7.5 mL of this solution and add it to the reaction system. Mix at 200 rpm until homogeneous. Seal the reaction system and raise the reaction temperature to 55 °C to carry out the polymerization reaction for 3.5 h. After the reaction is completed, allow the reaction system to cool to room temperature to obtain the polybutadiene reaction solution.

[0095] S2. Under a sealed, nitrogen atmosphere, accurately weigh 10 mL of hexamethylene diisocyanate and dissolve it in 100 mL of hexane to obtain a hexamethylene diisocyanate / hexane solution. Add 1.5 mL of the hexamethylene diisocyanate / hexane solution to the polybutadiene reaction solution prepared in step S1. Stir and mix at 200 rpm, then raise the reaction temperature to 55 °C to carry out the functionalization reaction for 3.5 h. After the reaction is completed, add anhydrous ethanol to terminate the reaction and a precipitate is formed. Filter, collect the precipitate, wash it repeatedly with anhydrous ethanol 5 times, and then dry it under vacuum at 50 °C to constant weight to obtain amide-functionalized polybutadiene.

[0096] S3. Under a dry nitrogen atmosphere, place the amide-functionalized polybutadiene prepared in step S2 into an anhydrous flask, add 20 mL of anhydrous THF to dissolve the reactants, and then transfer to an ice-water bath. Stir at 200 rpm for thorough cooling. Accurately weigh 5 g of lithium aluminum hydride and 1.1 mL of titanium tetrachloride, dissolve them in 100 mL of anhydrous THF, and slowly add 1.5 mL of the solution to the reaction system at a rate of 1 drop / s. Maintain the ice-water bath conditions and stir at 300 rpm for the reduction reaction. The reaction should last for 4 hours. After the reaction is complete, a saturated ammonium chloride aqueous solution is added while stirring at 500 rpm until no more bubbles are generated. The mixture is then allowed to stand, filtered to remove the aluminum hydroxide precipitate, and the filtrate is collected. The filtrate is allowed to separate into layers. Due to the large amount of ammonium chloride in the deionized water, the deionized water and THF separate into two phases: the upper layer is the THF phase, and the lower layer is the ammonium chloride aqueous solution phase. The upper reaction layer is collected, and the lower reaction layer is washed with anhydrous THF. The THF phases are combined, dried over anhydrous magnesium sulfate to remove water, and then anhydrous ethanol / n-hexane solution (V...) is added. 乙醇 :V 正己烷 The mixture was precipitated using a ratio of 1:3, filtered, the precipitate was collected, washed, and dried to obtain amino-terminated polybutadiene.

[0097] The preparation method of the reinforcing agent specifically includes the following steps:

[0098] S4. Accurately weigh 2.0 g of dibromonepentyl glycol and place it in a dry flask. Purge with flowing nitrogen to keep the reaction system anhydrous and oxygen-free. Add 150 mL of anhydrous 1,4-dioxane to completely dissolve the dibromonepentyl glycol. Then, add 7.0 g of bis(pinacol)diboron and 5.0 g of anhydrous potassium acetate to the reaction system in sequence. Stir at 300 rpm until the reactants are completely dissolved. Dissolve 67 mg of palladium acetate and 0.3 g of triphenylphosphine in 10 mL of anhydrous 1,4-dioxane and add them to the reaction system at a rate of 1 drop / s. Raise the reaction temperature to 65 °C for activation. After 20 min, continue to raise the temperature to 80 °C for borylation. React for 12 h. After the reaction is completed, let the reaction system cool to room temperature, add diatomaceous earth, filter, collect the filtrate, and wash the filter cake repeatedly with anhydrous 1,4-dioxane 3 times. Combine the washing liquid and filtrate, concentrate under reduced pressure to obtain intermediate A.

[0099] S5. Accurately weigh 6.0 g of 5-bromo-2-mercaptobenzothiazole and place it in a flask. Purge with flowing nitrogen to maintain anhydrous and oxygen-free reaction system. Add 50 mL of anhydrous THF and transfer to an ice-water bath for thorough cooling. Add 3.0 mL of trimethylchlorosilane and stir the reaction at room temperature for 3 h. After the reaction is complete, distill under reduced pressure to obtain the TSM-S-intermediate. Dissolve the TSM-S-intermediate in 100 mL of anhydrous 1,4-dioxane / anhydrous ethanol mixed solvent (V... 1,4-二氧六环 :V乙醇 In a mixture of 6:1, intermediate A prepared in step S4 and 1.6 g of anhydrous potassium carbonate were added and mixed thoroughly. Then, 0.13 g of tetra(triphenylphosphine)palladium was added to the reaction system. Under a nitrogen atmosphere, the reaction temperature was raised to 80 °C and refluxed for 16 h. After the reaction was completed, the reaction system was cooled to room temperature, filtered, and the filtrate was collected. The filtrate was cooled thoroughly in an ice-water bath. 8.0 g of tetrabutylammonium fluoride was dissolved in 30 mL of anhydrous ethanol. The mixture was stirred at room temperature for 4 h. Then, saturated ammonium chloride aqueous solution was added and stirred until no bubbles were generated. The organic phase was collected, dried with anhydrous magnesium sulfate, and distilled under reduced pressure to obtain intermediate B.

[0100] S6. Dissolve intermediate B prepared in step S5 in 80 mL of anhydrous dichloromethane. Purge the reaction system with flowing nitrogen to keep it anhydrous and oxygen-free. Transfer the system to an ice-water bath and stir at 400 rpm. After the reaction system is fully cooled, slowly add 35 μL of boron trifluoride diethyl ether complex. After mixing evenly, add 4.0 mL of glycidyl ether to the reaction system at a rate of 1 drop / s through a constant pressure dropping funnel. Stir at 400 rpm during the drop addition. After the drop addition is complete, stir for 30 min under ice-water bath conditions. After heating to room temperature, continue stirring at room temperature for 10 h to carry out the epoxidation reaction. After the reaction is completed, add saturated sodium bicarbonate aqueous solution and stir at 300 rpm for 10 min. Allow the mixture to stand and separate into layers. Collect the organic phase and wash it with saturated sodium bicarbonate aqueous solution. Combine the organic phases, dry them with anhydrous magnesium sulfate to remove water, and then concentrate the organic phase under reduced pressure to obtain the fortifying agent.

[0101] The preparation method of the toughening agent specifically includes the following steps:

[0102] S7. Place 4.0g of amino-terminated polybutadiene, 0.9g of amino-terminated polysiloxane, 0.6g of epoxidized soybean oil and 9.0g of fortifying agent in a flask, purge with flowing nitrogen to keep the reaction system anhydrous and oxygen-free, add 10mL of anhydrous toluene, turn on mechanical stirring, adjust the speed to 400rpm, mix evenly until the system forms a uniform pale yellow viscous liquid, add 2.3mL of 0.1mol / L acetic acid / anhydrous toluene solution at a rate of 1 drop / s, control the nitrogen flow rate at 5mL / min, raise the reaction temperature to 35℃ to carry out the first step reaction, react for 6h. After the reaction is completed, increase the nitrogen flow rate to 25mL / min, raise the reaction temperature to 60℃ to carry out the second step reaction, react for 5h. After the reaction is completed, cool, remove excess reaction solvent by vacuum distillation, vacuum dry, seal and store to obtain toughening agent;

[0103] This embodiment also provides a method for preparing a high-strength, low-temperature resistant, and aging-resistant polymeric rubber material, which specifically includes the following steps:

[0104] ① Start the open mill, set the front roller temperature to 95℃ and the rear roller temperature to 90℃, adjust the roller gap to 1.0mm, add NR, and plasticize for 5 minutes until the rubber surface is smooth and free of particles. Add styrene-butadiene rubber and cis-butadiene rubber, and continue plasticizing for 4 minutes to mix evenly to obtain the blended rubber base material.

[0105] ② Start the internal mixer, set the temperature to 135℃, the rotor speed to 60rpm, and the filling factor to 0.75. Add the blended rubber base material prepared in step ①, and mix for 1 minute until completely melted. Add carbon black in batches, along with silane coupling agent Si-69, zinc oxide, stearic acid, paraffin wax, and antioxidant 4020. Raise the temperature to 135℃ and continue mixing for 6 minutes. Open the discharge door of the internal mixer to discharge the masterbatch. Sheet the masterbatch on the open mill (roll gap 3mm), cool to room temperature, and let it stand for 2 hours to obtain the masterbatch.

[0106] ③ Adjust the internal mixer temperature to 85℃ and the rotor speed to 50rpm, add the masterbatch rubber prepared in step ②, internal mix for 1min until melted, add toughening agent, internal mix for 2min, finally add sulfur and accelerator CZ, internal mix for 4min, after unloading, sheet out on the open mill, cut the triangular bag three times with the cutter to ensure that each component is evenly dispersed, and obtain the compound rubber.

[0107] ④ Cut the final compounded rubber into sheets and place them in a cool, ventilated place for curing for 6 hours. Turn on the flat vulcanizing machine, set the temperature to 150℃ and the pressure to 12MPa, and preheat for 30 minutes. Take the compounded rubber prepared in step ③, place it in the mold, put it into the flat vulcanizing machine, and vulcanize for 20 minutes. During this time, keep the pressure stable. After vulcanization, quickly turn on the flat vulcanizing machine, take out the product, and place it on a room temperature cooling rack to cool to 25℃ to obtain the polymer rubber material.

[0108] Example 3

[0109] This embodiment proposes a high-strength, low-temperature resistant, and aging-resistant polymeric rubber material, which comprises the following components in parts by weight: 120 parts of rubber matrix, 62.5 parts of interface additives, 14 parts of vulcanization system, 4.5 parts of protective system, and 10 parts of toughening agent;

[0110] The rubber matrix comprises the following components in parts by weight: 50 parts natural rubber, 35 parts styrene-butadiene rubber, and 35 parts cis-butadiene rubber;

[0111] The interface additives include the following components in parts by weight: 60 parts carbon black and 2.5 parts silane coupling reagent Si-69;

[0112] The vulcanization system comprises the following components in parts by weight: 1.8 parts sulfur, 2.4 parts accelerator CZ, 2.8 parts stearic acid, and 7.0 parts zinc oxide;

[0113] The protective system comprises the following components in parts by weight: 1.5 parts paraffin wax and 3.0 parts antioxidant 4020;

[0114] The toughening agent is prepared from the following components in parts by weight: 4.2 parts of amino-terminated polybutadiene, 10 parts of reinforcing agent, 1.0 g of amino-terminated polysiloxane (poly(dimethylsiloxane) bis(3-aminopropyl)-terminated, PDMS, Aladdin P477941), and 0.8 g of epoxidized soybean oil.

[0115] The preparation method of amino-terminated polybutadiene specifically includes the following steps:

[0116] S1. Accurately weigh 20 mL of 1,3-butadiene / hexane solution (Innochem A93353, purity: 1.9 M solution inhexane) and place it in a dry flask. Purge the air in the reaction system with flowing nitrogen. Add 0.02 mL of pyridine and mix thoroughly. Accurately weigh 0.1 g of CoCl2 and 0.2 g of AlEt2Cl and dissolve them in 100 mL of anhydrous toluene. Take 10 mL of this solution and add it to the reaction system. Mix at 200 rpm until homogeneous. Seal the reaction system and raise the reaction temperature to 60 °C to carry out the polymerization reaction for 3 h. After the reaction is completed, allow the reaction system to cool to room temperature to obtain the polybutadiene reaction solution.

[0117] S2. Under a sealed, nitrogen atmosphere, accurately weigh 10 mL of hexamethylene diisocyanate and dissolve it in 100 mL of hexane to obtain a hexamethylene diisocyanate / hexane solution. Add 2.0 mL of the hexamethylene diisocyanate / hexane solution to the polybutadiene reaction solution prepared in step S1. Stir and mix at 200 rpm, then raise the reaction temperature to 60 °C to carry out the functionalization reaction. After the reaction is completed, add anhydrous ethanol to terminate the reaction and a precipitate is formed. Filter, collect the precipitate, wash it repeatedly with anhydrous ethanol 5 times, and then dry it under vacuum at 50 °C to constant weight to obtain amide-functionalized polybutadiene.

[0118] S3. Under a dry nitrogen atmosphere, place the amide-functionalized polybutadiene prepared in step S2 into an anhydrous flask, add 20 mL of anhydrous THF to dissolve the reactants, and then transfer to an ice-water bath. Stir at 200 rpm for thorough cooling. Accurately weigh 5 g of lithium aluminum hydride and 1.1 mL of titanium tetrachloride, dissolve them in 100 mL of anhydrous THF, and slowly add 2.0 mL of the solution to the reaction system at a rate of 1 drop / s. Maintain the ice-water bath conditions and stir at 400 rpm for the reduction reaction. The reaction should last for 3 hours. After the reaction is complete, a saturated ammonium chloride aqueous solution is added while stirring at 500 rpm until no more bubbles are generated. The mixture is then allowed to stand, filtered to remove the aluminum hydroxide precipitate, and the filtrate is collected. The filtrate is allowed to separate into layers. Due to the large amount of ammonium chloride in the deionized water, the deionized water and THF separate into two phases: the upper layer is the THF phase, and the lower layer is the ammonium chloride aqueous solution phase. The upper reaction layer is collected, and the lower reaction layer is washed with anhydrous THF. The THF phases are combined, dried over anhydrous magnesium sulfate to remove water, and then anhydrous ethanol / n-hexane solution (V...) is added. 乙醇 :V 正己烷 The mixture was precipitated using a ratio of 1:3, filtered, the precipitate was collected, washed, and dried to obtain amino-terminated polybutadiene.

[0119] The preparation method of the reinforcing agent specifically includes the following steps:

[0120] S4. Accurately weigh 2.0 g of dibromonepentyl glycol and place it in a dry flask. Purge with flowing nitrogen to keep the reaction system anhydrous and oxygen-free. Add 150 mL of anhydrous 1,4-dioxane to completely dissolve the dibromonepentyl glycol. Then, add 8.5 g of bis(pinacol)diboron and 6.3 g of anhydrous potassium acetate to the reaction system in sequence. Stir at 300 rpm until the reactants are completely dissolved. Dissolve 75 mg of palladium acetate and 0.35 g of triphenylphosphine in 10 mL of anhydrous 1,4-dioxane and add them to the reaction system at a rate of 1 drop / s. Raise the reaction temperature to 60 °C for activation. After 20 min, continue to raise the temperature to 90 °C for borylation. React for 8 h. After the reaction is completed, let the reaction system cool to room temperature, add diatomaceous earth, filter, collect the filtrate, and wash the filter cake repeatedly with anhydrous 1,4-dioxane 3 times. Combine the washing liquid and filtrate, concentrate under reduced pressure to obtain intermediate A.

[0121] S5. Accurately weigh 7.5 g of 5-bromo-2-mercaptobenzothiazole and place it in a flask. Purge with flowing nitrogen to maintain anhydrous and oxygen-free reaction system. Add 50 mL of anhydrous THF and transfer to an ice-water bath for thorough cooling. Add 4.0 mL of trimethylchlorosilane and stir the reaction at room temperature for 4 h. After the reaction is complete, distill under reduced pressure to obtain the TSM-S-intermediate. Dissolve the TSM-S-intermediate in 100 mL of anhydrous 1,4-dioxane / anhydrous ethanol mixed solvent (V... 1,4-二氧六环 :V乙醇 In a mixture of 6:1, intermediate A prepared in step S4 and 2.2 g of anhydrous potassium carbonate were added and mixed thoroughly. Then, 0.15 g of tetra(triphenylphosphine)palladium was added to the reaction system. Under a nitrogen atmosphere, the reaction temperature was raised to 90 °C and refluxed for 12 h. After the reaction was completed, the reaction system was cooled to room temperature, filtered, and the filtrate was collected. The filtrate was cooled thoroughly in an ice-water bath. 8.5 g of tetrabutylammonium fluoride was dissolved in 30 mL of anhydrous ethanol. The mixture was stirred at room temperature for 5 h. Then, saturated ammonium chloride aqueous solution was added and stirred until no bubbles were generated. The organic phase was collected, dried with anhydrous magnesium sulfate, and distilled under reduced pressure to obtain intermediate B.

[0122] S6. Dissolve intermediate B prepared in step S5 in 80 mL of anhydrous dichloromethane. Purge the reaction system with flowing nitrogen to keep it anhydrous and oxygen-free. Transfer the system to an ice-water bath and stir at 400 rpm. After the reaction system is fully cooled, slowly add 40 μL of boron trifluoride diethyl ether complex. After mixing evenly, add 4.8 mL of glycidyl ether to the reaction system at a rate of 1 drop / s through a constant pressure dropping funnel. Stir at 500 rpm during the drop addition. After the drop addition is complete, stir for 30 min under ice-water bath conditions. After heating to room temperature, continue stirring at room temperature for 8 h to carry out the epoxidation reaction. After the reaction is completed, add saturated sodium bicarbonate aqueous solution and stir at 300 rpm for 10 min. Allow the mixture to stand and separate into layers. Collect the organic phase and wash it with saturated sodium bicarbonate aqueous solution. Combine the organic phases, dry them with anhydrous magnesium sulfate to remove water, and then concentrate the organic phase under reduced pressure to obtain the fortifying agent.

[0123] The preparation method of the toughening agent specifically includes the following steps:

[0124] S7. Place 4.2g of amino-terminated polybutadiene, 1.0g of amino-terminated polysiloxane, 0.8g of epoxidized soybean oil and 10.0g of reinforcing agent in a flask, purge with flowing nitrogen to keep the reaction system anhydrous and oxygen-free, add 10mL of anhydrous toluene, turn on mechanical stirring, adjust the speed to 400rpm, mix evenly until the system forms a uniform pale yellow viscous liquid, add 2.2mL of 0.1mol / L acetic acid / anhydrous toluene solution at a rate of 1 drop / s, control the nitrogen flow rate at 5mL / min, raise the reaction temperature to 45℃ to carry out the first step reaction, react for 6h. After the reaction is completed, increase the nitrogen flow rate to 25mL / min, raise the reaction temperature to 70℃ to carry out the second step reaction, react for 4h. After the reaction is completed, cool, remove excess reaction solvent by vacuum distillation, vacuum dry, seal and store to obtain toughening agent;

[0125] This embodiment also provides a method for preparing a high-strength, low-temperature resistant, and aging-resistant polymeric rubber material, which specifically includes the following steps:

[0126] ① Start the open mill, set the front roller temperature to 95℃ and the rear roller temperature to 90℃, adjust the roller gap to 1.0mm, add 40 parts of NR, and plasticize for 5 minutes until the rubber surface is smooth and free of particles. Add styrene-butadiene rubber and cis-butadiene rubber, continue plasticizing for 5 minutes, mix evenly, and obtain the blended rubber base material.

[0127] ② Start the internal mixer, set the temperature to 135℃, the rotor speed to 60rpm, and the filling factor to 0.75. Add the blended rubber base material prepared in step ①, and mix for 1 minute until completely melted. Add carbon black in batches, along with silane coupling agent Si-69, zinc oxide, stearic acid, paraffin wax, and antioxidant 4020. Raise the temperature to 145℃ and continue mixing for 4 minutes. Open the discharge door of the internal mixer to discharge the masterbatch. Sheet the masterbatch on the open mill (roll gap 3mm), cool to room temperature, and let it stand for 2 hours to obtain the masterbatch.

[0128] ③ Adjust the internal mixer temperature to 85℃ and the rotor speed to 50rpm, add the masterbatch rubber prepared in step ②, internal mix for 1min until melted, add toughening agent, internal mix for 2min, finally add sulfur and accelerator CZ, internal mix for 5min, after unloading, sheet out on the open mill, cut the blade 3 times to make triangular wrapping to ensure that each component is evenly dispersed, and obtain the compound rubber.

[0129] ④ Cut the final compounded rubber into sheets and place them in a cool, ventilated place for curing for 8 hours. Turn on the flat vulcanizing machine, set the temperature to 150℃ and the pressure to 12MPa, and preheat for 30 minutes. Take the compounded rubber prepared in step ③, place it in the mold, put it into the flat vulcanizing machine, and vulcanize for 15 minutes. During this period, keep the pressure stable. After vulcanization, quickly turn on the flat vulcanizing machine, take out the product, and place it on a room temperature cooling rack to cool to 25℃ to obtain the polymer rubber material.

[0130] Comparative Example 1

[0131] This comparative example provides a polymeric rubber material and its preparation method. The only difference between this material and Example 1 is that the toughening agent is made by replacing the amino-terminated polybutadiene with commercially available polybutadiene in the same weight proportions. The remaining components and their contents are the same as in Example 1.

[0132] Comparative Example 2

[0133] This comparative example provides a polymer rubber material and its preparation method. The only difference between this material and Example 1 is that the toughening agent is replaced with the same weight parts of commercially available epoxidized soybean oil as the reinforcing agent. The remaining components and their contents are the same as in Example 1.

[0134] Comparative Example 3

[0135] This comparative example provides a polymer rubber material and its preparation method. The only difference between this material and Example 1 is that the toughening agent is replaced with the same weight parts of commercially available polysiloxane (Aladdin D283296, dimethyl polysiloxane) instead of the amino-terminated polysiloxane. The remaining components and their contents are the same as in Example 1.

[0136] Experimental Example

[0137] Performance tests were conducted on Examples 1-3 and Comparative Examples 1-3:

[0138] 1. Perform mechanical property testing according to GB / T 528-2019. Measure the thickness and width of the working part of each specimen at three different locations using calipers, and take the average value as the effective size of the specimen. Turn on the universal testing machine, set the test temperature to (23±2)℃, the tensile rate to (500±50) mm / min, and preheat for 30 minutes. Symmetrically clamp both ends of the specimen in the fixture, ensuring that the specimen axis is aligned with the direction of the tensile force and that the clamping force is moderate. Start the testing machine and record the stress-strain curve until the specimen breaks. Read the maximum tensile force (F) at fracture. max The tensile strength (σ, MPa) and elongation at break (ε) are calculated using the following formulas: gauge length elongation (ΔL) at break. β ,%):

[0139] ;

[0140] Among them, F max denoted as maximum tensile force (N), b as width of the working part of the specimen (mm), and d as thickness of the working part of the specimen (mm).

[0141] ;

[0142] Where L0 is the initial length of the working part of the sample (25mm), and ΔL is the gauge length elongation at fracture (mm).

[0143] 2. Conduct low-temperature resistance tests according to GB / T 528-2019. Place the cut sample into a low-temperature environment chamber, set the temperature to (-30±1)℃, maintain the temperature for (30±5) min, turn on the universal testing machine, quickly clamp the sample in the low-temperature chamber, set the tensile rate to (500±50) mm / min, start the test, record the tensile force and elongation at break, and calculate the tensile strength and elongation at break at -30℃.

[0144] 3. Perform the embrittlement temperature test according to GB / T 15256-2014. Set the initial temperature of the low-temperature chamber (e.g., -40℃), place the sample in the low-temperature chamber, maintain the temperature for (30±2) min, start the impact device, and impact the sample. Observe whether the sample breaks. If the sample does not break, lower the temperature by 5℃ and repeat the steps. If the sample breaks, raise the temperature by 5℃ and repeat the steps until the temperature at which 50% of the samples break is found. This temperature is the embrittlement temperature (T). β );

[0145] 4. Aging resistance tests were conducted according to GB / T 3512-2014. Aging conditions were set as follows: Aging temperature: (100±1)℃ (accelerated aging to simulate long-term use environment); Aging time: 72h (accelerated aging cycle commonly used for rubber, balancing testing efficiency and aging effect); Aging environment: air atmosphere, samples suspended; The tensile strength (σ0) and elongation at break (ε0) of the blank group samples were tested. The aged group samples were placed in a hot air aging chamber and aged for 72h under the set conditions. After aging, the samples were removed and placed in an environment with a temperature of (23±2)℃ and a relative humidity of (50±5)% for (24±2)h. The tensile strength (σ0) of the aged group samples was then tested. a ) and elongation at break (ε a ), calculate the tensile strength retention rate (K) according to the following formula. σ (%) and elongation at break retention rate (K) ε ,%):

[0146] ;

[0147] ;

[0148] Figure 1 The graphs show the tensile strength results of the polymer rubber materials prepared in Examples 1-3 and Comparative Examples 1-3 of this invention. Figure 2The figures show the elongation at break of the polymeric rubber materials prepared in Examples 1-3 and Comparative Examples 1-3 of this invention. As shown, in a low-temperature environment, the polymeric rubber materials prepared in Examples 1-3 maintained a tensile strength of 18.7-22.4 MPa and an elongation at break of 595-680%. The sulfenamide dynamic bonds all exhibit low-temperature reversibility; at -30°C, the -S-NH- bonds can still break and recombine rapidly, alleviating stress concentration caused by increased molecular chain rigidity at low temperatures. The terminal amino polysiloxanes have interfacial lubrication properties; the siloxane segments remain flexible at low temperatures, reducing the frictional resistance between the rubber, toughening agent, and carbon black. To enhance the mobility of molecular chains, Comparative Example 1 lacks dynamic bonds (-S-NH- bonds) and relies solely on a cross-linked network for support. At low temperatures, the network is prone to brittle fracture, with a significant decrease in elongation at break and tensile strength at -30°C, exhibiting clear brittle characteristics. Comparative Example 2, lacking the dynamic bonds and cross-linking sites of the reinforcing agent, results in rigid rubber chains at low temperatures, preventing molecular chain slippage. At -30°C, the elongation at break is only 320%, and the tensile strength retention rate is 71.1%, exhibiting typical brittle fracture. Comparative Example 3 retains the dynamic bonds of the reinforcing agent, partially alleviating stress at low temperatures. However, the poor interfacial compatibility of ordinary polysilanes exacerbates interfacial cracking at low temperatures, failing to achieve the low-temperature toughness of the examples.

[0149] Figure 3The figures show the aging resistance results of the polymer rubber materials prepared in Examples 1-3 and Comparative Examples 1-3 of this invention. As shown in the figures, the polymer rubber materials prepared in Examples 1-3 all exhibited excellent aging resistance, with Example 3 showing the best performance, Example 1 showing balanced performance, and Example 2 showing slightly lower performance but still at a high level. The reinforcing agent, amino-terminated polybutadiene, and amino-terminated polysiloxane formed a dense cross-linked network through an epoxy-amino reaction. Combined with high-filler carbon black, a physical barrier layer was formed, which significantly hindered the diffusion and penetration of oxygen and heat, preventing the interface from debonding and creating permeation channels during aging. The sulfenamide dynamic bonds can be reversibly broken and recombined during aging, self-repairing the microcracks in the molecular chains and maintaining the stability of the system structure.Comparative Example 1 exhibited poor aging resistance, with a tensile strength retention rate of only 72% and an elongation at break retention rate of 68%. The main reason for this was the substitution of terminal-amino polybutadiene with commercially available ordinary polybutadiene, leading to the failure of two core anti-aging mechanisms. Commercially available polybutadiene lacks amino functional groups and cannot form sulfenamide dynamic bonds with the -SH group in the reinforcing agent, thus lacking the dynamic repair function for aging damage. This prevents the molecular chain microcracks generated during aging from reorganizing and instead allows them to continue to expand. Without amino groups participating in the cross-linking reaction, its oxygen barrier capacity is insufficient. Furthermore, ordinary polybutadiene has poor interfacial compatibility with the rubber matrix and carbon black, resulting in problems during the aging process. It is prone to interfacial debonding, forming gaps where oxygen can quickly penetrate, accelerating the internal oxidative degradation of the rubber, and ultimately leading to a significant decline in performance. Comparative Example 2 has the worst aging resistance, with a tensile strength retention rate of 68% and an elongation at break retention rate of 65%, making it the weakest in anti-aging ability among all samples. It uses commercially available epoxidized soybean oil (ESO) to replace the chemical reinforcing agent, completely losing the multiple anti-aging functions brought by the reinforcing agent. Lacking benzothiazole groups, it cannot form a synergistic free radical scavenging system with antioxidant 4020. Relying solely on antioxidant 4020, the free radical scavenging efficiency decreases. ESO contains only a small amount of epoxy groups and cannot... The formation of a dense cross-linked network fails to effectively block oxygen diffusion. After aging, the cross-linked network collapses severely, lacking the repair effect of sulfenamide dynamic bonds and the interface optimization provided by benzothiazole groups. During aging, significant carbon black debonding occurs, forming interfacial gaps. Oxygen rapidly penetrates through these gaps, triggering double aging and a comprehensive decline in all properties. Comparative Example 3 exhibits slightly better aging resistance than Comparative Examples 1 and 2, but still significantly lower than Examples 1-3, with a tensile strength retention rate of 75% and an elongation at break retention rate of 70%. Ordinary polysilane was used instead of ATPDMS. Ordinary polysilane lacks amino functional groups and cannot participate in cross-linking. While the reaction enhances network density, it also fails to form stable chemical bonds with rubber and carbon black, resulting in poor interfacial compatibility. During aging, the interfacial tension increases, leading to the formation of numerous interfacial microcracks, through which oxygen rapidly penetrates into the material's interior. Simultaneously, ordinary polysilanes tend to be rigid at low temperatures, unlike amino-terminated polysiloxanes which maintain interfacial flexibility, further exacerbating interfacial damage. Although it retains the synergistic free radical scavenging function of the benzothiazole group of the reinforcing agent and the antioxidant 4020, which inhibits direct molecular chain degradation to some extent, the interface becomes a weak link in aging, ultimately resulting in a performance retention rate far lower than that of the example.

[0150] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention.

[0151] The present invention and its embodiments have been described above. This description is not restrictive, and the accompanying drawings are only one embodiment of the present invention. The actual application is not limited to this. In conclusion, if those skilled in the art are inspired by this description and design similar methods and embodiments without departing from the spirit of the present invention, they should all fall within the protection scope of the present invention.

Claims

1. A high-strength, low-temperature resistant, and aging-resistant polymeric rubber material, characterized in that: The polymer rubber material comprises the following components in parts by weight: 100-120 parts rubber matrix, 44-62.5 parts interface additives, 8-15 parts vulcanization system, 4-5 parts protective system, and 8-12 parts toughening agent; the rubber matrix comprises the following components in parts by weight: 38-50 parts natural rubber, 30-35 parts styrene-butadiene rubber, and 30-40 parts cis-butadiene rubber; the interface additives comprise the following components in parts by weight: 42-60 parts carbon black and 1.5-2.5 parts silane coupling reagent Si-69; the vulcanization system comprises the following components in parts by weight: 1.2-1.8 parts sulfur, 1.8-2.4 parts accelerator CZ, 1.6-2.8 parts stearic acid, and 4.6-7.0 parts zinc oxide; the protective system comprises the following components in parts by weight: 1.5-2.5 parts paraffin wax and antioxidant 4020. 2.0-3.0 parts; the raw materials for preparing the toughening agent include the following components in parts by weight: 3.8-4.2 parts of amino-terminated polybutadiene, 8-10 parts of reinforcing agent, 0.8-1.0 g of amino-terminated polysiloxane, and 0.5-0.8 g of epoxidized soybean oil.

2. The high-strength, low-temperature resistant, and aging-resistant polymeric rubber material according to claim 1, characterized in that: The preparation method of the amino-terminated polybutadiene specifically includes the following steps: S1. Place a 1,3-butadiene / hexane solution in a dry flask, introduce flowing nitrogen gas, add pyridine and mix well. Dissolve CoCl2 and AlEt2Cl in anhydrous toluene and add it to the reaction system. Under sealed conditions, raise the reaction temperature to carry out the polymerization reaction. After the reaction is completed, cool to obtain polybutadiene reaction solution. S2. Under a sealed, nitrogen atmosphere, hexamethylene diisocyanate / hexane solution is added to the polybutadiene reaction solution prepared in step S1. The reaction temperature is increased to carry out the functionalization reaction. After the reaction is completed, anhydrous ethanol is added to terminate the reaction and a precipitate is generated. The precipitate is filtered, collected, washed repeatedly, and dried to obtain amide-functionalized polybutadiene. S3. Under a dry nitrogen atmosphere, the amide-functionalized polybutadiene prepared in step S3 was dissolved in anhydrous THF and transferred to an ice-water bath for cooling. Lithium aluminum hydride and titanium tetrachloride were slowly added, and the reduction reaction was carried out under ice-water bath conditions. After the reaction was completed, saturated ammonium chloride aqueous solution was added until no bubbles were generated. The mixture was allowed to stand, filtered, and the filtrate was collected. After standing and separating into layers, the upper reaction layer was collected, and the lower reaction layer was extracted with anhydrous THF. The THF phases were combined, dried with anhydrous magnesium sulfate, and precipitated with ethanol / n-hexane solution. The precipitate was filtered, collected, washed, and dried to obtain amino-terminated polybutadiene.

3. The high-strength, low-temperature resistant, and aging-resistant polymeric rubber material according to claim 2, characterized in that: In step S1, the volume fraction of pyridine in the 1,3-butadiene / hexane solution is 0.05%-0.1%; the mass-to-volume ratio of CoCl2 to 1,3-butadiene is 0.25-0.5 mg / mL; the mass-to-volume ratio of AlEt2Cl to 1,3-butadiene is 0.5-1.0 mg / mL; the polymerization temperature is 50-60℃; and the polymerization time is 3-4 h.

4. The high-strength, low-temperature resistant, and aging-resistant polymeric rubber material according to claim 3, characterized in that: In step S2, the hexamethylene diisocyanate has a mass fraction of 0.5%-1.0% in the 1,3-butadiene / hexane solution described in step S1; the functionalization reaction temperature is 50-60℃, and the functionalization reaction time is 3-4h. In step S3, the mass-to-volume ratio of lithium aluminum hydride to hexamethylene diisocyanate in step S2 is 0.5-0.95 g / mL; the volume ratio of titanium tetrachloride to hexamethylene diisocyanate in step S2 is 0.11-0.22:1; the stirring speed of the reduction reaction is 200-400 rpm, and the reduction reaction time is 3-5 h.

5. The high-strength, low-temperature resistant, and aging-resistant polymeric rubber material according to claim 4, characterized in that: The preparation method of the reinforcing agent specifically includes the following steps: S4. Dissolve dibromonepentylene glycol in anhydrous 1,4-dioxane. Under a nitrogen atmosphere, add bis(pinacolyl)diboron and anhydrous potassium acetate to the reaction system in sequence. Stir until the reactants are completely dissolved. Prepare a palladium acetate and triphenylphosphine catalytic system and slowly add it to the reaction system. Increase the temperature to carry out the activation reaction. Continue to increase the temperature to carry out the borylation reaction. After the reaction is completed, cool, add diatomaceous earth, filter, collect the filtrate, and distill under reduced pressure to obtain intermediate A. S5. Dissolve 5-bromo-2-mercaptobenzothiazole in anhydrous THF, transfer to an ice-water bath for thorough cooling, add trimethylchlorosilane, and stir the reaction at room temperature for 2-4 hours. After the reaction is complete, distill under reduced pressure to obtain TSM-S-intermediate. Dissolve TSM-S-intermediate in anhydrous 1,4-dioxane / anhydrous ethanol mixed solvent, add intermediate A prepared in step S4 and anhydrous potassium carbonate, mix well, add tetra(triphenylphosphine)palladium to the reaction system, and reflux the reaction under a nitrogen atmosphere. After the reaction is complete, cool, filter, collect the filtrate, cool the filtrate thoroughly in an ice-water bath, add tetrabutylammonium fluoride, stir the reaction at room temperature for 3-5 hours, add saturated ammonium chloride aqueous solution and stir until no bubbles are generated, collect the organic phase, dry the organic phase with anhydrous magnesium sulfate, and distill under reduced pressure to obtain intermediate B. S6. Dissolve intermediate B prepared in step S5 in anhydrous dichloromethane, transfer it to an ice-water bath for cooling under a nitrogen atmosphere, add boron trifluoride diethyl ether complex, mix well, add glycidyl ether through a constant pressure dropping funnel, and after the addition is complete, carry out an epoxidation reaction at room temperature. After the reaction is complete, wash with saturated sodium bicarbonate aqueous solution, collect the organic phase, dry it with anhydrous magnesium sulfate to remove water, and then distill under reduced pressure to obtain the fortifying agent.

6. The high-strength, low-temperature resistant, and aging-resistant polymeric rubber material according to claim 5, characterized in that: In step S4, the mass ratio of dibromonepentyl glycol to bis(pinacol)diboron is 0.34-0.47:1; the mass ratio of dibromonepentyl glycol to anhydrous potassium acetate is 0.54-0.64:1; the mass ratio of palladium acetate, triphenylphosphine, and dibromonepentyl glycol is 0.05-0.75:0.27-0.35:2-4; the activation reaction temperature is 60-65℃, and the activation reaction time is 20-30 min; the borylation reaction time is 80-90℃, and the borylation reaction temperature is 8-12 h.

7. The high-strength, low-temperature resistant, and aging-resistant polymeric rubber material according to claim 6, characterized in that: In step S5, the mass-to-volume ratio of 5-bromo-2-mercaptobenzothiazole to trimethylchloropropane is 1.8-2.0 g / mL; the mass ratio of 5-bromo-2-mercaptobenzothiazole to bis(pinacol)diboron in step S4 is 0.78-0.88:1; the mass ratio of anhydrous potassium carbonate to 5-bromo-2-mercaptobenzothiazole is 1:3.4-4.5; the mass fraction of tetra(triphenylphosphine)palladium in 5-bromo-2-mercaptobenzothiazole is 2.0%-2.2%; the mass-to-volume ratio of tetrabutylammonium fluoride to trimethylchloroalkane is 2.1-3.0 g / mL; the reflux reaction temperature is 80-90℃, and the reflux reaction time is 12-16 h.

8. The high-strength, low-temperature resistant, and aging-resistant polymeric rubber material according to claim 7, characterized in that: In step S6, the mass-to-volume ratio of dibromonepentylene glycol to glycidyl ether in step S4 is 0.67-0.83 g / mL; the volume fraction of the boron trifluoride diethyl ether complex in glycidyl ether is 8.3%-10.0%; the stirring speed of the epoxidation reaction is 300-500 rpm, and the reaction time of the epoxidation reaction is 8-12 h.

9. The high-strength, low-temperature resistant, and aging-resistant polymeric rubber material according to claim 8, characterized in that: The preparation method of the toughening agent specifically includes the following steps: S7. Place amino-terminated polybutadiene, amino-terminated polysiloxane, epoxidized soybean oil and the fortifying agent in a flask, introduce flowing nitrogen gas, add anhydrous toluene, mix well, add acetic acid / anhydrous toluene solution, control the flow rate of nitrogen gas, increase the reaction temperature to carry out the first step reaction, after the reaction is completed, increase the flow rate of nitrogen gas, increase the reaction temperature to carry out the second step reaction, after the reaction is completed, cool, remove excess reaction solvent by vacuum distillation, vacuum dry, seal and store to obtain toughening agent; In step S7, the mass-volume ratio of the reinforcing agent to acetic acid is 3.2-4.5 g / mL; the reaction temperature of the first step reaction is 35-45℃, the nitrogen flow rate of the first step reaction is 2-5 mL / min, and the reaction time of the first step reaction is 6-8 h; the reaction temperature of the second step reaction is 60-70℃, the nitrogen flow rate of the second step reaction is 20-25 mL / min, and the reaction time of the second step reaction is 4-6 h.

10. A method for preparing a high-strength, low-temperature resistant, and aging-resistant polymeric rubber material according to claim 9, characterized in that: Specifically, the steps include the following: ① Start the open mill, set the front roll temperature and rear roll temperature, adjust the roll gap, add natural rubber, and plasticize until the rubber surface is smooth and free of particles. Add styrene-butadiene rubber and cis-butadiene rubber, continue plasticizing for 3-5 minutes, mix evenly, and obtain the blended rubber base material. ② Start the internal mixer, set the temperature, rotor speed, and filling factor, add the blended rubber base material prepared in step ①, and mix until completely melted. Add carbon black in batches, along with silane coupling agent Si-69, zinc oxide, stearic acid, paraffin wax, and antioxidant 4020. Raise the temperature to 135-145℃ and continue mixing for 4-6 minutes. Open the discharge door of the internal mixer to discharge the masterbatch. Sheet the masterbatch on the open mill, cool it to room temperature, and let it stand to obtain the masterbatch. ③ Adjust the temperature and rotor speed of the internal mixer, add the masterbatch rubber prepared in step ②, mix until melted, add toughening agent, mix, and finally add sulfur and accelerator CZ, mix for 3-5 minutes, unload and sheet on the open mill, cut the triangular package with a cutter to ensure that each component is evenly dispersed to obtain the compound rubber. ④ Cut the final compounded rubber into sheets and place them in a cool, ventilated place for curing for 4-8 hours. Turn on the flat vulcanizing machine, set the temperature and pressure, and preheat it. Take the compounded rubber prepared in step ③, place it in the mold, put it into the flat vulcanizing machine, and vulcanize it for 15-20 minutes. During this time, keep the pressure stable. After vulcanization, quickly turn on the flat vulcanizing machine, take out the product, and place it on a room temperature cooling rack to cool to 25°C to obtain the polymer rubber material.

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