A rubber composite material and a preparation method and application thereof

Abstract

The application discloses a rubber composite material and a preparation method and application thereof, and belongs to the technical field of high polymer composite materials.The composite material comprises, in weight parts, 60-100 parts of hydrogenated nitrile rubber, 15-30 parts of peroxide fluororubber, 5-15 parts of polyvinyl chloride, 25-50 parts of reinforcing agent, 5-15 parts of plasticizer, 3-10 parts of fluorocarbon resin, 3.3-5.2 parts of vulcanization system and 5-13.5 parts of auxiliary agent, wherein the fluorocarbon resin is a hydroxyl fluorine-containing acrylic resin.The preparation adopts a sectional mixing process, and different components are premixed and then compounded and vulcanized.The application cooperates with a multi-phase rubber system, and introduces fluorocarbon resin to improve the interface bonding performance, so that the obtained material has excellent oil resistance, oil and gas barrier performance and good mechanical strength, and can be widely applied to rubber products, such as ship oil conveying pipelines, oil-resistant rubber pipes and sealing elements, which are in long-term contact with oil and gas media.

Description

Technical Field

[0001] This application relates to the field of polymer composite materials technology, specifically to a rubber composite material and its preparation method and application. Background Technology

[0002] Rubber materials, due to their excellent elasticity, fatigue resistance, and ease of processing and molding, are widely used in oil pipelines, seals, mechanical components, and marine equipment. Marine oil pipelines, in particular, are constantly exposed to crude oil, fuel oil, and oil and gas media, and are also affected by seawater, ultraviolet radiation, ozone, and temperature fluctuations. Therefore, rubber materials used in oil pipelines must not only have good oil resistance, but also excellent resistance to oil and gas permeation, ozone aging, hydrogen sulfide corrosion, and high mechanical strength.

[0003] Currently, nitrile rubber (NBR) is commonly used as the main matrix material for marine oil pipelines. While NBR possesses some oil resistance due to the presence of polar acrylonitrile structures in its molecular chain, its resistance to crude oil, hydrogen sulfide, and ozone remains insufficient. During long-term transportation of oil and gas media, it is susceptible to corrosion and performance degradation, leading to problems such as oil and gas leakage, material expansion, and even structural failure, thus affecting the service life and operational safety of the oil pipeline.

[0004] To address the aforementioned issues, existing technologies also employ hydrogenated nitrile butadiene rubber (HNBR) instead of ordinary nitrile butadiene rubber. HNBR improves the material's heat aging resistance, ozone resistance, and chemical resistance by reducing the content of unsaturated double bonds in its molecular chain, while also exhibiting good mechanical properties. However, a single HNBR system still has limitations in its long-term resistance to oil and gas permeation in complex oil and gas environments, making it difficult to meet the long-term stable performance requirements of marine oil pipelines.

[0005] Furthermore, fluororubber possesses excellent resistance to fuel oil and chemical media, but its processing and mechanical properties have certain limitations; polyvinyl chloride (PVC) exhibits good oil and gas barrier properties, but its compatibility with the rubber matrix is ​​poor when used alone. Therefore, how to achieve synergistic effects through composite modification of multiple polymer materials, while simultaneously improving the interfacial bonding properties between multi-component systems, is an important direction for enhancing the overall performance of rubber materials.

[0006] Therefore, there is an urgent need to develop a rubber composite material with excellent oil resistance and good mechanical properties to meet the long-term use requirements in harsh environments such as marine oil pipelines. Summary of the Invention

[0007] This application aims to provide a rubber composite material, its preparation method, and its application, in order to solve the problems of insufficient resistance to oil and gas permeation, susceptibility to media corrosion during long-term service, and difficulty in achieving comprehensive mechanical properties in existing rubber materials used in oil pipelines.

[0008] To address the aforementioned technical problems, this application provides a rubber composite material, comprising the following components by weight:

[0009] 60-100 parts of hydrogenated nitrile butadiene rubber; 15-30 parts of peroxyfluororubber; 5-15 parts of polyvinyl chloride; 25-50 parts of reinforcing agent; Plasticizer 5-15 parts; 3-10 parts of fluorocarbon resin; Vulcanization system: 3.3-5.2 parts; Additives: 5-13.5 parts.

[0010] Furthermore, the hydrogenated nitrile rubber contains 40%-55% acrylonitrile and has a hydrogenation saturation of 95%-100%.

[0011] Furthermore, the degree of polymerization of the polyvinyl chloride is 1400-1600.

[0012] Furthermore, the reinforcing agent is selected from one or more of carbon black, silica, kaolin, calcium carbonate, silicate, graphene, and carbon nanotubes.

[0013] Furthermore, the plasticizer is selected from one or more of trimellitic ester plasticizers, phthalate plasticizers, adipate plasticizers, sebacic ester plasticizers, and phosphate plasticizers.

[0014] Furthermore, the fluorocarbon resin is a hydroxyl-containing fluorinated acrylic resin with a hydroxyl content of 10 wt%.

[0015] Furthermore, the vulcanization system comprises di-tert-butylperoxide diisopropylbenzene and triallyl isocyanurate.

[0016] Furthermore, the additives include one or more of zinc oxide, stearic acid, antioxidants, and processing aids.

[0017] This application also provides a method for preparing the above-mentioned rubber composite material, comprising the following steps: (1) First stage of mixing: Part of the hydrogenated nitrile rubber is plasticized, and then mixed with fluororubber and fluorocarbon resin to obtain the first compound. (2) Second stage of mixing: After the remaining hydrogenated nitrile rubber is plasticized, polyvinyl chloride is added and mixed to obtain the second compound; (3) Third stage mixing: The first compound and the second compound are mixed to obtain a mixed rubber; (4) Fourth stage of mixing: Add reinforcing agent, plasticizer and additives to the mixed rubber and mix; (5) Vulcanization treatment: After being added to the vulcanization system and passing through a thin sheet, the rubber composite material is vulcanized to obtain the rubber composite material.

[0018] Furthermore, in step (1), the mixing temperature is below 60°C, and the standing time after mixing is 20-30 hours.

[0019] Furthermore, in step (2), the mixing temperature after adding polyvinyl chloride is not higher than 120°C.

[0020] Furthermore, in step (4), the mixing temperature after adding the reinforcing agent is not higher than 135°C.

[0021] Furthermore, the vulcanization treatment includes primary vulcanization and post-vulcanization treatment, wherein the primary vulcanization temperature is 170-180℃ and the vulcanization time is 5-10 min; the post-vulcanization treatment includes first treating at 150℃ for 30 min, then raising the temperature to 170-180℃ and holding at that temperature for 3-5 h.

[0022] This application also provides a rubber article, which includes the above-mentioned rubber composite material.

[0023] The beneficial effects of this application are as follows: Compared with the prior art, the rubber composite material provided in this application adopts a composite system composed of hydrogenated nitrile rubber, peroxy fluororubber and polyvinyl chloride, and improves the bonding performance between different rubber components by introducing fluorocarbon resin, so that the obtained rubber composite material has better oil resistance and mechanical properties.

[0024] Meanwhile, this application employs a segmented mixing process, premixing different components separately before compounding, which improves the dispersion uniformity of each component and enhances the overall performance of the material by combining it with a peroxide vulcanization system. Furthermore, the rubber composite material prepared in this application can be used in rubber products that are in long-term contact with oil and gas media, such as oil pipelines, improving the stability of these products in use. Attached Figure Description

[0025] Figure 1 Tensile test diagram of the rubber composite material prepared in Example 1 of this application; Figure 2 Tensile test diagram of the rubber composite material prepared in Example 2 of this application; Figure 3 Tensile test diagram of the rubber composite material prepared in Example 3 of this application; Figure 4Tensile test diagram of the rubber composite material prepared in Example 4 of this application; Figure 5 Tensile test diagram of the rubber composite material prepared in Example 5 of this application; Figure 6 Tensile test diagram of the rubber composite material prepared in Comparative Example 1 of this application; Figure 7 Tensile test diagram of the rubber composite material prepared in Comparative Example 2 of this application; Figure 8 The tensile test diagram of the rubber composite material prepared in Comparative Example 3 of this application is shown. Figure 9 Tensile test diagram of the rubber composite material prepared in Comparative Example 4 of this application; Figure 10 Tensile test diagram of the rubber composite material prepared in Comparative Example 5 of this application; Figure 11 Tensile test diagram of the rubber composite material prepared in Comparative Example 6 of this application; Figure 12 Tensile test diagram of the rubber composite material prepared in Comparative Example 7 of this application; Detailed Implementation The technical solutions in the embodiments of this application will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of this application, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of this application without creative effort are within the scope of protection of this application.

[0026] This application provides a rubber composite material comprising 60-100 parts of hydrogenated nitrile rubber, 15-30 parts of fluoropolymer, 5-15 parts of polyvinyl chloride, 25-50 parts of reinforcing agent, 5-15 parts of plasticizer, 3-10 parts of fluorocarbon resin, 3.3-5.2 parts of vulcanization system, and 5-13.5 parts of additives.

[0027] In some specific embodiments, the hydrogenated nitrile rubber contains 40%-55% acrylonitrile and has a hydrogenation saturation of 95%-100%.

[0028] In some specific embodiments, the peroxyfluororubber is a fluorinated rubber material. Due to the presence of fluorine-containing structures in its molecular chain, peroxyfluororubber exhibits good resistance to fuels, chemical media, and high temperatures.

[0029] In some specific embodiments, the degree of polymerization of the polyvinyl chloride (PVC) is 1400-1600. PVC has good oil resistance and barrier properties; by combining PVC with rubber materials, the barrier ability of the rubber composite material against oil and gas media can be improved.

[0030] In some specific embodiments, the reinforcing agent is selected from one or more of carbon black, silica, kaolin, calcium carbonate, silicate, graphene, and carbon nanotubes.

[0031] In some specific embodiments, the carbon black and clay together serve as a reinforcing system, wherein the mass ratio of carbon black to clay is 1:(0.5-1.5).

[0032] In some specific embodiments, the plasticizer is selected from one or more of trimellitate plasticizers, phthalate plasticizers, adipate plasticizers, sebacic acid ester plasticizers, and phosphate plasticizers.

[0033] In some specific embodiments, the fluorocarbon resin is a hydroxyl-containing fluorinated acrylic resin. This hydroxyl-containing fluorinated acrylic resin simultaneously contains hydroxyl, fluorinated, and acrylic structures. These different functional structures synergistically enhance the bonding performance between the components in the rubber composite material. The hydroxyl structure, with its strong polarity, improves the interaction between the hydroxyl-containing fluorinated acrylic resin and polar components such as hydrogenated nitrile rubber and polyvinyl chloride, strengthening the bonding force between different material interfaces, reducing interface defects caused by differences in component polarity, and resulting in a more stable structure in the multi-component composite system. The fluorinated structure has lower surface energy and higher chemical stability, improving the oil resistance, chemical resistance, and aging resistance of the hydroxyl-containing fluorinated acrylic resin itself. Simultaneously, the fluorinated structure interacts well with the fluorinated structure in the peroxyfluorinated rubber, which is beneficial for improving the bonding effect between the fluorocarbon resin and the peroxyfluorinated rubber, and promoting the uniform dispersion of the peroxyfluorinated rubber in the rubber matrix. The acrylic structure provides excellent polymerization stability and molecular chain regulation capabilities, giving hydroxyl-containing fluorinated acrylic resins good film-forming properties, flexibility, and bonding ability with polymer materials. This is beneficial for improving the dispersion effect of fluorocarbon resins in rubber systems and enhancing the stability of composite materials during processing. Through the synergistic effect of the hydroxyl, fluorinated, and acrylic structures, the hydroxyl-containing fluorinated acrylic resin can simultaneously improve the interfacial bonding properties between hydrogenated nitrile rubber, peroxyfluorinated rubber, and polyvinyl chloride, enhancing the compatibility and stability of the multi-component system. This results in rubber composite materials with good oil resistance, media resistance, and mechanical properties.

[0034] In some specific embodiments, the vulcanization system includes a peroxide vulcanizing agent and a crosslinking agent.

[0035] Furthermore, the peroxide vulcanizing agent is di-tert-butylperoxide diisopropylbenzene, and the crosslinking agent is triallyl isocyanurate.

[0036] In some specific embodiments, the additives include one or more of zinc oxide, stearic acid, antioxidants, and processing aids.

[0037] In some specific embodiments, this application also provides a method for preparing the above-mentioned rubber composite material, including steps such as mixing, adding compounding agents, and vulcanization treatment.

[0038] In some specific embodiments, the preparation method of the rubber composite material includes the following steps: First, partially hydrogenated nitrile rubber is plasticized. After the rubber compound reaches a suitable processing state, fluoropolymer and fluorocarbon resin are added and mixed to obtain the first compound.

[0039] By premixing hydrogenated nitrile rubber with peroxy fluororubber and fluorocarbon resin, the peroxy fluororubber and fluorocarbon resin can be fully dispersed in the hydrogenated nitrile rubber matrix, improving the dispersion and bonding effect between different rubber components.

[0040] In some specific implementations, during the first stage of mixing, the mixing temperature is controlled below 60°C, and after mixing is completed, the mixture is left to stand for 20-30 hours.

[0041] In some specific embodiments, the remaining hydrogenated nitrile rubber is plasticized and then mixed with polyvinyl chloride to obtain a second compound.

[0042] In some specific implementations, during the second-stage mixing process, the mixing temperature after the addition of polyvinyl chloride is controlled below 120°C.

[0043] In some specific embodiments, the first compound rubber and the second compound rubber are mixed to obtain a composite compound rubber.

[0044] In some specific embodiments, reinforcing agents, plasticizers, and additives are added to the composite compound and then mixed. The mixing temperature after adding the reinforcing agent is controlled below 135°C.

[0045] In some specific embodiments, after the compounding agents are mixed, a vulcanization system is added, and after uniform mixing, thin-passing and sheeting, vulcanization treatment is performed to obtain the rubber composite material.

[0046] In some specific embodiments, the vulcanization treatment includes primary vulcanization and post-vulcanization. The primary vulcanization temperature is 170-180℃, and the vulcanization time is 5-10 minutes. The post-vulcanization treatment includes first treating at 150℃ for 30 minutes, then raising the temperature to 170-180℃ and holding at that temperature for 3-5 hours.

[0047] In some specific embodiments, this application also provides a rubber article, which includes the above-mentioned rubber composite material.

[0048] In some specific embodiments, the rubber product can be an oil pipeline, an oil-resistant hose, a seal, or other rubber product that needs to be in long-term contact with oil and gas media.

[0049] Example 1 This embodiment provides a rubber composite material, which, by weight, comprises the following components: Hydrogenated nitrile butadiene rubber (acrylonitrile content 43wt%, saturation 98%): 70 parts; Peroxyfluororubber: 30 parts; Polyvinyl chloride (degree of polymerization 1500): 15 parts; Fluorocarbon resin (hydroxyl-containing fluorinated acrylic resin, hydroxyl content 10wt%): 8 parts; Reinforcing agent: 25 parts carbon black, 25 parts kaolin; Plasticizer (trioctyl trimellitate): 5 parts; Vulcanization system: 3.2 parts BIBP, 1.4 parts TAIC; Additives: 5 parts zinc oxide, 1.2 parts stearic acid, 2 parts aromatic amine antioxidants, and 2 parts processing aids.

[0050] The preparation method is as follows: (1) First stage of mixing: Half the weight of hydrogenated nitrile rubber is plasticized on an open mill, and all the peroxy fluororubber and all the fluorocarbon resin are added in sequence. The roller temperature is controlled below 60°C, and the mixture is mixed by repeatedly making triangular wraps 6 times. After the rubber compound is sheeted and left to stand for 24 hours, it is hot-milled again. The roller gap is <0.3mm and it is thin-passed 6 times. After standing for 24 hours again, the first stage of mixed rubber is obtained. (2) Two-stage mixing: The remaining half weight of hydrogenated nitrile rubber is put into the internal mixer for plasticizing, and all the polyvinyl chloride is added. The mixing time is 7 minutes and the discharge temperature is ≤120℃ to obtain the two-stage compound. (3) Three-stage mixing: The cooled first-stage and second-stage compound rubbers are fed into the open mill and mixed thoroughly to obtain the composite masterbatch; (4) Four-stage mixing: The compound masterbatch is put into the internal mixer, and zinc oxide, stearic acid, aromatic amine antioxidants and processing aids are added in sequence. Then carbon black and clay are added in batches. The temperature is controlled throughout the process and the discharge temperature is ≤135℃. (5) Vulcanizing agent mixing: The masterbatch is transferred to the open mill for re-mixing, and BIBP and TAIC are added in batches. After passing through the thin mill 5 times, the sheet is produced; Vulcanization molding: First vulcanization at 175℃, holding for 8 minutes; subsequent vulcanization is first held at 150℃ for 30 minutes, and then heated to 175℃ and held for 4 hours.

[0051] Example 2 This embodiment provides a rubber composite material, which, by weight, comprises the following components: Hydrogenated nitrile butadiene rubber (acrylonitrile content 40wt%, saturation 95%): 60 parts; Peroxyfluororubber: 15 parts; Polyvinyl chloride (degree of polymerization 1400): 5 parts; Fluorocarbon resin (hydroxyl-containing fluorinated acrylic resin, hydroxyl content 10wt%): 3 parts; Reinforcing agent: 15 parts carbon black, 10 parts kaolin; Plasticizer (trioctyl trimellitate): 5 parts; Vulcanization system: 1.8 parts BIBP, 1.5 parts TAIC; Additives: 3 parts zinc oxide, 0.6 parts stearic acid, 1 part hindered phenolic antioxidant, and 1 part processing aid.

[0052] The preparation method is as follows: (1) First stage of mixing: Half the weight of hydrogenated nitrile rubber is plasticized on an open mill, and all the peroxy fluororubber and all the fluorocarbon resin are added in sequence. The roller temperature is controlled below 60°C, and the mixture is mixed by repeatedly making triangular wraps 6 times. After the rubber compound is sheeted and left to stand for 22 hours, it is hot-milled again. The roller gap is <0.3mm and it is thin-passed 6 times. After standing for 22 hours again, the first stage of mixed rubber is obtained. (2) Two-stage mixing: The remaining half weight of hydrogenated nitrile rubber is put into the internal mixer for plasticizing, and all the polyvinyl chloride is added. The mixing time is 6 minutes and the discharge temperature is ≤120℃ to obtain the two-stage compound. (3) Three-stage mixing: The cooled first-stage and second-stage compound rubbers are fed into the open mill and mixed thoroughly to obtain the composite masterbatch; (4) Four-stage mixing: The compound masterbatch is put into the internal mixer, and zinc oxide, stearic acid, hindered phenolic antioxidants and processing aids are added in sequence. Then carbon black and clay are added in batches. The temperature is controlled throughout the process and the discharge temperature is ≤135℃. (5) Vulcanizing agent mixing: The masterbatch is transferred to the open mill for re-mixing, and BIBP and TAIC are added in batches. After passing through the thin mill 5 times, the sheet is produced; Vulcanization molding: First vulcanization at 170℃ and holding for 10 min; subsequent vulcanization is first held at 150℃ for 30 min, and then heated to 170℃ and held for 3 h.

[0053] Example 3 This embodiment provides a rubber composite material, which, by weight, comprises the following components: Hydrogenated nitrile butadiene rubber (acrylonitrile content 55wt%, saturation 100%): 100 parts; Peroxyfluororubber: 30 parts; Polyvinyl chloride (degree of polymerization 1600): 15 parts; Fluorocarbon resin (hydroxyl-containing fluorinated acrylic resin, hydroxyl content 10wt%): 10 parts; Reinforcing agent: 30 parts carbon black, 20 parts kaolin; Plasticizer (trioctyl trimellitate): 15 parts; Vulcanization system: 3.0 parts BIBP, 2.2 parts TAIC; Additives: 6 parts zinc oxide, 1.5 parts stearic acid, 3 parts thioester antioxidants, and 3 parts processing aids.

[0054] The preparation method is as follows: (1) First stage of mixing: Half the weight of hydrogenated nitrile rubber is plasticized on an open mill, and all the peroxy fluororubber and all the fluorocarbon resin are added in sequence. The roller temperature is controlled below 60°C, and the mixture is mixed by repeatedly making triangular wraps 6 times. After the rubber compound is sheeted and left to stand for 30 hours, it is hot-milled again. The roller gap is <0.3mm and it is thin-passed 6 times. After standing for 30 hours again, the first stage of mixed rubber is obtained. (2) Two-stage mixing: The remaining half weight of hydrogenated nitrile rubber is put into the internal mixer for plasticizing, and all the polyvinyl chloride is added. The mixing time is 8 minutes and the discharge temperature is ≤120℃ to obtain the two-stage compound. (3) Three-stage mixing: The cooled first-stage and second-stage compound rubbers are fed into the open mill and mixed thoroughly to obtain the composite masterbatch; (4) Four-stage mixing: The compound masterbatch is put into the internal mixer, and zinc oxide, stearic acid, thioester antioxidants and processing aids are added in sequence. Then carbon black and clay are added in batches. The temperature is controlled throughout the process and the discharge temperature is ≤135℃. (5) Vulcanizing agent mixing: The masterbatch is transferred to the open mill for re-mixing, and BIBP and TAIC are added in batches. After passing through the thin mill 5 times, the sheet is produced; Vulcanization molding: First vulcanization at 180℃, holding for 5 minutes; subsequent vulcanization is first held at 150℃ for 30 minutes, and then heated to 180℃ and held for 5 hours.

[0055] Example 4 This embodiment provides a rubber composite material, which, by weight, comprises the following components: Hydrogenated nitrile butadiene rubber (acrylonitrile content 48wt%, saturation 97%): 80 parts; Peroxyfluororubber: 22 parts; Polyvinyl chloride (degree of polymerization 1500): 10 parts; Fluorocarbon resin (hydroxyl-containing fluorinated acrylic resin, hydroxyl content 10wt%): 8 parts; Reinforcing agent: 22 parts carbon black, 20 parts kaolin; Plasticizer (trioctyl trimellitate): 15 parts; Vulcanization system: 2.5 parts BIBP, 1.8 parts TAIC; Additives: 4 parts zinc oxide, 1.0 part stearic acid, 1 part aromatic amine antioxidant, 1 part hindered phenolic antioxidant, and 2 parts processing aids.

[0056] The preparation method is as follows: (1) First stage of mixing: Half the weight of hydrogenated nitrile rubber is plasticized on an open mill, and all the peroxy fluororubber and all the fluorocarbon resin are added in sequence. The roller temperature is controlled below 60°C, and the mixture is mixed by repeatedly making triangular wraps 6 times. After the rubber compound is sheeted and left to stand for 24 hours, it is hot-milled again. The roller gap is <0.3mm and it is thin-passed 6 times. After standing for 24 hours again, the first stage of mixed rubber is obtained. (2) Two-stage mixing: The remaining half weight of hydrogenated nitrile rubber is put into the internal mixer for plasticizing, and all the polyvinyl chloride is added. The mixing time is 7 minutes and the discharge temperature is ≤120℃ to obtain the two-stage compound. (3) Three-stage mixing: The cooled first-stage and second-stage compound rubbers are fed into the open mill and mixed thoroughly to obtain the composite masterbatch; (4) Four-stage mixing: The compound masterbatch is put into the internal mixer, and zinc oxide, stearic acid, compound antioxidant and processing aid are added in sequence. Then carbon black and clay are added in batches. The temperature is controlled throughout the process and the discharge temperature is ≤135℃. (5) Vulcanizing agent mixing: The masterbatch is transferred to the open mill for re-mixing, and BIBP and TAIC are added in batches. After passing through the thin mill 5 times, the sheet is produced; Vulcanization molding: First vulcanization at 175℃, holding for 7 minutes; subsequent vulcanization is first held at 150℃ for 30 minutes, and then heated to 170℃ and held for 4 hours.

[0057] Example 5 This embodiment provides a rubber composite material, which, by weight, comprises the following components: Hydrogenated nitrile butadiene rubber (acrylonitrile content 50wt%, saturation 99%): 90 parts; Peroxyfluororubber: 20 parts; PVC (degree of polymerization 1400): 12 parts; Fluorocarbon resin (hydroxyl-containing fluorinated acrylic resin, hydroxyl content 10wt%): 6 parts; Reinforcing agent: 20 parts carbon black, 18 parts kaolin; Plasticizer (trioctyl trimellitate): 10 parts; Vulcanization system: 2.8 parts BIBP, 1.6 parts TAIC; Additives: 4.5 parts zinc oxide, 0.8 parts stearic acid, 1.2 parts aromatic amine antioxidant, 1.3 parts thioester antioxidant, and 1.5 parts processing aid.

[0058] The preparation method is as follows: (1) First stage of mixing: Half the weight of hydrogenated nitrile rubber is plasticized on an open mill, and all the peroxy fluororubber and all the fluorocarbon resin are added in sequence. The roller temperature is controlled below 60°C, and the mixture is mixed by repeatedly making triangular wraps 6 times. After the rubber compound is sheeted and left to stand for 24 hours, it is hot-milled again. The roller gap is <0.3mm and it is thin-passed 6 times. After standing for 24 hours again, the first stage of mixed rubber is obtained. (2) Two-stage mixing: The remaining half weight of hydrogenated nitrile rubber was put into the internal mixer for plasticizing, and all the PVC was added. The mixing time was 7 minutes and the discharge temperature was ≤120℃ to obtain the two-stage compound. (3) Three-stage mixing: The cooled first-stage and second-stage compound rubbers are fed into the open mill and mixed thoroughly to obtain the composite masterbatch; (4) Four-stage mixing: The compound masterbatch is put into the internal mixer, and zinc oxide, stearic acid, compound antioxidant and processing aid are added in sequence. Then carbon black and clay are added in batches. The temperature is controlled throughout the process and the discharge temperature is ≤135℃. (5) Vulcanizing agent mixing: The masterbatch is transferred to the open mill for re-mixing, and BIBP and TAIC are added in batches. After passing through the thin mill 5 times, the sheet is produced; Vulcanization molding: First vulcanization at 175℃, holding for 9 minutes; subsequent vulcanization is first held at 150℃ for 30 minutes, and then heated to 180℃ and held for 4 hours.

[0059] Comparative Example 1 The only difference between this comparative example and Example 1 is that no fluoropolymer was added in this comparative example, while the other components and preparation process are the same as in Example 1.

[0060] Comparative Example 2 The only difference between this comparative example and Example 1 is that no polyvinyl chloride is added in this comparative example, while the other components are the same as in Example 1.

[0061] The preparation method is as follows: (1) Mixing: Plasticize all hydrogenated nitrile rubber on a rolling mill, add all fluoropolymer and fluorocarbon resin in sequence, control the roller temperature below 60°C, and mix by repeatedly making triangular wraps 6 times; after the rubber compound is sheeted and left to stand for 24 hours, it is hot-mixed again by rolling mill, passing through the roller gap <0.3mm 6 times, and then left to stand for 24 hours again to obtain the mixed rubber. (2) Add the mixed rubber into the internal mixer, add zinc oxide, stearic acid, aromatic amine antioxidants and processing aids in sequence, and then add carbon black and clay in batches. Control the temperature throughout the process and the discharge temperature is ≤135℃ to obtain the internal masterbatch. (3) Vulcanizing agent mixing: The masterbatch is transferred to the open mill for re-mixing, and BIBP and TAIC are added in batches. After passing through the thin mill 5 times, the sheet is produced; Vulcanization molding: First vulcanization at 175℃, holding for 8 minutes; subsequent vulcanization is first held at 150℃ for 30 minutes, and then heated to 175℃ and held for 4 hours.

[0062] Comparative Example 3 The only difference between this comparative example and Example 1 is that this comparative example uses 35 parts of hydrogenated nitrile butadiene rubber with an acrylonitrile content of 36% and 35 parts of nitrile butadiene rubber with an acrylonitrile content of 36%, replacing the 70 parts of hydrogenated nitrile butadiene rubber in Example 1. All other components and preparation processes are the same as in Example 1.

[0063] Comparative Example 4 The only difference between this comparative example and Example 1 is that the degree of polymerization of polyvinyl chloride in this comparative example is 1100, while the other components and preparation process are the same as in Example 1.

[0064] Comparative Example 5 The only difference between this comparative example and Example 1 is that the degree of polymerization of polyvinyl chloride in this comparative example is 1800, while the other components and preparation process are the same as in Example 1.

[0065] Comparative Example 6 The only difference between this comparative example and Example 1 is that this comparative example uses commercially available FEVE fluorocarbon resin to replace the hydroxyl-containing fluoroacrylic resin, while the other components and preparation process are the same as in Example 1.

[0066] Comparative Example 7 The only difference between this comparative example and Example 1 is the preparation method. The components are the same as in Example 1.

[0067] The preparation method for this comparative example is as follows: (1) Mixing: Plasticize hydrogenated nitrile rubber on a rolling mill, add all the peroxy fluororubber, all the fluorocarbon resin and polyvinyl chloride in sequence, control the roller temperature below 60℃, and mix by repeatedly making triangular wraps 6 times; after the rubber compound is sheeted and left to stand for 24 hours, it is hot-mixed again by rolling mill, with a roller gap of <0.3mm for 6 thin passes, and left to stand for 24 hours again to obtain the mixed rubber. (2) Internal mixing: The internal mixer is fed with the compound rubber, and zinc oxide, stearic acid, aromatic amine antioxidants and processing aids are added in sequence. Then carbon black and clay are added in batches. The temperature is controlled throughout the process and the discharge temperature is ≤135℃ to obtain the compound masterbatch. (3) Vulcanizing agent mixing: The masterbatch is transferred to the open mill for re-mixing, and BIBP and TAIC are added in batches. After passing through the thin mill 5 times, the sheet is produced; Vulcanization molding: First vulcanization at 175℃, holding for 8 minutes; subsequent vulcanization is first held at 150℃ for 30 minutes, and then heated to 175℃ and held for 4 hours.

[0068] Test method: Shore A hardness: According to GB / T531.1 standard, the rubber sample was tested at room temperature using a Shore A hardness tester; Tensile strength and elongation at break: Dumbbell-shaped specimens were prepared according to GB / T528 standard, and tensile tests were conducted at room temperature using a universal testing machine. Oil resistance performance (weight change rate, volume change rate): According to GB / T1690 standard, the sample was immersed in fuel C (50% toluene + 50% isooctane) medium at 40℃ for 48h. The weight and volume of the sample before and after immersion were weighed and measured, and the change rate was calculated.

[0069] Table 1. Properties of the rubber composite materials prepared in Examples 1-5 and Comparative Examples 1-7

[0070] The embodiments of this invention exhibit balanced and excellent overall performance. In terms of mechanical properties, the material has moderate hardness and high tensile strength, while maintaining good elongation at break, thus balancing strength and toughness. In terms of media resistance, the composite material exhibits low weight and volume changes after fuel immersion, demonstrating excellent oil resistance and oil-gas barrier properties.

[0071] After removing the fluoropolymer component from Comparative Example 1, the oil resistance of the composite material decreased significantly, and the weight and volume change rates after fuel immersion increased significantly. This indicates that the fluoropolymer plays a key role in improving the material's resistance to fuel oil and chemical media, and is an indispensable functional component in the composite system of this invention.

[0072] In Comparative Example 2, the removal of polyvinyl chloride (PVC) resulted in a decline in the material's oil resistance and barrier properties, while the volume change rate increased significantly. This indicates that the introduction of PVC effectively improved the rubber matrix's barrier ability against oil and gas media, making a significant contribution to improving the material's long-term impermeability.

[0073] Comparative Example 3 shows that when the acrylonitrile content is lower than the range of the present invention, the oil resistance of the composite material deteriorates significantly, and the volume expansion after fuel immersion increases significantly, proving that controlling the appropriate acrylonitrile content in hydrogenated nitrile rubber is the basis for ensuring the oil resistance of the material.

[0074] Comparative Example 4 shows that as the degree of polymerization of polyvinyl chloride decreases, the oil barrier effect of the material is slightly weakened, and the hardness also decreases slightly. This indicates that polyvinyl chloride with a low degree of polymerization has limited barrier effect on oil and gas and cannot fully play its function in the composite system.

[0075] Comparative Example 5 shows that when the degree of polymerization of polyvinyl chloride is too high, the hardness of the material increases and the elongation at break decreases accordingly. This reflects that the compatibility between polyvinyl chloride with a high degree of polymerization and the rubber matrix deteriorates, which will affect the flexibility of the material to a certain extent.

[0076] In Comparative Example 6, after replacing the hydroxyl-containing fluorinated acrylic resin with ordinary FEVE fluorocarbon resin, the tensile strength and elongation at break of the composite material decreased significantly. The fluoropolymer and hydrogenated nitrile phases separated, resulting in poor compatibility and a significant adverse impact on oil resistance. This indicates that the hydroxyl-containing fluorinated acrylic resin selected in this invention can effectively improve the interfacial bonding of multiple components and enhance the compatibility and overall performance of the composite system.

[0077] In Comparative Example 7, after replacing the segmented mixing process of the present invention with a one-time mixing process, the mechanical properties of the material decreased across the board, and the oil resistance also decreased. This indicates that the segmented premixing process is beneficial for the uniform dispersion of each functional component in the rubber matrix, which is crucial for ensuring the overall performance of the final product.

[0078] It should be understood that this application is not limited to the processes and structures described above and shown in the accompanying drawings, and various modifications and changes can be made without departing from its scope. The scope of this application is limited only by the appended claims.

Claims

1. A rubber composite material, characterized in that, Based on parts by weight, it includes the following components: 60-100 parts of hydrogenated nitrile butadiene rubber; 15-30 parts of peroxyfluororubber; 5-15 parts of polyvinyl chloride; 25-50 parts of reinforcing agent; Plasticizer 5-15 parts; 3-10 parts of fluorocarbon resin; Vulcanization system: 3.3-5.2 parts; Additives: 5-13.5 parts.

2. The rubber composite material according to claim 1, characterized in that, The hydrogenated nitrile rubber contains 40%-55% acrylonitrile and has a hydrogenation saturation of 95%-100%.

3. The rubber composite material according to claim 1, characterized in that, The degree of polymerization of the polyvinyl chloride is 1400-1600.

4. The rubber composite material according to claim 1, characterized in that, The reinforcing agent is selected from one or more of carbon black, silica, clay, calcium carbonate, silicate, graphene, and carbon nanotubes.

5. The rubber composite material according to claim 1, characterized in that, The plasticizer is selected from one or more of trimellitic ester plasticizers, phthalate plasticizers, adipate plasticizers, sebacic ester plasticizers, and phosphate plasticizers.

6. The rubber composite material according to claim 1, characterized in that, The fluorocarbon resin is a hydroxyl-containing fluorinated acrylic resin with a hydroxyl content of 10 wt%.

7. The rubber composite material according to claim 1, characterized in that, The vulcanization system includes di-tert-butylperoxide diisopropylbenzene and triallyl isocyanurate; the additives include one or more of zinc oxide, stearic acid, antioxidants, and processing aids.

8. The method for preparing the rubber composite material according to any one of claims 1-7, characterized in that, Includes the following steps: (1) First stage of mixing: Part of the hydrogenated nitrile rubber is plasticized, and then mixed with fluororubber and fluorocarbon resin to obtain the first compound. (2) Second stage of mixing: After the remaining hydrogenated nitrile rubber is plasticized, polyvinyl chloride is added and mixed to obtain the second compound; (3) Third stage mixing: Mix the first compound and the second compound until they are uniform; (4) Fourth stage of mixing: Add reinforcing agents, plasticizers and additives and mix. (5) Add to the vulcanization system, and after thinning and sheeting, vulcanize to obtain the rubber composite material.

9. The method for preparing the rubber composite material according to claim 8, characterized in that, In step (1), the mixing temperature is below 60℃, and the standing time after mixing is 20-30h; In step (2), the mixing temperature after adding polyvinyl chloride shall not exceed 120°C; In step (4), the mixing temperature after adding the reinforcing agent shall not exceed 135℃; The vulcanization treatment includes: First vulcanization: temperature 170-180℃, time 5-10min; Post-vulcanization: First, treat at 150℃ for 30 minutes, then raise the temperature to 170-180℃ and keep it at that temperature for 3-5 hours.

10. A rubber product, characterized in that, Including the rubber composite material according to any one of claims 1-7.

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