A low-temperature and oil-resistant hydrogenated nitrile rubber compound and preparation method thereof

Abstract

The present invention discloses a low-temperature and oil-resistant hydrogenated nitrile rubber compound and a preparation method thereof. The present invention first adopts a "carboxyl-terminated polyester resin-alcohol-HNBR" ternary polymer system as a basis, which can reduce the friction between chain segments in the cross-linked network, improve the mechanical properties of the compound, and rely on its chemical polymerization connection to prevent the test oil from precipitating; on this basis, it is mixed with the same compound that has been grafted and modified, and a grafted substance containing fluorine elements can be added to the ternary polymer system to obtain a modified fluororubber, which introduces fluorine atoms to contribute to the oil resistance of the material. The modified tungsten disulfide added to the compound can not only prevent the agglomeration of the filler itself, but also better meet the requirements of the rubber low-temperature resistant additive. The preparation method of the present invention is simple to operate, rationally designed, can be further regulated according to different requirements, has high universality, and is worthy of promotion and use.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer compound synthesis, and in particular to a low-temperature and oil-resistant hydrogenated nitrile rubber compound and a preparation method thereof. Background Art

[0002] Nitrile rubber (NBR) is a random polymer formed by the emulsion copolymerization of acrylonitrile and butadiene. Due to the presence of highly polar cyano groups in the NBR molecular chain, NBR possesses excellent oil and corrosion resistance, as well as good mechanical properties, making it widely used in various key fields such as oil exploration and machinery manufacturing. Hydrogenated nitrile rubber (HNBR) is a highly saturated specialty elastomer produced by selectively hydrogenating the unsaturated carbon-carbon double bonds in the NBR molecular chain. It exhibits excellent oil and corrosion resistance, as well as good resistance to high temperatures and ozone aging. It is widely used in the oil exploration, machinery manufacturing, automotive, and other industries. Patent document CN107619512B discloses a "high-performance hydrogenated nitrile rubber compound and its preparation method." The high-performance hydrogenated nitrile rubber compound's matrix consists of highly saturated hydrogenated nitrile rubber, carboxyl hydrogenated nitrile rubber, and a multifunctional epoxy resin. While the hydrogenated nitrile rubber undergoes crosslinking under the action of an organic peroxide, the carboxyl hydrogenated nitrile rubber and the multifunctional epoxy resin also undergo self-crosslinking, forming a diversified polymer crosslinking system that meets the oil resistance, heat resistance, hydrogen sulfide resistance, high hardness, and good compression resistance required for oilfield rubber sealing products. Patent document CN114262394B discloses a "liquid hydrogenated nitrile rubber, its preparation method, and application." This liquid hydrogenated nitrile rubber has a low molecular weight and a wide molecular weight distribution. It also exhibits excellent flowability during processing and excellent mechanical properties after curing. It has unique application value in the specialty rubber field and provides a new direction for the preparation and application of liquid hydrogenated nitrile rubber.

[0003] However, for HNBR, there is a contradiction between oil resistance and low-temperature resistance. Low-temperature resistance is not only related to the nitrile group content, but also to the crystallization of the molecular chain segments: the higher the nitrile group content, the greater the polarity of the molecular chain and the less flexible the molecular chain, resulting in poorer low-temperature resistance but better oil resistance; the higher the carbon-carbon double bond content, the more flexible the molecular chain, resulting in better low-temperature resistance but correspondingly poorer oil resistance. With the development of society and the progress of the times, various fields have increasingly stringent requirements for the comprehensive performance of rubber materials. However, the biggest characteristic of HNBR is the contradiction between oil resistance and low-temperature resistance.

[0004] In view of this, we disclose a low-temperature and oil-resistant hydrogenated nitrile rubber compound and a preparation method thereof. Summary of the Invention

[0005] In view of the deficiencies in the prior art, the present invention aims to provide a low-temperature and oil-resistant hydrogenated nitrile rubber compound and a preparation method thereof.

[0006] To achieve the above objectives, the present invention proposes the following technical solutions:

[0007] A low-temperature and oil-resistant hydrogenated nitrile rubber compound, comprising the following raw materials in parts by weight:

[0008] 100 parts of hydrogenated nitrile rubber, 35-45 parts of modified fluorine-containing rubber, 15-20 parts of reinforcing agent, 10-20 parts of small molecule plasticizer, 10-20 parts of compatibilizer, 0.5-2 parts of internal release agent, and 0.5-2 parts of dispersant.

[0009] The modified fluorine-containing rubber is a fluorine-containing HNBR ternary rubber modified by fluoride grafting, and the reinforcing agent is modified tungsten disulfide.

[0010] On the basis of the above scheme and as a preferred scheme of the above scheme, the hydrogenated nitrile rubber is a blend of highly saturated hydrogenated nitrile rubber and carboxyl hydrogenated nitrile rubber, and the blending ratio of the two is 70:30.

[0011] On the basis of the above scheme and as a preferred scheme of the above scheme, the modified fluorine-containing rubber includes 60-80 parts of carboxylic hydrogenated nitrile rubber, 35-50 parts of ethylene glycol, 5-15 parts of zinc oxide, 5-10 parts of vulcanizing agent, 5-10 parts of cross-linking agent, and 1-5 parts of thermal oxidation inhibitor.

[0012] On the basis of the above solution and as a preferred solution of the above solution, the preparation of the modified fluorine-containing rubber includes the following steps:

[0013] (1) Solution preparation: Using chlorobenzene as solvent, prepare a 7.5 wt% HNBR glue solution with carboxyl hydrogenated nitrile rubber, and divide the solution into two equal parts, namely glue solution A and glue solution B;

[0014] (2) Solution pretreatment:

[0015] Add carboxyl-terminated polyester resin to glue solution A, and mechanically stir at room temperature for 6 hours. After ethanol coagulation, dry in a 50°C oven to obtain a mixed glue.

[0016] (3) Pre-plasticization treatment:

[0017] The mixed rubber is masticated on an open mill, and ethylene glycol, zinc oxide, vulcanizing agent, cross-linking agent, and thermal oxidant are added in sequence. After each addition, the rubber is tapped 7-8 times. After adding zinc oxide, triangle packing is performed 7-8 times, and the rubber is rolled 4-5 times. After adding the thermal oxidant, the rubber is tapped 7-8 times and the rubber is rolled 4-5 times to obtain a uniformly mixed rubber material. The mastication conditions are normal pressure and 145°C.

[0018] (4) Grafting:

[0019] Graphene oxide and trifluoroethyl methacrylate were uniformly stirred in a mass ratio of 0.45:1 to obtain a mixed liquid. Glue B and the mixed liquid were then weighed in a mass ratio of 90:27. The two were stirred at room temperature for 30 minutes. Nitrogen was evacuated three times to maintain a nitrogen atmosphere in the system. The temperature was slowly raised to 80°C. 1% initiator AIBN was dissolved in chlorobenzene and then added dropwise to the reaction system for 4 hours. After the reaction was completed, the mixture was precipitated with anhydrous ethanol to obtain a grafted product, which was dried and set aside.

[0020] (5) Hydrogenation:

[0021] The grafted product was prepared into a glue solution with a mass fraction of 5.5%, hydrogenated in a hydrogenation kettle, precipitated with anhydrous ethanol after the hydrogenation reaction was completed, and dried for later use;

[0022] (6) Plasticizing and vulcanization:

[0023] First, the hydrogenated grafted product and the uniformly mixed rubber material are plasticized on an open mill, 2.5-5 parts of a cross-linking agent based on the total mass of the grafted product and the uniformly mixed rubber material are added, the rubber is tapped 7-8 times, and the rubber is rolled 4-5 times to obtain a uniform rubber material;

[0024] (7) Film packaging:

[0025] The uniform rubber material is sheeted to obtain a film, which is cooled for 24 hours and then vulcanized at a temperature of 135° C. and a pressure of 5 MPa for 30 minutes to obtain a fluorinated methacrylate grafted fluorinated HNBR ternary rubber, which is then packaged.

[0026] On the basis of the above scheme and as a preferred scheme of the above scheme, the modified tungsten disulfide is prepared by hydrothermal reaction of hydroxylamine hydrochloride, sodium tungstate dihydrate, thiourea and graphene oxide.

[0027] On the basis of the above scheme and as a preferred scheme of the above scheme, the small molecule plasticizer is one of TP-59, DBP, and TP-90B; the compatibilizer is benzotriazole; the internal release agent is microcrystalline wax; and the dispersant is one of dispersant NAS, polycarboxylate, and polyethylene wax.

[0028] On the basis of the above scheme and as a preferred embodiment of the above scheme, the preparation method of the low-temperature and oil-resistant hydrogenated nitrile rubber compound comprises the following steps:

[0029] (a) Rubber mixing: hydrogenated nitrile rubber and modified fluorinated rubber are added to an open mill using a thin-pass plasticating method, and a reinforcing agent, a small molecule plasticizer, a compatibilizer, an internal release agent, and a dispersant are added and uniformly mixed;

[0030] (b) Compound curing: The mixed material is returned to the top of the roller gap and passed through the roller gap again, an internal release agent and a dispersant are added, the material is uniformly mixed, and triangular packages are formed to obtain the initial compound;

[0031] (c) Compound refining: adding the initial compound to the open mill, returning it to the top of the roll gap several times and re-passing the roll gap, and forming a triangular package to obtain a low-temperature and oil-resistant hydrogenated nitrile rubber compound; finally, the low-temperature and oil-resistant hydrogenated nitrile rubber compound is extruded and molded into a product.

[0032] On the basis of the above scheme and as a preferred scheme of the above scheme, the mixing times in (a) are 7-8 times and the mixing temperature is 50-60°C; the triangle packing times in (b) are 3-5 times.

[0033] On the basis of the above solution and as a preferred solution of the above solution, the rubber material in (c) is refining for 3-5 times and triangle packing for 3-5 times.

[0034] Compared with the prior art, the technical solution of the present invention has the following beneficial effects:

[0035] The present invention discloses a low-temperature and oil-resistant hydrogenated nitrile rubber compound and a preparation method thereof. The present invention first uses a "carboxyl-terminated polyester resin-alcohol-HNBR" ternary polymer system as a basis, which can reduce the friction between chain segments in the cross-linked network and improve the mechanical properties of the compound. Moreover, due to its chemical polymerization connection, it can prevent the precipitation of test oil. On this basis, it is mixed with the same compound that has been grafted and modified, and a grafted substance containing fluorine elements can be added to the ternary polymer system to obtain a modified fluororubber. After fluorine atoms are introduced into the hydrogenated nitrile rubber molecular chain with a certain degree of hydrogenation, a fluororubber material is prepared. While ensuring that the proportion of carbon-carbon double bonds does not affect the low-temperature resistance, it helps to improve the oil resistance of the material. The modified tungsten disulfide added to the compound can not only prevent the agglomeration of the filler itself, but also increase the contact area between the tungsten disulfide and the rubber matrix, making it have better surface bonding, thereby making the modified tungsten disulfide more in line with the requirements of a low-temperature-resistant rubber additive. The preparation method of the present invention is simple to operate, rationally designed, and can be further adjusted according to different requirements. It has high universality and is worthy of promotion and use.

[0036] It should be appreciated that all combinations of the foregoing concepts, as well as additional concepts described in greater detail below, to the extent such concepts are not mutually inconsistent, can be considered to be part of the present subject matter disclosure.

[0037] The foregoing and other aspects, embodiments and features of the present invention will be more fully understood from the following description. Other additional aspects of the present invention, such as the features and / or beneficial effects of the exemplary embodiments, will become apparent from the following description or will be learned from the practice of the specific embodiments according to the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] The above and / or additional aspects and advantages of the present invention will become apparent and readily understood from the following description of the embodiments with reference to the accompanying drawings, in which:

[0039] Figure 1 This is a scanning electron microscope image of the material at the same magnification:

[0040] (a) SEM cross-sectional morphology of tungsten disulfide after calcination in Comparative Example 6;

[0041] (b) SEM cross-sectional morphology of tungsten disulfide treated with coupling agent in Comparative Example 5;

[0042] (c) SEM cross-sectional morphology of modified tungsten disulfide in Example 3 of the present invention. DETAILED DESCRIPTION

[0043] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the described embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention. Unless otherwise defined, the technical terms or scientific terms used herein should be the common meanings understood by people with ordinary skills in the field to which the present invention belongs.

[0044] The words “first”, “second” and similar words used in the patent application specification and claims of the present invention do not indicate any order, quantity or importance, but are only used to distinguish different components. Similarly, unless the context clearly indicates otherwise, the singular forms of “a”, “an” or “the” and similar words do not indicate a quantity limitation, but rather indicate the presence of at least one. Words such as “include” or “comprise” mean that the elements or objects appearing before “include” or “comprises” cover the features, wholes, steps, operations, elements and / or components listed after “include” or “comprises”, and do not exclude the existence or addition of one or more other features, wholes, steps, operations, elements, components and / or their collections. “Up”, “down”, “left”, “right” and the like are only used to indicate relative positional relationships. When the absolute position of the described object changes, the relative positional relationship may also change accordingly.

[0045] In the present invention, the hydrogenated nitrile rubber is a blend of high-saturation hydrogenated nitrile rubber and carboxyl hydrogenated nitrile rubber, and the blending ratio of the two is 70:30; the high-saturation hydrogenated nitrile rubber is brand ZN43056, produced by Zannan Technology (Shanghai) Co., Ltd., and the carboxyl hydrogenated nitrile rubber is brand Therban XT VP KA 8889, produced by Lanxess AG, Germany; the high-saturation hydrogenated nitrile rubber has a saturation of ≥99% and an acrylonitrile content of 43%; the carboxyl hydrogenated nitrile rubber has a saturation of 96.5%, a carboxyl content of 10%, and an acrylonitrile content of 33%.

[0046] Furthermore, the modified fluorine-containing rubber is a fluorine-containing HNBR ternary rubber grafted with a fluoride, and the fluoride is trifluoroethyl methacrylate. Specifically, HNBR glue is used as the grafting object, and the grafting of fluorinated methacrylate is achieved through a thermal initiation system; the preparation process includes "solution preparation → solution pretreatment → pre-mastication treatment → grafting reaction → product hydrogenation → plastication and vulcanization → sheeting and packaging", and the specific steps are as follows:

[0047] (1) Solution preparation: Using chlorobenzene as solvent, prepare a 7.5 wt% HNBR glue solution with carboxyl hydrogenated nitrile rubber, and divide the solution into two equal parts, namely glue solution A and glue solution B;

[0048] (2) Solution pretreatment:

[0049] The glue solution A was added with a carboxyl-terminated polyester resin, and mechanically stirred at room temperature for 6 hours. After ethanol coagulation, it was dried in an oven at 50° C. to obtain a mixed glue; the carboxyl-terminated polyester resin was purchased from Guangdong Shengke Biochemical Technology Co., Ltd.

[0050] (3) Pre-plasticization treatment:

[0051] The mixed rubber is masticated on an open mill, and ethylene glycol, zinc oxide, vulcanizing agent, cross-linking agent, and thermal oxidant are added in sequence. After each addition, the rubber is tapped 7-8 times. After adding zinc oxide, triangle packing is performed 7-8 times, and the rubber is rolled 4-5 times. After adding the thermal oxidant, the rubber is tapped 7-8 times and the rubber is rolled 4-5 times to obtain a uniformly mixed rubber material. The mastication conditions are normal pressure and 145°C.

[0052] (4) Grafting:

[0053] Graphene oxide and trifluoroethyl methacrylate were uniformly stirred in a mass ratio of 0.45:1 to obtain a mixed liquid. Glue B and the mixed liquid were then weighed in a mass ratio of 90:27. The two were stirred at room temperature for 30 minutes. Nitrogen was evacuated three times to maintain a nitrogen atmosphere in the system. The temperature was slowly raised to 80°C. 1% initiator AIBN was dissolved in chlorobenzene and added dropwise to the reaction system for 4 hours. After the reaction was completed, the mixture was precipitated with anhydrous ethanol to obtain a grafted product, which was dried for later use.

[0054] (5) Hydrogenation:

[0055] The grafted product was prepared into a glue solution with a mass fraction of 5.5%, and hydrogenated in a hydrogenation kettle. After the hydrogenation reaction was completed, it was precipitated with anhydrous ethanol and dried for later use.

[0056] (6) Plasticizing and vulcanization:

[0057] First, the hydrogenated grafted product and the uniformly mixed rubber material are plasticized on an open mill, 2.5-5 parts of a cross-linking agent based on the total mass of the grafted product and the uniformly mixed rubber material are added, the rubber is tapped 7-8 times, and the rubber is rolled 4-5 times to obtain a uniform rubber material;

[0058] (7) Film packaging:

[0059] The uniform rubber material is sheeted to obtain a film, which is cooled for 24 hours and then vulcanized at a temperature of 135° C. and a pressure of 5 MPa for 30 minutes to obtain a fluorinated methacrylate grafted fluorinated HNBR ternary rubber, which is then packaged.

[0060] An appropriate amount of ethylene glycol is added to the mixed rubber system, controlling the theoretical ratio of hydroxyl groups in the ethylene glycol to carboxyl groups in the carboxyl hydrogenated nitrile rubber in glue A to 0.75:1. Under high temperature conditions, ester bonds can form between the carboxyl-terminated polyester resin in glue A and the ethylene glycol under these conditions. Ester bonds also exist between the hydroxyl groups in the ethylene glycol and the carboxyl hydrogenated nitrile rubber, thus forming a "carboxyl-terminated polyester resin-alcohol-HNBR" ternary polymer system centered on ethylene glycol. This can increase the chain length and flexibility of the rubber system, thereby enhancing the rubber's low-temperature resistance. Furthermore, the unequal mixing of hydroxyl and carboxyl groups allows the carboxyl groups on the carboxyl hydrogenated nitrile rubber to form hydrogen bonds with the grafted product during the subsequent steps of plastication, uniform mixing of the rubber materials, and vulcanization, thereby ensuring interfacial bonding and stability between the matrix and the additive.

[0061] Furthermore, in a single HNBR treatment system, a 90:15 mass ratio of glue B to mixed liquid can achieve highly efficient grafting and surface modification of the rubber with fluoride. However, in this system, since the HNBR glue consists of two parts, the excess mixed liquid also produces a fluorine-containing treatment effect on the glue A system during the subsequent mastication and vulcanization stages, equivalent to fluoride grafting modification. Furthermore, because the ternary system in the mixed glue produced by glue A consumes some carboxyl groups, the mass ratio in this system is not a simple 90:30 ratio. After trial and error, the ratio was determined to be 90:27.

[0062] Furthermore, the use of graphene oxide not only promotes the vulcanization process of rubber in the system and improves the physical properties of rubber; it can also use the functional groups on its surface to attract the electron cloud density of the nitrile group in the HNBR rubber system, thereby weakening the effect of excessive nitrile group content on low-temperature resistance. The use of fluorine in trifluoroethyl methacrylate can be understood as graphene oxide folds surrounding the outside of the molecule to ensure its oil resistance and mechanical properties.

[0063] Furthermore, when the temperature exceeds 110°C, part of the graphene oxide will be thermally reduced. In the rubber film with the same degree of hydrogenation, the partially reduced graphene oxide has a certain catalytic effect, thereby causing the rubber to undergo secondary cross-linking under thermal conditions and possessing more excellent mechanical properties. The present invention introduces fluorine atoms into the molecular chain of hydrogenated nitrile rubber with a certain degree of hydrogenation through the grafting reaction of fluorinated methacrylate to prepare a fluorine-containing rubber material. While ensuring that the proportion of carbon-carbon double bonds does not affect the low-temperature resistance, it contributes to the oil resistance of the material. While the ternary polymer system is formed, the fluorine-containing elements on the rubber surface not only improve the oil resistance of the hydrogenated nitrile rubber and give it good hydrophobic properties, but also maintain the excellent tensile properties and low-temperature resistance of HNBR.

[0064] Furthermore, the preparation method of the modified tungsten disulfide of the present invention comprises the following steps:

[0065] Under nitrogen atmosphere, hydroxylamine hydrochloride, sodium tungstate dihydrate, and thiourea are weighed in a molar ratio of 1:5:2, and stirred at a speed of 600-850 rpm for 0.5-2h to obtain a mixed solution A; at the same time, a 0.15 mg / mL graphene oxide aqueous solution is prepared, and an active agent is added to the graphene oxide aqueous solution at a mass volume ratio of 0.2 g:10 mL. The present invention uses hexadecyltrimethylammonium bromide as the active agent, and the mixture is stirred evenly to obtain a mixed solution B; the mixed solution B is added dropwise to the mixed solution A at a drop rate of 0.15 mL / min and stirred at the same speed, and then the pH is adjusted to 6 with ammonia water. After stirring for 0.5h, the mixture is transferred to a reactor, reacted at 180°C for 16h, naturally cooled to room temperature, ethanol condensed, and the precipitate was dried at 60°C to obtain modified tungsten disulfide.

[0066] Tungsten disulfide nanosheets are a low-dimensional, sheet-like transition metal sulfide material with a layered structure similar to graphene. This structure gives it a high mechanical melting temperature and a large chemical diffusion coefficient, and these properties enable it to maintain good electrochemical properties in low-temperature environments. Tungsten disulfide has a wide range of applications in lubrication, catalysis, and lithium batteries. To this end, we use tungsten disulfide as a filler for modification. However, direct use is very prone to filler agglomeration problems, such as Figure 1 (a) Figure 1 (b) are scanning electron micrographs of tungsten disulfide after calcination and coupling agent treatment. It can be clearly seen that these two methods still cannot maintain the flaky morphology of tungsten disulfide well, and there is still agglomeration. However, the modified tungsten disulfide used in the present invention has its own flaky morphology, such as Figure 1 (c) Moreover, since the energy required for the binding sites on the surface of graphene oxide is low, the flake-shaped tungsten disulfide grows and extends with the help of the binding sites. Moreover, since the obvious layered structure of graphene oxide after thermal reduction to graphene is equivalent to expansion and growth between the two layers, the tungsten disulfide presents a blooming layered structure. This can increase the contact area between the tungsten disulfide and the rubber matrix, reduce the agglomeration of the filler, and have better surface bonding force, thereby making the modified tungsten disulfide more in line with the requirements of rubber low-temperature resistant additives.

[0067] Example 1

[0068] A low-temperature and oil-resistant hydrogenated nitrile rubber compound, comprising the following raw materials in parts by weight:

[0069] 100 parts of hydrogenated nitrile rubber, 35 parts of modified fluorine-containing rubber, 15 parts of reinforcing agent, 10 parts of small molecule plasticizer, 10 parts of compatibilizer, 0.5 parts of internal release agent, and 0.5 parts of dispersant.

[0070] The modified fluorine-containing rubber is a fluorine-containing HNBR ternary rubber modified by fluoride grafting, and the reinforcing agent is modified tungsten disulfide.

[0071] Furthermore, the hydrogenated nitrile rubber is a blend of highly saturated hydrogenated nitrile rubber and carboxyl hydrogenated nitrile rubber, and the blending ratio of the two is 70:30.

[0072] Furthermore, the modified fluorine-containing rubber includes 60 parts of carboxyl hydrogenated nitrile rubber, 30 parts of ethylene glycol, 5 parts of zinc oxide, 5 parts of vulcanizing agent, 5 parts of cross-linking agent, and 1 part of thermal oxidation inhibitor.

[0073] Preferably, the preparation of the modified fluorine-containing rubber comprises the following steps:

[0074] (1) Solution preparation: Using chlorobenzene as solvent, prepare a 7.5 wt% HNBR glue solution with carboxyl hydrogenated nitrile rubber, and divide the solution into two equal parts, namely glue solution A and glue solution B;

[0075] (2) Solution pretreatment:

[0076] Add carboxyl-terminated polyester resin to glue solution A, and mechanically stir at room temperature for 6 hours. After ethanol coagulation, dry in a 50°C oven to obtain a mixed glue.

[0077] (3) Pre-plasticization treatment:

[0078] The mixed rubber is masticated on an open mill, and ethylene glycol, zinc oxide, vulcanizing agent, cross-linking agent, and thermal oxidant are added in sequence. After each addition, the rubber is tapped 7-8 times. After adding zinc oxide, triangle packing is performed 7-8 times, and the rubber is rolled 4-5 times. After adding the thermal oxidant, the rubber is tapped 7-8 times and the rubber is rolled 4-5 times to obtain a uniformly mixed rubber material. The mastication conditions are normal pressure and 145°C.

[0079] (4) Grafting:

[0080] Graphene oxide and trifluoroethyl methacrylate were uniformly stirred in a mass ratio of 0.45:1 to obtain a mixed liquid. Glue B and the mixed liquid were then weighed in a mass ratio of 90:27. The two were stirred at room temperature for 30 minutes. Nitrogen was evacuated three times to maintain a nitrogen atmosphere in the system. The temperature was slowly raised to 80°C. 1% initiator AIBN was dissolved in chlorobenzene and then added dropwise to the reaction system for 4 hours. After the reaction was completed, the mixture was precipitated with anhydrous ethanol to obtain a grafted product, which was dried and set aside.

[0081] (5) Hydrogenation:

[0082] The grafted product was prepared into a glue solution with a mass fraction of 5.5%, hydrogenated in a hydrogenation kettle, precipitated with anhydrous ethanol after the hydrogenation reaction was completed, and dried for later use;

[0083] (6) Plasticizing and vulcanization:

[0084] First, the hydrogenated grafted product and the uniformly mixed rubber material are plasticized on an open mill, 2.5 parts of a cross-linking agent based on the total mass of the grafted product and the uniformly mixed rubber material are added, the rubber is tapped 7-8 times, and rolled 4-5 times to obtain a uniform rubber material;

[0085] (7) Film packaging:

[0086] The uniform rubber material is sheeted to obtain a film, which is cooled for 24 hours and then vulcanized at a temperature of 135° C. and a pressure of 5 MPa for 30 minutes to obtain a fluorinated methacrylate grafted fluorinated HNBR ternary rubber, which is then packaged.

[0087] Furthermore, the vulcanization activator is sulfur; the small molecule plasticizer is TP-59; the compatibilizer is benzotriazole; the internal release agent is microcrystalline wax; and the dispersant is dispersant NAS.

[0088] A method for preparing a low-temperature and oil-resistant hydrogenated nitrile rubber compound comprises the following steps:

[0089] (a) Rubber mixing: hydrogenated nitrile rubber and modified fluorinated rubber are added to an open mill using a thin-pass plasticating method, and a reinforcing agent, a small molecule plasticizer, a compatibilizer, an internal release agent, and a dispersant are added and uniformly mixed;

[0090] (b) Compound curing: The mixed material is returned to the top of the roller gap and passed through the roller gap again, an internal release agent and a dispersant are added, the material is uniformly mixed, and triangular packages are formed to obtain the initial compound;

[0091] (c) Compound refining: adding the initial compound to the open mill, returning it to the top of the roll gap several times and re-passing the roll gap, and forming a triangular package to obtain a low-temperature and oil-resistant hydrogenated nitrile rubber compound; finally, the low-temperature and oil-resistant hydrogenated nitrile rubber compound is extruded and molded into a product.

[0092] Furthermore, the mixing times in step (a) are 7-8 times, and the mixing temperature is 50-60°C; the triangle-shaped packages in step (b) are 3-5 times; and further, the rubber material in step (c) is re-mixed 3-5 times, and the triangle-shaped packages are 3-5 times.

[0093] Example 2

[0094] Different from the above-mentioned embodiment 1, a low-temperature and oil-resistant hydrogenated nitrile rubber compound comprises the following raw materials in parts by weight:

[0095] 100 parts of hydrogenated nitrile rubber, 45 parts of modified fluorine-containing rubber, 20 parts of reinforcing agent, 20 parts of small molecule plasticizer, 20 parts of compatibilizer, 2 parts of internal release agent, and 2 parts of dispersant.

[0096] The modified fluorine-containing rubber is a fluorine-containing HNBR ternary rubber modified by fluoride grafting, and the reinforcing agent is modified tungsten disulfide.

[0097] Furthermore, the hydrogenated nitrile rubber is a blend of highly saturated hydrogenated nitrile rubber and carboxyl hydrogenated nitrile rubber, and the blending ratio of the two is 70:30.

[0098] Furthermore, the modified fluorine-containing rubber includes 80 parts of carboxyl hydrogenated nitrile rubber, 50 parts of ethylene glycol, 15 parts of zinc oxide, 10 parts of vulcanizing agent, 10 parts of cross-linking agent, and 5 parts of thermal oxidation inhibitor.

[0099] Preferably, the preparation of the modified fluorine-containing rubber comprises the following steps:

[0100] (1) Solution preparation: Using chlorobenzene as solvent, prepare a 7.5 wt% HNBR glue solution with carboxyl hydrogenated nitrile rubber, and divide the solution into two equal parts, namely glue solution A and glue solution B;

[0101] (2) Solution pretreatment:

[0102] Add carboxyl-terminated polyester resin to glue solution A, and mechanically stir at room temperature for 6 hours. After ethanol coagulation, dry in a 50°C oven to obtain a mixed glue.

[0103] (3) Pre-plasticization treatment:

[0104] The mixed rubber is masticated on an open mill, and ethylene glycol, zinc oxide, vulcanizing agent, cross-linking agent, and thermal oxidant are added in sequence. After each addition, the rubber is tapped 7-8 times. After adding zinc oxide, triangle packing is performed 7-8 times, and the rubber is rolled 4-5 times. After adding the thermal oxidant, the rubber is tapped 7-8 times and the rubber is rolled 4-5 times to obtain a uniformly mixed rubber material. The mastication conditions are normal pressure and 145°C.

[0105] (4) Grafting: Graphene oxide and trifluoroethyl methacrylate were uniformly stirred at a mass ratio of 0.45:1 to obtain a mixed liquid. Glue B and the mixed liquid were weighed at a mass ratio of 90:27, and the two were stirred at room temperature for 30 min. Nitrogen was evacuated 3 times to maintain a nitrogen atmosphere in the system. The temperature was slowly raised to 80°C. 1% initiator AIBN was dissolved in chlorobenzene and then added dropwise to the reaction system for 4 h. After the reaction was completed, the mixture was precipitated with anhydrous ethanol to obtain a grafted product, which was dried for later use.

[0106] (5) Hydrogenation: The grafted product is prepared into a glue solution with a mass fraction of 5.5%, and hydrogenated in a hydrogenation kettle. After the hydrogenation reaction is completed, it is precipitated with anhydrous ethanol and dried for later use;

[0107] (6) Plasticizing and vulcanization:

[0108] First, the hydrogenated grafted product and the uniformly mixed rubber material are plasticized on an open mill, 5 parts of a cross-linking agent based on the total mass of the grafted product and the uniformly mixed rubber material are added, the rubber is tapped 7-8 times, and rolled 4-5 times to obtain a uniform rubber material;

[0109] (7) Film packaging:

[0110] The uniform rubber material is sheeted to obtain a film, which is cooled for 24 hours and then vulcanized at a temperature of 135° C. and a pressure of 5 MPa for 30 minutes to obtain a fluorinated methacrylate grafted fluorinated HNBR ternary rubber, which is then packaged.

[0111] Other process flows refer to Example 1.

[0112] Example 3

[0113] Different from the above-mentioned embodiment 1, a low-temperature and oil-resistant hydrogenated nitrile rubber compound comprises the following raw materials in parts by weight:

[0114] 100 parts of hydrogenated nitrile rubber, 40 parts of modified fluorine-containing rubber, 17 parts of reinforcing agent, 15 parts of small molecule plasticizer, 15 parts of compatibilizer, 1.5 parts of internal release agent, and 1.2 parts of dispersant.

[0115] The modified fluorine-containing rubber is a fluorine-containing HNBR ternary rubber modified by fluoride grafting, and the reinforcing agent is modified tungsten disulfide.

[0116] Furthermore, the hydrogenated nitrile rubber is a blend of highly saturated hydrogenated nitrile rubber and carboxyl hydrogenated nitrile rubber, and the blending ratio of the two is 70:30.

[0117] Furthermore, the modified fluorine-containing rubber includes 75 parts of carboxyl hydrogenated nitrile rubber, 40 parts of ethylene glycol, 10 parts of zinc oxide, 6 parts of vulcanizing agent, 8 parts of cross-linking agent, and 3 parts of thermal oxidation inhibitor.

[0118] Preferably, the preparation of the modified fluorine-containing rubber comprises the following steps:

[0119] (1) Solution preparation: Using chlorobenzene as solvent, prepare a 7.5 wt% HNBR glue solution with carboxyl hydrogenated nitrile rubber, and divide the solution into two equal parts, namely glue solution A and glue solution B;

[0120] (2) Solution pretreatment:

[0121] Add carboxyl-terminated polyester resin to glue solution A, and mechanically stir at room temperature for 6 hours. After ethanol coagulation, dry in a 50°C oven to obtain a mixed glue.

[0122] (3) Pre-plasticization treatment:

[0123] The mixed rubber is masticated on an open mill, and ethylene glycol, zinc oxide, vulcanizing agent, cross-linking agent, and thermal oxidant are added in sequence. After each addition, the rubber is tapped 7-8 times. After adding zinc oxide, triangle packing is performed 7-8 times, and the rubber is rolled 4-5 times. After adding the thermal oxidant, the rubber is tapped 7-8 times and the rubber is rolled 4-5 times to obtain a uniformly mixed rubber material. The mastication conditions are normal pressure and 145°C.

[0124] (4) Grafting: Graphene oxide and trifluoroethyl methacrylate were uniformly stirred at a mass ratio of 0.45:1 to obtain a mixed liquid. Glue B and the mixed liquid were weighed at a mass ratio of 90:27, and the two were stirred at room temperature for 30 min. Nitrogen was evacuated 3 times to maintain a nitrogen atmosphere in the system. The temperature was slowly raised to 80°C. 1% initiator AIBN was dissolved in chlorobenzene and then added dropwise to the reaction system for 4 h. After the reaction was completed, the mixture was precipitated with anhydrous ethanol to obtain a grafted product, which was dried for later use.

[0125] (5) Hydrogenation: The grafted product is prepared into a glue solution with a mass fraction of 5.5%, and hydrogenated in a hydrogenation kettle. After the hydrogenation reaction is completed, it is precipitated with anhydrous ethanol and dried for later use;

[0126] (6) Plasticizing and vulcanization:

[0127] First, the hydrogenated grafted product and the uniformly mixed rubber material are masticated on an open mill, 3.5 parts of a cross-linking agent based on the total mass of the grafted product and the uniformly mixed rubber material are added, the rubber is tapped 7-8 times, and rolled 4-5 times to obtain a uniform rubber material;

[0128] (7) Film packaging:

[0129] The uniform rubber material is sheeted to obtain a film, which is cooled for 24 hours and then vulcanized at a temperature of 135° C. and a pressure of 5 MPa for 30 minutes to obtain a fluorinated methacrylate grafted fluorinated HNBR ternary rubber, which is then packaged.

[0130] Other process flows refer to Example 1.

[0131] Comparative Example 1

[0132] Different from the above-mentioned embodiment 3, the hydrogenated nitrile rubber compound comprises the following raw materials in parts by weight:

[0133] 100 parts of hydrogenated nitrile rubber, 40 parts of modified fluorine-containing rubber, 17 parts of reinforcing agent, 15 parts of small molecule plasticizer, 15 parts of compatibilizer, 1.5 parts of internal release agent, and 1.2 parts of dispersant.

[0134] The preparation of the modified fluorine-containing rubber comprises the following steps:

[0135] (1) Solution preparation: Using chlorobenzene as solvent, prepare a 7.5 wt% HNBR glue solution with carboxyl hydrogenated nitrile rubber, and divide the solution into two equal parts, namely glue solution A and glue solution B;

[0136] (2) Solution pretreatment:

[0137] Add carboxyl-terminated polyester resin to glue solution A, and mechanically stir at room temperature for 6 hours. After ethanol coagulation, dry in a 50°C oven to obtain a mixed glue.

[0138] (3) Pre-plasticization treatment:

[0139] The mixed rubber is plasticized on an open mill, and ethylene glycol, zinc oxide, vulcanizing agent, cross-linking agent, and thermal oxidant are added in sequence. After each addition, the rubber is tapped 7-8 times. After adding zinc oxide, triangle bags are made 7-8 times, and rolls are rolled 4-5 times. After adding the cross-linking agent, the rubber is tapped 7-8 times and rolled 4-5 times to obtain a uniformly mixed rubber material.

[0140] (4) Synchronous processing:

[0141] Weigh glue solution B and refer to the above processing steps of glue solution A to obtain a uniformly mixed glue material B;

[0142] (5) Hydrogenation:

[0143] The grafted product was prepared into a glue solution with a mass fraction of 5.5%, hydrogenated in a hydrogenation kettle, precipitated with anhydrous ethanol after the hydrogenation reaction was completed, and dried for later use;

[0144] (6) Plasticizing and vulcanization:

[0145] First, the hydrogenated uniformly mixed rubber material B and the uniformly mixed rubber material are plasticized on an open mill, 3.5 parts of a cross-linking agent based on the total mass of the rubber material are added, the rubber material is tapped 7-8 times, and rolled 4-5 times to obtain a uniform rubber material;

[0146] (7) Film packaging:

[0147] The uniform rubber material is sheeted to obtain a film, which is cooled for 24 hours and then vulcanized at a temperature of 135° C. and a pressure of 5 MPa for 30 minutes to obtain a fluorinated methacrylate grafted fluorinated HNBR ternary rubber, which is then packaged.

[0148] For other processes and parameters, refer to Example 3.

[0149] Comparative Example 2

[0150] Different from the above-mentioned embodiment 3, the hydrogenated nitrile rubber compound comprises the following raw materials in parts by weight:

[0151] 100 parts of hydrogenated nitrile rubber, 40 parts of modified fluorine-containing rubber, 17 parts of reinforcing agent, 15 parts of small molecule plasticizer, 15 parts of compatibilizer, 1.5 parts of internal release agent, and 1.2 parts of dispersant.

[0152] The preparation of the modified fluorine-containing rubber comprises the following steps:

[0153] (1) Solution configuration:

[0154] Using chlorobenzene as solvent, carboxyl hydrogenated nitrile rubber was prepared into HNBR glue with a mass fraction of 7.5wt%, and the HNBR glue was evenly divided into two parts, namely glue A and glue B.

[0155] (2) Grafting:

[0156] Graphene oxide and trifluoroethyl methacrylate were uniformly stirred in a mass ratio of 0.45:1 to obtain a mixed liquid. Glue B and the mixed liquid, and glue A and the mixed liquid were weighed in a mass ratio of 90:27, respectively. The two were stirred at room temperature for 30 minutes, nitrogen was evacuated three times, and the system was kept in a nitrogen atmosphere. The temperature was slowly raised to 80°C, 1% initiator AIBN was dissolved in chlorobenzene and then added dropwise to the reaction system for 4 hours. After the reaction was completed, the mixture was precipitated with anhydrous ethanol to obtain grafted product B and grafted product A, which were dried and set aside.

[0157] (5) Hydrogenation:

[0158] The grafted product was prepared into a glue solution with a mass fraction of 5.5%, hydrogenated in a hydrogenation kettle, precipitated with anhydrous ethanol after the hydrogenation reaction was completed, and dried for later use;

[0159] (6) Plasticizing and vulcanization:

[0160] First, the hydrogenated graft product B and the graft product A are masticated on an open mill, 3.5 parts of a cross-linking agent based on the total mass of the rubber are added, the rubber is tapped 7-8 times, and rolled 4-5 times to obtain a uniform rubber;

[0161] (7) Film packaging:

[0162] The uniform rubber material was sheeted to obtain a film, which was cooled for 24 hours and then vulcanized at 135°C and 5 MPa for 30 minutes to obtain a fluorinated methacrylate graft-modified fluorinated HNBR ternary rubber, which was then packaged. Other processes and parameters were similar to those in Example 3.

[0163] Comparative Example 3

[0164] Unlike Comparative Example 2, in step (2), deionized water and trifluoroethyl methacrylate were directly stirred at a mass ratio of 0.45:1 to obtain a mixed liquid. Glue B and glue A were then weighed separately at a mass ratio of 90:27 to the mixed liquid. Other processes and parameters were similar to those in Comparative Example 2.

[0165] Comparative Example 4

[0166] Unlike Comparative Example 2, in step (2), graphene oxide and deionized water were directly stirred at a mass ratio of 0.45:1 to obtain a mixed liquid, and then glue B and glue A were weighed and added to the mixed liquid at a mass ratio of 90:27. Other processes and parameters were the same as those in Comparative Example 2.

[0167] Comparative Example 5

[0168] Different from the above-mentioned embodiment 1, the hydrogenated nitrile rubber compound comprises the following raw materials in parts by weight:

[0169] 100 parts of hydrogenated nitrile rubber, 40 parts of modified fluorine-containing rubber, 17 parts of reinforcing agent, 15 parts of small molecule plasticizer, 15 parts of compatibilizer, 1.5 parts of internal release agent, and 1.2 parts of dispersant.

[0170] The reinforcing agent is modified tungsten disulfide, and the preparation method of the modified tungsten disulfide comprises the following steps:

[0171] Under nitrogen atmosphere, hydroxylamine hydrochloride, sodium tungstate dihydrate, and thiourea were weighed in a molar ratio of 1:5:2, and stirred at a speed of 600-850rpm for 0.5-2h to obtain a mixed solution A; 1.5wt% of a siloxane coupling agent was added, and the siloxane coupling agent was KH550 to obtain a mixed solution B; the mixed solution B was added dropwise to the mixed solution A at a delivery rate of 0.15mL / min, and stirred at the same speed, and then the pH was adjusted to 6 with ammonia water. After stirring for 0.5h, the mixture was transferred to a reactor and reacted at 180℃ for 16h. After naturally cooling to room temperature, ethanol was condensed, and the sediment was dried at 60℃ to obtain modified tungsten disulfide. The modified tungsten disulfide was photographed by scanning electron microscopy, as shown in FIG. Figure 1 (b) shown.

[0172] For other processes and parameters, refer to Example 3.

[0173] Comparative Example 6

[0174] Different from the above-mentioned embodiment 3, the hydrogenated nitrile rubber compound comprises the following raw materials in parts by weight:

[0175] 100 parts of hydrogenated nitrile rubber, 40 parts of modified fluorine-containing rubber, 17 parts of reinforcing agent, 15 parts of small molecule plasticizer, 15 parts of compatibilizer, 1.5 parts of internal release agent, and 1.2 parts of dispersant.

[0176] The reinforcing agent is tungsten disulfide, and the preparation method of the tungsten disulfide comprises the following steps:

[0177] Under nitrogen atmosphere, hydroxylamine hydrochloride, sodium tungstate dihydrate, and thiourea were weighed in a molar ratio of 1:5:2 and stirred at 600-850 rpm for 0.5-2 hours to obtain a mixed solution A. The mixed solution A was transferred to a reactor and reacted at 180°C for 16 hours. After naturally cooling to room temperature, ethanol was condensed and the sediment was dried at 60°C to obtain tungsten disulfide. Before adding the rubber material for blending, the tungsten disulfide was purified by calcining at 800°C and photographed by scanning electron microscopy. Figure 1 As shown in (a).

[0178] For other processes and parameters, refer to Example 3.

[0179] Performance Testing

[0180] Examples 1 to 3 and Comparative Examples 1 to 6 were tested according to the physical property test method in Table 1. The results are shown in Table 2.

[0181] Table 1 Test methods for physical properties of rubber compounds

[0182]

[0183] The oil resistance test was conducted with reference to GB / T 1690-2010, "Test Method for Liquid Resistance of Vulcanized Rubber or Thermoplastic Rubber," using 10# diesel as the standard oil. The specific procedure involved placing each hydrogenated nitrile rubber vulcanizate sample from each example in 10# diesel and immersing it at 150°C for 24 hours. The volume change was then recorded to determine the standard oil resistance volume change rate.

[0184] Table 2 Performance test comparison results

[0185]

[0186] It can be seen from the test data in Table 1 that after the optimized formula and process improvement of the present invention, the overall comprehensive performance of the hydrogenated nitrile rubber compound is significantly improved, including tensile properties, oil resistance, compression deformation properties and low temperature performance.

[0187] In terms of low-temperature resistance, conventional rubbers have poor low-temperature resistance and cannot meet the requirements for normal operation of the products produced at -45°C. The modified tungsten disulfide and modified fluororubber used in the present invention not only help improve mechanical strength, but also enable the rubber to maintain good performance in extremely low-temperature environments, with the rubber's low-temperature performance exceeding -60°C. The modified fluororubber used has a certain "lubricating" effect due to the formation of the "carboxyl-terminated polyester resin-alcohol-HNBR" ternary polymer system. In the rubber, this ternary polymer can reduce the friction between chain segments in the cross-linked network, thereby increasing elongation at break and improving comprehensive mechanical properties. Furthermore, the ternary polymer present in the rubber cross-linking system can prevent compression deformation. The use of graphene oxide not only promotes the vulcanization process of the rubber in the system and improves its physical properties; it also utilizes its surface functional groups to attract the electron cloud density of the nitrile group in the HNBR rubber system, thereby reducing the impact of excessive nitrile content on low-temperature resistance. Furthermore, the use of fluorine in trifluoroethyl methacrylate can be understood as surrounding the graphene oxide wrinkles on the outside of the molecule, ensuring its oil resistance. Furthermore, in the low-temperature brittleness test, the actual reinforcement dosage of Comparative Examples 5-6 was insufficient due to the poor interfacial bonding of the modified tungsten disulfide in the rubber, resulting in brittle cracking of the samples.

[0188] As for oil resistance, the HNBR vulcanizate of the present invention has a volume change rate of standard oil resistance and a volume change rate of liquid resistance in 10# diesel that are better than the standard requirements. In Comparative Example 1, the "carboxyl-terminated polyester resin-alcohol-HNBR" ternary polymer system used is connected together by chemical polymerization, not a simple physical blend, which can prevent the test oil from precipitating to a certain extent; but compared with the ternary polymer system, the introduction of fluorine atoms has a greater effect on the oil resistance test of the rubber. There is a grafted reactant modified fluorine-containing rubber between HNBR, and there is a strong force between its molecules, and the glue B is also coated with a layer of graphene oxide film, which will cause the volume expansion rate of the vulcanizate to decrease in the standard test oil, thereby increasing the oil resistance. In Comparative Example 4, due to the lack of fluorine atoms, the oil resistance test of the rubber cannot meet the relevant standards. Fluorine atoms are introduced into the hydrogenated nitrile rubber molecular chain with a certain degree of hydrogenation to prepare fluorine-containing rubber materials. While ensuring that the proportion of carbon-carbon double bonds does not affect the low-temperature resistance, it helps the oil resistance of the material. While the ternary polymer system is being formed, the fluorine-containing elements on the rubber surface not only improve the oil resistance of hydrogenated nitrile rubber and give it good hydrophobic properties, but also maintain the excellent tensile properties and low-temperature resistance of HNBR.

[0189] While the present invention has been disclosed above with reference to preferred embodiments, this is not intended to limit the present invention. Persons skilled in the art will readily appreciate that various modifications and variations can be made without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention shall be determined by the claims.

Claims

1. A low-temperature and oil-resistant hydrogenated nitrile rubber compound, characterized in that: The raw materials include the following parts by weight: 100 parts of hydrogenated nitrile rubber, 35-45 parts of modified fluorinated rubber, 15-20 parts of reinforcing agent, 10-20 parts of small molecule plasticizer, 10-20 parts of compatibilizer, 0.5-2 parts of internal release agent, and 0.5-2 parts of dispersant; The modified fluorine-containing rubber is a fluorine-containing HNBR ternary rubber grafted with fluoride, and the reinforcing agent is modified tungsten disulfide; The modified tungsten disulfide is prepared by hydrothermal reaction of hydroxylamine hydrochloride, sodium tungstate dihydrate, thiourea and graphene oxide; The preparation of the modified fluorine-containing rubber comprises the following steps: (1) Solution preparation: Using chlorobenzene as solvent, prepare a 7.5 wt% HNBR glue solution with carboxyl hydrogenated nitrile rubber, and divide the solution into two equal parts, namely glue solution A and glue solution B; (2) Solution pretreatment: Add carboxyl-terminated polyester resin to glue solution A, and mechanically stir at room temperature for 6 hours. After ethanol coagulation, dry in a 50°C oven to obtain a mixed glue. (3) Pre-plasticization treatment: The mixed rubber is masticated on an open mill, and ethylene glycol, zinc oxide, vulcanizing agent, cross-linking agent, and thermal oxidant are added in sequence. After each addition, the rubber is tapped 7-8 times. After adding zinc oxide, triangle packing is performed 7-8 times, and the rubber is rolled 4-5 times. After adding the thermal oxidant, the rubber is tapped 7-8 times and the rubber is rolled 4-5 times to obtain a uniformly mixed rubber material. The mastication conditions are normal pressure and 145°C. (4) Grafting: Graphene oxide and trifluoroethyl methacrylate were uniformly stirred in a mass ratio of 0.45:1 to obtain a mixed liquid. Glue B and the mixed liquid were then weighed in a mass ratio of 90:

27. The two were stirred at room temperature for 30 minutes. Nitrogen was evacuated three times to maintain a nitrogen atmosphere in the system. The temperature was slowly raised to 80°C. 1% initiator AIBN was dissolved in chlorobenzene and then added dropwise to the reaction system for 4 hours. After the reaction was completed, the mixture was precipitated with anhydrous ethanol to obtain a grafted product, which was dried and set aside. (5) Hydrogenation: The grafted product was prepared into a glue solution with a mass fraction of 5.5%, hydrogenated in a hydrogenation kettle, precipitated with anhydrous ethanol after the hydrogenation reaction was completed, and dried for later use; (6) Plasticizing and vulcanization: First, the hydrogenated grafted product and the uniformly mixed rubber material are plasticized on an open mill, 2.5-5 parts of a cross-linking agent based on the total mass of the grafted product and the uniformly mixed rubber material are added, the rubber is tapped 7-8 times, and the rubber is rolled 4-5 times to obtain a uniform rubber material; (7) Film packaging: The uniform rubber material is sheeted to obtain a film, which is cooled for 24 hours and then vulcanized at a temperature of 135° C. and a pressure of 5 MPa for 30 minutes to obtain a fluorinated methacrylate grafted fluorinated HNBR ternary rubber, which is then packaged.

2. A low temperature and oil resistant hydrogenated nitrile rubber compound according to claim 1, characterized in that: The hydrogenated nitrile rubber is a blend of high-saturation hydrogenated nitrile rubber and carboxyl hydrogenated nitrile rubber, and the blending ratio of the two is 70:

30.

3. A low temperature and oil resistant hydrogenated nitrile rubber compound according to claim 1, characterized in that: The modified fluorine-containing rubber comprises 60-80 parts of carboxyl hydrogenated nitrile rubber, 35-50 parts of ethylene glycol, 5-15 parts of zinc oxide, 5-10 parts of vulcanizing agent, 5-10 parts of crosslinking agent and 1-5 parts of thermal oxidation inhibitor.

4. A low temperature and oil resistant hydrogenated nitrile rubber compound according to claim 3, characterized in that: The vulcanizing agent is one or more of sulfur, selenium, and tellurium; the cross-linking agent is one of polymaleimide and DCP; and the thermal oxidation inhibitor is calcium stearate.

5. The low-temperature and oil-resistant hydrogenated nitrile rubber compound according to claim 1, characterized in that: The small molecule plasticizer is one of TP-59, DBP, and TP-90B; the compatibilizer is benzotriazole; the internal release agent is microcrystalline wax; and the dispersant is one of dispersant NAS, polycarboxylate, and polyethylene wax.

6. A method for preparing the low-temperature and oil-resistant hydrogenated nitrile rubber compound according to any one of claims 1 to 5, characterized in that: The following steps are involved: (a) Rubber mixing: hydrogenated nitrile rubber and modified fluorinated rubber are added to an open mill using a thin-pass plasticating method, and a reinforcing agent, a small molecule plasticizer, a compatibilizer, an internal release agent, and a dispersant are added and uniformly mixed; (b) Compound curing: The mixed material is returned to the top of the roller gap and passed through the roller gap again, an internal release agent and a dispersant are added, the material is uniformly mixed, and triangular packages are formed to obtain the initial compound; (c) Compound refining: adding the initial compound to the open mill, returning it to the top of the roll gap several times and re-passing the roll gap, and forming a triangular package to obtain a low-temperature and oil-resistant hydrogenated nitrile rubber compound; finally, the low-temperature and oil-resistant hydrogenated nitrile rubber compound is extruded and molded into a product.

7. The method for preparing the low-temperature and oil-resistant hydrogenated nitrile rubber compound according to claim 6, characterized in that: The mixing times in the step (a) are 7-8 times, and the mixing temperature is 50-60° C.; the triangle packing times in the step (b) are 3-5 times.

8. The method for preparing the low-temperature and oil-resistant hydrogenated nitrile rubber compound according to claim 6, characterized in that: In the step (c), the rubber material is re-mixed 3-5 times and the triangular packages are formed 3-5 times.

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