Preparation method of low-temperature-resistant and high-wear-resistant fluorinated nitrile rubber

Abstract

The invention aims to provide the preparation method of the low-temperature-resistant and high-wear-resistant fluorinated nitrile rubber. The preparation method comprises the following steps: firstly, carrying out variable-temperature polymerization on reaction monomers, namely 4-trifluoromethyl styrene, styrene, N-(4-hydroxyl straight-chain alkyl) acrylamide and 1, 3-butadiene by utilizing an anionic polymerization method to prepare a functional reaction type macromolecular fluorine monomer containing wide vinyl distribution and a long branched chain; then, the functionalized reaction type macromolecular fluorine monomer is subjected to pre-emulsification treatment, and finally, the functionalized reaction type macromolecular fluorine monomer is grafted into an NBR main chain structure through low-temperature emulsion polymerization, so that the low-temperature-resistant and high-wear-resistant fluorinated nitrile rubber is prepared. According to the method, the problem of inversion contradiction between high wear resistance and low temperature resistance of the FNBR is solved, the balance between high wear resistance and low temperature resistance of the FNBR is realized, and the operation requirement of a submersible screw pump stator rubber material of oil exploration equipment in an extremely cold oil field is met.

Description

Technical Field

[0001] The invention belongs to the technical field of rubber, and in particular relates to a method for preparing low-temperature-resistant and highly wear-resistant fluorinated nitrile rubber. Background Art

[0002] Submersible screw pump production technology, owing to its exceptional adaptability under complex operating conditions, has become a significant breakthrough in modern oil and gas development. Compared to traditional production methods, this technology demonstrates significant advantages in challenging reservoirs such as those with high-viscosity crude oil, high wax / sand content, and high gas-to-oil ratios. Its high mechanical efficiency, low energy consumption, and long maintenance cycles further enhance its operating cost advantages in specialized well types such as deviated and horizontal wells. However, the system's long-term stability is highly dependent on the service life of the stator rubber material, and the core of this lifespan bottleneck lies in the material's performance.

[0003] Fluorinated nitrile rubber (FNBR) has excellent oil resistance, high temperature resistance, and resistance to ozone aging due to the strong electronegativity of the fluorine atoms (F) in its molecular chain and the high bond energy of the FC bond. This gives FNBR an irreplaceable tolerance to extreme environments, making it a perfect match for downhole high-temperature, high-pressure, and corrosive media working conditions, making it an irreplaceable key material for stator rubber. However, the high bond energy of the FC bond leads to the rigidification of the molecular chain segments, significantly increasing their glass transition temperature (Tg). Under the coupling of high-speed shear and cyclic stress loading in screw pumps, FNBR is prone to low-temperature brittle fracture and a surge in wear rate, which directly threatens the reliability of the system. Therefore, in order to meet the operating requirements of submersible screw pumps in the extremely low-temperature environment of -40°C in western and northeastern my country's oil fields, extremely high requirements are placed on the wear resistance and low-temperature resistance of FNBR.

[0004] Numerous patents exist regarding methods for preparing fluorinated nitrile rubber (FNBR), primarily employing methods such as blending and modification and emulsion polymerization. For example, CN200610119299.8 discloses a method for mechanically blending and vulcanizing NBR and fluororubber. The fluororubber is a copolymer of vinylidene fluoride and hexafluoropropylene or a terpolymer of vinylidene fluoride, tetrafluoroethylene, and hexafluoropropylene. During vulcanization and bonding, the difference in the positive cure time (T90) between the NBR and the fluororubber must be controlled within a range of 0.3 to 12 minutes. CN115043991B discloses a method for preparing a fluorinated thermoplastic elastomer by emulsion polymerization and the resulting product. The method involves adding styrene, a portion of an emulsifier, a regulator, and water to a polymerization reactor. After nitrogen displacement, a conjugated diene is added, followed by a portion of an initiator to initiate emulsion polymerization. When the conversion rate reaches 50-60%, the remaining emulsifier, regulator, initiator, and a mixture of acrylonitrile / fluoroester are added to produce a fluorinated polymer elastomer containing both the main chain and side chains. This method, by introducing a fourth monomer, a fluorinated ester, imparts excellent heat resistance, oxidation resistance, oil resistance, and corrosion resistance to the material, making it widely used in aerospace, automotive, petroleum, and other fields. CN108610452B discloses a method for preparing fluorinated nitrile rubber by low-temperature emulsion polymerization and the product obtained by this method. The method utilizes a fluorinated monomer emulsion polymerization method to prepare fluorinated nitrile rubber. The use of a chelate titanate coupling agent during the polymerization process can significantly improve the ternary copolymerization efficiency of the fluorinated monomer, acrylonitrile, and butadiene. The prepared fluorinated nitrile rubber has good oil resistance and high tensile strength, which is more than 20% higher than that of fluorinated nitrile rubber prepared by conventional methods. The Mooney viscosity is 50-110, the tensile strength is above 30 MPa, and the elongation at break is above 500%. At the same time, it has outstanding high and low temperature resistance, excellent aging resistance, and a glass transition temperature that is lowered by more than 10°C. CN113372504B discloses a fluorinated hydrogenated nitrile rubber material and its preparation method and application. This invention introduces fluorine atoms into the HNBR molecular chain through a grafting reaction using a small molecule fluorine monomer, thereby improving its oil resistance and hydrophobicity while maintaining the original tensile strength, elongation at break, Shore hardness, and low-temperature resistance of HNBR, thereby solving the problems existing in the existing physical mixing modified HNBR. Pei Shihong et al. synthesized a stable fluorinated modified acrylate emulsion using a semi-continuous seed emulsion polymerization method using fluorinated acrylate and acrylate monomers. When the fluorinated acrylate dosage is only 2%, the water resistance can be significantly improved. (Pei Shihong, Shi Bowen, Song Wei. Synthesis of organic fluorine and epoxy resin modified acrylate emulsion [J]. Chinese Adhesives, 2012, 21(10):13-17).

[0005] Although the aforementioned prior art can improve the high temperature resistance, aging resistance, and tensile strength of fluorinated nitrile rubber to a certain extent by adding small molecule fluorine monomers and fluorine rubber through emulsion polymerization and blending, these methods still have certain limitations. The preparation methods require large amounts of addition, are costly, have limited modification effects, and have significant stability fluctuations in the modified products. Summary of the Invention

[0006] In order to solve the problems existing in the prior art, the purpose of the present invention is to provide a method for preparing a low-temperature resistant and highly wear-resistant fluorinated nitrile rubber. The present invention first uses an anionic polymerization method to prepare a functionalized reactive macromolecular fluorine monomer containing a wide vinyl distribution and long chain branches by temperature-variable polymerization of reactive monomers 4-trifluoromethylstyrene, styrene, N-(4-hydroxy linear alkyl) acrylamide and 1,3-butadiene; then the functionalized reactive macromolecular fluorine monomer is pre-emulsified, and finally the functionalized reactive macromolecular fluorine monomer is grafted onto the NBR main chain structure by low-temperature emulsion polymerization to prepare a low-temperature resistant and highly wear-resistant fluorinated nitrile rubber; this method solves the "high wear resistance-low temperature resistance" inversion contradiction problem of FNBR, achieves a balance between the high wear resistance and low temperature resistance of FNBR, and meets the operating requirements of the stator rubber material of the submersible screw pump of oil exploration equipment in extremely cold oil fields.

[0007] Unless otherwise specified, the “parts” described in the present invention refer to parts by mass, the “%” described refers to mass percentage, and the “ratio” described refers to mass ratio.

[0008] In order to achieve the above object, the present invention adopts the following technical solution: a method for preparing a low-temperature resistant and highly wear-resistant fluorinated nitrile rubber, the specific preparation process comprising the following steps:

[0009] (1) Preparation of functionalized reactive macromolecular fluorine monomer: Based on 100 parts by mass of 4-trifluoromethylstyrene, argon is introduced into a polymerization kettle to replace the system 3 to 5 times, and a solvent, 1,3-butadiene, and a structure regulator are added to the polymerization kettle in sequence, and the mixture is stirred and heated by 1 minute. An initiator is added for the initial reaction, which is a temperature-switching polymerization. Within 50 to 60 minutes, the temperature is gradually increased from 30°C to 50°C to form a BR segment with a wide vinyl distribution. Then, 4-trifluoromethylstyrene, styrene, and N-(4-hydroxy linear alkyl) acrylamide are added to the polymerization kettle in sequence, the mixture is heated by 2 minutes, and the reaction is carried out for 2 minutes. After the reaction, the glue is subjected to wet coagulation and drying to obtain a functionalized reactive macromolecular fluorine monomer.

[0010] (2) Preparation of low-temperature-resistant and highly wear-resistant fluorinated nitrile rubber: Based on 100 parts by total weight of 1,3-butadiene and acrylonitrile monomers, deionized water, emulsifier, activator, acrylonitrile, and molecular weight regulator are added to a polymerization kettle, and nitrogen pressure-vacuum replacement is performed 3 to 5 times, and stirring is performed; then the functionalized reactive macromolecular fluorine monomer, emulsifier, and deionized water are stirred and mixed at 11 to 14°C for 25 to 35 minutes to form a functionalized reactive macromolecular fluorine monomer pre-emulsion, which is added to the polymerization kettle; finally, a deoxidizer and 1,3-butadiene are added, the temperature is lowered, and initiator 2 is added to carry out polymerization reaction. When the conversion rate reaches 75% to 78%, a terminator is added to terminate the polymerization, and the material is discharged, condensed, washed, and dried to prepare low-temperature-resistant and highly wear-resistant fluorinated nitrile rubber.

[0011] The functionalized reactive macromolecular fluorine monomer of the present invention has the following structure:

[0012]

[0013] Wherein, BR is a broad distribution 1,3-butadiene homopolymer segment, R is a C3-C7 alkyl group, and n is the number of repeating units, which is a positive integer of n≥1. The number average molecular weight (Mn) of the functionalized reactive macromolecular fluorine monomer is 5000-7000.

[0014] Furthermore, the initiator 1 is a hydrocarbon monolithium compound, namely, RLi, where R is a saturated aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or a composite of the foregoing groups containing 1 to 20 carbon atoms. This hydrocarbon monolithium compound is selected from n-butyllithium, sec-butyllithium, methylbutyllithium, phenylbutyllithium, naphthalenelithium, cyclohexyllithium, and dodecyllithium, with n-butyllithium being preferred. The amount of organolithium added is determined by the molecular weight of the designed polymer. For example, the amount of butyllithium can be calculated using the following formula.

[0015] Butyl lithium molar amount (mol) = total mass m (g) / molecular weight M (g / mol)

[0016] The total mass refers to the sum of the masses of 1,3-butadiene + 4-trifluoromethylstyrene + styrene + N-(4-hydroxy linear alkyl) acrylamide; and the molecular weight refers to the molecular weight of the target product, the functionalized reactive macromolecular fluorine monomer.

[0017] Furthermore, the N-(4-hydroxy linear alkyl) acrylamide is selected from one of N-(4-hydroxybutyl) acrylamide, N-(4-hydroxypentyl) acrylamide, N-(4-hydroxyhexyl) acrylamide, N-(4-hydroxyheptyl) acrylamide and N-(4-hydroxyoctyl), preferably N-(4-hydroxybutyl) acrylamide.

[0018] Furthermore, the structure modifier is a polar organic compound that produces a solvation effect in the polymerization system. Such polar organic compound is selected from one of diethylene glycol dimethyl ether (DGE), tetrahydrofuran (THF), ethyl ether, ethyl methyl ether, anisole, diphenyl ether, ethylene glycol dimethyl ether (DME), and triethylamine, preferably tetrahydrofuran (THF).

[0019] Furthermore, the solvent of the present invention can be selected from one of cyclohexane, hexane, carbon disulfide (CS2), nitrobenzene, petroleum ether, tetrachloroethane, toluene, and xylene, preferably cyclohexane.

[0020] Furthermore, the emulsifier is an emulsifier that is stable in acidic medium, and the options include alkyl sulfates and alkyl or aryl sulfonates, which can be selected from potassium rosinate soap, oleic acid methyl soap, sodium pyrophosphate, fatty acid, disproportionated potassium rosinate, sodium fatty acid C8-C 20 The amount of the sodium alkyl sulfate is conventional in the art and is not particularly limited in the present invention. The amount is 3.0 to 8.0 parts based on 100 parts by weight of the total weight of the two monomers 1,3-butadiene and acrylonitrile.

[0021] Furthermore, the initiator 2 is a redox initiator selected from the group consisting of cumene hydroperoxide, dicumyl hydroperoxide, isopropyl tert-butyl peroxide, and isopropyl n-butyl peroxide, preferably dicumyl hydroperoxide. The amount of initiator used is conventional in the art, preferably 0.03 to 0.2 parts, more preferably 0.06 to 0.15 parts, based on 100 parts by weight of the total weight of the 1,3-butadiene and acrylonitrile monomers.

[0022] Furthermore, the activator can be selected from one or more of ferrous sulfate, EDTA tetrasodium salt or EDTA sodium iron salt, and the amount used is the conventional amount in this field. The added amount is preferably 0.3 to 0.9 parts based on 100 parts of the total mass of the two monomers 1,3-butadiene and acrylonitrile.

[0023] Furthermore, the molecular weight regulator is a common regulator for emulsion polymerization and can be selected from one of tert-dodecyl mercaptan and dodecyl mercaptan, preferably tert-dodecyl mercaptan. The amount used is conventional in the art, preferably 0.6 to 1.2 parts by weight based on 100 parts by weight of the total weight of the 1,3-butadiene and acrylonitrile monomers.

[0024] Furthermore, the oxygen scavenger is selected from one of sodium dithionite, dimethyl ketoxime, isoascorbic acid, carbohydrazide, and N-isopropylhydroxylamine, preferably sodium dithionite. The amount used is conventional in the art, preferably 0.02 to 0.06 parts by weight based on 100 parts by weight of the total weight of the 1,3-butadiene and acrylonitrile monomers.

[0025] Furthermore, the terminator can be selected from one of NaNO2, hydroxylamine sulfate, diethylhydroxylamine, 2,5-pentylbutylbenzene, sodium dimethyldithiocarbamate, sodium nitrite, actinium ferric reagent, or p-aminoazobenzene, preferably sodium dimethyldithiocarbamate. The amount used is the conventional amount in the art, which is 0.4 to 0.7 parts per 100 parts by weight of the total weight of the two monomers 1,3-butadiene and acrylonitrile.

[0026] Furthermore, the added amount of the functionalized reactive macromolecular fluorine monomer is preferably 1.5 to 4.0 parts based on 100 parts of the total mass of the two monomers, 1,3-butadiene and acrylonitrile.

[0027] The present invention does not particularly limit the coagulation and drying process. The coagulation and drying process commonly used in the art can be used. The calcium chloride aqueous solution is added for coagulation, filtered and dehydrated, and dried at 85-90°C until the moisture content is below 0.5%.

[0028] In step (1) of the present invention, based on 100 parts by mass of 4-trifluoromethylstyrene, the mass ratio of the solvent, 1,3-butadiene, styrene, N-(4-hydroxy linear alkyl) acrylamide and the structure regulator is (400-500):(10.0-14.0):(9.0-13.0):(10.0-15.0):(0.3-0.7); the stirring speed is 300-400 rpm; the temperature of the heating step 1 is 30° C.; the temperature of the heating step 2 is 70-80° C.; and the reaction time of the reaction step 2 is 70-80 min.

[0029] In step (ii) of the present invention, based on 100 parts by total mass of the two monomers 1,3-butadiene and acrylonitrile, the mass ratio of the deionized water, emulsifier, activator, acrylonitrile, molecular weight regulator, scavenger, 1,3-butadiene, macromolecular fluorinated long-chain branched monomer, initiator and terminator is (400-500): (3.0-8.0):

[0030] (0.3~0.9):(28~34):(0.6~1.2):(0.02~0.06):(66~72):(1.5~4.0):

[0031] (0.03~0.2):(0.4~0.7).

[0032] In step (2) of the present invention, the mass ratio of ionized water, emulsifier and functionalized reactive macromolecular fluorine monomer in the functionalized reactive macromolecular fluorine monomer pre-emulsion is (300-400): (5.0-9.0):100.

[0033] In step (2) of the present invention, the stirring speed is 300-400 rpm; the cooling means that the polymerization reaction temperature is reduced to 4-13°C.

[0034] In step (2) of the present invention, the polymerization conversion rate refers to the conversion rate of acrylonitrile during the polymerization process.

[0035] The reactor of the present invention can be a loop reactor or a tank reactor, preferably a tank reactor.

[0036] The present invention also provides a low-temperature-resistant and highly wear-resistant fluorinated nitrile rubber obtained by the above-mentioned preparation method.

[0037] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0038] (1) The present invention provides an innovative method for preparing functionalized reactive macromolecular fluorine monomers based on anionic polymerization technology. By constructing a terpolymer of 4-trifluoromethylstyrene, styrene, and N-(4-hydroxy linear alkyl) acrylamide and a broadly distributed 1,3-butadiene homopolymer to form a precisely controllable block copolymer system, a functionalized reactive macromolecular fluorine monomer with both reactivity and structural stability is successfully synthesized. This technical solution effectively alleviates the rigid accumulation of molecular chains caused by the high bond energy of C-F bonds and the strong polarity of nitrile groups through the "structural buffer effect" produced by the branched structure and wide distribution of macromolecular long-chain alkyl groups. At the same time, based on the low-temperature plasticization effect of ether bonds and the "group synergistic effect" of unsaturated double bonds and hydroxyl groups, it gives the material molecular chains the ability to move in low-temperature environments, significantly reducing the glass transition temperature (Tg) of fluorinated nitrile rubber (FNBR) to ≤-42°C. In addition, by utilizing the "directional enrichment effect" of C-F bonds and the "three-dimensional steric effect" of benzene rings, the mechanical strength and dynamic energy dissipation capacity are synergistically enhanced at the molecular scale. The wear resistance of the vulcanized rubber is ≤0.19cm 3 / km, 300% modulus of elongation ≥ 21.0MPa, tensile strength ≥ 27.0MPa; the low-temperature resistant and highly wear-resistant fluorinated nitrile rubber prepared by this method can fully meet the long-term stable operation requirements of submersible screw pumps in western / northeastern oil fields in my country under low temperature of -40°C and high shear conditions.

[0039] (2) The functionalized reactive macromolecular fluorine monomer prepared by the present invention contains hydroxyl groups, ether groups and C=C unsaturated double bonds. Firstly, the hydroxyl groups and ether groups are used to construct a molecular amphiphilic block, which gives the monomer an active interface in the deionized water system, significantly improving the monomer solubility. It can synergize with the emulsifier to form a micelle system with uniform particle size distribution, effectively promoting the penetration and diffusion of the macromolecular monomer into the butadiene-acrylonitrile copolymer latex, thereby greatly improving the probability of grafting reaction; secondly, the C=C unsaturated double bond is used to construct an active reaction micro-region, so that the macromolecular fluorinated monomer exhibits a high grafting efficiency under free radical initiation conditions, thereby obtaining a fluorinated nitrile rubber with a molecular structure of a multi-polymer structure.

[0040] (3) The preparation method of the low-temperature-resistant and highly wear-resistant fluorinated nitrile rubber provided by the present invention is green and environmentally friendly, has a stable process, uses a low amount of modifier, and has a significant modification effect.

[0041] Figures and descriptions of the figures

[0042] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the present application and, together with the description, serve to explain the principles of the present application.

[0043] Figure 1 : Infrared spectrum of the functionalized reactive macromolecular fluorine monomer in Example 1.

[0044] from Figure 1 It can be seen that at wave numbers of 1230-1260 cm -1 The asymmetric stretching vibration absorption peak of the CF bond appears at the wave number of 3100~3200cm -1 The characteristic peak of benzene ring appears at the wave number of 3300~3350cm -1 The characteristic peaks of secondary amide appeared at wave numbers of 3260-3390 cm -1 The characteristic peak of hydroxyl group appeared. DETAILED DESCRIPTION

[0045] The following examples and comparative examples illustrate the effects of the present invention, but the scope of protection of the present invention is not limited to these examples and comparative examples. The raw materials used in the examples are all industrial grade and purified before use, with no other special requirements. The "parts" mentioned in the examples and comparative examples are all parts by mass.

[0046] ⑴Source of raw materials:

[0047] Acrylonitrile, industrial polymer grade, PetroChina Lanzhou Petrochemical Company

[0048] 1,3-Butadiene, 99% purity, PetroChina Lanzhou Petrochemical Company

[0049] Styrene, 99% purity, PetroChina Lanzhou Petrochemical Company

[0050] N-(4-Hydroxybutyl)acrylamide, purity 99%, Shanghai Jizhi Biochemical Technology Co., Ltd.

[0051] 4-Trifluoromethylstyrene, purity 98%, Zhengzhou Alpha Chemical Co., Ltd.

[0052] n-Butyllithium, 98% purity Nanjing Tonglian Chemical Co., Ltd.

[0053] Diisopropylbenzene hydroperoxide, Lanzhou Additive Factory

[0054] Other reagents are commercially available industrial products

[0055] ⑵Analysis and testing methods:

[0056] Molecular weight and distribution were determined using a 2414 gel permeation chromatograph (GPC) produced by Waters, USA. Polystyrene standards were used as the calibration curve, the mobile phase was tetrahydrofuran, the column temperature was 40°C, 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 .

[0057] Determination of glass transition temperature Tg: The glass transition temperature of the product was measured using DSC. The instrument model was DSC1, owned by Mettler, Switzerland. The heating range was -80 to 80°C, and the heating rate was 10°C / min.

[0058] 300% modulus stress test: Execute the method in standard GB / T 528-2009.

[0059] Tensile strength test: Execute the method in standard GB / T 1690-2010.

[0060] Abrasion resistance test: Execute the method in standard GB / T 1689-1998.

[0061] (3) Formulation and process of vulcanized rubber:

[0062] The following examples and comparative examples were prepared by mixing raw rubber to prepare vulcanized rubber using the same formula and process, as shown in Table 1 below.

[0063] Table 1 Vulcanized rubber formula and process

[0064]

[0065] Example 1

[0066] (1) Preparation of functionalized reactive macromolecular fluorine monomer: In a 10L stainless steel polymerization kettle with a jacket, the system was replaced three times with argon, and 4000g of cyclohexane, 100g of 1,3-butadiene, and 3.0g of THF were added to the polymerization kettle in sequence. The stirring speed was turned on at 300rpm, the temperature was raised to 30°C, and 261mmol of n-butyllithium was added for reaction. Within 50min, the temperature was gradually raised from 30°C to 50°C to form a BR segment with a wide vinyl distribution; then 1000g of 4-trifluoromethylstyrene, 90g of styrene, and 100g of N-(4-hydroxybutyl)acrylamide were added to the polymerization kettle in sequence, the temperature was raised to 70°C, and the reaction was carried out for 70min. After the reaction, the glue was wet-coagulated and dried to obtain a functionalized reactive macromolecular fluorine monomer (Mn is 5000).

[0067] (II) Preparation of low-temperature-resistant and highly wear-resistant fluorinated nitrile rubber: 4000 g of deionized water, 30 g of sodium dodecylbenzenesulfonate soap, 2.2 g of white powder, 0.8 g of EDTA-sodium iron salt, 280 g of acrylonitrile and 6.0 g of tert-dodecyl mercaptan were added to a 15 L stirred autoclave, and nitrogen pressure-vacuum replacement was performed three times, and the stirring speed was turned on at 300 rpm; then 15.0 g of functionalized reactive macromolecular fluorine monomer, 0.75 g of sodium dodecylbenzenesulfonate soap and 45 g of deionized water were stirred and mixed at 11 ° C for 25 min to form a functionalized reactive macromolecular fluorine monomer pre-emulsion, which was added to the polymerization kettle, and finally 0.2 g of sodium dithionite and 720 g of 1,3-Butadiene. When the polymerization kettle temperature was lowered to 4.0°C, 0.3g of diisopropylbenzene hydroperoxide (initiator) was added to initiate polymerization. When the polymerization conversion reached 75%, 4.0g of sodium thiamethoxam (terminator) was added to terminate the polymerization. The product was stirred, discharged, and coagulated with an aqueous solution of calcium chloride. After filtration and dehydration, it was dried at 85°C to a moisture content of less than 0.5%, producing a low-temperature-resistant, highly wear-resistant fluorinated nitrile rubber. Sampling and Analysis: Mixing and vulcanization were performed according to the formulation and conditions in Table 1 to produce standard specimens for testing. The results are shown in Table 2.

[0068] Example 2

[0069] (1) Preparation of functionalized reactive macromolecular fluorine monomer: In a 10L stainless steel polymerization kettle with a jacket, the system was replaced three times with argon, and 4300g of cyclohexane, 110g of 1,3-butadiene, and 4.2g of THF were added to the polymerization kettle in sequence. The stirring speed was turned on at 330rpm, the temperature was raised to 30°C, and 243mmol of n-butyllithium was added for reaction. Within 52min, the temperature was gradually raised from 30°C to 50°C to form a BR segment with a wide vinyl distribution; then 1000g of 4-trifluoromethylstyrene, 100g of styrene, and 110g of N-(4-hydroxybutyl)acrylamide were added to the polymerization kettle in sequence, the temperature was raised to 72°C, and the reaction was carried out for 73min. After the reaction, the glue was wet-coagulated and dried to obtain a functionalized reactive macromolecular fluorine monomer (Mn was 5500).

[0070] (II) Preparation of low-temperature-resistant and highly wear-resistant fluorinated nitrile rubber: 4200 g of deionized water, 42 g of sodium dodecylbenzenesulfonate soap, 3.9 g of white powder, 1.1 g of EDTA-sodium iron salt, 290 g of acrylonitrile and 7.6 g of tert-dodecyl mercaptan were added to a 15 L stirred autoclave, and nitrogen was pressurized and vacuumed for 3 times, and the stirring speed was turned on at 330 rpm; then 26.0 g of functionalized reactive macromolecular fluorine monomer, 1.55 g of sodium dodecylbenzenesulfonate soap and 86 g of deionized water were stirred and mixed at 12 ° C for 27 min to form a functionalized reactive macromolecular fluorine monomer pre-emulsion, which was added to the polymerization kettle, and finally 0.3 g of sodium dithionite and 710 g of 1,3-Butadiene. When the polymerization kettle temperature was lowered to 6.0°C, 0.8g of diisopropylbenzene hydroperoxide (initiator) was added to initiate polymerization. When the polymerization conversion reached 76%, 5.3g of sodium thiamethoxam (terminator) was added to terminate the polymerization. The product was stirred, discharged, and coagulated with an aqueous solution of calcium chloride. After filtration and dehydration, it was dried at 86°C to a moisture content of less than 0.5%, producing a low-temperature-resistant, highly wear-resistant fluorinated nitrile rubber. Sampling and analysis: Mixing and vulcanization were performed according to the formulation and conditions in Table 1 to produce standard specimens for testing. The results are shown in Table 2.

[0071] Example 3

[0072] (1) Preparation of functionalized reactive macromolecular fluorine monomer: In a 10L stainless steel polymerization kettle with a jacket, the system was replaced 4 times with argon, and 4500g of cyclohexane, 120g of 1,3-butadiene, and 5.3g of THF were added to the polymerization kettle in sequence. The stirring speed was turned on at 350rpm, the temperature was raised to 30°C, and 225mmol of n-butyllithium was added for reaction. Within 55min, the temperature was gradually raised from 30°C to 50°C to form a BR segment with a wide vinyl distribution; then 1000g of 4-trifluoromethylstyrene, 110g of styrene, and 130g of N-(4-hydroxybutyl)acrylamide were added to the polymerization kettle in sequence, the temperature was raised to 75°C, and the reaction was carried out for 75min. After the reaction, the glue was wet-coagulated and dried to obtain a functionalized reactive macromolecular fluorine monomer (Mn was 6100).

[0073] (II) Preparation of low-temperature-resistant and highly wear-resistant fluorinated nitrile rubber: 4600 g of deionized water, 56 g of sodium dodecylbenzenesulfonate soap, 4.7 g of white powder, 1.3 g of EDTA-sodium iron salt, 310 g of acrylonitrile and 8.5 g of tert-dodecyl mercaptan were added to a 15 L stirred autoclave, and nitrogen pressure-vacuum replacement was performed 4 times, and the stirring speed was turned on at 350 rpm; then 30.0 g of functionalized reactive macromolecular fluorine monomer, 2.12 g of sodium dodecylbenzenesulfonate soap and 108 g of deionized water were stirred and mixed at 13 ° C for 31 min to form a functionalized reactive macromolecular fluorine monomer pre-emulsion, which was added to the polymerization kettle, and finally 0.4 g of sodium dithionite and 690 g of 1,3-Butadiene. When the polymerization kettle temperature was lowered to 9.0°C, 1.3g of diisopropylbenzene hydroperoxide (initiator) was added to initiate polymerization. When the polymerization conversion reached 76%, 5.9g of sodium thiamethoxam (terminator) was added to terminate the polymerization. The product was stirred, discharged, and coagulated with an aqueous solution of calcium chloride. After filtration and dehydration, it was dried at 88°C to a moisture content of less than 0.5%, producing a low-temperature-resistant, highly wear-resistant fluorinated nitrile rubber. Sampling and Analysis: Mixing and vulcanization were performed according to the formulation and conditions in Table 1 to produce standard specimens for testing. The results are shown in Table 2.

[0074] Example 4

[0075] (I) Preparation of functionalized reactive macromolecular fluorine monomer: In a 10L stainless steel polymerizer with a jacket, the system was replaced four times with argon, and 4700g of cyclohexane, 130g of 1,3-butadiene, and 6.1g of THF were added to the polymerizer in sequence. The stirring speed was turned on at 360rpm, and the temperature was raised to 30°C. 216mmol of n-butyllithium was added for reaction. Within 58min, the temperature was gradually raised from 30°C to 50°C to form a BR segment with a broad vinyl distribution. Then, 1000g of 4-trifluoromethylstyrene, 120g of styrene, and 140g of N-(4-hydroxybutyl)acrylamide were added to the polymerizer in sequence. The temperature was raised to 78°C and the reaction was carried out for 77min. After the reaction, the glue was subjected to wet coagulation and drying to obtain a functionalized reactive macromolecular fluorine monomer (Mn of 6500 and Mw / Mn of 5.63).

[0076] (II) Preparation of low-temperature-resistant and highly wear-resistant fluorinated nitrile rubber: 4700 g of deionized water, 68 g of sodium dodecylbenzenesulfonate soap, 5.2 g of white powder, 1.8 g of EDTA-sodium iron salt, 320 g of acrylonitrile and 9.8 g of tert-dodecyl mercaptan were added to a 15 L stirred autoclave, and nitrogen pressure-vacuum replacement was performed 4 times, and the stirring speed was turned on at 370 rpm; then 35.0 g of functionalized reactive macromolecular fluorine monomer, 2.45 g of sodium dodecylbenzenesulfonate soap and 130 g of deionized water were stirred and mixed at 13 ° C for 33 min to form a functionalized reactive macromolecular fluorine monomer pre-emulsion, which was added to the polymerization kettle, and finally 0.5 g of sodium dithionite and 680 g of sodium bisulfite were added. 1,3-Butadiene. When the polymerization kettle temperature was lowered to 11.0°C, 1.6g of diisopropylbenzene hydroperoxide (initiator) was added to initiate polymerization. When the polymerization conversion reached 77%, 6.2g of sodium thiamethoxam (terminator) was added to terminate the polymerization. The product was stirred, discharged, and coagulated with an aqueous calcium chloride solution. After filtration and dehydration, it was dried at 89°C to a moisture content of less than 0.5%, producing a low-temperature-resistant, highly wear-resistant fluorinated nitrile rubber. Sampling and Analysis: Mixing and vulcanization were performed according to the formulation and conditions in Table 1 to produce standard specimens for testing. The results are shown in Table 2.

[0077] Example 5

[0078] (1) Preparation of functionalized reactive macromolecular fluorine monomer: In a 10L stainless steel polymerization kettle with a jacket, the system was replaced 5 times with argon, and 5000g of cyclohexane, 140g of 1,3-butadiene, and 7.0g of THF were added to the polymerization kettle in sequence. The stirring speed was turned on at 400rpm, the temperature was raised to 30°C, and 205mmol of n-butyllithium was added for reaction. Within 60min, the temperature was gradually raised from 30°C to 50°C to form a BR segment with a wide vinyl distribution; then 1000g of 4-trifluoromethylstyrene, 130g of styrene, and 150g of N-(4-hydroxybutyl)acrylamide were added to the polymerization kettle in sequence, the temperature was raised to 80°C, and the reaction was carried out for 80min. After the reaction, the glue was wet-coagulated and dried to obtain a functionalized reactive macromolecular fluorine monomer (Mn was 7000).

[0079] (II) Preparation of low-temperature-resistant and highly wear-resistant fluorinated nitrile rubber: 5000 g of deionized water, 80 g of sodium dodecylbenzenesulfonate soap, 6.8 g of white powder, 2.2 g of EDTA-sodium iron salt, 340 g of acrylonitrile and 12.0 g of tert-dodecyl mercaptan were added to a 15 L stirred autoclave, and nitrogen was pressurized and vacuumed for 5 times, and the stirring speed was turned on at 400 rpm; then 40.0 g of functionalized reactive macromolecular fluorine monomer, 3.60 g of sodium dodecylbenzenesulfonate soap and 160 g of deionized water were stirred and mixed at 14 ° C for 35 min to form a functionalized reactive macromolecular fluorine monomer pre-emulsion, which was added to the polymerization kettle, and finally 0.6 g of sodium dithionite and 660 g of 1,3-Butadiene. When the polymerization kettle temperature was lowered to 13.0°C, 2.0g of diisopropylbenzene hydroperoxide (initiator) was added to initiate polymerization. When the polymerization conversion reached 78%, 7.0g of sodium thiamethoxam (terminator) was added to terminate the polymerization. The product was stirred, discharged, and coagulated with an aqueous solution of calcium chloride. After filtration and dehydration, it was dried at 90°C to a moisture content of less than 0.5%, producing a low-temperature-resistant, highly wear-resistant fluorinated nitrile rubber. Sampling and analysis: Mixing and vulcanization were performed according to the formulation and conditions in Table 1 to produce standard specimens for testing. The results are shown in Table 2.

[0080] Comparative Example 1

[0081] (I) Preparation of functionalized reactive macromolecular fluorine monomer: Other conditions were the same as those in Example 1, except that 1000 g of trifluoroethyl methacrylate was added instead of 4-trifluoromethylstyrene during the preparation of the functionalized reactive macromolecular fluorine monomer. That is, in a 10 L stainless steel polymerizer with a jacket, argon was passed through the system for three times, and 4000 g of cyclohexane, 100 g of 1,3-butadiene, 3.0 g of THF, turn on the stirring speed to 300 rpm, raise the temperature to 30°C, add 261 mmol n-butyl lithium to react, and within 50 minutes, gradually increase the temperature from 30°C to 50°C to form a BR chain segment with a wide vinyl distribution; then add 1000g trifluoroethyl methacrylate, 90g styrene, and 100g N-(4-hydroxybutyl) acrylamide to the polymerization kettle in sequence, raise the temperature to 70°C, and react for 70 minutes. After the reaction, the glue is wet-coagulated and dried to obtain a functionalized reactive macromolecular fluorine monomer a (Mn is 4950).

[0082] (2) Preparation of low-temperature-resistant and highly wear-resistant fluorinated nitrile rubber: Other conditions are the same as those in Example 1, except that in the preparation process of low-temperature-resistant and highly wear-resistant fluorinated nitrile rubber, no functionalized reactive macromolecular fluorine monomer is added, but functionalized reactive macromolecular fluorine monomer a is added in an amount of 15.0 g, that is, 4000 g of deionized water, 30 g of sodium dodecylbenzenesulfonate soap, 2.2 g of Diaobai block, 0.8 g of EDTA-sodium iron salt, 280 acrylonitrile and 6.0 g of tert-dodecyl mercaptan are added to a 15 L stirred pressure autoclave, nitrogen pressurization-vacuum replacement is performed 3 times, and the stirring speed is turned on to 300 rpm; then 15.0 g of functionalized reactive macromolecular fluorine monomer a, 0.75 g of sodium dodecylbenzenesulfonate soap and 45 g of deionized water are stirred and mixed at 11 ° C for 25 min to form a functionalized reactive macromolecular fluorine monomer pre-emulsion, which is added to the polymerization kettle, and finally 0.2 g of sodium dithionite and 720 g of sodium bisulfite are added. 1,3-Butadiene. When the polymerization kettle temperature was lowered to 4.0°C, 0.3g of diisopropylbenzene hydroperoxide (initiator) was added to initiate polymerization. When the polymerization conversion reached 75%, 4.0g of sodium thiamethoxam (terminator) was added to terminate the polymerization. The product was stirred, discharged, and coagulated with an aqueous solution of calcium chloride. After filtration and dehydration, it was dried at 85°C to a moisture content of less than 0.5%, producing a low-temperature-resistant, highly wear-resistant fluorinated nitrile rubber. Sampling and Analysis: Mixing and vulcanization were performed according to the formulation and conditions in Table 1 to produce standard specimens for testing. The results are shown in Table 2.

[0083] Comparative Example 2

[0084] (I) Preparation of functionalized reactive macromolecular fluorine monomer: The other conditions were the same as those in Example 2, except that N-(4-hydroxybutyl)acrylamide was not added during the preparation of the functionalized reactive macromolecular fluorine monomer, that is, in a 10 L stainless steel polymerizer with a jacket, the system was replaced three times with argon, 4300 g of cyclohexane, 110 g of 1,3-butadiene, and 4.2 g of THF were added to the polymerizer in sequence, the stirring speed was turned on at 330 rpm, the temperature was raised to 30 ° C, 243 mmol of n-butyl lithium was added to react, and the temperature was gradually increased from 30 ° C to 50 ° C within 52 minutes to form a BR segment with a wide vinyl distribution; then 1000 g of 4-trifluoromethylstyrene and 100 g of styrene were added to the polymerizer in sequence, the temperature was raised to 72 ° C, and the reaction was carried out for 73 minutes. After the reaction, the glue was wet-coagulated and dried to obtain a functionalized reactive macromolecular fluorine monomer b (Mn is 5100).

[0085] (2) Preparation of low-temperature-resistant and highly wear-resistant fluorinated nitrile rubber: Other conditions are the same as those in Example 2, except that functionalized reactive macromolecular fluorine monomer is not added during the preparation of low-temperature-resistant and highly wear-resistant fluorinated nitrile rubber. Instead, functionalized reactive macromolecular fluorine monomer b is added in an amount of 26.0, i.e., 4200 g of deionized water, 42 g of sodium dodecylbenzenesulfonate soap, 3.9 g of Diaobai block, 1.1 g of EDTA-sodium iron salt, 290 g of acrylonitrile and 7.6 g of tert-dodecyl mercaptan are added to a 15 L stirred autoclave, nitrogen pressurization-vacuum replacement is performed 3 times, and the stirring speed is turned on to 330 rpm; then 26.0 g of functionalized reactive macromolecular fluorine monomer b, 1.55 g of sodium dodecylbenzenesulfonate soap and 86 g of deionized water are stirred and mixed at 12 ° C for 27 min to form a functionalized reactive macromolecular fluorine monomer pre-emulsion, which is added to the polymerization kettle, and finally 0.3 g of sodium dithionite and 710 g of sodium bisulfite are added. 1,3-Butadiene. When the polymerization kettle temperature was lowered to 6.0°C, 0.8g of diisopropylbenzene hydroperoxide (initiator) was added to initiate polymerization. When the polymerization conversion reached 76%, 5.3g of sodium thiamethoxam (terminator) was added to terminate the polymerization. The product was stirred, discharged, and coagulated with an aqueous solution of calcium chloride. After filtration and dehydration, it was dried at 86°C to a moisture content of less than 0.5%, producing a low-temperature-resistant, highly wear-resistant fluorinated nitrile rubber. Sampling and analysis: Mixing and vulcanization were performed according to the formulation and conditions in Table 1 to produce standard specimens for testing. The results are shown in Table 2.

[0086] Comparative Example 3

[0087] (I) Preparation of functionalized reactive macromolecular fluorine monomer: Other conditions were the same as those in Example 3, except that N-(4-hydroxybutyl)acrylamide was not added during the preparation of the functionalized reactive macromolecular fluorine monomer, but N-(4-hydroxymethyl)acrylamide was added in an amount of 130 g, that is: in a 10 L stainless steel polymerizer with a jacket, the system was replaced 4 times with argon, 4500 g of cyclohexane, 120 g of 1,3-butadiene, and 5.3 g of THF were added to the polymerizer in sequence, the stirring speed was turned on at 350 rpm, the temperature was raised to 30° C., 225 mmol of n-butyl lithium was added for reaction, and the temperature was gradually raised from 30° C. to 50° C. within 55 min to form a BR segment with a broad vinyl distribution; and then 1000 g of cyclohexane was added to the polymerizer in sequence. 4-Trifluoromethylstyrene, 110g styrene, 130g N-(4-hydroxymethyl)acrylamide, heated to 75℃, reacted for 75min, after the reaction, the glue was wet coagulated and dried to obtain functionalized reactive macromolecular fluorine monomer c (Mn is 6000).

[0088] (2) Preparation of low-temperature-resistant and highly wear-resistant fluorinated acrylonitrile-butadiene rubber: Other conditions are the same as those in Example 3, except that in the preparation process of low-temperature-resistant and highly wear-resistant fluorinated acrylonitrile-butadiene rubber, no functionalized reactive macromolecular fluorine monomer is added, but functionalized reactive macromolecular fluorine monomer c is added in an amount of 30.0 g, that is, 4600 g of deionized water, 56 g of sodium dodecylbenzenesulfonate soap, 4.7 g of Diaobai block, 1.3 g of EDTA-sodium iron salt, 310 acrylonitrile and 8.5 g of tert-dodecyl mercaptan are added to a 15 L stirred pressure autoclave, nitrogen pressurization-vacuum replacement is performed 4 times, and the stirring speed is turned on to 350 rpm; then 30.0 g of functionalized reactive macromolecular fluorine monomer c, 2.12 g of sodium dodecylbenzenesulfonate soap and 108 g of deionized water are stirred and mixed at 13 ° C for 31 min to form a functionalized reactive macromolecular fluorine monomer pre-emulsion, which is added to the polymerization kettle, and finally 0.4 g of sodium dithionite and 690 g of sodium bisulfite are added. 1,3-Butadiene. When the polymerization kettle temperature was lowered to 9.0°C, 1.3g of diisopropylbenzene hydroperoxide (initiator) was added to initiate polymerization. When the polymerization conversion reached 76%, 5.9g of sodium thiamethoxam (terminator) was added to terminate the polymerization. The product was stirred, discharged, and coagulated with an aqueous solution of calcium chloride. After filtration and dehydration, it was dried at 88°C to a moisture content of less than 0.5%, producing a low-temperature-resistant, highly wear-resistant fluorinated nitrile rubber. Sampling and Analysis: Mixing and vulcanization were performed according to the formulation and conditions in Table 1 to produce standard specimens for testing. The results are shown in Table 2.

[0089] Comparative Example 4

[0090] (I) Preparation of functionalized reactive macromolecular fluorine monomer: Other conditions were the same as those in Example 4, except that in the preparation process of the functionalized reactive macromolecular fluorine monomer, temperature-variable polymerization was not used in the synthesis of the BR segment, and polymerization was performed only at 30°C, that is, in a 10L stainless steel polymerization kettle with a jacket, the system was replaced 4 times with argon, 4700g of cyclohexane, 130g of 1,3-butadiene, and 6.1g of THF were added to the polymerization kettle in sequence, the stirring speed was turned on at 360rpm, the temperature was raised to 30°C, 216mmol of n-butyllithium was added and the reaction was carried out for 58min to form the BR segment; then 1000g of 4-trifluoromethylstyrene, 120g of styrene, and 140g of N-(4-hydroxybutyl)acrylamide were added to the polymerization kettle in sequence, the temperature was raised to 78°C, and the reaction was carried out for 77min. After the reaction, the glue was subjected to wet coagulation and drying to obtain functionalized reactive macromolecular fluorine monomer d (Mn was 6400, Mw / Mn was 3.12).

[0091] (2) Preparation of low-temperature-resistant and highly wear-resistant fluorinated nitrile rubber: Other conditions are the same as those in Example 4, except that in the preparation process of low-temperature-resistant and highly wear-resistant fluorinated nitrile rubber, no functionalized reactive macromolecular fluorine monomer is added, but functionalized reactive macromolecular fluorine monomer d is added in an amount of 35.0 g, that is, 4700 g of deionized water, 68 g of sodium dodecylbenzenesulfonate soap, 5.2 g of Diaobai block, 1.8 g of EDTA-sodium iron salt, 320 acrylonitrile and 9.8 g of tert-dodecyl mercaptan are added to a 15 L stirred pressure-resistant autoclave, and nitrogen pressure-vacuum replacement is performed 4 times, and the stirring speed is turned on to 370 rpm; then 35.0 g of functionalized reactive macromolecular fluorine monomer d, 2.45 g of sodium dodecylbenzenesulfonate soap and 130 g of deionized water are stirred and mixed at 13 ° C for 33 min to form a functionalized reactive macromolecular fluorine monomer pre-emulsion, which is added to the polymerization kettle, and finally 0.5 g of sodium dithionite and 680 g of sodium bisulfite are added. 1,3-Butadiene. When the polymerization kettle temperature was lowered to 11.0°C, 1.6g of diisopropylbenzene hydroperoxide (initiator) was added to initiate polymerization. When the polymerization conversion reached 77%, 6.2g of sodium thiamethoxam (terminator) was added to terminate the polymerization. The product was stirred, discharged, and coagulated with an aqueous calcium chloride solution. After filtration and dehydration, it was dried at 89°C to a moisture content of less than 0.5%, producing a low-temperature-resistant, highly wear-resistant fluorinated nitrile rubber. Sampling and Analysis: Mixing and vulcanization were performed according to the formulation and conditions in Table 1 to produce standard specimens for testing. The results are shown in Table 2.

[0092] Comparative Example 5

[0093] (1) Preparation of functionalized reactive macromolecular fluorine monomer: Same as in Example 5.

[0094] (2) Preparation of low-temperature-resistant and highly wear-resistant fluorinated nitrile rubber: Other conditions are the same as those in Example 5, except that the functionalized reactive macromolecular fluorine monomer is not pre-emulsified during the preparation of the low-temperature-resistant and highly wear-resistant fluorinated nitrile rubber. Instead, the functionalized reactive macromolecular fluorine monomer is directly added in an amount of 40.0 g, that is, 5000 g of deionized water, 80 g of sodium dodecylbenzenesulfonate soap, 6.8 g of Diaobai block, 2.2 g of EDTA-sodium iron salt, 340 g of acrylonitrile and 12.0 g of tert-dodecyl mercaptan are added to a 15 L stirred pressure autoclave, and nitrogen pressure-vacuum replacement is performed 5 times, and the stirring speed is turned on at 400 rpm; then 40.0 g of the functionalized reactive macromolecular fluorine monomer is added to the polymerization kettle, and finally 0.6 g of sodium dithionite and 660 g of sodium bisulfite are added. 1,3-Butadiene. When the polymerization kettle temperature was lowered to 13.0°C, 2.0g of diisopropylbenzene hydroperoxide (initiator) was added to initiate polymerization. When the polymerization conversion reached 78%, 7.0g of sodium thiamethoxam (terminator) was added to terminate the polymerization. The product was stirred, discharged, and coagulated with an aqueous solution of calcium chloride. After filtration and dehydration, it was dried at 90°C to a moisture content of less than 0.5%, producing a low-temperature-resistant, highly wear-resistant fluorinated nitrile rubber. Sampling and analysis: Mixing and vulcanization were performed according to the formulation and conditions in Table 1 to produce standard specimens for testing. The results are shown in Table 2.

[0095] Table 2 Properties of low temperature resistant and high wear resistant fluorinated nitrile rubber

[0096]

[0097] As shown in Table 2, the glass transition temperature Tg of the fluorinated nitrile rubber prepared by the present invention using the functionalized reactive macromolecular fluorine monomer is ≤-42°C, and the wear resistance of the vulcanized rubber is ≤0.19cm 3 / km, 300% modulus of elongation ≥ 21.0MPa, tensile strength ≥ 27.0MPa, fully meeting the long-term stable operation requirements of submersible screw pumps in western / northeastern oil fields of my country under low temperature of -40℃ and high shear conditions.

[0098] Of course, the present invention may have many other embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art may make various corresponding changes and modifications based on the present invention, but these corresponding changes and modifications should all fall within the scope of protection of the present invention.

Claims

1. A low-temperature-resistant and highly wear-resistant fluorinated nitrile rubber, characterized by: It is polymerized by, but not limited to, the following monomers: 1,3-butadiene, acrylonitrile and a functionalized reactive macromolecular fluorine monomer.

2. The low-temperature-resistant, highly wear-resistant fluorinated nitrile rubber according to claim 1, characterized in that The functionalized reactive macromolecular fluorine monomer has the following structure: Wherein, BR is a 1,3-butadiene homopolymer segment, R is a C3 to C7 alkyl group, and n is the number of repeating units, which is a positive integer of n≥1.

3. The low-temperature-resistant, highly wear-resistant fluorinated nitrile rubber according to claim 2, characterized in that The preparation method of the reactive macromolecular fluorine monomer comprises the following steps: based on 100 parts by mass of 4-trifluoromethylstyrene, introducing argon gas into a polymerization kettle to replace the system 3 to 5 times, sequentially adding a solvent, 1,3-butadiene, and a structure regulator into the polymerization kettle, stirring, raising the temperature to T1, adding initiator 1, starting the reaction as a temperature-variable polymerization, and gradually raising the temperature from 30° C. to 50° C. within 50 to 60 minutes; then sequentially adding 4-trifluoromethylstyrene, styrene, and N-(4-hydroxy linear alkyl) acrylamide into the polymerization kettle, raising the temperature to T2, and reacting for S2. After the reaction, the glue solution is subjected to wet coagulation and drying to obtain a functionalized reactive macromolecular fluorine monomer.

4. The low-temperature-resistant, highly wear-resistant fluorinated nitrile rubber according to claim 3, characterized in that The initiator 1 is a hydrocarbon monolithium compound, namely RLi, wherein R is a saturated aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or a composite group of the above groups containing 1 to 20 carbon atoms.

5. The low-temperature-resistant, highly wear-resistant fluorinated nitrile rubber according to claim 3, characterized in that The structure regulator is selected from one of diethylene glycol dimethyl ether, tetrahydrofuran, ethyl ether, ethyl methyl ether, anisole, diphenyl ether, ethylene glycol dimethyl ether, and triethylamine.

6. The low-temperature-resistant, highly wear-resistant fluorinated nitrile rubber according to claim 3, characterized in that The N-(4-hydroxy linear alkyl) acrylamide is selected from one of N-(4-hydroxybutyl) acrylamide, N-(4-hydroxypentyl) acrylamide, N-(4-hydroxyhexyl) acrylamide, N-(4-hydroxyheptyl) acrylamide and N-(4-hydroxyoctyl).

7. The low-temperature-resistant, highly wear-resistant fluorinated nitrile rubber according to claim 3, characterized in that The temperature of T1 is 30° C.; the temperature of T2 is 70-80° C.; and the reaction time of S2 is 70-80 min.

8. A method for preparing a low-temperature-resistant, highly wear-resistant fluorinated nitrile rubber according to any one of claims 1 to 7, characterized in that The method comprises the following steps: first, 1,3-butadiene, acrylonitrile and the reactive macromolecular fluorine monomer react to obtain a functionalized reactive macromolecular fluorine monomer pre-emulsion; second, the functionalized reactive macromolecular fluorine monomer pre-emulsion reacts with a scavenger and 1,3-butadiene to obtain a low-temperature-resistant and highly wear-resistant fluorinated nitrile rubber.

9. The method for preparing the low-temperature-resistant and highly wear-resistant fluorinated nitrile rubber according to claim 8, characterized in that It consists of the following steps: (1) Based on 100 parts by weight of the total weight of 1,3-butadiene and acrylonitrile monomers, deionized water, an emulsifier, an activator, acrylonitrile, and a molecular weight regulator are added to a polymerization kettle, and nitrogen pressure-vacuum replacement is performed 3 to 5 times, and the mixture is stirred; then, the functionalized reactive macromolecular fluorine monomer, the emulsifier, and deionized water are stirred and mixed at 11 to 14° C. for 25 to 35 minutes to form a functionalized reactive macromolecular fluorine monomer pre-emulsion; (2) adding the functionalized reactive macromolecular fluorine monomer pre-emulsion into the polymerization kettle; finally, adding deoxidizer and 1,3-butadiene, cooling, adding initiator 2 to carry out polymerization reaction, and when the conversion rate reaches 75% to 78%, adding terminator to terminate the polymerization, discharging, condensing, washing, and drying to prepare low-temperature resistant and highly wear-resistant fluorinated nitrile rubber.

10. The method for preparing the low-temperature-resistant and highly wear-resistant fluorinated nitrile rubber according to claim 9, characterized in that The initiator 2 is a redox initiator selected from cumene hydroperoxide, dicumyl hydroperoxide, isopropyl tert-butyl peroxide, isopropyl n-butyl peroxide; the emulsifier is selected from potassium rosinate soap, oleic acid methyl soap, sodium pyrophosphate, fatty acid, disproportionated potassium rosinate, fatty acid sodium C8-C 20 The activator is selected from one of the following:

1. one of the sodium alkyl sulfates; 2. one of the sodium alkyl sulfates; 3. one of the sodium alkyl sulfates; 4. one of the sodium alkyl sulfates; 5. one of the sodium alkyl sulfates; 6. one of the sodium alkyl sulfates; 7. one of the sodium alkyl sulfates; 8. one of the sodium alkyl sulfates; 9. one of the sodium alkyl sulfates; 10. one of the sodium alkyl sulfates; 11. one of the sodium alkyl sulfates; 12. one of the sodium alkyl sulfates; 13. one of the sodium alkyl sulfates; 14. one of the sodium alkyl sulfates; 15. one of the sodium alkyl sulfates; 16. one of the sodium alkyl sulfates; 17. one of the sodium alkyl sulfates; 18. one of the sodium alkyl sulfates; 19. one of the sodium alkyl sulfates; 20. one

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