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

Abstract

The application provides a hydrogenated nitrile rubber raw material composition, a hydrogenated nitrile rubber and a preparation method thereof. The hydrogenated nitrile rubber raw material composition comprises acrylonitrile, butadiene monomers and functional monomers. The functional monomers have free radical reactivity, and phenyl, ester groups and long-chain alkyl branched structures are integrated on a macromolecular chain, so that the hydrogenated nitrile rubber obtained by polymerization has good low-temperature resistance.

Description

Technical Field

[0001] This invention relates to the field of hydrogenated nitrile butadiene rubber, specifically to a hydrogenated nitrile butadiene rubber raw material composition, hydrogenated nitrile butadiene rubber, and a method for preparing the same. Background Technology

[0002] Oil exploration equipment faces the challenge of operating in low-temperature environments, which places high demands on the oil resistance and low-temperature resistance of rubber sealing materials.

[0003] In the prior art, there are many patent documents reporting on methods for preparing low-temperature resistant hydrogenated nitrile butadiene rubber. For example, CN106349410B discloses a special hydrogenated nitrile butadiene rubber with compression cold resistance and its preparation method. The rubber main chain contains epoxy groups, and some epoxy groups are also attached with ester side groups; the ester side groups are C6-C 24 The reaction of acid anhydrides with epoxy groups produces the product. The preparation method involves introducing epoxy groups into the main chain of the rubber molecule, and then reacting some of the epoxy groups with acid anhydrides under the action of a catalyst to introduce ester groups, resulting in a special hydrogenated nitrile butadiene rubber containing epoxy groups and ester groups. This special hydrogenated nitrile butadiene rubber has a low glass transition temperature and no crystalline regions, and its compression set can reach 0.4, making it a special rubber with excellent compression set and cold resistance. CN105294939B discloses a low-temperature grade hydrogenated nitrile butadiene rubber raw rubber, which is a copolymer of butadiene, acrylonitrile, and dibutyl transbutenedioate, with a number-average molecular weight of 1.05–3.25 × 10⁻⁶. 5 The weight-average molecular weight is 3.02–9.32 × 10⁻⁶. 5The polydispersity index is 2.0–2.7; the degree of hydrogenation of the low-temperature grade hydrogenated nitrile butadiene rubber raw rubber is above 90%, and the glass transition temperature is -38℃ to -42℃. CN112592461B discloses a modified hydrogenated nitrile butadiene rubber material with low-temperature resistance and high damping characteristics, its preparation method, and its application. The modified hydrogenated nitrile butadiene rubber material is prepared using HNBR / PNB block copolymer as raw material; the HNBR / PNB block copolymer is obtained by modifying NBR or HNBR through olefin metathesis reaction using norbornene monomer as a modifier. The resulting block copolymer combines the performance characteristics of both HNBR and PNB, not only maintaining the basic properties of hydrogenated nitrile butadiene rubber, but also utilizing polynorbornene to absorb a large amount of plasticizing oil, thereby obtaining a modified hydrogenated nitrile butadiene rubber material with excellent low-temperature resistance. CN115594898A discloses a low-temperature resistant hydrogenated nitrile butadiene rubber compound and its internal mixing preparation method. The method mainly involves blending and internal mixing hydrogenated nitrile butadiene raw rubber, a plasticizer, and a hardness modifier to obtain a low-temperature resistant hydrogenated nitrile butadiene rubber compound with a Shore A hardness of 67±5, tensile strength ≥14MPa, elongation at break ≥180%, compression set ≤35%, and a -45℃ compression set coefficient ≥0.16. CN105754164A discloses a low-temperature resistant rubber material. Although the material's low-temperature resistance is improved, the addition of the plasticizer dioctyl phthalate (DOP) reduces the material's mechanical properties and oil resistance. Furthermore, DOP is not environmentally friendly and is prone to leaching. CN200810118420.4 discloses a method for preparing a cold-resistant nitrile butadiene rubber composition. This method involves adding a specific co-crosslinking agent during vulcanization to prepare a cold-resistant nitrile butadiene rubber composition with low hardness and low compression set.

[0004] While the existing technologies described above can improve the low-temperature resistance of hydrogenated nitrile butadiene rubber to some extent by adding small-molecule modifiers, copolymerization, and blending, these methods still have limitations. They involve complex preparation processes, difficult practical operation, large additive amounts, high costs, and insignificant modification effects. Therefore, it is necessary to provide a new method for preparing low-temperature resistant hydrogenated nitrile butadiene rubber for oilfield applications to address these issues. Summary of the Invention

[0005] To address the aforementioned technical problems, the present invention aims to provide a hydrogenated nitrile butadiene rubber raw material composition, hydrogenated nitrile butadiene rubber, and a method for preparing the same, wherein the hydrogenated nitrile butadiene rubber exhibits good low-temperature resistance.

[0006] To achieve the above objectives, the present invention provides a hydrogenated nitrile butadiene rubber raw material composition, comprising a first component and a second component;

[0007] The first component includes acrylonitrile and butadiene monomer;

[0008] The second component includes functionalized monomers having the structure shown in Formula I;

[0009]

[0010] In Formula I, R1 is a C1-C4 alkyl group, and R2 is a C6-C4 alkyl group. 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.

[0011] The aforementioned functionalized monomers possess free radical reactivity, integrating phenyl, ester, and long-chain alkyl branched structures onto a single macromolecular chain. This structure fully leverages the "group effect" during hydrogenation, reducing the crystallinity of HNBR, lowering its glass transition temperature (Tg), and improving its low-temperature resistance. Simultaneously, it utilizes the benzene ring and ester group to avoid the drawbacks of reduced tear strength and oil resistance caused by the destruction of HNBR crystallinity. This achieves a balance between HNBR's tear resistance, low-temperature resistance, and oil resistance, meeting the oil well operation requirements of submersible screw pump stator rubber materials.

[0012] Furthermore, the long-chain alkyl branched structure in the aforementioned macromolecular functionalized long-branched monomers can effectively reduce gel formation during the synthesis of functionalized nitrile butadiene rubber (HNBR) and effectively increase the content of ester and cyano groups in HNBR, thus fully leveraging its oil resistance. In addition, the "cumulative effect" of the macromolecular groups results in significant modification effects at low addition levels in improving the tear strength, oil resistance, and lowering the glass transition temperature (Tg) of HNBR, achieving high efficiency in the modification process while maintaining a balance between tear resistance, oil resistance, and cold resistance.

[0013] Furthermore, the number-average molecular weight of the functionalized monomers is 4000–5000.

[0014] Furthermore, the weight ratio of acrylonitrile, butadiene monomer, and functionalized monomer is 30–37:58–69:1.0–5.0.

[0015] Furthermore, the hydrogenated nitrile butadiene rubber raw material composition also includes a third component; the third component includes a terminator.

[0016] Furthermore, the first component also includes deionized water, emulsifier, activator, molecular weight regulator, oxygen scavenger, and first initiator.

[0017] 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: 30-37: 0.5-3.0: 0.01-0.05: 58-69: 1.0-5.0: 0.3-0.5.

[0018] Furthermore, the emulsifier is an emulsifier stable in acidic media, and can be selected from one or more combinations of alkyl sulfate emulsifiers, alkyl sulfonate emulsifiers, and aryl sulfonate emulsifiers. For example, it can be selected from potassium rosinate soap, methyl oleate soap, sodium pyrophosphate, fatty acids, disproportionated potassium rosinate, sodium fatty acid sodium salt (C8-C20), and sodium alkyl sulfate. The amount of emulsifier used is conventional in the art and is not particularly limited in this invention. It is 2.0 to 6.0 parts, more preferably 3.0 to 4.0 parts, based on 100 parts of the total weight of monomers (acrylonitrile, butadiene monomers, and functionalized monomers).

[0019] 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).

[0020] Furthermore, the activator is selected from one or a combination of two or more of the following: sodium formaldehyde sulfoxylate, ferrous sulfate, tetrasodium EDTA (tetrasodium EDTA salt), and ferric sodium EDTA (ferric sodium EDTA salt). The amount of activator used is conventional in the art and is not particularly limited in this invention. 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 (acrylonitrile, butadiene monomers, and functionalized monomers).

[0021] Furthermore, the molecular weight regulator is a common regulator used in emulsion polymerization and can be 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 make any particular limitation. It is 0.5 to 3.0 parts, more preferably 1.0 to 2.0 parts, based on 100 parts of the total weight of monomers (the total weight of acrylonitrile, butadiene monomers and functionalized monomers).

[0022] 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).

[0023] 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).

[0024] This invention also provides a method for preparing hydrogenated nitrile butadiene rubber, which uses the aforementioned raw material composition to prepare hydrogenated nitrile butadiene rubber; the preparation method includes the following steps:

[0025] The first component is mixed to carry out the first polymerization reaction in the first stage. When the acrylonitrile conversion rate reaches 30% to 35%, 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.

[0026] 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 hydrogenated nitrile rubber.

[0027] For the reasons mentioned above, the aforementioned functionalized monomers possess free radical reactivity. They integrate phenyl, ester, and long-chain alkyl branched structures onto a single macromolecular chain. This structure fully leverages the "group effect" during hydrogenation, which reduces the crystallinity of HNBR, lowers its glass transition temperature (Tg), and improves its low-temperature resistance. Simultaneously, it utilizes the benzene ring and ester group to avoid the drawbacks of reduced tear strength and oil resistance caused by the destruction of HNBR crystallinity. This achieves a balance between HNBR's tear resistance, low-temperature resistance, and oil resistance, meeting the oil well operation requirements of submersible screw pump stator rubber materials.

[0028] Furthermore, the long-chain alkyl branched structure in the aforementioned macromolecular functionalized long-branched monomers can effectively reduce gel formation during the synthesis of functionalized nitrile butadiene rubber (HNBR) and effectively increase the content of ester and cyano groups in HNBR, thus fully leveraging its oil resistance. In addition, the "cumulative effect" of the macromolecular groups results in significant modification effects at low addition levels in improving the tear strength, oil resistance, and lowering the glass transition temperature (Tg) of HNBR, achieving high efficiency in the modification process while maintaining a balance between tear resistance, oil resistance, and cold resistance.

[0029] In addition, this preparation method is green and environmentally friendly, has significant modification effects, stable process, and small product quality fluctuations, making it suitable for industrial production.

[0030] Furthermore, the reaction temperature of the first polymerization reaction is 4–11 °C.

[0031] Furthermore, the hydrogenation reaction is carried out at a pressure of 13–16 MPa, a temperature of 110–130 °C, and a time of 11–14 h.

[0032] In one optional embodiment, the preparation method of the above-mentioned hydrogenated nitrile rubber includes the following steps:

[0033] 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.

[0034] Step 2: Dissolve the above-mentioned functionalized nitrile rubber in an organic solvent (e.g., chlorobenzene solution) to prepare a rubber solution. Then, add the rubber 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 cold-resistant and oil-resistant hydrogenated nitrile rubber for oil fields.

[0035] Furthermore, the gel content in the obtained functionalized nitrile rubber is <1.8%.

[0036] Furthermore, the weight ratio of functionalized nitrile rubber to the toluene solution of Grubbs II catalyst is 100:0.08–0.3. 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%.

[0037] Furthermore, the treatment time for removing the inert gas from the reactor with hydrogen is 20–30 min; the pressure is increased to 13–16 MPa; the temperature is increased to 110–130 °C; and the hydrogenation reaction time is 11–14 h.

[0038] Furthermore, the degree of hydrogenation (HD) of cold-resistant and oil-resistant hydrogenated nitrile butadiene rubber for oil fields is ≥95%.

[0039] 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.

[0040] Furthermore, the reactor of the present invention can be a loop reactor or a batch reactor, preferably a batch reactor.

[0041] 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.

[0042] In a preferred embodiment, the functionalized monomer in the second component is prepared by the following steps:

[0043] Styrene, a first solvent, trans-butenedioic acid diester, 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 an esterified block copolymer.

[0044] A third polymerization reaction is carried out by mixing esterified block copolymers, α-olefins, ethylene, main catalysts, co-catalysts, and a second solvent to obtain functionalized monomers.

[0045] Furthermore, the weight ratio of styrene, the first solvent, trans-butenedioic acid diester, the structure modifier, and the butadiene monomer is 100:200-300:50-70:0.2-0.5:1.0-3.0.

[0046] Furthermore, the weight ratio of the second solvent, co-catalyst, esterified block copolymer, α-olefin, and main catalyst is 200–300: 20–30: 5–10: 10–15: 1.

[0047] Furthermore, the transbutenedioic acid diester is selected from one or more combinations of dimethyl transbutenedioic acid, diethyl transbutenedioic acid, dipropyl transbutenedioic acid, dibutyl transbutenedioic acid, and diisobutyl transbutenedioic acid.

[0048] 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.

[0049] Furthermore, 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 nickel.

[0050] Furthermore, the general structural formula of the second initiator is 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.

[0051] Furthermore, the cocatalyst is an alkylaluminoxane cocatalyst, such as methylaluminoxane (MAO) and / or ethylaluminoxane (EAO), with methylaluminoxane being preferred.

[0052] 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.

[0053] 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.

[0054] In one alternative implementation, the functionalized monomer is prepared by the following steps:

[0055] Step 1: In the polymerization reactor, argon gas is introduced to purge the system. The first solvent, styrene, trans-butenedioic acid diester, structure modifier, and second initiator are added to the polymerization reactor in sequence. The temperature is raised to 70-80℃ and the reaction is carried out for 80-90 minutes. Finally, butadiene monomer is added to the polymerization reactor for a 20-30 minute end-capping reaction until no free monomers are present. The adhesive solution is then wet-coagulated and dried to obtain the esterified block copolymer.

[0056] 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). Stirring continues for 20-30 minutes under inert gas protection. Then, the esterified block copolymer, long-chain α-olefin, and main catalyst are added sequentially to the high-pressure reactor. Ethylene is introduced at this time, and the reaction is carried out (reaction pressure 15-20 MPa; time 6.0-7.0 h). After the reaction is completed, the product is centrifuged and dried to obtain the functionalized monomer.

[0057] The present invention also provides a hydrogenated nitrile butadiene rubber, which is prepared by the aforementioned preparation method. For the reasons stated above, this hydrogenated nitrile butadiene rubber can simultaneously achieve good tear resistance, low-temperature resistance, and oil resistance, thus meeting the oil well operation requirements for stator rubber materials in submersible screw pumps. Attached Figure Description

[0058] Figure 1 The image shows the infrared spectrum of the functionalized monomer in Embodiment 1 of the present invention. Detailed Implementation

[0059] 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.

[0060] 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.

[0061] (1) Source of raw materials:

[0062] Acrylonitrile, industrial polymerization grade, China National Petroleum Corporation Lanzhou Petrochemical Company

[0063] Styrene, industrial polymer grade, China National Petroleum Corporation Lanzhou Petrochemical Company

[0064] 1,3-Butadiene, 99% purity, Lanzhou Petrochemical Company, China National Petroleum Corporation

[0065] Dibutyl transbutenedioic acid, 99% purity, Shandong Tongli New Material Co., Ltd.

[0066] Ethylene, 99% purity, Lanzhou Petrochemical Company, China National Petroleum Corporation

[0067] 1-Octenene, 99.5% purity, Shandong Heze Xileng Chemical Co., Ltd.

[0068] Grubbs II catalyst, 99% purity, Hubei Xinyuhong Biomedical Technology Co., Ltd.

[0069] Dicumyl peroxide, Lanzhou Additives Factory

[0070] All other reagents are commercially available industrial products.

[0071] (2) Analysis and testing methods:

[0072] 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 .

[0073] 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).

[0074] 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 .

[0075] Gel content test: Perform the method in standard SH / T1050-91.

[0076] 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.

[0077] Oil resistance test: The method in standard GB / T1690-2010 shall be followed.

[0078] Tear strength: The method specified in standard GB / T529-2009 shall be applied. (3) Specific implementation:

[0080] Example 1

[0081] (I) Preparation of functionalized monomers:

[0082] S1. Preparation of esterified block copolymer: In a 10L stainless steel polymerization reactor with a jacket, the system was purged with argon gas three times. 2000g cyclohexane, 1000g styrene, 500g dibutyl fumarate, 2.0g THF, and 230mmol n-butyllithium were added to the polymerization reactor in sequence. The temperature was raised to 70℃ and the reaction was carried out for 80min. 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 esterified block copolymer.

[0083] 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, 200g of methylaluminoxane co-catalyst was added dropwise under uniform stirring at 600rpm. Stirring was continued for 20min under nitrogen protection. Subsequently, 50g of esterified block 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 15MPa for 6.0h. After the reaction was completed, the functionalized monomer (number average molecular weight Mn of 4000) was obtained by separation, devolatilization and drying. Figure 1 This is the infrared spectrum of the functionalized monomer in Embodiment 1 of the present invention. Figure 1 It can be seen from this that at wavenumbers of 700–720 cm⁻¹ -1 The characteristic absorption peak of the saturated methylene group appears at a wavenumber of 1680–1800 cm⁻¹. -1 An absorption peak for the condensation vibration of the ester group appears at a wavenumber of 1650–1670 cm⁻¹. -1 A sharp absorption peak for vinyl groups appeared; at wavenumbers of 2900–3050 cm⁻¹. -1 The characteristic absorption peak of the benzene ring appears at [location].

[0084] (II) Preparation of Functionalized Nitrile Rubber: 2000g of deionized water, 30g of sodium dodecylbenzenesulfonate soap, 1.3g of bleaching agent, 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 30%, 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 functionalized nitrile rubber (gel content of 1.79%).

[0085] (III) Preparation of tear-resistant and low-temperature resistant hydrogenated nitrile butadiene rubber for oilfields: First, 200g of functionalized nitrile butadiene rubber was dissolved in chlorobenzene solution to prepare a 3% (w / w) 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, 0.16g of a toluene solution containing Grubbs II catalyst (6% (w / w)) was added. The hydrogen pressure in the reactor was increased to 13MPa, and the temperature was raised to 110℃. After reacting for 11 hours, the system was cooled, condensed, and vacuum dried to obtain tear-resistant and low-temperature resistant hydrogenated nitrile butadiene rubber for oilfields. Sampling and analysis: Standard samples were prepared, and the tested properties are shown in Table 1.

[0086] Example 2

[0087] (I) Preparation of functionalized monomers:

[0088] S1. Preparation of esterified block copolymer: In a 10L stainless steel polymerization reactor with a jacket, the system was purged with argon gas three times. 2300g cyclohexane, 1000g styrene, 600g dibutyl fumarate, 3.0g THF, and 240mmol n-butyllithium were added to the polymerization reactor in sequence. The temperature was raised to 72℃ and the reaction was carried out for 82min. Finally, 15g 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 the esterified block copolymer.

[0089] 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, 230g of methylaluminoxane co-catalyst was added dropwise under uniform stirring at 630rpm. Stirring was continued for 24min under nitrogen protection. Subsequently, 60g of esterified block copolymer, 120g 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 17MPa for 6.2h. After the reaction was completed, the functionalized monomer (number average molecular weight Mn of 4300) was obtained by separation, devolatilization and drying.

[0090] (II) Preparation of Functionalized Nitrile Rubber: 2400g of deionized water, 33g of sodium dodecylbenzenesulfonate soap, 1.4g of bleaching agent, 0.3g of EDTA-iron sodium salt, 320g of acrylonitrile monomer, and 13g of tert-dodecyl mercaptan were added to a 10L stirred pressure vessel. After evacuation, the mixture was purged with nitrogen three times. Then, 0.2g of sodium dithionite, an oxygen scavenger, and 660g of 1,3-butadiene monomer were added. When the temperature of the polymerization vessel dropped to 7℃, 1.6g of dicumyl peroxide initiator was added to start the polymerization reaction. When the polymerization conversion rate reached 32%, 20g of functionalized monomer was added, and the reaction continued. When the conversion rate reached 86.0%, 4.0g of sodium thiram, a terminator, was added to terminate the polymerization. The mixture was stirred, discharged, coagulated, washed, and dried to obtain functionalized nitrile rubber (gel content of 1.75%).

[0091] (III) Preparation of tear-resistant and low-temperature resistant hydrogenated nitrile butadiene rubber for oilfields: First, 200g of functionalized nitrile butadiene rubber was dissolved in chlorobenzene solution to prepare a 4% (w / w) 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 25 minutes. Then, under nitrogen protection, 0.35g of a toluene solution containing Grubbs II catalyst (8% (w / w)) was added. The hydrogen pressure in the reactor was increased to 14MPa, and the temperature was raised to 120℃. After reacting for 12 hours, the system was cooled, condensed, and vacuum dried to obtain tear-resistant and low-temperature resistant hydrogenated nitrile butadiene rubber for oilfields. Sampling and analysis: Standard samples were prepared, and the tested properties are shown in Table 1.

[0092] Example 3

[0093] (I) Preparation of functionalized monomers:

[0094] S1. Preparation of esterified block copolymer: In a 10L stainless steel polymerization reactor with a jacket, the system was purged with argon gas three times. 2700g cyclohexane, 1000g styrene, 650g dibutyl fumarate, 4.0g THF, and 255mmol n-butyllithium were added to the polymerization reactor in sequence. The temperature was raised to 76℃ and the reaction was carried out for 86min. Finally, 23g 1,3-butadiene was added to the polymerization reactor for end-capping reaction for 26min until no free monomers were present. The solution was wet-coagulated and dried to obtain the esterified block copolymer.

[0095] S2. Preparation of functionalized monomers: Nitrogen gas was purged three times in a 10L high-pressure reactor, 2600g of cyclohexane was added, and the temperature was raised to 87℃. Then, 260g of methylaluminoxane co-catalyst was added dropwise under uniform stirring at 660rpm. Stirring was continued for 28min under nitrogen protection. Subsequently, 80g of esterified block copolymer, 140g 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 18MPa for 6.5h. After the reaction was completed, the functionalized monomer (number average molecular weight Mn of 4500) was obtained by separation, devolatilization and drying.

[0096] (II) Preparation of Functionalized Nitrile Rubber: 2800g of deionized water, 38g of sodium dodecylbenzenesulfonate soap, 1.5g of bleaching agent, 0.4g of EDTA-iron sodium salt, 350g 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 10℃, 2.0g of dicumyl peroxide initiator was added to start the polymerization reaction. When the polymerization conversion rate reached 34%, 40g of functionalized monomer was added to continue the reaction. When the conversion rate reached 88.0%, 4.5g of sodium thiram, a terminator, was added to terminate the polymerization. The mixture was stirred, discharged, coagulated, washed, and dried to obtain functionalized nitrile rubber (gel content of 1.71%).

[0097] (III) Preparation of tear-resistant and low-temperature resistant hydrogenated nitrile butadiene rubber for oilfields: First, 200g of functionalized nitrile butadiene rubber was dissolved in chlorobenzene solution to prepare a 4.5% (w / w) 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, 0.45g of a toluene solution containing Grubbs II catalyst (10% (w / w)) was added. The hydrogen pressure in the reactor was increased to 15MPa, and the temperature was raised to 125℃. After reacting for 13 hours, the system was cooled, condensed, and vacuum dried to obtain tear-resistant and low-temperature resistant hydrogenated nitrile butadiene rubber for oilfields. Sampling and analysis: Standard samples were prepared, and the tested properties are shown in Table 1.

[0098] Example 4

[0099] (I) Preparation of functionalized monomers:

[0100] S1. Preparation of esterified block copolymer: In a 10L stainless steel polymerization reactor with a jacket, the system was purged with argon gas three times. 3000g cyclohexane, 1000g styrene, 700g dibutyl fumarate, 5.0g THF, and 268mmol n-butyllithium were added to the polymerization reactor in sequence. The temperature was raised to 80℃ and the reaction was carried out for 90min. Finally, 30g 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 esterified block copolymer.

[0101] 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, 300g of methylaluminoxane co-catalyst was added dropwise under uniform stirring at 700rpm. Stirring was continued for 30min under nitrogen protection. Subsequently, 100g of esterified block copolymer, 150g 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 20MPa for 7.0h. After the reaction was completed, the functionalized monomer (number average molecular weight Mn of 5000) was obtained by separation, devolatilization and drying.

[0102] (II) Preparation of Functionalized Nitrile Rubber: 3000g of deionized water, 40g of sodium dodecylbenzenesulfonate soap, 1.6g of bleaching agent, 0.4g of EDTA-sodium iron salt, 370g 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, an oxygen 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 35%, 50g of functionalized monomer was added, and the reaction continued. When the conversion rate reached 90%, 5.0g of sodium thiram, a terminator, was added to terminate the polymerization. The mixture was stirred, discharged, coagulated, washed, and dried to obtain functionalized nitrile rubber (gel content of 1.68%).

[0103] (III) Preparation of tear-resistant and low-temperature resistant hydrogenated nitrile butadiene rubber for oilfields: First, 200g of functionalized nitrile butadiene rubber was dissolved in chlorobenzene solution to prepare a 5.0% (w / w) 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% (w / w)) was added. The hydrogen pressure in the reactor was increased to 16MPa, and the temperature was raised to 130℃. After reacting for 14 hours, the system was cooled, condensed, and vacuum dried to obtain tear-resistant and low-temperature resistant hydrogenated nitrile butadiene rubber for oilfields. Sampling and analysis: Standard samples were prepared, and the tested properties are shown in Table 1.

[0104] Comparative Example 1

[0105] (I) Preparation of functionalized monomers:

[0106] S1. Preparation of esterified block copolymer: In a 10L stainless steel polymerization reactor with a jacket, the system was purged with argon gas three times. 2000g cyclohexane, 1000g styrene, 500g ethyl methacrylate, 2.0g THF, and 230mmol n-butyllithium were added to the polymerization reactor in sequence. The temperature was raised to 70℃ and the reaction was carried out for 80min. 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 esterified block copolymer a.

[0107] 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, 200g of methylaluminoxane co-catalyst was added dropwise under uniform stirring at 600rpm. Stirring was continued for 20min under nitrogen protection. Subsequently, 50g of esterified block copolymer a, 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 15MPa for 6.0h. After the reaction was completed, functionalized monomer a (number average molecular weight Mn of 3800) was obtained by separation, devolatilization and drying.

[0108] (II) Preparation of Functionalized Nitrile Rubber: 2000g of deionized water, 30g of sodium dodecylbenzenesulfonate soap, 1.3g of bleaching agent, 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 30%, 10g of functionalized monomer a was added, and the reaction continued. 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 prepare functionalized nitrile rubber a (gel content of 1.97%).

[0109] (III) Preparation of tear-resistant and low-temperature resistant hydrogenated nitrile butadiene rubber for oilfields: First, 200g of functionalized nitrile butadiene rubber a was dissolved in chlorobenzene solution to prepare a 3% (w / w) 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, 0.16g of a toluene solution containing Grubbs II catalyst (6% (w / w)) was added. The hydrogen pressure in the reactor was increased to 13MPa, and the temperature was raised to 110℃. After reacting for 11 hours, the system was cooled, condensed, and vacuum dried to obtain tear-resistant and low-temperature resistant hydrogenated nitrile butadiene rubber for oilfields. Sampling and analysis: Standard samples were prepared, and the tested properties are shown in Table 1.

[0110] Comparative Example 2

[0111] (I) Preparation of functionalized monomers:

[0112] S1. Preparation of esterified block copolymer: In a 10L stainless steel polymerization reactor with a jacket, the system was purged with argon gas three times. 2300g cyclohexane, 600g dibutyl fumarate, 3.0g THF, and 240mmol n-butyllithium were added to the polymerization reactor in sequence. The temperature was raised to 72℃ and the reaction was carried out for 82min. Finally, 15g 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 esterified block copolymer b.

[0113] 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, 230g of methylaluminoxane co-catalyst was added dropwise under uniform stirring at 630rpm. Stirring was continued for 24min under nitrogen protection. Subsequently, 60g of esterified block copolymer b, 120g 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 17MPa for 6.2h. After the reaction was completed, functionalized monomer b (number average molecular weight Mn of 3500) was obtained by separation, devolatilization and drying.

[0114] (II) Preparation of Functionalized Nitrile Rubber: 2400g of deionized water, 33g of sodium dodecylbenzenesulfonate soap, 1.4g of bleaching agent, 0.3g of EDTA-iron sodium salt, 320g of acrylonitrile monomer, and 13g of tert-dodecyl mercaptan were added to a 10L stirred pressure vessel. After evacuation, the mixture was purged with nitrogen three times. Then, 0.2g of sodium dithionite scavenger and 660g of 1,3-butadiene monomer were added. When the temperature of the polymerization vessel dropped to 7℃, 1.6g of dicumyl peroxide initiator was added to start the polymerization reaction. When the polymerization conversion rate reached 32%, 20g of functionalized monomer b was added, and the reaction continued. When the conversion rate reached 86.0%, 4.0g of sodium thimerosal terminating agent was added to terminate the polymerization. The mixture was stirred, discharged, coagulated, washed, and dried to prepare functionalized nitrile rubber b (gel content of 1.82%).

[0115] (III) Preparation of tear-resistant and low-temperature resistant hydrogenated nitrile butadiene rubber for oilfields: First, 200g of functionalized nitrile butadiene rubber b was dissolved in chlorobenzene solution to prepare a 4% (w / w) 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 25 minutes. Then, under nitrogen protection, 0.35g of a toluene solution containing Grubbs II catalyst (8% (w / w)) was added. The hydrogen pressure in the reactor was increased to 14MPa, and the temperature was raised to 120℃. After reacting for 12 hours, the system was cooled, condensed, and vacuum dried to obtain tear-resistant and low-temperature resistant hydrogenated nitrile butadiene rubber for oilfields. Sampling and analysis: Standard samples were prepared, and the tested properties are shown in Table 1.

[0116] Comparative Example 3

[0117] (I) Preparation of functionalized monomers:

[0118] S1. Preparation of functionalized monomers: Nitrogen gas was purged three times in a 10L high-pressure reactor, 2600g of cyclohexane was added, and the temperature was raised to 87℃. Then, 260g of methylaluminoxane co-catalyst was added dropwise under uniform stirring at 660rpm. Stirring was continued for 28min under nitrogen protection. Subsequently, 80g of styrene, 140g 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 18MPa for 6.5h. After the reaction was completed, the functionalized monomer c (number average molecular weight Mn of 3100) was obtained by separation, devolatilization and drying.

[0119] (II) Preparation of Functionalized Nitrile Rubber: 2800g of deionized water, 38g of sodium dodecylbenzenesulfonate soap, 1.5g of bleaching agent, 0.4g of EDTA-iron sodium salt, 350g 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 scavenger and 610g of 1,3-butadiene monomer were added. When the temperature of the polymerization vessel dropped to 10℃, 2.0g of dicumyl peroxide initiator was added to start the polymerization reaction. When the polymerization conversion rate reached 34%, 40g of functionalized monomer c was added, and the reaction continued. When the conversion rate reached 88.0%, 4.5g of sodium thiram termite was added to terminate the polymerization. The mixture was stirred, discharged, coagulated, washed, and dried to prepare functionalized nitrile rubber c (gel content of 1.96%).

[0120] (III) Preparation of tear-resistant and low-temperature resistant hydrogenated nitrile butadiene rubber for oilfields: First, 200g of functionalized nitrile butadiene rubber c was dissolved in chlorobenzene solution to prepare a 4.5% (w / w) 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, 0.45g of a toluene solution containing Grubbs II catalyst (10% (w / w)) was added. The hydrogen pressure in the reactor was increased to 15MPa, and the temperature was raised to 125℃. After reacting for 13 hours, the system was cooled, condensed, and vacuum dried to obtain tear-resistant and low-temperature resistant hydrogenated nitrile butadiene rubber for oilfields. Sampling and analysis: Standard samples were prepared, and the tested properties are shown in Table 1.

[0121] Comparative Example 4

[0122] (I) Preparation of functionalized monomers:

[0123] S1. 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, 300g of methylaluminoxane co-catalyst was added dropwise under uniform stirring at 700rpm. Stirring was continued for 30min under nitrogen protection. Subsequently, 100g of dibutyl fumarate, 150g of 1-octene, and 10g of trans-phenyl bromide (di(triphenylphosphine)) nickel main catalyst were added to the high-pressure reactor in sequence. Ethylene was introduced, and the pressure was maintained at 20MPa for 7.0h. After the reaction was completed, the functionalized monomer d (number average molecular weight Mn of 3600) was obtained by separation, devolatilization, and drying.

[0124] (II) Preparation of Functionalized Nitrile Rubber: 3000g of deionized water, 40g of sodium dodecylbenzenesulfonate soap, 1.6g of bleaching agent, 0.4g of EDTA-iron sodium salt, 370g 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 35%, 50g of functionalized monomer d was added, and the reaction continued. 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 functionalized nitrile rubber d (gel content of 1.92%).

[0125] (III) Preparation of tear-resistant and low-temperature resistant hydrogenated nitrile butadiene rubber for oilfields: First, 200g of functionalized nitrile butadiene rubber d was dissolved in chlorobenzene solution to prepare a 5.0% (w / w) 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% (w / w)) was added. The hydrogen pressure in the reactor was increased to 16MPa, and the temperature was raised to 130℃. After reacting for 14 hours, the system was cooled, condensed, and vacuum dried to obtain tear-resistant and low-temperature resistant hydrogenated nitrile butadiene rubber for oilfields. Sampling and analysis: Standard samples were prepared, and the tested properties are shown in Table 1.

[0126] Comparative Example 5

[0127] (I) Preparation of functionalized nitrile butadiene rubber: 3000g of deionized water, 40g of sodium dodecylbenzene sulfonate soap, 1.6g of bleaching agent, 0.4g of EDTA-iron sodium salt, 370g 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 35%, 50g of dibutyl fumarate 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 functionalized nitrile butadiene rubber e (gel content of 7.98%).

[0128] (III) Preparation of tear-resistant and low-temperature resistant hydrogenated nitrile butadiene rubber for oilfields: First, 200g of functionalized nitrile butadiene rubber e was dissolved in chlorobenzene solution to prepare a 5.0% (w / w) 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% (w / w)) was added. The hydrogen pressure in the reactor was increased to 16MPa, and the temperature was raised to 130℃. After reacting for 14 hours, the system was cooled, condensed, and vacuum dried to obtain tear-resistant and low-temperature resistant hydrogenated nitrile butadiene rubber for oilfields. Sampling and analysis: Standard samples were prepared, and the tested properties are shown in Table 1.

[0129] Comparative Example 6

[0130] (I) Preparation of functionalized monomers:

[0131] S1. Preparation of esterified block copolymer: Same as in Example 4.

[0132] S2. Preparation of functionalized monomers: Same as in Example 4.

[0133] (II) Preparation of Functionalized Nitrile Rubber: 3000g of deionized water, 40g of sodium dodecylbenzene sulfonate soap, 1.6g of bleaching agent, 0.4g of EDTA-iron sodium salt, 370g 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 35%, 6.0g of functionalized monomer was added to continue the reaction. When the conversion rate reached 90%, 5.0g of sodium thimerosal terminating agent was added to terminate the polymerization. The mixture was stirred, discharged, coagulated, washed, and dried to obtain functionalized nitrile rubber f (gel content of 1.83%).

[0134] (III) Preparation of tear-resistant and low-temperature resistant hydrogenated nitrile butadiene rubber for oilfields: First, 200g of functionalized nitrile butadiene rubber f was dissolved in chlorobenzene solution to prepare a 5.0% (w / w) 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% (w / w)) was added. The hydrogen pressure in the reactor was increased to 16MPa, and the temperature was raised to 130℃. After reacting for 14 hours, the system was cooled, condensed, and vacuum dried to obtain tear-resistant and low-temperature resistant hydrogenated nitrile butadiene rubber for oilfields. Sampling and analysis: Standard samples were prepared, and the tested properties are shown in Table 1.

[0135] Table 1

[0136]

[0137]

[0138] As shown in Table 1, the hydrogenated nitrile butadiene rubber (HNBR) for oilfields of the present invention exhibits high degree of hydrogenation, tear strength ≥47.2 KN / m, volume change rate <10% under the condition of 150℃×42h in No. 1 standard oil, and glass transition temperature Tg <-40℃. It demonstrates high tear resistance, good oil resistance, and low-temperature resistance. The HNBR products prepared by further low-temperature plasticizing and compounding can meet the requirements of oil well operations under low-temperature conditions of -48℃.

Claims

1. A 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 Formula I, R1 is a C1-C4 alkyl group, and R2 is a C6-C4 alkyl group. 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 hydrogenated nitrile butadiene rubber raw material composition according to claim 1, wherein, The number-average molecular weight of the functionalized monomer is 4000–5000; and / or, The weight ratio of the acrylonitrile, butadiene monomer and the functionalized monomer is 30-37:58-69:1.0-5.

0.

3. The 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 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.

5. The hydrogenated nitrile butadiene rubber raw material composition according to claim 4, wherein, 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: 30–37: 0.5–3.0: 0.01–0.05: 58–69: 1.0–5.0: 0.3–0.

5.

6. The 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.

7. A method for preparing hydrogenated nitrile butadiene rubber, wherein, Hydrogenated nitrile butadiene rubber is prepared using the raw material composition according to any one of claims 3 to 6; 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 30% to 35%, 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 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 hydrogenated nitrile rubber.

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

9. The method for preparing hydrogenated nitrile butadiene rubber according to claim 7, wherein, The hydrogenation reaction is carried out at a pressure of 13–16 MPa, a temperature of 110–130 °C, and a time of 11–14 h.

10. The method for preparing hydrogenated nitrile butadiene rubber according to claim 7, wherein, The functionalized monomer in the second component is prepared by the following steps: Styrene, a first solvent, trans-butenedioic acid diester, 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 an esterified block copolymer. The esterified block 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.

11. The method for preparing hydrogenated nitrile butadiene rubber according to claim 10, wherein, The weight ratio of the styrene, the first solvent, the trans-butenedioic acid diester, the structure modifier, and the butadiene monomer is 100:200–300:50–70:0.2–0.5:1.0–3.0; and / or The weight ratio of the second solvent, the co-catalyst, the esterified block copolymer, the α-olefin, and the main catalyst is 200–300: 20–30: 5–10: 10–15:

1.

12. The method for preparing hydrogenated nitrile butadiene rubber according to claim 10, wherein, The transbutenedioic acid diester is selected from one or more combinations of dimethyl transbutenedioic acid, diethyl transbutenedioic acid, dipropyl transbutenedioic acid, dibutyl transbutenedioic acid, and diisobutyl transbutenedioic acid; and / or, 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.

13. A hydrogenated nitrile butadiene rubber, wherein, It is prepared by the preparation method according to any one of claims 7 to 12.

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