Preparation method of wear-resistant fluorinated nitrile rubber for submersible screw pump stator

Abstract

The invention provides a preparation method of wear-resistant fluorinated nitrile rubber for a stator of a submersible screw pump, which comprises the following steps: 1) synthesizing a reactive macromolecular fluorine monomer by using fluorostyrene, diethylene glycol monovinyl ether and 1, 3-butadiene as raw materials through an anionic polymerization method; 2) the fluorine monomer is grafted to an NBR main chain through low-temperature emulsion polymerization, fluorine atom molecular-level dispersion is realized, and the modification defect of physical mixing is overcome; the aging resistance and wear resistance of the obtained fluorinated nitrile rubber can be remarkably improved by using a small amount of fluorine monomer, and the raw rubber Mooney viscosity ML (1 + 4, 100 DEG C) is 50-65; the 300% stress at definite elongation of vulcanized rubber is larger than or equal to 19.0 MPa, the tensile strength is larger than or equal to 30.0 MPa, the elongation at break is 360-420%, the abrasion loss is smaller than or equal to 0.22 cm < 3 > / km, and the performance change rate after 120 DEG C * 72 hr thermal aging is smaller than or equal to 3.2%. The method is efficient in process, suitable for industrial production and capable of meeting the strict working condition requirements of high temperature resistance and abrasion resistance of the submersible screw pump stator rubber.

Description

Technical Field

[0001] The invention belongs to the technical field of rubber, and in particular relates to a method for preparing wear-resistant fluorinated nitrile rubber for a submersible screw pump stator. 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 offers significant advantages in challenging reservoirs such as those with high-viscosity crude oil, high wax / sand content, and high gas-to-oil ratios: high mechanical efficiency, low energy consumption, and long maintenance cycles. These advantages are particularly pronounced in operating costs for specialized well types, such as deviated and horizontal wells. The longevity of the system's performance hinges crucially on the service life of the stator rubber assembly, and the choice of stator rubber material is crucial to this technological breakthrough.

[0003] Fluorinated nitrile rubber (FNBR) is produced by the targeted introduction of fluorine atoms into the main chain / side chain of nitrile rubber (NBR) or by mixing fluorine elastomers into the NBR matrix. Because fluorine atoms have a very small covalent radius, the bond energy of the FC bond is greater than that of the CH bond, the shielding effect of the fluorine atom's electron cloud on the CC bond is stronger than that of hydrogen atoms, and the polarizability of fluorine atoms is low, fluorinated nitrile rubber not only retains the oil resistance and viscoelasticity of NBR, but also exhibits superior aging resistance, ozone resistance, high temperature resistance, and strong tensile strength, making it adaptable to harsh environmental requirements and becoming an irreplaceable key material for stator rubber. However, as a core component, stator rubber is frequently subjected to the frictional forces during the rotation and lifting of the screw pump. In order to prevent the stator rubber from failing, such as rotting and debonding, in addition to excellent oil resistance, gas infiltration resistance, and aging resistance, FNBR also needs to possess a certain degree of wear resistance, which is crucial. Therefore, extremely high requirements are placed on the wear resistance of FNBR, the stator rubber material, which is the key point to ensure that the submersible screw pump can work for a long time.

[0004] In the prior art, there are many patent documents reporting on the preparation methods of fluorinated nitrile rubber, which mainly adopt the blending modification method and emulsion polymerization method. For example, CN200610119299.8 discloses a mechanical blending and vulcanization method of NBR and fluororubber. The fluororubber adopts a copolymer of vinylidene fluoride and hexafluoropropylene or a terpolymer of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene. During the vulcanization bonding, the curing time (T 90) is within the range of 0.3 to 12 minutes. CN115043991B discloses a method for preparing fluorine-containing thermoplastic elastomers by emulsion polymerization and its products. The preparation method comprises adding styrene, part of the emulsifier, the regulator and water into a polymerization kettle, adding a conjugated diene after nitrogen substitution, adding part of the initiator to start the emulsion polymerization, and when the conversion rate reaches 50-60%, adding the remaining emulsifier, the regulator, the initiator and the acrylonitrile / fluoroester mixture to prepare a main chain / side chain fluorine-containing polymer elastomer. This method, by combining the fourth monomer fluorine-containing ester, gives the material excellent heat resistance, oxidation resistance, oil resistance and corrosion resistance, and is widely used in aerospace, automobile, petroleum and other fields. CN108610452B discloses a method for preparing fluorine-containing nitrile rubber by low-temperature emulsion polymerization and the products obtained by this method. This method utilizes the emulsion polymerization method of fluorine-containing monomers to prepare fluorine-containing nitrile rubber. The use of a chelate titanate coupling agent in the polymerization process can significantly improve the ternary copolymerization efficiency of fluorine-containing monomers, acrylonitrile and butadiene. The prepared fluorinated nitrile rubber exhibits excellent oil resistance and high tensile strength, surpassing conventional fluorinated nitrile rubber by more than 20%. Its Mooney viscosity ranges from 50 to 110, its tensile strength exceeds 30 MPa, and its elongation at break exceeds 500%. It also exhibits outstanding high and low temperature resistance, excellent aging resistance, and a glass transition temperature reduction of more than 10°C. CN113372504B discloses a fluorinated hydrogenated nitrile rubber material, its preparation method, and its application. This invention introduces fluorine atoms onto the HNBR molecular chain through a grafting reaction using small molecule fluorinated monomers, improving its oil resistance and hydrophobicity while maintaining the original tensile strength, elongation at break, Shore hardness, and low-temperature resistance of the HNBR. This addresses the problems of existing physically mixed modified HNBR. Pei Shihong et al. synthesized a stable fluorinated modified acrylate emulsion using a semi-continuous seeded emulsion polymerization method using fluorinated acrylate and acrylate monomers. Water resistance was significantly improved with a fluorinated acrylate dosage of only 2%. (Pei Shihong, Shi Bowen, Song Wei. Study on the synthesis of organic fluorine and epoxy resin modified acrylic emulsion [J]. China Adhesives, 2012, 21(10):13-17).

[0005] Although the aforementioned prior art methods can improve the high-temperature resistance, aging resistance, and tensile strength of fluorinated nitrile rubber to a certain extent by adding small-molecule fluorinated monomers and fluorinated rubber, these methods still have certain limitations. When modifying by blending, the amount of modified fluorinated rubber required is large, making it difficult to achieve uniform molecular-level dispersion, resulting in a weak modification effect and large fluctuations in the stability of the modified product. Emulsion polymerization modification also requires large amounts of small-molecule fluorinated monomers, resulting in high costs and the inability to achieve significant performance improvements with a small amount of modified monomer. Furthermore, there is no research on the fluorinated grafting modification of NBR using large-molecule fluorinated grafting agents. Summary of the Invention

[0006] To address the problems of the prior art, the present invention aims to provide a method for preparing wear-resistant fluorinated nitrile rubber for submersible screw pump stators. The method first utilizes fluorostyrene, diethylene glycol monovinyl ether, and 1,3-butadiene to synthesize a reactive macromolecular fluorine monomer via anionic polymerization. The reactive macromolecular fluorine monomer is then grafted onto the NBR backbone structure via low-temperature emulsion polymerization to prepare a wear-resistant fluorinated nitrile rubber for submersible screw pump stators. This method overcomes the problems of existing physical mixing and modification methods, achieving a molecularly dispersed structure of fluorine atoms on the NBR backbone. This method significantly improves the aging resistance and wear resistance of FNBR with a small amount of macromolecular fluorine monomer, meeting the requirements for rubber materials used in submersible screw pump stators in oil exploration equipment. The preparation method of the present invention is simple, efficient, and highly practical, enabling large-scale industrial production.

[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 wear-resistant fluorinated nitrile rubber for a submersible screw pump stator, the specific preparation process comprising the following steps:

[0009] (1) Preparation of reactive macromolecular fluorine monomer: Based on 100 parts by mass of p-fluorostyrene, introduce argon into a polymerization kettle to replace the system 3 to 5 times, add solvent, p-fluorostyrene, diethylene glycol monovinyl ether, and structure regulator into the polymerization kettle in sequence, stir, heat, add initiator 1 to react, and finally add 1,3-butadiene to the polymerization kettle for activation and end-capping reaction until no free monomer is present. The glue solution is wet-coagulated and dried to obtain a reactive macromolecular fluorine monomer.

[0010] (2) Preparation of wear-resistant fluorinated nitrile rubber for submersible screw pump stators: Based on 100 parts by total mass 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 reactive macromolecular fluorine monomer, emulsifier, and deionized water are stirred and mixed at 10 to 15°C for 20 to 30 minutes to form a 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 80%, a terminator is added to terminate the polymerization, and the material is discharged, condensed, washed, and dried to prepare a wear-resistant fluorinated nitrile rubber for submersible screw pump stators.

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

[0012]

[0013] Wherein, B is end-capped 1,3-butadiene; n is the number of repeating units, and is a positive integer of n≥1. The number average molecular weight (Mn) of the reactive macromolecular fluorine monomer is 4000 to 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 p-fluorostyrene and diethylene glycol monovinyl ether; and the molecular weight refers to the molecular weight of the target product, the reactive macromolecular fluorine monomer.

[0017] Furthermore, the structure modifier is a polar organic compound that produces a solvation effect in the polymerization system, which can adjust the reactivity ratio of styrene and isoprene, thereby causing the two to copolymerize randomly. This type of 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).

[0018] 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.

[0019] 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 of the sodium alkyl sulfate added is 3.0 to 9.0 parts, more preferably 4.0 to 6.0 parts, based on 100 parts of the total weight of the two monomers 1,3-butadiene and acrylonitrile.

[0020] 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 0.5 parts by weight, more preferably 0.07 to 0.21 parts by weight, based on 100 parts by weight of the total weight of the 1,3-butadiene and acrylonitrile monomers.

[0021] 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 amount added is preferably 0.2 to 0.8 parts, more preferably 0.4 to 0.6 parts, based on 100 parts of the total mass of the two monomers 1,3-butadiene and acrylonitrile.

[0022] Furthermore, the molecular weight regulator is a common regulator for emulsion polymerization and can be selected from tert-dodecyl mercaptan and dodecyl mercaptan, preferably tert-dodecyl mercaptan. The amount used is conventional in the art, preferably 0.3 to 2.0 parts by weight based on 100 parts by weight of the total weight of the 1,3-butadiene and acrylonitrile monomers.

[0023] 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 0.01 to 0.06 parts by weight based on 100 parts by weight of the total weight of the 1,3-butadiene and acrylonitrile monomers.

[0024] 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.

[0025] Furthermore, the addition amount of the reactive macromolecular fluorine monomer is preferably 0.5 to 2.0 parts based on 100 parts of the total mass of the two monomers, 1,3-butadiene and acrylonitrile.

[0026] 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%.

[0027] In step (1) of the present invention, based on 100 parts by mass of p-fluorostyrene, the mass ratio of the solvent, diethylene glycol monovinyl ether, structure regulator and 1,3-butadiene is (200-300):(3.0-5.0):(0.1-0.5):(1.0-2.0); the stirring speed is 200-300 rpm; the heating temperature is 60-70°C; the reaction time is 70-80 min; and the end-capping reaction time is 20-30 min.

[0028] In step (ii) of the present invention, based on 100 parts of the 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 (300-400): (3.0-9.0):

[0029] (0.2~0.8):(31~38):(0.3~2.0):(0.01~0.06):(62~69):(0.5~2.0):(0.03~0.5):(0.4~0.7).

[0030] In step (2) of the present invention, the mass ratio of ionized water, emulsifier and reactive macromolecular fluorine monomer in the reactive macromolecular fluorine monomer pre-emulsion is (400-500): (4.0-6.0):100.

[0031] In step (2) of the present invention, the stirring speed is 400-500 rpm; the cooling means that the polymerization reaction temperature is reduced to 1-12°C.

[0032] In step (2) of the present invention, the polymerization conversion rate refers to the conversion rate of acrylonitrile during the polymerization process.

[0033] The reactor of the present invention can be a loop reactor or a tank reactor, preferably a tank reactor.

[0034] The present invention also provides a wear-resistant fluorinated nitrile rubber for a submersible screw pump stator obtained by the above preparation method.

[0035] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0036] (1) The present invention provides an innovative method for preparing reactive macromolecular fluorinated monomers based on anionic polymerization technology. By constructing a ternary copolymerization system of para-fluorostyrene, diethylene glycol monovinyl ether and 1,3-butadiene, a new macromolecular fluorinated monomer with both reactive activity and structural stability is successfully synthesized. Through precise molecular design, this technical solution integrates fluorine atoms and phenyl groups into the main chain of nitrile rubber in the form of covalent bonds, forming a stable molecular-level dispersion system. By utilizing the steric hindrance effect and electronic effect of the macromolecular chain structure, the "accumulation effect" of fluorine atoms and phenyl groups is fully activated, thereby significantly improving the thermal aging and physical and mechanical properties of fluorinated nitrile rubber, especially the wear resistance at 120°C. It is suitable for high-temperature and high-pressure downhole operating environments, and shows significant advantages in core performance indicators such as wear resistance and thermal oxidation aging resistance of rubber materials used in the stators of key components of submersible screw pumps, providing an innovative solution for the reliable operation of deep-well oil and gas exploration equipment. The Mooney viscosity ML (1+4, 100℃) of the fluorinated nitrile rubber prepared by the method is between 50 and 65, the 300% elongation stress of the vulcanized rubber is ≥19.0MPa, the tensile strength is ≥30.0MPa, the elongation at break is 360-420%, and the wear resistance is ≤0.22cm 3 / km, the change rate of tensile strength and elongation at break of the vulcanized rubber after thermal aging at 120℃×72hr is ≤3.2%.

[0037] (2) The reactive macromolecular fluorinated 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 two hydrophilic blocks of the molecule, 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 the grafting reaction; secondly, the C=C unsaturated double bonds are used to construct active reaction micro-regions, so that the macromolecular fluorinated monomer exhibits high grafting efficiency under free radical initiation conditions, ensuring the regularity of the nitrile rubber molecular chain, thereby obtaining a fluorinated nitrile rubber with a molecular structure of a multi-polymer structure.

[0038] (3) The preparation method of the wear-resistant fluorinated nitrile rubber for the submersible screw pump stator of the present invention is green and environmentally friendly, has a significant modification effect, a stable process, small fluctuations in product quality, and is suitable for industrial production.

[0039] Figures and descriptions of the figures

[0040] 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.

[0041] Attachment Figure 1 : Infrared spectrum of the reactive macromolecular fluorine monomer in Example 1. Figure 1 It can be seen that: at wave numbers of 1100-1250 cm -1 The characteristic peak of ether group appears at the wave number of 1200~1300cm -1 The asymmetric stretching vibration absorption peak of the CF bond appears at the wave number of 3100~3200cm -1 The sharp absorption peak of the benzene ring appears at the wave number of 3200~3300cm -1 A sharp absorption peak of hydroxyl group appeared. DETAILED DESCRIPTION

[0042] 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.

[0043] ⑴Source of raw materials:

[0044]

[0045] Other reagents are commercially available industrial products

[0046] ⑵Analysis and testing methods:

[0047] Molecular weight determination: A 2414 gel permeation chromatograph (GPC) manufactured by Waters, USA, was used for determination. The polystyrene standard was 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 .

[0048] Mooney viscosity test: Execute the method in standard SH / T 1050-91.

[0049] 300% modulus stress test: Execute the method in standard GB / T 528-2009.

[0050] Tensile strength test: Execute the method in standard GB / T 1690-2010.

[0051] Elongation at break test: Execute the method in standard GB / T 1690-2010.

[0052] Abrasion resistance test: Execute the method in standard GB / T 1689-1998.

[0053] Aging resistance test: Execute the method in standard GB / T 3512-2014.

[0054] (3) Formulation and process of vulcanized rubber:

[0055] 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.

[0056] Table 1 Vulcanized rubber formula and process

[0057]

[0058]

[0059] Example 1

[0060] (1) Preparation of reactive macromolecular fluorine monomer: In a 10L stainless steel polymerizer with a jacket, the system was replaced three times with argon, and 2000g of cyclohexane, 1000g of p-fluorostyrene, 30g of diethylene glycol monovinyl ether, and 1.0g of THF were added to the polymerizer in sequence, with the stirring speed set at 200rpm; the temperature was raised to 60°C, 263mmol of n-butyl lithium was added and the reaction was carried out for 70min, and finally 10g of 1,3-butadiene was added to the polymerizer for end-capping reaction for 20min, until no free monomer was present. The gel was wet-coagulated and dried to obtain a reactive macromolecular fluorine monomer (Mn of 4000).

[0061] (II) Preparation of wear-resistant fluorinated nitrile rubber for submersible screw pump stator: 3000g deionized water, 30g sodium dodecylbenzenesulfonate soap, 1.5g Diaobai block, 0.5g EDTA-sodium iron salt, 310g monomer acrylonitrile and 3.0g tert-dodecyl mercaptan were added to a 15L stirred pressure-resistant autoclave, and nitrogen pressure-vacuum replacement was performed 3 times, and the stirring speed was turned on to 400rpm; then 5g reactive macromolecular fluorine monomer, 0.2g sodium dodecylbenzenesulfonate soap and 20g deionized water were stirred and mixed at 10℃ for 20min to form a reactive macromolecular fluorine monomer pre-emulsion, which was added to the polymerization kettle, and finally 0.1g sodium dithionite and 690g 1,3-Butadiene. When the polymerization kettle temperature was lowered to 1.0°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 wear-resistant fluorinated nitrile rubber for submersible screw pump stators. Sampling and analysis: Mixing and vulcanization were performed according to the formulation and conditions in Table 1 to produce standard samples for testing. The results are shown in Table 2.

[0062] Example 2

[0063] (1) Preparation of reactive macromolecular fluorine monomer: In a 10L stainless steel polymerizer with a jacket, the system was replaced three times with argon, and 2200g of cyclohexane, 1000g of p-fluorostyrene, 35g of diethylene glycol monovinyl ether, and 2.2g of THF were added to the polymerizer in sequence, with the stirring speed set at 220rpm; the temperature was raised to 62°C, 235mmol of n-butyl lithium was added and the reaction was carried out for 72min, and finally 12g of 1,3-butadiene was added to the polymerizer for end-capping reaction for 22min, until no free monomer was present. The gel was wet-coagulated and dried to obtain a reactive macromolecular fluorine monomer (Mn of 4500).

[0064] (II) Preparation of wear-resistant fluorinated nitrile rubber for submersible screw pump stator: 3200g deionized water, 40g sodium dodecylbenzenesulfonate soap, 3.1g Diaobai block, 0.9g EDTA-sodium iron salt, 330g monomer acrylonitrile and 8.0g tert-dodecyl mercaptan were added to a 15L stirred pressure-resistant autoclave, and nitrogen pressure-vacuum replacement was performed 3 times, and the stirring speed was turned on to 420rpm; then 7g reactive macromolecular fluorine monomer, 0.31g sodium dodecylbenzenesulfonate soap and 29g deionized water were stirred and mixed at 11°C for 22min to form a reactive macromolecular fluorine monomer pre-emulsion, which was added to the polymerization kettle, and finally 0.2g sodium dithionite and 670g 1,3-Butadiene. When the polymerization kettle temperature was lowered to 3.0°C, 1.5g of diisopropylbenzene hydroperoxide (initiator) was added to initiate polymerization. When the polymerization conversion reached 76%, 4.5g 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 wear-resistant fluorinated nitrile rubber for submersible screw pump stators. Sampling and analysis: Mixing and vulcanization were performed according to the formulation and conditions in Table 1 to produce standard samples for testing. The results are shown in Table 2.

[0065] Example 3

[0066] (1) Preparation of reactive macromolecular fluorine monomer: In a 10L stainless steel polymerizer with a jacket, the system was replaced four times with argon, and 2400g of cyclohexane, 1000g of p-fluorostyrene, 39g of diethylene glycol monovinyl ether, and 3.1g of THF were added to the polymerizer in sequence, with the stirring speed set at 240rpm; the temperature was raised to 65°C, 198mmol of n-butyl lithium was added and the reaction was carried out for 75min, and finally 14g of 1,3-butadiene was added to the polymerizer for end-capping reaction for 24min, until no free monomer was present. The gel was wet-coagulated and dried to obtain a reactive macromolecular fluorine monomer (Mn of 5300).

[0067] (II) Preparation of wear-resistant fluorinated nitrile rubber for submersible screw pump stator: 3500g deionized water, 46g sodium dodecylbenzenesulfonate soap, 3.5g Diaobai block, 1.1g EDTA-sodium iron salt, 340g monomer acrylonitrile and 11.0g tert-dodecyl mercaptan were added to a 15L stirred pressure-resistant autoclave, and nitrogen pressure-vacuum replacement was performed 4 times, and the stirring speed was turned on to 440rpm; then 10g reactive macromolecular fluorine monomer, 0.5g sodium dodecylbenzenesulfonate soap and 45g deionized water were stirred and mixed at 12°C for 24min to form a reactive macromolecular fluorine monomer pre-emulsion, which was added to the polymerization kettle, and finally 0.3g sodium dithionite and 660g 1,3-Butadiene. When the polymerization kettle temperature was lowered to 6.0°C, 2.4g of diisopropylbenzene hydroperoxide (initiator) was added to initiate polymerization. When the polymerization conversion reached 77%, 5.1g 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 wear-resistant fluorinated nitrile rubber for submersible screw pump stators. Sampling and analysis: Mixing and vulcanization were performed according to the formulation and conditions in Table 1 to produce standard samples for testing. The results are shown in Table 2.

[0068] Example 4

[0069] (1) Preparation of reactive macromolecular fluorine monomer: In a 10L stainless steel polymerizer with a jacket, the system was replaced four times with argon, and 2600g of cyclohexane, 1000g of p-fluorostyrene, 42g of diethylene glycol monovinyl ether, and 3.7g of THF were added to the polymerizer in sequence, with the stirring speed set at 260rpm; the temperature was raised to 66°C, 179mmol of n-butyl lithium was added and the reaction was carried out for 76min, and finally 16g of 1,3-butadiene was added to the polymerizer for end-capping reaction for 26min, until no free monomer was present. The gel was wet-coagulated and dried to obtain a reactive macromolecular fluorine monomer (Mn of 5900).

[0070] (II) Preparation of wear-resistant fluorinated nitrile rubber for submersible screw pump stator: 3600g deionized water, 51g sodium dodecylbenzenesulfonate soap, 3.8g Diaobai block, 1.4g EDTA-sodium iron salt, 350g monomer acrylonitrile and 14.0g tert-dodecyl mercaptan were added to a 15L stirred pressure-resistant autoclave, and nitrogen pressure-vacuum replacement was performed 4 times, and the stirring speed was turned on to 460rpm; then 13g reactive macromolecular fluorine monomer, 0.6g sodium dodecylbenzenesulfonate soap and 59g deionized water were stirred and mixed at 13°C for 26min to form a reactive macromolecular fluorine monomer pre-emulsion, which was added to the polymerization kettle, and finally 0.4g sodium dithionite and 650g 1,3-Butadiene. When the polymerization kettle temperature was lowered to 8.0°C, 3.6g of diisopropylbenzene hydroperoxide (initiator) was added to initiate polymerization. When the polymerization conversion reached 78%, 5.7g 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 wear-resistant fluorinated nitrile rubber for submersible screw pump stators. Sampling and analysis: Mixing and vulcanization were performed according to the formulation and conditions in Table 1 to produce standard samples for testing. The results are shown in Table 2.

[0071] Example 5

[0072] (1) Preparation of reactive macromolecular fluorine monomer: In a 10L stainless steel polymerizer with a jacket, the system was replaced four times with argon, and 2800g of cyclohexane, 1000g of p-fluorostyrene, 46g of diethylene glycol monovinyl ether, and 4.3g of THF were added to the polymerizer in sequence, with the stirring speed set at 280rpm; the temperature was raised to 68°C, 165mmol of n-butyl lithium was added and the reaction was carried out for 78min, and finally 18g of 1,3-butadiene was added to the polymerizer for end-capping reaction for 28min, until no free monomer was present. The gel was wet-coagulated and dried to obtain a reactive macromolecular fluorine monomer (Mn: 6400).

[0073] (II) Preparation of wear-resistant fluorinated nitrile rubber for submersible screw pump stator: 3800g deionized water, 56g sodium dodecylbenzenesulfonate soap, 4.7g Diaobai block, 1.6g EDTA-sodium iron salt, 360g monomer acrylonitrile and 16.0g tert-dodecyl mercaptan were added to a 15L stirred pressure-resistant autoclave, and nitrogen pressure-vacuum replacement was performed 4 times, and the stirring speed was turned on to 480rpm; then 17g reactive macromolecular fluorine monomer, 0.9g sodium dodecylbenzenesulfonate soap and 81g deionized water were stirred and mixed at 14°C for 28min to form a reactive macromolecular fluorine monomer pre-emulsion, which was added to the polymerization kettle, and finally 0.5g sodium dithionite and 640g 1,3-Butadiene. When the polymerization kettle temperature was lowered to 10.0°C, 4.3g of diisopropylbenzene hydroperoxide (initiator) was added to initiate polymerization. When the polymerization conversion reached 79%, 6.3g 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 85°C to a moisture content of less than 0.5%, producing a wear-resistant fluorinated nitrile rubber for submersible screw pump stators. Sampling and analysis: Mixing and vulcanization were performed according to the formulation and conditions in Table 1 to produce standard samples for testing. The results are shown in Table 2.

[0074] Example 6

[0075] (1) Preparation of reactive macromolecular fluorine monomer: In a 10L stainless steel polymerizer with a jacket, the system was replaced 5 times with argon, and 3000g of cyclohexane, 1000g of p-fluorostyrene, 50g of diethylene glycol monovinyl ether, and 5.0g of THF were added to the polymerizer in sequence, and the stirring speed was turned on at 300rpm; the temperature was raised to 70°C, 152mmol of n-butyl lithium was added and the reaction was carried out for 80min, and finally 20g of 1,3-butadiene was added to the polymerizer for end-capping reaction for 30min, until no free monomer was present. The gel was wet-coagulated and dried to obtain a reactive macromolecular fluorine monomer (Mn was 7000).

[0076] (II) Preparation of wear-resistant fluorinated nitrile rubber for submersible screw pump stator: 4000g of deionized water, 60g of sodium dodecylbenzenesulfonate soap, 5.2g of white cake, 1.8g of EDTA-sodium iron salt, 380g of monomer acrylonitrile and 20.0g of tert-dodecyl mercaptan were added to a 15L stirred pressure-resistant autoclave, and nitrogen pressure-vacuum replacement was performed 5 times, and the stirring speed was turned on to 500rpm; then 20g of reactive macromolecular fluorine monomer, 1.2g of sodium dodecylbenzenesulfonate soap and 100g of deionized water were stirred and mixed at 15°C for 30min to form a reactive macromolecular fluorine monomer pre-emulsion, which was added to the polymerization kettle, and finally 0.6g of sodium dithionite and 620g of 1,3-Butadiene. When the polymerization kettle temperature was lowered to 12.0°C, 5.0g of diisopropylbenzene hydroperoxide (initiator) was added to initiate polymerization. When the polymerization conversion reached 80%, 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 85°C to a moisture content of less than 0.5%, producing a wear-resistant fluorinated nitrile rubber for submersible screw pump stators. Sampling and analysis: Mixing and vulcanization were performed according to the formulation and conditions in Table 1 to produce standard samples for testing. The results are shown in Table 2.

[0077] Comparative Example 1

[0078] (1) Preparation of reactive macromolecular fluorine monomer: Other conditions are the same as those in Example 1, except that p-fluorostyrene is not added during the preparation of the reactive macromolecular fluorine monomer, but trifluoroethyl methacrylate is added in an amount of 1000 g, that is: in a 10 L stainless steel polymerizer with a jacket, the system is replaced three times with argon, 2000 g of cyclohexane, 1000 g of trifluoroethyl methacrylate, 30 g of diethylene glycol monovinyl ether, and 1.0 g of THF are added to the polymerizer in sequence, and the stirring speed is turned to 200 rpm; the temperature is raised to 60° C., 263 mmol of n-butyl lithium is added and the reaction is carried out for 70 min, and finally 10 g of 1,3-butadiene is added to the polymerizer for end-capping reaction for 20 min, until no free monomer is present, and the glue is wet-coagulated and dried to obtain reactive macromolecular fluorine monomer a (Mn is 3900).

[0079] (II) Preparation of wear-resistant fluorinated nitrile rubber for submersible screw pump stator: Other conditions are the same as those in Example 1, except that reactive macromolecular fluorine monomer a is added in the preparation process of wear-resistant fluorinated nitrile rubber for submersible screw pump stator instead of reactive macromolecular fluorine monomer a in an amount of 5.0 g, i.e., 3000 g of deionized water, 30 g of sodium dodecylbenzenesulfonate soap, 1.5 g of white block, 0.5 g of chlorinated nitrile, and 1.0 g of chlorinated nitrile were added to a 15 L stirred autoclave. EDTA-sodium iron salt, 310g of monomer acrylonitrile and 3.0g of tert-dodecyl mercaptan were replaced by nitrogen pressure-vacuum replacement three times, and the stirring speed was turned on at 400rpm. Then, 5.0g of reactive macromolecular fluoromonomer a, 0.2g of sodium dodecylbenzenesulfonate soap and 20g of deionized water were stirred and mixed at 10°C for 20 minutes to form a reactive macromolecular fluoromonomer a pre-emulsion, which was added to a polymerization kettle. Finally, 0.1g of sodium dithionite and 690g of 1,3-butadiene were added. When the polymerization kettle temperature was lowered to 1.0°C, 0.3g of initiator diisopropylbenzene hydroperoxide was added to start the polymerization reaction. When the polymerization conversion rate reached 75%, 4.0g of terminator sodium fumei was added to terminate the polymerization. The material was stirred and discharged, and calcium chloride aqueous solution was added for coagulation. After filtration and dehydration, it was dried at 85°C until the moisture content was below 0.5%, thereby preparing a wear-resistant fluorinated nitrile rubber for a submersible screw pump stator. Sampling and analysis: Mix and vulcanize according to the formula and conditions in Table 1 to make standard samples, which are then tested. The results are shown in Table 2.

[0080] Comparative Example 2

[0081] (1) Preparation of reactive macromolecular fluorine monomer: Other conditions are the same as those in Example 2, except that diethylene glycol monovinyl ether is not added during the preparation of the reactive macromolecular fluorine monomer, but 1,4-butenediol is added in an amount of 35 g, that is: in a 10 L stainless steel polymerizer with a jacket, the system is replaced three times with argon, 2200 g cyclohexane, 1000 g p-fluorostyrene, 35 g 1,4-butenediol, and 2.2 g THF are added to the polymerizer in sequence, and the stirring speed is turned to 220 rpm; the temperature is raised to 62 ° C, 235 mmol n-butyl lithium is added and the reaction is carried out for 72 min, and finally 12 g 1,3-butadiene is added to the polymerizer for end-capping reaction for 22 min, until no free monomer is present, and the glue is wet-coagulated and dried to obtain reactive macromolecular fluorine monomer b (Mn is 4400).

[0082] (II) Preparation of wear-resistant fluorinated nitrile rubber for submersible screw pump stator: Other conditions are the same as those in Example 2, except that reactive macromolecular fluorine monomer b is not added during the preparation of wear-resistant fluorinated nitrile rubber for submersible screw pump stator, and the amount of reactive macromolecular fluorine monomer b is 7.0 g, that is, 3200 g of deionized water, 40 g of sodium dodecylbenzenesulfonate soap, 3.1 g of white block, 0.9 g of chlorinated nitrile, and 0.8 g of chlorinated nitrile were added to a 15 L stirred autoclave. EDTA-sodium iron salt, 330g of monomer acrylonitrile and 8.0g of tert-dodecyl mercaptan were replaced by nitrogen pressure-vacuum replacement three times, and the stirring speed was turned on at 420 rpm. Then, 7.0g of reactive macromolecular fluoromonomer b, 0.31g of sodium dodecylbenzenesulfonate soap and 29g of deionized water were stirred and mixed at 11°C for 22 minutes to form a reactive macromolecular fluoromonomer pre-emulsion b, which was added to a polymerization kettle. Finally, 0.2g of sodium dithionite and 670g of 1,3-butadiene were added. When the polymerization kettle temperature was lowered to 3.0°C, 1.5g of initiator diisopropylbenzene hydroperoxide was added to start the polymerization reaction. When the polymerization conversion rate reached 76%, 4.5g of terminator sodium fumei was added to terminate the polymerization. The material was stirred and discharged, and calcium chloride aqueous solution was added for coagulation. After filtration and dehydration, it was dried at 85°C until the moisture content was below 0.5%, thereby preparing a wear-resistant fluorinated nitrile rubber for a submersible screw pump stator. Sampling and analysis: Mix and vulcanize according to the formula and conditions in Table 1 to make standard samples, which are then tested. The results are shown in Table 2.

[0083] Comparative Example 3

[0084] (1) Preparation of reactive macromolecular fluorine monomer: Other conditions were the same as those in Example 3, except that 1,3-butadiene was not added during the preparation of the reactive macromolecular fluorine monomer, that is, in a 10 L stainless steel polymerizer with a jacket, the system was replaced four times with argon, 2400 g of cyclohexane, 1000 g of p-fluorostyrene, 39 g of diethylene glycol monovinyl ether, and 3.1 g of THF were added to the polymerizer in sequence, and the stirring speed was turned to 240 rpm; the temperature was raised to 65 ° C, 198 mmol of n-butyl lithium was added, and the reaction was carried out for 75 minutes. The gel was wet-coagulated and dried to obtain reactive macromolecular fluorine monomer C (Mn was 5100).

[0085] (II) Preparation of wear-resistant fluorinated nitrile rubber for submersible screw pump stator: Other conditions are the same as those in Example 3, except that reactive macromolecular fluorine monomer c is added in an amount of 10.0 g instead of reactive macromolecular fluorine monomer c in a preparation process of wear-resistant fluorinated nitrile rubber for submersible screw pump stator. In a 15 L stirred autoclave, 3500 g of deionized water, 46 g of sodium dodecylbenzenesulfonate soap, 3.5 g of white block, and 1.1 g of EDTA-sodium iron salt, 340g of monomer acrylonitrile and 11.0g of tert-dodecyl mercaptan were replaced by nitrogen pressure-vacuum replacement four times, and the stirring speed was turned on at 440 rpm. Then, 10g of reactive macromolecular fluoromonomer C, 0.5g of sodium dodecylbenzenesulfonate soap and 45g of deionized water were stirred and mixed at 12°C for 24 minutes to form a reactive macromolecular fluoromonomer pre-emulsion C, which was added to a polymerization kettle. Finally, 0.3g of sodium dithionite and 660g of 1,3-butadiene were added. When the polymerization kettle temperature was lowered to 6.0°C, 2.4g of initiator diisopropylbenzene hydroperoxide was added to start the polymerization reaction. When the polymerization conversion rate reached 77%, 5.1g of terminator sodium fumei was added to terminate the polymerization. The material was stirred and discharged, and calcium chloride aqueous solution was added for coagulation. After filtration and dehydration, it was dried at 85°C until the moisture content was below 0.5%, thereby preparing a wear-resistant fluorinated nitrile rubber for a submersible screw pump stator. Sampling and analysis: Mix and vulcanize according to the formula and conditions in Table 1 to make standard samples, which are then tested. The results are shown in Table 2.

[0086] Comparative Example 4

[0087] (1) Preparation of reactive macromolecular fluorine monomer: Other conditions were the same as those in Example 4, except that 65 mmol of n-butyl lithium was added during the preparation of the reactive macromolecular fluorine monomer. That is, in a 10 L stainless steel polymerizer with a jacket, the system was replaced four times with argon, 2600 g of cyclohexane, 1000 g of p-fluorostyrene, 42 g of diethylene glycol monovinyl ether, and 3.7 g of THF were added to the polymerizer in sequence, and the stirring speed was set to 260 rpm; the temperature was raised to 66° C., 65 mmol of n-butyl lithium was added, and the reaction was carried out for 76 min. Finally, 16 g of 1,3-butadiene was added to the polymerizer for end-capping reaction for 26 min until no free monomer was present. The gel was wet-coagulated and dried to obtain reactive macromolecular fluorine monomer d (Mn was 16900).

[0088] (II) Preparation of wear-resistant fluorinated nitrile rubber for submersible screw pump stator: Other conditions are the same as those in Example 4, except that reactive macromolecular fluorine monomer d is added in the preparation process of wear-resistant fluorinated nitrile rubber for submersible screw pump stator instead of reactive macromolecular fluorine monomer d in an amount of 13.0 g, that is, 3600 g of deionized water, 51 g of sodium dodecylbenzenesulfonate soap, 3.8 g of white block, 1.4 g of EDTA-sodium iron salt, 350g of monomer acrylonitrile and 14.0g of tert-dodecyl mercaptan were replaced by nitrogen pressure-vacuum replacement four times, and the stirring speed was turned on at 460 rpm. Then, 13g of reactive macromolecular fluoromonomer d, 0.6g of sodium dodecylbenzenesulfonate soap and 59g of deionized water were stirred and mixed at 13°C for 26 minutes to form a reactive macromolecular fluoromonomer pre-emulsion d, which was added to a polymerization kettle. Finally, 0.4g of sodium dithionite and 650g of 1,3-butadiene were added. When the polymerization kettle temperature was lowered to 8.0°C, 3.6g of initiator diisopropylbenzene hydroperoxide was added to start the polymerization reaction. When the polymerization conversion rate reached 78%, 5.7g of terminator sodium fumei was added to terminate the polymerization. The material was stirred and discharged, and calcium chloride aqueous solution was added for coagulation. After filtration and dehydration, it was dried at 85°C until the moisture content was below 0.5%, thereby preparing a wear-resistant fluorinated nitrile rubber for a submersible screw pump stator. Sampling and analysis: Mix and vulcanize according to the formula and conditions in Table 1 to make standard samples, which are then tested. The results are shown in Table 2.

[0089] Comparative Example 5

[0090] (1) Preparation of reactive macromolecular fluorine monomer: same as in Example 5.

[0091] (2) Preparation of wear-resistant fluorinated nitrile rubber for submersible screw pump stator: Other conditions are the same as those in Example 5, except that the reactive macromolecular fluorine monomer is not pre-emulsified during the preparation of the wear-resistant fluorinated nitrile rubber for submersible screw pump stator, that is, the reactive macromolecular fluorine monomer pre-emulsification liquid is not added, but the reactive macromolecular fluorine monomer is directly added in an amount of 17.0 g, that is, 3800 g of deionized water, 56 g of sodium dodecylbenzenesulfonate soap, 4.7 g of Diaobai block, 1.6 g of EDTA-sodium iron salt, 360 g of monomer acrylonitrile and 16.0 g of tert-dodecyl mercaptan are added to a 15 L stirred autoclave, and nitrogen pressure-vacuum replacement is performed 4 times, and the stirring speed is turned on at 480 rpm; then 17 g of reactive macromolecular fluorine monomer is added, and finally 0.5 g of sodium dithionite and 640 g of 1,3-Butadiene. When the polymerization kettle temperature was lowered to 10.0°C, 4.3g of diisopropylbenzene hydroperoxide (initiator) was added to initiate polymerization. When the polymerization conversion reached 79%, 6.3g 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 85°C to a moisture content of less than 0.5%, producing a wear-resistant fluorinated nitrile rubber for submersible screw pump stators. Sampling and analysis: Mixing and vulcanization were performed according to the formulation and conditions in Table 1 to produce standard samples for testing. The results are shown in Table 2.

[0092] Comparative Example 6

[0093] Preparation of wear-resistant fluorinated nitrile rubber for submersible screw pump stator: other conditions are the same as those in Example 6, except that reactive macromolecular fluorine monomer pre-emulsion is not added during the preparation of wear-resistant fluorinated nitrile rubber for submersible screw pump stator, but p-fluorostyrene is directly added in an amount of 20 g, that is, 4000 g of deionized water, 60 g of sodium dodecylbenzenesulfonate soap, 5.2 g of white block, 1.8 g of EDTA-sodium iron salt, 380 g of monomer acrylonitrile and 20.0 g of tert-dodecyl mercaptan are added to a 15 L stirred autoclave, nitrogen pressure-vacuum replacement is performed 5 times, and the stirring speed is turned on at 500 rpm; then 20 g of p-fluorostyrene is added to the polymerization kettle, and finally 0.6 g of sodium dithionite, 620 g of 1,3-Butadiene. When the polymerization kettle temperature was lowered to 12.0°C, 5.0g of diisopropylbenzene hydroperoxide (initiator) was added to initiate polymerization. When the polymerization conversion reached 80%, 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 85°C to a moisture content of less than 0.5%, producing a wear-resistant fluorinated nitrile rubber for submersible screw pump stators. Sampling and analysis: Mixing and vulcanization were performed according to the formulation and conditions in Table 1 to produce standard samples for testing. The results are shown in Table 2.

[0094] Table 2 Properties of wear-resistant fluorinated nitrile rubber for submersible screw pump stators

[0095]

[0096]

[0097] As shown in Table 2, the Mooney viscosity ML (1+4, 100°C) of the fluorinated nitrile rubber prepared by the present invention using the synthesized reactive macromolecular fluorine monomer is between 50 and 65, and the 300% modulus of the vulcanized rubber is ≥19.0 MPa, the tensile strength is ≥30.0 MPa, the elongation at break is 360-420%, and the wear resistance is ≤0.22 cm 3 / km, and the change rate of tensile strength and elongation at break of the vulcanized rubber after thermal aging at 120℃×72hr is ≤3.2%, which fully meets the requirements of submersible screw pump stator rubber in high temperature and high pressure underground operating environment.

[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 wear-resistant fluorinated nitrile rubber for a submersible screw pump stator, characterized in that It is polymerized by, but not limited to, the following monomers: 1,3-butadiene, acrylonitrile, and a reactive macromolecular fluorine monomer.

2. The wear-resistant fluorinated nitrile rubber for a submersible screw pump stator according to claim 1, characterized in that The reactive macromolecular fluorine monomer has the following structure: Wherein, B is end-capped 1,3-butadiene; n is the number of repeating units, and n is a positive integer greater than or equal to 1.

3. The wear-resistant fluorinated nitrile rubber for a submersible screw pump stator 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 p-fluorostyrene, introducing argon into a polymerization kettle to replace the system 3 to 5 times, sequentially adding a solvent, p-fluorostyrene, diethylene glycol monovinyl ether, and a structure regulator into the polymerization kettle, stirring, heating, adding initiator 1 for reaction, and finally adding 1,3-butadiene into the polymerization kettle for activation and end-capping reaction until no free monomer is present, and wet-coagulating and drying the glue solution to obtain the reactive macromolecular fluorine monomer.

4. The wear-resistant fluorinated nitrile rubber for a submersible screw pump stator 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 wear-resistant fluorinated nitrile rubber for a submersible screw pump stator 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. A method for preparing the wear-resistant fluorinated nitrile rubber for a submersible screw pump stator according to any one of claims 1 to 5, characterized in that The method comprises the following steps: first, reacting 1,3-butadiene, acrylonitrile and the reactive macromolecular fluorine monomer to obtain a reactive macromolecular fluorine monomer pre-emulsion; second, reacting the reactive macromolecular fluorine monomer pre-emulsion with a deoxidizer and 1,3-butadiene to obtain a wear-resistant fluorinated nitrile rubber for a submersible screw pump stator.

7. The method for preparing the wear-resistant fluorinated nitrile rubber for the stator of a submersible screw pump according to claim 6, characterized in that It consists of the following steps: (1) Deionized water, an emulsifier, an activator, acrylonitrile, and a molecular weight regulator are added to 100 parts by weight of the total weight of 1,3-butadiene and acrylonitrile monomers in a polymerization kettle, and nitrogen pressure-vacuum replacement is performed 3 to 5 times, and the mixture is stirred; then, the reactive macromolecular fluorine monomer, the emulsifier, and deionized water are stirred and mixed at 10 to 15° C. for 20 to 30 minutes to form a reactive macromolecular fluorine monomer pre-emulsion; (2) Adding the reactive macromolecular fluorine monomer pre-emulsion into the polymerization kettle; finally, adding the deoxidizer and 1,3-butadiene, cooling, adding the initiator 2 to carry out the polymerization reaction, and when the conversion rate reaches 75% to 80%, adding the terminator to terminate the polymerization, discharging, condensing, washing, and drying to prepare the wear-resistant fluorinated nitrile rubber for the submersible screw pump stator.

8. The method for preparing the wear-resistant fluorinated nitrile rubber for the stator of a submersible screw pump according to claim 7, characterized in that The initiator 2 is a redox initiator, which is selected from one of cumene hydroperoxide, dicumyl hydroperoxide, isopropyl tert-butyl peroxide, and isopropyl n-butyl peroxide.

9. The method for preparing the wear-resistant fluorinated nitrile rubber for the submersible screw pump stator according to claim 7, characterized in that The emulsifier is selected from potassium rosinate soap, oleic acid soap, sodium pyrophosphate, fatty acid, disproportionated potassium rosinate, fatty acid sodium C8~C 20 The scavenger is selected from one of sodium dithionite, dimethyl ketoxime, isoascorbic acid, carbohydrazide, and N-isopropylhydroxylamine; the activator is selected from one of white cake, ferrous sulfate, EDTA tetrasodium salt or EDTA sodium iron salt.

10. The method for preparing the wear-resistant fluorinated nitrile rubber for the stator of a submersible screw pump according to claim 7, characterized in that The molecular weight regulator is a universal regulator for emulsion polymerization and is selected from one of tert-dodecyl mercaptan and dodecyl mercaptan.

Images