Tear-resistant and cold-resistant hydrogenated nitrile rubber for oil field and preparation method thereof

Abstract

The invention discloses tear-resistant and cold-resistant hydrogenated butadiene-acrylonitrile rubber for an oil field and a preparation method of the tear-resistant and cold-resistant hydrogenated butadiene-acrylonitrile rubber. The preparation method comprises the following steps: (1) preparing a macromolecular composite functional grafting agent; and (2) preparing the tear-resistant and cold-resistant hydrogenated butadiene-acrylonitrile rubber for the oil field. The macromolecular composite functional grafting agent has the following structure: # imgabs0 #, wherein R is straight chain alkyl of C1 to C6; b is terminated 1, 3-butadiene; n and m are repetitive unit numbers, n > = 1, and m > = 1; the number-average molecular weight (Mn) of the macromolecular composite functional grafting agent is 7000 to 8000. The preparation method of the tear-resistant and cold-resistant hydrogenated butadiene-acrylonitrile rubber for the oil field has the characteristics of environment friendliness, efficient modification effect, low modifier dosage, commercially available and easily available raw materials, suitability for industrial production and the like.

Description

Technical Field

[0001] The invention belongs to the technical field of rubber, and specifically relates to a tear-resistant and cold-resistant hydrogenated nitrile rubber for oil fields prepared by a macromolecular composite functional 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. The lowest temperature 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 tear-resistant and cold-resistant hydrogenated nitrile rubber for oil fields, which has a tear strength of ≥74KN / m and a glass transition temperature Tg<-75°C, and can meet the use requirements within the range of -75°C to -78°C. The invention firstly hydrolyzes 2,4,6-tribromophenyl allyl ether to synthesize 2,4,6-trihydroxyphenyl allyl ether, and then uses 2,4,6-trihydroxyphenyl allyl ether and 4-hydroxy-3-alkoxy-1-propenylbenzene to prepare a macromolecular composite functional monomer; secondly, the macromolecular composite functional monomer and the reactive monomer p-alkylstyrene are anion polymerized to prepare a macromolecular composite functional grafting agent with free radical reaction activity; finally, the macromolecular composite functional grafting agent is grafted onto the main chain of hydrogenated nitrile rubber to prepare tear-resistant and cold-resistant hydrogenated nitrile rubber for oil fields. The method not only solves the problem of easy crystallization of hydrogenated nitrile rubber, but also avoids the problem of decreased tear strength due to decreased crystallinity, so that the hydrogenated nitrile rubber can show very excellent cold resistance while maintaining sufficient tear strength, thus achieving a balance between the cold resistance and tear strength of the hydrogenated nitrile rubber, and meeting the oil well operation requirements of the submersible screw pump stator rubber material under low temperature conditions of -75°C.

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

[0010] (1) Preparation of macromolecular composite functionalized grafting agent:

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

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

[0013] c Preparation of macromolecular composite functionalized grafting agent: In a polymerization kettle, argon gas is introduced to replace the system, and a solvent, p-alkylstyrene, and a structure regulator are sequentially added to the polymerization kettle, the temperature is raised, and an initiator 1 is added to react to form a p-alkylstyrene homopolymer segment; then, the macromolecular composite functionalized monomer and the solution are mixed and stirred to dissolve, and the mixture is added to the polymerization kettle until it is completely dissolved and then heated to react; finally, 1,3-butadiene is added to the polymerization kettle for end-capping, and the reaction is carried out until no free monomer exists, and the glue solution is wet-coagulated and dried to obtain a macromolecular composite functionalized grafting agent;

[0014] (2) Preparation of tear-resistant and cold-resistant hydrogenated nitrile rubber for oil fields:

[0015] a Preparation of hydrogenated nitrile rubber (HNBR): dissolve nitrile rubber in chlorobenzene solution to prepare a rubber solution, then add the rubber solution into a reactor and introduce inert gas to remove the air in the reactor, then remove the inert gas in the reactor with hydrogen, add a xylene solution of Grubbs I catalyst under nitrogen protection, pressurize, heat up, after reaction, cool the system, condense, and vacuum dry to obtain HNBR rubber (hydrogenation degree HD<90%);

[0016] b. Preparation of tear-resistant and cold-resistant hydrogenated nitrile rubber for oil fields: HNBR rubber is dissolved in chlorobenzene solution to prepare a glue solution, and then the glue solution is added to a reactor, and an inert gas is introduced for replacement, and then a macromolecular composite functionalized grafting agent is added to the reactor, stirred and mixed, heated, and a mixed solution of initiator 2 and chlorobenzene is added. After the reaction, flocculation, washing, and drying are performed to obtain tear-resistant and cold-resistant hydrogenated nitrile rubber for oil fields;

[0017] The macromolecular composite functionalized grafting agent has the following structure:

[0018]

[0019] Among them, R is a straight-chain alkyl of C1 to C6; B is end-capped 1,3-butadiene; n and m are positive integers of the number of repeating units, n≥1, m≥1; and the number average molecular weight (Mn) of the macromolecular composite functionalized grafting agent is 7000 to 8000.

[0020] The p-alkylstyrene described in the present invention is an aromatic vinyl compound selected from p-methylstyrene, p-ethylstyrene, p-propylstyrene, p-butylstyrene, p-pentylstyrene and p-hexylstyrene, preferably p-methylstyrene.

[0021] The 4-hydroxy-3-alkoxy-1-propenylbenzene of the present invention is an unsaturated organic compound selected from the group consisting of 4-hydroxy-3-methoxy-1-propenylbenzene, 4-hydroxy-3-ethoxy-1-propenylbenzene, 4-hydroxy-3-propoxy-1-propenylbenzene, 4-hydroxy-3-butoxy-1-propenylbenzene, 4-hydroxy-3-pentyloxy-1-propenylbenzene and 4-hydroxy-3-hexyloxy-1-propenylbenzene, preferably 4-hydroxy-3-ethoxy-1-propenylbenzene.

[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 DCP, and its addition amount is 0.2 to 0.5 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 p-alkylstyrene and 1,3-butadiene to make the two copolymerize randomly. This type of polar organic compound is selected from one of diethylene glycol dimethyl ether (2G), tetrahydrofuran (THF), ethyl ether, ethyl methyl ether, anisole, diphenyl ether, ethylene glycol dimethyl ether (DME), and triethylamine, preferably tetrahydrofuran (THF).

[0026] The solvent or solution of the present invention can be selected from one of cyclohexane, chloroform, carbon disulfide (CS2), nitrobenzene, petroleum ether, tetrachloroethane, toluene and xylene, preferably cyclohexane.

[0027] In step (1) a of the present invention, the mass ratio of the deionized water, 2,4,6-tribromophenyl allyl ether and the NaOH aqueous solution is 300-400:100:20-30.

[0028] In step (1) a of the present invention, the mass concentration of the NaOH aqueous solution is 10% to 20%.

[0029] In step (1) a of the present invention, the temperature is raised to 130-140° C. and the reaction time is 6-8 hr.

[0030] In step (1) a of the present invention, the yield of 2,4,6-trihydroxyphenyl allyl ether is 80% to 83%.

[0031] In step (1) b of the present invention, the mass ratio of the solvent, 4-hydroxy-3-alkoxy-1-propenylbenzene, 2,4,6-trihydroxyphenyl allyl ether, structure regulator and 1,3-butadiene is 200-300: 30-40: 60-70: 0.3-0.5: 2-5.

[0032] In step (1) b of the present invention, the temperature is raised to 70-80°C.

[0033] In step (1) b of the present invention, the reaction time after adding the initiator 1 is 90 to 100 minutes; the reaction time after adding 1,3-butadiene for end-capping is 30 to 40 minutes.

[0034] In step (1) c of the present invention, the mass ratio of the solvent, p-alkylstyrene, structure regulator, macromolecular composite functional monomer, solution and 1,3-butadiene is 200-300:100:0.3-0.6:20-30:100-200:2-5.

[0035] In step (1) of the present invention, after adding initiator 1, the reaction temperature is 50-60° C. and the reaction time is 80-90 min.

[0036] In step (1) of the present invention, the stirring and dissolving time is 80 to 90 minutes.

[0037] In step (1) c of the present invention, after adding the macromolecular composite functional monomer and the solution, the temperature is raised to 80-90° C. and the reaction time is 80-90 min; and the reaction time of adding 1,3-butadiene for end-capping is 30-40 min.

[0038] 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.

[0039] In step (2) a of the present invention, the mass fraction of nitrile rubber in the rubber solution is 3% to 6%.

[0040] 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%.

[0041] 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.

[0042] In step (2) a of the present invention, the degree of hydrogenation HD of the HNBR rubber is less than 90%.

[0043] In step (2) b of the present invention, the mass ratio of the HNBR rubber, the macromolecular composite functionalized grafting agent, and chlorobenzene is 100:2-5:50-100.

[0044] In step (2) b of the present invention, the mass fraction of HNBR rubber in the rubber solution is 6% to 9%.

[0045] In step (2) b of the present invention, the reaction temperature after adding the mixed solution of initiator 2 and chlorobenzene is 70-80° C. and the reaction time is 12.0-13.0 hr.

[0046] In step (2) b of the present invention, the grafting rate of the tear-resistant and cold-resistant hydrogenated nitrile rubber for oil fields is 1.8% to 3.9%.

[0047] 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.

[0048] The reactor described in the present invention can be a loop reactor or a tank reactor, preferably a tank reactor.

[0049] 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.

[0050] The present invention also provides a tear-resistant and cold-resistant hydrogenated nitrile rubber for oil fields obtained by the preparation method.

[0051] Compared with the prior art, the present invention has at least the following advantages and beneficial effects:

[0052] (1) The macromolecular composite functional monomer prepared by the present invention is prepared by anionic polymerization using 2,4,6-trihydroxyphenyl allyl ether and 4-hydroxy-3-alkoxy-1-propenylbenzene. This long-chain monomer integrates alkoxy, polyhydroxy and phenyl on a macromolecular chain, making full use of the "aggregation effect" of macromolecules and the "group effect" of ether, polyhydroxy and alkoxy groups, which can effectively destroy the crystallinity of HNBR and avoid the decrease of its tear strength due to the decrease of HNBR crystallinity by utilizing the rigidity of phenyl. It can prepare a tear-resistant and cold-resistant hydrogenated nitrile rubber for oil fields with a glass transition temperature Tg<-75°C of raw rubber, which can meet the requirements of oil well operation under low temperature conditions of -75°C.

[0053] (2) The macromolecular composite functionalized grafting agent prepared by the present invention integrates the p-alkylstyrene homopolymer chain segment and the macromolecular composite functionalized monomer on a macromolecular chain, fully utilizing the "aggregation effect" of the p-alkylbenzene homopolymer and the "group effect" of the polyphenyl rings in the macromolecular composite functionalized monomer with large steric hindrance and high rigidity to produce a certain "synergistic effect", thereby more effectively improving the tear strength of HNBR, while avoiding the damage to the crystallinity of HNBR caused by ether groups, polyhydroxyl groups and alkoxy groups, thereby causing a decrease in the tear strength of HNBR, and being able to prepare a tear-resistant and cold-resistant hydrogenated nitrile rubber for oil fields with a raw rubber tear strength of ≥74KN / m, which can meet the oil well operation requirements of the stator rubber material of the submersible screw pump.

[0054] (3) The macromolecular composite functionalized grafting agent prepared by the present invention can significantly improve the tear strength of HNBR and reduce the glass transition temperature (Tg) of HNBR with a low addition amount, and achieves high efficiency of modification in achieving a balanced relationship between the tear strength and cold resistance of HNBR.

[0055] (4) The preparation method of the tear-resistant and cold-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, has readily available raw materials on the market, and is suitable for industrial production. DETAILED DESCRIPTION

[0056] 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.

[0057] (1) Source of raw materials:

[0058]

[0059]

[0060] (2) Analytical testing methods:

[0061] 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:

[0062]

[0063] Where: m0 is the total mass of the mortar (g); m is the mass of the sample weighed after the reaction (g); m —Total mass of monomers in the reactants (g); m HNBR —The mass of hydrogenated nitrile rubber in the sample (g); m1—The mass of the sample after extraction (g).

[0064] 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 .

[0065] 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:

[0066] Degree of hydrogenation HD (%) = 1-unsaturation (U)

[0067] 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.

[0068] Tear strength: Execute the method in standard GB / T 529-2009.

[0069] Example 1

[0070] (1) Preparation of macromolecular composite functionalized grafting agent:

[0071] a Preparation of 2,4,6-trihydroxyphenyl allyl ether: First, in a 5L stainless steel polymerizer with a jacket, argon gas was replaced three times, and 1500 g of deionized water, 500 g of 2,4,6-tribromophenyl allyl ether, and 100 g of a 10% NaOH aqueous solution were added to the polymerizer in sequence, stirred, mixed, and heated to 130°C. After reacting for 6.0 hours, 2,4,6-trihydroxyphenyl allyl ether was finally extracted, separated, washed, and dried to obtain 2,4,6-trihydroxyphenyl allyl ether (yield: 80%).

[0072] b. Preparation of macromolecular composite functional monomers: In a 10L stainless steel polymerizer with a jacket, the system was replaced three times by passing argon, and 2000g of cyclohexane, 300g of 4-hydroxy-3-alkoxy-1-propenylbenzene, 700g of 2,4,6-trihydroxyphenyl allyl ether, and 3.0g of THF were added to the polymerizer in sequence. The temperature was raised to 70°C, and 320mmol of n-butyl lithium was added to the polymerizer to react for 90min. Finally, 20g of 1,3-butadiene was added to the polymerizer for end-capping, and the reaction was carried out for 30min until no free monomers were present. The colloid was wet-coagulated and dried to obtain a macromolecular composite functional monomer.

[0073] c Preparation of macromolecular composite functionalized grafting agent: In a 10L stainless steel polymerizer with a jacket, argon was passed through the system to replace it three times, and 2000g cyclohexane, 1000g p-methylstyrene, and 3.0g THF were added to the polymerizer in sequence. After the temperature was raised to 50°C, 210mmol n-butyl lithium was added to start the reaction for 80min to form p-methylstyrene segments; then 200g macromolecular composite functionalized monomer and 1000g cyclohexane were mixed and stirred to dissolve for 80min, until they were completely dissolved, they were added to the polymerizer and heated to 80°C and reacted for 80min; finally, 20g 1,3-butadiene was added to the polymerizer for end-capping reaction for 30min until no free monomers were present, and the colloid was wet-coagulated and dried to obtain a macromolecular composite functionalized grafting agent (Mn was 7000).

[0074] (2) Preparation of tear-resistant and cold-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 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%).

[0076] b Preparation of tear-resistant and cold-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 4.0g of macromolecular composite functional grafting agent was added to the reactor, stirred and mixed, and heated. When the temperature of the reactor reached 70°C, a mixture of 0.40g DCP and 100g 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 tear-resistant and cold-resistant hydrogenated nitrile rubber for oil fields (grafting rate 1.8%). Sampling analysis: Standard samples were made, and the tested properties are shown in Table 1.

[0077] Example 2

[0078] (1) Preparation of macromolecular composite functionalized grafting agent:

[0079] a Preparation of 2,4,6-trihydroxyphenyl allyl ether: same as Example 1.

[0080] b. Preparation of macromolecular composite functional monomers: In a 10L stainless steel polymerizer with a jacket, the system was replaced three times with argon, 2200g of cyclohexane, 320g of 4-hydroxy-3-alkoxy-1-propenylbenzene, 680g of 2,4,6-trihydroxyphenyl allyl ether, and 3.5g of THF were added to the polymerizer in sequence, the temperature was raised to 72°C, and 316mmol of n-butyl lithium was added to the polymerizer to react for 92min; finally, 30g of 1,3-butadiene was added to the polymerizer for end-capping, and the reaction was carried out for 32min until no free monomers were present. The colloid was wet-coagulated and dried to obtain a macromolecular composite functional monomer.

[0081] c Preparation of macromolecular composite functionalized grafting agent: In a 10L stainless steel polymerizer with a jacket, argon was passed through the system to replace it three times, and 2200g cyclohexane, 1000g p-methylstyrene, and 3.5g THF were added to the polymerizer in sequence. After the temperature was raised to 52°C, 207mmol n-butyl lithium was added to start the reaction for 82min to form p-methylstyrene segments; then 220g macromolecular composite functionalized monomer and 1200g cyclohexane were mixed and stirred to dissolve for 82min, until they were completely dissolved, and then added to the polymerizer and heated to 82°C and reacted for 82min; finally, 26g 1,3-butadiene was added to the polymerizer for end-capping reaction for 32min until no free monomer was present, and the colloid was wet-coagulated and dried to obtain a macromolecular composite functionalized grafting agent (Mn was 7100).

[0082] (2) Preparation of tear-resistant and cold-resistant hydrogenated nitrile rubber for oil fields:

[0083] a. Preparation of hydrogenated nitrile rubber (HNBR): Same as in Example 1.

[0084] b Preparation of tear-resistant and cold-resistant hydrogenated nitrile rubber for oil fields: First, 200g HNBR rubber was dissolved in chlorobenzene solution to prepare a 6.5% glue solution by mass, and then the glue solution was added to a 10L stainless steel reactor with a jacket, and nitrogen was introduced for replacement 3 times, and then 5.5g of macromolecular composite functionalized grafting agent was added to the reactor, stirred and mixed, and heated. When the temperature of the reactor reached 72°C, a mixture of 0.52g DCP and 120g chlorobenzene was added. After reacting for 12.2 hours, it was flocculated with anhydrous ethanol, washed, and dried in a 70°C oven to constant weight to obtain tear-resistant and cold-resistant hydrogenated nitrile rubber for oil fields (grafting rate 2.3%). Sampling analysis: Standard samples were made, and the tested properties are shown in Table 1.

[0085] Example 3

[0086] (1) Preparation of macromolecular composite functionalized grafting agent:

[0087] a Preparation of 2,4,6-trihydroxyphenyl allyl ether: same as Example 1.

[0088] b. Preparation of macromolecular composite functional monomers: In a 10L stainless steel polymerizer with a jacket, the system was replaced 4 times by passing argon, and 2400g of cyclohexane, 340g of 4-hydroxy-3-alkoxy-1-propenylbenzene, 660g of 2,4,6-trihydroxyphenyl allyl ether, and 4.0g of THF were added to the polymerizer in sequence. The temperature was raised to 74°C, and 309mmol of n-butyl lithium was added to the polymerizer to react for 94min. Finally, 35g of 1,3-butadiene was added to the polymerizer for end-capping, and the reaction was carried out for 34min until no free monomers were present. The colloid was wet-coagulated and dried to obtain a macromolecular composite functional monomer.

[0089] c Preparation of macromolecular composite functionalized grafting agent: In a 10L stainless steel polymerizer with a jacket, argon was passed through the system to replace it 4 times, and 2400g cyclohexane, 1000g p-methylstyrene, and 4.0g THF were added to the polymerizer in sequence. After the temperature was raised to 54°C, 202mmol n-butyl lithium was added to start the reaction for 84min to form p-methylstyrene segments; then 240g macromolecular composite functionalized monomer and 1400g cyclohexane were mixed and stirred to dissolve for 84min, until they were completely dissolved, they were added to the polymerizer and heated to 84°C and reacted for 84min; finally, 30g 1,3-butadiene was added to the polymerizer for end-capping reaction for 34min until no free monomer was present, and the colloid was wet-coagulated and dried to obtain a macromolecular composite functionalized grafting agent (Mn was 7400).

[0090] (2) Preparation of tear-resistant and cold-resistant hydrogenated nitrile rubber for oil fields:

[0091] a. Preparation of hydrogenated nitrile rubber (HNBR): Same as in Example 1.

[0092] b Preparation of tear-resistant and cold-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 7.6%, and then the glue solution was added to a 10L stainless steel reactor with a jacket, and nitrogen was introduced for replacement 4 times, and then 6.3g of macromolecular composite functional grafting agent was added to the reactor, stirred and mixed, and heated. When the temperature of the reactor reached 74°C, a mixed solution of 0.61g DCP and 140g chlorobenzene was added. After reacting for 12.4 hours, it was flocculated with anhydrous ethanol, washed, and dried in a 70°C oven to constant weight to obtain tear-resistant and cold-resistant hydrogenated nitrile rubber for oil fields (grafting rate 2.8%). Sampling analysis: Standard samples were made, and the tested properties are shown in Table 1.

[0093] Example 4

[0094] (1) Preparation of macromolecular composite functionalized grafting agent:

[0095] a Preparation of 2,4,6-trihydroxyphenyl allyl ether: First, in a 5L stainless steel polymerizer with a jacket, argon gas was replaced 4 times, and 2000 g of deionized water, 500 g of 2,4,6-tribromophenyl allyl ether, and 150 g of a 20% NaOH aqueous solution were added to the polymerizer in sequence, stirred, mixed, and heated to 140°C. After reacting for 8.0 hours, 2,4,6-trihydroxyphenyl allyl ether was finally extracted, separated, washed, and dried to obtain 2,4,6-trihydroxyphenyl allyl ether (yield: 83%).

[0096] b. Preparation of macromolecular composite functional monomers: In a 10L stainless steel polymerizer with a jacket, the system was replaced 4 times by passing argon, and 2600g of cyclohexane, 350g of 4-hydroxy-3-alkoxy-1-propenylbenzene, 650g of 2,4,6-trihydroxyphenyl allyl ether, and 4.3g of THF were added to the polymerizer in sequence. The temperature was raised to 76°C, and 303mmol of n-butyl lithium was added to the polymerizer to react for 96min. Finally, 40g of 1,3-butadiene was added to the polymerizer for end-capping, and the reaction was carried out for 36min until no free monomers were present. The colloid was wet-coagulated and dried to obtain a macromolecular composite functional monomer.

[0097] c Preparation of macromolecular composite functionalized grafting agent: In a 10L stainless steel polymerizer with a jacket, argon was passed through the system to replace it 4 times, and 2600g cyclohexane, 1000g p-methylstyrene, and 4.5g THF were added to the polymerizer in sequence. After the temperature was raised to 56°C, 197mmol n-butyllithium was added to start the reaction for 86min to form p-methylstyrene segments; then 260g macromolecular composite functionalized monomer and 1600g cyclohexane were mixed and stirred to dissolve for 86min, until completely dissolved, added to the polymerizer and heated to 86°C, and reacted for 86min; finally, 35g 1,3-butadiene was added to the polymerizer for end-capping reaction for 36min until no free monomer was present, and the colloid was wet-coagulated and dried to obtain a macromolecular composite functionalized grafting agent (Mn was 7600).

[0098] (2) Preparation of tear-resistant and cold-resistant hydrogenated nitrile rubber for oil fields:

[0099] 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%).

[0100] b Preparation of tear-resistant and cold-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 7.9%, 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 7.8g of macromolecular composite functional 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 0.73g DCP and 160g chlorobenzene was added. After reacting for 12.5 hours, it was flocculated with anhydrous ethanol, washed, and dried in a 70°C oven to constant weight to obtain tear-resistant and cold-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.

[0101] Example 5

[0102] (1) Preparation of macromolecular composite functionalized grafting agent:

[0103] a Preparation of 2,4,6-trihydroxyphenyl allyl ether: same as Example 4.

[0104] b. Preparation of macromolecular composite functional monomers: In a 10L stainless steel polymerizer with a jacket, the system was replaced 5 times by passing argon, and 2800g of cyclohexane, 370g of 4-hydroxy-3-alkoxy-1-propenylbenzene, 630g of 2,4,6-trihydroxyphenyl allyl ether, and 4.8g of THF were added to the polymerizer in sequence. The temperature was raised to 78°C, and 297mmol of n-butyl lithium was added to the polymerizer to react for 98min. Finally, 45g of 1,3-butadiene was added to the polymerizer for end-capping, and the reaction was carried out for 38min until no free monomers were present. The colloid was wet-coagulated and dried to obtain a macromolecular composite functional monomer.

[0105] c Preparation of macromolecular composite functionalized grafting agent: In a 10L stainless steel polymerizer with a jacket, argon was passed through the system to replace it 5 times, and 2800g cyclohexane, 1000g p-methylstyrene, and 5.2g THF were added to the polymerizer in sequence. After the temperature was raised to 57°C, 193mmol n-butyl lithium was added to start the reaction for 88min to form p-methylstyrene segments; then 280g macromolecular composite functionalized monomer and 1800g cyclohexane were mixed and stirred to dissolve for 88min, until they were completely dissolved, they were added to the polymerizer and heated to 88°C and reacted for 88min; finally, 40g 1,3-butadiene was added to the polymerizer for end-capping reaction for 38min until no free monomer was present, and the colloid was wet condensed and dried to obtain a macromolecular composite functionalized grafting agent (Mn was 7800).

[0106] (2) Preparation of tear-resistant and cold-resistant hydrogenated nitrile rubber for oil fields:

[0107] a Preparation of hydrogenated nitrile rubber (HNBR): same as Example 4.

[0108] b Preparation of tear-resistant and cold-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 8.4%, 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 9.1g of macromolecular composite functionalized 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 0.84g DCP and 180g chlorobenzene was added. After reacting for 12.7 hours, it was flocculated with anhydrous ethanol, washed, and dried in a 70°C oven to constant weight to obtain tear-resistant and cold-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.

[0109] Example 6

[0110] (1) Preparation of macromolecular composite functionalized grafting agent:

[0111] a Preparation of 2,4,6-trihydroxyphenyl allyl ether: same as Example 4.

[0112] b. Preparation of macromolecular composite functional monomers: In a 10L stainless steel polymerizer with a jacket, the system was replaced 5 times by passing argon, and 3000g of cyclohexane, 400g of 4-hydroxy-3-alkoxy-1-propenylbenzene, 600g of 2,4,6-trihydroxyphenyl allyl ether, and 5.0g of THF were added to the polymerizer in sequence. The temperature was raised to 80°C, and 289mmol of n-butyl lithium was added to the polymerizer to react for 100min; finally, 50g of 1,3-butadiene was added to the polymerizer for end-capping, and the reaction was carried out for 40min until no free monomers were present. The colloid was wet-coagulated and dried to obtain a macromolecular composite functional monomer.

[0113] c Preparation of macromolecular composite functionalized grafting agent: In a 10L stainless steel polymerizer with a jacket, argon was passed through the system to replace it 5 times, and 3000g cyclohexane, 1000g p-methylstyrene, and 6.0g THF were added to the polymerizer in sequence. After the temperature was raised to 60°C, 187mmol n-butyl lithium was added to start the reaction for 90min to form p-methylstyrene segments; then 300g macromolecular composite functionalized monomer and 2000g cyclohexane were mixed and stirred to dissolve for 90min, until they were completely dissolved, and then added to the polymerizer and heated to 90°C and reacted for 90min; finally, 50g 1,3-butadiene was added to the polymerizer for end-capping reaction for 40min until no free monomer was present, and the colloid was wet-coagulated and dried to obtain a macromolecular composite functionalized grafting agent (Mn was 8000).

[0114] (2) Preparation of tear-resistant and cold-resistant hydrogenated nitrile rubber for oil fields:

[0115] a Preparation of hydrogenated nitrile rubber (HNBR): same as Example 4.

[0116] b Preparation of tear-resistant and cold-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 10.0g of macromolecular composite functional grafting agent was added to the reactor, stirred and mixed, and heated. When the temperature of the reactor reached 80°C, a mixture of 1.00g DCP and 200g chlorobenzene was added. After reacting for 13.0 hours, it was flocculated with anhydrous ethanol, washed, and dried in a 70°C oven to constant weight to obtain tear-resistant and cold-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.

[0117] Comparative Example 1

[0118] (1) Preparation of macromolecular composite functionalized grafting agent:

[0119] a Preparation of 2,4,6-trihydroxyphenyl allyl ether: same as Example 1.

[0120] b. Preparation of macromolecular composite functional monomer: Other conditions are the same as those in Example 1, except that the amount of 2,4,6-trihydroxyphenyl allyl ether added in the preparation of the macromolecular composite functional monomer is 400 g, that is, in a 10L stainless steel polymerizer with a jacket, the system is replaced three times by passing argon, 2000 g of cyclohexane, 300 g of 4-hydroxy-3-alkoxy-1-propenylbenzene, 400 g of 2,4,6-trihydroxyphenyl allyl ether, and 3.0 g of THF are added to the polymerizer in sequence, the temperature is raised to 70° C., and 320 mmol of n-butyl lithium is added to the polymerizer for reaction for 90 min; finally, 20 g of 1,3-butadiene is added to the polymerizer for end-capping, and the reaction is carried out for 30 min until no free monomer is present. The colloid is wet-coagulated and dried to obtain a macromolecular composite functional monomer a.

[0121] c Preparation of macromolecular composite functionalized grafting agent: Other conditions are the same as those in Example 1, except that in the preparation process of the macromolecular composite functionalized grafting agent, no macromolecular composite functionalized monomer is added, but macromolecular composite functionalized monomer a is added in an amount of 200 g, that is: in a 10L stainless steel polymerizer with a jacket, the system is replaced 3 times by passing argon gas, 2000 g cyclohexane, 1000 g p-methylstyrene, and 3.0 g THF are added to the polymerizer in sequence, and after heating to 50° C., 210 mmol n-butyl lithium is added to start the reaction for 80 min to form p-methylstyrene segments; then 200 g macromolecular composite functionalized monomer a and 1000 g cyclohexane are mixed and stirred to dissolve for 80 min, until completely dissolved, the mixture is added to the polymerizer and heated to 80° C., and the mixture is reacted for 80 min; finally, 20 g The 1,3-butadiene capping reaction was carried out for 30 minutes until no free monomer was present. The colloid was coagulated and dried by a wet method to obtain a macromolecular composite functional grafting agent a (Mn was 6700).

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

[0123] a. Preparation of hydrogenated nitrile rubber (HNBR): Same as in Example 1.

[0124] b Preparation of tear-resistant and cold-resistant hydrogenated nitrile rubber for oil fields: The other conditions are the same as those in Example 1, except that no macromolecular composite functionalized grafting agent is added during the preparation of tear-resistant and cold-resistant hydrogenated nitrile rubber for oil fields, but a macromolecular composite functionalized grafting agent a is added in an amount of 4.0 g, namely: first, 200 g of HNBR rubber is dissolved in a chlorobenzene solution to prepare a 6% glue solution by mass, and then the glue solution is added to a 10L stainless steel reactor with a jacket, and nitrogen is introduced for replacement 3 times, and then 4.0 g of macromolecular composite functionalized 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 0.40 g of DCP and 100 g of chlorobenzene is added, and after reacting for 12.0 hours, it is flocculated with anhydrous ethanol, washed, and dried in a 70°C oven to constant weight to obtain tear-resistant and cold-resistant hydrogenated nitrile rubber for oil fields (grafting rate 1.8%). Sampling and analysis: Standard samples were made and the tested properties are shown in Table 1.

[0125] Comparative Example 2

[0126] (1) Preparation of macromolecular composite functionalized grafting agent:

[0127] Preparation of macromolecular composite functional monomer a: The other conditions are the same as those in Example 2, except that 2,4,6-trihydroxyphenyl allyl ether is not added in the preparation of the macromolecular composite functional monomer, that is: in a 10L stainless steel polymerizer with a jacket, the system is replaced three times by passing argon gas, 2200g of cyclohexane, 320g of 4-hydroxy-3-alkoxy-1-propenylbenzene, and 3.5g of THF are added to the polymerizer in sequence, the temperature is raised to 72°C, and 316mmol of n-butyl lithium is added to the polymerizer for reaction for 92min; finally, 30g of 1,3-butadiene is added to the polymerizer for end-capping, and the reaction is carried out for 32min until no free monomer is present, and the colloid is wet-coagulated and dried to obtain macromolecular composite functional monomer b.

[0128] c Preparation of macromolecular composite functionalized grafting agent: Other conditions are the same as those in Example 2, except that in the preparation process of the macromolecular composite functionalized grafting agent, no macromolecular composite functionalized monomer is added, but macromolecular composite functionalized monomer b is added in an amount of 220 g, that is: in a 10L stainless steel polymerizer with a jacket, the system is replaced 3 times by argon, 2200 g cyclohexane, 1000 g p-methylstyrene, and 3.5 g THF are added to the polymerizer in sequence, and after the temperature is raised to 52° C., 207 mmol n-butyl lithium is added to start the reaction for 82 min to form p-methylstyrene segments; then 220 g macromolecular composite functionalized monomer b and 1200 g cyclohexane are mixed and stirred to dissolve for 82 min, until completely dissolved, the mixture is added to the polymerizer and the temperature is raised to 82° C., and the reaction is carried out for 82 min; finally, 26 g The 1,3-butadiene capping reaction was carried out for 32 minutes until no free monomer was present. The colloid was coagulated and dried by wet method to obtain a macromolecular composite functional grafting agent b (Mn was 6300).

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

[0130] a Preparation of hydrogenated nitrile rubber (HNBR): same as in Example 2.

[0131] b Preparation of tear-resistant and cold-resistant hydrogenated nitrile rubber for oil fields: The other conditions are the same as those in Example 2, except that no macromolecular composite functionalized grafting agent is added during the preparation of tear-resistant and cold-resistant hydrogenated nitrile rubber for oil fields, but a macromolecular composite functionalized grafting agent b is added in an amount of 5.5 g, namely: first, 200 g of HNBR rubber is dissolved in a chlorobenzene solution to form a glue solution with a mass fraction of 6.5%, and then the glue solution is added to a 10L stainless steel reactor with a jacket, and nitrogen is introduced for replacement 3 times, and then 5.5 g of macromolecular composite functionalized 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 0.52 g of DCP and 120 g of chlorobenzene is added, and after reacting for 12.2 hours, it is flocculated with anhydrous ethanol, washed, and dried in a 70°C oven to constant weight to obtain tear-resistant and cold-resistant hydrogenated nitrile rubber for oil fields (grafting rate 1.7%). Sampling and analysis: Standard samples were made and the tested properties are shown in Table 1.

[0132] Comparative Example 3

[0133] (1) Preparation of macromolecular composite functionalized grafting agent:

[0134] a Preparation of 2,4,6-trihydroxyphenyl allyl ether: same as Example 3.

[0135] b. Preparation of macromolecular composite functional monomer: Other conditions are the same as those in Example 3, except that 2,4,6-trihydroxyphenyl allyl ether is not added during the preparation of the macromolecular composite functional monomer, but 3,4-dihydroxystyrene is added in an amount of 660 g, that is, in a 10L stainless steel polymerizer with a jacket, the system is replaced 4 times by passing argon gas, 2400 g of cyclohexane, 340 g of 4-hydroxy-3-alkoxy-1-propenylbenzene, 660 g of 3,4-dihydroxystyrene, and 4.0 g of THF are added to the polymerizer in sequence, the temperature is raised to 74° C., and 309 mmol of n-butyl lithium is added to the polymerizer for reaction for 94 min; finally, 35 g of 1,3-butadiene is added to the polymerizer for end-capping, and the reaction is carried out for 34 min until no free monomer is present, and the colloid is wet-coagulated and dried to obtain a macromolecular composite functional monomer c.

[0136] Preparation of macromolecular composite functionalized grafting agent c: other conditions are the same as those in Example 3, except that macromolecular composite functionalized monomer is not added in the preparation process of macromolecular composite functionalized grafting agent, but macromolecular composite functionalized monomer c is added in an amount of 240 g, that is: in a 10L stainless steel polymerizer with a jacket, the system is replaced 4 times by argon, 2400 g cyclohexane, 1000 g p-methylstyrene, and 4.0 g THF are added to the polymerizer in sequence, and after heating to 54° C., 202 mmol n-butyl lithium is added to start the reaction for 84 min to form p-methylstyrene segments; then 240 g macromolecular composite functionalized monomer c and 1400 g cyclohexane are mixed and stirred to dissolve for 84 min, until completely dissolved, the mixture is added to the polymerizer and heated to 84° C., and the mixture is reacted for 84 min; finally, 30 g The 1,3-butadiene capping reaction was carried out for 34 minutes until no free monomer was present. The colloid was coagulated and dried by wet method to obtain a macromolecular composite functional grafting agent c (Mn was 7100).

[0137] (2) Preparation of tear-resistant and cold-resistant hydrogenated nitrile rubber for oil fields:

[0138] a. Preparation of hydrogenated nitrile rubber (HNBR): Same as Example 3.

[0139] b Preparation of tear-resistant and cold-resistant hydrogenated nitrile rubber for oil fields: The other conditions are the same as those in Example 3, except that no macromolecular composite functionalized grafting agent is added during the preparation of tear-resistant and cold-resistant hydrogenated nitrile rubber for oil fields, but a macromolecular composite functionalized grafting agent c is added in an amount of 6.3 g, namely: first, 200 g of HNBR rubber is dissolved in a chlorobenzene solution to form a glue solution with a mass fraction of 7.6%, 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 6.3 g of macromolecular composite functionalized 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 0.61 g of DCP and 140 g of chlorobenzene is added, and after reacting for 12.4 hours, it is flocculated with anhydrous ethanol, washed, and dried in an oven at 70°C to constant weight to obtain tear-resistant and cold-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.

[0140] Comparative Example 4

[0141] (1) Preparation of macromolecular composite functionalized grafting agent:

[0142] a Preparation of 2,4,6-trihydroxyphenyl allyl ether: same as Example 4.

[0143] b. Preparation of macromolecular composite functionalized grafting agent: Other conditions are the same as those in Example 4, except that no macromolecular composite functionalized monomer is added during the preparation of the macromolecular composite functionalized grafting agent, but 2,4,6-trihydroxyphenyl allyl ether is added in an amount of 260 g, that is: in a 10L stainless steel polymerizer with a jacket, the system is replaced 4 times by passing argon gas, 2600 g of cyclohexane, 1000 g of p-methylstyrene, and 4.5 g of THF are added to the polymerizer in sequence, and after heating to 56° C., 197 mmol of n-butyl lithium is added to start the reaction for 86 min to form p-methylstyrene segments; then 260 g of 2,4,6-trihydroxyphenyl allyl ether and 1600 g of cyclohexane are mixed and stirred to dissolve for 86 min, until completely dissolved, the mixture is added to the polymerizer and heated to 86° C., and the reaction is carried out for 86 min; finally, 35 g of The 1,3-butadiene capping reaction was carried out for 36 minutes until no free monomer was present. The colloid was coagulated and dried by wet method to obtain a macromolecular composite functional grafting agent d (Mn was 5600).

[0144] (2) Preparation of tear-resistant and cold-resistant hydrogenated nitrile rubber for oil fields:

[0145] a Preparation of hydrogenated nitrile rubber (HNBR): same as Example 4.

[0146] b Preparation of tear-resistant and cold-resistant hydrogenated nitrile rubber for oil fields: The other conditions are the same as those in Example 4, except that no macromolecular composite functionalized grafting agent is added during the preparation of tear-resistant and cold-resistant hydrogenated nitrile rubber for oil fields, but a macromolecular composite functionalized grafting agent d is added in an amount of 7.8 g, namely: first, 200 g of HNBR rubber is dissolved in a chlorobenzene solution to form a glue solution with a mass fraction of 7.9%, 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 7.8 g of macromolecular composite functionalized grafting agent d is added to the reactor, stirred and mixed, and heated. When the temperature of the reactor reaches 76°C, a mixed solution of 0.73 g of DCP and 160 g of chlorobenzene is added, and after reacting for 12.5 hours, it is flocculated with anhydrous ethanol, washed, and dried in an oven at 70°C to constant weight to obtain tear-resistant and cold-resistant hydrogenated nitrile rubber for oil fields (grafting rate 3.1%). Sampling and analysis: Standard samples were made and the tested properties are shown in Table 1.

[0147] Comparative Example 5

[0148] (1) Preparation of macromolecular composite functionalized grafting agent:

[0149] a Preparation of 2,4,6-trihydroxyphenyl allyl ether: same as Example 5.

[0150] b. Preparation of macromolecular composite functionalized monomer: same as Example 5.

[0151] c Preparation of macromolecular composite functionalized grafting agent: Other conditions are the same as those in Example 5, except that the amount of p-methylstyrene added during the preparation of the macromolecular composite functionalized grafting agent is 400.0 g, that is: in a 10L stainless steel polymerizer with a jacket, the system is replaced 5 times by argon, 2800 g cyclohexane, 400 g p-methylstyrene, and 5.2 g THF are added to the polymerizer in sequence, and after the temperature is raised to 57° C., 193 mmol n-butyl lithium is added to start the reaction for 88 min to form p-methylstyrene segments; then 280 g macromolecular composite functionalized monomer and 1800 g cyclohexane are mixed and stirred to dissolve for 88 min, until completely dissolved, the mixture is added to the polymerizer and the temperature is raised to 88° C., and the reaction is carried out for 88 min; finally, 40 g The 1,3-butadiene capping reaction was carried out for 38 minutes until no free monomer was present. The colloid was coagulated and dried by wet method to obtain a macromolecular composite functional grafting agent e (Mn was 6700).

[0152] (2) Preparation of tear-resistant and cold-resistant hydrogenated nitrile rubber for oil fields:

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

[0154] b Preparation of tear-resistant and cold-resistant hydrogenated nitrile rubber for oil fields: The other conditions are the same as those in Example 5, except that no macromolecular composite functionalized grafting agent is added during the preparation of tear-resistant and cold-resistant hydrogenated nitrile rubber for oil fields, but a macromolecular composite functionalized grafting agent e is added in an amount of 9.1 g, namely: first, 200 g of HNBR rubber is dissolved in a chlorobenzene solution to form a glue solution with a mass fraction of 8.4%, 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 9.1 g of macromolecular composite functionalized 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 0.84 g of DCP and 180 g of chlorobenzene is added, and after reacting for 12.7 hours, it is flocculated with anhydrous ethanol, washed, and dried in a 70°C oven to constant weight to obtain tear-resistant and cold-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.

[0155] Comparative Example 6

[0156] (1) Preparation of macromolecular composite functionalized grafting agent:

[0157] a Preparation of 2,4,6-trihydroxyphenyl allyl ether: same as Example 6.

[0158] b. Preparation of macromolecular composite functional monomer: Other conditions are the same as those in Example 6, except that 4-hydroxy-3-alkoxy-1-propenylbenzene is not added during the preparation of the macromolecular composite functional monomer, but N-(hydroxymethyl)acrylamide is added in an amount of 400 g, that is, in a 10L stainless steel polymerizer with a jacket, the system is replaced 5 times by argon, 3000 g of cyclohexane, 400 g of N-(hydroxymethyl)acrylamide, 600 g of 2,4,6-trihydroxyphenyl allyl ether, and 5.0 g of THF are added to the polymerizer in sequence, the temperature is raised to 80° C., and 289 mmol of n-butyl lithium is added to the polymerizer to react for 100 min; finally, 50 g of 1,3-butadiene is added to the polymerizer for end-capping, and the reaction is carried out for 40 min until no free monomer is present, and the colloid is wet-coagulated and dried to obtain a macromolecular composite functional monomer d.

[0159] c Preparation of macromolecular composite functionalized grafting agent: Other conditions are the same as those in Example 6, except that in the preparation process of the macromolecular composite functionalized grafting agent, no macromolecular composite functionalized monomer is added, but macromolecular composite functionalized monomer d is added in an amount of 300 g, that is: in a 10L stainless steel polymerizer with a jacket, the system is replaced 5 times by passing argon gas, 3000 g cyclohexane, 1000 g p-methylstyrene, and 6.0 g THF are added to the polymerizer in sequence, and after heating to 60° C., 187 mmol n-butyl lithium is added to start the reaction for 90 min to form p-methylstyrene segments; then 300 g macromolecular composite functionalized monomer d and 2000 g cyclohexane are mixed and stirred to dissolve for 90 min, until completely dissolved, the mixture is added to the polymerizer and heated to 90° C., and the mixture is reacted for 90 min; finally, 50 g The 1,3-butadiene capping reaction was carried out for 40 minutes until no free monomer was present. The colloid was coagulated and dried by wet method to obtain a macromolecular composite functional grafting agent f (Mn was 7200).

[0160] (2) Preparation of tear-resistant and cold-resistant hydrogenated nitrile rubber for oil fields:

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

[0162] b Preparation of tear-resistant and cold-resistant hydrogenated nitrile rubber for oil fields: The other conditions are the same as those in Example 6, except that no macromolecular composite functionalized grafting agent is added during the preparation of tear-resistant and cold-resistant hydrogenated nitrile rubber for oil fields, but a macromolecular composite functionalized grafting agent f is added in an amount of 10.0 g, namely: first, 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 10.0 g of macromolecular composite functionalized 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 1.00 g of DCP and 200 g of chlorobenzene is added, and after reacting for 13.0 hours, it is flocculated with anhydrous ethanol, washed, and dried in a 70°C oven to constant weight to obtain tear-resistant and cold-resistant hydrogenated nitrile rubber for oil fields (grafting rate 3.1%). Sampling and analysis: Standard samples were made and the tested properties are shown in Table 1.

[0163] Table 1 Properties of tear-resistant and cold-resistant hydrogenated nitrile rubber for oil fields

[0164]

[0165]

[0166] It can be seen from Table 1 that the tear-resistant and cold-resistant hydrogenated nitrile rubber for oil fields of the present invention has high tear strength and low glass transition temperature, and is suitable for oil well operation requirements of submersible screw pump stator rubber materials under working conditions of tear strength ≥ 74KN / m and ambient temperature at a low temperature of -75°C.

[0167] 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 tear-resistant and cold-resistant hydrogenated nitrile rubber for oil fields, characterized in that: The steps include: (1) Preparation of macromolecular composite functionalized grafting agent: a Preparation of 2,4,6-trihydroxyphenyl allyl ether: In a polymerization kettle, argon gas is introduced for replacement, deionized water, 2,4,6-tribromophenyl allyl ether, and NaOH aqueous solution are added to the polymerization kettle in sequence, stirred, mixed, heated, heated, reacted, and finally extracted, separated, washed, and dried to obtain 2,4,6-trihydroxyphenyl allyl ether; b. Preparation of macromolecular composite functional monomer: In a polymerization kettle, argon gas is introduced to replace the system, and a solvent, 4-hydroxy-3-alkoxy-1-propenylbenzene, 2,4,6-trihydroxyphenyl allyl ether, and a structure regulator are added to the polymerization kettle in sequence, and the temperature is raised, and then initiator 1 is added to the polymerization kettle for reaction; finally, 1,3-butadiene is added to the polymerization kettle for end-capping, and the reaction is continued until no free monomer exists. The gel solution is wet-coagulated and dried to obtain a macromolecular composite functional monomer; c Preparation of macromolecular composite functionalized grafting agent: In a polymerization kettle, argon gas is introduced to replace the system, and a solvent, p-alkylstyrene, and a structure regulator are sequentially added to the polymerization kettle, the temperature is raised, and an initiator 1 is added to react to form a p-alkylstyrene homopolymer segment; then, the macromolecular composite functionalized monomer and the solution are mixed and stirred to dissolve, and the mixture is added to the polymerization kettle until it is completely dissolved and then heated to react; finally, 1,3-butadiene is added to the polymerization kettle for end-capping, and the reaction is carried out until no free monomer exists, and the glue solution is wet-coagulated and dried to obtain a macromolecular composite functionalized grafting agent; (2) Preparation of tear-resistant and cold-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 and introduce inert gas to remove the air in the reactor, then remove the inert gas in the reactor with hydrogen, add a xylene solution of Grubbs I catalyst under nitrogen protection, pressurize, heat up, after reaction, cool the system, condense, and vacuum dry to obtain HNBR rubber (hydrogenation degree HD<90%); b. Preparation of tear-resistant and cold-resistant hydrogenated nitrile rubber for oil fields: HNBR rubber is dissolved in chlorobenzene solution to prepare a glue solution, and then the glue solution is added to a reactor, and an inert gas is introduced for replacement, and then a macromolecular composite functionalized grafting agent is added to the reactor, stirred and mixed, heated, and a mixed solution of initiator 2 and chlorobenzene is added. After the reaction, flocculation, washing, and drying are performed to obtain tear-resistant and cold-resistant hydrogenated nitrile rubber for oil fields; The macromolecular composite functionalized grafting agent has the following structure: Among them, R is a straight-chain alkyl of C1 to C6; B is end-capped 1,3-butadiene; n and m are positive integers of the number of repeating units, n≥1, m≥1; and the number average molecular weight (Mn) of the macromolecular composite functionalized grafting agent is 7000 to 8000.

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

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

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

5. The preparation method according to claim 1, characterized in that: The initiator 2 is selected from one of diacetyl peroxide, diisobutyryl peroxide, cumene hydroperoxide, dicumyl peroxide (DCP) and dibenzoyl peroxide (BPO), and its addition amount is 0.2-0.5 parts based on 100 parts of the mass of the HNBR rubber.

6. 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%.

7. 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.

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

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

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

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

12. The preparation method according to claim 1, characterized in that: In step (1) (c), the mass ratio of the solvent, p-alkylstyrene, structure regulator, macromolecular composite functional monomer, solution and 1,3-butadiene is 200-300:100:0.3-0.6:20-30:100-200:2-5.

13. 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.

14. 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%.

15. The preparation method according to claim 1, characterized in that: In step (2) b, the mass ratio of the HNBR rubber, the macromolecular composite functionalized grafting agent, and chlorobenzene is 100:2-5:50-100.

16. The preparation method according to claim 1, characterized in that: In step (2) b, the grafting rate of the tear-resistant and cold-resistant hydrogenated nitrile rubber for oil fields is 1.8% to 3.9%.

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

Images