Cold-resistant and compression-resistant hydrogenated nitrile rubber for oil field and preparation method thereof

Abstract

The invention discloses cold-resistant and compression-resistant hydrogenated butadiene-acrylonitrile rubber for an oil field and a preparation method of the cold-resistant and compression-resistant hydrogenated butadiene-acrylonitrile rubber. The preparation method comprises the following steps: (1) preparing a functionalized macromolecular long branch chain grafting agent; and (2) preparing the cold-resistant and compression-resistant hydrogenated butadiene-acrylonitrile rubber for the oil field. The functionalized macromolecular long branch chain grafting agent has the following structure: # imgabs0 #, wherein IR is an isoprene homopolymer segment with wide vinyl distribution; r is straight chain alkyl of C6 to C12; b is terminated 1, 3-butadiene, n is the number of repetitive units, and n is a positive integer greater than or equal to 1; the number-average molecular weight (Mn) of the functionalized macromolecular long branch chain grafting agent is 6000-8000, and the molecular weight distribution (Mw / Mn) of the functionalized macromolecular long branch chain grafting agent is 7.26-8.35. The preparation method of the cold-resistant and compression-resistant hydrogenated butadiene-acrylonitrile rubber for the 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 in particular relates to a cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields modified by a functionalized macromolecular long-branch grafting agent 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, the present invention provides a method for preparing cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields, which has a compression permanent deformation resistance of ≤22% and a glass transition temperature Tg<-64°C and can meet the use requirements within the range of -64°C to -67°C. The invention first uses allyl glycol and long-chain α-olefins to prepare functionalized macromolecular long-chain monomers under the action of a nickel-based complex catalyst; secondly, an anionic polymerization method is used to convert the reaction monomers from isoprene and functionalized macromolecular long-chain monomers to prepare a functionalized macromolecular long-chain branching grafting agent with free radical reaction activity containing a wide vinyl distribution by variable temperature polymerization; finally, the functionalized macromolecular long-chain branching grafting agent is grafted onto the main chain of hydrogenated nitrile rubber to prepare cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields. This method not only solves the problem of easy crystallization of hydrogenated nitrile rubber, but also improves the viscoelasticity of hydrogenated nitrile rubber, making hydrogenated nitrile rubber show very excellent low temperature resistance and deformation resistance, and achieves a balance between the low temperature resistance and deformation resistance of hydrogenated nitrile rubber. It is very suitable for oil well operations under working temperature of -64℃.

[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 cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields, the preparation method comprising the following steps:

[0010] (1) Preparation of functionalized macromolecular long-branched grafting agent:

[0011] a. Inert gas is introduced into the reaction kettle for replacement, a solvent is added, the temperature is raised, an alkylaluminoxane co-catalyst is added under stirring, and stirring is continued under the protection of the inert gas; then allyl glycol, long-chain α-olefin, and nickel-based complex catalyst are added into the reaction kettle, and ethylene is introduced at this time for reaction; after the reaction is completed, the functionalized macromolecular long-chain monomer is obtained by centrifugal separation and drying;

[0012] b. In a polymerization kettle, argon gas is introduced to replace the system, and a solvent, isoprene, a first structural regulator, and an initiator 1 are added to the polymerization kettle in sequence. The reaction is a temperature-variable polymerization. Within 60 to 70 minutes, the temperature gradually rises from 50° C. to 70° C. to form an IR segment with a wide vinyl distribution. Then, the functionalized macromolecular long-chain monomer and the solution are mixed and stirred to dissolve until they are completely dissolved and then added to the polymerization kettle to react with the second structural regulator. Finally, 1,3-butadiene is added to the polymerization kettle for end-capping, and the reaction is continued until no free monomer exists. The glue solution is wet-coagulated and dried to obtain a functionalized macromolecular long-chain grafting agent.

[0013] (2) Preparation of cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields:

[0014] 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, 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, react, cool the system, condense, and dry to obtain HNBR rubber;

[0015] b. Preparation of cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields: HNBR rubber is dissolved in a 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 functionalized macromolecular long-branched chain grafting agent is added to the reactor, stirred and mixed, heated, and a mixed solution of initiator 2 and chlorobenzene is added, reacted, flocculated, washed, and dried to obtain a cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields;

[0016] The functionalized macromolecular long-branched grafting agent has the following structure:

[0017]

[0018] Among them, IR is an isoprene homopolymer segment with a wide vinyl distribution; R is a straight-chain alkyl group of C6 to C12; B is a terminal 1,3-butadiene, n is the number of repeating units, and n is a positive integer of ≥1; the number average molecular weight (Mn) of the functionalized macromolecular long-branched grafting agent is 6000 to 8000, and the molecular weight distribution (Mw / Mn) is 7.26 to 8.35.

[0019] The long-chain α-olefin described in the present invention is a C6-C12 straight-chain olefin, which can be selected from 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene and 1-dodecene, preferably 1-octene.

[0020] The nickel-based complex catalyst of the present invention is selected from one of (1-naphthyl)〔8-(diphenylphosphino)quinoline〕nickel chloride, trans-phenyl(bis(triphenylphosphine))nickel bromide and 2,5-diformylpyrrolenickel dibromide, preferably trans-phenyl(bis(triphenylphosphine))nickel bromide.

[0021] The alkylaluminoxane cocatalyst of the present invention is selected from one of methylaluminoxane (MAO) and ethylaluminoxane (EAO), preferably methylaluminoxane.

[0022] 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.

[0023] 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 BPO, and its addition amount is 0.05-0.1 parts based on 100 parts by mass of HNBR rubber.

[0024] 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%.

[0025] 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 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).

[0026] The solvent or solution of the present invention can be selected from cyclohexane, carbon disulfide (CS 2 ), one of nitrobenzene, petroleum ether, tetrachloroethane, toluene, and xylene, preferably cyclohexane.

[0027] In step (1) a of the present invention, the mass ratio of the solvent, the alkylaluminoxane co-catalyst, the allyl glycol, the long-chain α-olefin, and the nickel-based complex catalyst is 200-300:10-20:5-10:10-20:1.

[0028] In step (1) a of the present invention, the temperature is raised to 80-90° C.; the stirring speed is 700-800 rpm; and the stirring time is continued for 20-30 min.

[0029] In step (1) a of the present invention, the reaction pressure is 10-15 MPa and the reaction time is 2.0-3.0 hr.

[0030] In step (1) b of the present invention, the mass ratio of the solvent, isoprene, the first structural regulator, the functionalized macromolecular long-chain monomer, the solution, the second structural regulator, and 1,3-butadiene is 200-400:100:0.2-0.5:5-10:100-200:0.05-0.3:2-4.

[0031] In step (1) b of the present invention, the time for stirring and dissolving after mixing is 60 to 70 minutes.

[0032] In step (1) b of the present invention, the reaction time in the polymerization kettle is 60 to 70 minutes.

[0033] In step (1) b of the present invention, the end-capping reaction time is 20 to 30 minutes.

[0034] 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.

[0035] In step (2) a of the present invention, the mass fraction of nitrile rubber in the rubber solution is 3% to 6%.

[0036] 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%.

[0037] 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.

[0038] In step (2) a of the present invention, the degree of hydrogenation HD of the HNBR rubber is less than 90%.

[0039] In step (2) b of the present invention, the mass ratio of the HNBR rubber, the functionalized macromolecular long-chain branching grafting agent, and chlorobenzene is 100:3-5:100-200.

[0040] In step (2) b of the present invention, the mass fraction of HNBR rubber in the rubber solution is 6% to 9%.

[0041] In step (2) b of the present invention, the reaction temperature is 70-80° C. and the reaction time is 10.0-12.0 hr.

[0042] In step (2) b of the present invention, the grafting rate of the cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields is 2.7% to 3.9%.

[0043] 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.

[0044] The reactor described in the present invention can be a loop reactor or a tank reactor, preferably a tank reactor.

[0045] 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.

[0046] The present invention also provides a cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields obtained by the preparation method.

[0047] Compared with the prior art, the present invention has at least the following advantages and beneficial effects:

[0048] (1) The functionalized macromolecular long-chain branching grafting agent prepared by the present invention first adopts allyl glycol and long-chain α-olefin to prepare functionalized macromolecular long-chain monomer under the action of nickel-based complex catalyst; then, an anionic polymerization method is used to prepare functionalized macromolecular long-chain branching copolymer with free radical reaction activity, containing isoprene homopolymer segment (IR) with wide vinyl distribution, long chain branching, ether group and hydroxyl group through variable temperature process; so that it can be grafted onto hydrogenated nitrile rubber, and a branched structure containing wide distribution unsaturated double bonds, long chain branching, hydroxyl group and ether group is formed on the main chain structure of hydrogenated nitrile rubber. This structure has a very significant effect in destroying the crystallinity of HNBR and improving viscoelasticity, and achieves a good "synergistic effect" in achieving a balance between low temperature resistance and deformation resistance, and can prepare cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields with a glass transition temperature Tg of the raw rubber <-64°C and a compression permanent deformation resistance of ≤22%.

[0049] (2) The cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields prepared by the present invention fully utilizes the "aggregation effect" of macromolecules, the "group effect" of hydroxyl and ether groups, and the "structural effect" of wide distribution and long-chain branched structures under the condition of ensuring a certain degree of hydrogenation. It can greatly reduce the glass transition temperature (Tg) of HNBR with a low addition amount, and can also significantly improve the compression permanent deformation resistance of HNBR, so that it is suitable for oil well operations under low temperature conditions of -64°C.

[0050] (3) The preparation method of the cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields 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

[0051] 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.

[0052] (1) Source of raw materials:

[0053]

[0054] (2) Analytical testing methods:

[0055] 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:

[0056]

[0057] Where: m 0 —Total mass of glue (g); m—Mass of sample weighed after reaction (g); m m —Total mass of monomers in the reactants (g); m HNBR —Mass of hydrogenated nitrile rubber in the sample (g); m 1 —The mass of the sample after extraction (g).

[0058] Molecular weight determination: The determination was performed using a 2414 gel permeation chromatograph (GPC) produced by Waters, USA. The polystyrene standard was used as the calibration curve, the mobile phase was tetrahydrofuran, the column temperature was 40°C, the sample concentration was 1 mg / ml, the injection volume was 50 μL, the elution time was 40 min, and the flow rate was 1 ml·min -1 .

[0059] 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:

[0060] Degree of hydrogenation HD (%) = 1-unsaturation (U)

[0061] 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.

[0062] Compression set: Execute the method in standard GB / T 7759.1-2015.

[0063] Example 1

[0064] (1) Preparation of functionalized macromolecular long-branched grafting agent:

[0065] a Preparation of functionalized macromolecular long-chain monomers: First, an inert gas was introduced into a 10L autoclave for replacement three times, 2000g of cyclohexane was added, and the temperature was raised to 80°C. Then, 100g of methylaluminoxane co-catalyst was gradually added dropwise under uniform stirring at a stirring speed of 700rpm, and stirring was continued for 20min under the protection of inert gas; then, 50g of allyl glycol, 100g of 1-octene and 10g of trans-bromphenyl (bis(triphenylphosphine)) nickel main catalyst were added into the autoclave, ethylene was introduced at this time, and the pressure was maintained at 10MPa for reaction for 2.0hr; after the reaction was completed, the functionalized macromolecular long-chain monomer was obtained by centrifugation and drying.

[0066] b Preparation of functionalized macromolecular long-chain branching grafting agent: In a 10L stainless steel polymerization kettle with a jacket, argon was passed through the system to replace it three times, 1000g cyclohexane, 500g isoprene, and 1.0g THF were added to the polymerization kettle in sequence, the temperature was raised to 50°C, 89mmol n-butyl lithium was added to start the reaction, and the reaction temperature gradually increased from 50°C to 70°C within 60min to form an IR segment with a wide vinyl distribution; then 25g of functionalized macromolecular long-chain monomer and 500g cyclohexane were mixed and stirred to dissolve for 60min, and then 0.3g THF was added to the polymerization kettle to react for 60min; finally, 10g 1,3-butadiene was added to the polymerization kettle for end-capping, and the reaction was continued for 20min until no free monomer was present. The gel was wet-coagulated and dried to obtain a functionalized macromolecular long-chain branching grafting agent (Mn was 6000, Mw / Mn was 7.26).

[0067] (2) Preparation of cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields:

[0068] 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%).

[0069] b Preparation of cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields: First, 200g 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, and then 6.0g of functionalized macromolecular long-branched grafting agent was added to the reactor, stirred and mixed, and heated. When the temperature of the reactor reached 70°C, a mixture of 0.10g BPO and 200g chlorobenzene was added. After reacting for 10.0 hours, it was flocculated with anhydrous ethanol, washed, and dried in a 70°C oven to constant weight to obtain cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields (grafting rate 2.7%). Sampling analysis: Standard samples were made, and the tested properties are shown in Table 1.

[0070] Example 2

[0071] (1) Preparation of functionalized macromolecular long-branched grafting agent:

[0072] a Preparation of functionalized macromolecular long-chain monomers: First, an inert gas was passed through a 10L autoclave for replacement three times, 2200g of cyclohexane was added, and the temperature was raised to 82°C. Then, 110g of methylaluminoxane co-catalyst was gradually added dropwise under uniform stirring at a stirring speed of 720rpm, and stirring was continued for 22min under the protection of inert gas; then 60g of allyl glycol, 120g of 1-octene and 10g of trans-bromphenyl (bis(triphenylphosphine)) nickel main catalyst were added to the autoclave, ethylene was passed through at this time, and the pressure was maintained at 11MPa for reaction for 2.1hr; after the reaction was completed, the functionalized macromolecular long-chain monomer was obtained by centrifugation and drying.

[0073] b Preparation of functionalized macromolecular long-chain branching grafting agent: In a 10L stainless steel polymerization kettle with a jacket, argon was passed through the system to replace it three times, 1200g cyclohexane, 500g isoprene, and 1.3g THF were added to the polymerization kettle in sequence, the temperature was raised to 50°C, 85mmol n-butyl lithium was added to start the reaction, and the reaction temperature gradually increased from 50°C to 70°C within 62min to form an IR segment with a wide vinyl distribution; then 26g of functionalized macromolecular long-chain monomer and 600g cyclohexane were mixed and stirred to dissolve for 62min, and then 0.6g THF was added to the polymerization kettle to react for 62min; finally, 12g 1,3-butadiene was added to the polymerization kettle for end-capping, and the reaction was continued for 22min until no free monomer was present. The gel was wet-coagulated and dried to obtain a functionalized macromolecular long-chain branching grafting agent (Mn was 6400, Mw / Mn was 7.41).

[0074] (2) Preparation of cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields:

[0075] 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 32 minutes, and then 0.03g of GrubbsⅠ catalyst xylene solution (mass concentration of 6%) was added under nitrogen protection. The hydrogen pressure in the pressurized reactor was 12MPa, the temperature was raised to 105℃, and after reacting for 9.5hr, the system was cooled, condensed, and vacuum dried to obtain HNBR rubber (hydrogenation degree HD=85.7%).

[0076] b Preparation of cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields: First, 200g 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 7.0g of functionalized macromolecular long-branched grafting agent was added to the reactor, stirred and mixed, and heated. When the temperature of the reactor reached 72°C, a mixture of 0.12g BPO and 260g chlorobenzene was added. After reacting for 10.5 hours, it was flocculated with anhydrous ethanol, washed, and dried in a 70°C oven to constant weight to obtain cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields (grafting rate 3.0%). Sampling analysis: Standard samples were made, and the tested properties are shown in Table 1.

[0077] Example 3

[0078] (1) Preparation of functionalized macromolecular long-branched grafting agent:

[0079] a Preparation of functionalized macromolecular long-chain monomers: First, in a 10L autoclave, inert gas was passed through and replaced for 4 times, 2400g of cyclohexane was added, and the temperature was raised to 84°C. Then, 130g of methylaluminoxane co-catalyst was gradually added dropwise under uniform stirring at a stirring speed of 740rpm, and stirring was continued for 24min under the protection of inert gas; then 70g of allyl glycol, 140g of 1-octene and 10g of trans-bromphenyl (bis(triphenylphosphine)) nickel main catalyst were added to the autoclave, ethylene was passed through at this time, and the pressure was maintained at 12MPa for reaction for 2.3hr; after the reaction was completed, the functionalized macromolecular long-chain monomer was obtained by centrifugation and drying.

[0080] b Preparation of functionalized macromolecular long-chain branching grafting agent: In a 10L stainless steel polymerization kettle with a jacket, argon was passed through the system to replace it 4 times, 1400g cyclohexane, 500g isoprene, and 1.7g THF were added to the polymerization kettle in sequence, the temperature was raised to 50°C, 78mmol n-butyl lithium was added to start the reaction, and the reaction temperature gradually increased from 50°C to 70°C within 64min to form an IR segment with a wide vinyl distribution; then 27g of functionalized macromolecular long-chain monomer and 700g cyclohexane were mixed and stirred to dissolve for 64min, and then 0.9g THF was added to the polymerization kettle to react for 64min; finally, 14g 1,3-butadiene was added to the polymerization kettle for end-capping, and the reaction was continued for 24min until no free monomer was present. The gel was wet-coagulated and dried to obtain a functionalized macromolecular long-chain branching grafting agent (Mn was 6900, Mw / Mn was 7.82).

[0081] (2) Preparation of cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields:

[0082] a Preparation of hydrogenated nitrile rubber (HNBR): First, 100g of nitrile rubber 2907 was dissolved in chlorobenzene solution to prepare a 4% 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 34 minutes, and then 0.05g of GrubbsⅠ catalyst xylene solution (mass concentration was 7%) was added under nitrogen protection. The hydrogen pressure in the pressurized reactor was 12MPa, and the temperature was raised to 110°C. After reacting for 10 hours, the system was cooled, condensed, and vacuum dried to obtain HNBR rubber (hydrogenation degree HD=86.2%).

[0083] b Preparation of cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields: First, 200g HNBR rubber was dissolved in chlorobenzene solution to prepare a 7.6% 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 4 times, and then 8.0g of functionalized macromolecular long-branched grafting agent was added to the reactor, stirred and mixed, and heated. When the temperature of the reactor reached 74°C, a mixture of 0.14g BPO and 290g 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 cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields (grafting rate 3.2%). Sampling analysis: Standard samples were made, and the tested properties are shown in Table 1.

[0084] Example 4

[0085] (1) Preparation of functionalized macromolecular long-branched grafting agent:

[0086] a Preparation of functionalized macromolecular long-chain monomers: First, in a 10L autoclave, inert gas was passed through and replaced for 4 times, 2600g of cyclohexane was added, and the temperature was raised to 86°C. Then, 150g of methylaluminoxane co-catalyst was gradually added dropwise under uniform stirring at a stirring speed of 760rpm, and stirring was continued for 26min under the protection of inert gas; then 80g of allyl glycol, 160g of 1-octene and 10g of trans-bromphenyl (bis(triphenylphosphine)) nickel main catalyst were added to the autoclave, ethylene was passed through at this time, and the pressure was maintained at 13MPa for reaction for 2.5hr; after the reaction was completed, the functionalized macromolecular long-chain monomers were obtained by centrifugation and drying.

[0087] b Preparation of functionalized macromolecular long-chain branching grafting agent: In a 10L stainless steel polymerization kettle with a jacket, argon was passed through the system to replace it 4 times, 1600g cyclohexane, 500g isoprene, and 1.9g THF were added to the polymerization kettle in sequence, the temperature was raised to 50°C, 74mmol n-butyl lithium was added to start the reaction, and the reaction temperature gradually increased from 50°C to 70°C within 66min to form an IR segment with a wide vinyl distribution; then 28g of functionalized macromolecular long-chain monomer and 800g cyclohexane were mixed and stirred to dissolve for 64min, and then 1.2g THF was added to the polymerization kettle to react for 66min; finally, 16g 1,3-butadiene was added to the polymerization kettle for end-capping, and the reaction was continued for 26min until no free monomer was present. The gel was wet-coagulated and dried to obtain a functionalized macromolecular long-chain branching grafting agent (Mn was 7300, Mw / Mn was 7.96).

[0088] (2) Preparation of cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields:

[0089] 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%).

[0090] b Preparation of cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields: First, 200g HNBR rubber was dissolved in chlorobenzene solution to prepare a glue solution with a mass fraction of 8.1%, 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 9.0g of functionalized macromolecular long-branched grafting agent was added to the reactor, stirred and mixed, and heated. When the temperature of the reactor reached 76°C, a mixed solution of 0.16g BPO and 320g chlorobenzene was added. After reacting for 11.3 hours, it was flocculated with anhydrous ethanol, washed, and dried in a 70°C oven to constant weight to obtain cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields (grafting rate 3.5%). Sampling analysis: Standard samples were made, and the tested properties are shown in Table 1.

[0091] Example 5

[0092] (1) Preparation of functionalized macromolecular long-branched grafting agent:

[0093] a Preparation of functionalized macromolecular long-chain monomers: First, in a 10L autoclave, inert gas was passed through and replaced for 5 times, 2800g of cyclohexane was added, and the temperature was raised to 88°C. Then, 170g of methylaluminoxane co-catalyst was gradually added dropwise under uniform stirring at a stirring speed of 780rpm, and stirring was continued for 28min under the protection of inert gas; then, 90g of allyl glycol, 180g of 1-octene and 10g of trans-bromphenyl (bis(triphenylphosphine)) nickel main catalyst were added to the autoclave, ethylene was passed through at this time, and the pressure was maintained at 14MPa for reaction for 2.7hr; after the reaction was completed, the functionalized macromolecular long-chain monomer was obtained by centrifugation and drying.

[0094] b Preparation of functionalized macromolecular long-chain branching grafting agent: In a 10L stainless steel polymerization kettle with a jacket, argon was passed through the system to replace it 5 times, 1800g cyclohexane, 500g isoprene, and 2.2g THF were added to the polymerization kettle in sequence, the temperature was raised to 50°C, 69mmol n-butyl lithium was added to start the reaction, and the reaction temperature gradually increased from 50°C to 70°C within 68min to form an IR segment with a wide vinyl distribution; then 29g of functionalized macromolecular long-chain monomer and 900g cyclohexane were mixed and stirred to dissolve for 68min, and then 1.3g THF was added to the polymerization kettle to react for 68min; finally, 18g 1,3-butadiene was added to the polymerization kettle for end-capping, and the reaction was continued for 28min until no free monomer was present. The gel was wet-coagulated and dried to obtain a functionalized macromolecular long-chain branching grafting agent (Mn was 7700, Mw / Mn was 8.16).

[0095] (2) Preparation of cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields:

[0096] 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%).

[0097] b Preparation of cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields: First, 200g HNBR rubber was dissolved in chlorobenzene solution to prepare a glue solution with a mass fraction of 8.1%, 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 9.5g of functionalized macromolecular long-branched grafting agent was added to the reactor, stirred and mixed, and heated. When the temperature of the reactor reached 78°C, a mixed solution of 0.18g BPO and 380g chlorobenzene was added. After reacting for 11.8 hours, it was flocculated with anhydrous ethanol, washed, and dried in a 70°C oven to constant weight to obtain cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields (grafting rate 3.8%). Sampling analysis: Standard samples were made, and the tested properties are shown in Table 1.

[0098] Example 6

[0099] (1) Preparation of functionalized macromolecular long-branched grafting agent:

[0100] a Preparation of functionalized macromolecular long-chain monomers: First, in a 10L autoclave, inert gas was passed through for replacement 5 times, 3000g of cyclohexane was added, and after the temperature was raised to 90°C, 200g of ethylaluminoxane co-catalyst was gradually added dropwise under uniform stirring at a stirring speed of 800rpm, and stirring was continued for 30min under the protection of inert gas; then 100g of allyl glycol, 200g of 1-hexene and 10g of 2,5-diformylpyrrole nickel dibromide main catalyst were added to the autoclave, ethylene was passed through at this time, and the pressure was maintained at 15MPa for reaction for 3.0hr; after the reaction was completed, the functionalized macromolecular long-chain monomer was obtained by centrifugal separation and drying.

[0101] b Preparation of functionalized macromolecular long-chain branching grafting agent: In a 10L stainless steel polymerization kettle with a jacket, argon was passed through the system to replace it 5 times, 2000g cyclohexane, 500g isoprene, and 2.5g THF were added to the polymerization kettle in sequence, the temperature was raised to 50°C, 65mmol n-butyl lithium was added to start the reaction, and the reaction temperature gradually increased from 50°C to 70°C within 70min to form an IR segment with a wide vinyl distribution; then 50g of functionalized macromolecular long-chain monomer and 1000g cyclohexane were mixed and stirred to dissolve for 70min, and then 1.4g THF was added to the polymerization kettle to react for 70min; finally, 20g 1,3-butadiene was added to the polymerization kettle for end-capping, and the reaction was continued for 30min until no free monomer was present. The gel was wet-coagulated and dried to obtain a functionalized macromolecular long-chain branching grafting agent (Mn was 8000, Mw / Mn was 8.35).

[0102] (2) Preparation of cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields:

[0103] a Preparation of hydrogenated nitrile rubber (HNBR): First, 100g of nitrile rubber 2907 was dissolved in chlorobenzene solution to prepare a 6.0% 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 by hydrogen for 40 minutes, and then 0.1g of GrubbsⅠ catalyst xylene solution (mass concentration of 10%) was added under nitrogen protection. The hydrogen pressure in the pressurized reactor was 14MPa, and the temperature was raised to 120°C. After reacting for 11 hours, the system was cooled, condensed, and vacuum dried to obtain HNBR rubber (hydrogenation degree HD=89.4%).

[0104] b Preparation of cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields: First, 200g 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 10g of functionalized macromolecular long-branched grafting agent was added to the reactor, stirred and mixed, and heated. When the temperature of the reactor reached 80°C, a mixed solution of 0.20g BPO and 400g 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 cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields (grafting rate 3.9%). Sampling analysis: Standard samples were made, and the tested properties are shown in Table 1.

[0105] Comparative Example 1

[0106] (1) Preparation of functionalized macromolecular long-branched grafting agent:

[0107] Preparation of a functionalized macromolecular long-chain monomer: Other conditions are the same as those in Example 1, except that allyl glycol is not added during the preparation of the functionalized macromolecular long-chain monomer, but allyl alcohol is added in an amount of 50 g, that is: first, in a 10L autoclave, an inert gas is passed through for replacement 3 times, 2000 g of cyclohexane is added, and after the temperature is raised to 80°C, 100 g of methylaluminoxane co-catalyst is gradually added dropwise under uniform stirring at a stirring speed of 700 rpm, and stirring is continued for 20 min under the protection of inert gas; then 50 g of allyl alcohol, 100 g of 1-octene and 10 g of trans-brominated phenyl (bis (triphenylphosphine)) nickel main catalyst are added to the autoclave, ethylene is passed through at this time, and the pressure is maintained at 10 MPa for reaction for 2.0 hr; after the reaction is completed, the functionalized macromolecular long-chain monomer a is obtained by centrifugation and drying.

[0108] b Preparation of functionalized macromolecular long-chain branching grafting agent: Other conditions are the same as those in Example 1, except that in the preparation process of the functionalized macromolecular long-chain branching grafting agent, no functionalized macromolecular long-chain monomer is added, but functionalized macromolecular long-chain monomer a is added in an amount of 25 g, that is: in a 10L stainless steel polymerization kettle with a jacket, the system is replaced 3 times by argon, 1000g cyclohexane, 500g isoprene, and 1.0g THF are added to the polymerization kettle in sequence, the temperature is raised to 50°C, 89mmol n-butyl lithium is added to start the reaction, and the reaction temperature is gradually increased from 50°C to 70°C within 60min to form an IR segment with a wide vinyl distribution; then 25g of functionalized macromolecular long-chain monomer a and 500g of cyclohexane are mixed and stirred to dissolve for 60min, and then added to the polymerization kettle with 0.3g THF to react for 60min; finally, 10g of 1,3-butadiene was capped and the reaction was continued for 20 min until no free monomer was present. The gel was coagulated and dried by wet method to obtain functionalized macromolecular long-branched grafting agent a (Mn was 5800, Mw / Mn was 7.05).

[0109] (2) Preparation of cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields:

[0110] a. Preparation of hydrogenated nitrile rubber (HNBR): Same as in Example 1.

[0111] b Preparation of cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields: The other conditions are the same as those in Example 1, except that in the preparation process of cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields, no functionalized macromolecular long-branched chain grafting agent is added, but functionalized macromolecular long-branched chain grafting agent a is added, and the addition amount is 6.0 g, that is: first, 200 g of HNBR rubber is dissolved in chlorobenzene solution to prepare a glue solution with a mass fraction of 6%, 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 6.0 g of functionalized macromolecular long-branched chain grafting agent a is added to the reactor, stirred and mixed, and heated. When the temperature of the reactor reaches 70°C, a mixed solution of 0.10 g of BPO and 200 g of chlorobenzene is added, and after reacting for 10.0 hours, it is flocculated with anhydrous ethanol, washed, and dried in a 70°C oven to constant weight to obtain cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields (grafting rate 2.5%). Sampling and analysis: Standard samples were made and the tested properties are shown in Table 1.

[0112] Comparative Example 2

[0113] (1) Preparation of functionalized macromolecular long-branched grafting agent:

[0114] Preparation of a functionalized macromolecular long-chain monomer: Other conditions are the same as those in Example 2, except that 1-octene is not added during the preparation of the functionalized macromolecular long-chain monomer, but 1-butene is added in an amount of 120 g, that is: first, in a 10L autoclave, an inert gas is passed through for replacement 3 times, 2200 g of cyclohexane is added, and after the temperature is raised to 82°C, 110 g of methylaluminoxane co-catalyst is gradually added dropwise under uniform stirring at a stirring speed of 720 rpm, and stirring is continued for 22 min under the protection of inert gas; then 60 g of allyl glycol, 120 g of 1-butene and 10 g of trans-brominated phenyl (bis (triphenylphosphine)) nickel main catalyst are added to the autoclave, ethylene is passed through at this time, and the pressure is maintained at 11 MPa for reaction for 2.1 hr; after the reaction is completed, the functionalized macromolecular long-chain monomer b is obtained by centrifugation and drying.

[0115] b Preparation of functionalized macromolecular long-chain branching grafting agent: Other conditions are the same as those in Example 2, except that in the preparation process of the functionalized macromolecular long-chain branching grafting agent, no functionalized macromolecular long-chain monomer is added, but functionalized macromolecular long-chain monomer b is added in an amount of 26 g, that is: in a 10L stainless steel polymerization kettle with a jacket, the system is replaced 3 times by passing argon gas, 1200g cyclohexane, 500g isoprene, and 1.3g THF are added to the polymerization kettle in sequence, the temperature is raised to 50°C, 85mmol n-butyl lithium is added to start the reaction, and the reaction temperature is gradually increased from 50°C to 70°C within 62min to form an IR segment with a wide vinyl distribution; then 26g of functionalized macromolecular long-chain monomer b and 600g of cyclohexane are mixed and stirred to dissolve for 62min, and then added to the polymerization kettle with 0.6g THF to react for 62min; finally, 12g The 1,3-butadiene was capped and the reaction was continued for 22 min until no free monomer was present. The gel was coagulated and dried by wet method to obtain a functional macromolecular long-branched grafting agent b (Mn was 5600, Mw / Mn was 5.82).

[0116] (2) Preparation of cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields:

[0117] a. Preparation of hydrogenated nitrile rubber (HNBR): same as in Example 2.

[0118] b Preparation of cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields: The other conditions are the same as those in Example 2, except that in the preparation process of cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields, no functionalized macromolecular long-branched grafting agent is added, but a functionalized macromolecular long-branched grafting agent b is added in an amount of 7.0 g, that is, firstly, 200 g of HNBR rubber is dissolved in a chlorobenzene solution to prepare 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 7.0 g of functionalized macromolecular long-branched grafting agent b is added to the reactor, stirred and mixed, and heated. When the temperature of the reactor reaches 72°C, a mixed solution of 0.12 g of BPO and 260 g of chlorobenzene is added, and after reacting for 10.5 hours, it is flocculated with anhydrous ethanol, washed, and dried in an oven at 70°C to constant weight to obtain cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields (grafting rate 3.0%). Sampling and analysis: Standard samples were made and the tested properties are shown in Table 1.

[0119] Comparative Example 3

[0120] (1) Preparation of functionalized macromolecular long-branched grafting agent:

[0121] The other conditions are the same as those in Example 3, except that in the preparation process of the functionalized macromolecular long-chain branching grafting agent, no functionalized macromolecular long-chain monomer is added, but a small molecular reactive monomer allyl glycol is added in an amount of 27 g, that is: in a 10L stainless steel polymerization kettle with a jacket, the system is replaced 4 times by argon, 1400g cyclohexane, 500g isoprene, and 1.7g THF are added to the polymerization kettle in sequence, the temperature is raised to 50°C, 78mmol n-butyl lithium is added to start the reaction, and the reaction temperature is gradually increased from 50°C to 70°C within 64min to form an IR segment with a wide vinyl distribution; then 27g allyl glycol and 700g cyclohexane are mixed and stirred to dissolve for 64min, and then added to the polymerization kettle with 0.9g THF to react for 64min; finally, 14g The 1,3-butadiene was capped and the reaction was continued for 24 min until no free monomer was present. The gel was coagulated and dried by wet method to obtain functionalized macromolecular long-branched grafting agent c (Mn was 4700, Mw / Mn was 5.32).

[0122] (2) Preparation of cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields:

[0123] a. Preparation of hydrogenated nitrile rubber (HNBR): Same as Example 3.

[0124] b Preparation of cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields: The other conditions are the same as those in Example 3, except that in the preparation process of cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields, no functionalized macromolecular long-branched chain grafting agent is added, but a functionalized macromolecular long-branched chain grafting agent c is added in an amount of 8.0 g, that is, firstly, 200 g of HNBR rubber is dissolved in a chlorobenzene solution to prepare a glue solution with a mass fraction of 7.6%, 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 8.0 g of functionalized macromolecular long-branched chain grafting agent c is added to the reactor, stirred and mixed, and heated. When the temperature of the reactor reaches 74°C, a mixed solution of 0.14 g of BPO and 290 g of chlorobenzene is added, and after reacting for 11.0 hours, it is flocculated with anhydrous ethanol, washed, and dried in an oven at 70°C to constant weight to obtain cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields (grafting rate 2.9%). Sampling and analysis: Standard samples were made and the tested properties are shown in Table 1.

[0125] Comparative Example 4

[0126] (1) Preparation of functionalized macromolecular long-branched grafting agent:

[0127] a. Preparation of functionalized macromolecular long-chain monomers: same as Example 4.

[0128] b Preparation of functionalized macromolecular long-chain branching grafting agent: Other conditions are the same as those in Example 4, except that the amount of functionalized macromolecular long-chain monomer added during the preparation of the functionalized macromolecular long-chain branching grafting agent is 10 g, that is: in a 10L stainless steel polymerization kettle with a jacket, the system is replaced 4 times by passing argon gas, 1600 g cyclohexane, 500 g isoprene, and 1.9 g THF are added to the polymerization kettle in sequence, the temperature is raised to 50°C, 74 mmol n-butyl lithium is added to start the reaction, and the reaction temperature is gradually raised from 50°C to 70°C within 66 min to form an IR segment with a wide vinyl distribution; then 10 g of functionalized macromolecular long-chain monomer and 800 g cyclohexane are mixed and stirred to dissolve for 64 min, and then added to the polymerization kettle with 1.2 g THF to react for 66 min; finally, 16 g The 1,3-butadiene was capped and the reaction was continued for 26 min until no free monomer was present. The gel was coagulated and dried by wet method to obtain functionalized macromolecular long-branched grafting agent d (Mn was 5900, Mw / Mn was 7.21).

[0129] (2) Preparation of cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields:

[0130] a Preparation of hydrogenated nitrile rubber (HNBR): same as Example 4.

[0131] b Preparation of cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields: The other conditions are the same as those in Example 4, except that in the preparation process of cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields, no functionalized macromolecular long-branched grafting agent is added, but a functionalized macromolecular long-branched grafting agent d is added in an amount of 9.0 g, that is, firstly, 200 g of HNBR rubber is dissolved in a chlorobenzene solution to prepare a glue solution with a mass fraction of 8.1%, 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 9.0 g of a functionalized macromolecular long-branched grafting agent is added to the reactor, stirred and mixed, and heated. When the temperature of the reactor reaches 76°C, a mixed solution of 0.16 g of BPO and 320 g of chlorobenzene is added, and after reacting for 11.3 hours, it is flocculated with anhydrous ethanol, washed, and dried in an oven at 70°C to constant weight to obtain cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields (grafting rate 2.6%). Sampling and analysis: Standard samples were made and the tested properties are shown in Table 1.

[0132] Comparative Example 5

[0133] (1) Preparation of functionalized macromolecular long-branched grafting agent:

[0134] a. Preparation of functionalized macromolecular long-chain monomers: same as Example 5.

[0135] b. Preparation of functionalized macromolecular long-chain branching grafting agent: Other conditions were the same as those in Example 5, except that in the preparation process of the functionalized macromolecular long-chain branching grafting agent, the IR segments were not polymerized at variable temperatures to generate narrowly distributed IR segments, namely: in a 10L stainless steel polymerization kettle with a jacket, the system was replaced 5 times by passing argon gas, 1800g of cyclohexane, 500g of isoprene, and 2.2g of THF were added to the polymerization kettle in sequence, the temperature was raised to 50°C, 69mmol of n-butyl lithium was added, and the reaction was carried out for 68min to form IR segments with narrow vinyl distribution; then 29g of functionalized macromolecular long-chain monomer and 900g of cyclohexane were mixed, stirred and dissolved for 68min, and then added to the polymerization kettle with 1.3g of THF to react for 68min; finally, 18g of 1,3-butadiene was capped and the reaction was carried out for 28 minutes until no free monomer was present. The gel was coagulated and dried by wet method to obtain functionalized macromolecular long-branched grafting agent e (Mn was 7600, Mw / Mn was 4.12).

[0136] (2) Preparation of cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields:

[0137] a Preparation of hydrogenated nitrile rubber (HNBR): same as in Example 5.

[0138] b Preparation of cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields: The other conditions are the same as those in Example 5, except that in the preparation process of cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields, no functionalized macromolecular long-branched chain grafting agent is added, but a functionalized macromolecular long-branched chain grafting agent e is added, and the amount added is 9.5 g, that is, first, 200 g of HNBR rubber is dissolved in a chlorobenzene solution to prepare a glue solution with a mass fraction of 8.1%, 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 9.5 g of functionalized macromolecular long-branched chain grafting agent e is added to the reactor, stirred and mixed, and heated. When the temperature of the reactor reaches 78°C, a mixed solution of 0.18 g of BPO and 380 g of chlorobenzene is added, and after reacting for 11.8 hours, it is flocculated with anhydrous ethanol, washed, and dried in an oven at 70°C to constant weight to obtain cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields (grafting rate 3.5%). Sampling and analysis: Standard samples were made and the tested properties are shown in Table 1.

[0139] Comparative Example 6

[0140] (1) Preparation of functionalized macromolecular long-branched grafting agent:

[0141] Preparation of a functionalized macromolecular long-chain monomer: Other conditions are the same as those in Example 6, except that the amount of allyl glycol added during the preparation of the functionalized macromolecular long-chain monomer is 30 g, namely: first, inert gas was passed through a 10L autoclave for replacement 5 times, 3000 g of cyclohexane was added, and after the temperature was raised to 90°C, 200 g of ethylaluminoxane co-catalyst was gradually added dropwise under uniform stirring at a stirring speed of 800 rpm, and stirring was continued for 30 min under the protection of inert gas; then 30 g of allyl glycol, 200 g of 1-hexene and 10 g of 2,5-diformylpyrrole nickel dibromide main catalyst were added to the autoclave, ethylene was passed through at this time, and the pressure was maintained at 15 MPa for reaction for 3.0 hr; after the reaction was completed, the functionalized macromolecular long-chain monomer c was obtained by centrifugation and drying.

[0142] b Preparation of functionalized macromolecular long-chain branching grafting agent: Other conditions are the same as those in Example 6, except that in the preparation process of the functionalized macromolecular long-chain branching grafting agent, no functionalized macromolecular long-chain monomer is added, but functionalized macromolecular long-chain monomer c is added in an amount of 50 g, that is: in a 10L stainless steel polymerization kettle with a jacket, argon is passed through the system to replace 5 times, 2000g cyclohexane, 500g isoprene, and 2.5g THF are added to the polymerization kettle in sequence, the temperature is raised to 50°C, 65mmol n-butyl lithium is added to start the reaction, and the reaction temperature is gradually raised from 50°C to 70°C within 70min to form an IR segment with a wide vinyl distribution; then 50g of functionalized macromolecular long-chain monomer c and 1000g of cyclohexane are mixed and stirred for 70min and then 1.4g THF was added into the polymerization kettle and reacted for 70 minutes; finally, 20g 1,3-butadiene was added into the polymerization kettle for end-capping and reacted for 30 minutes until no free monomer was present. The gel was coagulated and dried by wet method to obtain functionalized macromolecular long-branched grafting agent f (Mn was 6600, Mw / Mn was 7.15).

[0143] (2) Preparation of cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields:

[0144] a. Preparation of hydrogenated nitrile rubber (HNBR): Same as Example 6.

[0145] b Preparation of cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields: The other conditions are the same as those in Example 6, except that in the preparation process of cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields, no functionalized macromolecular long-branched chain grafting agent is added, but a functionalized macromolecular long-branched chain grafting agent f is added in an amount of 10 g, that is, firstly, 200 g of HNBR rubber is dissolved in a chlorobenzene solution to prepare a glue solution with a mass fraction of 9.0%, 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 10 g of functionalized macromolecular long-branched chain grafting agent f is added to the reactor, stirred and mixed, and heated. When the temperature of the reactor reaches 80°C, a mixed solution of 0.20 g of BPO and 400 g of chlorobenzene is added, and after reacting for 12.0 hours, it is flocculated with anhydrous ethanol, washed, and dried in an oven at 70°C to constant weight to obtain cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields (grafting rate 2.4%). Sampling and analysis: Standard samples were made and the tested properties are shown in Table 1.

[0146] Table 1 Performance of cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields

[0147]

[0148]

[0149] It can be seen from Table 1 that the cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields of the present invention has a small compression permanent deformation and a low glass transition temperature and is suitable for oil well operations under low temperature conditions of -64°C.

[0150] 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 cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields, characterized in that: The steps include: (1) Preparation of functionalized macromolecular long-branched grafting agent: a. Inert gas is introduced into the reaction kettle for replacement, a solvent is added, the temperature is raised, an alkylaluminoxane co-catalyst is added under stirring, and stirring is continued under the protection of the inert gas; then allyl glycol, long-chain α-olefin, and nickel-based complex catalyst are added into the reaction kettle, and ethylene is introduced at this time for reaction; after the reaction is completed, the functionalized macromolecular long-chain monomer is obtained by centrifugal separation and drying; b. In a polymerization kettle, argon gas is introduced to replace the system, and a solvent, isoprene, a first structural regulator, and an initiator 1 are added to the polymerization kettle in sequence. The reaction is a temperature-variable polymerization. Within 60 to 70 minutes, the temperature gradually rises from 50° C. to 70° C. to form an IR segment with a wide vinyl distribution. Then, the functionalized macromolecular long-chain monomer and the solution are mixed and stirred to dissolve until they are completely dissolved and then added to the polymerization kettle to react with the second structural regulator. Finally, 1,3-butadiene is added to the polymerization kettle for end-capping, and the reaction is continued until no free monomer exists. The glue solution is wet-coagulated and dried to obtain a functionalized macromolecular long-chain grafting agent. (2) Preparation of cold-resistant and compression-resistant hydrogenated nitrile rubber for 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, 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, react, cool the system, condense, and dry to obtain HNBR rubber; b. Preparation of cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields: HNBR rubber is dissolved in a 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 functionalized macromolecular long-branched chain grafting agent is added to the reactor, stirred and mixed, heated, and a mixed solution of initiator 2 and chlorobenzene is added, reacted, flocculated, washed, and dried to obtain a cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields; The functionalized macromolecular long-branched grafting agent has the following structure: Among them, IR is an isoprene homopolymer segment with a wide vinyl distribution; R is a straight-chain alkyl group of C6 to C12; B is a terminal 1,3-butadiene, n is the number of repeating units, and n is a positive integer of ≥1; the number average molecular weight (Mn) of the functionalized macromolecular long-branched grafting agent is 6000 to 8000, and the molecular weight distribution (Mw / Mn) is 7.26 to 8.

35.

2. The preparation method according to claim 1, characterized in that: The long-chain α-olefin is selected from one of 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene and 1-dodecene.

3. The preparation method according to claim 1, characterized in that: The nickel-based complex catalyst is selected from one of (1-naphthyl)〔8-(diphenylphosphino)quinoline〕nickel chloride, trans-phenyl(bis(triphenylphosphine))nickel bromide and 2,5-diformylpyrrole nickel dibromide.

4. The preparation method according to claim 1, characterized in that: The alkylaluminoxane cocatalyst is selected from one of methylaluminoxane (MAO) and ethylaluminoxane (EAO).

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

6. 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 0.05-0.1 parts based on 100 parts of the mass of the HNBR rubber.

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 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 solvent, the alkylaluminoxane co-catalyst, the allyl glycol, the long-chain α-olefin, and the nickel-based complex catalyst is 200-300:10-20:5-10:10-20:

1.

11. The preparation method according to claim 1, characterized in that: In step (1) b, the mass ratio of the solvent, isoprene, the first structural regulator, the functionalized macromolecular long-chain monomer, the solution, the second structural regulator, and 1,3-butadiene is 200-400:100:0.2-0.5:5-10:100-200:0.05-0.3:2-4.

12. 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.

13. 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%.

14. The preparation method according to claim 1, characterized in that: In step (2) b, the mass ratio of the HNBR rubber, the functionalized macromolecular long-chain branching grafting agent, and chlorobenzene is 100:3-5:100-200.

15. The preparation method according to claim 1, characterized in that: In step (2) b, the grafting rate of the cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields is 2.7% to 3.9%.

16. A cold-resistant and compression-resistant hydrogenated nitrile rubber for oil fields obtained according to the preparation method according to any one of claims 1 to 15.

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