Sealing ring as well as preparation method and application thereof

Abstract

The invention provides a sealing ring suitable for an alpine region and a preparation method and application thereof. The sealing ring comprises the following components in parts by weight: 30-50 parts of nitrile rubber, 10-20 parts of fluorinated silicone rubber, 10-20 parts of fluoroether rubber, 10-15 parts of butadiene-isoprene rubber, 5-10 parts of a modifier, 10-30 parts of white carbon black, 40-80 parts of carbon black, 5-20 parts of light calcium carbonate, 5-15 parts of a coupling agent, 0.5-5 parts of an accelerant, 1.0-3.0 parts of a vulcanizing agent, 0.2-0.8 part of stearic acid, 3-8 parts of zinc oxide, 1-3 parts of an anti-aging agent and 5-30 parts of a plasticizer. The nitrile rubber, the fluorosilicone rubber, the fluoroether rubber and the butadiene-isoprene rubber form a bridging network through the modifier, and the interaction between the rubber matrix and the filler is utilized, so that the low-temperature performance, the tear resistance and the wear resistance of the cross-linked sealing ring product can be greatly improved, and the compression set of the sealing ring is reduced at the same time.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer products, and particularly relates to a sealing ring applicable to alpine regions, a preparation method thereof, and an application thereof. Background Art

[0002] A sealing ring is a general term for a class of products that maintain the sealing performance between device units under certain dynamic or static conditions. Sealing rings are usually rubber products or composite products of rubber and other materials, and the application fields of sealing rings are very wide, covering almost industries such as machinery, chemical industry, construction, and transportation. Rubber materials are polymer materials that exhibit a "rubber state" at room temperature. At low temperatures (glass transition temperature), they will change from a rubber state to a glass state, making their products hard and brittle, ultimately resulting in the sealing failure of rubber and its composite products, seriously affecting the application of sealing rings in alpine regions (-40°C - 60°C).

[0003] CN202211413078.7 provides a preparation method for an ultra-low cold-resistant ethylene-propylene-diene monomer rubber sealing ring. The preparation of the sealing ring mainly involves mixing sodium-based montmorillonite modified by an alkene with ethylene-propylene-diene monomer rubber and other additives, and vulcanizing with a platinum vulcanizing agent to obtain an ultra-low cold-resistant sealing ring.

[0004] CN202110652334.7 relates to a preparation method for a cold air valve sealing ring. It describes using nitrile rubber as the main rubber material, and composite fiber, phthalate, aluminum stearate, cold-resistant enhancer, polyethylene glycol, silane coupling agent, bentonite, and talc powder as additives, and preparing the cold air valve sealing ring through programmed temperature and time control. CN202110211299.5 gives a method for preparing a low-temperature-resistant sealing ring using cold-resistant acrylate rubber, reinforcing agent, glass fiber, paraffin oil, zinc oxide, sulfur, accelerator, and antioxidant as the main materials through mixing and vulcanization molding.

[0005] CN201611003159.4 invented a method for preparing a cold-resistant sealing ring based on graphene / polymer composite materials using graphene as the main filler, in combination with fluororubber, EO / PO block polyether, activator zinc oxide, plasticizer, antioxidant, reinforcing agent, plasticizer, accelerator, and sulfur.

[0006] CN201410129201.1 invented a preparation method of a cold-resistant rubber sealing ring. The preparation of the cold-resistant rubber includes ethylene propylene diene monomer (EPDM), cis-1,4-polybutadiene rubber, zinc stearate, diphenylsilanediol, dioctyl phthalate, microcrystalline wax, highly wear-resistant carbon black, magnesium oxide, modified silica powder, rutile titanium dioxide, alum powder, nano calcium carbonate, naphthenic rubber oil, sodium pyrophosphate, antioxidant, accelerator, sodium lignosulfonate, solid coumarone, turpentine, cold-resistant agent and sulfur. CN201310683812.6 relates to a preparation method of a cold-resistant O-ring containing nano calcium carbonate. The main materials include zinc stearate, stearic acid, nano calcium carbonate, attapulgite, vegetable oil, sulfur powder, chloroprene rubber, nitrile rubber, accelerator DM, aluminate coupling agent, aluminum stearate, trioctyl trimellitate, chitin, active calcium silicate, accelerator 808, modified filler. The modified filler is prepared from the following raw materials: silane coupling agent KH560, antioxidant 1046, antioxidant 1010, fatty acid, citric acid, magnesium hydroxide, diphenyl isooctyl phosphite, clay, jade powder, tremolite powder, fluorite slag.

[0007] Existing technologies similar to the present invention are all based on ethylene propylene diene monomer (EPDM), nitrile rubber, cold-resistant acrylate rubber, cis-1,4-polybutadiene rubber, chloroprene rubber, fluorine rubber and EO / PO block polyether as base rubbers, adding low-temperature modification aids such as modified sodium montmorillonite, cold-resistant reinforcing agent, cold-resistant agent, etc., and finally preparing sealing ring products through mixing. The existing technologies only stay at the level of traditional rubber processing and modification, and do not reconstruct and design the molecular structure of the raw rubber for preparing the sealing ring rubber. Therefore, the improvement of indexes such as the low-temperature performance, tear resistance, wear resistance and compression set of the sealing ring is also very limited. The present invention starts from the regulation of the molecular structure of the raw rubber of the sealing ring rubber, grafts maleic anhydride, acrylic anhydride, p-aminophenol, o-aminophenol, 2-hydroxyethylamine into the molecular chain of the raw rubber of the sealing ring rubber through photothermal reaction, and then uses calcium oxide, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate and 2,6-di-tert-butyl-p-cresol to terminate the reaction, and finally obtains the raw rubber of the sealing ring rubber with a designable molecular structure. The present invention solves the technical problem of the sealing failure of existing sealing ring products in alpine regions (low temperature -40°C - 60°C), and the technical route and preparation method have not been reported in the literature. Summary of the Invention

[0008] Aiming at the deficiencies of the existing technologies, the purpose of the present invention is to provide a sealing ring applicable to alpine regions, a preparation method and an application thereof. By grafting maleic anhydride, acrylic anhydride, p-aminophenol, o-aminophenol, 2-hydroxyethylamine into the molecular chain of the raw rubber of the sealing ring rubber and then cooperating with additives, the low-temperature performance, tear resistance, wear resistance and compression set of the sealing ring products are greatly improved compared with the existing technologies.

[0009] To achieve this purpose, the present invention adopts the following technical solutions:

[0010] In a first aspect, the present invention provides a sealing ring applicable to alpine regions, a preparation method thereof, and an application. The components of the raw rubber of the sealing ring include, by weight: 30-50 parts of nitrile rubber, 10-20 parts of fluorosilicone rubber, 10-20 parts of fluoroether rubber, 10-15 parts of ethylene acrylate rubber, 10-15 parts of butyl isoprene rubber, 5-10 parts of modifier, 10-30 parts of silica, 40-80 parts of carbon black, 5-20 parts of light calcium carbonate, 5-15 parts of coupling agent, 0.5-5 parts of accelerator, 1.0-3.0 parts of vulcanizing agent, 0.2-0.8 parts of stearic acid, 3-8 parts of zinc oxide, 1-3 parts of antioxidant, and 5-30 parts of plasticizer.

[0011] Preferably, the weight of the nitrile rubber is 30-50 parts, for example, it can be 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, and specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0012] Preferably, the weight of the fluorosilicone rubber is 10-20 parts, for example, it can be 10 parts, 15 parts, 20 parts, and specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0013] Preferably, the weight of the fluoroether rubber is 10-20 parts, for example, it can be 10 parts, 15 parts, 20 parts, and specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0014] Preferably, the weight of the ethylene acrylate rubber is 10-15 parts, for example, it can be 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, and specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0015] Preferably, the weight of the butyl isoprene rubber is 10-15 parts, for example, it can be 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, and specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0016] Preferably, the weight of the modifier is 5-10 parts, for example, it can be 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, and specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0017] Preferably, the weight parts of the silica are 10 - 30 parts. For example, they can be 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0018] Preferably, the weight parts of the carbon black are 40 - 80 parts. For example, they can be 40 parts, 50 parts, 60 parts, 70 parts, 80 parts, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0019] Preferably, the weight parts of the light calcium carbonate are 5 - 20 parts. For example, they can be 5 parts, 10 parts, 15 parts, 20 parts, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0020] Preferably, the weight parts of the coupling agent are 5 - 15 parts. For example, they can be 5 parts, 10 parts, 15 parts, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0021] Preferably, the weight parts of the accelerator are 0.5 - 5 parts. For example, they can be 0.5 parts, 1.0 parts, 1.5 parts, 2.0 parts, 2.5 parts, 3.0 parts, 3.5 parts, 4.0 parts, 4.5 parts, 5.0 parts, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0022] Preferably, the weight parts of the vulcanizing agent are 1.0 - 3.0 parts. For example, they can be 1.0 parts, 2.0 parts, 3.0 parts, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0023] Preferably, the weight parts of the stearic acid are 0.2 - 0.8 parts. For example, they can be 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0024] Preferably, the weight parts of the zinc oxide are 3 - 8 parts. For example, they can be 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0025] Preferably, the antioxidant is 1-3 parts by weight, for example, it can be 1 part, 2 parts, 3 parts, and specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the range.

[0026] Preferably, the plasticizer is 5-30 parts by weight, for example, it can be 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, and specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the range.

[0027] As a preferred technical solution of the present invention, the nitrile rubber used in the present invention is a binary copolymer of butadiene and acrylonitrile.

[0028] Preferably, the nitrile rubber is any one or a combination of at least two of NBR1704 (acrylonitrile content 17%-20%), NBR2707 (acrylonitrile content 27%-30%), N41 (acrylonitrile content 29%), NBR3308 (acrylonitrile content 33%), and N21 (acrylonitrile content 39%-41%);

[0029] Preferably, the acrylonitrile content in the nitrile rubber is 17%-41%, for example, it can be 17%, 20%, 27%, 29%, 30%, 33%, 39%, 41%, and specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the range.

[0030] As a preferred technical solution of the present invention, the fluorosilicone rubber used in the present invention is γ-trifluoropropylmethyl polysiloxane, which is a copolymer of methyl siloxane, vinyl siloxane, and trifluoropropyl siloxane.

[0031] As a preferred technical solution of the present invention, the fluoroether rubber used in the present invention is a binary copolymer of perfluoroalkyl vinyl ether and tetrafluoroethylene.

[0032] As a preferred technical solution of the present invention, the ethylene acrylate rubber used in the present invention is a binary copolymer of ethylene and methyl acrylate.

[0033] As a preferred technical solution of the present invention, the butyl isoprene rubber used in the present invention is a binary copolymer of butadiene and isoprene by solution polymerization.

[0034] The modifier used in the present invention includes any one or a combination of at least two of maleic anhydride, acrylic anhydride, p-aminophenol, o-aminophenol, 2-hydroxyethylamine, calcium oxide, n-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, and 2,6-di-tert-butyl-p-cresol.

[0035] The silica used in the present invention includes any one or a combination of at least two of fumed A200, fumed A380, fumed N20, precipitated Z175, precipitated DL-600, and precipitated DL-808;

[0036] The carbon black used in the present invention includes any one or a combination of at least two of N330, N550, N660, N774, and N220;

[0037] As a preferred technical solution of the present invention, the light calcium carbonate used in the present invention is precipitated calcium carbonate, which is a general filler prepared by mixing limestone and anthracite, followed by high-temperature calcination, carbonization, dehydration, drying, water separation, and pulverization.

[0038] As a preferred technical solution of the present invention, the stearic acid used in the present invention is a product of Xilong Science Co., Ltd., grade: analytical pure (AR);

[0039] As a preferred technical solution of the present invention, the zinc oxide used in the present invention is a product of Tianjin Yongda Chemical Reagent Co., Ltd., grade: analytical pure (AR);

[0040] The coupling agent used in the present invention includes any one or a combination of at least two of vinyltris(β-methoxyethoxy)silane, vinyltrichlorosilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, methylmercaptopropyldimethoxysilane, or bis[(3-triethoxysilyl)propyl]tetrasulfide;

[0041] The accelerator used in the present invention includes any one or a combination of at least two of hexamethylenetetramine (accelerator H), diphenylguanidine (accelerator D), tetramethylthiuram disulfide (accelerator TMTD), 2-mercaptobenzothiazole (accelerator M), zinc dimethyldithiocarbamate (accelerator ZDMC), zinc butylxanthate (accelerator ZBX), N-cyclohexyl-2-benzothiazolesulfenamide (accelerator CZ), triallyl isocyanurate (accelerator TAIC), N,N'-m-phenylene bismaleimide (HVA2), trimethylolpropane trimethacrylate (TMPTMA);

[0042] The vulcanizing agent used in the present invention includes any one or a combination of at least two of sulfur, hexamethylenediamine carbamate (Diak No.1), 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane (bis 2-5), or di-tert-butyl peroxide (DTBP);

[0043] The anti-aging agents used in the present invention include any one or a combination of at least two of 2,2'-methylenebis(4-methyl-6-tert-butylphenol) (anti-aging agent 2246), N-phenyl-β-naphthylamine (anti-aging agent D), 2,2,4-trimethyl-1,2-dihydroquinoline polymer (anti-aging agent RD), 2-mercaptobenzothiazole (anti-aging agent MB), nickel dibutyldithiocarbamate (anti-aging agent NBC), and N-isopropyl-N'-phenyl-p-phenylenediamine (anti-aging agent 4010NA);

[0044] The plasticizers used in the present invention include any one or a combination of at least two of dibutyl phthalate (DBP), dioctyl phthalate (DOP), and dioctyl sebacate (DOS);

[0045] In a second aspect, the present invention provides a method for preparing a sealing ring as described in the first aspect, and the preparation method includes:

[0046] Mixing nitrile rubber, fluorosilicone rubber, fluoroether rubber, ethylene acrylate rubber, butyl isoprene rubber, and a modifier to obtain a modified sealing ring raw rubber; mixing the modified sealing ring raw rubber with silica, carbon black, light calcium carbonate, coupling agent, accelerator, vulcanizing agent, stearic acid, zinc oxide, anti-aging agent, and plasticizer to obtain the sealing ring compound; vulcanizing and molding the sealing ring compound in a flat vulcanizer to obtain the sealing ring.

[0047] Preferably, the preparation method specifically includes:

[0048] (1) Mixing nitrile rubber, fluorosilicone rubber, fluoroether rubber, ethylene acrylate rubber, and butyl isoprene rubber in an open mill to obtain a mixed raw rubber;

[0049] (2) Mixing the mixed raw rubber obtained in step (1) with a modifier in an open mill to obtain a modified sealing ring raw rubber;

[0050] (3) Preparing the modified sealing ring raw rubber obtained in step (2) into a 0.5-1.5 mm thin sheet in an open mill, and placing it in a sunny environment for 4-6 hours to obtain a modified sealing ring raw rubber sheet;

[0051] (4) Mixing the modified sealing ring raw rubber sheet obtained in step (3) with silica, carbon black, light calcium carbonate, coupling agent, accelerator, vulcanizing agent, stearic acid, zinc oxide, anti-aging agent, and plasticizer in a closed mill to obtain the sealing ring compound;

[0052] (5) Vulcanize and mold the kneaded rubber obtained in step (4). Take 250 - 400 g (preferably 260 - 390 g, more preferably 270 - 350 g) and put it into a sealing ring mold with a wire diameter of 29.0 ± 0.5 mm and an inner diameter of 124.0 ± 0.5 mm. The vulcanization and molding temperature is 150 - 180 °C (preferably 155 - 175 °C, more preferably 165 - 175 °C), the pressure is 5 - 15 MPa (preferably 6 - 14 MPa, more preferably 8 - 12 MPa), and the time is 20 - 40 min to obtain the said sealing ring.

[0053] Preferably, the mixing in steps (1) and (2) is carried out on an open mill.

[0054] Preferably, the mixing temperature of the open mill in steps (1) and (2) is 60 - 90 °C. For example, it can be 60 °C, 70 °C, 80 °C, 90 °C, and specific point values between the above point values. Due to space limitations and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the said range.

[0055] Preferably, the roll gap of the open mill in steps (1) and (2) is 1 - 2 mm. For example, it can be 1.0 mm, 1.5 mm, 2.0 mm, and specific point values between the above point values. Due to space limitations and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the said range.

[0056] Preferably, the mixing time of the open mill in steps (1) and (2) is 10 - 20 minutes. For example, it can be 10 minutes, 15 minutes, 20 minutes, and specific point values between the above point values. Due to space limitations and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the said range.

[0057] Preferably, the mixing in step (3) is carried out on an open mill.

[0058] Preferably, the mixing temperature of the open mill in step (3) is 35 - 50 °C. For example, it can be 35 °C, 40 °C, 45 °C, 50 °C, and specific point values between the above point values. Due to space limitations and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the said range.

[0059] Preferably, the roll gap of the open mill in step (3) is 0.3 - 1.2 mm. For example, it can be 0.3 mm, 0.5 mm, 0.8 mm, 1.0 mm, 1.2 mm, and specific point values between the above point values. Due to space limitations and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the said range.

[0060] Preferably, the mixing time on the open mill in step (3) is 5 - 10 minutes. For example, it can be 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, 10 minutes, and specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the said range.

[0061] Preferably, the mixing in step (4) is carried out in a closed rubber mixer;

[0062] Preferably, the temperature of mixing in the closed rubber mixer in step (4) is 70 - 90 °C. For example, it can be 70 °C, 75 °C, 80 °C, 85 °C, 90 °C, and specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the said range.

[0063] Preferably, the rotational speed of the closed rubber mixer in step (4) is 40 - 60 revolutions per minute. For example, it can be 40 revolutions per minute, 45 revolutions per minute, 50 revolutions per minute, 55 revolutions per minute, 60 revolutions per minute, and specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the said range.

[0064] Preferably, the mixing time in the internal mixer in step (4) is 2 - 5 minutes. For example, it can be 2 minutes, 3 minutes, 4 minutes, 5 minutes, and specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the said range.

[0065] Preferably, the mixing in step (5) is carried out in a vulcanizing molding machine;

[0066] Preferably, the temperature of vulcanizing molding in step (5) is 150 - 180 °C, more preferably 165 - 175 °C. For example, it can be 150 °C, 155 °C, 160 °C, 165 °C, 170 °C, 175 °C, 180 °C, and specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the said range.

[0067] Preferably, the pressure of vulcanizing molding in step (5) is 5 - 15 MPa, more preferably 8 - 12 MPa. For example, it can be 5 MPa, 6 MPa, 7 MPa, 8 MPa, 9 MPa, 10 MPa, 12 MPa, 15 MPa, and specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the said range.

[0068] Preferably, the vulcanization molding time in step (5) is 20 - 40 min, for example, it can be 20 min, 25 min, 30 min, 35 min, 40 min, and specific point values between the above point values. Due to space limitations and for the sake of simplicity, the specific point values included in the scope of the present invention are not exhaustively listed herein.

[0069] In the present invention, first, nitrile rubber, fluorosilicone rubber, fluoroether rubber, ethylene acrylate rubber, butyl isoprene rubber, and a modifier are mixed to obtain a modified sealing ring raw rubber. Then, the modified sealing ring raw rubber is mixed with silica, carbon black, light calcium carbonate, coupling agent, accelerator, vulcanizing agent, stearic acid, zinc oxide, antioxidant, and plasticizer to obtain the sealing ring mixing rubber. Finally, the sealing ring mixing rubber is vulcanized and molded in a flat vulcanizer to obtain the sealing ring. Compared with the prior art, the materials of the present invention can significantly improve the low-temperature performance, tear strength, and wear resistance of the sealing ring, and at the same time reduce the compression set of the sealing ring.

[0070] The open mill used in the present invention is a general rubber mixing equipment, and the model and condition parameters are not limited. As long as it can prepare various filler additives of raw rubber into modified raw rubber.

[0071] The internal mixer used in the present invention is a general rubber mixing equipment, with the temperature control range of 30 - 200 °C and the rotational speed control range of 20 - 120 revolutions per minute. The specific model is not limited. As long as the equipment is safe to use and can mix rubber, fillers, and additives evenly.

[0072] The vulcanization molding machine used in the present invention, also known as a flat vulcanizer, is a general equipment for vulcanizing and molding mixing rubber, with the temperature control range of 20 - 200 °C and the pressure control range of 1 - 20 MPa. The specific model is not limited. As long as the equipment is safe to use and can form the product.

[0073] In the third aspect, the present invention provides a preparation of the sealing ring as described in the first aspect and its application in alpine regions (-40 °C - 60 °C).

[0074] In the present invention, first, a bridging network is formed between nitrile rubber, fluorosilicone rubber, fluoroether rubber, and butyl isoprene rubber through a modifier, and then, by utilizing the interaction between the rubber matrix and the filler, the low-temperature performance, tear resistance, and wear resistance of the cross-linked sealing ring product can be significantly improved, and at the same time, the compression set of the sealing ring can be reduced.

[0075] Compared with the prior art, the present invention has the following beneficial effects:

[0076] A sealing ring applicable to alpine regions, a preparation method and an application provided by the present invention graft maleic anhydride, acrylic anhydride, p-aminophenol, o-aminophenol, and 2-hydroxyethylamine onto the molecular chain of the raw rubber of the sealing ring, increasing the polarity of the raw rubber of the rubber, and making its compatibility with fillers and additives better. Then, the modified raw rubber is combined with additives, so that the low-temperature performance, tear resistance, wear resistance, and compression set of the sealing ring product are greatly improved. The low-temperature performance is significantly improved compared with the prior art, and the compression cold resistance coefficient at -50 °C can reach more than 0.6. The tear resistance is twice that of the prior art product, reaching 50 kN / m. The wear resistance is greatly improved compared with the prior art product, and the Akron abrasion is reduced to 2 / 3 of the prior art product, less than 0.3 cm 3 / 3415 revolutions. The compression set is reduced, reaching 1 / 2 of the prior art product, less than 16%. Specific embodiments

[0077] The technical solutions of the present invention will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments are only for helping to understand the present invention and should not be regarded as specific limitations on the present invention.

[0078] The experimental materials used in the examples and comparative examples of the present invention are as follows:

[0079] (1) Nitrile rubber is a binary copolymer of butadiene and acrylonitrile, a product of PetroChina Lanzhou Petrochemical Company. Grades NBR1704 (combined acrylonitrile content 17%-20%), NBR2707 (combined acrylonitrile content 27%-30%), N41 (combined acrylonitrile content 29%), NBR3308 (combined acrylonitrile content 33%), N21 (combined acrylonitrile content 39%-41%);

[0080] (2) Fluorosilicone rubber is γ-trifluoropropylmethyl polysiloxane, a copolymer of methyl siloxane, vinyl siloxane, and trifluoropropyl siloxane, a product of DuPont Company, USA, grade FVMQ;

[0081] (3) Fluoroether rubber is a binary copolymer of perfluoroalkyl vinyl ether and tetrafluoroethylene, a product of Solvay Group (Solvay), grade Tecnoflon FFKM PFR 94;

[0082] (4) Ethylene acrylate rubber is a binary copolymer of ethylene and methyl acrylate, a product of DuPont Company, USA, grade GLS;

[0083] (5) Butyl isoprene rubber is a binary copolymer of butadiene and isoprene prepared by solution polymerization, prepared by the method of Example 4 according to Patent ZL202210989443.2 by the Dalian Institute of Chemical Physics, Chinese Academy of Sciences, grade BIR-DICP;

[0084] (6) Maleic anhydride, acrylic anhydride, p-aminophenol, o-aminophenol, 2-hydroxyethylamine, calcium oxide, n-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, and 2,6-di-tert-butyl-p-cresol are products of Dalian Bono Reagent Co., Ltd.

[0085] (7) Fumed silica A200 and A380 are products of Evonik (China) Investment Co., Ltd. Fumed N2 is a product of Wacker Chemie (China) Co., Ltd. Precipitated Z175 is a product of Rhodia-Solvay Investment Co., Ltd. Precipitated DL-600 and precipitated DL-808 are products of Jinan Delan Chemical Co., Ltd.

[0086] (8) Carbon black N330, N550, N660, N774, and N220 are products of Cabot Corporation

[0087] (9) Light calcium carbonate is precipitated calcium carbonate, which is a general filler prepared by mixing limestone and anthracite, followed by high-temperature calcination, carbonization, dehydration, drying, water separation, and pulverization. It is a product of Shanghai Liangjiang Titanium Dioxide Chemical Products Co., Ltd., grade: PT (reagent grade);

[0088] (10) Stearic acid is a product of Xilong Scientific Co., Ltd., grade: analytical pure (AR);

[0089] (11) Zinc oxide is a product of Tianjin Yongda Chemical Reagent Co., Ltd., grade: analytical pure (AR);

[0090] (12) Coupling agents vinyltris(β-methoxyethoxy)silane, vinyltrichlorosilane are from Nanjing Xiangqian Chemical Co., Ltd., brand A172; γ-aminopropyltriethoxysilane is a product of Wuhan Lvjing Fenghua Biotechnology Co., Ltd., brand KH550; vinyltriethoxysilane is a product of Shandong Yuanjin New Materials Co., Ltd., brand A151; methylmercaptopropyldimethoxysilane or bis[(3-triethoxysilyl)propyl]tetrasulfide is a product of Shandong Yuanjin New Materials Co., Ltd., brand Si69;

[0091] (13) Accelerators hexamethylenetetramine (accelerator H), diphenylguanidine (accelerator D), tetramethylthiuram disulfide (accelerator TMTD), 2-mercaptobenzothiazole (accelerator M), zinc dimethyldithiocarbamate (accelerator ZDMC), zinc butylxanthate (accelerator ZBX), N-cyclohexyl-2-benzothiazolesulfenamide (accelerator CZ), triallyl isocyanurate (accelerator TAIC), N,N'-m-phenylene bismaleimide (HVA2), trimethylolpropane trimethacrylate (TMPTMA) are products of Dalian Ruisheng Rubber and Plastic Materials Co., Ltd.;

[0092] (14) Sulfur, hexamethylenediamine carbamate (Diak No.1), 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane (Di-25), or di-tert-butyl peroxide (DTBP) are products of Dalian Ruisheng Rubber and Plastic Materials Co., Ltd.;

[0093] (15) Antioxidants include 2,2'-methylenebis(4-methyl-6-tert-butylphenol) (Antioxidant 2246), N-phenyl-β-naphthylamine (Antioxidant D), 2,2,4-trimethyl-1,2-dihydroquinoline polymer (Antioxidant RD), 2-mercaptobenzothiazole (Antioxidant MB), nickel dibutyldithiocarbamate (Antioxidant NBC), and N-isopropyl-N'-phenyl-p-phenylenediamine (Antioxidant 4010NA), which are products of Dalian Ruisheng Rubber and Plastic Materials Co., Ltd.;

[0094] (16) Plasticizers dibutyl phthalate (DBP), dioctyl phthalate (DOP), and dioctyl sebacate (DOS) are products of Dalian Ruisheng Rubber and Plastic Materials Co., Ltd.

[0095] Example 1

[0096] This example provides a sealing ring applicable to alpine regions, its preparation method and application. The components include, by weight: 30 parts of nitrile rubber NBR1704 (combined acrylonitrile content 17%-20%), 10 parts of fluorosilicone rubber, 10 parts of fluoroether rubber, 10 parts of ethylene acrylate rubber, 10 parts of butylisoprene rubber, 4 parts of maleic anhydride, 1 part of n-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 10 parts of fumed silica A200, 20 parts of carbon black N330, 20 parts of carbon black N550, 5 parts of light calcium carbonate, 5 parts of coupling agent A172, 0.3 part of accelerator H, 0.2 part of accelerator TAIC, 0.5 part of vulcanizing agent sulfur, 0.2 part of vulcanizing agent Diak No.1, 0.3 part of vulcanizing agent Di-25, 0.2 part of stearic acid, 3 parts of zinc oxide, 1 part of antioxidant 2246, and 5 parts of plasticizer DBP.

[0097] This example also provides a sealing ring applicable to alpine regions, its preparation method and application. The preparation method includes:

[0098] (1) Mix nitrile rubber, fluorosilicone rubber, fluoroether rubber, ethylene acrylate rubber, and butylisoprene rubber in an open mill. The mixing temperature of the open mill is 60°C, the roll gap is 1 mm, and the mixing time is 10 minutes to obtain a mixed raw rubber;

[0099] (2) Mix the mixed raw rubber obtained in step (1) and the modifier in an open mill. The mixing temperature of the open mill is 60°C, the roll gap is 1 mm, and the mixing time is 10 minutes to obtain a modified sealing ring raw rubber;

[0100] (3) Prepare the modified sealing ring raw rubber obtained in step (2) into a 0.5-mm-thick sheet on an open mill. The mixing temperature is 35°C, the roll gap is 0.3 mm, the mixing time is 5 minutes, and it is placed in a sunny environment for 4 hours to obtain the modified sealing ring raw rubber sheet;

[0101] (4) Mix the modified sealing ring raw rubber sheet obtained in step (3) with silica, carbon black, light calcium carbonate, coupling agent, accelerator, vulcanizing agent, stearic acid, zinc oxide, antioxidant, and plasticizer in a closed mill. The mixing temperature of the closed mill is 70°C, the rotation speed is 40 revolutions per minute, and the mixing time is 2 minutes to obtain the sealing ring mixing rubber;

[0102] (5) Vulcanize and mold the sealing ring mixing rubber obtained in step (4) in a flat vulcanizer. Take 250 g of the sealing ring mixing rubber and put it into a sealing ring mold with a wire diameter of 29.0 ± 0.5 mm and an inner diameter of 124.0 ± 0.5 mm. The vulcanization temperature is 150°C, the vulcanization pressure is 5 MPa, and the vulcanization time is 40 min to obtain the sealing ring. Conduct modulus tests at -40°C, -50°C, and -60°C on the sealing ring, Akron abrasion test (cm 3 / 3415 revolutions), test piece tear strength test, and compression set (25%, 150°C × 72 hours). The test results are shown in Table 1 and Table 2.

[0103] Example 2:

[0104] This example provides a sealing ring applicable to alpine regions, its preparation method and application. Its components in parts by weight include: 50 parts of nitrile rubber N21 (combined acrylonitrile content 39% - 41%), 20 parts of fluorosilicone rubber, 20 parts of fluoroether rubber, 15 parts of ethylene acrylate rubber, 15 parts of butyl isoprene rubber, 8 parts of p-aminophenol, 2 parts of calcium oxide, 30 parts of precipitated silica DL-808, 50 parts of carbon black N330, 10 parts of carbon black N660, 10 parts of carbon black N774, 10 parts of carbon black N220, 20 parts of light calcium carbonate, 5 parts of coupling agent Si69, 3 parts of accelerator CZ, 2 parts of accelerator TMPTMA, 1 part of vulcanizing agent sulfur, 1 part of vulcanizing agent Diak No.1, 1 part of vulcanizing agent DTBP, 0.8 part of stearic acid, 8 parts of zinc oxide, 1 part of antioxidant RD, 1 part of antioxidant MB, 1 part of antioxidant 4010NA, and 30 parts of plasticizer DOS.

[0105] This example also provides a sealing ring applicable to alpine regions, its preparation method and application. The preparation method includes:

[0106] (1) Mix acrylonitrile-butadiene rubber, fluorosilicone rubber, fluoroether rubber, ethylene acrylate rubber, and butyl isoprene rubber in an open mill. The mixing temperature of the open mill is 90 °C, the roll gap is 2 mm, and the mixing time is 20 minutes to obtain a mixed raw rubber.

[0107] (2) Mix the mixed raw rubber obtained in step (1) and a modifier in an open mill. The mixing temperature of the open mill is 90 °C, the roll gap is 2 mm, and the mixing time is 20 minutes to obtain a modified sealing ring raw rubber.

[0108] (3) Prepare the modified sealing ring raw rubber obtained in step (2) into a 1.5-mm-thick sheet in an open mill. The mixing temperature is 50 °C, the roll gap is 1.2 mm, and the mixing time is 10 minutes. Place it in a sunny environment for 6 hours to obtain a modified sealing ring raw rubber sheet.

[0109] (4) Mix the modified sealing ring raw rubber sheet obtained in step (3) with silica, carbon black, light calcium carbonate, coupling agent, accelerator, vulcanizing agent, stearic acid, zinc oxide, antioxidant, and plasticizer in a closed mill. The mixing temperature of the closed mill is 90 °C, the rotation speed is 60 revolutions per minute, and the mixing time is 5 minutes to obtain the sealing ring mixed rubber.

[0110] (5) Vulcanize and mold the sealing ring mixed rubber obtained in step (4) in a flat vulcanizer. Take 400 g of the sealing ring mixed rubber and put it into a sealing ring mold with a wire diameter of 29.0 ± 0.5 mm and an inner diameter of 124.0 ± 0.5 mm. The vulcanization temperature is 180 °C, the vulcanization pressure is 15 MPa, and the vulcanization time is 20 min to obtain the sealing ring. Conduct modulus tests at -40 °C, -50 °C, and -60 °C on the sealing ring, Akron abrasion test (cm 3 / 3415 revolutions), test piece tear strength test, and compression set (25%, 150 °C × 72 hours). The test results are shown in Table 1 and Table 2.

[0111] Example 3:

[0112] This embodiment provides a sealing ring applicable to alpine regions, its preparation method and application. The components include, by weight: 20 parts of nitrile rubber NBR2707 (combined acrylonitrile content 27%-30%), 10 parts of nitrile rubber N41 (combined acrylonitrile content 29%), 10 parts of nitrile rubber NBR3308 (combined acrylonitrile content 33%), 15 parts of fluorosilicone rubber, 15 parts of fluoroether rubber, 12 parts of ethylene acrylate rubber, 12 parts of butyl isoprene rubber, 3 parts of acrylic anhydride, 2 parts of o-aminophenol, 1 part of 2-hydroxyethylamine, 1 part of calcium oxide, 1 part of 2,6-di-tert-butyl-p-cresol, 5 parts of fumed silica A380, 5 parts of fumed silica N20, 5 parts of precipitated silica Z175, 5 parts of precipitated silica DL-600, 30 parts of carbon black N550, 10 parts of carbon black N660, 10 parts of carbon black N774, 10 parts of carbon black N220, 10 parts of light calcium carbonate, 3 parts of coupling agent KH550, 2 parts of coupling agent A151, 5 parts of coupling agent Si69, 0.5 part of accelerator D, 0.5 part of accelerator TMTD, 0.5 part of accelerator M, 1 part of accelerator HVA2, 0.5 part of accelerator TMPTMA, 0.5 part of sulfur curing agent, 0.5 part of curing agent Diak No.1, 1 part of curing agent bis-2-5, 0.5 part of stearic acid, 5 parts of zinc oxide, 0.5 part of antioxidant D, 0.5 part of antioxidant RD, 0.5 part of antioxidant MB, 0.5 part of antioxidant NBC, 10 parts of plasticizer DOP and 10 parts of plasticizer DOS.

[0113] This embodiment also provides a sealing ring applicable to alpine regions, its preparation method and application. The preparation method includes:

[0114] (1) Mix nitrile rubber, fluorosilicone rubber, fluoroether rubber, ethylene acrylate rubber and butyl isoprene rubber in an open mill. The mixing temperature of the open mill is 80°C, the roll gap is 1.5 mm, and the mixing time is 15 minutes to obtain a mixed raw rubber.

[0115] (2) Mix the mixed raw rubber obtained in step (1) and the modifier in an open mill. The mixing temperature of the open mill is 80°C, the roll gap is 1.5 mm, and the mixing time is 15 minutes to obtain a modified sealing ring raw rubber.

[0116] (3) Prepare the modified sealing ring raw rubber obtained in step (2) into a 1.0-mm-thick sheet in an open mill. The mixing temperature is 40°C, the roll gap is 1.0 mm, and the mixing time is 8 minutes. Place it in a sunny environment for 5 hours to obtain a modified sealing ring raw rubber sheet.

[0117] (4) Mix the modified sealing ring raw rubber film obtained in step (3) with silica, carbon black, light calcium carbonate, coupling agent, accelerator, vulcanizing agent, stearic acid, zinc oxide, antioxidant and plasticizer in a closed mixer. The mixing temperature of the closed mixer is 80 °C, the rotation speed is 50 revolutions per minute, and the mixing time is 3 minutes to obtain the mixed rubber of the sealing ring;

[0118] (5) Vulcanize and mold the mixed rubber of the sealing ring obtained in step (4) in a flat vulcanizer. Take 320 grams of the mixed rubber of the sealing ring and put it into a sealing ring mold with a wire diameter of 29.0 ± 0.5 mm and an inner diameter of 124.0 ± 0.5 mm. The vulcanization temperature is 170 °C, the vulcanization pressure is 10 MPa, and the vulcanization time is 30 min to obtain the sealing ring. Conduct modulus tests at -40 °C, -50 °C, and -60 °C on the sealing ring, Akron abrasion test (cm 3 / 3415 revolutions), test piece tear strength test and compression set (25%, 150 °C × 72 hours). The test results are shown in Table 1 and Table 2.

[0119] Example 4:

[0120] This example provides a sealing ring applicable to alpine regions, its preparation method and application. The components are as follows in parts by weight: 20 parts of nitrile rubber NBR1704 (combined acrylonitrile content 17% - 20%), 20 parts of nitrile rubber N21 (combined acrylonitrile content 39% - 41%), 10 parts of fluorosilicone rubber, 20 parts of fluoroether rubber, 15 parts of ethylene acrylate rubber, 15 parts of butyl isoprene rubber, 5 parts of fumed silica A200, 5 parts of fumed silica A380, 5 parts of fumed silica N20, 5 parts of precipitated silica Z175, 5 parts of precipitated silica DL-600, 10 parts of carbon black N330, 10 parts of carbon black N550, 10 parts of carbon black N660, 10 parts of carbon black N774, 10 parts of carbon black N220, 12 parts of light calcium carbonate, 2 parts of coupling agent A172, 5 parts of coupling agent KH550, 2 parts of coupling agent A151, 5 parts of coupling agent Si69, 0.1 part of accelerator H, 0.1 part of accelerator D, 0.5 part of accelerator TMTD, 0.1 part of accelerator M, 0.1 part of accelerator ZDMC, 0.1 part of accelerator ZBX, 0.5 part of accelerator TAIC, 0.5 part of accelerator HVA2, 0.5 part of accelerator TMPTMA, 1 part of vulcanizing agent sulfur, 0.5 part of vulcanizing agent Diak No.1, 0.5 part of vulcanizing agent bis-2,5, 0.5 part of vulcanizing agent DTBP, 0.5 part of stearic acid, 5 parts of zinc oxide, 0.5 part of antioxidant 2246, 0.5 part of antioxidant D, 0.5 part of antioxidant RD, 0.5 part of antioxidant MB, 0.5 part of antioxidant NBC, 0.5 part of antioxidant 4010NA, 5 parts of plasticizer DBP, 10 parts of plasticizer DOP and 10 parts of plasticizer DOS.

[0121] This embodiment also provides a sealing ring applicable to alpine regions, a preparation method thereof, and an application. The preparation method includes:

[0122] (1) Mix acrylonitrile-butadiene rubber, fluorosilicone rubber, fluoroether rubber, ethylene acrylate rubber, and butyl isoprene rubber in an open mill. The mixing temperature of the open mill is 70°C, the roll gap is 1 mm, and the mixing time is 15 minutes to obtain a mixed raw rubber.

[0123] (2) Mix the mixed raw rubber obtained in step (1) and a modifier in an open mill. The mixing temperature of the open mill is 75°C, the roll gap is 2 mm, and the mixing time is 15 minutes to obtain a modified sealing ring raw rubber.

[0124] (3) Prepare the modified sealing ring raw rubber obtained in step (2) into a 1.2-mm-thick sheet in an open mill. The mixing temperature is 45°C, the roll gap is 0.8 mm, and the mixing time is 7 minutes. Place it in a sunny environment for 5 hours to obtain a modified sealing ring raw rubber sheet.

[0125] (4) Mix the modified sealing ring raw rubber sheet obtained in step (3) with white carbon black, carbon black, light calcium carbonate, coupling agent, accelerator, vulcanizing agent, stearic acid, zinc oxide, antioxidant, and plasticizer in a closed mill. The mixing temperature of the closed mill is 85°C, the rotation speed is 55 revolutions per minute, and the mixing time is 3 minutes to obtain the sealing ring mixing rubber.

[0126] (5) Vulcanize and mold the sealing ring mixing rubber obtained in step (4) in a flat vulcanizer. Take 300 g of the sealing ring mixing rubber and put it into a sealing ring mold with a wire diameter of 29.0 ± 0.5 mm and an inner diameter of 124.0 ± 0.5 mm. The vulcanization and molding temperature is 160°C, the vulcanization and molding pressure is 12 MPa, and the vulcanization and molding time is 25 min to obtain the sealing ring. Conduct modulus tests at -40°C, -50°C, and -60°C on the sealing ring, Akron abrasion test (cm 3 / 3415 revolutions), test piece tear strength test, and compression set (25%, 150°C × 72 hours). The test results are shown in Table 1 and Table 2.

[0127] Example 5:

[0128] This embodiment provides a sealing ring applicable to alpine regions, a preparation method thereof, and an application. The components thereof in parts by weight include: 10 parts of nitrile rubber NBR1704 (with a combined acrylonitrile content of 17%-20%), 20 parts of nitrile rubber NBR2707 (with a combined acrylonitrile content of 27%-30%), 10 parts of nitrile rubber N41 (with a combined acrylonitrile content of 29%), 12 parts of fluorosilicone rubber, 12 parts of fluoroether rubber, 12 parts of ethylene acrylate rubber, 12 parts of butyl isoprene rubber, 5 parts of maleic anhydride, 1 part of acrylic anhydride, 1 part of 2,6-di-tert-butyl-p-cresol, 10 parts of fumed silica A200, 10 parts of fumed silica A380, 5 parts of fumed silica N20, 20 parts of carbon black N330, 20 parts of carbon black N774, 20 parts of carbon black N220, 12 parts of light calcium carbonate, 5 parts of coupling agent A172, 10 parts of coupling agent KH550, 1 part of accelerator TMTD, 0.5 part of accelerator CZ, 0.5 part of accelerator TAIC, 0.5 part of accelerator TMPTMA, 0.5 part of vulcanizing agent sulfur, 0.5 part of vulcanizing agent Diak No.1, 1 part of vulcanizing agent DTBP, 0.5 part of stearic acid, 5 parts of zinc oxide, 1 part of antioxidant RD, 1 part of antioxidant 4010NA, and 25 parts of plasticizer DOP.

[0129] This embodiment also provides a sealing ring applicable to alpine regions, a preparation method thereof, and an application. The preparation method includes:

[0130] (1) Mix nitrile rubber, fluorosilicone rubber, fluoroether rubber, ethylene acrylate rubber, and butyl isoprene rubber in an open mill. The mixing temperature of the open mill is 65°C, the roll gap is 1.2 mm, and the mixing time is 13 minutes to obtain a mixed raw rubber.

[0131] (2) Mix the mixed raw rubber obtained in step (1) and a modifier in an open mill. The mixing temperature of the open mill is 85°C, the roll gap is 1.8 mm, and the mixing time is 18 minutes to obtain a modified sealing ring raw rubber.

[0132] (3) Prepare the modified sealing ring raw rubber obtained in step (2) into a 1.2-mm-thick sheet in an open mill. The mixing temperature is 40°C, the roll gap is 1.1 mm, and the mixing time is 6 minutes. Place it in a sunny environment for 4-6 hours to obtain a modified sealing ring raw rubber sheet.

[0133] (4) Mix the modified sealing ring raw rubber sheet obtained in step (3) with fumed silica, carbon black, light calcium carbonate, coupling agent, accelerator, vulcanizing agent, stearic acid, zinc oxide, antioxidant, and plasticizer in a closed mill. The mixing temperature of the closed mill is 75°C, the rotation speed is 55 revolutions per minute, and the mixing time is 2.5 minutes to obtain the sealing ring mixed rubber.

[0134] (5) Vulcanize and form the seal ring compound obtained in step (4) in a flat vulcanizer. Take 290 g of the seal ring compound and put it into a seal ring mold with a wire diameter of 29.0 ± 0.5 mm and an inner diameter of 124.0 ± 0.5 mm. The vulcanization temperature is 165 °C, the vulcanization pressure is 8 MPa, and the vulcanization time is 35 min to obtain the said seal ring. Conduct modulus tests on the seal ring at -40 °C, -50 °C, and -60 °C, Akron abrasion test (cm 3 / 3415 revolutions), test piece tear strength test and compression set (25%, 150 °C × 72 h). The test results are shown in Table 1 and Table 2.

[0135] Example 6:

[0136] This example provides a seal ring applicable to alpine regions, its preparation method and application. Its components are as follows by weight: 20 parts of nitrile rubber N41 (combined acrylonitrile content 29%), 10 parts of nitrile rubber NBR3308 (combined acrylonitrile content 33%), 10 parts of nitrile rubber N21 (combined acrylonitrile content 39% - 41%), 18 parts of fluorosilicone rubber, 18 parts of fluoroether rubber, 18 parts of ethylene acrylate rubber, 18 parts of butyl isoprene rubber, 2 parts of p-aminophenol, 2 parts of o-aminophenol, 2 parts of 2-hydroxyethylamine, 2 parts of calcium oxide, 10 parts of precipitated silica Z175, 10 parts of precipitated silica DL-600, 5 parts of precipitated silica DL-808, 20 parts of carbon black N550, 30 parts of carbon black N660, 20 parts of carbon black N774, 12 parts of light calcium carbonate, 10 parts of coupling agent Si69, 1 part of accelerator M, 0.5 part of accelerator ZDMC, 0.5 part of accelerator ZBX, 0.5 part of accelerator CZ, 1 part of accelerator HVA2, 1 part of accelerator TMPTMA, 0.5 part of vulcanizing agent sulfur, 0.5 part of vulcanizing agent Diak No.1, 1.5 parts of vulcanizing agent DTBP, 0.5 part of stearic acid, 5 parts of zinc oxide, 1 part of antioxidant 2246, 1 part of antioxidant MB, and 20 parts of plasticizer DOS.

[0137] This example also provides a seal ring applicable to alpine regions, its preparation method and application. The said preparation method includes:

[0138] (1) Mix nitrile rubber, fluorosilicone rubber, fluoroether rubber, ethylene acrylate rubber, and butyl isoprene rubber in an open mill. The mixing temperature of the open mill is 85 °C, the roll gap is 1.6 mm, and the mixing time is 15 minutes to obtain a mixed raw rubber;

[0139] (2) Mix the mixed raw rubber obtained in step (1) and the modifier in an open mill. The mixing temperature of the open mill is 85 °C, the roll gap is 1.3 mm, and the mixing time is 15 minutes to obtain a modified seal ring raw rubber;

[0140] (3) Prepare the modified sealing ring raw rubber obtained in step (2) into a 0.5 - 1.5 mm thin sheet in an open mill, with a mixing temperature of 40 °C, a roll gap of 0.7 mm, a mixing time of 8 minutes, and place it in a sunny environment for 6 hours to obtain the modified sealing ring raw rubber sheet;

[0141] (4) Mix the modified sealing ring raw rubber sheet obtained in step (3) with silica, carbon black, light calcium carbonate, coupling agent, accelerator, vulcanizing agent, stearic acid, zinc oxide, antioxidant, and plasticizer in a closed mill. The mixing temperature of the closed mill is 85 °C, the rotation speed is 45 revolutions per minute, and the mixing time is 3 minutes to obtain the sealing ring compound;

[0142] (5) Vulcanize and mold the sealing ring compound obtained in step (4) in a flat vulcanizer. Take 280 g of the sealing ring compound and put it into a sealing ring mold with a wire diameter of 29.0 ± 0.5 mm and an inner diameter of 124.0 ± 0.5 mm. The vulcanization and molding temperature is 155 °C, the vulcanization and molding pressure is 12 MPa, and the vulcanization and molding time is 35 min to obtain the sealing ring. Conduct modulus tests at - 40 °C, - 50 °C, and - 60 °C on the sealing ring, Akron abrasion test (cm 3 / 3415 revolutions), test piece tear strength test, and compression set (25%, 150 °C × 72 h). The test results are shown in Table 1 and Table 2.

[0143] Comparative Example 1:

[0144] This comparative example provides a method for preparing the raw rubber of a sealing ring. Its components in parts by weight include: 20 parts of nitrile rubber NBR1704 (with a combined acrylonitrile content of 17%-20%), 20 parts of nitrile rubber N21 (with a combined acrylonitrile content of 39%-41%), 10 parts of fluorosilicone rubber, 20 parts of fluoroether rubber, 15 parts of ethylene acrylate rubber, 15 parts of butyl isoprene rubber, 1 part of maleic anhydride, 1 part of acrylic anhydride, 1 part of p-aminophenol, 1 part of o-aminophenol, 1 part of 2-hydroxyethylamine, 1 part of calcium oxide, 1 part of n-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 1 part of 2,6-di-tert-butyl-p-cresol, 5 parts of fumed silica A200, 5 parts of fumed silica A380, 5 parts of fumed silica N20, 5 parts of precipitated silica Z175, 5 parts of precipitated silica DL-600, 10 parts of carbon black N330, 10 parts of carbon black N550, 10 parts of carbon black N660, 10 parts of carbon black N774, 10 parts of carbon black N220, 12 parts of light calcium carbonate, 2 parts of coupling agent A172, 5 parts of coupling agent KH550, 2 parts of coupling agent A151; 5 parts of coupling agent Si69, 0.1 part of accelerator H, 0.1 part of accelerator D, 0.5 part of accelerator TMTD, 0.1 part of accelerator M, 0.1 part of accelerator ZDMC, 0.1 part of accelerator ZBX, 0.5 part of accelerator TAIC, 0.5 part of accelerator HVA2, 0.5 part of accelerator TMPTMA, 1.0 part of vulcanizing agent sulfur, 0.5 part of vulcanizing agent Diak No.1, 0.5 part of vulcanizing agent bis-2-5, 0.5 part of vulcanizing agent DTBP, 0.5 part of stearic acid, 5 parts of zinc oxide, 0.5 part of antioxidant 2246, 0.5 part of antioxidant D, 0.5 part of antioxidant RD, 0.5 part of antioxidant MB, 0.5 part of antioxidant NBC, 0.5 part of antioxidant 4010NA, 5 parts of plasticizer DBP, 10 parts of plasticizer DOP and 10 parts of plasticizer DOS.

[0145] This comparative example also provides a method for preparing the raw rubber of a sealing ring. The preparation method includes:

[0146] (1) Mix nitrile rubber, fluorosilicone rubber, fluoroether rubber, ethylene acrylate rubber, butyl isoprene rubber and a modifier in an open mill. The mixing temperature of the open mill is 75°C, the roll gap is 2 mm, and the mixing time is 15 minutes to obtain a modified raw rubber of the sealing ring;

[0147] (2) Prepare the modified raw rubber of the sealing ring obtained in step (1) into a 1.2-mm-thick sheet in an open mill. The mixing temperature is 45°C, the roll gap is 0.8 mm, and the mixing time is 7 minutes. Place it in a sunny environment for 5 hours to obtain a modified raw rubber film of the sealing ring;

[0148] (3) Mix the modified sealing ring raw rubber film obtained in step (2) with silica, carbon black, light calcium carbonate, coupling agent, accelerator, vulcanizing agent, stearic acid, zinc oxide, antioxidant and plasticizer in a closed mixer. The mixing temperature of the closed mixer is 85 °C, the rotation speed is 55 revolutions per minute, and the mixing time is 3 minutes to obtain the sealing ring mixed rubber;

[0149] (4) Vulcanize and mold the sealing ring mixed rubber obtained in step (3) in a flat vulcanizer. Take 300 grams of the sealing ring mixed rubber and put it into a sealing ring mold with a wire diameter of 29.0 ± 0.5 mm and an inner diameter of 124.0 ± 0.5 mm. The vulcanization and molding temperature is 160 °C, the vulcanization and molding pressure is 12 MPa, and the vulcanization and molding time is 25 min to obtain the sealing ring. Conduct modulus tests at -40 °C, -50 °C, and -60 °C on the sealing ring, Akron abrasion test (cm 3 / 3415 revolutions), test piece tear strength test and compression set (25%, 150 °C × 72 hours). The test results are shown in Table 1 and Table 2.

[0150] Comparative Example 2:

[0151] This comparative example provides a method for preparing the raw rubber of the sealing ring. Its components by weight include: 20 parts of nitrile rubber NBR1704 (combined acrylonitrile content 17%-20%), 20 parts of nitrile rubber N21 (combined acrylonitrile content 39%-41%), 10 parts of fluorosilicone rubber, 20 parts of fluoroether rubber, 15 parts of ethylene acrylate rubber, 15 parts of butyl isoprene rubber, 1 part of maleic anhydride, 1 part of acrylic anhydride, 1 part of p-aminophenol, 1 part of o-aminophenol, 1 part of 2-hydroxyethylamine, 1 part of calcium oxide, 1 part of n-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1 part of 2,6-di-tert-butyl-p-cresol, 5 parts of fumed silica A200, 5 parts of fumed silica A380, 5 parts of fumed silica N20, 5 parts of precipitated silica Z175, 5 parts of precipitated silica DL-600, 10 parts of carbon black N330, 10 parts of carbon black N550, 10 parts of carbon black N660, 10 parts of carbon black N774, 10 parts of carbon black N220, 12 parts of light calcium carbonate, 2 parts of coupling agent A172, 5 parts of coupling agent KH550, 2 parts of coupling agent A151; 5 parts of coupling agent Si69, 0.1 part of accelerator H, 0.1 part of accelerator D, 0.5 part of accelerator TMTD, 0.1 part of accelerator M, 0.1 part of accelerator ZDMC, 0.1 part of accelerator ZBX, 0.5 part of accelerator TAIC, 0.5 part of accelerator HVA2, 0.5 part of accelerator TMPTMA, 1 part of sulfur curing agent, 0.5 part of Diak No.1 curing agent, 0.5 part of bis(2,5-dimethyl-2,5-di(tert-butylperoxy)hexane) curing agent, 0.5 part of DTBP curing agent, 0.5 part of stearic acid, 5 parts of zinc oxide, 0.5 part of antioxidant 2246, 0.5 part of antioxidant D, 0.5 part of antioxidant RD, 0.5 part of antioxidant MB, 0.5 part of antioxidant NBC, 0.5 part of antioxidant 4010NA, 5 parts of plasticizer DBP, 10 parts of plasticizer DOP and 10 parts of plasticizer DOS.

[0152] This comparative example also provides a method for preparing the raw rubber of the sealing ring. The preparation method includes:

[0153] (1) Mix nitrile rubber, fluorosilicone rubber, fluoroether rubber, ethylene acrylate rubber, butyl isoprene rubber and modifier in an open mill. The mixing temperature of the open mill is 75°C, the roll gap is 2 mm, and the mixing time is 15 minutes to obtain the modified raw rubber of the sealing ring;

[0154] (2) Mix the modified raw rubber of the sealing ring obtained in step (1) with fumed silica, carbon black, light calcium carbonate, coupling agent, accelerator, curing agent, stearic acid, zinc oxide, antioxidant and plasticizer in a closed mill. The mixing temperature of the closed mill is 85°C, the rotation speed is 55 revolutions per minute, and the mixing time is 3 minutes to obtain the mixed rubber of the sealing ring;

[0155] (3) Vulcanize and mold the sealing ring compound obtained in step (2). Take 300 g of the sealing ring compound and put it into a sealing ring mold with a wire diameter of 29.0 ± 0.5 mm and an inner diameter of 124.0 ± 0.5 mm. The vulcanization temperature is 160 °C, the vulcanization pressure is 12 MPa, and the vulcanization time is 25 min to obtain the sealing ring. Conduct modulus tests on the sealing ring at -40 °C, -50 °C, and -60 °C, Akron abrasion test (cm 3 / 3415 revolutions), test piece tear strength test, and compression set (25%, 150 °C × 72 h). The test results are shown in Table 1 and Table 2.

[0156] Comparative Example 3:

[0157] This comparative example provides a method for preparing the raw rubber of the sealing ring. Its components are as follows in parts by weight: 20 parts of nitrile rubber NBR1704 (combined acrylonitrile content 17% - 20%), 20 parts of nitrile rubber N21 (combined acrylonitrile content 39% - 41%), 10 parts of fluorosilicone rubber, 20 parts of fluoroether rubber, 15 parts of ethylene acrylate rubber, 15 parts of butyl isoprene rubber, 1 part of maleic anhydride, 1 part of acrylic anhydride, 1 part of p-aminophenol, 1 part of o-aminophenol, 1 part of 2-hydroxyethylamine, 1 part of calcium oxide, 1 part of n-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1 part of 2,6-di-tert-butyl-p-cresol, 5 parts of fumed silica A200, 5 parts of fumed silica A380, 5 parts of fumed silica N20, 5 parts of precipitated silica Z175, 5 parts of precipitated silica DL-600, 10 parts of carbon black N330, 10 parts of carbon black N550, 10 parts of carbon black N660, 10 parts of carbon black N774, 10 parts of carbon black N220, 12 parts of light calcium carbonate, 2 parts of coupling agent A172, 5 parts of coupling agent KH550, 2 parts of coupling agent A151; 5 parts of coupling agent Si69, 0.1 part of accelerator H, 0.1 part of accelerator D, 0.5 part of accelerator TMTD, 0.1 part of accelerator M, 0.1 part of accelerator ZDMC, 0.1 part of accelerator ZBX, 0.5 part of accelerator TAIC, 0.5 part of accelerator HVA2, 0.5 part of accelerator TMPTMA, 1.0 part of sulfur curing agent, 0.5 part of curing agent Diak No.1, 0.5 part of curing agent bis-2-5, 0.5 part of curing agent DTBP, 0.5 part of stearic acid, 5 parts of zinc oxide, 0.5 part of antioxidant 2246, 0.5 part of antioxidant D, 0.5 part of antioxidant RD, 0.5 part of antioxidant MB, 0.5 part of antioxidant NBC, 0.5 part of antioxidant 4010NA, 5 parts of plasticizer DBP, 10 parts of plasticizer DOP, and 10 parts of plasticizer DOS.

[0158] This comparative example also provides a method for preparing the raw rubber of the sealing ring. The preparation method includes:

[0159] (1) Mix nitrile rubber, fluorosilicone rubber, fluoroether rubber, ethylene acrylate rubber, butyl isoprene rubber, modifier with silica, carbon black, light calcium carbonate, coupling agent, accelerator, vulcanizing agent, stearic acid, zinc oxide, antioxidant and plasticizer in a closed mixer. The mixing temperature of the closed mixer is 85 °C, the rotation speed is 55 revolutions per minute, and the mixing time is 3 minutes to obtain the seal ring compound.

[0160] (2) Vulcanize and mold the seal ring compound obtained in step (1) in a flat vulcanizer. Take 300 grams of the seal ring compound and put it into a seal ring mold with a wire diameter of 29.0 ± 0.5 mm and an inner diameter of 124.0 ± 0.5 mm. The vulcanization and molding temperature is 160 °C, the vulcanization and molding pressure is 12 MPa, and the vulcanization and molding time is 25 min to obtain the seal ring. Conduct modulus tests at -40 °C, -50 °C, and -60 °C on the seal ring, Akron abrasion test (cm 3 / 3415 revolutions), test piece tear strength test and compression set (25%, 150 °C × 72 hours). The test results are shown in Table 1 and Table 2.

[0161] Comparative Example 4:

[0162] This comparative example provides a method for preparing the raw rubber of the seal ring. Its components are in parts by weight and include: 20 parts of nitrile rubber NBR1704 (combined acrylonitrile content 17% - 20%), 20 parts of nitrile rubber N21 (combined acrylonitrile content 39% - 41%), 10 parts of fluorosilicone rubber, 20 parts of fluoroether rubber, 15 parts of ethylene acrylate rubber, 15 parts of butyl isoprene rubber, 5 parts of fumed silica A200, 5 parts of fumed silica A380, 5 parts of fumed silica N20, 5 parts of precipitated silica Z175, 5 parts of precipitated silica DL-600, 10 parts of carbon black N330, 10 parts of carbon black N550, 10 parts of carbon black N660, 10 parts of carbon black N774, 10 parts of carbon black N220, 12 parts of light calcium carbonate, 2 parts of coupling agent A172, 5 parts of coupling agent KH550, 2 parts of coupling agent A151; 5 parts of coupling agent Si69, 0.1 part of accelerator H, 0.1 part of accelerator D, 0.5 part of accelerator TMTD, 0.1 part of accelerator M, 0.1 part of accelerator ZDMC, 0.1 part of accelerator ZBX, 0.5 part of accelerator TAIC, 0.5 part of accelerator HVA2, 0.5 part of accelerator TMPTMA, 1 part of vulcanizing agent sulfur, 0.5 part of vulcanizing agent Diak No.1, 0.5 part of vulcanizing agent bis-2-5, 0.5 part of vulcanizing agent DTBP, 0.5 part of stearic acid, 5 parts of zinc oxide, 0.5 part of antioxidant 2246, 0.5 part of antioxidant D, 0.5 part of antioxidant RD, 0.5 part of antioxidant MB, 0.5 part of antioxidant NBC, 0.5 part of antioxidant 4010NA, 5 parts of plasticizer DBP, 10 parts of plasticizer DOP and 10 parts of plasticizer DOS.

[0163] This comparative example also provides a preparation method for the raw rubber of the sealing ring, and the preparation method includes:

[0164] (1) Mix nitrile rubber, fluorosilicone rubber, fluoroether rubber, ethylene acrylate rubber, butyl isoprene rubber with silica, carbon black, light calcium carbonate, coupling agent, accelerator, vulcanizing agent, stearic acid, zinc oxide, antioxidant and plasticizer in a closed mixer. The mixing temperature of the closed mixer is 85°C, the rotation speed is 55 revolutions per minute, and the mixing time is 3 minutes to obtain the mixed rubber for the sealing ring;

[0165] (2) Vulcanize and mold the mixed rubber for the sealing ring obtained in step (1) in a flat vulcanizer. Take 300 grams of the mixed rubber for the sealing ring and put it into a sealing ring mold with a wire diameter of 29.0 ± 0.5 mm and an inner diameter of 124.0 ± 0.5 mm. The vulcanization and molding temperature is 160°C, the vulcanization and molding pressure is 12 MPa, and the vulcanization and molding time is 25 min to obtain the sealing ring. Conduct modulus tests at -40°C, -50°C, and -60°C on the sealing ring, Akron abrasion test (cm 3 / 3415 revolutions), test piece tear strength test and compression set (25%, 150°C × 72 hours). The test results are shown in Table 1 and Table 2.

[0166] Comparative Example 5:

[0167] This comparative example provides a preparation method for the raw rubber of the sealing ring. Its components are as follows in parts by weight: 30 parts of nitrile rubber NBR1704 (combined acrylonitrile content 17% - 20%), 10 parts of fluorosilicone rubber, 10 parts of fluoroether rubber, 10 parts of ethylene acrylate rubber, 10 parts of butyl isoprene rubber, 10 parts of fumed silica A200, 20 parts of carbon black N330, 20 parts of carbon black N550, 5 parts of light calcium carbonate, 5 parts of coupling agent A172, 0.3 part of accelerator H, 0.2 part of accelerator TAIC, 0.5 part of vulcanizing agent sulfur, 0.2 part of Diak No.1, 0.3 part of bis(2,5-dimethyl-2,5-di(t-butylperoxy)hexane), 0.5 part of stearic acid, 5 parts of zinc oxide, 1 part of antioxidant 2246, and 5 parts of plasticizer DBP.

[0168] This comparative example also provides a preparation method for the raw rubber of the sealing ring, and the preparation method includes:

[0169] (1) Mix nitrile rubber, fluorosilicone rubber, fluoroether rubber, ethylene acrylate rubber, butyl isoprene rubber with silica, carbon black, light calcium carbonate, coupling agent, accelerator, vulcanizing agent, stearic acid, zinc oxide, antioxidant and plasticizer in a closed mixer. The mixing temperature of the closed mixer is 70°C, the rotation speed is 40 revolutions per minute, and the mixing time is 2 minutes to obtain the mixed rubber for the sealing ring;

[0170] (2) Vulcanize and mold the seal ring compound obtained in step (1) in a flat vulcanizer. Take 250 grams of the seal ring compound and put it into a seal ring mold with a wire diameter of 29.0 ± 0.5 mm and an inner diameter of 124.0 ± 0.5 mm. The vulcanization and molding temperature is 150 °C, the vulcanization and molding pressure is 5 MPa, and the vulcanization and molding time is 40 min to obtain the seal ring. Conduct modulus tests at -40 °C, -50 °C, and -60 °C on the seal ring, Akron abrasion test (cm 3 / 3415 revolutions), test piece tear strength test and compression set (25%, 150 °C × 72 hours). The test results are shown in Table 1 and Table 2.

[0171] Comparative Example 6:

[0172] This comparative example provides a method for preparing the raw rubber of the seal ring. Its components are in parts by weight and include: 50 parts of nitrile rubber N21 (combined acrylonitrile content 39% - 41%), 20 parts of fluorosilicone rubber, 20 parts of fluoroether rubber, 15 parts of ethylene acrylate rubber, 15 parts of butyl isoprene rubber, 30 parts of precipitated silica DL-808, 50 parts of carbon black N330, 10 parts of carbon black N660, 10 parts of carbon black N774, 10 parts of carbon black N220, 20 parts of light calcium carbonate, 5 parts of coupling agent Si69, 3 parts of accelerator CZ, 2 parts of accelerator TMPTMA, 1.0 part of vulcanizing agent sulfur, 1 part of vulcanizing agent Diak No.1, 1 part of vulcanizing agent DTBP, 0.5 part of stearic acid, 5 parts of zinc oxide, 1 part of antioxidant RD, 1 part of antioxidant MB, 1 part of antioxidant 4010NA, and 30 parts of plasticizer DOS.

[0173] This comparative example also provides a method for preparing the raw rubber of the seal ring. The preparation method includes:

[0174] (1) Mix nitrile rubber, fluorosilicone rubber, fluoroether rubber, ethylene acrylate rubber, butyl isoprene rubber with silica, carbon black, light calcium carbonate, coupling agent, accelerator, vulcanizing agent, stearic acid, zinc oxide, antioxidant, and plasticizer in a closed mixer. The mixing temperature of the closed mixer is 90 °C, the rotation speed is 60 revolutions per minute, and the mixing time is 5 minutes to obtain the seal ring compound;

[0175] (2) Vulcanize and mold the seal ring compound obtained in step (1) in a flat vulcanizer. Take 400 grams of the seal ring compound and put it into a seal ring mold with a wire diameter of 29.0 ± 0.5 mm and an inner diameter of 124.0 ± 0.5 mm. The vulcanization and molding temperature is 180 °C, the vulcanization and molding pressure is 15 MPa, and the vulcanization and molding time is 20 min to obtain the seal ring. Conduct modulus tests at -40 °C, -50 °C, and -60 °C on the seal ring, Akron abrasion test (cm 3 / 3415 turns), the tear strength test of the test piece and the compression set (25%, 150 °C × 72 h) were tested, and the test results are shown in Table 1 and Table 2.

[0176] Comparative Example 7:

[0177] This comparative example provides a method for preparing the raw rubber of the sealing ring. The components include, by weight: 20 parts of nitrile rubber NBR2707 (combined acrylonitrile content 27%-30%), 10 parts of nitrile rubber N41 (combined acrylonitrile content 29%), 10 parts of nitrile rubber NBR3308 (combined acrylonitrile content 33%), 15 parts of fluorosilicone rubber, 15 parts of fluoroether rubber, 12 parts of ethylene acrylate rubber, 12 parts of butyl isoprene rubber, 5 parts of fumed silica A380, 5 parts of fumed silica N20, 5 parts of precipitated silica Z175, 5 parts of precipitated silica DL-600, 30 parts of carbon black N550, 10 parts of carbon black N660, 10 parts of carbon black N774, 10 parts of carbon black N220, 10 parts of light calcium carbonate, 3 parts of coupling agent KH550, 2 parts of coupling agent A151; 5 parts of coupling agent Si69, 0.5 part of accelerator D, 0.5 part of accelerator TMTD, 0.5 part of accelerator M, 1 part of accelerator HVA2, 0.5 part of accelerator TMPTMA, 0.5 part of vulcanizing agent sulfur, 0.5 part of vulcanizing agent Diak No.1, 1 part of vulcanizing agent bis-2-5, 0.5 part of stearic acid, 5 parts of zinc oxide, 0.5 part of antioxidant D, 0.5 part of antioxidant RD, 0.5 part of antioxidant MB, 0.5 part of antioxidant NBC, 10 parts of plasticizer DOP and 10 parts of plasticizer DOS.

[0178] This comparative example also provides a method for preparing the raw rubber of the sealing ring, and the preparation method includes:

[0179] (1) Mix the nitrile rubber, fluorosilicone rubber, fluoroether rubber, ethylene acrylate rubber, butyl isoprene rubber with fumed silica, carbon black, light calcium carbonate, coupling agent, accelerator, vulcanizing agent, stearic acid, zinc oxide, antioxidant and plasticizer in a closed mixer. The mixing temperature of the closed mixer is 80 °C, the rotation speed is 50 revolutions per minute, and the mixing time is 3 minutes to obtain the mixed rubber of the sealing ring;

[0180] (2) Vulcanize and mold the mixed rubber of the sealing ring obtained in step (1) in a flat vulcanizer. Take 320 g of the mixed rubber of the sealing ring and put it into a sealing ring mold with a wire diameter of 29.0 ± 0.5 mm and an inner diameter of 124.0 ± 0.5 mm. The vulcanization temperature is 170 °C, the vulcanization pressure is 10 MPa, and the vulcanization time is 30 min to obtain the sealing ring. The modulus tests of the sealing ring at -40 °C, -50 °C, and -60 °C were carried out, and the Akron abrasion test (cm 3 / 3415 revolutions), test piece tear strength test and compression set (25%, 150 °C × 72 h), and the test results are shown in Tables 1 and 2.

[0181] Comparative Example 8:

[0182] This comparative example provides a method for preparing the raw rubber of the sealing ring. The components include, by weight: 10 parts of nitrile rubber NBR1704 (combined acrylonitrile content 17%-20%), 20 parts of nitrile rubber NBR2707 (combined acrylonitrile content 27%-30%), 10 parts of nitrile rubber N41 (combined acrylonitrile content 29%), 12 parts of fluorosilicone rubber, 12 parts of fluoroether rubber, 12 parts of ethylene acrylate rubber, 12 parts of butyl isoprene rubber, 10 parts of fumed silica A200, 10 parts of fumed silica A380, 5 parts of fumed silica N20, 20 parts of carbon black N330, 20 parts of carbon black N774, 20 parts of carbon black N220, 12 parts of light calcium carbonate, 5 parts of coupling agent A172, 10 parts of coupling agent KH550, 1 part of accelerator TMTD, 0.5 part of accelerator CZ, 0.5 part of accelerator TAIC, 0.5 part of accelerator TMPTMA, 0.5 part of vulcanizing agent sulfur, 0.5 part of vulcanizing agent Diak No.1, 1 part of vulcanizing agent DTBP, 0.5 part of stearic acid, 5 parts of zinc oxide, 1 part of antioxidant RD, 1 part of antioxidant 4010NA, and 25 parts of plasticizer DOP.

[0183] This comparative example also provides a method for preparing the raw rubber of the sealing ring. The preparation method includes:

[0184] (1) Mix nitrile rubber, fluorosilicone rubber, fluoroether rubber, ethylene acrylate rubber, butyl isoprene rubber with fumed silica, carbon black, light calcium carbonate, coupling agent, accelerator, vulcanizing agent, stearic acid, zinc oxide, antioxidant, and plasticizer in a closed mixer. The mixing temperature of the closed mixer is 75 °C, the rotation speed is 55 revolutions per minute, and the mixing time is 2.5 minutes to obtain the mixed rubber of the sealing ring;

[0185] (2) Vulcanize and mold the mixed rubber of the sealing ring obtained in step (1) in a flat vulcanizer. Take 290 grams of the mixed rubber of the sealing ring and put it into a sealing ring mold with a wire diameter of 29.0 ± 0.5 mm and an inner diameter of 124.0 ± 0.5 mm. The vulcanization and molding temperature is 165 °C, the vulcanization and molding pressure is 8 MPa, and the vulcanization and molding time is 35 min to obtain the sealing ring. Conduct modulus tests at -40 °C, -50 °C, and -60 °C on the sealing ring, Akron abrasion test (cm 3 / 3415 revolutions), test piece tear strength test and compression set (25%, 150 °C × 72 h), and the test results are shown in Tables 1 and 2.

[0186] Comparative Example 9:

[0187] This comparative example provides a method for preparing the raw rubber of the sealing ring. Its components in parts by weight include: 20 parts of nitrile rubber N41 (acrylonitrile content 29%), 10 parts of nitrile rubber NBR3308 (acrylonitrile content 33%), 10 parts of nitrile rubber N21 (acrylonitrile content 39%-41%), 18 parts of fluorosilicone rubber, 18 parts of fluorinated ether rubber, 18 parts of ethylene acrylate rubber, 18 parts of butyl isoprene rubber, 10 parts of precipitated silica Z175, 10 parts of precipitated silica DL-600, 5 parts of precipitated silica DL-808, 20 parts of carbon black N550, 30 parts of carbon black N660, 20 parts of carbon black N774, 12 parts of light calcium carbonate, 10 parts of coupling agent Si69, 1 part of accelerator M, 0.5 part of accelerator ZDMC, 0.5 part of accelerator ZBX, 0.5 part of accelerator CZ, 1 part of accelerator HVA2, 1 part of accelerator TMPTMA, 0.5 part of sulfur curing agent, 0.5 part of Diak No.1 curing agent, 1.5 parts of DTBP curing agent, 0.5 part of stearic acid, 5 parts of zinc oxide, 1 part of antioxidant 2246, 1 part of antioxidant MB, and 20 parts of plasticizer DOS.

[0188] This comparative example also provides a method for preparing the raw rubber of the sealing ring. The preparation method includes:

[0189] (1) Mix nitrile rubber, fluorosilicone rubber, fluorinated ether rubber, ethylene acrylate rubber, butyl isoprene rubber with silica, carbon black, light calcium carbonate, coupling agent, accelerator, curing agent, stearic acid, zinc oxide, antioxidant and plasticizer in a closed mixer. The mixing temperature of the closed mixer is 85°C, the rotation speed is 45 revolutions per minute, and the mixing time is 3 minutes to obtain the mixed rubber of the sealing ring;

[0190] (2) Vulcanize and mold the mixed rubber of the sealing ring obtained in step (1) in a flat vulcanizer. Take 280 grams of the mixed rubber of the sealing ring and put it into a sealing ring mold with a wire diameter of 29.0±0.5 mm and an inner diameter of 124.0±0.5 mm. The vulcanization and molding temperature is 155°C, the vulcanization and molding pressure is 12 MPa, and the vulcanization and molding time is 35 min to obtain the sealing ring. Conduct modulus tests at -40°C, -50°C, and -60°C on the sealing ring, Akron abrasion test (cm 3 / 3415 revolutions), test piece tear strength test, and compression set (25%, 150°C×72 hours). The test results are shown in Table 1 and Table 2.

[0191] Table 1

[0192]

[0193] *Tested in accordance with the industry standard "HG / T 3866-2008 Determination of compression cold resistance coefficient of vulcanized rubber", the test temperature is -50°C. Sample preparation: Cut a 10±0.2 mm rubber block from the sealing ring and obtain it by cutting with a round hole punch with a diameter of 10±0.2 mm;

[0194] *Tested in accordance with the national standard "GB / T 7757-2009 Determination of compression stress-strain properties of vulcanized rubber or thermoplastic rubber", take the compression modulus value at a compression of 20%. Sample preparation: Cut a 12.5±0.5 mm cylindrical rubber sample from the sealing ring.

[0195] Table 2

[0196] <![CDATA[*Ackermann abrasion / cm 3 > <![CDATA[*Tear strength / KNm -1 > *Compression set / % Example 1 0.32 45.6 20.7 Example 2 0.25 51.2 16.2 Example 3 0.28 48.1 18.5 Example 4 0.27 47.6 17.8 Example 5 0.31 49.0 19.2 Example 6 0.26 45.7 18.7 Comparative Example 1 0.29 40.2 21.3 Comparative Example 2 0.32 38.5 26.5 Comparative Example 3 0.36 35.4 27.6 Comparative Example 4 0.45 30.7 32.4 Comparative Example 5 0.46 29.1 33.0 Comparative Example 6 0.51 25.4 35.2 Comparative Example 7 0.52 21.5 38.1 Comparative Example 8 0.48 22.0 37.0 Comparative Example 9 0.47 20.1 38.8

[0197] *Determined in accordance with the national standard "GB / T 1689-2014 Determination of abrasion resistance of vulcanized rubber (using Akron abrasion tester)", take the abrasion volume (cm 3 ) after 3415 revolutions. Sample preparation: Cut off the sealing ring, cut a 3.2±0.2 mm thick rubber sheet with a cutter, and cut a rubber strip more than 234 mm with a cutter with a width of 12.7±0.2 mm;

[0198] *Determined in accordance with the national standard "GB / T 529-2008 Determination of tear strength of vulcanized rubber or thermoplastic rubber (trousers, right-angle and crescent specimens)", using right-angle specimens. Sample preparation: Put 40-60 g of the sealing ring compounded rubber into a test piece mold with a length×width×thickness of (150 mm×150 mm×2 mm), vulcanize and form according to the conditions of the example to obtain a sealing ring test piece. Cut the test piece perpendicular to the calendering direction with a cutter to obtain a sealing ring tear test piece;

[0199] *Determined in accordance with the national standard "GB / T 7759.1-2015 Determination of compression set of vulcanized rubber or thermoplastic rubber - Part 1: At normal and high temperatures", the compression is 25%, the specimen size is type A (diameter 29.0±0.5 mm, height 12.5±0.5 mm), and the test conditions are 150°C×72 h. Sample preparation: Cut a 12.5±0.5 mm cylindrical rubber sample from the sealing ring.

[0200] It can be seen from Examples 1-6 that with the different addition amounts of various raw rubbers, fillers and additives, although there are slight differences in the compression cold resistance coefficient, low-temperature compression modulus, Akron abrasion, tear strength and compression set of the sealing ring products, the products provided by the examples have excellent low-temperature performance and mechanical properties compared with the products of the prior art, and have the value of popularization and application.

[0201] From the analysis of Examples 4 and Comparative Examples 1-4, it can be seen that the performance of the sealing ring products provided in the examples is superior to that of Comparative Example 1 in which step (1) is reduced, Comparative Example 2 in which steps (1) and (2) are reduced, Comparative Example 3 in which steps (1), (2) and (3) are reduced, and Comparative Example 4 in which steps (1), (2) and (3) are reduced and no modifier is added. Among them, Comparative Example 4 is a prior art product, indicating that the present invention has remarkable effects in improving the low-temperature performance and tear performance of the product, and reducing the wear and compression set of the product.

[0202] Comparative Examples 5, 6, 7, 8 and 9 are the performance data of the existing process technologies of the products corresponding to Examples 1, 2, 3, 5 and 6 respectively. From the data analysis, it can be seen that the compression cold resistance coefficient, low-temperature compression modulus, tear strength, wear and compression set of the sealing ring products of the prior art are lower than those of the corresponding example products, indicating that the products and preparation methods of the present invention have remarkable effects.

[0203] Based on the above data analysis, compared with the prior art, the preparation method of the sealing ring products provided in the examples can improve the low-temperature performance, wear performance and tear performance of the products, and reduce the compression set of the products, solving the problem that the sealing ring products of the prior art are not suitable for use in alpine regions (-40°C to -60°C) and have poor comprehensive performance.

[0204] The applicant declares that the present invention uses the above examples to illustrate a sealing ring applicable to alpine regions, its preparation method and application, but the present invention is not limited to the above examples, that is, it does not mean that the present invention must rely on the above examples to be implemented. Those skilled in the art should understand that any improvement of the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, and the selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A sealing ring, characterized in that, the components of the sealing ring are by weight parts and include: 30 - 50 (preferably 32 - 48, more preferably 35 - 45) parts of nitrile rubber, 10 - 20 (preferably 12 - 18, more preferably 14 - 16) parts of fluorosilicone rubber, 10 - 20 (preferably 12 - 18, more preferably 14 - 16) parts of fluoroether rubber, 10 - 15 (preferably 11 - 14, more preferably 12 - 13) parts of ethylene acrylate rubber, 10 - 15 (preferably 11 - 14, more preferably 12 - 13) parts of butyl isoprene rubber; also includes: 5 - 10 (preferably 5.5 - 9.5, more preferably 6 - 9) parts of modifier; also includes in total: 10 - 30 (preferably 12 - 28, more preferably 15 - 25) parts of silica, 40 - 80 (preferably 45 - 75, more preferably 50 - 70) parts of carbon black, 5 - 20 (preferably 8 - 17, more preferably 10 - 15) parts of light calcium carbonate, 5 - 15 (preferably 6 - 14, more preferably 8 - 12) parts of coupling agent, 0.5 - 5 (preferably 0.6 - 4.5, more preferably 1 - 4) parts of accelerator, 1.0 - 3.0 (preferably 1.1 - 2.9, more preferably 1.2 - 2.8) parts of vulcanizing agent, 0.2 - 0.8 (preferably 0.3 - 0.7, more preferably 0.4 - 0.6) parts of stearic acid, 3 - 8 (preferably 3.5 - 7.5, more preferably 4 - 7) parts of zinc oxide, 1 - 3 (preferably 1.2 - 2.8, more preferably 1.5 - 2.5) parts of antioxidant and 5 - 30 (preferably 8 - 27, more preferably 10 - 25) parts of plasticizer.

2. The preparation method of the sealing ring according to claim 1, characterized in that, preferably, the nitrile rubber is a binary copolymer of butadiene and acrylonitrile, a product of PetroChina Lanzhou Petrochemical Company; including any one or a combination of at least two of NBR1704 (combined acrylonitrile content 17% - 20%), NBR2707 (combined acrylonitrile content 27% - 30%), N41 (combined acrylonitrile content 29%), NBR3308 (combined acrylonitrile content 33%), N21 (combined acrylonitrile content 39% - 41%); preferably, the fluorosilicone rubber is γ - trifluoropropylmethyl polysiloxane, a copolymer of methyl siloxane, vinyl siloxane and trifluoropropyl siloxane, a product of DuPont Company, USA, grade FVMQ; preferably, the fluoroether rubber is a binary copolymer of perfluoroalkyl vinyl ether and tetrafluoroethylene, a product of Solvay Group (Solvay), grade Tecnoflon FFKM PFR 94; preferably, the ethylene acrylate rubber is a binary copolymer of ethylene and methyl acrylate, a product of DuPont Company, USA, grade GLS; preferably, the butyl isoprene rubber is a binary copolymer of butadiene and isoprene prepared by solution polymerization, prepared by the method of Example 4 according to Patent ZL202210989443.2 by Dalian Institute of Chemical Physics, Chinese Academy of Sciences, grade BIR - DICP; Preferably, the modifier includes any one or a combination of at least two of maleic anhydride, acrylic anhydride, p-aminophenol, o-aminophenol, 2-hydroxyethylamine, calcium oxide, n-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and 2,6-di-tert-butyl-p-cresol; the main function of the modifier is to introduce polar groups into non-polar or weakly polar rubber molecular chains, improving the compatibility of several rubber materials and the interaction with fillers; Preferably, the white carbon black includes any one or a combination of at least two of fumed A200, fumed A380, fumed N20, precipitated Z175, precipitated DL-600, and precipitated DL-808; Preferably, the carbon black includes any one or a combination of at least two of N330, N550, N660, N774, and N220; Preferably, the light calcium carbonate is precipitated calcium carbonate, which is a general filler prepared by mixing limestone and anthracite, followed by high-temperature calcination, carbonization, dehydration, drying, water separation, and pulverization; a product of Shanghai Liangjiang Titanium White Chemical Products Co., Ltd., grade: PT (reagent grade); Preferably, the stearic acid is a product of Xilong Science Co., Ltd., grade: analytical pure (AR); Preferably, the zinc oxide is a product of Tianjin Yongda Chemical Reagent Co., Ltd., grade: analytical pure (AR); Preferably, the coupling agent includes any one or a combination of at least two of vinyltris(β-methoxyethoxy)silane, vinyltrichlorosilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, methylmercapto propyl dimethoxysilane, or bis[(3-triethoxysilyl)propyl]tetrasulfide; Preferably, the accelerator includes any one or a combination of at least two of hexamethylenetetramine (accelerator H), diphenylguanidine (accelerator D), tetramethylthiuram disulfide (accelerator TMTD), 2-mercaptobenzothiazole (accelerator M), zinc dimethyldithiocarbamate (accelerator ZDMC), zinc butylxanthate (accelerator ZBX), N-cyclohexyl-2-benzothiazolesulfenamide (accelerator CZ), triallyl isocyanurate (accelerator TAIC), N,N'-m-phenylene bismaleimide (HVA2), trimethylolpropane trimethacrylate (TMPTMA); Preferably, the vulcanizing agent includes any one or a combination of at least two of sulfur, hexamethylenediamine carbamate (Diak No.1), 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane (bis 2-5), or di-tert-butyl peroxide (DTBP); Preferably, the anti-aging agent includes any one or a combination of at least two of 2,2'-methylenebis(4-methyl-6-tert-butylphenol) (anti-aging agent 2246), N-phenyl-β-naphthylamine (anti-aging agent D), 2,2,4-trimethyl-1,2-dihydroquinoline polymer (anti-aging agent RD), 2-mercaptobenzothiazole (anti-aging agent MB), nickel dibutyldithiocarbamate (anti-aging agent NBC), and N-isopropyl-N'-phenyl-p-phenylenediamine (anti-aging agent 4010NA); Preferably, the plasticizer is any one or a combination of at least two of dibutyl phthalate (DBP), dioctyl phthalate (DOP), and dioctyl sebacate (DOS).

3. The method for preparing the sealing ring according to claim 1 or 2, characterized in that, the preparation process includes: Mixing nitrile rubber, fluorosilicone rubber, fluoroether rubber, ethylene acrylate rubber, butyl isoprene rubber and a modifier to obtain a modified sealing ring raw rubber; Mixing the modified sealing ring raw rubber with silica, carbon black, light calcium carbonate, coupling agent, accelerator, vulcanizing agent, stearic acid, zinc oxide, anti-aging agent and plasticizer to obtain the sealing ring compound; Vulcanizing and molding the sealing ring compound in a flat vulcanizer. In the sealing ring mold, the vulcanizing and molding temperature is 150-180 °C (preferably 155-175 °C, more preferably 165-175 °C), the pressure is 5-15 MPa (preferably 6-14 MPa, more preferably 8-12 MPa), and the time is 20-40 min to obtain the sealing ring.

4. A method for preparing the sealing ring according to any one of claims 1-3, characterized in that, the preparation method specifically includes: (1) Mixing nitrile rubber, fluorosilicone rubber, fluoroether rubber, ethylene acrylate rubber and butyl isoprene rubber in an open mill to obtain a mixed raw rubber; (2) Mixing the mixed raw rubber obtained in step (1) with a modifier in an open mill to obtain a modified sealing ring raw rubber; (3) Preparing the modified sealing ring raw rubber obtained in step (2) into a 0.5-1.5 mm thin sheet in an open mill and placing it in the sun for 4-6 hours to obtain a modified sealing ring raw rubber sheet; (4) Mixing the modified sealing ring raw rubber sheet obtained in step (3) with silica, carbon black, light calcium carbonate, coupling agent, accelerator, vulcanizing agent, stearic acid, zinc oxide, anti-aging agent and plasticizer in a closed mill to obtain the sealing ring compound; (5) Vulcanizing and molding the sealing ring compound obtained in step (4) in a flat vulcanizer. In the sealing ring mold, the vulcanizing and molding temperature is 150-180 °C (preferably 155-175 °C, more preferably 165-175 °C), the pressure is 5-15 MPa (preferably 6-14 MPa, more preferably 8-12 MPa), and the time is 20-40 min to obtain the sealing ring.

5. According to the preparation method of claim 4, characterized in that, the mixing in step (1) and step (2) includes mixing in an open mill; Preferably, the mixing temperature of the open mill is 60-90 °C; Preferably, the roll gap of the open mill is 1-2 mm; Preferably, the mixing time of the open mill is 10-20 minutes.

6. The preparation method according to claim 4, characterized in that the preparation of the modified sealing ring raw rubber film in step (3) includes mixing by an open mill; Preferably, the mixing temperature of the open mill is 35-50 °C; Preferably, the roll gap of the open mill is 0.3-1.2 mm; Preferably, the mixing time of the open mill is 5-10 minutes.

7. The preparation method according to claim 4, characterized in that the preparation of the sealing ring mixed rubber in step (4) includes mixing by a closed mixer; Preferably, the mixing temperature of the closed mixer is 65-95 °C; More preferably, the mixing temperature of the closed mixer is 70-90 °C; Preferably, the rotation speed of the closed mixer is 30-80 rpm; More preferably, the rotation speed of the closed mixer is 40-60 rpm; Preferably, the mixing time of the internal mixer is 1.5-5.5 minutes; More preferably, the mixing time of the internal mixer is 2-5 minutes.

8. The preparation method according to claim 4, characterized in that the preparation of the sealing ring in step (5) further includes vulcanization and molding; Preferably, the temperature of the vulcanization and molding is 150-180 °C, more preferably 165-175 °C; Preferably, the pressure of the vulcanization and molding is 5-15 MPa, more preferably 8-12 MPa; Preferably, the time of the vulcanization and molding is 20-40 min.

9. The preparation method according to claim 4, characterized in that Vulcanize and mold the sealing ring mixed rubber in a flat vulcanizer, and take 250-400 g (preferably 260-390 g, more preferably 270-350 g) and put it into a sealing ring mold with a wire diameter of 29.0 ± 0.5 mm and an inner diameter of 124.0 ± 0.5 mm.

10. An application of the sealing ring according to claim 1 under low temperature conditions of -40 °C to -60 °C.

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