High-elastic wear-resistant rubber composite material and preparation method thereof

Abstract

The preparation method comprises the following steps: adding zinc-based porous carbon sphere composite material modified hydrogenated butadiene-acrylonitrile rubber into chlorobenzene, carrying out ultrasonic dispersion, adding aramid fibers, carrying out shear emulsification, dropwise adding ethanol to precipitate rubber, standing, filtering, and carrying out vacuum drying to obtain masterbatch; adding the master batch, clay gel, nano zinc oxide, an anti-aging agent 4020 and stearic acid into an internal mixer, mixing, discharging rubber, and curing at room temperature to obtain a rubber compound; and adding an accelerant CZ, sulfur, an antioxidant 1010 and CTAC into the rubber compound in an open mill, carrying out thin-passing batch-out, placing the obtained product in a press vulcanizer, carrying out vulcanization, and carrying out secondary vulcanization so as to obtain the finally vulcanized and molded high-elastic wear-resistant rubber composite material. According to the composite material, the zinc-based porous carbon spheres and an MOF modification technology are introduced, so that the mechanical strength and wear resistance of the rubber composite material are remarkably improved, stress concentration is effectively reduced through a hierarchical pore structure and uniform interface combination, and the high elasticity and high-pressure impact resistance of the material are enhanced.

Description

Technical Field

[0001] The invention belongs to the technical field of rubber, and in particular relates to a high-elasticity and wear-resistant rubber composite material and a preparation method thereof. Background Art

[0002] Rubber is a polymer elastic material that is divided into two categories: natural rubber and synthetic rubber. Natural rubber is mainly extracted from rubber trees, while synthetic rubber is polymerized from petrochemical raw materials. Due to its unique physical and chemical properties, rubber is widely used in tires, seals, shock absorbers, conveyor belts, hoses and various industrial products. It is one of the indispensable materials in modern industry and daily life.

[0003] Chinese patent application CN119684692A discloses a highly elastic, high-pressure, impact-resistant, wear-resistant rubber carpet and its preparation process. By adding modified hydrogenated nitrile rubber, the service life of the nitrile rubber composite material is extended. The carbon-carbon double bonds on the main chain of the nitrile rubber molecule are hydrogenated into saturated single bonds, thereby improving the heat resistance of the nitrile rubber composite material. By grafting aminoimidazole monomers onto the hydrogenated nitrile rubber molecular chain, the low-temperature resistance of the nitrile rubber composite material is improved.

[0004] In the above-mentioned patented technical solution, by introducing hexadecyltrimethylammonium chloride, the modified hydrogenated nitrile rubber molecular chain is made to slide more easily from the clay surface, thereby improving the interfacial interaction between the clay and the rubber matrix, reducing the stress concentration defect at the interface, and improving the tensile strength of the nitrile rubber composite material. However, the introduced hexadecyltrimethylammonium chloride can only reduce stress concentration by improving interfacial slip, has a single function, and the effect achieved is limited, which has certain limitations. Summary of the Invention

[0005] The object of the present invention is to provide a highly elastic and wear-resistant rubber composite material and a preparation method thereof. By introducing zinc-based porous carbon spheres as a reinforcing phase, high-temperature carbonization and MOF in-situ growth are used to construct a multi-level pore structure to improve the mechanical strength and wear resistance of the material. The uniform growth of MOF crystals on the surface of the carbon spheres is then used to improve the interface bonding between the filler and the rubber matrix and reduce stress concentration, in order to solve the technical problem in the prior art that the introduction of hexadecyltrimethylammonium chloride can only reduce stress concentration by improving interfacial slip, but the effect achieved is limited and has certain limitations.

[0006] The purpose of the present invention can be achieved through the following technical solutions: A high-elasticity and wear-resistant rubber composite material and a preparation method thereof, comprising the following steps: Step 1: adding zinc-based porous carbon sphere composite material modified hydrogenated nitrile rubber to chlorobenzene, ultrasonically dispersing at 45-55° C. for 1-2 hours, adding aramid fiber treated with silane coupling agent KH550, shearing and emulsifying at 10000-10020 rpm for 30-40 minutes, adding ethanol dropwise to precipitate the rubber, letting it stand for 6-7 hours, filtering, and vacuum drying at 60-80° C. for 24-26 hours to obtain a masterbatch; Add masterbatch, clay gel, nano zinc oxide, antioxidant 4020 and stearic acid in an internal mixer at 70-80°C in sequence, mix for 15-25 minutes, then discharge the rubber, and mature at room temperature for 16-18 hours to obtain a rubber mix; Add accelerator CZ, sulfur, antioxidant 1010 and CTAC to the rubber mix in an open mill at 60-70°C, pass the mixture 5-7 times, remove the sheet, leave it for 16-18 hours, and then place it in a flat vulcanizer for vulcanization at 160-170°C and 15-25MPa for 15-20 minutes, and then perform secondary vulcanization at 150-160°C for 2-3 hours to obtain the final vulcanized high-elasticity and wear-resistant rubber composite material.

[0007] Furthermore, the zinc-based porous carbon sphere composite material modified hydrogenated nitrile rubber is prepared by the following steps: Step 1, hydrogenated nitrile rubber and chlorobenzene are placed in a high-pressure reactor, stirred at 60-70°C for 3-4 hours under the condition of 800-1000r / min, and then potassium hydroxide is added. After three nitrogen-hydrogen replacements, hydrogen is filled to 2-3MPa, and stirred at 80-90°C under the condition of 200-300r / min for 4-5 hours; the pressure is released, and a zinc-based porous carbon ball composite material composite material is added, and the reaction is carried out at 90-100°C for 5-6 hours under nitrogen protection; after the reaction is completed, the product is separated by centrifugation at 3000-3200rpm for 10-15min, washed with ethanol 3-5 times, and then vacuum dried at 60-80°C for 12-14 hours to obtain a zinc-based porous carbon ball composite material modified hydrogenated nitrile rubber.

[0008] Furthermore, the MOF-composite zinc-based porous carbon sphere composite material is prepared by the following steps: Step 1: Place zinc-based porous carbon spheres and deionized water in a reactor and ultrasonically disperse for 1-2 hours to form a uniform dispersion. Add zinc nitrate hexahydrate and methanol to the reactor for dissolution reaction. Then add 2,5-diaminoterephthalic acid and continue stirring at 300-400 r / min. Add the resulting solution dropwise to the zinc-based porous carbon sphere dispersion. Control the addition rate to keep the reaction system clear. Continue stirring at 300-400 r / min at room temperature for 6-7 hours to allow MOF crystals to fully grow on the surface of the zinc-based porous carbon spheres. After the reaction is complete, centrifuge the mixture and wash it with methanol and deionized water 3-5 times each. The resulting solid product is dried in a vacuum drying oven at 60-70°C for 12-14 hours to obtain a MOF-composite zinc-based porous carbon sphere composite material.

[0009] Furthermore, zinc-based porous carbon spheres are prepared by the following steps: Step 1, add 0.4 mol / L sucrose solution and hexadecyltrimethylammonium bromide to the reactor, stir for 30-36 minutes at 20-25 ° C and 500-600 r / min to form a uniform mixture, then add 20 mmol / L zinc chloride solution, continue stirring for 30-40 minutes to fully combine, transfer to a high-pressure reactor, seal and place in a 170-180 ° C oven for 7-9 hours, and naturally cool to room temperature after the reaction. The reaction product is centrifuged, washed with deionized water and anhydrous ethanol 5-7 times in sequence, and vacuum dried at 60-70 ° C for 12-14 hours to obtain zinc-doped carbon spheres; The zinc-doped carbon spheres were thoroughly ground and mixed with an equal mass of potassium hydroxide powder in a mortar, transferred to a tube furnace, and heated to 700-800°C at a heating rate of 5-6°C / min under nitrogen protection. The mixture was kept warm for 1-2 hours and naturally cooled to room temperature. The product was soaked in 0.3 mol / L hydrochloric acid solution for 12-14 hours to remove residual zinc species, then washed with deionized water until neutral, and vacuum dried at 80-85°C for 24-26 hours to obtain zinc-based porous carbon spheres.

[0010] Furthermore, in the step, the usage ratio of sucrose solution, hexadecyltrimethylammonium bromide, zinc chloride solution, and hydrochloric acid solution is: 100-110 mL: 12.5-13 g: 62.5-64.5 mL: 50-60 mL.

[0011] Furthermore, in the step, the usage ratio of zinc-based porous carbon spheres, deionized water, zinc nitrate hexahydrate, methanol, and 2,5-diaminoterephthalic acid is 10-20 g: 500-550 mL: 3-5 g: 100-110 mL: 3-5 g.

[0012] Furthermore, in the step, the usage ratio of hydrogenated butyronitrile, chlorobenzene, potassium hydroxide, and MOF-compounded zinc-based porous carbon sphere composite material is 80-90 g: 400-500 mL: 8-12 g: 10-14 g.

[0013] Furthermore, in the step, the dosage ratio of the zinc-based porous carbon ball composite material modified hydrogenated nitrile rubber, chlorobenzene, aramid fiber, ethanol precipitated glue, masterbatch, clay gel, nano zinc oxide, antioxidant 4020, stearic acid, accelerator CZ, sulfur, antioxidant 1010, and CTAC is 50-60g:250-260mL:5-7g:500-550mL:100-120g:2-4g:5-7g:2-4g:1-2g:1.5-2.5g:2-4g:1-2g:0.5-1.5g.

[0014] Beneficial effects of the present invention: 1. The present invention significantly improves the mechanical strength, wear resistance and impact resistance of rubber composite materials by introducing zinc-based porous carbon spheres and MOF modification technology. The multi-level pore structure and uniform interface effectively reduce stress concentration, enhance the material's high elasticity and high-pressure impact resistance, and the optimized process parameters further improve the material's overall performance. At the same time, the zinc-based porous carbon spheres also give the material additional thermal conductivity or damping functions, giving it a wider application prospect in the field of wear-resistant rubber. DETAILED DESCRIPTION

[0015] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0016] Example 1: A highly elastic and wear-resistant rubber composite material and a preparation method thereof, comprising the following steps: S1. Add 100 mL of 0.4 mol / L sucrose solution and 12.5 g of hexadecyltrimethylammonium bromide into a reactor, stir at 20°C and 500 r / min for 30 min to form a uniform mixture, then add 62.5 mL of 20 mmol / L zinc chloride solution, continue stirring at 500 r / min for 30 min to fully combine, transfer to a high-pressure reactor, seal and place in a 170°C oven for 7 h, and naturally cool to room temperature after the reaction. The reaction product is centrifuged, washed with deionized water and anhydrous ethanol 5 times in sequence, and dried in vacuo at 60°C for 12 h to obtain zinc-doped carbon spheres; Zinc-doped carbon spheres were thoroughly ground and mixed with an equal mass of potassium hydroxide powder in a mortar, transferred to a tube furnace, and heated to 700°C at a heating rate of 5°C / min under nitrogen protection. The mixture was kept warm for 1 hour and naturally cooled to room temperature. The product was soaked in 50mL0.3 mol / L hydrochloric acid solution for 12 hours to remove residual zinc species, then washed with deionized water until neutral, and dried in vacuum at 80°C for 24 hours to obtain zinc-based porous carbon spheres.

[0017] Sucrose was converted into a mesoporous carbon sphere skeleton under the guidance of hexadecyltrimethylammonium bromide template through a two-step method of hydrothermal carbonization and potassium hydroxide activation.

[0018] S2. Place 10g of zinc-based porous carbon spheres and 500mL of deionized water in a reactor and ultrasonically disperse for 1h to form a uniform dispersion. Add 3g of zinc nitrate hexahydrate and 100mL of methanol to the reactor for dissolution reaction. Then add 3g of 2,5-diaminoterephthalic acid and continue stirring at 300-400r / min. Slowly add the obtained solution dropwise to the zinc-based porous carbon sphere dispersion, controlling the dropwise addition speed to keep the reaction system clear. Then continue stirring at 300r / min at room temperature for 6h to allow MOF crystals to fully grow on the surface of the zinc-based porous carbon spheres. After the reaction is complete, the mixed solution is centrifuged and washed three times with methanol and deionized water respectively. The resulting solid product is dried in a vacuum drying oven at 60°C for 12h to obtain a MOF-composite zinc-based porous carbon sphere composite material.

[0019] The oxygen-containing functional groups on the surface of zinc-based porous carbon spheres are used as nucleation sites, and the in situ growth of MOF crystals on the surface of carbon spheres is achieved through coordination self-assembly of zinc ions and 2-methylimidazole.

[0020] S3. Put 80g of hydrogenated nitrile rubber and 400mL of chlorobenzene into a high-pressure reactor, stir at 60℃ at 800r / min for 3h, then add 8g of potassium hydroxide, and charge with hydrogen to 2MPa after three nitrogen-hydrogen replacements. Stir and react at 80℃ at 200r / min for 4h, release the pressure, and then add 10g of MOF-composite zinc-based porous carbon ball composite material. React at 90℃ for 5h under nitrogen protection. After the reaction, centrifuge at 3000rpm for 10min to separate the product, wash with ethanol 3 times, and vacuum dry at 60℃ for 12h to obtain zinc-based porous carbon ball composite material modified hydrogenated nitrile rubber.

[0021] The MOF-compounded zinc-based porous carbon spheres are mixed into hydrogenated nitrile rubber, and the amino groups on the MOF-compounded zinc-based porous carbon sphere composite material are reacted and grafted with the epoxy groups in the hydrogenated nitrile rubber to improve the bonding strength between the MOF-compounded zinc-based porous carbon spheres and the hydrogenated nitrile rubber.

[0022] S4. Add 50g of zinc-based porous carbon ball composite material modified hydrogenated nitrile rubber into 250mL of chlorobenzene, ultrasonically disperse at 45℃ for 1h, add 5g of aramid fiber treated with silane coupling agent KH550, emulsify at high speed shear at 10000rpm for 30min, slowly add 500mL of ethanol to precipitate the glue, let it stand for 6h and then filter, and vacuum dry at 60℃ for 24h to obtain a masterbatch; add 100g of masterbatch, 2g of clay gel, 5g of nano zinc oxide, 2g of antioxidant 4020 and 1g of stearic acid in a 70℃ internal mixer in sequence, mix for 15min and then discharge the glue, and mature at room temperature for 16h to obtain a mixed rubber.

[0023] The surface of aramid fibers was modified with silane coupling agent KH550, and the fibers were oriented in the rubber matrix through ultrasonic dispersion and high-speed shearing.

[0024] S5. Add 1.5g of accelerator CZ, 2g of sulfur, 1g of antioxidant 1010 and 0.5g of CTAC to the rubber mix in an open mill at 60°C, pass the mixture through the mill 5 times, remove the sheet, let it rest for 16 hours, and then place it in a flat vulcanizer for vulcanization at 160°C and 15MPa for 15 minutes. Then, perform a secondary vulcanization at 150°C for 2 hours to obtain the final vulcanized high-elasticity and wear-resistant rubber composite material.

[0025] A sulfur-peroxide composite vulcanization system is used in combination with CTAC to promote clay exfoliation and construct a three-dimensional network with coexisting polysulfide bonds and CC bonds.

[0026] Example 2: A highly elastic and wear-resistant rubber composite material and a preparation method thereof, comprising the following steps: S1. Add 105 mL of 0.4 mol / L sucrose solution and 12.75 g of hexadecyltrimethylammonium bromide into a reactor, stir at 22.5 ° C and 550 r / min for 33 min to form a uniform mixture, then add 63.5 mL of 20 mmol / L zinc chloride solution, continue stirring at 550 r / min for 35 min to fully combine, transfer to a high-pressure reactor, seal and place in a 175 ° C oven for 8 h, and naturally cool to room temperature after the reaction. The reaction product is centrifuged, washed with deionized water and anhydrous ethanol 6 times, and vacuum dried at 65 ° C for 13 h to obtain zinc-doped carbon spheres; Zinc-doped carbon spheres were thoroughly ground and mixed with an equal mass of potassium hydroxide powder in a mortar, transferred to a tube furnace, and heated to 750°C at a heating rate of 5.5°C / min under nitrogen protection. The mixture was kept warm for 1.5 h and naturally cooled to room temperature. The product was soaked in 55 mL of 0.3 mol / L hydrochloric acid solution for 13 h to remove residual zinc species, then washed with deionized water until neutral, and dried in vacuum at 82.5°C for 25 h to obtain zinc-based porous carbon spheres.

[0027] S2. Place 15g of zinc-based porous carbon spheres and 525mL of deionized water in a reactor and ultrasonically disperse for 1.5h to form a uniform dispersion. Add 4g of zinc nitrate hexahydrate and 105mL of methanol to the reactor for dissolution reaction. Then add 4g of 2,5-diaminoterephthalic acid and continue stirring at 300-400r / min. Slowly add the obtained solution dropwise to the zinc-based porous carbon sphere dispersion, controlling the dropwise addition speed to keep the reaction system clear. Then continue stirring at 350r / min at room temperature for 6.5h to allow MOF crystals to fully grow on the surface of the zinc-based porous carbon spheres. After the reaction is complete, the mixed solution is centrifuged and washed 4 times with methanol and deionized water respectively. The resulting solid product is dried in a vacuum drying oven at 65°C for 13h to obtain a MOF-composite zinc-based porous carbon sphere composite material.

[0028] S3. Put 85g of hydrogenated nitrile rubber and 450mL of chlorobenzene into a high-pressure reactor, stir at 65℃ at 900r / min for 3.5h, then add 10g of potassium hydroxide, and hydrogenate to 2.5MPa after three nitrogen-hydrogen replacements. Stir and react at 85℃ at 250r / min for 4.5h, release the pressure, and then add 12g of MOF-composite zinc-based porous carbon ball composite material. React at 95℃ under nitrogen protection for 5.5h. After the reaction, centrifuge at 3100rpm for 12.5min to separate the product, wash with ethanol 4 times, and vacuum dry at 70℃ for 13h to obtain zinc-based porous carbon ball composite material modified hydrogenated nitrile rubber.

[0029] S4. Add 55g of zinc-based porous carbon ball composite material modified hydrogenated nitrile rubber into 255mL of chlorobenzene, ultrasonically disperse at 50℃ for 1.5h, add 6g of aramid fiber treated with silane coupling agent KH550, emulsify at high speed shear at 10010rpm for 35min, slowly add 525mL of ethanol to precipitate the glue, let it stand for 6.5h and then filter, and vacuum dry at 70℃ for 25h to obtain a masterbatch; add 110g of masterbatch, 3g of clay gel, 6g of nano zinc oxide, 3g of antioxidant 4020 and 1.5g of stearic acid in a 75℃ internal mixer in sequence, mix for 20min and then discharge the glue, and mature at room temperature for 17h to obtain a mixed rubber.

[0030] S5. Add 2g of accelerator CZ, 3g of sulfur, 1.5g of antioxidant 1010 and 1g of CTAC to the rubber mix in an open mill at 65°C, pass the mixture through the mill six times, remove the sheet, let it rest for 17 hours, and then place it in a flat vulcanizer. Vulcanize it at 165°C and 20MPa for 17.5 minutes, and then perform a secondary vulcanization at 155°C for 2.5 hours to obtain the final vulcanized high-elasticity and wear-resistant rubber composite material.

[0031] Example 3: A highly elastic and wear-resistant rubber composite material and a preparation method thereof, comprising the following steps: S1. Add 110 mL of 0.4 mol / L sucrose solution and 13 g of hexadecyltrimethylammonium bromide into a reactor, stir at 25 ° C and 600 r / min for 36 min to form a uniform mixture, then add 64.5 mL of 20 mmol / L zinc chloride solution, continue stirring at 600 r / min for 40 min to fully combine, transfer to a high-pressure reactor, seal and place in an oven at 180 ° C for 9 h, and naturally cool to room temperature after the reaction. The reaction product is centrifuged, washed with deionized water and anhydrous ethanol 7 times in sequence, and dried in vacuo at 70 ° C for 14 h to obtain zinc-doped carbon spheres; Zinc-doped carbon spheres were thoroughly ground and mixed with an equal mass of potassium hydroxide powder in a mortar, transferred to a tube furnace, and heated to 800°C at a heating rate of 6°C / min under nitrogen protection. The mixture was kept warm for 2 h and naturally cooled to room temperature. The product was soaked in 60 mL of 0.3 mol / L hydrochloric acid solution for 14 h to remove residual zinc species, then washed with deionized water until neutral, and dried in vacuum at 85°C for 26 h to obtain zinc-based porous carbon spheres.

[0032] S2, put 20g zinc-based porous carbon spheres and 550mL deionized water into a reactor, ultrasonically disperse for 2h to form a uniform dispersion, add 5g zinc nitrate hexahydrate and 110mL methanol into the reactor, dissolve and react, then add 5g 2,5-diaminoterephthalic acid, continue stirring at 300-400r / min, slowly add the obtained solution dropwise to the zinc-based porous carbon sphere dispersion, control the dropwise addition speed to keep the reaction system clear, and continue stirring at 400r / min at room temperature for 7h to allow MOF crystals to fully grow on the surface of the zinc-based porous carbon spheres. After the reaction is complete, the mixed solution is centrifuged and washed 5 times with methanol and deionized water respectively. The obtained solid product is dried in a vacuum drying oven at 70℃ for 14h to finally obtain a MOF-composite zinc-based porous carbon sphere composite material.

[0033] S3. Put 90g of hydrogenated nitrile rubber and 500mL of chlorobenzene into a high-pressure reactor, stir at 70℃ at 1000r / min for 4h, then add 12g of potassium hydroxide, and charge with hydrogen to 3MPa after three nitrogen-hydrogen replacements. Stir and react at 90℃ at 300r / min for 5h, release the pressure, add 14g of MOF-composite zinc-based porous carbon ball composite material, and react at 100℃ under nitrogen protection for 6h. After the reaction, centrifuge at 3200rpm for 15min to separate the product, wash with ethanol 5 times, and vacuum dry at 80℃ for 14h to obtain zinc-based porous carbon ball composite material modified hydrogenated nitrile rubber.

[0034] S4. Add 60g of zinc-based porous carbon ball composite material modified hydrogenated nitrile rubber into 260mL of chlorobenzene and ultrasonically disperse it at 55℃ for 2h; add 7g of aramid fiber treated with silane coupling agent KH550, emulsify it at high speed shear at 10020rpm for 40min, slowly add 550mL of ethanol to precipitate the glue, let it stand for 7h and then filter it, and vacuum dry it at 80℃ for 26h to obtain a masterbatch; add 120g of masterbatch, 4g of clay gel, 7g of nano zinc oxide, 4g of antioxidant 4020 and 2g of stearic acid in an internal mixer at 80℃ in sequence, mix it for 25min and then discharge the glue, and mature it at room temperature for 18h to obtain a mixed rubber.

[0035] S5. Add 2.5g of accelerator CZ, 4g of sulfur, 2g of antioxidant 1010 and 1.5g of CTAC to the rubber mix in an open mill at 70°C, pass the mixture through the mill 7 times, remove the sheet, let it rest for 18 hours, and then place it in a flat vulcanizer for vulcanization at 170°C and 25MPa for 20 minutes. Then, perform a secondary vulcanization at 160°C for 3 hours to obtain the final vulcanized high-elasticity and wear-resistant rubber composite material.

[0036] Comparative Example 1: Based on Example 3, the zinc-doped carbon balls were omitted in step S1, and the remaining steps remained unchanged to prepare a highly elastic and wear-resistant rubber composite material.

[0037] Comparative Example 2: Based on Example 3, the MOF crystals were omitted in step S2, and the remaining steps remained unchanged to prepare a highly elastic and wear-resistant rubber composite material.

[0038] Comparative Example 3: Based on Example 3, 2,5-diaminoterephthalic acid in step S2 was replaced with 2-methylimidazole, and the other steps remained unchanged to prepare a high-elasticity and wear-resistant rubber composite material.

[0039] Performance tests were performed on Examples 1 to 3 and Comparative Examples 1 to 3: Test 1 Tensile property test: The samples prepared in Examples 1-3 and Comparative Examples 1-3 were tested according to the national standard GB528-2009 method, and the tensile strength and elongation at break of the samples were recorded; Test 2 Compression permanent deformation performance test: The samples prepared in Examples 1-3 and Comparative Examples 1-3 were tested according to the national standard GB / T7759-2015 method, and the sample data were recorded; Test 3 Heat air aging resistance test: The samples prepared in Examples 1-3 and Comparative Examples 1-3 were tested according to the national standard GB / T3512-2001 method, and the tensile strength retention and elongation at break retention of the samples were recorded. Tensile strength retention = (tensile strength after aging / tensile strength before aging) × 100%, and elongation at break retention = (elongation at break after aging / elongation at break before aging) × 100%.

[0040] The test results of the sample performance test are shown in the following table: As can be seen from Table 1, the tensile properties, compression permanent deformation properties and hot air aging resistance of the high-elasticity and wear-resistant rubber composite materials prepared in Examples 1 to 3 of the present invention are significantly better than those of the comparative example.

[0041] Since the zinc-doped carbon balls are omitted in Comparative Example 1, the multi-level pore structure and interface reinforcement effect of the zinc-based porous carbon balls may be lacking, and the wear resistance of the material will also be greatly weakened; at the same time, the lack of zinc-doped carbon balls leads to the loss of additional functions such as thermal conductivity or damping of the material, and the interface bonding strength between the filler and the rubber matrix is ​​insufficient, which easily leads to stress concentration and material failure, resulting in various performances slightly worse than those of Examples 1 to 3.

[0042] Since the MOF crystals are omitted in Comparative Example 2, the surface modification effect of the MOF crystals on the zinc-based porous carbon spheres may be lost, resulting in a decrease in the interfacial bonding strength between the filler and the rubber matrix, affecting the stress transfer efficiency, and thus resulting in various performances being worse than those of Examples 1 to 3.

[0043] In Comparative Example 3, since 2,5-diaminoterephthalic acid is replaced with 2-methylimidazole, due to the change in ligand structure, the generated MOF crystals have significant differences in pore size, specific surface area and chemical properties from the original terephthalic acid-based MOF, resulting in a decrease in the interfacial bonding ability of the composite material and a weakening of the synergistic reinforcement effect between MOF and zinc-based porous carbon spheres; at the same time, the elastic recovery performance of the rubber composite material may be reduced, resulting in overall performance lower than that of Examples 1 to 3.

[0044] It should be noted that, in this document, terms such as "comprises", "includes" or any other variations thereof are intended to cover non-exclusive inclusion, so that a process, method, article or apparatus that includes a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements that are inherent to such process, method, article or apparatus.

[0045] While the embodiments of the present invention have been shown and described, it will be apparent to those skilled in the art that various changes, modifications, substitutions, and alterations can be made to the embodiments without departing from the principles and spirit of the invention.

Claims

1. A high elasticity and wear-resistant rubber composite material and a preparation method thereof, characterized in that: The method comprises the following steps: adding hydrogenated nitrile rubber modified by a zinc-based porous carbon ball composite material into chlorobenzene, ultrasonically dispersing at 45-55° C. for 1-2 hours, adding aramid fiber treated with a silane coupling agent KH550, shearing and emulsifying at 10000-10020 rpm for 30-40 minutes, dripping ethanol to precipitate the rubber, standing for 6-7 hours, filtering, and vacuum drying at 60-80° C. for 24-26 hours to obtain a masterbatch; Add masterbatch, clay gel, nano zinc oxide, antioxidant 4020 and stearic acid in an internal mixer at 70-80°C in sequence, mix for 15-25 minutes, then discharge the rubber, and mature at room temperature for 16-18 hours to obtain a rubber mix; Add accelerator CZ, sulfur, antioxidant 1010 and CTAC to the rubber mix in an open mill at 60-70°C, pass the mixture 5-7 times, remove the sheet, leave it for 16-18 hours, and then place it in a flat vulcanizer for vulcanization at 160-170°C and 15-25MPa for 15-20 minutes, and then perform secondary vulcanization at 150-160°C for 2-3 hours to obtain the final vulcanized high-elasticity and wear-resistant rubber composite material.

2. A highly elastic and wear-resistant rubber composite material and a preparation method thereof according to claim 1, characterized in that: The zinc-based porous carbon ball composite material modified hydrogenated nitrile rubber, chlorobenzene, aramid fiber, ethanol-precipitated rubber, masterbatch, clay gel, nano zinc oxide, antioxidant 4020, stearic acid, accelerator CZ, sulfur, antioxidant 1010, and CTAC have a usage ratio of 50-60g:250-260mL:5-7g:500-550mL:100-120g:2-4g:5-7g:2-4g:1-2g:1.5-2.5g:2-4g:1-2g:0.5-1.5g.

3. The high-elasticity and wear-resistant rubber composite material and its preparation method according to claim 2, characterized in that: The zinc-based porous carbon sphere composite material modified hydrogenated nitrile rubber is prepared by the following steps: The hydrogenated nitrile rubber and chlorobenzene are placed in a high-pressure reactor, stirred at 60-70°C for 3-4 hours at 800-1000 r / min, and then potassium hydroxide is added. After three nitrogen-hydrogen replacements, hydrogen is filled to 2-3 MPa, and the reaction is stirred at 80-90°C at 200-300 r / min for 4-5 hours; the pressure is released, and the MOF-composite zinc-based porous carbon ball composite material is added, and the reaction is carried out at 90-100°C for 5-6 hours under nitrogen protection; after the reaction is completed, the product is separated by centrifugation at 3000-3200 rpm for 10-15 minutes, washed with ethanol 3-5 times, and then vacuum dried at 60-80°C for 12-14 hours to obtain the zinc-based porous carbon ball composite material modified hydrogenated nitrile rubber.

4. The high-elasticity and wear-resistant rubber composite material and its preparation method according to claim 3, characterized in that: The usage ratio of the hydrogenated butyronitrile, chlorobenzene, potassium hydroxide, and MOF-compounded zinc-based porous carbon sphere composite material is 80-90 g: 400-500 mL: 8-12 g: 10-14 g.

5. The high elasticity and wear-resistant rubber composite material and its preparation method according to claim 4, characterized in that: The MOF-composite zinc-based porous carbon sphere composite material is prepared by the following steps: Zinc-based porous carbon spheres and deionized water were placed in a reactor and ultrasonically dispersed for 1-2 hours to form a uniform dispersion. Zinc nitrate hexahydrate and methanol were added to the reactor for dissolution reaction. 2,5-Diaminoterephthalic acid was then added and stirred continuously at 300-400 r / min. The resulting solution was added dropwise to the zinc-based porous carbon sphere dispersion, controlling the addition rate to maintain a clear reaction system. The mixture was stirred at 300-400 r / min at room temperature for 6-7 hours to allow MOF crystals to fully grow on the surface of the zinc-based porous carbon spheres. After the reaction was complete, the mixture was centrifuged and washed with methanol and deionized water 3-5 times each. The resulting solid product was dried in a vacuum drying oven at 60-70°C for 12-14 hours to obtain a MOF-composite zinc-based porous carbon sphere composite material.

6. The high-elasticity and wear-resistant rubber composite material and the preparation method thereof according to claim 5, characterized in that: The usage ratio of the zinc-based porous carbon spheres, deionized water, zinc nitrate hexahydrate, methanol, and 2,5-diaminoterephthalic acid is 10-20 g: 500-550 mL: 3-5 g: 100-110 mL: 3-5 g.

7. The high-elasticity and wear-resistant rubber composite material and its preparation method according to claim 6, characterized in that: The zinc-based porous carbon spheres are prepared by the following steps: 0.4 mol / L sucrose solution and hexadecyltrimethylammonium bromide were added to a reactor, stirred at 20-25°C and 500-600 r / min for 30-36 minutes to form a uniform mixture, and then 20 mmol / L zinc chloride solution was added and stirred for 30-40 minutes to fully combine. The mixture was transferred to a high-pressure reactor, sealed, and placed in an oven at 170-180°C for 7-9 hours. After the reaction, it was naturally cooled to room temperature. The reaction product was centrifuged, washed with deionized water and anhydrous ethanol for 5-7 times, and vacuum dried at 60-70°C for 12-14 hours to obtain zinc-doped carbon spheres. The zinc-doped carbon spheres were thoroughly ground and mixed with an equal mass of potassium hydroxide powder in a mortar, transferred to a tube furnace, and heated to 700-800°C at a heating rate of 5-6°C / min under nitrogen protection. The mixture was kept warm for 1-2 hours and naturally cooled to room temperature. The product was soaked in 0.3 mol / L hydrochloric acid solution for 12-14 hours to remove residual zinc species, then washed with deionized water until neutral, and vacuum dried at 80-85°C for 24-26 hours to obtain zinc-based porous carbon spheres.

8. The high-elasticity and wear-resistant rubber composite material and its preparation method according to claim 7, characterized in that: The dosage ratio of the sucrose solution, hexadecyltrimethylammonium bromide, zinc chloride solution and hydrochloric acid solution is: 100-110 mL: 12.5-13 g: 62.5-64.5 mL: 50-60 mL.

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