Compression-resistant, cold-resistant hydrogenated nitrile rubber for oil fields and method for producing the same

Abstract

This invention discloses a compression-resistant and cold-resistant hydrogenated nitrile butadiene rubber for oilfields and its preparation method. The preparation method includes: (1) preparation of a macromolecular three-hetero-arm star-shaped composite functionalized grafting agent, and (2) preparation of compression-resistant and cold-resistant hydrogenated nitrile butadiene rubber for oilfields. The macromolecular three-hetero-arm star-shaped composite functionalized grafting agent has the following structure: wherein, BR is a 1,3-butadiene homopolymer segment with a wide vinyl distribution; SB is a random segment of styrene and 1,3-butadiene; (S→B) is a gradient segment of styrene and 1,3-butadiene; B is a capped 1,3-butadiene; n, m, L are the number of repeating units, n≥1, m≥1, L≥1 are positive integers; the number average molecular weight (Mn) of the macromolecular three-hetero-arm star-shaped composite functionalized grafting agent is 6000~9000, and the molecular weight distribution (Mw / Mn) is 12.13~13.94. The method for preparing compression-resistant and cold-resistant hydrogenated nitrile butadiene rubber for oilfields according to the present invention has the characteristics of being green and environmentally friendly, having a high efficiency in modification, low dosage of modifier, readily available raw materials, and being suitable for industrial production.

Description

Technical Field

[0001] This invention belongs to the field of rubber technology, specifically relating to a compression-resistant and cold-resistant hydrogenated nitrile butadiene rubber for oilfields prepared by a macromolecular three-arm star-shaped composite functionalized grafting agent, and its preparation method. Background Technology

[0002] Hydrogenated nitrile butadiene rubber (HNBR) is prepared by selectively hydrogenating the carbon-carbon double bonds in nitrile butadiene rubber. Therefore, HNBR not only retains the oil resistance, corrosion resistance and elasticity of NBR, but also exhibits superior aging resistance and high temperature resistance. Furthermore, its mechanical properties such as tensile strength, elongation at break, abrasion resistance and hardness are improved. It is widely used in oil exploration equipment such as pump pistons, rotary hoses, valve seals, and drill pipe covers.

[0003] While hydrogenation of the carbon-carbon double bonds endows HNBR with excellent properties, it also introduces a serious drawback: the main chain of hydrogenated nitrile butadiene rubber (NBR) is a highly ordered polyethylene structure, which readily forms a crystalline structure, leading to an increase in temperature (Tg). Consequently, HNBR products exhibit poor cold resistance. Since most of my country's oil drilling operations are concentrated in the western and northeastern regions, where minimum temperatures can reach around -50°C, oil drilling equipment faces extremely demanding cold resistance requirements for rubber sealing materials.

[0004] In the prior art, there are many patent documents reporting methods for preparing low-temperature resistant hydrogenated nitrile butadiene rubber. For example:

[0005] CN 106349410 B discloses a special hydrogenated nitrile butadiene rubber with compression cold resistance and its preparation method. The rubber backbone contains epoxy groups, and some of these epoxy groups are also attached to ester side groups. The ester side groups are generated by a ring-opening reaction between a C6-C24 acid anhydride and the epoxy groups. The preparation method includes introducing epoxy groups into the rubber molecular backbone, and then reacting some of the epoxy groups with an acid anhydride under the action of a catalyst to introduce ester groups, thereby obtaining a special hydrogenated nitrile butadiene rubber containing epoxy groups and ester groups. CN 105294939 B discloses a low-temperature grade hydrogenated nitrile butadiene rubber raw rubber, which is a copolymer of butadiene, acrylonitrile, and dibutyl transbutenedioate, with a number-average molecular weight of 1.05–3.25 × 10⁻⁶. 5 The weight-average molecular weight is 3.02–9.32 × 10⁻⁶. 5The polydispersity index is 2.0–2.7; the degree of hydrogenation of the low-temperature grade hydrogenated nitrile butadiene rubber raw rubber is above 90%, and the glass transition temperature is -38℃ to -42℃. CN 112592461 B discloses a modified hydrogenated nitrile butadiene rubber material with low-temperature resistance and high damping characteristics, its preparation method, and its application. The modified hydrogenated nitrile butadiene rubber material is prepared using HNBR / PNB block copolymer as raw material; the HNBR / PNB block copolymer is obtained by modifying NBR or HNBR through olefin metathesis reaction using norbornene monomer as a modifier. CN 115594898A discloses a low-temperature resistant hydrogenated nitrile butadiene rubber compound and its internal mixing preparation method. The method mainly involves blending and internal mixing hydrogenated nitrile butadiene raw rubber, plasticizer, and hardness modifier to obtain a hydrogenated nitrile butadiene rubber compound with a Shore A hardness of 67±5, tensile strength ≥14MPa, elongation at break ≥180%, compression set ≤35%, and a cold resistance coefficient at 45℃ ≥0.16, exhibiting cold resistance. CN 105754164A discloses a low-temperature resistant rubber material. Although this material shows improved cold resistance, the addition of the plasticizer dioctyl phthalate (DOP) reduces the material's mechanical properties and oil resistance. Furthermore, DOP is not environmentally friendly and is prone to leaching. Zhang Dongheng et al. disclosed that by blending ethylene propylene rubber (EPDM) with HNBR, the cold resistance of HNBR was improved. When the EPDM content was 15%, the Tg decreased by 3°C. However, with further increasing the EPDM content, the Tg of the blended rubber no longer decreased (Synthetic Rubber Industry, 2002, 25(1)). ).

[0006] While the cold resistance of hydrogenated nitrile butadiene rubber can be improved to some extent by adding small molecule modifiers, copolymerization, and blending, these methods still have limitations. Their preparation methods are complex, difficult to implement, require large amounts of additives, are costly, and have limited modification effects. Summary of the Invention

[0007] To address the problems of existing technologies, this invention provides a method for preparing hydrogenated nitrile butadiene rubber (NBR) for oilfield use, exhibiting a compression set ≤11% and a glass transition temperature (Tg) <-74℃, meeting the requirements for use in the -74℃ to -76℃ temperature range. The invention first prepares a macromolecular composite functionalized long-chain monomer using 1,3-butadiene, dihydromyrcene alcohol, and N-(4-hydroxybutyl)acrylamide. Second, using an anionic polymerization method, the reactants are styrene, 1,3-butadiene, and the macromolecular composite functionalized long-chain monomer. Through temperature-variable polymerization, rate-variable polymerization, and coupling with a trihalomethane coupling agent, a macromolecular tri-hetero-arm star-shaped composite functionalized grafting agent with a wide vinyl distribution and random gradient segment is prepared. This grafting agent imparts excellent deformation resistance and cold resistance to hydrogenated NBR, achieving a balance between deformation resistance and low-temperature resistance, making it highly suitable for oil well operations requiring compression.

[0008] Unless otherwise specified, the term "parts" in this invention refers to parts by mass, "%" refers to percentage by mass, and "ratio" refers to mass ratio.

[0009] To achieve the above objectives, the present invention provides a method for preparing compression-resistant and cold-resistant hydrogenated nitrile butadiene rubber for oilfield use, the method comprising the following steps:

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

[0011] Preparation of macromolecular composite functionalized long-chain monomers: Argon gas was introduced into the polymerization reactor to replace the system. Solvent, dihydromyrcenol, N-(4-hydroxybutyl)acrylamide, and structure modifier were added to the polymerization reactor in sequence. The temperature was raised, and initiator 1 was added to the polymerization reactor for reaction. Finally, 1,3-butadiene was added to the polymerization reactor for end-capping. The reaction continued until no free monomers were present. The gel solution was wet coagulated and dried to obtain macromolecular composite functionalized long-chain monomers.

[0012] b. Preparation of SB / (S→B) copolymer: Argon gas was introduced into the polymerization reactor to replace the system. Solvent and structure modifier were added to the polymerization reactor in sequence. The temperature was raised and initiator 1 was added. Then, 1,3-butadiene and styrene were stirred and mixed and added to the polymerization reactor. The reaction was carried out until no free monomers were present. The glue solution was wet coagulated and dried to obtain random, long gradient segment SB / (S→B) copolymer.

[0013] Preparation of macromolecular three-hetero-arm star-shaped composite functionalized grafting agent: In a polymerization reactor, argon gas is introduced to replace the system. Solvent 1, 1,3-butadiene, and a structure modifier are added sequentially to the polymerization reactor. The temperature is raised, and initiator 1 is added. The reaction is a temperature-switching polymerization. The temperature is gradually raised from 40℃ to 70℃ within 50-70 minutes to form BR segments with a wide vinyl distribution. After the conversion rate of 1,3-butadiene monomer reaches 100%, the temperature is raised, and a coupling agent is added to carry out a coupling reaction. Then, the SB / (S→B) copolymer and the solution are mixed and stirred until completely dissolved, and then added to the polymerization reactor for a coupling reaction. Finally, the macromolecular composite functionalized long-chain monomer is mixed with solvent 2 and stirred until completely dissolved, and then added to the polymerization reactor for a coupling reaction until no free monomers are present. The glue solution is wet-coagulated and dried to obtain the macromolecular three-hetero-arm star-shaped composite functionalized grafting agent.

[0014] (2) Preparation of compression-resistant and cold-resistant hydrogenated nitrile butadiene rubber for oilfield use:

[0015] Preparation of hydrogenated nitrile butadiene rubber (HNBR): Nitrile butadiene rubber is dissolved in chlorobenzene solution to prepare a rubber solution. The rubber solution is then added to a reaction vessel, and an inert gas is introduced to remove the air from the reaction vessel. After the inert gas in the reaction vessel is removed by hydrogen, a xylene solution of Grubbs I catalyst is added under nitrogen protection. The system is pressurized, heated, and reacted. The system is then cooled, condensed, and vacuum dried to obtain HNBR rubber.

[0016] b. Preparation of compression-resistant and cold-resistant hydrogenated nitrile butadiene rubber for oilfields: HNBR rubber is dissolved in chlorobenzene solution to prepare a rubber solution. The rubber solution is then added to a reaction vessel, and an inert gas is introduced for purging. A macromolecular three-hetero-arm star-shaped composite functionalized grafting agent is then added to the reaction vessel. The mixture is stirred, heated, and a mixture of initiator 2 and chlorobenzene is added. The mixture is reacted, flocculated, washed, and dried to obtain compression-resistant and cold-resistant hydrogenated nitrile butadiene rubber for oilfields.

[0017] The macromolecular three-hetero-arm star-shaped composite functionalized grafting agent has the following structure:

[0018]

[0019] Wherein, BR is a 1,3-butadiene homopolymer segment with a broad vinyl distribution; SB is a random segment of styrene and 1,3-butadiene; (S→B) is a gradient segment of styrene and 1,3-butadiene; B is a capped 1,3-butadiene; n, m, L are the number of repeating units, n≥1, m≥1, L≥1 are positive integers; the number average molecular weight (Mn) of the macromolecular tri-hetero-arm star-shaped composite functionalized grafting agent is 6000~9000, and the molecular weight distribution (Mw / Mn) is 12.13~13.94.

[0020] The initiator 1 described in this invention is a hydrocarbon-based monolithium compound, namely RLi, wherein R is a saturated aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic group, or a complex group containing 1 to 20 carbon atoms. This hydrocarbon-based monolithium compound is selected from one of n-butyllithium, sec-butyllithium, methylbutyllithium, phenylbutyllithium, naphthenelithium, cyclohexyllithium, and dodecyllithium, preferably n-butyllithium. The amount of organolithium added is determined by the molecular weight of the designed polymer.

[0021] The initiator 2 described in this invention is an organic peroxide selected from one of diacetyl peroxide, diisobutyryl peroxide, cumene hydroperoxide, diisobutyryl peroxide (DCP), and benzoyl peroxide (BPO), preferably BPO, and its addition amount is 0.1 to 0.3 parts based on 100 parts by weight of HNBR rubber.

[0022] The nitrile rubber of this invention is copolymerized from 1,3-butadiene and acrylonitrile via emulsion polymerization. The acrylonitrile content of the nitrile rubber is 20 wt% to 42 wt%, preferably 22 wt% to 35 wt%.

[0023] The coupling agent described in this invention is one of 1,3,5-trichlorobenzene and 1,3,5-tribromobenzene, preferably 1,3,5-trichlorobenzene. Its dosage depends on the amount of initiator 1. Through excess coupling agent, polymerization proceeds stepwise, ultimately forming a star polymer with a heterostructure. The molar ratio of total initiator 1 to coupling agent is 3.0 to 4.0.

[0024] The structure modifier described in this invention is a polar organic compound that produces a solvation effect in the polymerization system, enabling it to adjust the reactivity ratio of styrene and butadiene, thus allowing them to copolymerize randomly. This type of polar organic compound is selected from one of diethylene glycol dimethyl ether (2G), tetrahydrofuran (THF), diethyl ether, ethyl methyl ether, anisole, diphenyl ether, diethylene glycol dimethyl ether (DME), and triethylamine, preferably tetrahydrofuran (THF).

[0025] The solvent, solvent 1, solvent 2 or solution described in this invention may be selected from one of cyclohexane, carbon disulfide (CS2), nitrobenzene, petroleum ether, tetrachloroethane, toluene, and xylene, with cyclohexane being preferred.

[0026] In step (1)a of the present invention, the mass ratio of the solvent, dihydromyrcenol, N-(4-hydroxybutyl)acrylamide, structure modifier, and 1,3-butadiene is 200-300:60-70, 30-40:0.1-0.3:2-5.

[0027] In step (1)a of the present invention, the temperature is raised to 50-60°C.

[0028] In step (1)a of the present invention, the reaction time for adding initiator 1 is 70-80 min; the time for adding 1,3-butadiene for end-capping reaction is 30-40 min.

[0029] In step (1)b of the present invention, the mass ratio of the solvent, structure modifier, 1,3-butadiene and styrene is 300-400: 0.1-0.4: 100: 30-40.

[0030] In step (1)b of the present invention, the temperature is raised to 60-70°C.

[0031] In step (1)b of the present invention, the stirring and mixing time is 20-30 min; the reaction time is 70-80 min; the initial feeding rate is >8.0% mixture / min; and the decrease in feeding rate depends on the reaction time.

[0032] In step (1)c of the present invention, the mass ratio of solvent 1, 1,3-butadiene, structure modifier, SB / (S→B) copolymer, solution, macromolecular complex functionalized long-chain monomer, and solvent 2 is 200-300:100:0.05-0.1:20-30:100-200:4-7:100-150.

[0033] In step (1)c of the present invention, after the conversion rate of 1,3-butadiene monomer reaches 100%, the temperature is raised to 80℃~90℃.

[0034] In step (1)c of the present invention, the coupling reaction time after adding the coupling agent is 70 min to 80 min; the coupling reaction time after adding the SB / (S→B) copolymer and solution is 90 min to 100 min; the coupling reaction time after adding the macromolecular complex functionalized long-chain monomer and solvent is 70 min to 80 min.

[0035] In step (1)c of the present invention, the stirring and dissolution time after adding the SB / (S→B) copolymer and solution is 70-80 min; the stirring and dissolution time after adding the macromolecular complex functionalized long-chain monomer and solvent is 60-70 min.

[0036] In step (2)a of the present invention, the mass ratio of the nitrile rubber and the Grubbs I catalyst is 100:0.02-0.1.

[0037] In step (2)a of the present invention, the mass fraction of nitrile rubber in the adhesive solution is 3% to 6%.

[0038] In step (2)a of the present invention, the mass concentration of GrubbsⅠ catalyst in the xylene solution of the GrubbsⅠ catalyst is 5% to 10%.

[0039] In step (2)a of the present invention, the pressure is increased to 11-14 MPa; the temperature is increased to 100-120°C; and the reaction time is 9-11 hours.

[0040] In step (2)a of the present invention, the degree of hydrogenation of the HNBR rubber is HD<90%.

[0041] 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.

[0042] In step (2)b of the present invention, the mass fraction of HNBR rubber in the adhesive solution is 6% to 9%.

[0043] In step (2)b of the present invention, the reaction temperature is 80-90°C and the time is 11.0-12.0hr.

[0044] In step (2)b of the present invention, the grafting rate of the compression-resistant and cold-resistant hydrogenated nitrile rubber for oil fields is 1.9% to 2.7%.

[0045] The polymerization reactions described in this invention are carried out in an oxygen-free, anhydrous, and inert gas environment. The inert gas is nitrogen or a gas of a group 0 element in the periodic table, excluding radon, with nitrogen being preferred.

[0046] The reaction vessel described in this invention can be a loop reactor or a batch reactor, preferably a batch reactor.

[0047] In step (2)a of this invention, pressurization is achieved by adding hydrogen gas. The amount of hydrogen gas added is well known to those skilled in the art, and the amount of hydrogen gas added is within the conventional addition range in the prior art. This invention does not impose any special limitations on this.

[0048] The present invention also provides a compression-resistant and cold-resistant hydrogenated nitrile butadiene rubber for oilfields obtained by the above preparation method.

[0049] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0050] (1) This invention uses a three-arm star structure design to combine three different microstructure segments on a macromolecular chain to form a three-arm star structure. This allows the properties of different segments to be organically combined and work synergistically. By utilizing the wide vinyl distribution in the BR segments, the randomness and gradation of the -SB / (S→B)- segments, and the different polymerization rates and steric hindrance effects of each segment in the hybrid arm structure, the disorder of the molecular chain segments increases during the graft polymerization of HNBR, which significantly destroys the regularity of the molecular chain and makes the molecular weight distribution significantly wider. This ensures that HNBR can obtain good viscoelastic properties and greatly improves the compression set resistance of HNBR. It can prepare compression set resistance and cold resistance hydrogenated nitrile rubber for oilfields with a compression set resistance of ≤11% for raw rubber.

[0051] (2) The macromolecular composite functionalized long-chain monomer prepared by the present invention is prepared by anionic polymerization of dihydromyrcenol and N-(4-hydroxybutyl)acrylamide. This long-chain monomer integrates ether groups, amide groups and hydroxyl groups containing long carbon chains into a macromolecular chain, making full use of the "cumulative effect" of macromolecules and the "group effect" of hydroxyl and amide groups, which can effectively destroy the crystallinity of HNBR. At the same time, it produces a certain "synergistic effect" with the three-arm star structure, which can more effectively reduce the glass transition temperature (Tg) of HNBR. It can prepare compression-resistant and cold-resistant hydrogenated nitrile rubber for oilfields with a glass transition temperature Tg < -74℃, which is suitable for oil well operations under low temperature conditions of -74℃.

[0052] (3) The macromolecular three-arm star-shaped composite functionalized grafting agent prepared by the present invention can significantly improve the compression set resistance of HNBR and reduce the glass transition temperature (Tg) of HNBR with a low addition amount, and achieve a good "synergistic effect" in achieving a balance between compression set resistance and cold resistance.

[0053] (4) The preparation method of the compression-resistant and cold-resistant hydrogenated nitrile rubber for oil fields of the present invention has the characteristics of being green and environmentally friendly, having a high efficiency of modification effect, low amount of modifier, readily available raw materials, and being suitable for industrial production. Detailed Implementation

[0054] The following examples and comparative examples illustrate the inventive effects of the present invention, but the scope of protection of the present invention is not limited to these examples and comparative examples. The raw materials used in the examples are all industrial grade, purified before use, and have no other special requirements. The "parts" mentioned in the examples and comparative examples refer to parts by weight.

[0055] (1) Source of raw materials:

[0056]

[0057]

[0058] (2) Analysis and testing methods:

[0059] Grafting rate determination: Approximately 4g of sample was pipetted from a three-necked flask into a weighing bottle. After weighing, 2-3 drops of hydroquinone solution were added, and the sample was dried to constant weight. The sample was then placed in a Soxhlet extractor and extracted with toluene in a 90°C water bath for 24 hours, followed by drying to constant weight. The monomer grafting rate was calculated using the following formula:

[0060]

[0061] Where: m0—total mass of adhesive (g); m—mass of the sample taken after reaction (g); m 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).

[0062] Molecular weight determination: Molecular weight was determined using a Waters 2414 gel permeation chromatography (GPC) system (Waters, Inc., USA). A polystyrene standard was used as the calibration curve. The mobile phase was tetrahydrofuran, the column temperature was 40℃, the sample concentration was 1 mg / mL, the injection volume was 50 μL, the elution time was 40 min, and the flow rate was 1 mL / min. -1 .

[0063] Determination of HNBR hydrogenation degree: using nuclear magnetic resonance hydrogen spectroscopy (NMR spectroscopy). 1 The degree of hydrogenation of hydrogenated nitrile butadiene rubber (NMR) is calculated using the following main methods: 1. The product is completely dissolved in deuterated chloroform to prepare a 1H NMR sample; 2. The 1H NMR spectrum is measured and analyzed: The degree of hydrogenation of hydrogenated nitrile butadiene rubber is determined by 1H NMR spectroscopy and calculated using the following methods: characteristic proton peak of 1,4-C=C-: 5.4 ppm, characteristic proton peak of 1,2-C=C-: 5.0 ppm, characteristic proton peak of saturated hydrocarbons: 1.25 ppm, characteristic proton peak of cyano-linked groups: 2.5 ppm. The formula for calculating the degree of hydrogenation is as follows:

[0064] Degree of hydrogenation (HD%) = 1 - Degree of unsaturation (U)

[0065] Determination of glass transition temperature (Tg): The glass transition temperature of the product was measured using DSC. The instrument model was DSC1, manufactured by Mettler AG, Switzerland. The heating range was -80 to 80 °C, and the heating rate was 10 °C / min.

[0066] Compression set: The method specified in standard GB / T 7759.1-2015 shall be followed.

[0067] Example 1

[0068] (1) Preparation of macromolecular three-hetero-arm star-shaped composite functionalized grafting agent:

[0069] Preparation of macromolecular composite functionalized long-chain monomers: In a 10L stainless steel polymerization reactor with a jacket, the system was purged three times with argon gas. 1000g cyclohexane, 300g dihydromyrcenol, 200g N-(4-hydroxybutyl)acrylamide, and 0.5g THF were added to the polymerization reactor in sequence. The temperature was raised to 50℃, and then 150mmol n-butyllithium was added to the polymerization reactor and reacted for 70min. Finally, 10g 1,3-butadiene was added to the polymerization reactor for end-capping, and the reaction was continued for 30min until no free monomers were present. The solution was then wet-coagulated and dried to obtain macromolecular composite functionalized long-chain monomers.

[0070] b. Preparation of SB / (S→B) copolymer: In a jacketed 10L stainless steel polymerization reactor, the system was purged three times with argon gas. 1500g of cyclohexane and 0.5g of THF were added to the polymerization reactor in sequence. The temperature was raised to 60℃, and 170mmol of n-butyllithium was added. Then, 500g of 1,3-butadiene and 150g of styrene were stirred and mixed for 20min. The mixture was then continuously added to the polymerization reactor at an initial feeding rate of 80g / min, with the feeding rate decreasing by 4g per minute. The reaction was continued for 70min until no free monomers were present. The solution was wet-coagulated and dried to obtain a random, long gradient segment SB / (S→B) copolymer.

[0071] Preparation of macromolecular three-hetero-arm star-shaped composite functionalized grafting agent: In a jacketed 10L stainless steel polymerization reactor, the system was purged three times with argon gas. 1000g cyclohexane, 500g 1,3-butadiene, and 0.25g THF were added sequentially to the reactor. After heating to 40℃, 310mmol n-butyllithium was added to initiate the reaction. The temperature was gradually increased from 40℃ to 70℃ over 55min to form BR segments with a broad vinyl distribution. After the 1,3-butadiene monomer conversion reached 100%, the temperature was raised to 80℃, and 100mmol 1,3,5-trichlorobenzene was added, followed by a coupling reaction for 70min. Then, 100g... The SB / (S→B) copolymer was mixed with 500g of cyclohexane and stirred for 70min until completely dissolved. Then, it was added to the polymerization reactor for a coupling reaction for 90min. Finally, 20g of macromolecular composite functionalized long-chain monomer was mixed with 500g of cyclohexane and stirred for 60min until completely dissolved. Then, it was added to the polymerization reactor for a coupling reaction for 70min until no free monomers were present. The solution was then wet-coagulated and dried to obtain a macromolecular three-hetero-arm star-shaped composite functionalized grafting agent (Mn = 6100, Mw / Mn = 12.13).

[0072] (2) Preparation of compression-resistant and cold-resistant hydrogenated nitrile butadiene rubber for oilfield use:

[0073] Preparation of hydrogenated nitrile butadiene rubber (HNBR): First, 100g of nitrile butadiene rubber 2907 was dissolved in chlorobenzene solution to prepare a 3% (w / w) rubber solution. Then, the rubber solution was added to a 10L high-pressure reactor, and nitrogen gas was introduced to remove air from the reactor. Next, hydrogen gas was used to purge the nitrogen from the reactor for 30 minutes. Then, under nitrogen protection, 0.02g of xylene solution containing Grubbs I catalyst (w / w) was added. The hydrogen pressure in the reactor was increased to 11MPa, and the temperature was raised to 100℃. After reacting for 9.0 hours, the system was cooled, condensed, and vacuum dried to obtain HNBR rubber (hydrogenation degree HD = 84.1%).

[0074] Preparation of compression-resistant and cold-resistant hydrogenated nitrile butadiene rubber (HNBR) for oilfields: First, 200g of HNBR rubber was dissolved in a chlorobenzene solution to prepare a 6% (by mass) rubber solution. Then, the solution was added to a 10L stainless steel reactor with a jacket, and nitrogen was introduced three times for purging. Next, 4.0g of a macromolecular three-hetero-arm star-shaped composite functionalized grafting agent was added to the reactor. The mixture was stirred, heated, and when the reactor temperature reached 80℃, a mixture of 0.20g BPO and 100g chlorobenzene was added. After reacting for 11.0 hours, the mixture was flocculated with anhydrous ethanol, washed, and dried in a 70℃ oven to constant weight to obtain compression-resistant and cold-resistant hydrogenated nitrile butadiene rubber for oilfields (grafting rate 1.9%). Sampling and analysis: Standard samples were prepared, and the tested properties are shown in Table 1.

[0075] Example 2

[0076] (1) Preparation of macromolecular three-hetero-arm star-shaped composite functionalized grafting agent:

[0077] Preparation of macromolecular composite functionalized long-chain monomers: In a 10L stainless steel polymerization reactor with a jacket, the system was purged three times with argon gas. 1100g of cyclohexane, 310g of dihydromyrcenol, 190g of N-(4-hydroxybutyl)acrylamide, and 0.7g of THF were added to the polymerization reactor in sequence. The temperature was raised to 52℃, and then 147mmol of n-butyllithium was added to the polymerization reactor and reacted for 72min. Finally, 13g of 1,3-butadiene was added to the polymerization reactor for end-capping, and the reaction was continued for 32min until no free monomers were present. The solution was then wet-coagulated and dried to obtain macromolecular composite functionalized long-chain monomers.

[0078] b. Preparation of SB / (S→B) copolymer: In a jacketed 10L stainless steel polymerization reactor, the system was purged three times with argon gas. 1600g of cyclohexane and 1.0g of THF were added to the polymerization reactor in sequence. The temperature was raised to 62℃, and 167mmol of n-butyllithium was added. Then, 500g of 1,3-butadiene and 160g of styrene were stirred and mixed for 22min. The mixture was then continuously added to the polymerization reactor at an initial feeding rate of 80g / min, with the feeding rate decreasing by 4g per minute. The reaction was carried out for 72min until no free monomers were present. The solution was wet-coagulated and dried to obtain a random, long gradient segment SB / (S→B) copolymer.

[0079] Preparation of macromolecular three-hetero-arm star-shaped composite functionalized grafting agent: In a jacketed 10L stainless steel polymerization reactor, the system was purged three times with argon gas. 1100g of cyclohexane, 500g of 1,3-butadiene, and 0.30g of THF were added sequentially to the reactor. After heating to 40℃, 300mmol of n-butyllithium was added to initiate the reaction. The temperature was gradually increased from 40℃ to 70℃ over 55min to form BR segments with a broad vinyl distribution. After the 1,3-butadiene monomer conversion reached 100%, the temperature was raised to 82℃, and 95mmol of 1,3,5-trichlorobenzene was added. The coupling reaction was carried out for 72min. Then, 110g of... The SB / (S→B) copolymer was mixed with 600g of cyclohexane and stirred for 72min until completely dissolved. Then, it was added to the polymerization reactor for a coupling reaction for 92min. Finally, 23g of macromolecular composite functionalized long-chain monomer was mixed with 550g of cyclohexane and stirred for 62min until completely dissolved. Then, it was added to the polymerization reactor for a coupling reaction for 72min until no free monomers were present. The solution was then wet-coagulated and dried to obtain a macromolecular three-hetero-arm star-shaped composite functionalized grafting agent (Mn = 6800, Mw / Mn = 12.52).

[0080] (2) Preparation of compression-resistant and cold-resistant hydrogenated nitrile butadiene rubber for oilfield use:

[0081] Preparation of hydrogenated nitrile butadiene rubber (HNBR): Same as in Example 1.

[0082] Preparation of compression-resistant and cold-resistant hydrogenated nitrile butadiene rubber (HNBR) for oilfields: First, 200g of HNBR rubber was dissolved in a chlorobenzene solution to prepare a 6.5% (w / w) rubber solution. Then, the solution was added to a 10L jacketed stainless steel reactor, and nitrogen was introduced three times for purging. Next, 5.0g of a macromolecular three-hetero-arm star-shaped composite functionalized grafting agent was added to the reactor. The mixture was stirred, heated, and when the reactor temperature reached 82℃, a mixture of 0.32g of BPO and 110g of chlorobenzene was added. After reacting for 11.2 hours, the mixture was flocculated with anhydrous ethanol, washed, and dried in a 70℃ oven to constant weight to obtain compression-resistant and cold-resistant hydrogenated nitrile butadiene rubber for oilfields (grafting rate 2.1%). Sampling and analysis: Standard samples were prepared, and the tested properties are shown in Table 1.

[0083] Example 3

[0084] (1) Preparation of macromolecular three-hetero-arm star-shaped composite functionalized grafting agent:

[0085] Preparation of macromolecular composite functionalized long-chain monomers: In a 10L stainless steel polymerization reactor with a jacket, the system was purged with argon gas four times. 1200g of cyclohexane, 320g of dihydromyrcenol, 180g of N-(4-hydroxybutyl)acrylamide, and 0.9g of THF were added to the polymerization reactor in sequence. The temperature was raised to 54℃, and then 143mmol of n-butyllithium was added to the polymerization reactor and reacted for 74min. Finally, 17g of 1,3-butadiene was added to the polymerization reactor for end-capping, and the reaction was continued for 34min until no free monomers were present. The solution was then wet-coagulated and dried to obtain macromolecular composite functionalized long-chain monomers.

[0086] b. Preparation of SB / (S→B) copolymer: In a jacketed 10L stainless steel polymerization reactor, the system was purged with argon gas four times. 1700g of cyclohexane and 1.3g of THF were added to the polymerization reactor sequentially. The temperature was raised to 64℃, and 163mmol of n-butyllithium was added. Then, 500g of 1,3-butadiene and 170g of styrene were stirred and mixed for 24min. The mixture was then continuously added to the polymerization reactor at an initial feeding rate of 65g / min, with the feeding rate decreasing by 2g per minute. The reaction was continued for 74min until no free monomers were present. The solution was then wet-coagulated and dried to obtain a random, long gradient-segment SB / (S→B) copolymer.

[0087] Preparation of macromolecular three-hetero-arm star-shaped composite functionalized grafting agent: In a jacketed 10L stainless steel polymerization reactor, the system was purged four times with argon gas. 1200g of cyclohexane, 500g of 1,3-butadiene, and 0.35g of THF were added sequentially to the reactor. After heating to 40℃, 300mmol of n-butyllithium was added to initiate the reaction. The temperature was gradually increased from 40℃ to 70℃ over 60min to form BR segments with a broad vinyl distribution. After the 1,3-butadiene monomer conversion reached 100%, the temperature was raised to 84℃, and 90mmol of 1,3,5-trichlorobenzene was added. The coupling reaction was carried out for 74min. Then, 120g of... The SB / (S→B) copolymer was mixed with 700g of cyclohexane and stirred for 74min until completely dissolved. Then, it was added to the polymerization reactor for a coupling reaction for 94min. Finally, 26g of macromolecular composite functionalized long-chain monomer was mixed with 600g of cyclohexane and stirred for 64min until completely dissolved. Then, it was added to the polymerization reactor for a coupling reaction for 74min until no free monomers were present. The solution was then wet-coagulated and dried to obtain a macromolecular three-hetero-arm star-shaped composite functionalized grafting agent (Mn = 7300, Mw / Mn = 12.86).

[0088] (2) Preparation of compression-resistant and cold-resistant hydrogenated nitrile butadiene rubber for oilfield use:

[0089] Preparation of hydrogenated nitrile butadiene rubber (HNBR): Same as in Example 1.

[0090] Preparation of compression-resistant and cold-resistant hydrogenated nitrile butadiene rubber (HNBR) for oilfields: First, 200g of HNBR rubber was dissolved in a chlorobenzene solution to prepare a 7.6% (w / w) rubber solution. Then, the solution was added to a 10L jacketed stainless steel reactor, and nitrogen was introduced four times for purging. Next, 5.5g of a macromolecular three-arm star-shaped composite functionalized grafting agent was added to the reactor. The mixture was stirred, heated, and when the reactor temperature reached 84℃, a mixture of 0.43g of BPO and 140g of chlorobenzene was added. After reacting for 11.4 hours, the mixture was flocculated with anhydrous ethanol, washed, and dried in a 70℃ oven to constant weight to obtain compression-resistant and cold-resistant hydrogenated nitrile butadiene rubber for oilfields (grafting rate 2.3%). Sampling and analysis: Standard samples were prepared, and the tested properties are shown in Table 1.

[0091] Example 4

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

[0093] Preparation of macromolecular composite functionalized long-chain monomers: In a 10L stainless steel polymerization reactor with a jacket, the system was purged with argon gas four times. 1300g of cyclohexane, 330g of dihydromyrcenol, 170g of N-(4-hydroxybutyl)acrylamide, and 1.1g of THF were added to the polymerization reactor in sequence. The temperature was raised to 56℃, and then 140mmol of n-butyllithium was added to the polymerization reactor and reacted for 76min. Finally, 20g of 1,3-butadiene was added to the polymerization reactor for end-capping, and the reaction was continued for 36min until no free monomers were present. The solution was then wet-coagulated and dried to obtain macromolecular composite functionalized long-chain monomers.

[0094] b. Preparation of SB / (S→B) copolymer: In a jacketed 10L stainless steel polymerization reactor, the system was purged with argon gas four times. 1800g of cyclohexane and 1.6g of THF were added to the polymerization reactor sequentially. The temperature was raised to 66℃, and 158mmol of n-butyllithium was added. Then, 500g of 1,3-butadiene and 180g of styrene were stirred and mixed for 26min. The mixture was then continuously added to the polymerization reactor at an initial feeding rate of 65g / min, with the feeding rate decreasing by 2g per minute. The reaction was continued for 76min until no free monomers were present. The solution was wet-coagulated and dried to obtain a random, long, gradient-segment SB / (S→B) copolymer.

[0095] Preparation of macromolecular three-hetero-arm star-shaped composite functionalized grafting agent: In a jacketed 10L stainless steel polymerization reactor, the system was purged four times with argon gas. 1300g of cyclohexane, 500g of 1,3-butadiene, and 0.40g of THF were added sequentially to the reactor. After heating to 40℃, 292mmol of n-butyllithium was added to initiate the reaction. The temperature was gradually increased from 40℃ to 70℃ over 63min, forming BR segments with a broad vinyl distribution. After the 1,3-butadiene monomer conversion reached 100%, the temperature was raised to 86℃, and 85mmol of 1,3,5-trichlorobenzene was added, followed by a coupling reaction for 76min. Then, 130g of... The SB / (S→B) copolymer was mixed with 800g of cyclohexane and stirred for 76min until completely dissolved. Then, it was added to the polymerization reactor for a coupling reaction for 96min. Finally, 29g of macromolecular composite functionalized long-chain monomer was mixed with 650g of cyclohexane and stirred for 66min until completely dissolved. Then, it was added to the polymerization reactor for a coupling reaction for 76min until no free monomers were present. The solution was then wet-coagulated and dried to obtain a macromolecular three-hetero-arm star-shaped composite functionalized grafting agent (Mn = 7900, Mw / Mn = 13.15).

[0096] (2) Preparation of compression-resistant and cold-resistant hydrogenated nitrile butadiene rubber for oilfield use:

[0097] Preparation of hydrogenated nitrile butadiene rubber (HNBR): First, 100g of nitrile butadiene rubber 2907 was dissolved in chlorobenzene solution to prepare a 4.5% (w / w) rubber solution. Then, the rubber solution was added to a 10L high-pressure reactor, and nitrogen gas was introduced to remove air from the reactor. Next, hydrogen gas was used to purge the nitrogen from the reactor for 36 min. Then, under nitrogen protection, 0.07g of xylene solution containing Grubbs I catalyst (w / w) was added. The hydrogen pressure in the reactor was increased to 12MPa, and the temperature was raised to 113℃. After reacting for 10 h, the system was cooled, condensed, and vacuum dried to obtain HNBR rubber (hydrogenation degree HD = 87.1%).

[0098] Preparation of compression-resistant and cold-resistant hydrogenated nitrile butadiene rubber (HNBR) for oilfields: First, 200g of HNBR rubber was dissolved in a chlorobenzene solution to prepare a rubber solution with a mass fraction of 8.2%. Then, the rubber solution was added to a 10L stainless steel reactor with a jacket, and nitrogen was introduced to purge the solution four times. Next, 6.0g of a macromolecular three-hetero-arm star-shaped composite functionalized grafting agent was added to the reactor. The mixture was stirred, heated, and when the reactor temperature reached 86℃, a mixture of 0.48g of BPO and 160g of chlorobenzene was added. After reacting for 11.6 hours, the mixture was flocculated with anhydrous ethanol, washed, and dried in a 70℃ oven to constant weight to obtain compression-resistant and cold-resistant hydrogenated nitrile butadiene rubber for oilfields (grafting rate 2.5%). Sampling and analysis: Standard samples were prepared, and the tested properties are shown in Table 1.

[0099] Example 5

[0100] (1) Preparation of macromolecular three-hetero-arm star-shaped composite functionalized grafting agent:

[0101] Preparation of macromolecular composite functionalized long-chain monomers: In a 10L stainless steel polymerization reactor with a jacket, the system was purged with argon gas five times. 1400g of cyclohexane, 340g of dihydromyrcenol, 160g of N-(4-hydroxybutyl)acrylamide, and 1.3g of THF were added to the polymerization reactor in sequence. The temperature was raised to 58℃, and then 145mmol of n-butyllithium was added to the polymerization reactor and reacted for 78min. Finally, 23g of 1,3-butadiene was added to the polymerization reactor for end-capping, and the reaction was continued for 38min until no free monomers were present. The solution was then wet-coagulated and dried to obtain macromolecular composite functionalized long-chain monomers.

[0102] b. Preparation of SB / (S→B) copolymer: In a jacketed 10L stainless steel polymerization reactor, the system was purged with argon five times. 1900g of cyclohexane and 1.8g of THF were added to the polymerization reactor sequentially. The temperature was raised to 68℃, and 152mmol of n-butyllithium was added. Then, 500g of 1,3-butadiene and 190g of styrene were stirred and mixed for 28min. The mixture was then continuously added to the polymerization reactor at an initial feeding rate of 65g / min, with the feeding rate decreasing by 2g per minute. The reaction was continued for 78min until no free monomers were present. The solution was then wet-coagulated and dried to obtain a random, long gradient segment SB / (S→B) copolymer.

[0103] Preparation of macromolecular three-hetero-arm star-shaped composite functionalized grafting agent: In a jacketed 10L stainless steel polymerization reactor, the system was purged five times with argon gas. 1400g of cyclohexane, 500g of 1,3-butadiene, and 0.45g of THF were added sequentially to the reactor. After heating to 40℃, 285mmol of n-butyllithium was added to initiate the reaction. The temperature was gradually increased from 40℃ to 70℃ over 66min, forming BR segments with a broad vinyl distribution. After the 1,3-butadiene monomer conversion reached 100%, the temperature was raised to 88℃, and 80mmol of 1,3,5-trichlorobenzene was added, followed by a coupling reaction for 78min. Then, 140g of... The SB / (S→B) copolymer was mixed with 900g of cyclohexane and stirred for 78min until completely dissolved. Then, it was added to the polymerization reactor for a coupling reaction for 98min. Finally, 32g of macromolecular composite functionalized long-chain monomer was mixed with 700g of cyclohexane and stirred for 68min until completely dissolved. Then, it was added to the polymerization reactor for a coupling reaction for 78min until no free monomers were present. The solution was then wet-coagulated and dried to obtain a macromolecular three-hetero-arm star-shaped composite functionalized grafting agent (Mn = 8400, Mw / Mn = 13.57).

[0104] (2) Preparation of compression-resistant and cold-resistant hydrogenated nitrile butadiene rubber for oilfield use:

[0105] Preparation of hydrogenated nitrile butadiene rubber (HNBR): Same as in Example 4.

[0106] Preparation of compression-resistant and cold-resistant hydrogenated nitrile butadiene rubber (HNBR) for oilfields: First, 200g of HNBR rubber was dissolved in a chlorobenzene solution to prepare a rubber solution with a mass fraction of 8.7%. Then, the rubber solution was added to a 10L stainless steel reactor with a jacket, and nitrogen gas was introduced to purge five times. Next, 7.2g of a macromolecular three-hetero-arm star-shaped composite functionalized grafting agent was added to the reactor. The mixture was stirred, heated, and when the reactor temperature reached 88℃, a mixture of 0.53g of BPO and 180g of chlorobenzene was added. After reacting for 11.8 hours, the mixture was flocculated with anhydrous ethanol, washed, and dried in a 70℃ oven to constant weight to obtain compression-resistant and cold-resistant hydrogenated nitrile butadiene rubber for oilfields (grafting rate 2.6%). Sampling and analysis: Standard samples were prepared, and the tested properties are shown in Table 1.

[0107] Example 6

[0108] (1) Preparation of macromolecular three-hetero-arm star-shaped composite functionalized grafting agent:

[0109] Preparation of macromolecular composite functionalized long-chain monomers: In a 10L stainless steel polymerization reactor with a jacket, the system was purged with argon gas five times. 1500g of cyclohexane, 350g of dihydromyrcenol, 150g of N-(4-hydroxybutyl)acrylamide, and 1.5g of THF were added to the polymerization reactor in sequence. The temperature was raised to 60℃, and then 132mmol of n-butyllithium was added to the polymerization reactor and reacted for 80min. Finally, 25g of 1,3-butadiene was added to the polymerization reactor for end-capping, and the reaction was continued for 40min until no free monomers were present. The solution was then wet-coagulated and dried to obtain macromolecular composite functionalized long-chain monomers.

[0110] b. Preparation of SB / (S→B) copolymer: In a jacketed 10L stainless steel polymerization reactor, the system was purged with argon five times. 2000g of cyclohexane and 2.0g of THF were added to the polymerization reactor sequentially. The temperature was raised to 70℃, and 149mmol of n-butyllithium was added. Then, 500g of 1,3-butadiene and 200g of styrene were stirred and mixed for 30min. The mixture was then continuously added to the polymerization reactor at an initial feeding rate of 65g / min, with the feeding rate decreasing by 2g per minute. The reaction was continued for 80min until no free monomers were present. The solution was then wet-coagulated and dried to obtain a random, long, gradient-segment SB / (S→B) copolymer.

[0111] Preparation of macromolecular three-heteroarm star-shaped composite functionalized grafting agent: In a jacketed 10L stainless steel polymerization reactor, the system was purged five times with argon gas. 1500g of cyclohexane, 500g of 1,3-butadiene, and 0.50g of THF were added sequentially to the reactor. After heating to 40℃, 279mmol of n-butyllithium was added to initiate the reaction. The temperature was gradually increased from 40℃ to 70℃ over 70min to form BR segments with a broad vinyl distribution. After the 1,3-butadiene monomer conversion reached 100%, the temperature was raised to 90℃, and 75mmol of 1,3,5-trichlorobenzene was added. The coupling reaction was carried out for 80min. Then, 150g of... The SB / (S→B) copolymer was mixed with 1000g of cyclohexane and stirred for 80min until completely dissolved. Then, it was added to the polymerization reactor for a coupling reaction for 100min. Finally, 35g of macromolecular composite functionalized long-chain monomer was mixed with 700g of cyclohexane and stirred for 70min until completely dissolved. Then, it was added to the polymerization reactor for a coupling reaction for 80min until no free monomers were present. The solution was then wet-coagulated and dried to obtain a macromolecular three-hetero-arm star-shaped composite functionalized grafting agent (Mn = 9000, Mw / Mn = 13.94).

[0112] (2) Preparation of compression-resistant and cold-resistant hydrogenated nitrile butadiene rubber for oilfield use:

[0113] Preparation of hydrogenated nitrile butadiene rubber (HNBR): Same as in Example 4.

[0114] Preparation of compression-resistant and cold-resistant hydrogenated nitrile butadiene rubber (HNBR) for oilfields: First, 200g of HNBR rubber was dissolved in a chlorobenzene solution to prepare a 9.0% (w / w) rubber solution. Then, the solution was added to a 10L stainless steel reactor with a jacket, and nitrogen was introduced to purge the mixture five times. Next, 8.0g of a macromolecular three-arm star-shaped composite functionalized grafting agent was added to the reactor. The mixture was stirred, heated, and when the reactor temperature reached 90℃, a mixture of 0.60g of BPO and 200g of chlorobenzene was added. After reacting for 12.0 hours, the mixture was flocculated with anhydrous ethanol, washed, and dried in a 70℃ oven to constant weight to obtain compression-resistant and cold-resistant hydrogenated nitrile butadiene rubber for oilfields (grafting rate 2.7%). Sampling and analysis: Standard samples were prepared, and the tested properties are shown in Table 1.

[0115] Comparative Example 1

[0116] (1) Preparation of macromolecular three-hetero-arm star-shaped composite functionalized grafting agent:

[0117] Preparation of macromolecular complex functionalized long-chain monomers: Same as in Example 1.

[0118] b. Preparation of SB / (S→B) copolymer: Other conditions are the same as in Example 1, except that variable-speed polymerization is not used in the preparation of SB / (S→B) copolymer. That is, in a 10L stainless steel polymerization reactor with a jacket, the system is purged with argon gas three times. 1500g of cyclohexane and 0.5g of THF are added to the polymerization reactor in sequence. The temperature is raised to 60°C, and 170mmol of n-butyllithium is added. Then, 500g of 1,3-butadiene and 150g of styrene are stirred and mixed for 20min and then added to the polymerization reactor together and reacted for 70min until no free monomers are present. The solution is wet coagulated and dried to obtain SBR copolymer.

[0119] Preparation of macromolecular tri-hetero-arm star-shaped composite functionalized grafting agent: Other conditions are the same as in Example 1, except that instead of adding SB / (S→B) copolymer, 100g of SBR copolymer is added during the preparation of the macromolecular tri-hetero-arm star-shaped composite functionalized grafting agent. Specifically: In a jacketed 10L stainless steel polymerization reactor, the system is purged three times with argon gas. Then, 1000g of cyclohexane, 500g of 1,3-butadiene, and 0.25g of THF are added sequentially. After heating to 40°C, 310 mmol of n-butyllithium is added to initiate the reaction. Within 55 minutes, the temperature is gradually increased from 40°C to 70°C to form BR segments with a broad vinyl distribution. After the 1,3-butadiene monomer conversion reaches 100%, the temperature is raised to 80°C, and 100 mmol of 1,3,5-trichlorobenzene is added. The coupling reaction is carried out for 70 minutes. Then, 100g of... The SBR copolymer was mixed with 500g of cyclohexane and stirred for 70min until completely dissolved. Then, it was added to the polymerization reactor for a coupling reaction for 90min. Finally, 20g of macromolecular composite functionalized long-chain monomer was mixed with 500g of cyclohexane and stirred for 60min until completely dissolved. Then, it was added to the polymerization reactor for a coupling reaction for 70min until no free monomers were present. The solution was then wet-coagulated and dried to obtain macromolecular three-hetero-arm star-shaped composite functionalized grafting agent a (Mn is 5900, Mw / Mn is 8.24).

[0120] (2) Preparation of compression-resistant and cold-resistant hydrogenated nitrile butadiene rubber for oilfield use:

[0121] Preparation of hydrogenated nitrile butadiene rubber (HNBR): Same as in Example 1.

[0122] Preparation of compression-resistant and cold-resistant hydrogenated nitrile butadiene rubber (HNBR) for oilfields: Other conditions are the same as in Example 1, except that a macromolecular three-arm star-shaped composite functionalized grafting agent is not added during the preparation of the compression-resistant and cold-resistant HNBR for oilfields. Instead, a macromolecular three-arm star-shaped composite functionalized grafting agent a is added, at a dosage of 4.0 g. Specifically: First, 200 g of HNBR rubber is dissolved in a chlorobenzene solution to prepare a 6% (by mass) adhesive solution. Then, the adhesive solution is added to a 10L stainless steel reactor with a jacket, and nitrogen is introduced three times for purging. Next, 4.0 g of macromolecular three-arm star-shaped composite functionalized grafting agent a is added to the reactor, stirred, mixed, and heated. When the reactor temperature reaches 80°C, 0.20 g of macromolecular three-arm star-shaped composite functionalized grafting agent a is added. A mixture of BPO and 100g of chlorobenzene was reacted for 11.0 hours, then flocculated with anhydrous ethanol, washed, and dried in a 70℃ oven to constant weight to obtain compression-resistant and cold-resistant hydrogenated nitrile butadiene rubber (grafting rate 1.7%) for oilfield use. Sampling and analysis: Standard samples were prepared, and the tested properties are shown in Table 1.

[0123] Comparative Example 2

[0124] (1) Preparation of macromolecular three-hetero-arm star-shaped composite functionalized grafting agent:

[0125] Preparation of macromolecular complex functionalized long-chain monomers: Same as in Example 2.

[0126] b. Preparation of SB / (S→B) copolymer: Other conditions are the same as in Example 2, except that the feeding rate of the 1,3-butadiene and styrene mixture is reduced by 1 g per minute during the preparation of the SB / (S→B) copolymer. That is, in a 10L stainless steel polymerization reactor with a jacket, the system is purged with argon gas three times, 1600 g of cyclohexane and 1.0 g of THF are added to the polymerization reactor in sequence, the temperature is raised to 62°C, 167 mmol of n-butyllithium is added, and then 500 g of 1,3-butadiene and 160 g of styrene are stirred and mixed for 22 min. Then, the mixture is continuously added to the polymerization reactor at an initial feeding rate of 80 g / min, with the feeding rate decreasing by 1 g per minute, and reacted for 72 min until no free monomers are present. The solution is wet coagulated and dried to obtain random, long gradient segment SB / (S→B) copolymer a.

[0127] Preparation of macromolecular tri-hetero-arm star-shaped composite functionalized grafting agent: Other conditions are the same as in Example 2, except that SB / (S→B) copolymer is not added during the preparation of macromolecular tri-hetero-arm star-shaped composite functionalized grafting agent. Instead, SB / (S→B) copolymer a is added, with an addition amount of 110g. That is, in a jacketed 10L stainless steel polymerization reactor, the system is purged with argon gas three times. 1100g of cyclohexane, 500g of 1,3-butadiene, and 0.30g of THF are added to the polymerization reactor sequentially. After heating to 40°C, 300mmol of n-butyllithium is added to start the reaction. Within 55min, the temperature is gradually increased from 40°C to 70°C to form BR segments with a wide vinyl distribution. After the conversion rate of 1,3-butadiene monomer reaches 100%, the temperature is raised to 82°C, and 95mmol of 1,3,5-trichlorobenzene is added. The coupling reaction is carried out for 72min. Then, 110g of cyclohexane, cyclohexane, cyclohexane, and 1,3,5-trichlorobenzene are added. SB / (S→B) copolymer a was mixed with 600g of cyclohexane and stirred for 72min until completely dissolved. Then, it was added to the polymerization reactor for a coupling reaction for 92min. Finally, 23g of macromolecular composite functionalized long-chain monomer was mixed with 550g of cyclohexane and stirred for 62min until completely dissolved. Then, it was added to the polymerization reactor for a coupling reaction for 72min until no free monomers were present. The solution was then wet-coagulated and dried to obtain macromolecular three-hetero-arm star-shaped composite functionalized grafting agent b (Mn is 6300, Mw / Mn is 10.46).

[0128] (2) Preparation of compression-resistant and cold-resistant hydrogenated nitrile butadiene rubber for oilfield use:

[0129] Preparation of hydrogenated nitrile butadiene rubber (HNBR): Same as in Example 2.

[0130] Preparation of compression-resistant and cold-resistant hydrogenated nitrile butadiene rubber (HNBR) for oilfields: Other conditions are the same as in Example 2, except that a macromolecular three-arm star-shaped composite functionalized grafting agent is not added during the preparation of the compression-resistant and cold-resistant HNBR for oilfields. Instead, a macromolecular three-arm star-shaped composite functionalized grafting agent (b) is added, with an addition amount of 5.0 g. Specifically: First, 200 g of HNBR rubber is dissolved in a chlorobenzene solution to prepare a 6.5% (w / w) adhesive solution. Then, the adhesive solution is added to a 10L stainless steel reactor with a jacket, and nitrogen is purged three times. Next, 5.0 g of macromolecular three-arm star-shaped composite functionalized grafting agent (b) is added to the reactor, stirred, mixed, and heated. When the reactor temperature reaches 82°C, 0.32 g of macromolecular three-arm star-shaped composite functionalized grafting agent (b) is added. A mixture of BPO and 110g of chlorobenzene was reacted for 11.2 hours, then flocculated with anhydrous ethanol, washed, and dried in a 70℃ oven to constant weight to obtain compression-resistant and cold-resistant hydrogenated nitrile butadiene rubber (grafting rate 1.8%) for oilfield use. Sampling and analysis: Standard samples were prepared, and the tested properties are shown in Table 1.

[0131] Comparative Example 3

[0132] (1) Preparation of macromolecular three-hetero-arm star-shaped composite functionalized grafting agent:

[0133] Preparation of macromolecular complex functionalized long-chain monomers: Same as in Example 3.

[0134] Preparation of b SB / (S→B) copolymer: Same as in Example 3.

[0135] Preparation of macromolecular tri-hetero-arm star-shaped composite functionalized grafting agent: Other conditions were the same as in Example 3, except that the BR segment was not subjected to temperature-switched polymerization during the preparation of the macromolecular tri-hetero-arm star-shaped composite functionalized grafting agent. Specifically, in a jacketed 10L stainless steel polymerization reactor, the system was purged four times with argon gas. 1200g of cyclohexane, 500g of 1,3-butadiene, and 0.35g of THF were added sequentially to the reactor. After heating to 40°C, 300mmol of n-butyllithium was added to initiate a reaction for 60min to form the BR segment. Once the 1,3-butadiene monomer conversion reached 100%, the temperature was raised to 84°C, and 90mmol of 1,3,5-trichlorobenzene was added, followed by a coupling reaction for 74min. Then, 120g of... The SB / (S→B) copolymer was mixed with 700g of cyclohexane and stirred for 74min until completely dissolved. Then, it was added to the polymerization reactor for a coupling reaction for 94min. Finally, 26g of macromolecular composite functionalized long-chain monomer was mixed with 600g of cyclohexane and stirred for 64min until completely dissolved. Then, it was added to the polymerization reactor for a coupling reaction for 74min until no free monomers were present. The solution was then wet-coagulated and dried to obtain macromolecular three-hetero-arm star-shaped composite functionalized grafting agent c (Mn is 7100, Mw / Mn is 9.86).

[0136] (2) Preparation of compression-resistant and cold-resistant hydrogenated nitrile butadiene rubber for oilfield use:

[0137] Preparation of hydrogenated nitrile butadiene rubber (HNBR): Same as in Example 3.

[0138] Preparation of compression-resistant and cold-resistant hydrogenated nitrile butadiene rubber (HNBR) for oilfields: Other conditions are the same as in Example 3, except that a macromolecular three-arm star-shaped composite functionalized grafting agent is not added during the preparation of the compression-resistant and cold-resistant HNBR for oilfields. Instead, a macromolecular three-arm star-shaped composite functionalized grafting agent c is added, with an addition amount of 5.5g. Specifically: First, 200g of HNBR rubber is dissolved in a chlorobenzene solution to prepare a 7.6% (w / w) adhesive solution. Then, the adhesive solution is added to a 10L stainless steel reactor with a jacket, and nitrogen is introduced four times for purging. Next, 5.5g of macromolecular three-arm star-shaped composite functionalized grafting agent c is added to the reactor, stirred, mixed, and heated. When the reactor temperature reaches 84℃, 0.43g of macromolecular three-arm star-shaped composite functionalized grafting agent c is added. A mixture of BPO and 140g of chlorobenzene was reacted for 11.4 hours, then flocculated with anhydrous ethanol, washed, and dried in a 70℃ oven to constant weight to obtain compression-resistant and cold-resistant hydrogenated nitrile butadiene rubber (grafting rate 2.1%) for oilfield use. Sampling and analysis: Standard samples were prepared, and the tested properties are shown in Table 1.

[0139] Comparative Example 4

[0140] (1) Preparation of macromolecular three-hetero-arm star-shaped composite functionalized grafting agent:

[0141] Preparation of macromolecular complex functionalized long-chain monomers: Same as in Example 4.

[0142] Preparation of b SB / (S→B) copolymer: Same as in Example 4.

[0143] Preparation of macromolecular three-hetero-arm star-shaped composite functionalized grafting agent: Other conditions were the same as in Example 4, except that 1,3,5-trichlorobenzene was not added during the preparation of the macromolecular three-hetero-arm star-shaped composite functionalized grafting agent. Specifically, in a jacketed 10L stainless steel polymerization reactor, the system was purged four times with argon gas. Then, 1300g of cyclohexane, 500g of 1,3-butadiene, and 0.40g of THF were added sequentially to the reactor. After heating to 40°C, 292mmol of n-butyllithium was added to initiate the reaction. The temperature was gradually increased from 40°C to 70°C within 63 minutes to form BR segments with a broad vinyl distribution. After the conversion rate of 1,3-butadiene monomer reached 100%, the temperature was raised to 86°C, and then 130g of... The SB / (S→B) copolymer was mixed with 800g of cyclohexane and stirred for 76min until completely dissolved. Then, it was added to the polymerization reactor for a coupling reaction for 96min. Finally, 29g of macromolecular composite functionalized long-chain monomer was mixed with 650g of cyclohexane and stirred for 66min until completely dissolved. Then, it was added to the polymerization reactor for a coupling reaction for 76min until no free monomers were present. The solution was then wet-coagulated and dried to obtain macromolecular three-hetero-arm star-shaped composite functionalized grafting agent d (Mn is 5600, Mw / Mn is 8.49).

[0144] (2) Preparation of compression-resistant and cold-resistant hydrogenated nitrile butadiene rubber for oilfield use:

[0145] Preparation of hydrogenated nitrile butadiene rubber (HNBR): Same as in Example 4.

[0146] Preparation of compression-resistant and cold-resistant hydrogenated nitrile butadiene rubber (NBR) for oilfields: Other conditions are the same as in Example 4, except that a macromolecular three-arm star-shaped composite functionalized grafting agent is not added during the preparation of the compression-resistant and cold-resistant NBR for oilfields. Instead, a macromolecular three-arm star-shaped composite functionalized grafting agent d is added, with an addition amount of 6.0 g. Specifically: First, 200 g of HNBR rubber is dissolved in a chlorobenzene solution to prepare a glue solution with a mass fraction of 8.2%. Then, the glue solution is added to a 10L stainless steel reactor with a jacket, and nitrogen is purged four times. Next, 6.0 g of macromolecular three-arm star-shaped composite functionalized grafting agent d is added to the reactor, stirred, mixed, and heated. When the reactor temperature reaches 86°C, 0.48 g of macromolecular three-arm star-shaped composite functionalized grafting agent d is added. A mixture of BPO and 160g of chlorobenzene was reacted for 11.6 hours, then flocculated with anhydrous ethanol, washed, and dried in a 70℃ oven to constant weight to obtain compression-resistant and cold-resistant hydrogenated nitrile butadiene rubber (grafting rate 1.6%) for oilfield use. Sampling and analysis: Standard samples were prepared, and the tested properties are shown in Table 1.

[0147] Comparative Example 5

[0148] (1) Preparation of macromolecular three-hetero-arm star-shaped composite functionalized grafting agent:

[0149] Preparation of macromolecular complex functionalized long-chain monomers: Same as in Example 5.

[0150] Preparation of b SB / (S→B) copolymer: Same as in Example 5.

[0151] Preparation of macromolecular tri-hetero-arm star-shaped composite functionalized grafting agent: Other conditions were the same as in Example 5, except that the amount of 1,3,5-trichlorobenzene added during the preparation of the macromolecular tri-hetero-arm star-shaped composite functionalized grafting agent was 300 mmol. Specifically: In a jacketed 10L stainless steel polymerization reactor, the system was purged with argon five times. 1400 g of cyclohexane, 500 g of 1,3-butadiene, and 0.45 g of THF were added sequentially to the polymerization reactor. After heating to 40°C, 285 mmol of n-butyllithium was added to initiate the reaction. Within 66 min, the temperature was gradually increased from 40°C to 70°C to form BR segments with a broad vinyl distribution. After the 1,3-butadiene monomer conversion reached 100%, the temperature was raised to 88°C, and 300 mmol of 1,3,5-trichlorobenzene was added. The coupling reaction was carried out for 78 min. Then, 140 g of cyclohexane, 500 g of 1,3,5-trichlorobenzene, and 140 g of THF were added to the reactor. The SB / (S→B) copolymer was mixed with 900g of cyclohexane and stirred for 78min until completely dissolved. Then, it was added to the polymerization reactor for a coupling reaction for 98min. Finally, 32g of macromolecular composite functionalized long-chain monomer was mixed with 700g of cyclohexane and stirred for 68min until completely dissolved. Then, it was added to the polymerization reactor for a coupling reaction for 78min until no free monomers were present. The solution was then wet-coagulated and dried to obtain macromolecular three-hetero-arm star-shaped composite functionalized grafting agent e (Mn is 7600, Mw / Mn is 11.26).

[0152] (2) Preparation of compression-resistant and cold-resistant hydrogenated nitrile butadiene rubber for oilfield use:

[0153] Preparation of hydrogenated nitrile butadiene rubber (HNBR): Same as in Example 5.

[0154] Preparation of compression-resistant and cold-resistant hydrogenated nitrile butadiene rubber (NBR) for oilfields: Other conditions are the same as in Example 5, except that a macromolecular three-arm star-shaped composite functionalized grafting agent is not added during the preparation of the compression-resistant and cold-resistant NBR for oilfields. Instead, a macromolecular three-arm star-shaped composite functionalized grafting agent e is added, with an addition amount of 7.2g. Specifically: First, 200g of HNBR rubber is dissolved in a chlorobenzene solution to prepare a glue solution with a mass fraction of 8.7%. Then, the glue solution is added to a 10L stainless steel reactor with a jacket, and nitrogen is purged five times. Next, 7.2g of macromolecular three-arm star-shaped composite functionalized grafting agent e is added to the reactor, stirred, mixed, and heated. When the reactor temperature reaches 88℃, 0.53g of macromolecular three-arm star-shaped composite functionalized grafting agent e is added. A mixture of BPO and 180g of chlorobenzene was reacted for 11.8 hours, then flocculated with anhydrous ethanol, washed, and dried in a 70℃ oven to constant weight to obtain compression-resistant and cold-resistant hydrogenated nitrile butadiene rubber (grafting rate 2.2%) for oilfield use. Sampling and analysis: Standard samples were prepared, and the tested properties are shown in Table 1.

[0155] Comparative Example 6

[0156] (1) Preparation of macromolecular three-hetero-arm star-shaped composite functionalized grafting agent:

[0157] Preparation of macromolecular complex functionalized long-chain monomers: Same as in Example 6.

[0158] Preparation of b SB / (S→B) copolymer: omitted.

[0159] Preparation of macromolecular tri-hetero-arm star-shaped composite functionalized grafting agent: Other conditions were the same as in Example 6, except that SB / (S→B) copolymer was not added during the preparation of the macromolecular tri-hetero-arm star-shaped composite functionalized grafting agent. That is, in a jacketed 10L stainless steel polymerization reactor, the system was purged with argon gas 5 times, and 1500g cyclohexane, 500g 1,3-butadiene, and 0.50g THF were added to the polymerization reactor in sequence. After heating to 40°C, 279 mmol of n-butyllithium was added to start the reaction. Within 70 min, the temperature was gradually increased from 40°C to 70°C to form BR segments with a wide vinyl distribution. After the conversion rate of 1,3-butadiene monomer reached 100%, the temperature was raised to 90°C, and 75 mmol of n-butyllithium was added. 1,3,5-Trichlorobenzene was coupled for 80 min; then 35 g of macromolecular complex functionalized long-chain monomer was mixed with 700 g of cyclohexane and stirred for 70 min until completely dissolved. The mixture was then added to a polymerization reactor for coupling reaction for 80 min until no free monomers were present. The solution was then wet-coagulated and dried to obtain a macromolecular two-heteroarm star-shaped complex functionalized grafting agent (Mn = 4800, Mw / Mn = 7.15).

[0160] (2) Preparation of compression-resistant and cold-resistant hydrogenated nitrile butadiene rubber for oilfield use:

[0161] Preparation of hydrogenated nitrile butadiene rubber (HNBR): Same as in Example 6.

[0162] Preparation of compression-resistant and cold-resistant hydrogenated nitrile butadiene rubber (HNBR) for oilfields: Other conditions are the same as in Example 6, except that a macromolecular three-arm star-shaped composite functionalized grafting agent is not added during the preparation of the compression-resistant and cold-resistant HNBR for oilfields. Instead, a macromolecular two-arm star-shaped composite functionalized grafting agent is added at a dosage of 8.0 g. Specifically: First, 200 g of HNBR rubber is dissolved in a chlorobenzene solution to prepare a 9.0% (w / w) adhesive solution. Then, the adhesive solution is added to a 10L stainless steel reactor with a jacket, and nitrogen is purged five times. Next, 8.0 g of the macromolecular two-arm star-shaped composite functionalized grafting agent is added to the reactor, stirred, mixed, and heated. When the reactor temperature reaches 90°C, 0.60 g of the macromolecular two-arm star-shaped composite functionalized grafting agent is added. A mixture of BPO and 200g of chlorobenzene was reacted for 12.0 hours, then flocculated with anhydrous ethanol, washed, and dried in a 70℃ oven to constant weight to obtain compression-resistant and cold-resistant hydrogenated nitrile butadiene rubber (grafting rate 1.8%) for oilfield use. Sampling and analysis: Standard samples were prepared, and the tested properties are shown in Table 1.

[0163] Table 1. Performance of compression-resistant and cold-resistant hydrogenated nitrile rubber for oilfield applications.

[0164]

[0165]

[0166] As shown in Table 1, the compression-resistant and cold-resistant hydrogenated nitrile rubber for oilfields of the present invention has small compression set and low glass transition temperature, and is suitable for oil well operations with compression set ≤11% and ambient temperature of -74℃.

[0167] Of course, the present invention may have other various embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art can make various corresponding changes and modifications according to the present invention, but these corresponding changes and modifications should all fall within the protection scope of the present invention.

Claims

1. A method for preparing a compression-resistant and cold-resistant hydrogenated nitrile butadiene rubber for oilfield use, characterized in that, Includes the following steps: (1) Preparation of macromolecular three-hetero-arm star-shaped composite functionalized grafting agent: Preparation of macromolecular composite functionalized long-chain monomers: Argon gas was introduced into the polymerization reactor to replace the system. Solvent, dihydromyrcenol, N-(4-hydroxybutyl)acrylamide, and structure modifier were added to the polymerization reactor in sequence. The temperature was raised, and initiator 1 was added to the polymerization reactor for reaction. Finally, 1,3-butadiene was added to the polymerization reactor for end-capping. The reaction continued until no free monomers were present. The gel solution was wet coagulated and dried to obtain macromolecular composite functionalized long-chain monomers. b. Preparation of SB / (S→B) copolymer: Argon gas was introduced into the polymerization reactor to replace the system. Solvent and structure modifier were added to the polymerization reactor in sequence. The temperature was raised and initiator 1 was added. Then, 1,3-butadiene and styrene were stirred and mixed and added to the polymerization reactor. The reaction was carried out until no free monomers were present. The glue solution was wet coagulated and dried to obtain random, long gradient segment SB / (S→B) copolymer. Preparation of macromolecular three-hetero-arm star-shaped composite functionalized grafting agent: In a polymerization reactor, argon gas is introduced to replace the system. Solvent 1, 1,3-butadiene, and a structure modifier are added sequentially to the polymerization reactor. The temperature is raised, and initiator 1 is added. The reaction is a temperature-switching polymerization. The temperature is gradually raised from 40℃ to 70℃ within 50-70 minutes to form BR segments with a wide vinyl distribution. After the conversion rate of 1,3-butadiene monomer reaches 100%, the temperature is raised, and a coupling agent is added to carry out a coupling reaction. Then, the SB / (S→B) copolymer and the solution are mixed and stirred until completely dissolved, and then added to the polymerization reactor for a coupling reaction. Finally, the macromolecular composite functionalized long-chain monomer is mixed with solvent 2 and stirred until completely dissolved, and then added to the polymerization reactor for a coupling reaction until no free monomers are present. The glue solution is wet-coagulated and dried to obtain the macromolecular three-hetero-arm star-shaped composite functionalized grafting agent. (2) Preparation of compression-resistant and cold-resistant hydrogenated nitrile butadiene rubber for oilfield use: Preparation of hydrogenated nitrile butadiene rubber (HNBR): Nitrile butadiene rubber is dissolved in chlorobenzene solution to prepare a rubber solution. The rubber solution is then added to a reaction vessel, and an inert gas is introduced to remove the air from the reaction vessel. After the inert gas in the reaction vessel is removed by hydrogen, a xylene solution of Grubbs I catalyst is added under nitrogen protection. The system is pressurized, heated, and reacted. The system is then cooled, condensed, and vacuum dried to obtain HNBR rubber. b. Preparation of compression-resistant and cold-resistant hydrogenated nitrile butadiene rubber for oilfields: HNBR rubber is dissolved in chlorobenzene solution to prepare a rubber solution. The rubber solution is then added to a reaction vessel, and an inert gas is introduced for purging. A macromolecular three-hetero-arm star-shaped composite functionalized grafting agent is then added to the reaction vessel. The mixture is stirred, heated, and a mixture of initiator 2 and chlorobenzene is added. The reaction proceeds, followed by flocculation, washing, and drying to obtain compression-resistant and cold-resistant hydrogenated nitrile butadiene rubber for oilfields. The macromolecular three-hetero-arm star-shaped composite functionalized grafting agent has the following structure: Wherein, BR is a 1,3-butadiene homopolymer segment with a broad vinyl distribution; SB is a random segment of styrene and 1,3-butadiene; (S→B) is a gradient segment of styrene and 1,3-butadiene; B is a capped 1,3-butadiene; n, m, L are the number of repeating units, n≥1, m≥1, L≥1 are positive integers; the number average molecular weight (Mn) of the macromolecular tri-hetero-arm star-shaped composite functionalized grafting agent is 6000~9000, and the molecular weight distribution (Mw / Mn) is 12.13~13.

94.

2. The preparation method according to claim 1, characterized in that, The initiator 1 is selected from one of n-butyllithium, sec-butyllithium, methylbutyllithium, phenylbutyllithium, naphthalenelithium, cyclohexyllithium, and dodecyllithium.

3. The preparation method according to claim 1, characterized in that, The initiator 2 is selected from one of diacetyl peroxide, diisobutyryl peroxide, cumene hydroperoxide, diisobutyryl peroxide (DCP), and benzoyl peroxide (BPO), and its addition amount is 0.1 to 0.3 parts based on 100 parts by weight of HNBR rubber.

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

5. 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.

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

7. 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.

8. The preparation method according to claim 1, characterized in that, In step (1)a, the mass ratio of the solvent, dihydromyrcenol, N-(4-hydroxybutyl)acrylamide, structure modifier, and 1,3-butadiene is 200-300:60-70:30-40:0.1-0.3:2-5.

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

10. The preparation method according to claim 1, characterized in that, In step (1)c, the mass ratio of solvent 1, 1,3-butadiene, structure modifier, SB / (S→B) copolymer, solution, macromolecular composite functionalized long-chain monomer, and solvent 2 is 200-300:100:0.05-0.1:20-30:100-200:4-7:100-150.

11. 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.

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

13. 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.

14. The preparation method according to claim 1, characterized in that, In step (2)b, the grafting rate of the compression-resistant and cold-resistant hydrogenated nitrile rubber for oilfields is 1.9% to 2.7%.

15. A compression-resistant and cold-resistant hydrogenated nitrile butadiene rubber for oilfield use, obtained by the preparation method according to any one of claims 1-14.

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