A rubber composite and a method for producing the same

Abstract

A rubber composite material, raw materials of the material include the following components in parts by weight: hydrogenated nitrile rubber 50-80 parts; nitrile rubber 20-50 parts; spherical filler 30-60 parts; lamellar filler 0.5-5 parts; modifier 1-5 parts; plasticizer 1-10 parts; damping molecule 5-30 parts; antioxidant 2-5 parts; zinc oxide 3-5 parts; stearic acid 1-3 parts; vulcanization accelerator 1-5 parts; sulfur 1-5 parts; peroxide vulcanizing agent 0.5-2 parts. The rubber composite material provided by the application ensures the matrix strength and oil resistance by selecting hydrogenated nitrile rubber with high hydrogenation degree and high acrylonitrile nitrile rubber; the load bearing strength of the rubber composite material is enhanced by introducing the combined system of spherical filler and lamellar filler in the blending system; the damping molecule with polymerization type or high molecular weight can form chemical crosslinking under the action of the vulcanization system between the damping molecule and the matrix, the damping effect of the damping molecule is played, meanwhile, the damping molecule has good anti-high-temperature insulating oil extraction effect, and the service life of the rubber composite material is prolonged.

Description

Technical Field

[0001] This invention belongs to the field of composite materials, specifically relating to a rubber composite material and its preparation method. Background Technology

[0002] A converter station is a site built in a high-voltage direct current (HVDC) transmission system to convert alternating current (AC) to direct current (DC) or vice versa, meeting the power system's requirements for safety, stability, and power quality. Converter stations are the most crucial link in a HVDC transmission system, enabling AC-DC power conversion. In ultra-high-voltage (UHV) converter stations, the core equipment is the silicon steel core. Due to the high voltage levels, the silicon steel core vibrates mechanically due to magnetostriction when the equipment is under load, and this vibration propagates through the transformer body, generating noise. Currently, environmental laws and regulations impose strict noise requirements on converter stations, explicitly stipulating low-noise requirements for the transmission and transformation equipment itself. Converter transformers are enormous; a typical ±800 kV converter transformer weighs approximately 500 tons. Currently, the industry lacks a field for the application of oil-resistant rubber in heavy-duty converter transformer equipment.

[0003] In recent years, with the urgent need for oil-resistant damping properties of rubber materials in power transmission and transformation equipment, numerous patents have been applied for in the field of oil-resistant damping rubber materials. Chinese patent CN202010312238.3 discloses an oil-resistant and high-temperature damping rubber, its preparation method, and its application. This damping rubber uses weakly polar chlorinated butyl rubber and strongly polar nitrile rubber as blend components, which not only broadens the rubber's operating temperature range but also greatly improves its internal friction damping, optimizes vibration isolation, and exhibits good damping and vibration isolation performance. When this rubber is used for noise reduction in transformers and reactors, it can effectively reduce the transmission of noise. Chinese patent CN202110417377.7 relates to a modified damping fluororubber for ultra-high voltage single-column parallel reactors. By adding silicon carbide to the fluororubber to improve its mechanical properties and using barium sulfate to reduce the compression deformation of the fluororubber and broaden its oil-resistant temperature range, a composite fluororubber material with a damping temperature range of -25 to 70℃ can be prepared, meeting the damping temperature range requirements under operating conditions. The above patents mainly target conventional equipment such as transformers and reactors, where conventional nitrile rubber, chlorinated butyl rubber, and fluororubber cannot meet the requirements of heavy-load operating conditions. Under heavy-load conditions, the rubber molecular chains are subjected to strong compression, restricting their movement and failing to provide a good damping effect.

[0004] There is a contradiction in the formulation design of damping oil-resistant rubber materials for heavy-load conditions. Under heavy load and pressure, the movement of the rubber chain is restricted, and the damping performance of the rubber matrix decreases. Therefore, in order to improve the noise reduction level of converter transformer equipment, it is urgent to develop high-load-bearing rubber materials with excellent damping and oil resistance to improve the service reliability of converter transformer equipment. Summary of the Invention

[0005] The purpose of this invention is to solve the contradiction between damping and oil resistance performance under heavy load conditions in converter transformer equipment in the prior art, and to provide a rubber composite material.

[0006] The objective of this invention is achieved through the following technical solution:

[0007] A rubber composite material, wherein the raw materials of the material comprise the following components by weight: 50-80 parts of hydrogenated nitrile rubber; 20-50 parts of nitrile rubber; 30-60 parts of spherical filler; 0.5-5 parts of lamellar filler; 1-5 parts of modifier; 1-10 parts of plasticizer; 5-30 parts of damping molecule; 2-5 parts of antioxidant; 3-5 parts of zinc oxide; 1-3 parts of stearic acid; 1-5 parts of vulcanization accelerator; 1-5 parts of sulfur; and 0.5-2 parts of peroxide vulcanizing agent.

[0008] Preferably, the hydrogenated nitrile rubber has a molecular weight of 20% to 50% acrylonitrile content, a degree of hydrogenation of 90% to 98%, and a Mooney viscosity ML(1+4min)@100℃ of 30 to 100.

[0009] Preferably, the molecular weight of the nitrile rubber is 20% to 50% propylene content, and the Mooney viscosity ML(1+4min)@100℃ is 30 to 100.

[0010] Preferably, the spherical filler is selected from at least one of carbon black and silicon dioxide.

[0011] Preferably, the sheet filler is selected from at least one of graphene, montmorillonite, hydrotalcite, and molybdenum disulfide.

[0012] Preferably, the sheet filler has a sheet thickness of 1–5 nm and a lateral dimension of 0.5–10 μm.

[0013] Preferably, the modifier comprises at least one of γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-(2,3-epoxypropoxy)propyltrimethoxysilane, vinyltris(2-methoxyethoxy)silane, 3-mercaptopropylmethyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, bis-(triethoxysilyl)propyltetrasulfide, bis(triethoxysilyl)-propyldisulfide, and γ-mercaptopropyltrimethoxysilane.

[0014] Preferably, the plasticizer includes at least one of diisooctyl sebacate, diisononyl adipate, C5 petroleum resin, C9 petroleum resin, liquid nitrile rubber, and liquid fluororubber.

[0015] Preferably, the damping molecule is selected from at least one of liquid polyisobutylene, hindered phenol AO80, n-butyl polyacrylate, and polyborosiloxane.

[0016] Preferably, the antioxidant is selected from at least one of antioxidant RD, antioxidant 4010NA, antioxidant 4020, antioxidant 264, antioxidant 2246, and antioxidant MB.

[0017] Preferably, the vulcanization accelerator is selected from at least one of vulcanization accelerator M, vulcanization accelerator DM, vulcanization accelerator CZ, vulcanization accelerator NOBS, vulcanization accelerator D, vulcanization accelerator TMTM, and vulcanization accelerator TMTD.

[0018] Preferably, the peroxide vulcanizing agent is selected from at least one of 1,3-di-tert-butylperoxyisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, and 3,5-trimethylcyclohexane.

[0019] The preparation method of any of the above-described rubber composite materials includes the following steps:

[0020] Spherical fillers and sheet fillers weighed in proportion were placed into an ethanol / water blend system, and a modifier was added to obtain wet solids in a vacuum homogenizing emulsifier.

[0021] The rubber composite material is obtained by mixing hydrogenated nitrile rubber and nitrile rubber, adding the wet solids and damping molecules after the first mixing, adding reagents after the second mixing, and adding additives after the third mixing.

[0022] Preferably, the first mixing time is 2 to 5 minutes and the temperature is 60 to 80°C.

[0023] Preferably, the second mixing time is 5 to 30 minutes, and the temperature at the end of the second mixing is 140 to 160°C.

[0024] Preferably, the third mixing time is 5-10 minutes and the temperature is 80-100℃.

[0025] Preferably, the fourth mixing time is 3 to 6 minutes.

[0026] Preferably, the reagents include: plasticizers, antioxidants, zinc oxide, and stearic acid.

[0027] Preferably, the additives include: vulcanization accelerators, sulfur, and peroxide vulcanizing agents.

[0028] Preferably, the modified dosage is 0.5% to 50% of the total mass of the filler.

[0029] Preferably, the emulsifier emulsifies at a temperature of 40–70°C and at a speed of 1000–5000 rpm.

[0030] Preferably, the solid content of the wet solids is 50% to 80%.

[0031] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0032] A rubber composite material, wherein the material comprises, by weight, the following components: 50-80 parts hydrogenated nitrile rubber; 20-50 parts nitrile rubber; 30-60 parts spherical filler; 0.5-5 parts lamellar filler; 1-5 parts modifier; 1-10 parts plasticizer; 5-30 parts damping molecule; 2-5 parts antioxidant; 3-5 parts zinc oxide; 1-3 parts stearic acid; 1-5 parts vulcanization accelerator; 1-5 parts sulfur; and 0.5-2 parts peroxide vulcanizing agent. This invention ensures matrix strength, oil resistance, and matrix compatibility by selecting hydrogenated nitrile butadiene rubber with a high degree of hydrogenation and adding high acrylonitrile nitrile butadiene rubber. The introduction of a combination of spherical and lamellar fillers into the blend system enhances the barrier properties of the rubber matrix and strengthens the load-bearing capacity of the rubber composite. The introduction of a dual vulcanization system of sulfur vulcanization and peroxide vulcanization improves the rubber material's resistance to high-temperature oil and its compression set, further enhancing its oil resistance and load-bearing capacity. The selection of polymeric or high-molecular-weight damping molecules allows for chemical cross-linking between the damping molecules and the matrix under the action of the vulcanization system, maximizing the damping effect of the damping molecules and providing good resistance to the extraction of high-temperature insulating oil, thus extending the service life of the rubber composite. Detailed Implementation

[0033] The technical solution provided by the present invention will be described in detail below with reference to specific embodiments:

[0034] A rubber composite material, the raw materials of which, by weight, comprise the following components: 50-80 parts hydrogenated nitrile rubber; 20-50 parts nitrile rubber; 30-60 parts spherical filler; 0.5-5 parts lamellar filler; 1-5 parts modifier; 1-10 parts plasticizer; 5-30 parts damping molecule; 2-5 parts antioxidant; 3-5 parts zinc oxide; 1-3 parts stearic acid; 1-5 parts vulcanization accelerator; 1-5 parts sulfur; and 0.5-2 parts peroxide vulcanizing agent.

[0035] Regarding the selection of the rubber matrix: A high degree of hydrogenation of hydrogenated nitrile butadiene rubber (NBR) combined with high acrylonitrile butadiene rubber (RABR) is chosen. This combination ensures both the strength of the matrix rubber material and excellent compatibility between the matrices. Regarding the reinforcing fillers: A blend of spherical and lamellar fillers is introduced into the blend system. After modification, a hybrid formulation of these two fillers is prepared, exhibiting a synergistic dispersion effect. The lamellar filler enhances the barrier properties of the rubber matrix and increases the elastic modulus, thereby strengthening the load-bearing capacity of the rubber composite. Regarding chemical crosslinking: A dual vulcanization system of sulfur vulcanization and peroxide vulcanization is introduced to improve the rubber material's resistance to high-temperature oil and its resistance to compression deformation, promoting higher oil resistance and load-bearing capacity. Regarding damping molecules: Polymerized or high-molecular-weight damping molecules are selected. Under the action of the vulcanization system between the damping molecules and the matrix, chemical crosslinking is formed, maximizing the damping effect of the damping molecules. Simultaneously, it provides good resistance to the extraction of high-temperature insulating oil, extending the service life of the rubber composite.

[0036] The molecular weight of hydrogenated nitrile rubber is 20% to 50% acrylonitrile content, 90% to 98% hydrogenation degree, and its Mooney viscosity ML(1+4min)@100℃ is 30 to 100.

[0037] The acrylonitrile content determines the oil resistance of rubber; the higher the content, the better the oil resistance. An acrylonitrile content in the range of 20% to 50% provides good oil resistance while maintaining the rubber's elasticity and processability. Hydrogenated nitrile butadiene rubber (HNBR) has excellent heat resistance; a hydrogenation degree of 90% to 98% further enhances its heat resistance, allowing it to maintain stable physical properties even at high temperatures. High-hydrogenated HNBR exhibits better aging resistance, resisting aging caused by oxygen, ozone, and ultraviolet radiation.

[0038] The molecular weight of nitrile rubber is 20% to 50% propylene content, and the Mooney viscosity ML(1+4min)@100℃ is 30 to 100.

[0039] Increasing the acrylonitrile content enhances the polarity of nitrile rubber molecules and increases intermolecular interactions, thereby improving the oil resistance of nitrile rubber. Furthermore, increasing the acrylonitrile content improves the aging properties of nitrile rubber, including its heat resistance, oxygen resistance, ozone resistance, and weather resistance. Additionally, increasing the acrylonitrile content can improve the tensile strength, hardness, modulus, and abrasion resistance of nitrile rubber.

[0040] The spherical filler is selected from at least one of carbon black and silicon dioxide.

[0041] Carbon black is easy to disperse, slightly acidic, and has good wettability, which helps to improve the mechanical properties and aging resistance of rubber.

[0042] The sheet filler is selected from at least one of graphene, montmorillonite, hydrotalcite, and molybdenum disulfide. The sheet thickness of the sheet filler is 1–5 nm, and the lateral dimension is 0.5–10 μm.

[0043] Graphene is a two-dimensional layered material with high electrical and thermal conductivity. In composite materials, graphene can improve the electrical and thermal conductivity, enhance mechanical properties, and improve chemical resistance. Montmorillonite is a layered silicate with good adsorption and barrier properties. In polymer matrices, montmorillonite can improve the mechanical and heat resistance of the material. Hydrotalcite is a type of layered bimetallic hydroxide with good anion exchange capacity and thermal stability. In composite materials, hydrotalcite can improve the adsorption performance of the material, effectively removing heavy metal ions and organic pollutants from wastewater.

[0044] The modifier includes at least one of γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-(2,3-epoxypropoxy)propyltrimethoxysilane, vinyltris(2-methoxyethoxy)silane, 3-mercaptopropylmethyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, bis-(triethoxysilyl)propyltetrasulfide, bis(triethoxysilyl)-propyldisulfide, and γ-mercaptopropyltrimethoxysilane.

[0045] γ-aminopropyltriethoxysilane possesses an active amine group and a hydrolyzable inorganic ethoxysilane bifunctional group, allowing it to react with synthetic resin molecules such as epoxy, phenolic, and polyester, as well as with hydroxyl groups on the surfaces of glass, minerals, and inorganic fillers to generate reactive silanols. γ-aminopropyltrimethoxysilane contains three methoxy groups, which can be used to improve the compatibility of fillers with polymers and enhance the processing and final properties of materials. γ-(2,3-epoxypropoxy)propyltrimethoxysilane contains an epoxy functional group, enabling it to react chemically with various polymers and improve the adhesive strength and water resistance of composite materials. Vinyltri(2-methoxyethoxy)silane has one vinyl functional group and three hydrolyzable alkoxy groups in its molecular structure. The dual reactivity of these compounds allows them to enhance the bonding, adhesion, and compatibility between inorganic materials and organic polymers through bidirectional chemical reactions, thereby improving the mechanical properties of resin-based composites or the adhesive strength and water resistance of resin coatings. 3-Mercaptopropylmethyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropyltriethoxysilane all contain thiol groups, which can form strong chemical bonds with metal surfaces, improving the metal adhesion and heat resistance of composites. Bis-(triethoxysilyl)propyltetrasulfide and bis(triethoxysilyl)-propyldisulfide contain thiol groups, which can form strong bonds with metals while exhibiting good compatibility with polymer matrices.

[0046] Plasticizers include at least one of diisooctyl sebacate, diisononyl adipate, C5 petroleum resin, C9 petroleum resin, liquid nitrile rubber, and liquid fluororubber.

[0047] Diisooctyl sebacate, as a cold-resistant plasticizer, features high plasticizing efficiency, low volatility, good cold resistance, heat resistance, light resistance, and good electrical insulation. Diisononyl adipate imparts good low-temperature flexibility and high-temperature resistance to products. C5 petroleum resin has high peel bond strength, good fast tack, stable adhesion, moderate melt viscosity, good heat resistance, good compatibility with polymer matrices, and low price. C9 petroleum resin has a cyclic structure, contains some double bonds, and has high cohesive force. Liquid nitrile rubber can improve the hardness and deformability of products. Liquid fluororubber can improve the chemical resistance and heat resistance of materials, making it suitable for demanding applications.

[0048] The damping molecule is selected from at least one of liquid polyisobutylene, hindered phenol AO80, n-butyl polyacrylate, and polyborosiloxane.

[0049] Liquid polyisobutylene has good heat resistance, aging resistance and ozone resistance, and can provide excellent vibration absorption characteristics; hindered phenol AO80 can improve the maximum loss factor of the material and effectively broaden the damping temperature range, thereby significantly improving the damping performance; polybutyl acrylate is a polymer with good adhesion properties; polyborosiloxane has high and low temperature resistance, weather resistance, electrical insulation and self-healing properties.

[0050] The antioxidant is selected from at least one of antioxidant RD, antioxidant 4010NA, antioxidant 4020, antioxidant 264, antioxidant 2246, and antioxidant MB.

[0051] Antioxidant RD has good compatibility with rubber compounds, is not easily sprayed out, has slight staining properties, and provides excellent protection against thermo-oxidative aging. Antioxidant 4010NA can prevent ozone, fatigue, and thermo-oxidative aging. Antioxidant 4020 has good antioxidant properties, as well as ozone resistance, flexural cracking resistance, and inhibition of harmful metals such as copper and manganese. Antioxidant 264 is a commonly used phenolic antioxidant with outstanding non-staining properties, and does not discolor, stain, or bloom. Antioxidant 2246 is non-polluting, non-toxic, and non-coloring to products, and provides excellent protection against heat, oxygen, and cracking aging. Antioxidant MB has good non-coloring properties and good resistance to thermal oxidation.

[0052] The vulcanization accelerator is selected from at least one of vulcanization accelerator M, vulcanization accelerator DM, vulcanization accelerator CZ, vulcanization accelerator NOBS, vulcanization accelerator D, vulcanization accelerator TMTM, and vulcanization accelerator TMTD.

[0053] Vulcanization accelerator M is an acidic accelerator with high vulcanization activity, imparting good aging and fatigue resistance to rubber; vulcanization accelerator DM has high vulcanization activity and can improve the physical and mechanical properties of vulcanized rubber; vulcanization accelerator CZ has excellent anti-scorch properties and processing safety, with a short vulcanization time; vulcanization accelerator NOBS is a slow-acting high-speed vulcanization accelerator with slow initial vulcanization but excellent after-effects. It is insoluble in water and gasoline, soluble in benzene, and readily soluble in chloroform; vulcanization accelerator D features rapid vulcanization and is suitable for effective and semi-effective vulcanization systems; vulcanization accelerator TMTM is a green and environmentally friendly rubber vulcanization accelerator, an odorless industrial raw material; vulcanization accelerator TMTD features rapid vulcanization.

[0054] The peroxide vulcanizing agent is selected from at least one of 1,3-di-tert-butylperoxyisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, and 3,5-trimethylcyclohexane.

[0055] 1,3-Di-tert-butylperoxyisopropylbenzene has high reactivity and can provide a rapid vulcanization reaction; dicumyl peroxide is a widely used peroxide vulcanizing agent with high crosslinking efficiency and excellent crosslinking performance; 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane is unstable at room temperature and contains inhibitors; 3,5-trimethylcyclohexane is stable at room temperature and pressure, but will spontaneously decompose under external conditions such as light, air, heat and metal ions.

[0056] The preparation method of the above-mentioned rubber composite material includes the following steps:

[0057] Spherical and lamellar fillers, weighed in proportion, are placed in an ethanol / water blend system. A modifier is added, and wet solids are obtained in a vacuum homogenizing emulsifier. Uniform dispersion of the fillers can improve the mechanical properties and functional characteristics of the composite material. After modification reaction, a modified dispersion is obtained to enhance the compatibility and interfacial bonding between the filler and the rubber matrix. The modified dispersion will have better dispersibility and reactivity. After separation to remove the reaction solvent, wet solids are obtained from the modified dispersion, which helps to reduce solvent residue and improve the environmental friendliness and safety of the composite material.

[0058] Hydrogenated nitrile butadiene rubber and nitrile butadiene rubber are compounded. After the first compounding, wet solids and damping molecules are added for the second compounding. After the second compounding, reagents are added for the third compounding. After the third compounding, additives are added for the fourth compounding to obtain the rubber composite material. The first compounding time is 2-5 min and the temperature is 60-80℃; the second compounding time is 5-30 min and the temperature is 140-160℃; the third compounding time is 5-10 min and the temperature is 80-100℃; and the fourth compounding time is 3-6 min.

[0059] The reagents include: plasticizers, antioxidants, zinc oxide, and stearic acid; they help improve the processing properties, aging resistance, and vulcanization properties of rubber.

[0060] Additives include: vulcanization accelerators, sulfur and peroxide vulcanizing agents.

[0061] The modifier dosage is 0.5% to 50% of the total filler mass. The main function of the modifier is to improve the compatibility and interfacial bonding between the filler and the rubber matrix. Within this range, the modifier can effectively cover the filler surface, forming a modified layer and enhancing the interaction between the filler and the matrix.

[0062] The emulsifier operates at a temperature of 40–70°C and an emulsification speed of 1000–5000 rpm, which ensures the uniformity and stability of the emulsion and prevents emulsion separation or demulsification.

[0063] The solid content of wet solids is 50% to 80%, which is beneficial to achieve uniform dispersion of fillers, reduce agglomeration, and thus improve the mechanical properties and stability of composite materials.

[0064] Example 1

[0065] A rubber composite material, the raw materials of which, by weight, comprise the following components: 50-80 parts hydrogenated nitrile rubber; 20-50 parts nitrile rubber; 30-60 parts spherical filler; 0.5-5 parts lamellar filler; 1-5 parts modifier; 1-10 parts plasticizer; 5-30 parts damping molecule; 2-5 parts antioxidant; 3-5 parts zinc oxide; 1-3 parts stearic acid; 1-5 parts vulcanization accelerator; 1-5 parts sulfur; and 0.5-2 parts peroxide vulcanizing agent.

[0066] The above-mentioned method for preparing a rubber composite material includes the following steps:

[0067] After dispersing 30 parts of spherical silica filler and 5 parts of montmorillonite sheet filler in an ethanol / water blend system, a dispersion was obtained.

[0068] Five parts of γ-aminopropyltriethoxysilane were added to the dispersion and mixed. After modification, the modified dispersion was obtained. The mixture was then placed in a vacuum homogenizing emulsifier for further modification. The amount of modifier was 14.3% of the total mass of the filler. The emulsification temperature was 50℃ and the emulsification speed was 5000 rpm. The modified dispersion was then centrifuged to remove the reaction solvent. After washing, a wet solid was obtained, and the solid content was controlled to be 80%.

[0069] After separation and removal of the reaction solvent, the modified dispersion yielded a wet solid.

[0070] 50 parts of hydrogenated nitrile rubber and 50 parts of nitrile rubber were mixed in an internal mixer at 80°C for 2 minutes to obtain the first intermediate colloid.

[0071] Add wet solids and 20 parts of n-butyl polyacrylate to the first intermediate colloid and mix for 30 minutes. When the temperature reaches 160°C, the second intermediate colloid is obtained.

[0072] After placing the second intermediate colloid into an internal mixer at 80°C, 10 parts of liquid nitrile rubber, 2 parts of antioxidant 1 antioxidant 4020 and 1 part of antioxidant 2 antioxidant 4010NA, 3 parts of zinc oxide and 1 part of stearic acid and other additives are added in sequence. After mixing for 5 minutes, a first-stage compound is obtained.

[0073] A section of compound rubber is placed in an internal mixer, and 1 part of vulcanization accelerator M, 1 part of vulcanization accelerator CZ, 0.1 part of vulcanization accelerator TMTD, 1.5 parts of sulfur and 0.5 parts of 1,3-di-tert-butylperoxyisopropylbenzene and other additives are added sequentially at 50°C. The mixture is then mixed for 3 minutes to obtain a rubber composite material.

[0074] Examples 2-5

[0075] Table 1 Summary of Raw Materials for the Embodiments

[0076]

[0077]

[0078] Table 2 Summary of Raw Material Proportions for Examples

[0079]

[0080] Table 3 Summary of preparation conditions for the examples

[0081]

[0082]

[0083] Comparative Example 1

[0084] To demonstrate the technical advantages of this invention, comparative examples 1 (without using the filler modification method in this patent) and 2 (without adding damping molecules) are compared with the examples, and performance tests and comparisons are performed on all samples.

[0085] 50 parts of hydrogenated nitrile rubber and 50 parts of nitrile rubber were mixed in an internal mixer at 80°C for 2 minutes. Then, 30 parts of spherical silica filler and 5 parts of montmorillonite sheet filler were added to obtain the first intermediate colloid.

[0086] Add 20 parts of n-butyl polyacrylate to the first intermediate colloid and mix for 30 minutes. When the temperature reaches 160℃, the second intermediate colloid is obtained.

[0087] After placing the second intermediate colloid into an internal mixer at 80°C, 10 parts of liquid nitrile rubber, 2 parts of antioxidant 1 antioxidant 4020 and 1 part of antioxidant 2 antioxidant 4010NA, 3 parts of zinc oxide and 1 part of stearic acid and other additives are added in sequence. After mixing for 5 minutes, a first-stage compound is obtained.

[0088] A section of compound rubber is placed in an internal mixer, and 1 part of vulcanization accelerator M, 1 part of vulcanization accelerator CZ, 0.1 part of vulcanization accelerator TMTD, 1.5 parts of sulfur and 0.5 parts of 1,3-di-tert-butylperoxyisopropylbenzene and other additives are added sequentially at 50°C. The mixture is then mixed for 3 minutes to obtain a rubber composite material.

[0089] Comparative Example 2

[0090] A dispersion was obtained by dispersing 60 parts of spherical carbon black filler and 0.5 parts of graphene sheet filler in an ethanol / water blend system.

[0091] Five parts of 3-mercaptopropylmethyldiethoxysilane were added to the dispersion and mixed. After modification, the modified dispersion was obtained. The mixture was then subjected to a modification reaction in a vacuum homogenizing emulsifier. The amount of modifier was 8.3% of the total mass of the filler. The emulsification temperature was 70℃ and the emulsification speed was 1000 rpm. The modified dispersion was then centrifuged to remove the reaction solvent. After washing, a wet solid was obtained, and the solid content was controlled to be 50%.

[0092] After separation and removal of the reaction solvent, the modified dispersion yielded a wet solid.

[0093] 80 parts of hydrogenated nitrile rubber and 20 parts of nitrile rubber were mixed in a 60°C internal mixer for 5 minutes to obtain the first intermediate colloid.

[0094] Add wet solids to the first intermediate colloid and mix for 5 minutes. When the temperature reaches 140°C, the second intermediate colloid is obtained.

[0095] After placing the second intermediate colloid into a 100°C internal mixer, add 5 parts of C5 petroleum resin, 2 parts of antioxidant RD, 1 part of antioxidant 264, 5 parts of zinc oxide, 3 parts of stearic acid and other additives in sequence. After mixing for 10 minutes, a first-stage compound is obtained.

[0096] A section of compound rubber is placed in an internal mixer, and 1 part of vulcanization accelerator NOBS, 2 parts of vulcanization accelerator D, 1 part of sulfur, and 2 parts of 1,3-di-tert-butylperoxyisopropylbenzene and other additives are added sequentially at 60°C. The mixture is then mixed for 4 minutes to obtain a rubber composite material.

[0097] Test case

[0098] The tensile strength, elongation at break, compression set, damping temperature threshold (tanδ>0.3), hardness change after immersion in oil at 125℃ for 168h, and volume change after immersion in oil at 125℃ for 168h were tested for the rubber composite materials obtained in Examples 1-5 and Comparative Examples 1-2 of this application, respectively. The results are shown in the table below.

[0099] In the embodiments of the present invention, if specific experimental steps or conditions are not specified, the conventional experimental steps or conditions described in the literature in the field can be followed. If the manufacturers of the reagents or instruments used are not specified, they are all conventional reagent products that can be obtained commercially.

[0100] Table 4 Comparison of material properties in the examples and comparative examples.

[0101]

[0102]

[0103] As shown in Table 4, comparing the results of Example 1 and Comparative Example 1 reveals that, without the filler modification method described in this invention, the filler modification method has a significant impact on the performance of the rubber material. The modified spherical / lamellae filler exhibits better dispersion performance in the rubber matrix. Using the modified filler can impart excellent mechanical properties, damping properties, and oil resistance to the rubber composite material. Comparing the results of Example 2 and Comparative Example 2, without the addition of the damping molecules proposed in this invention, the damping temperature threshold of the comparative example is very small, especially within the service temperature range, where the damping factor is low and cannot exert a damping effect in practical use. Simultaneously, the addition of damping molecules also benefits the material's strength and oil resistance. The interaction between the damping factor and the rubber matrix strengthens the intermolecular forces, enhances resistance to the swelling of the matrix by insulating oil molecules, and improves overall performance.

[0104] The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the embodiments described. Those skilled in the art can make various equivalent modifications or substitutions without departing from the spirit of the present invention, and these equivalent modifications or substitutions are all included within the scope defined by the claims of this application.

Claims

1. A rubber composite material, characterized in that, The raw materials of the material, by weight, include the following components: 50-80 parts hydrogenated nitrile rubber; 20-50 parts nitrile rubber; 30-60 parts spherical filler; 0.5-5 parts lamellar filler; 1-5 parts modifier; 1-10 parts plasticizer; 5-30 parts damping molecule; 2-5 parts antioxidant; 3-5 parts zinc oxide; 1-3 parts stearic acid; 1-5 parts vulcanization accelerator; 1-5 parts sulfur; and 0.5-2 parts peroxide vulcanizing agent.

2. The rubber composite material as described in claim 1, characterized in that, The hydrogenated nitrile butadiene rubber has a molecular weight of 20% to 50% acrylonitrile content, a degree of hydrogenation of 90% to 98%, and a Mooney viscosity ML(1+4min)@100℃ of 30 to 100.

3. The rubber composite material as described in claim 1, characterized in that, The nitrile rubber has a molecular weight of 20% to 50% propylene content and a Mooney viscosity of ML(1+4min)@100℃ of 30 to 100.

4. The rubber composite material as described in claim 1, characterized in that, The spherical filler is selected from at least one of carbon black and silicon dioxide.

5. A rubber composite material as described in claim 1, characterized in that, The sheet filler is selected from at least one of graphene, montmorillonite, hydrotalcite, and molybdenum disulfide.

6. A rubber composite material as described in claim 5, characterized in that, The sheet filler has a sheet thickness of 1–5 nm and a lateral dimension of 0.5–10 μm.

7. A rubber composite material as described in claim 1, characterized in that, The modifier includes at least one of γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-(2,3-epoxypropoxy)propyltrimethoxysilane, vinyltris(2-methoxyethoxy)silane, 3-mercaptopropylmethyldiethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3-mercaptopropyltriethoxysilane, bis-(triethoxysilyl)propyltetrasulfide, bis(triethoxysilyl)-propyldisulfide, and γ-mercaptopropyltrimethoxysilane.

8. A rubber composite material as described in claim 1, characterized in that, The plasticizer includes at least one of diisooctyl sebacate, diisononyl adipate, C5 petroleum resin, C9 petroleum resin, liquid nitrile rubber, and liquid fluororubber.

9. A rubber composite material as described in claim 1, characterized in that, The damping molecule is selected from at least one of liquid polyisobutylene, hindered phenol AO80, n-butyl polyacrylate, and polyborosiloxane.

10. A rubber composite material as described in claim 1, characterized in that, The antioxidant is selected from at least one of antioxidant RD, antioxidant 4010NA, antioxidant 4020, antioxidant 264, antioxidant 2246, and antioxidant MB.

11. A rubber composite material as described in claim 1, characterized in that, The vulcanization accelerator is selected from at least one of vulcanization accelerator M, vulcanization accelerator DM, vulcanization accelerator CZ, vulcanization accelerator NOBS, vulcanization accelerator D, vulcanization accelerator TMTM, and vulcanization accelerator TMTD.

12. The rubber composite material as described in claim 1, characterized in that, The peroxide vulcanizing agent is selected from at least one of 1,3-di-tert-butylperoxyisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, and 3,5-trimethylcyclohexane.

13. A method for preparing a rubber composite material according to any one of claims 1-12, characterized in that, Includes the following steps: Spherical fillers and sheet fillers weighed in proportion were placed into an ethanol / water blend system, and a modifier was added to obtain wet solids in a vacuum homogenizing emulsifier. The rubber composite material is obtained by mixing hydrogenated nitrile rubber and nitrile rubber, adding the wet solids and damping molecules after the first mixing, adding reagents after the second mixing, and adding additives after the third mixing.

14. The method for preparing a rubber composite material as described in claim 13, characterized in that, The first mixing time is 2-5 minutes, and the temperature is 60-80℃.

15. The method for preparing a rubber composite material as described in claim 13, characterized in that, The second mixing time is 5 to 30 minutes, and the temperature at the end of the second mixing is 140 to 160°C.

16. The method for preparing a rubber composite material as described in claim 13, characterized in that, The third mixing time is 5-10 minutes, and the temperature is 80-100℃.

17. The method for preparing a rubber composite material as described in claim 13, characterized in that, The fourth mixing time is 3 to 6 minutes.

18. The method for preparing a rubber composite material as described in claim 13, characterized in that, The reagents include: plasticizer, antioxidant, zinc oxide and stearic acid.

19. The method for preparing a rubber composite material as described in claim 13, characterized in that, The additives include: vulcanization accelerators, sulfur, and peroxide vulcanizing agents.

20. The method for preparing a rubber composite material as described in claim 13, characterized in that, The amount of modification is 0.5% to 50% of the total mass of the filler.

21. The method for preparing a rubber composite material as described in claim 13, characterized in that, The emulsifier emulsifies at a temperature of 40–70°C and at a speed of 1000–5000 rpm.

22. The method for preparing a rubber composite material as described in claim 13, characterized in that, The solid content of the wet solids is 50% to 80%.

Images