Low-temperature-resistant anti-aging rubber material and preparation process thereof

Abstract

The invention relates to a low-temperature-resistant anti-aging rubber material and a preparation process thereof, and belongs to the technical field of rubber materials, and the preparation process comprises the following steps: mixing ethylene-butadiene rubber, zinc oxide, stearic acid, a coupling agent, a low-temperature plasticizer, a reactive anti-aging agent, a reinforcing filler and a vulcanizing agent by adopting a three-section mixing method to obtain a mixed material; activating the mixed material to obtain a reinforced material; the reinforcing material is subjected to vulcanization treatment through a sectional vulcanization process, and finally the low-temperature-resistant and anti-aging rubber material is obtained. According to the technical scheme, the overall performance of the rubber material is well improved through a three-section mixing method, activating treatment and a sectional vulcanization process; the silanized nano material is combined with glycidyl ether and then combined with the composite modifier to prepare the low-temperature plasticizer, so that the low-temperature resistance, the aging resistance and the mechanical property of the rubber material are further improved, and the comprehensive performance of the rubber material is overall improved.

Description

Technical Field

[0001] This invention belongs to the field of rubber material technology, specifically relating to a low-temperature resistant and anti-aging rubber material and its preparation process. Background Technology

[0002] As a fundamental pillar industry of the national economy, the safe and stable operation of the power industry is directly related to industrial production, people's livelihood, and the implementation of the national energy strategy. GIS (Gas Insulated Switchgear) is a core device in high-voltage and ultra-high-voltage power systems, widely used in core nodes of transmission and distribution networks. It is filled with highly insulating SF6 gas, and the gas-sealing material is crucial for preventing gas leakage and maintaining the equipment's insulation and arc-extinguishing performance, directly determining the operational reliability of the GIS equipment. The Xinjiang region under the State Grid Corporation of China is a core hub of the "Xinjiang Electricity Transmission to Other Regions" energy strategy, and its power grid operates in extremely harsh environments. This region experiences long, cold winters with large diurnal temperature variations, and some areas can reach as low as -40°C, placing extremely high demands on the low-temperature adaptability of rubber seals. Furthermore, during long-term service, rubber is susceptible to molecular chain breakage or cross-linking network deterioration due to factors such as heat, oxygen, ozone, and ultraviolet radiation, leading to decreased mechanical properties, surface cracking, and even functional failure. Therefore, developing rubber materials with both excellent low-temperature resistance and long-term anti-aging capabilities has become a key technological requirement for improving the reliability and service life of high-end equipment.

[0003] Currently, to improve the low-temperature resistance of rubber materials, the industry commonly uses the addition of small-molecule plasticizers (such as phthalates and paraffin oils) to lower the glass transition temperature (Tg) of rubber. However, these traditional plasticizers have significant drawbacks: they have poor compatibility with the rubber matrix and are prone to migration, volatilization, or extraction by the medium. Especially under high and low temperature cycling or long-term service conditions, plasticizers continuously precipitate from the rubber matrix, not only causing the rubber material to harden and become brittle, accelerating its aging process, but also potentially contaminating the contact medium, posing safety hazards and environmental risks. In addition, conventional antioxidants (such as amines and phenols) also suffer from migration loss, making it difficult to achieve long-term protective effects. Therefore, there is an urgent need to develop a rubber material with excellent low-temperature resistance, long-lasting anti-aging ability, good mechanical properties, and high reliability to meet increasingly stringent application requirements. Summary of the Invention

[0004] The purpose of this invention is to provide a low-temperature resistant and anti-aging rubber material and its preparation process. The process involves mixing ethylene butyl rubber, zinc oxide, stearic acid, coupling agent, low-temperature plasticizer, reactive antioxidant, reinforcing filler, and vulcanizing agent using a three-stage mixing method to obtain a mixed material. The mixed material from step S1 is then activated to obtain a reinforcing material. The reinforcing material from step S2 is then vulcanized using a segmented vulcanization process to finally obtain the low-temperature resistant and anti-aging rubber material. The prepared low-temperature plasticizer effectively improves the low-temperature resistance, aging resistance, mechanical properties, and long-term durability of the rubber material, extending its service life and overall improving its comprehensive performance.

[0005] The technical problem this invention aims to solve is as follows: To improve the low-temperature resistance of rubber materials, the industry commonly uses the addition of small-molecule plasticizers (such as phthalates, paraffin oils, etc.) to lower the glass transition temperature (Tg) of rubber. However, these traditional plasticizers have significant drawbacks: they have poor compatibility with the rubber matrix and are prone to migration, volatilization, or extraction by the medium. Especially under high and low temperature cycling or long-term service conditions, the plasticizer continuously precipitates from the rubber matrix, not only causing the rubber material to harden and become brittle, accelerating its aging process, but also potentially contaminating the contact medium, posing safety hazards and environmental risks. In addition, conventional antioxidants (such as amines, phenols, etc.) also suffer from migration loss, making it difficult to achieve long-term protective effects.

[0006] The objective of this invention can be achieved through the following technical solutions: A preparation process for a low-temperature resistant and aging-resistant rubber material includes the following steps: S1: Ethylene-butadiene rubber, zinc oxide, stearic acid, coupling agent, low-temperature plasticizer, reactive antioxidant, reinforcing filler and vulcanizing agent are mixed using a three-stage mixing method to obtain the mixed material; S2: Activate the compounded material in step S1 to obtain the reinforced material; S3: The reinforcing material in step S2 is vulcanized through a segmented vulcanization process to obtain a low-temperature resistant and aging-resistant rubber material.

[0007] Further, in step S1, the mass ratio of the ethylene butyl rubber, zinc oxide, stearic acid, coupling agent, low-temperature plasticizer, reactive antioxidant, reinforcing filler, and vulcanizing agent is 95-105:5-7:1-2:0.5-1.5:10-12:2-3:40-50:2-3.

[0008] Furthermore, the coupling agent is the silane coupling agent Si-69.

[0009] Furthermore, the reactive antioxidant is composed of N-(4-anilinophenyl)methacrylamide and N-(4-anilinophenyl)maleimide mixed in a mass ratio of 1:1.

[0010] Furthermore, the reinforcing filler is at least one of silica, carbon black, and nano-calcium carbonate.

[0011] Furthermore, the vulcanizing agent is dicumyl peroxide (DCP).

[0012] Furthermore, step S1 specifically includes: Ethylene-butadiene rubber, coupling agent, and reinforcing filler are mixed at 140-160℃ for one stage. After the first stage, the system is cooled to 100-120℃, and then zinc oxide, stearic acid, low-temperature plasticizer, reactive antioxidant, and reinforcing filler are added. The second stage is then carried out. After the second stage, the system is cooled to 60-80℃, and then vulcanizing agent is added. The third stage is then carried out. After the third stage, the mixed material is obtained.

[0013] Furthermore, the mixing temperature of the first stage of mixing is 140-160℃ and the mixing time is 3-5 min; the mixing temperature of the second stage of mixing is 100-120℃ and the mixing time is 2-4 min; and the mixing temperature of the third stage of mixing is 60-80℃ and the mixing time is 1-3 min.

[0014] Furthermore, in step S2, the activation treatment includes low-temperature plasma treatment or ultraviolet ozone treatment.

[0015] Furthermore, the specific parameters of the low-temperature plasma treatment are as follows: the working gas for the low-temperature plasma treatment is a mixture of Ar and O2, the treatment power is 350-450W, the treatment frequency is 20-30kHz, the treatment temperature is 40-50℃, the treatment time is 40-50s, and the vertical distance between the plasma spray gun outlet and the surface of the mixed material is 6-8mm.

[0016] Furthermore, step S3 specifically includes: Place the reinforcing material from step S2 into a mold preheated to 160-165℃, close the mold and apply a pressure of 8-12MPa, perform the first stage of vulcanization, demold after completion, transfer to an oven for the second stage of vulcanization without applying pressure, remove after completion, and cool the system to 60-80℃ to obtain a low-temperature resistant and anti-aging rubber material.

[0017] Furthermore, the vulcanization temperature of the first vulcanization treatment is 160-165℃, and the vulcanization time is 10-15 min; the vulcanization temperature of the second vulcanization treatment is 150℃, and the vulcanization time is 4-5 h.

[0018] Further, in step S1, the method for preparing the low-temperature plasticizer includes the following steps: A1: The silane-grafted nanomaterials were mixed evenly with glycidyl ether. Under nitrogen protection, the system was heated and stirred. After the reaction was completed, it was cooled to room temperature, acetone was added, and the mixture was ultrasonically dispersed. After centrifugation, the mixture was washed with anhydrous ethanol and finally vacuum dried to obtain the functionalized nanomaterials. A2: Functionalized nanomaterials were added to anhydrous toluene and ultrasonically dispersed. Then, composite modifiers and catalysts were added and mixed evenly. The system was then heated to reflux reaction. After the reaction was completed, the mixture was cooled to room temperature, centrifuged, washed with hot toluene and anhydrous ethanol, and finally vacuum dried to obtain a low-temperature plasticizer.

[0019] In the above reaction process, in step A1, the silane-grafted nanomaterial has amino groups, and the glycidyl ether has epoxy groups and carbon-carbon double bonds. The amino groups on the silane-grafted nanomaterial can combine with the epoxy groups in the glycidyl ether through a ring-opening reaction, thus combining the silane-grafted nanomaterial with the glycidyl ether to finally obtain the functionalized nanomaterial. In step A2, the composite modifier has silane-hydrogen bonds, and the silane-grafted nanomaterial has carbon-carbon double bonds. The silane-hydrogen bonds on the composite modifier can combine with the carbon-carbon double bonds in the silane-grafted nanomaterial through a hydrosilylation reaction, thus combining the composite modifier with the functionalized nanomaterial to finally obtain the low-temperature plasticizer.

[0020] Further, in step A1, the mass ratio of the silane-grafted nanomaterial to the glycidyl ether is 4.8-5.2:4.4-4.6.

[0021] Furthermore, the glycidyl ether is composed of castor oil triglycidyl ether and cashew phenol glycidyl ether mixed in a mass ratio of 2-3:1.

[0022] Furthermore, in step A1, the temperature of the stirring reaction is 110-120℃, and the time is 4.5-5.5h.

[0023] Furthermore, in step A1, the vacuum drying temperature is 55-65℃ and the time is 12h.

[0024] Further, in step A2, the mass ratio of the functionalized nanomaterial, anhydrous toluene, composite modifier, and catalyst is 4.8-5.2: 75-85: 1.4-1.6: 0.01-0.03.

[0025] Furthermore, the composite modifier is composed of 1,1,3,3-tetramethyldisiloxane and 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane in a mass ratio of 0.9-1:0.6-0.7.

[0026] Furthermore, the catalyst is a Karstedt catalyst.

[0027] Furthermore, in step A2, the ultrasonic dispersion time is 20-30 minutes.

[0028] Furthermore, in step A2, the reflux reaction is carried out at a temperature of 80-90°C for 5-6 hours.

[0029] Further, in step A1, the specific method for preparing the silane-grafted nanomaterial is as follows: The nanomaterials were added to a mixed solution of anhydrous ethanol and deionized water and ultrasonically dispersed. The pH of the system was adjusted to 3.8-4.2 with glacial acetic acid aqueous solution. A silane coupling agent was added under nitrogen protection, and the reaction was carried out by stirring in a water bath. After the reaction was completed, the mixture was cooled to room temperature, centrifuged, washed with anhydrous ethanol, and finally vacuum dried to obtain silane-grafted nanomaterials.

[0030] During the above reaction process, the surface of the nanomaterial has hydroxyl groups. After the silane coupling agent is hydrolyzed, silanol groups are generated. The silanol groups on the silane coupling agent can react and combine with the hydroxyl groups on the nanomaterial, thereby grafting the silane coupling agent onto the surface of the nanomaterial, and finally obtaining silane-grafted nanomaterials.

[0031] Furthermore, the mass ratio of the nanomaterial, the mixed solution of anhydrous ethanol and deionized water, and the silane coupling agent is 4.8-5.2:90-110:0.9-1.1.

[0032] Furthermore, the nanomaterial is composed of nano-zirconia and halloysite nanotubes mixed in a mass ratio of 0.4-0.6:0.6-0.8.

[0033] Furthermore, the silane coupling agent is composed of 3-aminopropyltriethoxysilane and 3-(2,3-epoxypropoxy)propyltrimethoxysilane in a mass ratio of 3:2.

[0034] Furthermore, the ultrasonic dispersion time is 25-35 minutes.

[0035] Furthermore, the temperature of the stirring reaction is 75-85℃, and the time is 4.5-5.5h.

[0036] A low-temperature resistant and anti-aging rubber material prepared by the above-described process.

[0037] The beneficial effects of this invention are: (1) In the technical solution of this invention, the compounded material is obtained by mixing ethylene-butyl rubber, zinc oxide, stearic acid, coupling agent, low-temperature plasticizer, reactive antioxidant, reinforcing filler and vulcanizing agent in a three-stage mixing method; the three-stage mixing method fully utilizes the functional synergistic effect of various additives by precisely controlling the timing of addition and mixing temperature of each component. In the first stage of mixing, some reinforcing filler and coupling agent are added to promote the surface modification of filler and the initial wetting and dispersion in the rubber matrix; in the second stage of mixing, the remaining reinforcing filler, low-temperature plasticizer, reactive antioxidant, zinc oxide and stearic acid are introduced, which avoids the damage of heat-sensitive components by high temperature and ensures that the low-temperature plasticizer is effectively inserted between rubber molecular chains, significantly reducing the glass transition temperature of the material, giving the rubber material excellent low-temperature elasticity, and the reactive antioxidant can fully exert its long-term anti-aging effect; the addition of vulcanizing agent in the third stage of mixing can effectively prevent To mitigate the risk of scorching, the rubber compound maintains good flowability and component uniformity before entering the vulcanization stage. After vulcanization, a three-dimensional network with moderate crosslinking density and a uniform and dense network structure can be formed. Therefore, the three-stage mixing method not only significantly improves the dispersibility of reinforcing fillers in ethylene-butadiene rubber, inhibits their agglomeration, and enhances the tensile strength and abrasion resistance of the rubber material, but also effectively avoids low-temperature brittle fracture caused by local stress concentration, enhancing the oxidation stability and durability of the rubber material. The mixed materials in step S1 are activated to obtain reinforcing materials. The activation treatment includes low-temperature plasma treatment or ultraviolet ozone treatment. Low-temperature plasma treatment can effectively improve the interfacial bonding force between raw materials in the rubber material, improve the dispersion stability of reinforcing fillers, promote crosslinking reaction, optimize the vulcanization network structure, and improve the low-temperature toughness of the rubber material, avoiding low-temperature brittle fracture and further enhancing the aging resistance of the rubber material.

[0038] (2) In the technical solution of the present invention, a low-temperature plasticizer is prepared by combining silane-grafted nanomaterials with glycidyl ether and then combining them with a composite modifier; wherein, the silane-grafted nanomaterials are prepared by grafting nanomaterials with silane coupling agents, and the nanomaterials are composed of a mixture of nano-zirconia and halloysite nanotubes, which have a synergistic effect, which can not only effectively improve the mechanical properties and thermal stability of rubber materials, but also enhance their aging resistance and low-temperature resistance; the glycidyl ether is composed of a mixture of castor oil triglycidyl ether and cashew phenol glycidyl ether, which have a synergistic effect, which can not only increase its binding force with silanized nanomaterials, but also improve the antioxidant properties of rubber materials. The composite modifier is composed of a mixture of 1,1,3,3-tetramethyldisiloxane and 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane. The two have a good synergistic effect, which can not only improve the aging resistance and mechanical properties of rubber materials, but also improve their low-temperature performance. The low-temperature plasticizer prepared by combining the composite modifier with functionalized nanomaterials effectively improves the low-temperature resistance, aging resistance, mechanical properties and long-term service stability of rubber materials.

[0039] (3) In the technical solution of the present invention, the reinforcing material in step S2 is vulcanized by a segmented vulcanization process to obtain a rubber material that is resistant to low temperature and anti-aging. The segmented vulcanization process can improve the crosslinking density and thermal stability of the crosslinking network structure. After the first vulcanization, the strength and elasticity of the rubber material are already high, and it can withstand its own weight and the stress generated during demolding without permanent deformation or tearing. The second vulcanization is carried out at a relatively mild temperature lower than that of the first vulcanization, which can remove and decompose the byproducts generated during the vulcanization process and promote a more complete and stable crosslinking reaction, forming a more perfect and stable three-dimensional network structure, thereby improving the crosslinking density and ensuring sufficient vulcanization. At this point, segmented vulcanization can achieve uniform vulcanization, avoiding problems such as surface over-vulcanization and core under-vulcanization commonly found in traditional single-stage vulcanization. It synergistically improves the low-temperature elasticity and mechanical strength of rubber materials, and can reduce defects such as internal pores and microcracks, thereby improving the density, dimensional stability and long-term durability of rubber materials. In addition, segmented vulcanization, together with the previous three-stage mixing and activation treatment, can form a highly synergistic complete process loop, so that the resulting rubber materials not only exhibit good low-temperature resistance and resistance to thermo-oxidative aging, but also have high tensile strength, high elongation at break and excellent comprehensive mechanical properties, which can meet the stringent requirements of high-end application scenarios for the long-term reliability of rubber products.

[0040] (4) In the technical solution of the present invention, by mixing ethylene butadiene rubber, zinc oxide, stearic acid, coupling agent, low temperature plasticizer, reactive antioxidant, reinforcing filler and vulcanizing agent, then activating treatment, and finally vulcanizing treatment, a low temperature resistant and anti-aging rubber material is obtained. The prepared low temperature plasticizer effectively improves the low temperature resistance, aging resistance, mechanical properties and long-term durability of the rubber material, and extends the service life of the rubber material, thus improving the overall performance of the rubber material. Detailed Implementation

[0041] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0042] The specific parameters of the raw materials used in this invention are as follows: Ethylene-butadiene rubber, model: K9330M, supplied by Mitsui Chemicals, Inc., Japan; Zinc oxide, CAS No.: 1314-13-2, supplied by Shandong Zhijia Chemical Technology Co., Ltd.; Silica, 2000 mesh, supplied by Shijiazhuang Xuzhou New Material Technology Co., Ltd.; Carbon black, grade: n326, supplied by Boruida (Dongguan) New Material Co., Ltd.; Nano calcium carbonate, particle size: 20nm, supplied by Shijiazhuang Jinghuang Technology Co., Ltd.; Nano zirconium dioxide, average particle size: 30nm, supplied by Ningbo Luofei Nanotechnology Co., Ltd.; Halloysite nanotubes, CAS No. Product No.: 1332-58-7, Product No.: H698168, provided by Shanghai Maclean Biochemical Technology Co., Ltd.; Karstedt catalyst, CAS No.: 81032-58-8, Product No.: K855033, provided by Shanghai Maclean Biochemical Technology Co., Ltd.; castor oil triglycidyl ether, provided by Hubei Chuyuebang New Material Technology Co., Ltd.; cashew phenol glycidyl ether, CAS No.: 171263-25-5, Product No.: C963860, provided by Shanghai Maclean Biochemical Technology Co., Ltd.

[0043] Example 1 The preparation process of low-temperature resistant and aging-resistant rubber materials includes the following steps: S1: Ethylene-butadiene rubber, silane coupling agent Si-69, and 50% silica are mixed at 140℃ for 5 minutes. After the first stage of mixing, the system is cooled to 100℃. Then, zinc oxide, stearic acid, low-temperature plasticizer, reactive antioxidant, and 50% silica are added, followed by a second stage of mixing at 100℃ for 4 minutes. After this stage, the system is cooled to 60℃, DCP is added, and the mixing process continues. The mixture was subjected to a three-stage mixing process, with the mixing temperature controlled at 60℃ and the mixing time at 3 minutes. After the mixing process, a mixed material was obtained. The mass ratio of ethylene butyl rubber, zinc oxide, stearic acid, silane coupling agent Si-69, low-temperature plasticizer, reactive antioxidant, silica, and DCP was 95:5:1:0.5:10:2:40:2. The reactive antioxidant was composed of N-(4-anilinophenyl)methacrylamide and N-(4-anilinophenyl)maleimide mixed in a mass ratio of 1:1. S2: The mixed material in step S1 is subjected to low-temperature plasma treatment to obtain the reinforced material; wherein, the specific parameters of the low-temperature plasma treatment are: the working gas of the low-temperature plasma treatment is a mixture of Ar and O2 (the volume ratio of Ar and O2 is 97:3), the treatment power is 350W, the treatment frequency is 20kHz, the treatment temperature is 40℃, the treatment time is 50s, and the vertical distance between the plasma gun outlet and the surface of the mixed material is 6mm. S3: Place the reinforcing material from step S2 into a flat vulcanizing mold preheated to 160°C, close the mold and apply 8MPa pressure, perform the first stage of vulcanization, control the vulcanization temperature of the first stage of vulcanization at 160°C and the vulcanization time at 15min, demold after completion, transfer to an oven for the second stage of vulcanization, control the vulcanization temperature of the second stage of vulcanization at 150°C and the vulcanization time at 4h, without applying pressure, after completion, remove, cool the system to 60°C, and finally obtain a low-temperature resistant and anti-aging rubber material; The preparation method of the low-temperature plasticizer includes the following steps: A1: The silane-grafted nanomaterials and glycidyl ether were mixed evenly at a mass ratio of 4.8:4.4. Under nitrogen protection, the system was heated to 110℃ and stirred at 300 rpm for 5.5 h. After the reaction was completed, the mixture was cooled to room temperature, acetone (10 times the mass of the silane-grafted nanomaterials) was added, and the mixture was ultrasonically dispersed for 5 min (ultrasonic power 100 W, ultrasonic frequency 40 kHz). The mixture was then centrifuged at 10000 rpm for 10 min, washed three times with anhydrous ethanol (each time the mass of anhydrous ethanol was 4 times the mass of the silane-grafted nanomaterials), and finally vacuum dried at 55℃ for 12 h to obtain the functionalized nanomaterials. The glycidyl ether was composed of castor oil triglycidyl ether and cashew phenol glycidyl ether mixed at a mass ratio of 2:1. A2: Following a mass ratio of functionalized nanomaterials, anhydrous toluene, composite modifier, and Karstedt catalyst of 4.8:75:1.4:0.01, the functionalized nanomaterials were added to anhydrous toluene and ultrasonically dispersed for 20 min (ultrasonic power 100 W, ultrasonic frequency 40 kHz). Then, the composite modifier and Karstedt catalyst were added and mixed thoroughly. The system was then heated to 80℃ and refluxed at 300 rpm for 6 h. After the reaction was completed, the mixture was cooled. After cooling to room temperature, centrifuge at 10,000 rpm for 10 min, wash three times each with hot toluene at 50°C and anhydrous ethanol (each time the mass of hot toluene is 20% of the mass of anhydrous toluene, and each time the mass of anhydrous ethanol is 25% of the mass of anhydrous toluene), and finally vacuum dry at 55°C for 24 h to obtain a low-temperature plasticizer; wherein, the composite modifier is composed of 1,1,3,3-tetramethyldisiloxane and 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane in a mass ratio of 0.9:0.6; The specific preparation method of silane-grafted nanomaterials is as follows: The nanomaterials, anhydrous ethanol, and deionized water were mixed in a mass ratio of 4.8:90:0.9 with a silane coupling agent. The nanomaterials were added to the mixed solution of anhydrous ethanol and deionized water (volume ratio of anhydrous ethanol to deionized water was 4:1), and ultrasonically dispersed for 25 min (ultrasonic power 100 W, ultrasonic frequency 40 kHz). The pH of the system was adjusted to 3.8 with a 1 wt% aqueous solution of glacial acetic acid. The silane coupling agent was added under nitrogen protection, and the reaction was stirred in a 75°C water bath for 5.5 h. After the reaction was completed, the mixture was cooled... The mixture was cooled to room temperature, centrifuged at 10,000 rpm for 10 min, washed three times with anhydrous ethanol (each time the mass of anhydrous ethanol was 20% of the mass of the mixture of anhydrous ethanol and deionized water), and finally vacuum dried at 55 °C for 12 h to obtain silane-grafted nanomaterials. The silane coupling agent was composed of 3-aminopropyltriethoxysilane and 3-(2,3-epoxypropoxy)propyltrimethoxysilane in a mass ratio of 3:2. The nanomaterials were composed of nano-zirconia and halloysite nanotubes in a mass ratio of 0.4:0.6.

[0044] Example 2 The preparation process of low-temperature resistant and aging-resistant rubber materials includes the following steps: S1: Ethylene-butadiene rubber, silane coupling agent Si-69, and 50% carbon black are mixed at 150℃ for one stage, controlling the mixing temperature at 150℃ and the mixing time at 4 minutes. After the first stage, the system is cooled to 110℃, and then zinc oxide, stearic acid, low-temperature plasticizer, reactive antioxidant, and 50% carbon black are added. A second stage of mixing is then performed, controlling the mixing temperature at 110℃ and the mixing time at 3 minutes. After the second stage, the system is cooled to 70℃, and then DCP is added to continue the third stage. The mixing process was carried out at a temperature of 70℃ for 2 minutes in three stages, resulting in a mixed material. The mass ratio of ethylene butyl rubber, zinc oxide, stearic acid, silane coupling agent Si-69, low-temperature plasticizer, reactive antioxidant, carbon black, and DCP was 100:6:1.5:1:11:2.5:45:2.5. The reactive antioxidant was composed of N-(4-anilinophenyl)methacrylamide and N-(4-anilinophenyl)maleimide mixed in a mass ratio of 1:1. S2: The mixed material in step S1 is subjected to low-temperature plasma treatment to obtain the reinforced material; wherein, the specific parameters of the low-temperature plasma treatment are: the working gas of the low-temperature plasma treatment is a mixture of Ar and O2 (the volume ratio of Ar and O2 is 97:3), the treatment power is 400W, the treatment frequency is 25kHz, the treatment temperature is 45℃, the treatment time is 45s, and the vertical distance between the plasma gun outlet and the surface of the mixed material is 7mm. S3: Place the reinforcing material from step S2 into a flat vulcanizing mold preheated to 162°C, close the mold and apply a pressure of 10MPa. Perform the first stage of vulcanization treatment, controlling the vulcanization temperature of the first stage at 162°C and the vulcanization time at 13min. After completion, demold and transfer to an oven for the second stage of vulcanization treatment, controlling the vulcanization temperature of the second stage at 150°C and the vulcanization time at 4.5h without applying pressure. After completion, remove the material and cool the system to 70°C to obtain a low-temperature resistant and anti-aging rubber material. The preparation method of the low-temperature plasticizer includes the following steps: A1: The silane-grafted nanomaterials and glycidyl ether were mixed evenly at a mass ratio of 5:4.5. Under nitrogen protection, the system was heated to 115℃ and stirred at 350 rpm for 5 hours. After the reaction was completed, the mixture was cooled to room temperature, and acetone (10 times the mass of the silane-grafted nanomaterials) was added. The mixture was then ultrasonically dispersed for 8 minutes (ultrasonic power of 100W and ultrasonic frequency of 40kHz). The mixture was centrifuged at 10,000 rpm for 12 minutes and washed three times with anhydrous ethanol (each time with an anhydrous ethanol mass of 4 times the mass of the silane-grafted nanomaterials). Finally, the mixture was vacuum dried at 60℃ for 12 hours to obtain the functionalized nanomaterials. The glycidyl ether was composed of castor oil triglycidyl ether and cashew phenol glycidyl ether mixed at a mass ratio of 2.5:1. A2: Following a mass ratio of functionalized nanomaterials, anhydrous toluene, composite modifier, and Karstedt catalyst of 5:80:1.5:0.02, the functionalized nanomaterials were added to anhydrous toluene and ultrasonically dispersed for 25 min (ultrasonic power 100 W, ultrasonic frequency 40 kHz). Then, the composite modifier and Karstedt catalyst were added and mixed thoroughly. The system was then heated to 85℃ and refluxed at 350 rpm for 5.5 h. After the reaction was completed, the mixture was cooled to... The mixture was centrifuged at 10,000 rpm for 12 min at room temperature, and washed three times each with hot toluene at 50°C and anhydrous ethanol (each time the mass of hot toluene was 20% of the mass of anhydrous toluene, and each time the mass of anhydrous ethanol was 25% of the mass of anhydrous toluene). Finally, it was vacuum dried at 60°C for 24 h to obtain a low-temperature plasticizer. The composite modifier was composed of 1,1,3,3-tetramethyldisiloxane and 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane in a mass ratio of 0.95:0.65. The specific preparation method of silane-grafted nanomaterials is as follows: The nanomaterials, anhydrous ethanol, and deionized water were mixed in a mass ratio of 5:100:1 to a silane coupling agent. The nanomaterials were added to the mixed solution of anhydrous ethanol and deionized water (volume ratio of anhydrous ethanol to deionized water was 4:1), and ultrasonically dispersed for 30 min (ultrasonic power 100 W, ultrasonic frequency 40 kHz). The pH of the system was adjusted to 4 with a 1 wt% aqueous solution of glacial acetic acid. The silane coupling agent was added under nitrogen protection, and the reaction was stirred in an 80°C water bath for 5 h. After the reaction was completed, the mixture was cooled to room temperature. The solution was centrifuged at 10,000 rpm for 12 min, washed three times with anhydrous ethanol (each time the mass of anhydrous ethanol was 20% of the mass of the mixture of anhydrous ethanol and deionized water), and finally vacuum dried at 60 °C for 12 h to obtain silane-grafted nanomaterials. The silane coupling agent was composed of 3-aminopropyltriethoxysilane and 3-(2,3-epoxypropoxy)propyltrimethoxysilane in a mass ratio of 3:2. The nanomaterials were composed of nano-zirconia and halloysite nanotubes in a mass ratio of 0.5:0.7.

[0045] Example 3 The preparation process of low-temperature resistant and aging-resistant rubber materials includes the following steps: S1: Ethylene-butadiene rubber, silane coupling agent Si-69, and 50% nano-calcium carbonate are mixed at 160℃ for 3 minutes. After the first stage of mixing, the system is cooled to 120℃. Then, zinc oxide, stearic acid, low-temperature plasticizer, reactive antioxidant, and 50% nano-calcium carbonate are added, followed by a second stage of mixing at 120℃ for 2 minutes. After this stage, the system is cooled to 80℃, and DCP is added. The mixture was subjected to a three-stage mixing process, with the mixing temperature controlled at 80℃ and the mixing time at 1 minute. After the mixing was completed, a mixed material was obtained. The mass ratio of ethylene butyl rubber, zinc oxide, stearic acid, silane coupling agent Si-69, low-temperature plasticizer, reactive antioxidant, nano calcium carbonate, and DCP was 105:7:2:1.5:12:3:50:3. The reactive antioxidant was composed of N-(4-anilinophenyl)methacrylamide and N-(4-anilinophenyl)maleimide mixed in a mass ratio of 1:1. S2: The mixed material in step S1 is subjected to low-temperature plasma treatment to obtain the reinforced material; wherein, the specific parameters of the low-temperature plasma treatment are: the working gas of the low-temperature plasma treatment is a mixture of Ar and O2 (the volume ratio of Ar and O2 is 97:3), the treatment power is 450W, the treatment frequency is 30kHz, the treatment temperature is 50℃, the treatment time is 40s, and the vertical distance between the plasma gun outlet and the surface of the mixed material is 8mm. S3: Place the reinforcing material from step S2 into a flat vulcanizing mold preheated to 165°C, close the mold and apply 12MPa pressure, perform the first stage of vulcanization, control the vulcanization temperature of the first stage of vulcanization at 165°C and the vulcanization time at 10min, demold after completion, transfer to an oven for the second stage of vulcanization, control the vulcanization temperature of the second stage of vulcanization at 150°C and the vulcanization time at 5h, without applying pressure, after completion, cool the system to 80°C, and finally obtain a low-temperature resistant and anti-aging rubber material; The preparation method of the low-temperature plasticizer includes the following steps: A1: The silane-grafted nanomaterials and glycidyl ether were mixed evenly at a mass ratio of 5.2:4.6. Under nitrogen protection, the system was heated to 120°C and stirred at 400 rpm for 4.5 h. After the reaction was completed, the mixture was cooled to room temperature, acetone (10 times the mass of the silane-grafted nanomaterials) was added, and the mixture was ultrasonically dispersed for 10 min (ultrasonic power 100 W, ultrasonic frequency 40 kHz). The mixture was centrifuged at 10,000 rpm for 15 min, washed three times with anhydrous ethanol (each time the mass of anhydrous ethanol was 4 times the mass of the silane-grafted nanomaterials), and finally vacuum dried at 65°C for 12 h to obtain the functionalized nanomaterials. The glycidyl ether was composed of castor oil triglycidyl ether and cashew phenol glycidyl ether mixed at a mass ratio of 3:1. A2: Following the mass ratio of functionalized nanomaterials, anhydrous toluene, composite modifier, and Karstedt catalyst of 5.2:85:1.6:0.03, the functionalized nanomaterials were added to anhydrous toluene and ultrasonically dispersed for 30 min (ultrasonic power 100 W, ultrasonic frequency 40 kHz). Then, the composite modifier and Karstedt catalyst were added and mixed thoroughly. The system was then heated to 90℃ and refluxed at 400 rpm for 5 h. After the reaction was completed, the mixture was cooled... The mixture was cooled to room temperature and centrifuged at 10,000 rpm for 15 min. It was then washed three times each with hot toluene at 50 °C and anhydrous ethanol (each time the mass of hot toluene was 20% of the mass of anhydrous toluene, and each time the mass of anhydrous ethanol was 25% of the mass of anhydrous toluene). Finally, it was vacuum dried at 65 °C for 24 h to obtain a low-temperature plasticizer. The composite modifier is composed of 1,1,3,3-tetramethyldisiloxane and 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane in a mass ratio of 1:0.7. The specific preparation method of silane-grafted nanomaterials is as follows: The nanomaterials, anhydrous ethanol, and deionized water were mixed in a mass ratio of 5.2:110:1.1 with the silane coupling agent. The nanomaterials were added to the mixed solution of anhydrous ethanol and deionized water (volume ratio of anhydrous ethanol to deionized water was 4:1), and ultrasonically dispersed for 35 min (ultrasonic power 100 W, ultrasonic frequency 40 kHz). The pH of the system was adjusted to 4.2 with a 1 wt% glacial acetic acid aqueous solution. The silane coupling agent was added under nitrogen protection, and the reaction was stirred in a water bath at 85°C for 4.5 h. After the reaction was completed... The mixture was cooled to room temperature, centrifuged at 10,000 rpm for 15 min, washed three times with anhydrous ethanol (each time the mass of anhydrous ethanol was 20% of the mass of the mixture of anhydrous ethanol and deionized water), and finally vacuum dried at 65 °C for 12 h to obtain silane-grafted nanomaterials. The silane coupling agent was composed of 3-aminopropyltriethoxysilane and 3-(2,3-epoxypropoxy)propyltrimethoxysilane in a mass ratio of 3:2. The nanomaterials were composed of nano-zirconia and halloysite nanotubes in a mass ratio of 0.6:0.8.

[0046] Comparative Example 1 The difference between this comparative example and Example 3 is that, in the preparation of the low-temperature resistant and anti-aging rubber material, the compound material is not subjected to low-temperature plasma treatment in step S2, while the remaining steps and raw materials are the same as in Example 3. S1: Ethylene-butadiene rubber, silane coupling agent Si-69, and 50% nano-calcium carbonate are mixed at 160℃ for 3 minutes. After the first stage of mixing, the system is cooled to 120℃. Then, zinc oxide, stearic acid, low-temperature plasticizer, reactive antioxidant, and 50% nano-calcium carbonate are added, followed by a second stage of mixing at 120℃ for 2 minutes. After this stage, the system is cooled to 80℃, and DCP is added. The mixture was subjected to a three-stage mixing process, with the mixing temperature controlled at 80℃ and the mixing time at 1 minute. After the mixing was completed, a mixed material was obtained. The mass ratio of ethylene butyl rubber, zinc oxide, stearic acid, silane coupling agent Si-69, low-temperature plasticizer, reactive antioxidant, nano calcium carbonate, and DCP was 105:7:2:1.5:12:3:50:3. The reactive antioxidant was composed of N-(4-anilinophenyl)methacrylamide and N-(4-anilinophenyl)maleimide mixed in a mass ratio of 1:1. S2: Place the compound material from step S1 into a mold of a flat vulcanizing machine preheated to 165°C, close the mold and apply a pressure of 12MPa. Perform the first stage of vulcanization treatment, controlling the vulcanization temperature of the first stage at 165°C and the vulcanization time at 10min. After completion, demold and transfer to an oven for the second stage of vulcanization treatment, controlling the vulcanization temperature of the second stage at 150°C and the vulcanization time at 5h without applying pressure. After completion, cool the system to 80°C to finally obtain a low-temperature resistant and anti-aging rubber material.

[0047] Comparative Example 2 The difference between this comparative example and Example 3 is that, in the preparation of the low-temperature resistant and anti-aging rubber material, the reinforcing material is directly vulcanized in step S3, while the remaining steps and raw materials are the same as in Example 3. S3: Place the reinforcing material from step S2 into a flat vulcanizing mold preheated to 165°C, close the mold and apply a pressure of 12MPa, and then perform vulcanization treatment. Control the vulcanization temperature of the vulcanization treatment to 165°C and the vulcanization time to 10min. After the vulcanization is completed, demold the material and cool the system to 80°C to obtain a low-temperature resistant and anti-aging rubber material.

[0048] Comparative Example 3 The difference between this comparative example and Example 3 is that, in the preparation of the low-temperature resistant and anti-aging rubber material, in step A1, glycidyl ether is replaced by castor oil triglycidyl ether in equal mass, while the remaining steps and raw materials are the same as in Example 3. A1: The silane-grafted nanomaterials and castor oil triglycidyl ether were mixed evenly at a mass ratio of 5.2:4.6. Under nitrogen protection, the system was heated to 120°C and stirred at 400 rpm for 4.5 h. After the reaction was completed, the mixture was cooled to room temperature, and acetone (10 times the mass of the silane-grafted nanomaterials) was added. The mixture was then ultrasonically dispersed for 10 min (ultrasonic power of 100 W and ultrasonic frequency of 40 kHz). The mixture was centrifuged at 10,000 rpm for 15 min and washed three times with anhydrous ethanol (each time with an anhydrous ethanol mass of 4 times the mass of the silane-grafted nanomaterials). Finally, the mixture was vacuum dried at 65°C for 12 h to obtain the functionalized nanomaterials.

[0049] Comparative Example 4 The difference between this comparative example and Example 3 is that, in the preparation of the low-temperature resistant and anti-aging rubber material, in step A1, glycidyl ether is replaced by cashew phenol glycidyl ether in equal mass, while the remaining steps and raw materials are the same as in Example 3. A1: The silane-grafted nanomaterials and cashew phenol glycidyl ether were mixed evenly at a mass ratio of 5.2:4.6. Under nitrogen protection, the system was heated to 120°C and stirred at 400 rpm for 4.5 h. After the reaction was completed, the mixture was cooled to room temperature, acetone (10 times the mass of the silane-grafted nanomaterials) was added, and the mixture was ultrasonically dispersed for 10 min (ultrasonic power of 100 W and ultrasonic frequency of 40 kHz). The mixture was centrifuged at 10,000 rpm for 15 min, washed three times with anhydrous ethanol (each time with an anhydrous ethanol mass of 4 times the mass of the silane-grafted nanomaterials), and finally vacuum dried at 65°C for 12 h to obtain the functionalized nanomaterials.

[0050] Comparative Example 5 The difference between this comparative example and Example 3 is that, in the preparation of the low-temperature resistant and anti-aging rubber material, in step A1, the nanomaterials in the silane-grafted nanomaterials are replaced with nano-zirconia of equal mass, while the remaining steps and raw materials are the same as in Example 3. The specific preparation method of silane-grafted nanomaterials is as follows: According to the mass ratio of nano-zirconia, anhydrous ethanol, and deionized water to silane coupling agent of 5.2:110:1.1, nano-zirconia was added to the mixed solution of anhydrous ethanol and deionized water (volume ratio of anhydrous ethanol to deionized water was 4:1) and ultrasonically dispersed for 35 min (ultrasonic power 100W, ultrasonic frequency 40kHz). The pH of the system was adjusted to 4.2 with 1wt% glacial acetic acid aqueous solution. The silane coupling agent was added under nitrogen protection, and then the mixture was heated to 85°C. The reaction was stirred in a water bath at ℃ for 4.5 h. After the reaction was completed, it was cooled to room temperature, centrifuged at 10,000 rpm for 15 min, washed three times with anhydrous ethanol (each time the mass of anhydrous ethanol was 20% of the mass of the above mixture of anhydrous ethanol and deionized water), and finally dried under vacuum at 65℃ for 12 h to obtain silane-grafted nanomaterials. The silane coupling agent was composed of 3-aminopropyltriethoxysilane and 3-(2,3-epoxypropoxy)propyltrimethoxysilane in a mass ratio of 3:2.

[0051] Comparative Example 6 The difference between this comparative example and Example 3 is that, in the preparation of the low-temperature resistant and anti-aging rubber material, in step A1, the nanomaterials in the silane-grafted nanomaterials are replaced with halloysite nanotubes of equal mass, while the remaining steps and raw materials are the same as in Example 3. The specific preparation method of silane-grafted nanomaterials is as follows: The halloysite nanotubes were added to the mixed solution of anhydrous ethanol and deionized water (volume ratio of anhydrous ethanol to deionized water was 4:1) at a mass ratio of 5.2:110:1.1, and ultrasonically dispersed for 35 min (ultrasonic power 100 W, ultrasonic frequency 40 kHz). The pH of the system was adjusted to 4.2 with a 1 wt% aqueous solution of glacial acetic acid. The silane coupling agent was then added under nitrogen protection, and the mixture was then heated to 85 °C. The reaction was stirred in a water bath at ℃ for 4.5 h. After the reaction was completed, it was cooled to room temperature, centrifuged at 10,000 rpm for 15 min, washed three times with anhydrous ethanol (each time the mass of anhydrous ethanol was 20% of the mass of the above mixture of anhydrous ethanol and deionized water), and finally dried under vacuum at 65℃ for 12 h to obtain silane-grafted nanomaterials. The silane coupling agent was composed of 3-aminopropyltriethoxysilane and 3-(2,3-epoxypropoxy)propyltrimethoxysilane in a mass ratio of 3:2.

[0052] Comparative Example 7 The difference between this comparative example and Example 3 is that, in the preparation of the low-temperature resistant and anti-aging rubber material, in step A2, the composite modifier is replaced by 1,1,3,3-tetramethyldisiloxane by mass, while the remaining steps and raw materials are the same as in Example 3. A2: The functionalized nanomaterials, anhydrous toluene, 1,1,3,3-tetramethyldisiloxane, and Karstedt catalyst were mixed in a mass ratio of 5.2:85:1.6:0.03. The functionalized nanomaterials were added to anhydrous toluene and ultrasonically dispersed for 30 min (ultrasonic power 100 W, ultrasonic frequency 40 kHz). Then, 1,1,3,3-tetramethyldisiloxane and Karstedt catalyst were added and mixed evenly. The system was then heated to 90 °C and refluxed at 400 rpm for 5 h. After the reaction was completed, the mixture was cooled to room temperature and centrifuged at 10,000 rpm for 15 min. The mixture was washed three times each with hot toluene at 50 °C and anhydrous ethanol (each time the mass of hot toluene was 20% of the mass of anhydrous toluene, and each time the mass of anhydrous ethanol was 25% of the mass of anhydrous toluene). Finally, the mixture was vacuum dried at 65 °C for 24 h to obtain the low-temperature plasticizer.

[0053] Comparative Example 8 The difference between this comparative example and Example 3 is that, in the preparation of the low-temperature resistant and anti-aging rubber material, in step A2, the composite modifier is replaced by 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane by mass, while the remaining steps and raw materials are the same as in Example 3. A2: The functionalized nanomaterials, anhydrous toluene, 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane, and Karstedt catalyst were mixed in a mass ratio of 5.2:85:1.6:0.03. The functionalized nanomaterials were added to anhydrous toluene and ultrasonically dispersed for 30 min (ultrasonic power 100 W, ultrasonic frequency 40 kHz). Then, 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane and Karstedt catalyst were added and mixed evenly. The system was then heated to 90 °C and refluxed at 400 rpm for 5 h. After the reaction was completed, the mixture was cooled to room temperature and centrifuged at 10,000 rpm for 15 min. The mixture was washed three times each with hot toluene at 50 °C and anhydrous ethanol (each time the mass of hot toluene was 20% of the mass of anhydrous toluene, and each time the mass of anhydrous ethanol was 25% of the mass of anhydrous toluene). Finally, the mixture was vacuum dried at 65 °C for 24 h to obtain the low-temperature plasticizer.

[0054] The low-temperature resistant and anti-aging rubber materials prepared in Examples 1-3 and Comparative Examples 1-8 were tested for mechanical properties, low-temperature resistance, and aging resistance. Mechanical property testing: Shore A hardness was tested according to national standard GB / T 531.1-2008 "Test Method for Indentation Hardness of Vulcanized Rubber or Thermoplastic Rubber Part 1: Shore Hardness Tester Method (Shore Hardness)"; tensile strength and elongation at break were tested according to national standard GB / T 528-2009 "Test of Tensile Stress-Strain Properties of Vulcanized Rubber or Thermoplastic Rubber"; Low-temperature resistance testing: Low-temperature shrinkage TR10 was determined according to national standard GB / T 7758-2020 "Determination of Low-Temperature Properties of Vulcanized Rubber - Temperature Retraction Procedure (TR Test)" to test low-temperature resistance; Aging resistance testing: According to national standard GB / T According to 3512-2001 "Accelerated Aging and Heat Resistance Test of Vulcanized Rubber or Thermoplastic Rubber in Hot Air", the heat resistance aging performance (125℃×48h) was tested, and the tensile strength retention rate (%) after hot air aging was calculated; the test results are shown in Table 1.

[0055] Table 1 Performance parameters of rubber materials resistant to low temperatures and aging As shown in Table 1, comparing Comparative Examples 1-2 and Example 3, the test results of the low-temperature resistant and anti-aging rubber material prepared in step S2 (where the compound material is not subjected to low-temperature plasma treatment) or step S3 (where the reinforcing material is directly vulcanized) are worse than those in Example 3. This indicates that low-temperature plasma treatment of the compound material can better enhance the interfacial bonding between ethylene butyl rubber and other raw materials, improve the dispersion and compatibility of reinforcing fillers in ethylene butyl rubber, and thus further improve the mechanical properties, low-temperature resistance, and aging resistance of the rubber material. Vulcanizing the reinforcing material through a segmented vulcanization process can better improve the mechanical properties and dimensional stability of the rubber material, and can also improve the interfacial bonding between ethylene butyl rubber and other raw materials, thereby further improving the low-temperature resistance, aging resistance, and mechanical properties of the rubber material. Comparing Comparative Examples 3-6 and Example 3, it can be seen that in step A1, replacing glycidyl ether with castor oil triglycidyl ether or cashew phenol glycidyl ether by mass, or replacing the nanomaterials in the silane-grafted nanomaterials with nano-zirconia or halloysite nanotubes by mass, and finally preparing a low-temperature resistant and anti-aging rubber material, the test results are worse than those of Example 3. This indicates that the glycidyl ether composed of castor oil triglycidyl ether and cashew phenol glycidyl ether has a synergistic effect, which can not only improve the low-temperature resistance and antioxidant capacity of the rubber material, but also enhance the interfacial compatibility between the low-temperature plasticizer and ethylene butyl rubber and reinforcing fillers, thereby further improving the low-temperature resistance, aging resistance and mechanical properties of the rubber material. Comparing Comparative Examples 7-8 and Example 3, it can be seen that in step A2, replacing the composite modifier with 1,1,3,3-tetramethyldisiloxane or 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane by mass, and finally preparing a low-temperature resistant and anti-aging rubber material, the test results are worse than those of Example 3. This indicates that the composite modifier composed of a mixture of 1,1,3,3-tetramethyldisiloxane and 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane has a synergistic effect. It can not only improve the low-temperature resistance and aging resistance of the rubber material, but also increase the interfacial compatibility between the low-temperature plasticizer and ethylene butyl rubber, further improving the low-temperature resistance, aging resistance and mechanical properties of the rubber material.

[0056] As shown in Table 1, the low-temperature resistant and anti-aging rubber materials prepared in Examples 1-3, compared to those prepared in Comparative Examples 1-8, demonstrate that the low-temperature resistant and anti-aging rubber materials prepared in Examples 1-3, through mixing ethylene butyl rubber, zinc oxide, stearic acid, coupling agent, low-temperature plasticizer, reactive antioxidant, reinforcing filler, and vulcanizing agent, followed by activation treatment and finally vulcanization treatment, significantly improve the overall low-temperature resistance, aging resistance, and mechanical properties of the rubber materials, meeting the performance requirements. In contrast, the low-temperature resistant and anti-aging rubber materials prepared in Comparative Examples 1-8 did not meet the performance requirements. This indicates that the low-temperature resistant and anti-aging rubber materials prepared in this invention possess better low-temperature resistance, aging resistance, mechanical properties, and long-term durability, extending the service life of the rubber materials and overall improving their comprehensive performance.

[0057] In the description of this specification, the references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0058] The above description is merely an example and illustration of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described or use similar methods to replace them, as long as they do not deviate from the invention or exceed the scope defined by the present invention, they should all fall within the protection scope of the present invention.

Claims

1. A preparation process for a low-temperature resistant and anti-aging rubber material, characterized in that, Includes the following steps: S1: Ethylene-butadiene rubber, zinc oxide, stearic acid, coupling agent, low-temperature plasticizer, reactive antioxidant, reinforcing filler and vulcanizing agent are mixed using a three-stage mixing method to obtain the mixed material; S2: Activate the compounded material in step S1 to obtain the reinforced material; S3: The reinforcing material in step S2 is vulcanized through a segmented vulcanization process to obtain a low-temperature resistant and aging-resistant rubber material.

2. The preparation process of a low-temperature resistant and anti-aging rubber material according to claim 1, characterized in that, In step S1, the mass ratio of the ethylene butyl rubber, zinc oxide, stearic acid, coupling agent, low-temperature plasticizer, reactive antioxidant, reinforcing filler, and vulcanizing agent is 95-105:5-7:1-2:0.5-1.5:10-12:2-3:40-50:2-3.

3. The preparation process of a low-temperature resistant and anti-aging rubber material according to claim 1, characterized in that, Step S1 is as follows: Ethylene-butadiene rubber, coupling agent, and reinforcing filler are mixed at 140-160℃ for one stage. After the first stage, the system is cooled to 100-120℃, and then zinc oxide, stearic acid, low-temperature plasticizer, reactive antioxidant, and reinforcing filler are added. The second stage is then carried out. After the second stage, the system is cooled to 60-80℃, and then vulcanizing agent is added. The third stage is then carried out. After the third stage, the mixed material is obtained.

4. The preparation process of a low-temperature resistant and anti-aging rubber material according to claim 3, characterized in that, The mixing temperature for the first stage of mixing is 140-160℃, and the mixing time is 3-5 minutes; the mixing temperature for the second stage of mixing is 100-120℃, and the mixing time is 2-4 minutes; the mixing temperature for the third stage of mixing is 60-80℃, and the mixing time is 1-3 minutes.

5. The preparation process of a low-temperature resistant and anti-aging rubber material according to claim 1, characterized in that, In step S2, the activation treatment includes low-temperature plasma treatment or ultraviolet ozone treatment; the specific parameters of the low-temperature plasma treatment are as follows: the working gas of the low-temperature plasma treatment is a mixture of Ar and O2, the treatment power is 350-450W, the treatment frequency is 20-30kHz, the treatment temperature is 40-50℃, and the treatment time is 40-50s.

6. The preparation process of a low-temperature resistant and anti-aging rubber material according to claim 1, characterized in that, Step S3 is as follows: Place the reinforcing material from step S2 into a mold preheated to 160-165℃, close the mold and apply a pressure of 8-12MPa, perform the first stage of vulcanization, demold after completion, transfer to an oven for the second stage of vulcanization without applying pressure, remove after completion, and cool the system to 60-80℃ to obtain a low-temperature resistant and anti-aging rubber material.

7. The preparation process of a low-temperature resistant and anti-aging rubber material according to claim 6, characterized in that, The vulcanization temperature of the first stage of vulcanization treatment is 160-165℃, and the vulcanization time is 10-15 min; the vulcanization temperature of the second stage of vulcanization treatment is 150℃, and the vulcanization time is 4-5 h.

8. The preparation process of a low-temperature resistant and anti-aging rubber material according to claim 1, characterized in that, The preparation method of the low-temperature plasticizer includes the following steps: A1: The silane-grafted nanomaterials were mixed evenly with glycidyl ether. Under nitrogen protection, the system was heated and stirred. After the reaction was completed, it was cooled to room temperature, acetone was added, and the mixture was ultrasonically dispersed. After centrifugation, the mixture was washed with anhydrous ethanol and finally vacuum dried to obtain the functionalized nanomaterials. A2: Functionalized nanomaterials were added to anhydrous toluene and ultrasonically dispersed. Then, composite modifiers and catalysts were added and mixed evenly. The system was then heated to reflux reaction. After the reaction was completed, the mixture was cooled to room temperature, centrifuged, washed with hot toluene and anhydrous ethanol, and finally vacuum dried to obtain a low-temperature plasticizer.

9. The preparation process of a low-temperature resistant and anti-aging rubber material according to claim 8, characterized in that, In step A1, the glycidyl ether is composed of castor oil triglycidyl ether and cashew phenol glycidyl ether mixed in a mass ratio of 2-3:1; in step A2, the composite modifier is composed of 1,1,3,3-tetramethyldisiloxane and 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane mixed in a mass ratio of 0.9-1:0.6-0.

7.

10. A low-temperature resistant and anti-aging rubber material prepared by the preparation process according to any one of claims 1-9.

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