Hydrogenated nitrile rubber raw material composition and hydrogenated nitrile rubber and method for producing the same

Abstract

The application provides a hydrogenated fluorinated nitrile rubber raw material composition and a hydrogenated fluorinated nitrile rubber and a preparation method thereof. The hydrogenated fluorinated nitrile rubber raw material composition comprises a first component and a second component; the first component comprises acrylonitrile and butadiene monomers; and the second component comprises a functional monomer. The hydrogenated fluorinated nitrile rubber can simultaneously have good low-temperature resistance and oil and gas medium resistance.

Description

Technical Field

[0001] This invention belongs to the field of rubber technology, specifically relating to a fluorinated hydrogenated nitrile butadiene rubber raw material composition and a fluorinated hydrogenated nitrile butadiene rubber and its preparation method. Background Technology

[0002] For submersible screw pumps in oil exploration equipment, the stator rubber is a key component determining whether the structure can operate efficiently. Due to the demands of the working environment, the stator rubber must not only withstand the requirements of operation in extremely cold conditions but also resist corrosive media found in oil wells, such as small-molecule acids, amine compounds, methane, and ozone commonly found in oil fields. Therefore, the stator rubber's resistance to oil and gas media is paramount, placing extremely high demands on the rubber material's resistance to oil and gas media and its low-temperature resistance. Thus, balancing the low-temperature resistance and oil and gas media resistance of HNBR (hydrogen-free rubber) is a crucial challenge. Summary of the Invention

[0003] To address the aforementioned technical problems, the present invention aims to provide a fluorinated hydrogenated nitrile butadiene rubber raw material composition, a fluorinated hydrogenated nitrile butadiene rubber, and a method for preparing the same, wherein the fluorinated hydrogenated nitrile butadiene rubber can simultaneously achieve good low-temperature resistance and resistance to oil and gas media.

[0004] To achieve the above objectives, the present invention provides a fluorinated hydrogenated nitrile rubber raw material composition, comprising a first component and a second component; the first component comprises acrylonitrile and butadiene monomers; the second component comprises a functionalized monomer having the structure shown in Formula I.

[0005]

[0006] In Equation I, R is C6~C 12 The straight-chain alkyl group; B is a butadiene segment; L, m and n represent the number of repeating units, L≥1, n≥1, m≥1, and L, m and n are positive integers.

[0007] First, the aforementioned functionalized monomers have high reactivity. When used as raw material monomers for the preparation of HNBR, fluorine atoms, hydroxyl groups, ether groups, and long-chain alkyl groups can be introduced into the hydrogenated nitrile rubber molecular chain in a macromolecular form. This structure fully utilizes the "cumulative effect" of macromolecules during hydrogenation, giving full play to the "atomic effect" of fluorine atoms, the "group effect" of hydroxyl and ether groups, and the "structural effect" of long-chain alkyl branching. This can effectively destroy the crystallinity of HNBR and greatly reduce the glass transition temperature (Tg) of HNBR. The vulcanized products obtained through subsequent low-temperature plasticizing modification can be used for oil well exploration operations in extremely cold weather.

[0008] Secondly, when this functionalized monomer is subsequently used as a raw material monomer for the preparation of HNBR, the introduction of its long-chain alkyl branched structure and flexible segment ether bonds can effectively reduce the formation of gel during the synthesis of fluorinated nitrile butadiene rubber, ensure the stability of the polymerization process, effectively improve the stability of fluorine atoms in HNBR, significantly improve the oil and gas media resistance and weather resistance of HNBR, and reduce the volume deformation of HNBR in oilfield media.

[0009] Furthermore, the number-average molecular weight of the functionalized monomers is 3000–4000.

[0010] Furthermore, the weight ratio of acrylonitrile, butadiene monomer, and functionalized monomer is 30–38: 58–69: 1.0–4.0.

[0011] Furthermore, the fluorinated hydrogenated nitrile butadiene rubber raw material composition also includes a third component; the third component includes a terminator.

[0012] Furthermore, the first component also includes deionized water, emulsifier, activator, molecular weight regulator, oxygen scavenger, and first initiator.

[0013] Furthermore, the weight ratio of deionized water, emulsifier, activator, acrylonitrile, molecular weight regulator, oxygen scavenger, butadiene monomer, functionalized monomer and terminator is 200-400: 2.0-6.0: 0.1-0.3: 30-38: 0.5-3.0: 0.01-0.05: 58-69: 1.0-4.0: 0.3-0.5.

[0014] Further, the emulsifier is an emulsifier stable in acidic media. Preferably, the emulsifier is selected from one or a combination of two or more of alkyl sulfate emulsifiers, alkyl sulfonate emulsifiers, and aryl sulfonate emulsifiers. In some optional embodiments, the emulsifier is selected from potassium rosinate soap, methyl oleate soap, sodium pyrophosphate, fatty acids, disproportionated potassium rosinate, and sodium fatty acid C8-C6. 20 One or more of sodium alkyl sulfates are used. The amount of emulsifier added is the conventional amount used in the art, and is not particularly limited in this invention. It is 2.0 to 6.0 parts, more preferably 4.0 to 5.0 parts, based on 100 parts of the total weight of monomers (the total weight of acrylonitrile, butadiene monomer and functionalized monomer).

[0015] Furthermore, the first initiator is a redox initiator, such as a combination of one or more of cumene hydroperoxide, dicumene hydroperoxide, isopropyl tert-butyl hydroperoxide, and isopropyl n-butyl hydroperoxide, preferably dicumene hydroperoxide. The amount of initiator used is conventional in the art and is not particularly limited in this invention. It is 0.05 to 0.40 parts, more preferably 0.10 to 0.25 parts, based on 100 parts of the total weight of monomers (the total weight of acrylonitrile, butadiene monomer, and functionalized monomer).

[0016] Furthermore, the activator is selected from one or more combinations of sodium formaldehyde sulfoxylate, ferrous sulfate, tetrasodium EDTA (tetrasodium EDTA salt), and sodium ferric EDTA (sodium ferric EDTA salt). The amount of activator used is the conventional amount used in the art, and the present invention does not make any particular limitation. It is 0.1 to 0.3 parts, more preferably 0.15 to 0.20 parts, based on 100 parts of the total weight of monomers (the total weight of acrylonitrile, butadiene monomer, and functionalized monomer).

[0017] Furthermore, the oxygen scavenger is selected from one or more combinations of sodium dithionite, dimethyl ketoxime, isoascorbic acid, carbazide, and N-isopropylhydroxylamine, with sodium dithionite being preferred. The amount of oxygen scavenger used is a conventional amount in the art, and is not particularly limited in this invention, but is 0.01 to 0.05 parts per 100 parts of the total weight of monomers (acrylonitrile, butadiene monomers, and functionalized monomers).

[0018] Furthermore, the terminator is selected from one or more combinations of hydroxylamine sulfate, diethylhydroxylamine, 2,5-pentanebutylquinone, sodium dimethyl dithiocarbamate (sodium thimerosi), sodium nitrite (NaNO2), actinol reagent, and p-aminoazobenzene, with sodium thimerosi being preferred. The amount of terminator used is conventional in the art and is not particularly limited in this invention; it is 0.30 to 0.50 parts per 100 parts of the total weight of monomers (acrylonitrile, butadiene monomers, and functionalized monomers).

[0019] Furthermore, the molecular weight regulator is selected from tert-dodecyl mercaptan and / or dodecyl mercaptan, preferably tert-dodecyl mercaptan. The amount of molecular weight regulator used is the conventional amount used in the art, and the present invention does not particularly limit it, but it is 0.5 to 3.0 parts, preferably 1 to 2 parts, based on 100 parts of the total weight of monomers (the total weight of acrylonitrile, butadiene monomer and functionalized monomer).

[0020] This invention also provides a method for preparing hydrogenated fluorinated nitrile butadiene rubber, which uses the aforementioned raw material composition to prepare hydrogenated fluorinated nitrile butadiene rubber; the preparation method includes the following steps:

[0021] The first component is mixed to carry out the first polymerization reaction in the first stage. When the acrylonitrile conversion rate reaches 35% to 40%, the second component is added to the system to carry out the first polymerization reaction in the second stage. When the acrylonitrile conversion rate reaches 85% to 90%, the polymerization is terminated to obtain functionalized nitrile rubber.

[0022] Functionalized nitrile rubber is dissolved in an organic solvent to form a solution, and the solution is then subjected to a hydrogenation reaction under the action of a catalyst to obtain fluorinated hydrogenated nitrile rubber.

[0023] First, the aforementioned functionalized monomers have high reactivity. When used as raw material monomers for the preparation of HNBR, fluorine atoms, hydroxyl groups, ether groups, and long-chain alkyl groups can be introduced into the hydrogenated nitrile rubber molecular chain in a macromolecular form. This structure fully utilizes the "cumulative effect" of macromolecules during hydrogenation, giving full play to the "atomic effect" of fluorine atoms, the "group effect" of hydroxyl and ether groups, and the "structural effect" of long-chain alkyl branching. This can effectively destroy the crystallinity of HNBR and greatly reduce the glass transition temperature (Tg) of HNBR.

[0024] Secondly, when this functionalized monomer is subsequently used as a raw material monomer for the preparation of HNBR, the introduction of its long-chain alkyl branched structure and flexible segment ether bonds can effectively reduce the formation of gel during the synthesis of fluorinated nitrile butadiene rubber, ensure the stability of the polymerization process, effectively improve the stability of fluorine atoms in HNBR, significantly improve the oil and gas media resistance and weather resistance of HNBR, and reduce the volume deformation of HNBR in oilfield media.

[0025] Furthermore, this preparation method is green and environmentally friendly, has significant modification effects, stable processes, and minimal product quality fluctuations, making it suitable for industrial production.

[0026] Furthermore, the reaction temperature of the first polymerization reaction is 4–11 °C.

[0027] Furthermore, the hydrogenation reaction is carried out at a pressure of 13–16 MPa, a temperature of 120–130 °C, and a time of 10–13 h.

[0028] In one optional embodiment, the preparation method of the above-mentioned hydrogenated fluorinated nitrile rubber includes the following steps:

[0029] Step 1: Add deionized water, emulsifier, activator, acrylonitrile, and molecular weight regulator to the polymerization reactor. After vacuuming and nitrogen purging, add oxygen scavenger and butadiene monomer. Add the first initiator at low temperature (4-11℃) to carry out the first stage of polymerization reaction. When the acrylonitrile polymerization conversion rate reaches 35%-40%, add functionalized monomer to the system to carry out the second stage of polymerization reaction. When the acrylonitrile conversion rate reaches 85%-90%, add terminator to the system to terminate the polymerization. Discharge the polymerization product system and allow it to coagulate, wash, and dry to obtain functionalized nitrile rubber.

[0030] Step 2: Dissolve the above-mentioned functionalized nitrile rubber in an organic solvent (e.g., chlorobenzene solution) to prepare a glue solution. Then, add the glue solution to a reaction vessel and introduce an inert gas (e.g., nitrogen) to purge the air from the reaction vessel. Next, purge the inert gas (e.g., nitrogen) from the reaction vessel with hydrogen. Then, under the protection of an inert gas (e.g., nitrogen), add a toluene solution of Grubbs II catalyst. Pressurize and heat to carry out a hydrogenation reaction. After the reaction is completed, cool the hydrogenation product system and allow it to condense and dry to obtain fluorinated hydrogenated nitrile rubber.

[0031] Furthermore, the gel content of the functionalized nitrile rubber is <1.4%.

[0032] Furthermore, the weight ratio of functionalized nitrile rubber to the toluene solution of Grubbs II catalyst is 100:0.1–0.3. The weight percentage of functionalized nitrile rubber in the solution is 3%–5%. The weight concentration of Grubbs II catalyst in the toluene solution is 6%–12%.

[0033] Furthermore, the treatment time for removing the inert gas from the reactor with hydrogen is 20-30 minutes; the pressure is increased to 13-16 MPa; and the temperature is increased to 120-130℃.

[0034] Furthermore, the degree of hydrogenation (HD) of the fluorinated hydrogenated nitrile butadiene rubber is ≥96%.

[0035] Furthermore, the polymerization reactions of the present invention are carried out in an oxygen-free, anhydrous, and inert gas environment. The inert gas is nitrogen or a gas of a Group O element in the periodic table other than radon, with nitrogen being preferred.

[0036] Furthermore, the reactor of the present invention can be a loop reactor or a batch reactor, preferably a batch reactor.

[0037] Furthermore, the pressurization of the present invention is achieved by adding hydrogen gas. The amount of hydrogen gas added is well known to those skilled in the art, and the amount of hydrogen gas added is within the conventional addition range in the prior art. The present invention does not impose any particular limitation.

[0038] In a preferred embodiment, the functionalized monomer in the second component is prepared by the following steps: mixing diethylene glycol monovinyl ether, a first solvent, trifluorovinyl acetate, a structure modifier, and a second initiator to carry out a second polymerization reaction, then adding butadiene monomer to the system to carry out an end-capping reaction, terminating the polymerization when no free monomer is present, to obtain a fluorinated random copolymer; mixing the fluorinated random copolymer, α-olefin, ethylene, a main catalyst, a co-catalyst, and a second solvent to carry out a third polymerization reaction, to obtain the functionalized monomer.

[0039] Furthermore, the weight ratio of diethylene glycol monovinyl ether, the first solvent, trifluorovinyl acetate, the structure modifier, and the butadiene monomer is 100:200-300:40-50:0.1-0.5:1.0-3.0.

[0040] Furthermore, the weight ratio of the second solvent, co-catalyst, functionalized random copolymer, α-olefin, and main catalyst is 200–300:15–20:3–7:5–10:1.

[0041] Furthermore, the α-olefin is selected from one or more combinations of 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, and 1-dodecene, preferably 1-octene.

[0042] Furthermore, the main catalyst is a nickel-based complex catalyst, selected from one or more of (1-naphthyl)[8-(diphenylphosphine)quinoline]nickel chloride, trans-phenylbromo(di(triphenylphosphine))nickel and 2,5-dicarboxypyrrole dibromide, preferably trans-phenylbromo(di(triphenylphosphine))nickel.

[0043] Furthermore, the second initiator is a hydrocarbon-based monolithium compound with the general structural formula RLi, wherein R is selected from one or more combinations of C1-20 saturated aliphatic hydrocarbon groups, C1-20 alicyclic hydrocarbon groups, and C1-20 aromatic hydrocarbon groups (two or more combinations refer to complex groups of the above groups), for example, one or more combinations of n-butyllithium, sec-butyllithium, methylbutyllithium, phenylbutyllithium, naphthenelithium, cyclohexyllithium, and dodecyllithium, preferably n-butyllithium. The amount of the second initiator added is determined by the molecular weight of the designed polymer, which is known to those skilled in the art and will not be elaborated here.

[0044] Furthermore, the cocatalyst is an alkylaluminoxane cocatalyst, such as methylaluminoxane (MAO) and / or ethylaluminoxane (EAO), with methylaluminoxane being preferred.

[0045] Furthermore, the structure modifier is selected from one or more combinations of diethylene glycol dimethyl ether (2G), tetrahydrofuran (THF), diethyl ether, ethyl methyl ether, anisole, diphenyl ether, diethylene glycol dimethyl ether (DME), and triethylamine.

[0046] Furthermore, the first solvent and the second solvent are each independently selected from one or more combinations of cyclohexane, carbon disulfide (CS2), nitrobenzene, petroleum ether, tetrachloroethane, toluene, and xylene, with cyclohexane being preferred.

[0047] In one optional embodiment, the method for preparing the above-mentioned functionalized monomer includes the following steps:

[0048] Step 1: In the polymerization reactor, argon gas is introduced to purge the system. The first solvent, diethylene glycol monovinyl ether, trifluorovinyl acetate, structure modifier, and second initiator are added to the polymerization reactor in sequence. The temperature is raised to 50-60℃ and a second polymerization reaction is carried out for 60-70 minutes. Then, butadiene monomer is added to the polymerization reactor and a capping reaction is carried out for 20-30 minutes. The polymerization is terminated when no free monomers are present, and a glue solution is obtained. The glue solution is then wet-coagulated and dried to obtain a fluorinated random copolymer.

[0049] Step 2: Inert gas is introduced into the high-pressure reactor for purging, a second solvent is added, and the temperature is raised to 80-90°C. A co-catalyst is added while stirring (600-700 rpm for 20-30 min). Stirring continues under inert gas protection. Then, the fluorinated random copolymer, α-olefin, and main catalyst are added to the high-pressure reactor in sequence. At this time, ethylene is introduced to carry out the third reaction (reaction pressure 13-16 MPa; time 4.0-6.0 h). After the reaction is completed, the product is centrifuged and dried to obtain the aforementioned functionalized monomer.

[0050] This invention also provides a fluorinated hydrogenated nitrile butadiene rubber, which is prepared by the aforementioned method. For the reasons stated above, this fluorinated hydrogenated nitrile butadiene rubber can simultaneously achieve excellent low-temperature resistance and resistance to oil and gas media. Attached Figure Description

[0051] Figure 1 The infrared spectrum of the functionalized monomer in Embodiment 1 of the present invention is shown. Detailed Implementation

[0052] In order to provide a clearer understanding of the technical features, objectives and beneficial effects of the present invention, the technical solution of the present invention will now be described in detail below, but it should not be construed as limiting the scope of implementation of the present invention.

[0053] The following examples and comparative examples illustrate the inventive effects of the present invention, but the scope of protection of the present invention is not limited to these examples and comparative examples. All raw materials used in the examples are industrial grade, purified before use, and have no other special requirements. The "parts" in the examples and comparative examples refer to parts by weight.

[0054] Raw material source:

[0055] Acrylonitrile, industrial polymer grade, China Petroleum Lanzhou Petrochemical Company;

[0056] 1,3-Butadiene, 99% purity, Lanzhou Petrochemical Company of China National Petroleum Corporation;

[0057] Diethylene glycol monovinyl ether, 99% purity, Wuhan Huaxiang Kejie Biotechnology Co., Ltd.

[0058] Trifluorovinyl acetate, 97% purity, Shanghai Guchen Biotechnology Co., Ltd.

[0059] Ethylene, 99% purity, from Lanzhou Petrochemical Company of China National Petroleum Corporation;

[0060] 1-Octenene, purity 99.5%, Shandong Heze Xileng Chemical Co., Ltd.;

[0061] Grubbs II catalyst, 99% purity, Hubei Xinyuhong Biomedical Technology Co., Ltd.

[0062] Dicumyl peroxide, Lanzhou Additives Factory.

[0063] All other reagents are commercially available industrial products.

[0064] Molecular weight determination: Molecular weight was determined using a Waters 2414 gel permeation chromatography (GPC) system (Waters, Inc., USA). A polystyrene standard was used as the calibration curve. The mobile phase was tetrahydrofuran, the column temperature was 40℃, the sample concentration was 1 mg / mL, the injection volume was 50 μL, the elution time was 40 min, and the flow rate was 1 mL / min. -1 .

[0065] Determination of the degree of hydrogenation of HNBR: The degree of hydrogenation of hydrogenated nitrile butadiene rubber was calculated using 1H NMR spectroscopy. The main methods are as follows: 1. The product was completely dissolved in deuterated chloroform to prepare a 1H NMR spectroscopy sample; 2. The 1H NMR spectrum was measured and analyzed: The degree of hydrogenation of hydrogenated nitrile butadiene rubber was determined by 1H NMR spectroscopy and calculated according to the following methods: characteristic proton peak of 1,4-C=C-: 5.4 ppm, characteristic proton peak of 1,2-C=C-: 5.0 ppm, characteristic proton peak of saturated hydrocarbon: 1.25 ppm, characteristic proton peak of cyano-linked group: 2.5 ppm. The formula for calculating the degree of hydrogenation is as follows: Degree of hydrogenation HD (%) = 1 - Degree of unsaturation (U).

[0066] Infrared spectroscopy analysis of samples: Functional group analysis of samples before and after modification with nano-silica was performed using an infrared spectrometer from Bruke Spectroscopy Instruments, Germany. Samples were dried in a vacuum oven at 100℃, pressed into pellets using potassium bromide, and acquired at wavenumbers ranging from 400 to 4000 cm⁻¹. -1 .

[0067] Gel content test: Perform the method in standard SH / T1050-91.

[0068] Determination of glass transition temperature (Tg): The glass transition temperature of the product was measured using DSC. The instrument model was DSC1, manufactured by Mettler AG, Switzerland. The heating range was -80 to 80 °C, and the heating rate was 10 °C / min.

[0069] Oil and gas resistance test: The method in standard GB / T1690-2010 shall be followed.

[0070] Aging resistance test: The method in standard GB / T3512-2014 shall be followed.

[0071] Example 1

[0072] (I) Preparation of functionalized monomers:

[0073] S1. Preparation of fluorinated random copolymer: In a 10L stainless steel polymerization reactor with a jacket, the system was purged with argon gas three times. 2000g cyclohexane, 1000g diethylene glycol monovinyl ether, 400g trifluorovinyl acetate, 1.0g THF, and 270mmol n-butyllithium were added to the polymerization reactor in sequence. The temperature was raised to 50℃ and the reaction was carried out for 60min. Finally, 10g 1,3-butadiene was added to the polymerization reactor for end-capping reaction for 20min until no free monomers were present. The solution was wet-coagulated and dried to obtain the fluorinated random copolymer.

[0074] S2. Preparation of functionalized monomers: Nitrogen gas was purged three times in a 10L high-pressure reactor, 2000g of cyclohexane was added, and the temperature was raised to 80℃. Then, 150g of methylaluminoxane co-catalyst was added dropwise under uniform stirring at 600rpm. Stirring was continued for 20min under nitrogen protection. Subsequently, 30g of fluorinated random copolymer, 50g of 1-octene, and 10g of trans-bromophenyl (di(triphenylphosphine))nickel main catalyst were added to the high-pressure reactor in sequence. Ethylene was introduced, and the pressure was maintained at 13MPa for 4.0h. After the reaction was completed, the functionalized monomer (number average molecular weight Mn of 3100) was obtained by separation, devolatilization, and drying. Figure 1 The infrared spectrum of the functionalized monomer in Embodiment 1 of the present invention is shown. Figure 1 It can be seen from this that at wavenumbers of 700–720 cm⁻¹ -1The characteristic absorption peak of the saturated methylene group appears at a wavenumber of 1000–1050 cm⁻¹. -1 An absorption peak for the secondary condensation vibration of the alcohol group appears at a wavenumber of 1130–1200 cm⁻¹. -1 Characteristic absorption peaks for CF covalent bonds appeared; in the wavenumber range of 1210–1270 cm⁻¹. -1 An absorption peak appears due to the condensation vibration of the ether group; at wavenumbers of 1650–1670 cm⁻¹. -1 A sharp absorption peak for vinyl groups appeared; at wavenumbers of 1690–1750 cm⁻¹. -1 An absorption peak for the condensation vibration of the ester group appears at the location.

[0075] (II) Preparation of fluorinated nitrile butadiene rubber: 2000g of deionized water, 40g of sodium dodecylbenzene sulfonate soap, 1.3g of sodium formaldehyde sulfoxylate, 0.2g of EDTA-iron sodium salt, 300g of acrylonitrile monomer, and 10g of tert-dodecyl mercaptan were added to a 10L stirred pressure vessel. After evacuation, the mixture was purged with nitrogen three times. Then, 0.1g of sodium dithionite scavenger and 690g of 1,3-butadiene monomer were added. When the temperature of the polymerization vessel dropped to 4℃, 1.0g of dicumyl peroxide initiator was added to start the polymerization reaction. When the polymerization conversion rate reached 35%, 10g of functionalized monomer was added to continue the reaction. When the conversion rate reached 85.0%, 3.0g of sodium thiram termite was added to terminate the polymerization. The mixture was stirred, discharged, coagulated, washed, and dried to obtain fluorinated nitrile butadiene rubber (gel content of 1.38%).

[0076] (III) Preparation of Fluorinated Hydrogenated Nitrile Butadiene Rubber for Oilfield Use: First, 200g of fluorinated nitrile butadiene rubber was dissolved in a chlorobenzene solution to prepare a 3% (by weight) rubber solution. Then, the solution was added to a 10L high-pressure reactor, and nitrogen gas was introduced to remove air from the reactor. Next, hydrogen gas was used to purge the nitrogen from the reactor for 20 minutes. Then, under nitrogen protection, 0.20g of a toluene solution containing Grubbs II catalyst (6% by weight) was added. The hydrogen pressure in the reactor was increased to 13MPa, and the temperature was raised to 120℃. After reacting for 10 hours, the system was cooled, condensed, and vacuum dried to obtain fluorinated hydrogenated nitrile butadiene rubber for oilfield use. Sampling and Analysis: Standard samples were prepared, and the tested properties are shown in Table 1.

[0077] Example 2

[0078] (I) Preparation of functionalized monomers:

[0079] S1. Preparation of fluorinated random copolymer: In a 10L stainless steel polymerization reactor with a jacket, the system was purged with argon three times. 2300g cyclohexane, 1000g diethylene glycol monovinyl ether, 430g trifluorovinyl acetate, 2.8g THF, and 278mmol n-butyllithium were added to the polymerization reactor in sequence. The temperature was raised to 54℃ and the reaction was carried out for 63min. Finally, 18g 1,3-butadiene was added to the polymerization reactor for end-capping reaction for 23min until no free monomers were present. The solution was then wet-coagulated and dried to obtain the fluorinated random copolymer.

[0080] S2. Preparation of functionalized monomers: Nitrogen gas was purged three times in a 10L high-pressure reactor, 2400g of cyclohexane was added, and the temperature was raised to 84℃. Then, 170g of methylaluminoxane co-catalyst was added dropwise under uniform stirring at 630rpm. Stirring was continued for 24min under nitrogen protection. Subsequently, 48g of fluorinated random copolymer, 70g of 1-octene, and 10g of trans-bromophenyl (di(triphenylphosphine))nickel main catalyst were added to the high-pressure reactor in sequence. Ethylene was introduced, and the pressure was maintained at 14MPa for 4.8h. After the reaction was completed, the functionalized monomer (number average molecular weight Mn of 3300) was obtained by separation, devolatilization, and drying.

[0081] (II) Preparation of fluorinated nitrile butadiene rubber: 2600g of deionized water, 42g of sodium dodecylbenzene sulfonate soap, 1.4g of sodium formaldehyde sulfoxylate, 0.3g of EDTA-iron sodium salt, 330g of acrylonitrile monomer, and 12g of tert-dodecyl mercaptan were added to a 10L stirred pressure vessel. After evacuation, the mixture was purged with nitrogen three times. Then, 0.3g of sodium dithionite scavenger and 650g of 1,3-butadiene monomer were added. When the temperature of the polymerization vessel dropped to 8℃, 1.5g of dicumyl peroxide initiator was added to start the polymerization reaction. When the polymerization conversion rate reached 37%, 20g of functionalized monomer was added to continue the reaction. When the conversion rate reached 87.0%, 4.0g of sodium thiram termite was added to terminate the polymerization. The mixture was stirred, discharged, coagulated, washed, and dried to obtain fluorinated nitrile butadiene rubber (gel content of 1.36%).

[0082] (III) Preparation of Fluorinated Hydrogenated Nitrile-Butadiene Rubber for Oilfield Use: First, 200g of fluorinated nitrile-butadiene rubber was dissolved in a chlorobenzene solution to prepare a 3.8% (by weight) rubber solution. Then, the solution was added to a 10L high-pressure reactor, and nitrogen gas was introduced to remove air from the reactor. Next, hydrogen gas was used to purge the nitrogen from the reactor for 24 minutes. Then, under nitrogen protection, 0.42g of a toluene solution containing Grubbs II catalyst (10% by weight) was added. The hydrogen pressure in the reactor was increased to 14MPa, and the temperature was raised to 123℃. After reacting for 11 hours, the system was cooled, condensed, and vacuum dried to obtain fluorinated hydrogenated nitrile-butadiene rubber for oilfield use. Sampling and Analysis: Standard samples were prepared, and the tested properties are shown in Table 1.

[0083] Example 3

[0084] (I) Preparation of functionalized monomers:

[0085] S1. Preparation of fluorinated random copolymer: In a 10L stainless steel polymerization reactor with a jacket, the system was purged with argon three times. 2700g cyclohexane, 1000g diethylene glycol monovinyl ether, 480g trifluorovinyl acetate, 4.5g THF, and 280mmol n-butyllithium were added to the polymerization reactor in sequence. The temperature was raised to 58℃ and the reaction was carried out for 68min. Finally, 27g 1,3-butadiene was added to the polymerization reactor for end-capping reaction for 28min until no free monomers were present. The solution was then wet-coagulated and dried to obtain the fluorinated random copolymer.

[0086] S2. Preparation of functionalized monomers: Nitrogen gas was purged three times in a 10L high-pressure reactor, 2800g of cyclohexane was added, and the temperature was raised to 88℃. Then, 180g of methylaluminoxane co-catalyst was added dropwise under uniform stirring at 680rpm. Stirring was continued for 28min under nitrogen protection. Subsequently, 60g of fluorinated random copolymer, 80g of 1-octene, and 10g of trans-bromophenyl (di(triphenylphosphine))nickel main catalyst were added to the high-pressure reactor in sequence. Ethylene was introduced, and the pressure was maintained at 15MPa for 4.7h. After the reaction was completed, the functionalized monomer (number average molecular weight Mn of 3800) was obtained by separation, devolatilization, and drying.

[0087] (II) Preparation of Fluorinated Nitrile Butadiene Rubber: 3600g of deionized water, 48g of sodium dodecylbenzene sulfonate soap, 1.4g of sodium formaldehyde sulfoxylate, 0.5g of EDTA-iron sodium salt, 360g of acrylonitrile monomer, and 17g of tert-dodecyl mercaptan were added to a 10L stirred pressure vessel. After evacuation, the mixture was purged with nitrogen three times. Then, 0.4g of sodium dithionite, an oxygen scavenger, and 610g of 1,3-butadiene monomer were added. When the temperature of the polymerization vessel dropped to 9℃, 2.1g of dicumyl peroxide initiator was added to start the polymerization reaction. When the polymerization conversion rate reached 38%, 30g of functionalized monomer was added to continue the reaction. When the conversion rate reached 88.0%, 4.3g of sodium thiram, a terminator, was added to terminate the polymerization. The mixture was stirred, discharged, coagulated, washed, and dried to obtain fluorinated nitrile butadiene rubber (gel content of 1.34%).

[0088] (III) Preparation of Fluorinated Hydrogenated Nitrile Butadiene Rubber for Oilfield Use: First, 200g of fluorinated nitrile butadiene rubber was dissolved in a chlorobenzene solution to prepare a 4.8% (by weight) rubber solution. Then, the solution was added to a 10L high-pressure reactor, and nitrogen gas was introduced to remove air from the reactor. Next, hydrogen gas was used to purge the nitrogen from the reactor for 28 minutes. Then, under nitrogen protection, 0.52g of a toluene solution containing Grubbs II catalyst (11% by weight) was added. The hydrogen pressure in the reactor was increased to 15MPa, and the temperature was raised to 128℃. After reacting for 12 hours, the system was cooled, condensed, and vacuum dried to obtain fluorinated hydrogenated nitrile butadiene rubber for oilfield use. Sampling and Analysis: Standard samples were prepared, and the tested properties are shown in Table 1.

[0089] Example 4

[0090] (I) Preparation of functionalized monomers:

[0091] S1. Preparation of fluorinated random copolymer: In a 10L stainless steel polymerization reactor with a jacket, the system was purged with argon three times. Then, 3000g of cyclohexane, 1000g of diethylene glycol monovinyl ether, 500g of trifluorovinyl acetate, 5.0g of THF, and 287mmol of n-butyllithium were added to the polymerization reactor in sequence. The temperature was raised to 60℃ and the reaction was carried out for 70min. Finally, 30g of 1,3-butadiene was added to the polymerization reactor for end-capping reaction for 30min until no free monomers were present. The solution was wet-coagulated and dried to obtain the fluorinated random copolymer.

[0092] S2. Preparation of functionalized monomers: Nitrogen gas was purged three times in a 10L high-pressure reactor, 3000g of cyclohexane was added, and the temperature was raised to 90℃. Then, 200g of methylaluminoxane co-catalyst was added dropwise under uniform stirring at 700rpm. Stirring was continued for 30min under nitrogen protection. Subsequently, 70g of fluorinated random copolymer, 100g of 1-octene and 10g of trans-bromophenyl (di(triphenylphosphine))nickel main catalyst were added to the high-pressure reactor in sequence. Ethylene was introduced and the pressure was maintained at 16MPa for 6.0h. After the reaction was completed, the functionalized monomer (number average molecular weight Mn of 3900) was obtained by separation, devolatilization and drying.

[0093] (II) Preparation of fluorinated nitrile butadiene rubber: 4000g of deionized water, 50g of sodium dodecylbenzene sulfonate soap, 1.5g of sodium formaldehyde sulfoxylate, 0.5g of EDTA-iron sodium salt, 380g of acrylonitrile monomer, and 20g of tert-dodecyl mercaptan were added to a 10L stirred pressure vessel. After evacuation, the mixture was purged with nitrogen three times. Then, 0.5g of sodium dithionite scavenger and 580g of 1,3-butadiene monomer were added. When the temperature of the polymerization vessel dropped to 11℃, 2.5g of dicumyl peroxide initiator was added to start the polymerization reaction. When the polymerization conversion rate reached 40%, 40g of functionalized monomer was added to continue the reaction. When the conversion rate reached 90%, 5.0g of sodium thiram termite was added to terminate the polymerization. The mixture was stirred, discharged, coagulated, washed, and dried to obtain fluorinated nitrile butadiene rubber (gel content of 1.31%).

[0094] (III) Preparation of Fluorinated Hydrogenated Nitrile-Butadiene Rubber for Oilfield Use: First, 200g of fluorinated nitrile-butadiene rubber was dissolved in a chlorobenzene solution to prepare a 5.0% (by weight) rubber solution. Then, the solution was added to a 10L high-pressure reactor, and nitrogen gas was introduced to remove air from the reactor. Next, hydrogen gas was used to purge the nitrogen from the reactor for 30 minutes. Then, under nitrogen protection, 0.6g of a toluene solution containing Grubbs II catalyst (12% by weight) was added. The hydrogen pressure in the reactor was increased to 16MPa, and the temperature was raised to 130℃. After reacting for 13 hours, the system was cooled, condensed, and vacuum dried to obtain fluorinated hydrogenated nitrile-butadiene rubber for oilfield use. Sampling and Analysis: Standard samples were prepared, and the tested properties are shown in Table 1.

[0095] Comparative Example 1

[0096] (I) Preparation of functionalized monomers:

[0097] S1. Preparation of fluorinated random copolymer: In a 10L stainless steel polymerization reactor with a jacket, the system was purged with argon gas three times. 2000g cyclohexane, 1000g diethylene glycol monovinyl ether, 400g vinylidene fluoride, 1.0g THF, and 270mmol n-butyllithium were added to the polymerization reactor in sequence. The temperature was raised to 50℃ and the reaction was carried out for 60min. Finally, 10g 1,3-butadiene was added to the polymerization reactor for end-capping reaction for 20min until no free monomers were present. The solution was wet-coagulated and dried to obtain fluorinated random copolymer a.

[0098] S2. Preparation of functionalized monomers: Nitrogen gas was purged three times in a 10L high-pressure reactor, 2000g of cyclohexane was added, and the temperature was raised to 80℃. Then, 150g of methylaluminoxane co-catalyst was added dropwise under uniform stirring at 600rpm. Stirring was continued for 20min under nitrogen protection. Subsequently, 30g of fluorinated random copolymer a, 50g of 1-octene and 10g of trans-bromophenyl (di(triphenylphosphine))nickel main catalyst were added to the high-pressure reactor in sequence. Ethylene was introduced and the pressure was maintained at 13MPa for 4.0h. After the reaction was completed, functionalized monomer a (number average molecular weight Mn of 2800) was obtained by separation, devolatilization and drying.

[0099] (II) Preparation of fluorinated nitrile butadiene rubber: 2000g deionized water, 40g sodium dodecylbenzene sulfonate soap, 1.3g sodium formaldehyde sulfoxylate, 0.2g EDTA-iron sodium salt, 300g acrylonitrile monomer, and 10g tert-dodecyl mercaptan were added to a 10L stirred pressure vessel. After evacuation, the mixture was purged with nitrogen three times. Then, 0.1g sodium dithionite scavenger and 690g 1,3-butadiene monomer were added. When the temperature of the polymerization vessel dropped to 4℃, 1.0g dicumyl peroxide initiator was added to start the polymerization reaction. When the polymerization conversion rate reached 35%, 10g functionalized monomer a was added to continue the reaction. When the conversion rate reached 85.0%, 3.0g sodium thiram termite was added to terminate the polymerization. The mixture was stirred, discharged, coagulated, washed, and dried to prepare fluorinated nitrile butadiene rubber a (gel content of 2.26%).

[0100] (III) Preparation of Fluorinated Hydrogenated Nitrile Butadiene Rubber for Oilfield Use: First, 200g of fluorinated nitrile butadiene rubber a was dissolved in a chlorobenzene solution to prepare a 3% (by weight) rubber solution. Then, the solution was added to a 10L high-pressure reactor, and nitrogen gas was introduced to remove air from the reactor. Next, hydrogen gas was used to purge the nitrogen from the reactor for 20 minutes. Then, under nitrogen protection, 0.20g of a toluene solution containing Grubbs II catalyst (6% by weight) was added. The hydrogen pressure in the reactor was increased to 13MPa, and the temperature was raised to 120℃. After reacting for 10 hours, the system was cooled, condensed, and vacuum dried to obtain fluorinated hydrogenated nitrile butadiene rubber for oilfield use. Sampling and Analysis: Standard samples were prepared, and the tested properties are shown in Table 1.

[0101] Comparative Example 2

[0102] (I) Preparation of functionalized monomers:

[0103] S1. Preparation of fluorinated random copolymer: In a jacketed 10L stainless steel polymerization reactor, the system was purged with argon gas three times. 2300g cyclohexane, 430g vinyl trifluoroacetate, 2.8g THF, and 278mmol n-butyllithium were added to the polymerization reactor in sequence. The temperature was raised to 54℃ and the reaction was carried out for 63min. Finally, 18g 1,3-butadiene was added to the polymerization reactor for end-capping reaction for 23min until no free monomers were present. The solution was wet-coagulated and dried to obtain fluorinated random copolymer b.

[0104] S2. Preparation of functionalized monomers: Nitrogen gas was purged three times in a 10L high-pressure reactor, 2400g of cyclohexane was added, and the temperature was raised to 84℃. Then, 170g of methylaluminoxane co-catalyst was added dropwise under uniform stirring at 630rpm. Stirring was continued for 24min under nitrogen protection. Subsequently, 48g of fluorinated random copolymer b was introduced into the reactor, and the pressure was maintained at 14MPa for 4.8h. After the reaction was completed, functionalized monomer b (number average molecular weight Mn of 2200) was obtained by separation, devolatilization and drying.

[0105] (II) Preparation of fluorinated nitrile butadiene rubber: 2600g of deionized water, 42g of sodium dodecylbenzene sulfonate soap, 1.4g of sodium formaldehyde sulfoxylate, 0.3g of EDTA-iron sodium salt, 330g of acrylonitrile monomer, and 12g of tert-dodecyl mercaptan were added to a 10L stirred pressure vessel. After evacuation, the mixture was purged with nitrogen three times. Then, 0.3g of sodium dithionite scavenger and 650g of 1,3-butadiene monomer were added. When the temperature of the polymerization vessel dropped to 8℃, 1.5g of dicumyl peroxide initiator was added to start the polymerization reaction. When the polymerization conversion rate reached 37%, 20g of functionalized monomer b was added to continue the reaction. When the conversion rate reached 87.0%, 4.0g of sodium thiram termite was added to terminate the polymerization. The mixture was stirred, discharged, coagulated, washed, and dried to prepare fluorinated nitrile butadiene rubber b (gel content of 2.03%).

[0106] (III) Preparation of Fluorinated Hydrogenated Nitrile Butadiene Rubber for Oilfield Use: First, 200g of fluorinated nitrile butadiene rubber b was dissolved in a chlorobenzene solution to prepare a 3.8% (by weight) rubber solution. Then, the solution was added to a 10L high-pressure reactor, and nitrogen gas was introduced to remove air from the reactor. Next, hydrogen gas was used to purge the nitrogen from the reactor for 24 minutes. Then, under nitrogen protection, 0.42g of a toluene solution containing Grubbs II catalyst (10% by weight) was added. The hydrogen pressure in the reactor was increased to 14MPa, and the temperature was raised to 123℃. After reacting for 11 hours, the system was cooled, condensed, and vacuum dried to obtain fluorinated hydrogenated nitrile butadiene rubber for oilfield use. Sampling and Analysis: Standard samples were prepared, and the tested properties are shown in Table 1.

[0107] Comparative Example 3

[0108] (I) Preparation of functionalized monomers: Nitrogen gas was purged three times in a 10L high-pressure reactor, 2800g of cyclohexane was added, and the temperature was raised to 88℃. Then, 180g of methylaluminoxane co-catalyst was added dropwise under uniform stirring at 680rpm. Stirring was continued for 28min under nitrogen protection. Subsequently, 60g of diethylene glycol monovinyl ether, 80g of 1-octene and 10g of trans-bromophenyl (di(triphenylphosphine))nickel main catalyst were added to the high-pressure reactor in sequence. Ethylene was introduced and the pressure was maintained at 15MPa for 4.7h. After the reaction was completed, the functionalized monomer c (number average molecular weight Mn of 2600) was obtained by separation, devolatilization and drying.

[0109] (II) Preparation of Fluorinated Nitrile Butadiene Rubber: 3600g of deionized water, 48g of sodium dodecylbenzene sulfonate soap, 1.4g of sodium formaldehyde sulfoxylate, 0.5g of EDTA-iron sodium salt, 360g of acrylonitrile monomer, and 17g of tert-dodecyl mercaptan were added to a 10L stirred pressure vessel. After evacuation, the mixture was purged with nitrogen three times. Then, 0.4g of sodium dithionite, an oxygen scavenger, and 610g of 1,3-butadiene monomer were added. When the temperature of the polymerization vessel dropped to 9℃, 2.1g of dicumyl peroxide initiator was added to start the polymerization reaction. When the polymerization conversion rate reached 38%, 30g of functionalized monomer c was added, and the reaction continued. When the conversion rate reached 88.0%, 4.3g of sodium thiram, a terminator, was added to terminate the polymerization. The mixture was stirred, discharged, coagulated, washed, and dried to prepare fluorinated nitrile butadiene rubber c (gel content of 1.84%).

[0110] (III) Preparation of Fluorinated Hydrogenated Nitrile Butadiene Rubber for Oilfield Use: First, 200g of fluorinated nitrile butadiene rubber was dissolved in a chlorobenzene solution to prepare a 4.8% (by weight) rubber solution. Then, the solution was added to a 10L high-pressure reactor, and nitrogen gas was introduced to remove air from the reactor. Next, hydrogen gas was used to purge the nitrogen from the reactor for 28 minutes. Then, under nitrogen protection, 0.52g of a toluene solution containing Grubbs II catalyst (11% by weight) was added. The hydrogen pressure in the reactor was increased to 15MPa, and the temperature was raised to 128℃. After reacting for 12 hours, the system was cooled, condensed, and vacuum dried to obtain fluorinated hydrogenated nitrile butadiene rubber for oilfield use. Sampling and Analysis: Standard samples were prepared, and the tested properties are shown in Table 1.

[0111] Comparative Example 4

[0112] (I) Preparation of functionalized monomers: Nitrogen gas was purged three times in a 10L high-pressure reactor, 3000g of cyclohexane was added, and the temperature was raised to 90℃. Then, 200g of methylaluminoxane co-catalyst was added dropwise under uniform stirring at 700rpm. Stirring was continued for 30min under nitrogen protection. Then, 70g of trifluorovinyl acetate, 100g of 1-octene and 10g of trans-bromophenyl (di(triphenylphosphine))nickel main catalyst were added to the high-pressure reactor in sequence. Ethylene was introduced and the pressure was maintained at 16MPa for 6.0h. After the reaction was completed, the functionalized monomer d (number average molecular weight Mn of 2700) was obtained by separation, devolatilization and drying.

[0113] (II) Preparation of fluorinated nitrile butadiene rubber: 4000g of deionized water, 50g of sodium dodecylbenzene sulfonate soap, 1.5g of sodium formaldehyde sulfoxylate, 0.5g of EDTA-iron sodium salt, 380g of acrylonitrile monomer, and 20g of tert-dodecyl mercaptan were added to a 10L stirred pressure vessel. After evacuation, the mixture was purged with nitrogen three times. Then, 0.5g of sodium dithionite scavenger and 580g of 1,3-butadiene monomer were added. When the temperature of the polymerization vessel dropped to 11℃, 2.5g of dicumyl peroxide initiator was added to start the polymerization reaction. When the polymerization conversion rate reached 40%, 40g of functionalized monomer d was added to continue the reaction. When the conversion rate reached 90%, 5.0g of sodium thiram termite was added to terminate the polymerization. The mixture was stirred, discharged, coagulated, washed, and dried to prepare fluorinated nitrile butadiene rubber d (gel content of 1.92%).

[0114] (III) Preparation of Fluorinated Hydrogenated Nitrile Butadiene Rubber for Oilfield Use: First, 200g of fluorinated nitrile butadiene rubber (d) was dissolved in a chlorobenzene solution to prepare a 5.0% (by weight) rubber solution. Then, the solution was added to a 10L high-pressure reactor, and nitrogen gas was introduced to remove air from the reactor. Next, hydrogen gas was used to purge the nitrogen from the reactor for 30 minutes. Then, under nitrogen protection, 0.6g of a toluene solution containing Grubbs II catalyst (12% by weight) was added. The hydrogen pressure in the reactor was increased to 16MPa, and the temperature was raised to 130℃. After reacting for 13 hours, the system was cooled, condensed, and vacuum dried to obtain fluorinated hydrogenated nitrile butadiene rubber for oilfield use. Sampling and Analysis: Standard samples were prepared, and the tested properties are shown in Table 1.

[0115] Comparative Example 5

[0116] (I) Preparation of fluorinated nitrile butadiene rubber: 4000g of deionized water, 50g of sodium dodecylbenzene sulfonate soap, 1.5g of sodium formaldehyde sulfoxylate, 0.5g of EDTA-iron sodium salt, 380g of acrylonitrile monomer, and 20g of tert-dodecyl mercaptan were added to a 10L stirred pressure vessel. After evacuation, the mixture was purged with nitrogen three times. Then, 0.5g of sodium dithionite scavenger and 580g of 1,3-butadiene monomer were added. When the temperature of the polymerization vessel dropped to 11℃, 2.5g of dicumyl peroxide initiator was added to start the polymerization reaction. When the polymerization conversion rate reached 40%, 40g of trifluoroethyl methacrylate was added to continue the reaction. When the conversion rate reached 90%, 5.0g of sodium thiram terminator was added to terminate the polymerization. The mixture was stirred, discharged, coagulated, washed, and dried to prepare fluorinated nitrile butadiene rubber e (gel content of 7.31%).

[0117] (II) Preparation of Fluorinated Hydrogenated Nitrile Butadiene Rubber for Oilfield Use: First, 200g of fluorinated nitrile butadiene rubber (e) was dissolved in a chlorobenzene solution to prepare a 5.0% (by weight) rubber solution. Then, the solution was added to a 10L high-pressure reactor, and nitrogen gas was introduced to remove air from the reactor. Next, hydrogen gas was used to purge the nitrogen from the reactor for 30 minutes. Then, under nitrogen protection, 0.6g of a toluene solution containing Grubbs II catalyst (12% by weight) was added. The hydrogen pressure in the reactor was increased to 16MPa, and the temperature was raised to 130℃. After reacting for 13 hours, the system was cooled, condensed, and vacuum dried to obtain fluorinated hydrogenated nitrile butadiene rubber for oilfield use. Sampling and Analysis: Standard samples were prepared, and the tested properties are shown in Table 1.

[0118] Table 1

[0119]

[0120] As shown in Table 1, the fluorinated hydrogenated nitrile butadiene rubber of the present invention for oil fields has a high degree of hydrogenation, a glass transition temperature Tg < -40℃, a volume change rate < +6% under the condition of 150℃ × 48h in oil-based drilling fluid, and a tensile strength change rate < -10% after aging in hot air at 100℃ × 72h. It exhibits excellent resistance to oil and gas media, cold resistance and weather resistance. The vulcanized products that are further modified by low-temperature plasticizing can be used for oil well operations under extremely cold conditions with a working temperature of -50℃.

Claims

1. A fluorinated hydrogenated nitrile butadiene rubber raw material composition, wherein, Includes the first component and the second component; The first component includes acrylonitrile and butadiene monomer; The second component includes a functionalized monomer having the structure shown in Formula I; In Equation I, R is C6~C 12 The straight-chain alkyl group; B is a butadiene segment; L, m and n represent the number of repeating units, L≥1, n≥1, m≥1, and L, m and n are positive integers.

2. The fluorinated nitrile butadiene rubber raw material composition according to claim 1, wherein, The number-average molecular weight of the functionalized monomer is 3000–4000; and / or, The weight ratio of the acrylonitrile, the butadiene monomer, and the functionalized monomer is 30–38: 58–69: 1.0–4.

0.

3. The fluorinated hydrogenated nitrile butadiene rubber raw material composition according to claim 1, wherein, It also includes a third component; the third component includes a terminator.

4. The fluorinated hydrogenated nitrile butadiene rubber raw material composition according to claim 3, wherein, The first component also includes deionized water, emulsifier, activator, molecular weight regulator, oxygen scavenger and first initiator; The weight ratio of the deionized water, the emulsifier, the activator, the acrylonitrile, the molecular weight regulator, the oxygen scavenger, the butadiene monomer, the functionalized monomer, and the terminator is 200–400: 2.0–6.0: 0.1–0.3: 30–38: 0.5–3.0: 0.01–0.05: 58–69: 1.0–4.0: 0.3–0.

5.

5. The fluorinated hydrogenated nitrile butadiene rubber raw material composition according to claim 4, wherein, The emulsifier is selected from one or more combinations of alkyl sulfate emulsifiers, alkyl sulfonate emulsifiers, and aryl sulfonate emulsifiers; and / or, The first initiator is selected from one or more of cumene hydroperoxide, dicumene hydroperoxide, isopropyl tert-butyl peroxide, and isopropyl n-butyl peroxide; and / or, The activator is selected from one or more combinations of sodium formaldehyde sulfoxylate, ferrous sulfate, sodium EDTA, and sodium ferric EDTA; and / or, The oxygen scavenger is selected from one or more combinations of sodium dithionite, dimethyl ketoxime, isoascorbic acid, carbazide, and N-isopropylhydroxylamine; and / or, The terminating agent is selected from one or more combinations of hydroxylamine sulfate, diethylhydroxylamine, 2,5-pentanebutylquinone, sodium dimethyl dithiocarbamate, sodium nitrite, actinol reagent, and p-aminoazobenzene; and / or, The molecular weight regulator is selected from tert-dodecyl mercaptan and / or dodecyl mercaptan.

6. A method for preparing hydrogenated fluorinated nitrile butadiene rubber, wherein, Fluorinated hydrogenated nitrile butadiene rubber is prepared using the raw material composition according to any one of claims 1 to 5; the preparation method includes the following steps: The first component is mixed to carry out the first polymerization reaction in the first stage. When the conversion rate of acrylonitrile reaches 35% to 40%, the second component is added to the system to carry out the first polymerization reaction in the second stage. When the conversion rate of acrylonitrile reaches 85% to 90%, the polymerization is terminated to obtain functionalized nitrile rubber. The functionalized nitrile butadiene rubber is dissolved in an organic solvent to form a solution, and the solution is subjected to a hydrogenation reaction under the action of a catalyst to obtain the fluorinated hydrogenated nitrile butadiene rubber.

7. The method for preparing hydrogenated fluorinated nitrile butadiene rubber according to claim 6, wherein, The reaction temperature of the first polymerization reaction is 4–11 °C.

8. The method for preparing hydrogenated fluorinated nitrile butadiene rubber according to claim 6, wherein, The hydrogenation reaction is carried out at a pressure of 13–16 MPa, a temperature of 120–130 °C, and a time of 10–13 h.

9. The method for preparing hydrogenated fluorinated nitrile butadiene rubber according to claim 6, wherein, The functionalized monomer in the second component is prepared by the following steps: Diethylene glycol monovinyl ether, a first solvent, trifluorovinyl acetate, a structure modifier, and a second initiator are mixed to carry out a second polymerization reaction. Butadiene monomer is then added to the system to carry out an end-capping reaction. The polymerization is terminated when no free monomer is present, resulting in a fluorinated random copolymer. The fluorinated random copolymer, α-olefin, ethylene, main catalyst, co-catalyst, and second solvent are mixed to carry out a third polymerization reaction to obtain the functionalized monomer.

10. The method for preparing hydrogenated fluorinated nitrile butadiene rubber according to claim 9, wherein, The weight ratio of the diethylene glycol monovinyl ether, the first solvent, the trifluorovinyl acetate, the structure modifier, and the butadiene monomer is 100:200–300:40–50:0.1–0.5:1.0–3.0; and / or, The weight ratio of the second solvent, the co-catalyst, the functionalized random copolymer, the α-olefin, and the main catalyst is 200–300:15–20:3–7:5–10:

1.

11. The method for preparing hydrogenated fluorinated nitrile butadiene rubber according to claim 9, wherein, The α-olefin is selected from one or more combinations of 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, and 1-dodecene; and / or, The main catalyst is selected from one or more of (1-naphthyl)[8-(diphenylphosphino)quinoline]nickel chloride, trans-phenyl bromide (di(triphenylphosphine))nickel, and 2,5-dicarboxypyrrole dibromide; and / or, The second initiator has the general structural formula RLi, wherein R is selected from one or more combinations of saturated aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups of C1-20.

12. A fluorinated hydrogenated nitrile butadiene rubber, wherein, It is prepared by the preparation method according to any one of claims 6 to 11.

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