Hydrogenated nitrile rubber for special oil field and preparation method of hydrogenated nitrile rubber

Abstract

The invention discloses a preparation method of hydrogenated butadiene-acrylonitrile rubber for a special oil field. The preparation method comprises the following steps: (1) preparing a macromolecular three-miktoarm star-shaped composite functional grafting agent; and (2) preparing the hydrogenated butadiene-acrylonitrile rubber for the special oil field. The macromolecular three-miktoarm star-shaped composite functional grafting agent has the following structure: # imgabs0 #, wherein R is straight-chain alkyl of C1-C6; bR is a 1, 3-butadiene homopolymer segment with wide vinyl distribution; b is terminated 1, 3-butadiene; n, m and L are repeating unit numbers, and n > = 1, m > = 1 and L > = 1 are positive integers; the number-average molecular weight (Mn) of the macromolecular three-miktoarm star-shaped composite functional grafting agent is 7000 to 8000, and the molecular weight distribution (Mw / Mn) of the macromolecular three-miktoarm star-shaped composite functional grafting agent is 13.17 to 14.67. The preparation method of the hydrogenated butadiene-acrylonitrile rubber for the special oil field has the characteristics of environment friendliness, efficient modification effect, low dosage of a modifier, commercially available and easily available raw materials, suitability for industrial production and the like.

Description

Technical Field

[0001] The invention belongs to the technical field of rubber, and specifically relates to a macromolecular three-arm star-shaped composite functional grafting agent for preparing a special hydrogenated nitrile rubber for oil fields and a preparation method thereof. Background Art

[0002] Hydrogenated nitrile rubber (HNBR for short) is prepared by selective hydrogenation of carbon-carbon double bonds in nitrile rubber. Therefore, HNBR not only retains the oil resistance, corrosion resistance and elasticity of NBR, but also exhibits excellent aging resistance and high temperature resistance. The mechanical properties such as tensile strength, elongation at break, wear resistance and hardness are improved. It is widely used in oil exploration equipment such as pump pistons, rotary hoses, valve seals, drill pipe shields, etc.

[0003] Although hydrogenation of carbon-carbon double bonds gives HNBR very excellent performance, it also brings a serious defect to HNBR materials. The main chain of hydrogenated nitrile rubber (NBR) is a highly ordered polyethylene structure, which is very easy to form a crystalline structure and causes an increase in Tg. Therefore, the cold resistance of HNBR products is poor. Since most of my country's oil drilling business is concentrated in the western and northeastern regions, the lowest temperature in these regions can reach about -50℃. Oil drilling equipment faces an application environment under low temperature conditions, which puts forward extremely high requirements on the cold resistance of rubber sealing materials.

[0004] In the prior art, there are many patent documents reporting on the preparation method of low temperature resistant hydrogenated nitrile rubber. For example:

[0005] CN 106349410 B discloses a special hydrogenated nitrile rubber with compression cold resistance and a preparation method thereof, wherein the rubber main chain contains epoxy groups, and part of the epoxy groups are also connected to ester side groups; the ester side groups are generated by the ring-opening reaction of C6-C24 acid anhydride and the epoxy groups. The preparation method comprises introducing epoxy groups into the main chain of the rubber molecule, and then reacting part of the epoxy groups with acid anhydride under the action of a catalyst to introduce ester groups, thereby obtaining a special hydrogenated nitrile rubber containing epoxy groups and ester groups. CN 105294939B discloses a low-temperature grade hydrogenated nitrile rubber raw rubber, which is a copolymer of butadiene, acrylonitrile and dibutyl fumarate, and the number average molecular weight of the copolymer is 1.05 to 3.25×10 5 , weight average molecular weight is 3.02~9.32×10 5, the polydispersity coefficient is 2.0-2.7; the low-temperature grade hydrogenated nitrile rubber raw rubber has a hydrogenation degree of more than 90% and a glass transition temperature of -38°C to -42°C. CN 112592461 B discloses a modified hydrogenated nitrile rubber material with the characteristics of low temperature resistance and high damping, and its preparation method and application. The modified hydrogenated nitrile rubber material is prepared using HNBR / PNB block copolymer as raw material; the HNBR / PNB block copolymer is obtained by modifying NBR or HNBR through olefin metathesis reaction using norbornene monomer as a modifier. CN 115594898A discloses a low-temperature resistant hydrogenated nitrile rubber compound and a banburying preparation method thereof, which mainly comprises blending and banburying hydrogenated nitrile raw rubber, a plasticizer and a hardness regulator, and finally obtains a cold-resistant hydrogenated nitrile rubber compound having a Shore A hardness of 67±5, a tensile strength ≥14MPa, an elongation at break ≥180%, a compression permanent deformation ≤35%, and a 45°C compression cold resistance coefficient ≥0.16. CN 105754164A discloses a low-temperature resistant rubber material, although the cold resistance of the material is improved, the addition of the plasticizer dioctyl phthalate (DOP) reduces the mechanical properties and oil resistance of the material, and DOP is not environmentally friendly and is easy to precipitate. Zhang Dongheng et al. disclosed that ethylene propylene rubber (EPDM) and HNBR were blended to improve the cold resistance of HNBR. When the EPDM addition amount was 15%, the Tg dropped by 3°C. However, when the EPDM addition amount was further increased, the Tg of the blended rubber did not drop any more (Synthetic Rubber Industry, 2002, 25(1): ).

[0006] In the above-mentioned prior art, although the cold resistance of hydrogenated nitrile rubber can be improved to a certain extent by adding small molecule modifiers, copolymerization and blending, these methods still have certain limitations, and the preparation methods thereof have the problems of complex process, difficulty in actual operation, large addition amount, high cost, and unclear modification effect. Summary of the invention

[0007] In order to solve the problems existing in the prior art, a method for preparing hydrogenated nitrile rubber for special oil fields with a tear strength of ≥78KN / m, compression set resistance ≤9.0% and glass transition temperature Tg<-80℃ is provided. The invention firstly hydrolyzes 2,4,6-tribromophenyl allyl ether to synthesize 2,4,6-trihydroxyphenyl allyl ether, and then prepares a macromolecular composite functional monomer with 4-hydroxy-3-alkoxy-1-propenylbenzene; secondly, the macromolecular composite functional monomer is combined with para-alkylstyrene, 1,3-butadiene and styrene to prepare a macromolecular three-arm star-shaped composite functional grafting agent with a wide vinyl distribution and random gradient segments through variable temperature polymerization, variable speed polymerization and distributed coupling. The grafting agent imparts hydrogenated nitrile rubber with very excellent tear strength, deformation resistance and cold resistance, achieving a balance among the mechanical properties, deformation resistance and cold resistance of hydrogenated nitrile rubber. It is very suitable for the stator rubber material of submersible screw pumps that require tear resistance and compression resistance in oil well operations under low temperature conditions.

[0008] 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.

[0009] In order to achieve the above object, the present invention provides a method for preparing hydrogenated nitrile rubber for special oil fields, the preparation method comprising the following steps:

[0010] (1) Preparation of macromolecular three-arm star-shaped composite functionalized grafting agent:

[0011] a Preparation of 2,4,6-trihydroxyphenyl allyl ether: In a polymerization kettle, argon gas is introduced for replacement, deionized water, 2,4,6-tribromophenyl allyl ether, and NaOH aqueous solution are added to the polymerization kettle in sequence, stirred, mixed, heated, heated, reacted, and finally extracted, separated, washed, and dried to obtain 2,4,6-trihydroxyphenyl allyl ether;

[0012] b. Preparation of macromolecular composite functional monomer: In a polymerization kettle, argon gas is introduced to replace the system, and a solvent, 4-hydroxy-3-alkoxy-1-propenylbenzene, 2,4,6-trihydroxyphenyl allyl ether, and a structure regulator are added to the polymerization kettle in sequence, and the temperature is raised, and then initiator 1 is added to the polymerization kettle for reaction; finally, 1,3-butadiene is added to the polymerization kettle for end-capping, and the reaction is continued until no free monomer exists. The gel solution is wet-coagulated and dried to obtain a macromolecular composite functional monomer;

[0013] c Preparation of SB / (S→B) copolymer: In a polymerization kettle, argon gas is introduced to replace the system, and a solvent and a structure regulator are added to the polymerization kettle in sequence, the temperature is raised, and an initiator 1 is added, and then 1,3-butadiene and styrene are stirred and mixed, added to the polymerization kettle, and reacted until no free monomer is present. The colloid is wet-coagulated and dried to obtain a random, long gradient SB / (S→B) copolymer;

[0014] d Preparation of macromolecular three-arm star-shaped composite functionalized grafting agent: In a reactor, argon is introduced to replace the system, solvent 1, p-alkylstyrene, and the first structural regulator are added to the polymerization kettle in sequence, the temperature is raised, and initiator 1 is added to react to form a p-alkylstyrene homopolymer segment; then 1,3-butadiene and the second structural regulator are added to the polymerization kettle in sequence, the temperature is raised, and the reaction is a variable temperature polymerization. Within 40 to 60 minutes, the temperature gradually rises from 60°C to 90°C to form a BR segment with a wide vinyl distribution, and then a coupling agent is added to carry out a coupling reaction; then S The B / (S→B) copolymer and the solution are mixed and stirred to dissolve, and then added to a polymerization kettle for coupling reaction after being completely dissolved; finally, the macromolecular composite functional monomer is mixed with solvent 2 and stirred to dissolve, and then added to a polymerization kettle for coupling reaction after being completely dissolved, and finally 1,3-butadiene is added to the polymerization kettle for end-capping, and the reaction is carried out until no free monomer exists. After the reaction is completed, the reaction mixture after coupling is treated with water, and the glue solution is wet-coagulated and dried to obtain a macromolecular three-arm star-shaped composite functional grafting agent;

[0015] (2) Preparation of hydrogenated nitrile rubber for special oil fields:

[0016] a Preparation of hydrogenated nitrile rubber (HNBR): dissolve nitrile rubber in chlorobenzene solution to prepare a rubber solution, then add the rubber solution into a reactor and introduce inert gas to remove the air in the reactor, then remove the inert gas in the reactor with hydrogen, add a xylene solution of Grubbs I catalyst under nitrogen protection, pressurize, heat up, after reaction, cool the system, condense, and vacuum dry to obtain HNBR rubber;

[0017] b. Preparation of hydrogenated nitrile rubber for special oil fields: HNBR rubber is dissolved in chlorobenzene solution to prepare a glue solution, and then the glue solution is added to a reactor, and an inert gas is introduced for replacement, and then a macromolecular three-arm star-shaped composite functionalized grafting agent is added to the reactor, stirred and mixed, heated, and a mixed solution of initiator 2 and chlorobenzene is added. After the reaction, flocculation, washing, and drying are performed to obtain hydrogenated nitrile rubber for special oil fields;

[0018] The macromolecular three-arm star-shaped composite functionalized grafting agent has the following structure:

[0019]

[0020] Among them, R is a straight-chain alkyl of C1 to C6; BR is a 1,3-butadiene homopolymer segment with a wide vinyl distribution; B is a terminal 1,3-butadiene; n, m and L are the number of repeating units, and n≥1, m≥1 and L≥1 are positive integers; the number average molecular weight (Mn) of the macromolecular three-arm star-shaped composite functionalized grafting agent is 7000 to 8000, and the molecular weight distribution (Mw / Mn) is 13.17 to 14.67.

[0021] The p-alkylstyrene described in the present invention is an aromatic vinyl compound selected from p-methylstyrene, p-ethylstyrene, p-propylstyrene, p-butylstyrene, p-pentylstyrene and p-hexylstyrene, preferably p-methylstyrene.

[0022] The 4-hydroxy-3-alkoxy-1-propenylbenzene of the present invention is an unsaturated organic compound selected from the group consisting of 4-hydroxy-3-methoxy-1-propenylbenzene, 4-hydroxy-3-ethoxy-1-propenylbenzene, 4-hydroxy-3-propoxy-1-propenylbenzene, 4-hydroxy-3-butoxy-1-propenylbenzene, 4-hydroxy-3-pentyloxy-1-propenylbenzene and 4-hydroxy-3-hexyloxy-1-propenylbenzene, preferably 4-hydroxy-3-ethoxy-1-propenylbenzene.

[0023] The initiator 1 of the present invention 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. The hydrocarbon monolithium compound is selected from one of n-butyl lithium, sec-butyl lithium, methylbutyl lithium, phenylbutyl lithium, naphthalene lithium, cyclohexyl lithium and dodecyl lithium, preferably n-butyl lithium. The amount of organic lithium added is determined by the molecular weight of the designed polymer.

[0024] The initiator 2 described in the present invention is an organic peroxide, selected from one of diacetyl peroxide, diisobutyryl peroxide, cumene hydroperoxide, dicumyl peroxide (DCP) and dibenzoyl peroxide (BPO), preferably DCP, and its addition amount is 0.05-0.2 parts based on 100 parts by mass of HNBR rubber.

[0025] The coupling agent of the present invention is one of 1,3,5-trichlorobenzene and 1,3,5-tribromobenzene, preferably 1,3,5-trichlorobenzene. The amount of the coupling agent used depends on the amount of the initiator 1. The excess coupling agent is gradually polymerized to eventually form a star polymer with a hetero-arm structure. The molar ratio of the total amount of the initiator 1 to the coupling agent is 3.0 to 4.0.

[0026] The nitrile rubber of the present invention is copolymerized by emulsion polymerization of 1,3-butadiene and acrylonitrile, wherein the acrylonitrile content of the nitrile rubber is 20wt% to 42wt%, preferably 22wt% to 35wt%.

[0027] The structure regulator of the present invention is a polar organic compound that produces a solvation effect in the polymerization system, and can adjust the reactivity ratio of styrene and 1,3-butadiene to make the two copolymerize randomly. This type of polar organic compound is selected from one of diethylene glycol dimethyl ether (2G), tetrahydrofuran (THF), ethyl ether, ethyl methyl ether, anisole, diphenyl ether, ethylene glycol dimethyl ether (DME), and triethylamine, preferably tetrahydrofuran (THF).

[0028] The solvent, solvent 1, solvent 2 or solution described in the present invention can be selected from one of cyclohexane, carbon disulfide (CS2), nitrobenzene, petroleum ether, tetrachloroethane, toluene and xylene, preferably cyclohexane.

[0029] In step (1) a of the present invention, the mass ratio of the deionized water, 2,4,6-tribromophenyl allyl ether and the NaOH aqueous solution is 300-400:100:20-30.

[0030] In step (1) a of the present invention, the mass concentration of the NaOH aqueous solution is 10% to 20%.

[0031] In step (1) a of the present invention, the temperature is raised to 130-140° C. and the reaction time is 6-8 hr.

[0032] In step (1) a of the present invention, the yield of 2,4,6-trihydroxyphenyl allyl ether is 80% to 83%.

[0033] In step (1) b of the present invention, the mass ratio of the solvent, 4-hydroxy-3-alkoxy-1-propenylbenzene, 2,4,6-trihydroxyphenyl allyl ether, structure regulator and 1,3-butadiene is 200-300: 30-40: 60-70: 0.3-0.5: 2-5.

[0034] In step (1) b of the present invention, the temperature is raised to 70-80°C.

[0035] In step (1) b of the present invention, the reaction time after adding the initiator 1 is 90 to 100 minutes.

[0036] In step (1) b of the present invention, the reaction time for adding 1,3-butadiene for end-capping is 30 to 40 minutes.

[0037] In step (1) c of the present invention, the mass ratio of the solvent, the structure regulator, 1,3-butadiene and styrene is 300-400: 0.1-0.4: 100: 30-40.

[0038] In step (1) of the present invention, the temperature is raised to 60-70°C.

[0039] In step (1) c of the present invention, the stirring and mixing time is 20 to 30 minutes; the reaction time is 70 to 80 minutes, the initial feeding rate is >8.0% mixture / min, and the extent of the reduction in feeding rate depends on the reaction time.

[0040] In step (1) d of the present invention, the mass ratio of the solvent 1, para-alkylstyrene, the first structure regulator, 1,3-butadiene, the second structure regulator, SB / (S→B) copolymer, solution, macromolecular composite functional monomer, and solvent 2 is 200-300:100:0.3-0.6:50-60:0.05-0.1:20-30:100-200:5-10:50-100.

[0041] In step (1) of the present invention, before adding initiator 1, the temperature is raised to 50-60° C.; after adding initiator 1, the reaction time is 80-90 min.

[0042] In step (1) of the present invention, the time for adding the coupling agent to carry out the coupling reaction is 60 to 70 minutes.

[0043] In step (1) of the present invention, the time for stirring and dissolving the SB / (S→B) copolymer and the solution after mixing is 60 to 70 minutes.

[0044] In step (1) of the present invention, the coupling reaction time after adding the SB / (S→B) copolymer and mixing the solution is 80 to 90 minutes.

[0045] In step (1) d of the present invention, the time for stirring and dissolving after adding the macromolecular composite functional monomer and mixing with the solvent is 70 to 80 minutes.

[0046] In step (1) d of the present invention, the time for the coupling reaction after adding the macromolecular composite functionalized monomer and the solvent is 110 min to 120 min.

[0047] In step (1) d of the present invention, during the end-capping, the amount of 1,3-butadiene added is 2% to 5% based on the mass of p-alkylstyrene as 100%.

[0048] In step (1) of the present invention, the reaction time for adding 1,3-butadiene for end-capping is 30 to 40 minutes.

[0049] In step (2) a of the present invention, the mass ratio of the nitrile rubber to the Grubbs I catalyst is 100:0.02-0.1.

[0050] In step (2) a of the present invention, the mass fraction of nitrile rubber in the rubber solution is 3% to 6%.

[0051] In step (2) a of the present invention, the mass concentration of the Grubbs I catalyst in the xylene solution of the Grubbs I catalyst is 5% to 10%.

[0052] In step (2) a of the present invention, the pressurization is performed to a pressure of 11 to 14 MPa; the heating is performed to a temperature of 100 to 120° C.; and the reaction time is 9 to 11 hr.

[0053] In step (2) a of the present invention, the degree of hydrogenation HD of the HNBR rubber is less than 90%.

[0054] In step (2) b of the present invention, the mass ratio of the HNBR rubber, the macromolecular three-arm star-shaped composite functionalized grafting agent, and chlorobenzene is 100:2-4:50-100.

[0055] In step (2) b of the present invention, the mass fraction of HNBR rubber in the rubber solution is 6% to 9%.

[0056] In step (2) b of the present invention, the reaction temperature is 80-90° C. and the reaction time is 11.0-12.0 hr.

[0057] In step (2) b of the present invention, the grafting rate of the special oilfield hydrogenated nitrile rubber is 1.7% to 3.5%.

[0058] The polymerization reaction of the present invention is carried out in an oxygen-free, water-free and inert gas environment. The inert gas is nitrogen or a gas of a Group 0 element in the periodic table except radon, preferably nitrogen.

[0059] The reactor described in the present invention can be a loop reactor or a tank reactor, preferably a tank reactor.

[0060] The pressurization in step (2) a of the present invention is achieved by adding hydrogen. The amount of hydrogen added is well known to those skilled in the art and is within the conventional addition range in the prior art, and is not particularly limited in the present invention.

[0061] The present invention also provides a special hydrogenated nitrile rubber for oil fields obtained by the preparation method.

[0062] Compared with the prior art, the present invention has at least the following advantages and beneficial effects:

[0063] (1) The macromolecular composite functional monomer prepared by the present invention is prepared by anionic polymerization using 2,4,6-trihydroxyphenyl allyl ether and 4-hydroxy-3-alkoxy-1-propenylbenzene. This monomer integrates alkoxy, polyhydroxy and ether groups on a macromolecular chain, fully utilizing the "aggregation effect" of macromolecules, the "group effect" of ether, polyhydroxy and alkoxy groups, and at the same time produces a certain "synergistic effect" with the three-arm star structure, which can more effectively reduce the glass transition temperature (Tg) of HNBR, and can prepare a special hydrogenated nitrile rubber for oil fields with a glass transition temperature Tg of raw rubber <-80°C, which is suitable for oil well operations under low temperature conditions of -80°C.

[0064] (2) The macromolecular three-arm star-shaped composite functionalized grafting agent prepared by the present invention integrates the p-alkylstyrene homopolymer chain segment, SB / (S→B) copolymer and macromolecular composite functionalized monomer on a macromolecular chain, fully utilizing the "aggregation effect" of alkylbenzene in the p-alkylbenzene homopolymer, and the "group effect" of the phenyl groups in the SB / (S→B) copolymer and the macromolecular composite functionalized monomer to produce a certain "synergistic effect", thereby avoiding the destruction of the crystallinity of HNBR by the macromolecular composite functionalized monomer, thereby causing a decrease in the tear strength of HNBR, and more effectively improving the tear strength of HNBR, so as to prepare a special hydrogenated nitrile rubber for oil fields with a raw rubber tear strength of ≥78KN / m, which can meet the tear strength requirements of the stator rubber material of the submersible screw pump during oil well operation.

[0065] (3) The present invention combines three different microstructures of segments on a macromolecular chain to form a three-arm star structure through the design of a three-arm star structure, so that the performance of different segments can be organically combined and work synergistically. By utilizing the wide vinyl distribution in the BR segment, the randomness and gradual change of the -SB / (S→B)- segment, and the different reactivity ratios and steric hindrance effects of each segment in the three-arm structure, the disorder of the molecular segment increases during the graft polymerization of HNBR, which significantly destroys the regularity of the molecular chain, making the molecular weight distribution significantly wider, ensuring that HNBR can obtain good viscoelastic properties, greatly improving the compression set resistance of HNBR, and being able to prepare a special oilfield hydrogenated nitrile rubber with a compression set of ≤9.0% of the raw rubber, which can meet the compression resistance requirements of the stator rubber material of the submersible screw pump during oil well operations.

[0066] (4) The macromolecular three-arm star-shaped composite functionalized grafting agent can significantly improve the tear strength, compression set resistance and lower the glass transition temperature (Tg) of HNBR at a low addition amount, and achieve a good "synergistic effect" in achieving a balance between the tear strength, compression resistance and cold resistance of HNBR.

[0067] (5) The preparation method of the special oilfield hydrogenated nitrile rubber of the present invention is green and environmentally friendly, has a high modification effect, uses a low amount of modifier, and has readily available raw materials on the market, and is suitable for industrial production. DETAILED DESCRIPTION

[0068] The following examples and comparative examples are listed to illustrate the effects of the present invention, but the protection scope 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 used after purification without other special requirements. The "parts" described in the examples and comparative examples are all parts by mass.

[0069] (1) Source of raw materials:

[0070] Nitrile rubber 2907, acrylonitrile content 27% to 30%, PetroChina Lanzhou Petrochemical Company

[0071]

[0072] (2) Analytical testing methods:

[0073] Determination of grafting rate: Take about 4g of sample from the three-necked bottle with a pipette and put it into a weighing bottle. After weighing, add 2-3 drops of hydroquinone solution and dry to constant weight. Then put the sample in a Soxhlet fat extractor and extract it with toluene in a 90℃ water bath for 24 hours, and then dry it to constant weight. Calculate the monomer grafting rate according to the following formula:

[0074]

[0075] Where: m0 is the total mass of the mortar (g); m is the mass of the sample weighed after the reaction (g); m —Total mass of monomers in the reactants (g); m HNBR —The mass of hydrogenated nitrile rubber in the sample (g); m1—The mass of the sample after extraction (g).

[0076] Determination of molecular weight and distribution: 2414 gel permeation chromatograph (GPC) produced by Waters Company of the United States was used for determination. Polystyrene standard was used as calibration curve, mobile phase was tetrahydrofuran, column temperature was 40°C, sample concentration was 1 mg / ml, injection volume was 50 μL, elution time was 40 min, flow rate was 1 ml·min -1 .

[0077] Determination of HNBR hydrogenation degree: Using nuclear magnetic resonance hydrogen spectrum ( 1 The degree of hydrogenation of hydrogenated nitrile rubber is calculated by HNMR (HNMR), and the main method is as follows: 1. The product is completely dissolved in deuterated chloroform to prepare a nuclear magnetic resonance hydrogen spectrum sample; 2. After measuring the nuclear magnetic resonance hydrogen spectrum, its spectrum is analyzed: The degree of hydrogenation of hydrogenated nitrile rubber is measured by nuclear magnetic resonance hydrogen spectrum, and is calculated according to the following method: the proton characteristic peak of 1,4-C=C-: 5.4ppm, the proton characteristic peak of 1,2-C=C-: 5.0ppm, the proton characteristic peak of saturated hydrocarbons: 1.25ppm, the proton characteristic peak of cyano-linked: 2.5ppm, and the calculation formula of the degree of hydrogenation is as follows:

[0078] Degree of hydrogenation HD (%) = 1-unsaturation (U)

[0079] Determination of glass transition temperature Tg: DSC is used to measure the glass transition temperature of the product. The instrument model is DSC1, the company is Swiss Mettler, the temperature rise range is -80 to 80°C, and the temperature rise rate is 10°C / min.

[0080] Tear strength: Execute the method in standard GB / T 529-2009.

[0081] Compression set: Execute the method in standard GB / T 7759.1-2015.

[0082] Example 1

[0083] (1) Preparation of macromolecular three-arm star-shaped composite functionalized grafting agent:

[0084] a Preparation of 2,4,6-trihydroxyphenyl allyl ether: First, in a 5L stainless steel polymerizer with a jacket, argon gas was replaced three times, and 1500 g of deionized water, 500 g of 2,4,6-tribromophenyl allyl ether, and 100 g of a 10% NaOH aqueous solution were added to the polymerizer in sequence, stirred, mixed, and heated to 130°C. After reacting for 6.0 hours, 2,4,6-trihydroxyphenyl allyl ether was finally extracted, separated, washed, and dried to obtain 2,4,6-trihydroxyphenyl allyl ether (yield: 80%).

[0085] b. Preparation of macromolecular composite functional monomers: In a 10L stainless steel polymerizer with a jacket, the system was replaced three times by passing argon, and 2000g of cyclohexane, 300g of 4-hydroxy-3-alkoxy-1-propenylbenzene, 700g of 2,4,6-trihydroxyphenyl allyl ether, and 3.0g of THF were added to the polymerizer in sequence. The temperature was raised to 70°C, and 320mmol of n-butyl lithium was added to the polymerizer to react for 90min. Finally, 20g of 1,3-butadiene was added to the polymerizer for end-capping, and the reaction was carried out for 30min until no free monomers were present. The colloid was wet-coagulated and dried to obtain a macromolecular composite functional monomer.

[0086] Preparation of c SB / (S→B) copolymer: In a 10L stainless steel polymerizer with a jacket, the system was replaced three times with argon, 1500g cyclohexane and 0.5g THF were added to the polymerizer in sequence, the temperature was raised to 60°C, 170mmol n-butyl lithium was added, and then 500g 1,3-butadiene and 150g styrene were stirred and mixed for 20min. The mixture was added to the polymerizer by continuous injection at an initial feeding rate of 80g mixture / min and the feeding rate was reduced by 4g mixture per minute. The reaction was carried out for 70min until no free monomer was present. The rubber solution was wet coagulated and dried to obtain a random, long gradient SB / (S→B) copolymer.

[0087] d Preparation of macromolecular three-arm star-shaped composite functionalized grafting agent: In a 10L stainless steel polymerizer with a jacket, the system was replaced three times with argon, and 2000g cyclohexane, 1000g p-methylstyrene, and 3.0g THF were added to the polymerizer in sequence. After the temperature was raised to 50°C, 195mmol n-butyl lithium was added to start the reaction for 80min to form p-methylstyrene segments; then 500g 1,3-butadiene and 0.5g THF were added to the polymerizer in sequence. After the temperature was raised to 60°C, the temperature was gradually increased from 60°C to 90°C within 40min of reaction time to form BR segments with a wide vinyl distribution, and then 65mmol 1,3,5-trichlorobenzene was added for a coupling reaction for 60min; then 200g The SB / (S→B) copolymer was mixed with 1000g of cyclohexane and stirred for dissolution for 60min until it was completely dissolved, and then added to a polymerization kettle for coupling reaction for 80min; then 50g of a macromolecular composite functional monomer was mixed with 500g of cyclohexane and stirred for dissolution for 70min until it was completely dissolved, and then added to a polymerization kettle for coupling reaction for 110min; finally, 20g of 1,3-butadiene was added to the polymerization kettle for end-capping reaction for 30min until no free monomer was present. The colloid was wet-coagulated and dried to obtain a macromolecular three-arm star-shaped composite functional grafting agent (Mn was 7000, Mw / Mn was 13.17).

[0088] (2) Preparation of hydrogenated nitrile rubber for special oil fields:

[0089] a Preparation of hydrogenated nitrile rubber (HNBR): First, 100g of nitrile rubber 2907 was dissolved in chlorobenzene solution to prepare a 3% rubber solution by mass, and then the rubber solution was added to a 10L high-pressure reactor and nitrogen was introduced to remove the air in the reactor. Then, the nitrogen in the reactor was removed with hydrogen for 30 minutes, and then 0.02g of GrubbsⅠ catalyst xylene solution (mass concentration of 5%) was added under nitrogen protection. The hydrogen pressure in the pressurized reactor was 11MPa, the temperature was raised to 100℃, and after reacting for 9.0hr, the system was cooled, condensed, and vacuum dried to obtain HNBR rubber (hydrogenation degree HD=84.1%).

[0090] b Preparation of hydrogenated nitrile rubber for special oil fields: First, 200g of HNBR rubber was dissolved in chlorobenzene solution to prepare a 6% glue solution by mass, and then the glue solution was added to a 10L stainless steel reactor with a jacket, and nitrogen was introduced for replacement 3 times. Then 4.0g of a macromolecular three-arm star-shaped composite functionalized grafting agent was added to the reactor, stirred and mixed, and heated. When the temperature of the reactor reached 80°C, a mixture of 0.10g of DCP and 100g of chlorobenzene was added. After reacting for 11.0 hours, it was flocculated with anhydrous ethanol, washed, and dried in a 70°C oven to constant weight to obtain hydrogenated nitrile rubber for special oil fields (grafting rate 1.7%).

[0091] Example 2

[0092] (1) Preparation of macromolecular three-arm star-shaped composite functionalized grafting agent:

[0093] a Preparation of 2,4,6-trihydroxyphenyl allyl ether: same as Example 1.

[0094] b. Preparation of macromolecular composite functionalized monomer: Same as Example 1.

[0095] c Preparation of SB / (S→B) copolymer: same as Example 1.

[0096] d Preparation of macromolecular three-arm star-shaped composite functionalized grafting agent: In a 10L stainless steel polymerizer with a jacket, the system was replaced three times by passing argon, and 2200g cyclohexane, 1000g p-methylstyrene, and 3.5g THF were added to the polymerizer in sequence. After the temperature was raised to 52°C, 191mmol n-butyl lithium was added to start the reaction for 82min to form p-methylstyrene segments; then 520g 1,3-butadiene and 0.6g THF were added to the polymerizer in sequence. After the temperature was raised to 60°C, the temperature was gradually increased from 60°C to 90°C within 45min of reaction time to form BR segments with a wide vinyl distribution, and then 63mmol 1,3,5-trichlorobenzene was added for a coupling reaction for 62min; then 220g The SB / (S→B) copolymer was mixed with 1200g of cyclohexane and stirred for dissolution for 62min, and then added to a polymerization kettle for coupling reaction for 82min until it was completely dissolved; then 60g of a macromolecular composite functional monomer was mixed with 600g of cyclohexane and stirred for dissolution for 72min, and then added to a polymerization kettle for coupling reaction for 112min until it was completely dissolved; finally, 30g of 1,3-butadiene was added to the polymerization kettle for end-capping reaction for 32min until no free monomer was present, and the colloid was wet-coagulated and dried to obtain a macromolecular three-arm star-shaped composite functional grafting agent (Mn was 7100, Mw / Mn was 13.42).

[0097] (2) Preparation of hydrogenated nitrile rubber for special oil fields:

[0098] a. Preparation of hydrogenated nitrile rubber (HNBR): Same as in Example 1.

[0099] b Preparation of hydrogenated nitrile rubber for special oil fields: First, 200g of HNBR rubber was dissolved in chlorobenzene solution to prepare a 6.7% glue solution by mass, and then the glue solution was added to a 10L stainless steel reactor with a jacket, and nitrogen was introduced for replacement 3 times, and then 5.0g of a macromolecular three-arm star-shaped composite functionalized grafting agent was added to the reactor, stirred and mixed, and heated. When the temperature of the reactor reached 82°C, a mixture of 0.15g of DCP and 120g of chlorobenzene was added. After reacting for 11.2 hours, it was flocculated with anhydrous ethanol, washed, and dried in a 70°C oven to constant weight to obtain hydrogenated nitrile rubber for special oil fields (grafting rate 2.1%).

[0100] Example 3

[0101] (1) Preparation of macromolecular three-arm star-shaped composite functionalized grafting agent:

[0102] a Preparation of 2,4,6-trihydroxyphenyl allyl ether: same as Example 1.

[0103] b. Preparation of macromolecular composite functionalized monomer: Same as Example 1.

[0104] c Preparation of SB / (S→B) copolymer: same as Example 1.

[0105] d Preparation of macromolecular three-arm star-shaped composite functionalized grafting agent: In a 10L stainless steel polymerizer with a jacket, the system was replaced 4 times by passing argon, and 2400g cyclohexane, 1000g p-methylstyrene, and 4.0g THF were added to the polymerizer in sequence. After the temperature was raised to 54°C, 187mmol n-butyl lithium was added to start the reaction for 84min to form p-methylstyrene segments; then 540g 1,3-butadiene and 0.7g THF were added to the polymerizer in sequence. After the temperature was raised to 60°C, the temperature was gradually increased from 60°C to 90°C within 50min reaction time to form BR segments with wide vinyl distribution, and then 60mmol 1,3,5-trichlorobenzene was added for coupling reaction for 64min; then 240g The SB / (S→B) copolymer was mixed with 1400g of cyclohexane and stirred for dissolution for 64min, and then added to a polymerization kettle for coupling reaction for 84min until it was completely dissolved; then 70g of a macromolecular composite functional monomer was mixed with 700g of cyclohexane and stirred for dissolution for 74min, and then added to a polymerization kettle for coupling reaction for 114min until it was completely dissolved; finally, 35g of 1,3-butadiene was added to the polymerization kettle for end-capping reaction for 34min until no free monomer was present, and the colloid was wet-coagulated and dried to obtain a macromolecular three-arm star-shaped composite functional grafting agent (Mn was 7300, Mw / Mn was 13.73).

[0106] (2) Preparation of hydrogenated nitrile rubber for special oil fields:

[0107] a. Preparation of hydrogenated nitrile rubber (HNBR): Same as in Example 1.

[0108] b Preparation of hydrogenated nitrile rubber for special oil fields: First, 200g of HNBR rubber was dissolved in chlorobenzene solution to prepare a 7.1% glue solution by mass, and then the glue solution was added to a 10L stainless steel reactor with a jacket, and nitrogen was introduced for replacement 4 times, and then 5.5g of a macromolecular three-arm star-shaped composite functionalized grafting agent was added to the reactor, stirred and mixed, and heated. When the temperature of the reactor reached 84°C, a mixture of 0.20g of DCP and 140g of chlorobenzene was added. After reacting for 11.4 hours, it was flocculated with anhydrous ethanol, washed, and dried in a 70°C oven to constant weight to obtain hydrogenated nitrile rubber for special oil fields (grafting rate 2.4%).

[0109] Example 4

[0110] (1) Preparation of macromolecular three-arm star-shaped composite functionalized grafting agent:

[0111] a Preparation of 2,4,6-trihydroxyphenyl allyl ether: First, in a 5L stainless steel polymerizer with a jacket, argon gas was replaced 4 times, and 2000 g of deionized water, 500 g of 2,4,6-tribromophenyl allyl ether, and 150 g of a 20% NaOH aqueous solution were added to the polymerizer in sequence, stirred, mixed, and heated to 140°C. After reacting for 8.0 hours, 2,4,6-trihydroxyphenyl allyl ether was finally extracted, separated, washed, and dried to obtain 2,4,6-trihydroxyphenyl allyl ether (yield: 83%).

[0112] b. Preparation of macromolecular composite functional monomers: In a 10L stainless steel polymerizer with a jacket, the system was replaced 4 times by passing argon, and 2600g of cyclohexane, 350g of 4-hydroxy-3-alkoxy-1-propenylbenzene, 650g of 2,4,6-trihydroxyphenyl allyl ether, and 4.3g of THF were added to the polymerizer in sequence. The temperature was raised to 76°C, and 303mmol of n-butyl lithium was added to the polymerizer to react for 96min. Finally, 40g of 1,3-butadiene was added to the polymerizer for end-capping, and the reaction was carried out for 36min until no free monomers were present. The colloid was wet-coagulated and dried to obtain a macromolecular composite functional monomer.

[0113] Preparation of c SB / (S→B) copolymer: In a 10L stainless steel polymerizer with a jacket, argon was passed through the system to replace it 4 times, 1700g cyclohexane and 1.3g THF were added to the polymerizer in sequence, the temperature was raised to 64°C, 163mmol n-butyllithium was added, and then 500g 1,3-butadiene and 170g styrene were stirred and mixed for 24min. The mixture was added to the polymerizer by continuous injection at an initial feeding rate of 65g mixture / min. The feeding rate was reduced by 2g mixture per minute and the reaction was carried out for 74min until no free monomer was present. The rubber solution was wet coagulated and dried to obtain a random, long gradient SB / (S→B) copolymer.

[0114] d Preparation of macromolecular three-arm star-shaped composite functionalized grafting agent: In a 10L stainless steel polymerizer with a jacket, argon was passed through the system to replace it 4 times, and 2600g cyclohexane, 1000g p-methylstyrene, and 5.0g THF were added to the polymerizer in sequence. After the temperature was raised to 56°C, 183mmol n-butyl lithium was added to start the reaction for 86min to form p-methylstyrene segments; then 560g 1,3-butadiene and 0.8g THF were added to the polymerizer in sequence. After the temperature was raised to 60°C, the temperature was gradually increased from 60°C to 90°C within a reaction time of 55min to form a BR segment with a wide vinyl distribution, and then 56mmol 1,3,5-trichlorobenzene was added for a coupling reaction for 66min; then 260g The SB / (S→B) copolymer was mixed with 1600g of cyclohexane and stirred for dissolution for 66min, and then added to a polymerization kettle for coupling reaction for 86min until it was completely dissolved; then 80g of a macromolecular composite functional monomer was mixed with 800g of cyclohexane and stirred for dissolution for 76min, and then added to a polymerization kettle for coupling reaction for 116min until it was completely dissolved; finally, 40g of 1,3-butadiene was added to the polymerization kettle for end-capping reaction for 36min until no free monomer was present, and the colloid was wet-coagulated and dried to obtain a macromolecular three-arm star-shaped composite functional grafting agent (Mn was 7500, Mw / Mn was 14.01).

[0115] (2) Preparation of hydrogenated nitrile rubber for special oil fields:

[0116] a Preparation of hydrogenated nitrile rubber (HNBR): First, 100g of nitrile rubber 2907 was dissolved in chlorobenzene solution to prepare a 4.5% rubber solution by mass, and then the rubber solution was added to a 10L high-pressure reactor and nitrogen was introduced to remove the air in the reactor. Then, the nitrogen in the reactor was removed with hydrogen for 36 minutes, and then 0.07g of GrubbsⅠ catalyst xylene solution (mass concentration was 8%) was added under nitrogen protection. The hydrogen pressure in the pressurized reactor was 12MPa, and the temperature was raised to 113°C. After reacting for 10 hours, the system was cooled, condensed, and vacuum dried to obtain HNBR rubber (hydrogenation degree HD=87.1%).

[0117] b Preparation of hydrogenated nitrile rubber for special oil fields: First, 200g of HNBR rubber was dissolved in chlorobenzene solution to prepare a 7.8% glue solution by mass, and then the glue solution was added to a 10L stainless steel reactor with a jacket, and nitrogen was introduced for replacement 4 times, and then 6.0g of a macromolecular three-arm star-shaped composite functionalized grafting agent was added to the reactor, stirred and mixed, and heated. When the temperature of the reactor reached 86°C, a mixture of 0.30g of DCP and 160g of chlorobenzene was added. After reacting for 11.5 hours, it was flocculated with anhydrous ethanol, washed, and dried in a 70°C oven to constant weight to obtain hydrogenated nitrile rubber for special oil fields (grafting rate 2.7%).

[0118] Example 5

[0119] (1) Preparation of macromolecular three-arm star-shaped composite functionalized grafting agent:

[0120] a Preparation of 2,4,6-trihydroxyphenyl allyl ether: same as Example 4.

[0121] b. Preparation of macromolecular composite functionalized monomer: same as Example 4.

[0122] c Preparation of SB / (S→B) copolymer: same as Example 4.

[0123] d Preparation of macromolecular three-arm star-shaped composite functionalized grafting agent: In a 10L stainless steel polymerizer with a jacket, the system was replaced 5 times by passing argon, and 2800g cyclohexane, 1000g p-methylstyrene, and 5.5g THF were added to the polymerizer in sequence. After the temperature was raised to 58°C, 176mmol n-butyl lithium was added to start the reaction for 87min to form p-methylstyrene segments; then 580g 1,3-butadiene and 0.9g THF were added to the polymerizer in sequence. After the temperature was raised to 60°C, the temperature was gradually increased from 60°C to 90°C within a reaction time of 57min to form BR segments with a wide vinyl distribution, and then 51mmol 1,3,5-trichlorobenzene was added for a coupling reaction for 68min; then 280g The SB / (S→B) copolymer was mixed with 1800g of cyclohexane and stirred for dissolution for 68min, and then added to a polymerization kettle for coupling reaction for 87min until it was completely dissolved; then 90g of a macromolecular composite functional monomer was mixed with 900g of cyclohexane and stirred for dissolution for 78min, and then added to a polymerization kettle for coupling reaction for 117min until it was completely dissolved; finally, 46g of 1,3-butadiene was added to the polymerization kettle for end-capping reaction for 38min until no free monomer was present, and the colloid was wet-coagulated and dried to obtain a macromolecular three-arm star-shaped composite functional grafting agent (Mn was 7700, Mw / Mn was 14.29).

[0124] (2) Preparation of hydrogenated nitrile rubber for special oil fields:

[0125] a Preparation of hydrogenated nitrile rubber (HNBR): same as Example 4.

[0126] b Preparation of hydrogenated nitrile rubber for special oil fields: First, 200g of HNBR rubber was dissolved in chlorobenzene solution to prepare a glue solution with a mass fraction of 8.2%, and then the glue solution was added to a 10L stainless steel reactor with a jacket, and nitrogen was introduced for replacement 5 times, and then 7.0g of a macromolecular three-arm star-shaped composite functionalized grafting agent was added to the reactor, stirred and mixed, and heated. When the temperature of the reactor reached 88°C, a mixture of 0.35g of DCP and 180g of chlorobenzene was added. After reacting for 11.7 hours, it was flocculated with anhydrous ethanol, washed, and dried in a 70°C oven to constant weight to obtain hydrogenated nitrile rubber for special oil fields (grafting rate 3.0%).

[0127] Example 6

[0128] (1) Preparation of macromolecular three-arm star-shaped composite functionalized grafting agent:

[0129] a Preparation of 2,4,6-trihydroxyphenyl allyl ether: same as Example 4.

[0130] b. Preparation of macromolecular composite functional monomers: In a 10L stainless steel polymerizer with a jacket, the system was replaced 5 times by passing argon, and 3000g of cyclohexane, 400g of 4-hydroxy-3-alkoxy-1-propenylbenzene, 600g of 2,4,6-trihydroxyphenyl allyl ether, and 5.0g of THF were added to the polymerizer in sequence. The temperature was raised to 80°C, and 289mmol of n-butyl lithium was added to the polymerizer to react for 100min; finally, 50g of 1,3-butadiene was added to the polymerizer for end-capping, and the reaction was carried out for 40min until no free monomers were present. The colloid was wet-coagulated and dried to obtain a macromolecular composite functional monomer.

[0131] Preparation of c SB / (S→B) copolymer: In a 10L stainless steel polymerizer with a jacket, the system was replaced 5 times by passing argon, 2000g cyclohexane and 2.0g THF were added to the polymerizer in sequence, the temperature was raised to 70°C, 149mmol n-butyllithium was added, and then 500g 1,3-butadiene and 200g styrene were stirred and mixed for 30min. The mixture was added to the polymerizer by continuous injection at an initial feeding rate of 65g mixture / min. The feeding rate was reduced by 2g mixture per minute and the reaction was carried out for 80min until no free monomer was present. The rubber solution was wet coagulated and dried to obtain a random, long gradient SB / (S→B) copolymer.

[0132] d Preparation of macromolecular three-arm star-shaped composite functionalized grafting agent: In a 10L stainless steel polymerizer with a jacket, the system was replaced 5 times by passing argon, and 3000g cyclohexane, 1000g p-methylstyrene, and 6.0g THF were added to the polymerizer in sequence. After the temperature was raised to 60°C, 171mmol n-butyl lithium was added to start the reaction for 90min to form p-methylstyrene segments; then 600g 1,3-butadiene and 1.0g THF were added to the polymerizer in sequence. After the temperature was raised to 60°C, the temperature was gradually increased from 60°C to 90°C within 60min reaction time to form BR segments with wide vinyl distribution, and then 48mmol 1,3,5-trichlorobenzene was added for coupling reaction for 70min; then 300g The SB / (S→B) copolymer was mixed with 2000g of cyclohexane and stirred for dissolution for 70min until it was completely dissolved, and then added to a polymerization kettle for coupling reaction for 90min; then 100g of a macromolecular composite functional monomer was mixed with 1000g of cyclohexane and stirred for dissolution for 80min until it was completely dissolved, and then added to a polymerization kettle for coupling reaction for 120min; finally, 50g of 1,3-butadiene was added to the polymerization kettle for end-capping reaction for 40min until no free monomer was present, and the colloid was wet-coagulated and dried to obtain a macromolecular three-arm star-shaped composite functional grafting agent (Mn was 8000, Mw / Mn was 14.67).

[0133] (2) Preparation of hydrogenated nitrile rubber for special oil fields:

[0134] a Preparation of hydrogenated nitrile rubber (HNBR): same as Example 4.

[0135] b Preparation of hydrogenated nitrile rubber for special oil fields: First, 200g of HNBR rubber was dissolved in chlorobenzene solution to prepare a 9.0% glue solution by mass, and then the glue solution was added to a 10L stainless steel reactor with a jacket, and nitrogen was introduced for replacement 5 times, and then 8.0g of a macromolecular three-arm star-shaped composite functionalized grafting agent was added to the reactor, stirred and mixed, and heated. When the temperature of the reactor reached 90°C, a mixed solution of 0.40g of DCP and 200g of chlorobenzene was added. After reacting for 12.0 hours, it was flocculated with anhydrous ethanol, washed, and dried in a 70°C oven to constant weight to obtain hydrogenated nitrile rubber for special oil fields (grafting rate 3.5%).

[0136] Comparative Example 1

[0137] (1) Preparation of macromolecular three-arm star-shaped composite functionalized grafting agent:

[0138] a Preparation of 2,4,6-trihydroxyphenyl allyl ether: same as Example 1.

[0139] b. Preparation of macromolecular composite functionalized monomer: Same as Example 1.

[0140] c Preparation of SB / (S→B) copolymer: same as Example 1.

[0141] d Preparation of macromolecular three-arm star-shaped composite functionalized grafting agent: The other conditions are the same as those in Example 1, except that the variable temperature polymerization method is not used in the preparation process of the macromolecular three-arm star-shaped composite functionalized grafting agent, that is: in a 10L stainless steel polymerization kettle with a jacket, the system is replaced 3 times by passing argon gas, 2000g cyclohexane, 1000g p-methylstyrene, and 3.0g THF are added to the polymerization kettle in sequence, and after heating to 50°C, 195mmol n-butyllithium is added to start the reaction for 80min to form p-methylstyrene segments; then 500g 1,3-butadiene and 0.5g THF are added to the polymerization kettle in sequence, and after heating to 60°C, the reaction is carried out for 40min to form BR segments, and then 65mmol 1,3,5-trichlorobenzene is added for coupling reaction for 60min; then 200g The SB / (S→B) copolymer was mixed with 1000g of cyclohexane and stirred for dissolution for 60min until it was completely dissolved, and then added to a polymerization kettle for coupling reaction for 80min; then 50g of a macromolecular composite functional monomer was mixed with 500g of cyclohexane and stirred for dissolution for 70min until it was completely dissolved, and then added to a polymerization kettle for coupling reaction for 110min; finally, 20g of 1,3-butadiene was added to the polymerization kettle for end-capping reaction for 30min until no free monomer was present, and the colloid was wet-coagulated and dried to obtain a macromolecular three-arm star-shaped composite functional grafting agent a (Mn was 6900, Mw / Mn was 11.31).

[0142] (2) Preparation of hydrogenated nitrile rubber for special oil fields:

[0143] a. Preparation of hydrogenated nitrile rubber (HNBR): Same as in Example 1.

[0144] b Preparation of special oilfield hydrogenated nitrile rubber: Other conditions are the same as those in Example 1, except that in the preparation process of special oilfield hydrogenated nitrile rubber, no macromolecular three-arm star-shaped composite functionalized grafting agent is added, but a macromolecular three-arm star-shaped composite functionalized grafting agent a is added, and the addition amount is 4.0 g, that is, first, 200 g of HNBR rubber is dissolved in chlorobenzene solution to form a 6% glue solution by mass, and then the glue solution is added to a 10L stainless steel reactor with a jacket, and nitrogen is introduced for replacement 3 times, and then 4.0 g of macromolecular three-arm star-shaped composite functionalized grafting agent a is added to the reactor, stirred and mixed, and heated. When the reactor temperature reaches 80°C, a mixed solution of 0.10 g of DCP and 100 g of chlorobenzene is added, and after reacting for 11.0 hours, flocculation with anhydrous ethanol is performed, washing, and drying in a 70°C oven to constant weight to obtain special oilfield hydrogenated nitrile rubber (grafting rate 1.6%).

[0145] Comparative Example 2

[0146] (1) Preparation of macromolecular three-arm star-shaped composite functionalized grafting agent:

[0147] a Preparation of 2,4,6-trihydroxyphenyl allyl ether: same as Example 2.

[0148] b. Preparation of macromolecular composite functionalized monomer: same as Example 2.

[0149] c Preparation of SB / (S→B) copolymer: Other conditions were the same as those in Example 2, except that variable speed polymerization was not used in the preparation of SB / (S→B) copolymer, i.e., in a 10 L stainless steel polymerizer with a jacket, the system was replaced three times by passing argon gas, 1500 g of cyclohexane and 0.5 g of THF were added to the polymerizer in sequence, the temperature was raised to 60° C., 170 mmol of n-butyl lithium was added, and then 500 g of 1,3-butadiene and 150 g of styrene were stirred and mixed for 20 min, and then added to the polymerizer together to react for 70 min until no free monomer was present. The rubber solution was wet coagulated and dried to obtain SBR copolymer.

[0150] d Preparation of macromolecular three-arm star-shaped composite functionalized grafting agent: The other conditions are the same as those in Example 2, except that SB / (S→B) copolymer is not added during the preparation of the macromolecular three-arm star-shaped composite functionalized grafting agent, but SBR copolymer is added in an amount of 220.0 g, that is: in a 10L stainless steel polymerizer with a jacket, the system is replaced 3 times by argon, 2200 g cyclohexane, 1000 g p-methylstyrene, and 3.5 g THF are added to the polymerizer in sequence, and after the temperature is raised to 52°C, 191 mmol n-butyl lithium is added to start the reaction for 82 min to form p-methylstyrene segments; then 520 g 1,3-butadiene and 0.6 g THF are added to the polymerizer in sequence, and after the temperature is raised to 60°C, the temperature is gradually raised from 60°C to 90°C within a reaction time of 45 min to form BR segments with a wide vinyl distribution, and then 63 mmol 1,3,5-trichlorobenzene, coupling reaction for 62 minutes; then 220g SBR and 1200g cyclohexane were mixed and stirred for 62 minutes, until they were completely dissolved and then added to the polymerization kettle for coupling reaction for 82 minutes; then 60g macromolecular composite functional monomer and 600g cyclohexane were mixed and stirred for 72 minutes, until they were completely dissolved and then added to the polymerization kettle for coupling reaction for 112 minutes; finally, 30g 1,3-butadiene was added to the polymerization kettle for end-capping reaction for 32 minutes, until there was no free monomer, the glue was wet condensed and dried to obtain a macromolecular three-arm star-shaped composite functional grafting agent b (Mn was 7000, Mw / Mn was 10.08).

[0151] (2) Preparation of hydrogenated nitrile rubber for special oil fields:

[0152] a Preparation of hydrogenated nitrile rubber (HNBR): same as in Example 2.

[0153] b Preparation of special oilfield hydrogenated nitrile rubber: Other conditions are the same as those in Example 2, except that in the preparation process of special oilfield hydrogenated nitrile rubber, no macromolecular three-arm star-shaped composite functionalized grafting agent is added, but a macromolecular three-arm star-shaped composite functionalized grafting agent b is added, and the addition amount is 5.0 g, that is, first 200 g HNBR rubber is dissolved in chlorobenzene solution to form a glue solution with a mass fraction of 6.7%, and then the glue solution is added to a 10L stainless steel reactor with a jacket, and nitrogen is introduced for replacement 3 times, and then 5.0 g of macromolecular three-arm star-shaped composite functionalized grafting agent b is added to the reactor, stirred and mixed, and heated. When the reactor temperature reaches 82°C, a mixed solution of 0.15 g DCP and 120 g chlorobenzene is added, and after reacting for 11.2 hours, it is flocculated with anhydrous ethanol, washed, and dried in a 70°C oven to constant weight to obtain special oilfield hydrogenated nitrile rubber (grafting rate 1.9%).

[0154] Comparative Example 3

[0155] (1) Preparation of macromolecular three-arm star-shaped composite functionalized grafting agent:

[0156] a Preparation of 2,4,6-trihydroxyphenyl allyl ether: same as Example 3.

[0157] b. Preparation of macromolecular composite functionalized monomer: same as Example 3.

[0158] c Preparation of SB / (S→B) copolymer: same as Example 3.

[0159] d Preparation of a macromolecular three-arm star-shaped composite functionalized grafting agent: The other conditions are the same as those in Example 3, except that 1,3,5-trichlorobenzene is not added during the preparation of the macromolecular three-arm star-shaped composite functionalized grafting agent, that is: in a 10L stainless steel polymerizer with a jacket, the system is replaced 4 times by passing argon gas, 2400g of cyclohexane, 1000g of p-methylstyrene, and 4.0g of THF are added to the polymerizer in sequence, and after the temperature is raised to 54°C, 187mmol of n-butyllithium is added to start the reaction for 84min to form a p-methylstyrene segment; then 540g of 1,3-butadiene and 0.7g of THF are added to the polymerizer in sequence, and after the temperature is raised to 60°C, the temperature is gradually raised from 60°C to 90°C within a reaction time of 50min to form a BR segment with a wide vinyl distribution, and then 240g The SB / (S→B) copolymer was mixed with 1400g of cyclohexane and stirred for dissolution for 64min, and then added to a polymerization kettle for coupling reaction for 84min until it was completely dissolved; then 70g of a macromolecular composite functional monomer was mixed with 700g of cyclohexane and stirred for dissolution for 74min, and then added to a polymerization kettle for coupling reaction for 114min until it was completely dissolved; finally, 35g of 1,3-butadiene was added to the polymerization kettle for end-capping reaction for 34min until no free monomer was present, and the colloid was wet-coagulated and dried to obtain a macromolecular three-arm star-shaped composite functional grafting agent c (Mn was 4100, Mw / Mn was 9.87).

[0160] (2) Preparation of hydrogenated nitrile rubber for special oil fields:

[0161] a Preparation of hydrogenated nitrile rubber (HNBR): same as in Example 3.

[0162] b Preparation of special oilfield hydrogenated nitrile rubber: Other conditions are the same as those in Example 3, except that in the preparation process of special oilfield hydrogenated nitrile rubber, no macromolecular three-arm star-shaped composite functionalized grafting agent is added, but a macromolecular three-arm star-shaped composite functionalized grafting agent c is added in an amount of 5.5 g, namely: first, 200 g of HNBR rubber is dissolved in a chlorobenzene solution to form a glue solution with a mass fraction of 7.1%, and then the glue solution is added to a 10L stainless steel reactor with a jacket, and nitrogen is introduced for replacement 4 times, and then 5.5 g of a macromolecular three-arm star-shaped composite functionalized grafting agent c is added to the reactor, stirred and mixed, and heated. When the reactor temperature reaches 84°C, a mixed solution of 0.20 g of DCP and 140 g of chlorobenzene is added, and after reacting for 11.4 hours, flocculation with anhydrous ethanol is performed, washing, and drying in a 70°C oven to constant weight to obtain special oilfield hydrogenated nitrile rubber (grafting rate 2.3%).

[0163] Comparative Example 4

[0164] (1) Preparation of macromolecular three-arm star-shaped composite functionalized grafting agent:

[0165] a Preparation of 2,4,6-trihydroxyphenyl allyl ether: First, in a 5L stainless steel polymerizer with a jacket, argon gas was replaced 4 times, and 2000 g of deionized water, 500 g of 2,4,6-tribromophenyl allyl ether, and 150 g of a 20% NaOH aqueous solution were added to the polymerizer in sequence, stirred, mixed, and heated to 140°C. After reacting for 8.0 hours, 2,4,6-trihydroxyphenyl allyl ether was finally extracted, separated, washed, and dried to obtain 2,4,6-trihydroxyphenyl allyl ether (yield: 83%).

[0166] b Preparation of SB / (S→B) copolymer: same as Example 4.

[0167] c Preparation of macromolecular three-arm star-shaped composite functionalized grafting agent: The other conditions are the same as those in Example 4, except that no macromolecular composite functionalized monomer is added during the preparation of the macromolecular three-arm star-shaped composite functionalized grafting agent, but 2,4,6-trihydroxyphenyl allyl ether is added in an amount of 80 g, that is: in a 10L stainless steel polymerizer with a jacket, the system is replaced 4 times by argon, 2600g cyclohexane, 1000g p-methylstyrene, and 5.0g THF are added to the polymerizer in sequence, and after the temperature is raised to 56°C, 183mmol n-butyl lithium is added to start the reaction for 86min to form p-methylstyrene segments; then 560g 1,3-butadiene and 0.8g THF are added to the polymerizer in sequence, and after the temperature is raised to 60°C, the temperature is gradually raised from 60°C to 90°C within a reaction time of 55min to form BR segments with a wide vinyl distribution, and then 56mmol 1,3,5-trichlorobenzene, coupling reaction for 66 minutes; then 260g SB / (S→B) copolymer and 1600g cyclohexane were mixed and stirred for 66 minutes until they were completely dissolved and then added to the polymerization kettle for coupling reaction for 86 minutes; then 80g 2,4,6-trihydroxyphenyl allyl ether and 800g cyclohexane were mixed and stirred for 76 minutes until they were completely dissolved and then added to the polymerization kettle for coupling reaction for 116 minutes; finally, 40g 1,3-butadiene was added to the polymerization kettle for end-capping reaction for 36 minutes until no free monomers existed, and the glue was wet-coagulated and dried to obtain a macromolecular three-arm star-shaped composite functionalized grafting agent d (Mn was 5600, Mw / Mn was 12.07).

[0168] (2) Preparation of hydrogenated nitrile rubber for special oil fields:

[0169] a Preparation of hydrogenated nitrile rubber (HNBR): same as Example 4.

[0170] b Preparation of special oilfield hydrogenated nitrile rubber: The other conditions are the same as those in Example 4, except that in the preparation process of special oilfield hydrogenated nitrile rubber, no macromolecular three-arm star-shaped composite functionalized grafting agent is added, but a macromolecular three-arm star-shaped composite functionalized grafting agent d is added, and the addition amount is 6.0 g, that is, first, 200 g of HNBR rubber is dissolved in chlorobenzene solution to form a glue solution with a mass fraction of 7.8%, and then the glue solution is added to a 10L stainless steel reactor with a jacket, and nitrogen is introduced for replacement 4 times, and then 6.0 g of macromolecular three-arm star-shaped composite functionalized grafting agent d is added to the reactor, stirred and mixed, and heated. When the reactor temperature reaches 86°C, a mixed solution of 0.30 g of DCP and 160 g of chlorobenzene is added, and after reacting for 11.5 hours, it is flocculated with anhydrous ethanol, washed, and dried in a 70°C oven to constant weight to obtain special oilfield hydrogenated nitrile rubber (grafting rate 1.6%).

[0171] Comparative Example 5

[0172] (1) Preparation of macromolecular three-arm star-shaped composite functionalized grafting agent:

[0173] a Preparation of 2,4,6-trihydroxyphenyl allyl ether: same as Example 5.

[0174] b. Preparation of macromolecular composite functionalized monomer: same as Example 5.

[0175] c Preparation of SB / (S→B) copolymer: same as Example 5.

[0176] d Preparation of macromolecular three-arm star-shaped composite functionalized grafting agent: The other conditions are the same as those in Example 5, except that p-methylstyrene is not added during the preparation of the macromolecular three-arm star-shaped composite functionalized grafting agent, but styrene is added, that is: in a 10L stainless steel polymerizer with a jacket, the system is replaced 5 times by argon, 2800g cyclohexane, 1000g styrene, and 5.5g THF are added to the polymerizer in sequence, and after the temperature is raised to 58°C, 176mmol n-butyl lithium is added to start the reaction for 87min to form a p-methylstyrene segment; then 580g 1,3-butadiene and 0.9g THF are added to the polymerizer in sequence, and after the temperature is raised to 60°C, the temperature is gradually increased from 60°C to 90°C within a reaction time of 57min to form a BR segment with a wide vinyl distribution, and then 51mmol 1,3,5-trichlorobenzene is added for a coupling reaction for 68min; then 280g The SB / (S→B) copolymer was mixed with 1800g of cyclohexane and stirred for dissolution for 68min, and then added to a polymerization kettle for coupling reaction for 87min until it was completely dissolved; then 90g of a macromolecular composite functional monomer was mixed with 900g of cyclohexane and stirred for dissolution for 78min, and then added to a polymerization kettle for coupling reaction for 117min until it was completely dissolved; finally, 46g of 1,3-butadiene was added to the polymerization kettle for end-capping reaction for 38min until no free monomer was present, and the colloid was wet-coagulated and dried to obtain a macromolecular three-arm star-shaped composite functional grafting agent e (Mn was 7200, Mw / Mn was 12.98).

[0177] (2) Preparation of hydrogenated nitrile rubber for special oil fields:

[0178] a Preparation of hydrogenated nitrile rubber (HNBR): same as in Example 5.

[0179] b Preparation of special oilfield hydrogenated nitrile rubber: The other conditions are the same as those in Example 5, except that in the preparation process of special oilfield hydrogenated nitrile rubber, no macromolecular three-arm star-shaped composite functionalized grafting agent is added, but a macromolecular three-arm star-shaped composite functionalized grafting agent e is added, and the addition amount is 7.0 g, that is: first, 200 g of HNBR rubber is dissolved in chlorobenzene solution to form a glue solution with a mass fraction of 8.2%, and then the glue solution is added to a 10L stainless steel reactor with a jacket, and nitrogen is introduced for replacement 5 times, and then 7.0 g of macromolecular three-arm star-shaped composite functionalized grafting agent e is added to the reactor, stirred and mixed, and heated. When the reactor temperature reaches 88°C, a mixed solution of 0.35 g of DCP and 180 g of chlorobenzene is added, and after reacting for 11.7 hours, it is flocculated with anhydrous ethanol, washed, and dried in a 70°C oven to constant weight to obtain special oilfield hydrogenated nitrile rubber (grafting rate 2.8%).

[0180] Comparative Example 6

[0181] (1) Preparation of macromolecular three-arm star-shaped composite functionalized grafting agent:

[0182] a Preparation of 2,4,6-trihydroxyphenyl allyl ether: same as Example 6.

[0183] b. Preparation of macromolecular composite functionalized monomer: same as Example 6.

[0184] c Preparation of macromolecular three-arm star-shaped composite functionalized grafting agent: The other conditions were the same as those in Example 6, except that the SB / (S→B) copolymer was not added during the preparation of the macromolecular three-arm star-shaped composite functionalized grafting agent, that is, in a 10L stainless steel polymerization kettle with a jacket, the system was replaced 5 times by passing argon, 3000g of cyclohexane and 6.0g of THF were added to the polymerization kettle in sequence, and after the temperature was raised to 60°C, 171mmol was added, and then 600g of 1,3-butadiene and 1.0g of THF were added to the polymerization kettle in sequence, and after the temperature was raised to 60°C, the temperature was gradually raised from 60°C to 90°C within a reaction time of 60min to form a BR segment with a wide vinyl distribution, and then 48mmol was added 1,3,5-trichlorobenzene, coupling reaction for 70 minutes; then 100g of the macromolecular composite functionalized monomer and 1000g of cyclohexane were mixed and stirred for 80 minutes until they were completely dissolved and added to the polymerization kettle for coupling reaction for 120 minutes; finally, 50g of 1,3-butadiene was added to the polymerization kettle for end-capping reaction for 40 minutes until no free monomers were present, and the colloid was wet-coagulated and dried to obtain a macromolecular two-arm star-shaped composite functionalized grafting agent (Mn was 5800, Mw / Mn was 8.15).

[0185] (2) Preparation of hydrogenated nitrile rubber for special oil fields:

[0186] a. Preparation of hydrogenated nitrile rubber (HNBR): Same as Example 6.

[0187] b Preparation of special oilfield hydrogenated nitrile rubber: The other conditions are the same as those in Example 6, except that a macromolecular three-arm star-shaped composite functionalized grafting agent is not added during the preparation of the special oilfield hydrogenated nitrile rubber, but a macromolecular two-arm star-shaped composite functionalized grafting agent is added in an amount of 8.0 g, namely: first, 200 g of HNBR rubber is dissolved in a chlorobenzene solution to form a 9.0% glue solution by mass, and then the glue solution is added to a 10L stainless steel reactor with a jacket, and nitrogen is introduced for replacement 5 times, and then 8.0 g of a macromolecular two-arm star-shaped composite functionalized grafting agent is added to the reactor, stirred and mixed, and heated. When the reactor temperature reaches 90°C, a mixed solution of 0.40 g of DCP and 200 g of chlorobenzene is added, and after reacting for 12.0 hours, flocculation is performed with anhydrous ethanol, washing, and drying in a 70°C oven to constant weight to obtain a special oilfield hydrogenated nitrile rubber (grafting rate 3.0%).

[0188] Table 1 Properties of hydrogenated nitrile rubber for special oil fields

[0189]

[0190] It can be seen from Table 1 that the special hydrogenated nitrile rubber for oil fields of the present invention has high tear strength, small compression permanent deformation and low glass transition temperature, and can be used as a rubber material for the stator of a submersible screw pump to meet the requirements of oil well operations under low temperature conditions of -80°C.

[0191] Of course, the present invention may have many other embodiments. Without departing from the spirit and essence of the present invention, technicians familiar with the field may make various corresponding changes and deformations based on the present invention, but these corresponding changes and deformations should all fall within the scope of protection of the present invention.

Claims

1. A method for preparing hydrogenated nitrile rubber for special oil fields, characterized in that: The steps include: (1) Preparation of macromolecular three-arm star-shaped composite functionalized grafting agent: a Preparation of 2,4,6-trihydroxyphenyl allyl ether: In a polymerization kettle, argon gas is introduced for replacement, deionized water, 2,4,6-tribromophenyl allyl ether, and NaOH aqueous solution are added to the polymerization kettle in sequence, stirred, mixed, heated, heated, reacted, and finally extracted, separated, washed, and dried to obtain 2,4,6-trihydroxyphenyl allyl ether; b. Preparation of macromolecular composite functional monomer: In a polymerization kettle, argon gas is introduced to replace the system, and a solvent, 4-hydroxy-3-alkoxy-1-propenylbenzene, 2,4,6-trihydroxyphenyl allyl ether, and a structure regulator are added to the polymerization kettle in sequence, and the temperature is raised, and then initiator 1 is added to the polymerization kettle for reaction; finally, 1,3-butadiene is added to the polymerization kettle for end-capping, and the reaction is continued until no free monomer exists. The gel solution is wet-coagulated and dried to obtain a macromolecular composite functional monomer; c Preparation of SB / (S→B) copolymer: In a polymerization kettle, argon gas is introduced to replace the system, and a solvent and a structure regulator are added to the polymerization kettle in sequence, the temperature is raised, and an initiator 1 is added, and then 1,3-butadiene and styrene are stirred and mixed, added to the polymerization kettle, and reacted until no free monomer is present. The colloid is wet-coagulated and dried to obtain a random, long gradient SB / (S→B) copolymer; d Preparation of macromolecular three-arm star-shaped composite functionalized grafting agent: In a reactor, argon is introduced to replace the system, solvent 1, p-alkylstyrene, and the first structural regulator are added to the polymerization kettle in sequence, the temperature is raised, and initiator 1 is added to react to form a p-alkylstyrene homopolymer segment; then 1,3-butadiene and the second structural regulator are added to the polymerization kettle in sequence, the temperature is raised, and the reaction is a variable temperature polymerization. Within 40 to 60 minutes, the temperature gradually rises from 60°C to 90°C to form a BR segment with a wide vinyl distribution, and then a coupling agent is added to carry out a coupling reaction; then S The B / (S→B) copolymer and the solution are mixed and stirred to dissolve, and then added to a polymerization kettle for coupling reaction after being completely dissolved; finally, the macromolecular composite functional monomer is mixed with solvent 2 and stirred to dissolve, and then added to a polymerization kettle for coupling reaction after being completely dissolved, and finally 1,3-butadiene is added to the polymerization kettle for end-capping, and the reaction is carried out until no free monomer exists. After the reaction is completed, the reaction mixture after coupling is treated with water, and the glue solution is wet-coagulated and dried to obtain a macromolecular three-arm star-shaped composite functional grafting agent; (2) Preparation of hydrogenated nitrile rubber for special oil fields: a Preparation of hydrogenated nitrile rubber (HNBR): dissolve nitrile rubber in chlorobenzene solution to prepare a rubber solution, then add the rubber solution into a reactor and introduce inert gas to remove the air in the reactor, then remove the inert gas in the reactor with hydrogen, add a xylene solution of Grubbs I catalyst under nitrogen protection, pressurize, heat up, after reaction, cool the system, condense, and vacuum dry to obtain HNBR rubber; b. Preparation of hydrogenated nitrile rubber for special oil fields: HNBR rubber is dissolved in chlorobenzene solution to prepare a glue solution, and then the glue solution is added to a reactor, and an inert gas is introduced for replacement, and then a macromolecular three-arm star-shaped composite functionalized grafting agent is added to the reactor, stirred and mixed, heated, and a mixed solution of initiator 2 and chlorobenzene is added. After the reaction, flocculation, washing, and drying are performed to obtain hydrogenated nitrile rubber for special oil fields; The macromolecular three-arm star-shaped composite functionalized grafting agent has the following structure: Among them, R is a straight-chain alkyl of C1 to C6; BR is a 1,3-butadiene homopolymer segment with a wide vinyl distribution; B is a terminal 1,3-butadiene; n, m and L are the number of repeating units, and n≥1, m≥1 and L≥1 are positive integers; the number average molecular weight (Mn) of the macromolecular three-arm star-shaped composite functionalized grafting agent is 7000 to 8000, and the molecular weight distribution (Mw / Mn) is 13.17 to 14.

67.

2. The preparation method according to claim 1, characterized in that: The p-alkylstyrene is selected from one of p-methylstyrene, p-ethylstyrene, p-propylstyrene, p-butylstyrene, p-pentylstyrene and p-hexylstyrene.

3. The preparation method according to claim 1, characterized in that: The 4-hydroxy-3-alkoxy-1-propenylbenzene is selected from one of 4-hydroxy-3-methoxy-1-propenylbenzene, 4-hydroxy-3-ethoxy-1-propenylbenzene, 4-hydroxy-3-propoxy-1-propenylbenzene, 4-hydroxy-3-butoxy-1-propenylbenzene, 4-hydroxy-3-pentyloxy-1-propenylbenzene and 4-hydroxy-3-hexyloxy-1-propenylbenzene.

4. The preparation method according to claim 1, characterized in that: The initiator 1 is selected from one of n-butyl lithium, sec-butyl lithium, methylbutyl lithium, phenylbutyl lithium, naphthalene lithium, cyclohexyl lithium and dodecyl lithium.

5. The preparation method according to claim 1, characterized in that: The initiator 2 is selected from one of diacetyl peroxide, diisobutyryl peroxide, cumene hydroperoxide, dicumyl peroxide (DCP) and dibenzoyl peroxide (BPO), and its addition amount is 0.05-0.2 parts based on 100 parts of the mass of the HNBR rubber.

6. The preparation method according to claim 1, characterized in that: The coupling agent is one of 1,3,5-trichlorobenzene and 1,3,5-tribromobenzene.

7. The preparation method according to claim 1, characterized in that: The nitrile rubber is copolymerized by emulsion polymerization of 1,3-butadiene and acrylonitrile, wherein the acrylonitrile content of the nitrile rubber is 20wt% to 42wt%.

8. The preparation method according to claim 1, characterized in that: The structure regulator is selected from one of diethylene glycol dimethyl ether (2G), tetrahydrofuran (THF), ethyl ether, ethyl methyl ether, anisole, diphenyl ether, ethylene glycol dimethyl ether (DME), and triethylamine.

9. The preparation method according to claim 1, characterized in that: The solvent, solvent 1, solvent 2 or solution is selected from one of cyclohexane, carbon disulfide (CS2), nitrobenzene, petroleum ether, tetrachloroethane, toluene and xylene.

10. The preparation method according to claim 1, characterized in that: In step (1) a, the mass ratio of the deionized water, 2,4,6-tribromophenyl allyl ether, and the NaOH aqueous solution is 300-400:100:20-30.

11. The preparation method according to claim 1, characterized in that: In step (1) a, the mass concentration of the NaOH aqueous solution is 10% to 20%.

12. The preparation method according to claim 1, characterized in that: In step (1) a, the yield of 2,4,6-trihydroxyphenyl allyl ether is 80% to 83%.

13. The preparation method according to claim 1, characterized in that: In step (1) b, the mass ratio of the solvent, 4-hydroxy-3-alkoxy-1-propenylbenzene, 2,4,6-trihydroxyphenyl allyl ether, structure regulator, and 1,3-butadiene is 200-300: 30-40: 60-70: 0.3-0.5: 2-5.

14. The preparation method according to claim 1, characterized in that: In step (1) (c), the mass ratio of the solvent, the structure regulator, 1,3-butadiene and styrene is 300-400: 0.1-0.4: 100: 30-40.

15. The preparation method according to claim 1, characterized in that: In step (1) d, the mass ratio of the solvent 1, para-alkylstyrene, the first structural regulator, 1,3-butadiene, the second structural regulator, SB / (S→B) copolymer, solution, macromolecular composite functional monomer, and solvent 2 is 200-300:100:0.3-0.6:50-60:0.05-0.1:20-30:100-200:5-10:50-100.

16. The preparation method according to claim 1, characterized in that: In step (1) d, during the end-capping, the amount of 1,3-butadiene added is 2% to 5% based on the mass of p-alkylstyrene as 100%.

17. The preparation method according to claim 1, characterized in that: In step (2) a, the mass ratio of the nitrile rubber to the Grubbs I catalyst is 100:0.02-0.

1.

18. The preparation method according to claim 1, characterized in that: In step (2) a, the degree of hydrogenation HD of the HNBR rubber is less than 90%.

19. The preparation method according to claim 1, characterized in that: In step (2) b, the mass ratio of the HNBR rubber, the macromolecular three-arm star-shaped composite functionalized grafting agent, and chlorobenzene is 100:2-4:50-100.

20. The preparation method according to claim 1, characterized in that: In step (2) b, the grafting rate of the special oilfield hydrogenated nitrile rubber is 1.7% to 3.5%.

21. A special hydrogenated nitrile rubber for oil fields obtained by the preparation method according to any one of claims 1 to 20.

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