Special hydrogenated butadiene-acrylonitrile rubber for oil field and preparation method of special hydrogenated butadiene-acrylonitrile rubber

Abstract

The invention discloses special hydrogenated butadiene-acrylonitrile rubber for an oil field and a preparation method of the special hydrogenated butadiene-acrylonitrile rubber. The preparation method comprises the following steps: (1) preparing a macromolecular three-arm star-shaped composite functional grafting agent; and (2) preparing the special hydrogenated butadiene-acrylonitrile rubber for the oil field. The macromolecular three-arm star-shaped composite functional grafting agent has the following structure: # imgabs0 #, wherein R is straight-chain alkyl of C1-C6; bR is a homopolymer segment with wide vinyl distribution of 1, 3-butadiene; 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 three-arm star-shaped composite functional grafting agent is 7000 to 8000, and the molecular weight distribution (Mw / Mn) of the macromolecular three-arm star-shaped composite functional grafting agent is 9.26 to 10.92. The preparation method of the special 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 specifically relates to a macromolecular three-arm star-shaped composite functionalized grafting agent for preparing a special hydrogenated nitrile rubber for oil fields and a preparation method thereof. Background Art

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

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

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

[0005] CN 106349410 B discloses a special hydrogenated nitrile rubber with compression cold resistance and a preparation method thereof, wherein the rubber main chain contains epoxy groups, and some 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 includes introducing epoxy groups into the main chain of the rubber molecule, and then reacting some of the epoxy groups with acid anhydride under the action of a catalyst to introduce ester groups to obtain a special hydrogenated nitrile rubber containing epoxy groups and ester groups. CN 105294939 B 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 a special hydrogenated nitrile rubber for oil fields with a raw rubber tear strength of ≥71KN / m, compression permanent deformation resistance of ≤15% and glass transition temperature Tg<-73℃. The invention firstly hydrolyzes 2,4,6-tribromophenyl allyl ether to synthesize 2,4,6-trihydroxyphenyl allyl ether, and then prepares a macromolecular composite functional monomer with 4-hydroxy-3-alkoxy-1-propenylbenzene; secondly, the macromolecular composite functional monomer is reacted with para-alkylstyrene and 1,3-butadiene to prepare a macromolecular three-arm star-shaped composite functional grafting agent with a wide vinyl distribution through variable temperature polymerization and coupling reaction. The grafting agent gives hydrogenated nitrile rubber very excellent tear strength, deformation resistance and cold resistance, and achieves a balance between the mechanical properties, deformation resistance and cold resistance of hydrogenated nitrile rubber, and is very suitable for the stator rubber material of submersible screw pumps that require tear resistance and compression resistance in oil well operations under low temperature conditions.

[0008] Unless otherwise specified, the “parts” described in the present invention refer to parts by mass, the “%” described refers to mass percentage, and the “ratio” described refers to mass ratio.

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

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

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

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

[0013] c Preparation of macromolecular three-arm star-shaped composite functionalized grafting agent In a polymerization kettle, argon is introduced to replace the system, and a solvent, p-alkylstyrene, and a first structural 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 1,3-butadiene and a second structural regulator are sequentially added to the polymerization kettle, the temperature is raised, and the reaction is a variable temperature polymerization. Within 40 to 60 minutes, the temperature gradually rises from 60°C to 90°C to form a BR segment with a wide vinyl distribution; then the macromolecular composite functionalized monomer and the solution are mixed and stirred to dissolve, and then added to the polymerization kettle until they are completely dissolved and reacted; the temperature is raised, and a coupling agent is added to carry out a coupling reaction; finally, 1,3-butadiene is added to the polymerization kettle for end-capping, and the reaction is carried out until there is no free monomer. After the reaction is completed, the reaction mixture after coupling is treated with water, and the glue solution is wet-coagulated and dried to obtain a macromolecular three-arm star-shaped composite functionalized grafting agent;

[0014] (2) Preparation of special 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;

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

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

[0018]

[0019] Among them, R is a straight-chain alkyl group of C1 to C6; BR is a homopolymer segment of 1,3-butadiene with a wide vinyl distribution; B is end-capped 1,3-butadiene; n and m are the number of repeating units, and n≥1, m≥1 are positive integers; the number average molecular weight (Mn) of the macromolecular three-arm star-shaped composite functionalized grafting agent is 7000 to 8000, and the molecular weight distribution (Mw / Mn) is 9.26 to 10.92.

[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 of 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 the added amount is 0.1 to 0.3 parts based on 100 parts by mass of the HNBR rubber.

[0024] The coupling agent of the present invention is one of 1,3,5-trichlorobenzene and 1,3,5-tribromobenzene, preferably 1,3,5-trichlorobenzene. The amount of the coupling agent used depends on the amount of the initiator 1. The excess coupling agent is gradually polymerized to eventually form a star polymer with a hetero-arm structure. The molar ratio of the total amount of the initiator 1 to the coupling agent is 3.0 to 4.0.

[0025] 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%.

[0026] 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).

[0027] The solvent or solution of the present invention can be selected from one of cyclohexane, carbon disulfide (CS2), nitrobenzene, petroleum ether, tetrachloroethane, toluene and xylene, preferably cyclohexane.

[0028] 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.

[0029] In step (1) a of the present invention, the mass concentration of the NaOH aqueous solution is 10% to 20%.

[0030] In step (1) a of the present invention, the temperature is raised to 130-140° C. and the reaction time is 6-8 hr.

[0031] In step (1) a of the present invention, the yield of 2,4,6-trihydroxyphenyl allyl ether is 80% to 83%.

[0032] 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.

[0033] In step (1) b of the present invention, the temperature is raised to 70-80° C.; the reaction time after adding initiator 1 is 90-100 min; and the reaction time after adding 1,3-butadiene for end-capping is 30-40 min.

[0034] In step (1) of the present invention, in the process of forming the BR segment with a wide vinyl distribution, the mass ratio of the solvent, p-alkylstyrene, the first structural regulator, 1,3-butadiene, and the second structural regulator is 200-300:100:0.3-0.6:50-60:0.05-0.1;

[0035] During the end-capping process, the mass ratio of the macromolecular composite functionalized monomer, the solution, and 1,3-butadiene is 5-10:100-200:2-5.

[0036] In step (1) c of the present invention, the temperature is raised to 50-60° C. before adding the initiator 1; and the reaction time after adding the initiator 1 is 80-90 min.

[0037] In step (1) of the present invention, the stirring and dissolving time is 80 to 90 minutes.

[0038] In step (1) c of the present invention, the reaction time after adding the macromolecular composite functionalized monomer and the solution is 80 to 90 minutes.

[0039] In step (1) of the present invention, the temperature is raised to 90-100° C. before adding the coupling agent; and the time for adding the coupling agent to carry out the coupling reaction is 80-90 minutes.

[0040] In step (1) of the present invention, the reaction time for adding 1,3-butadiene for end-capping is 30 to 40 minutes.

[0041] 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.

[0042] In step (2) a of the present invention, the mass fraction of nitrile rubber in the rubber solution is 3% to 6%.

[0043] 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%.

[0044] 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.

[0045] In step (2) a of the present invention, the degree of hydrogenation HD of the HNBR rubber is less than 90%.

[0046] In step (2) b of the present invention, the mass ratio of the HNBR rubber, the macromolecular three-arm star-shaped composite functionalized grafting agent, and chlorobenzene is 100:2-5:50-100.

[0047] In step (2) b of the present invention, the mass fraction of HNBR rubber in the rubber solution is 6% to 9%.

[0048] In step (2) b of the present invention, the heating temperature is 80-90° C. and the reaction time is 10.0-12.0 hr.

[0049] In step (2) b of the present invention, the grafting rate of the special hydrogenated nitrile rubber for oil fields is 1.9% to 3.7%.

[0050] 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.

[0051] The reactor described in the present invention can be a loop reactor or a tank reactor, preferably a tank reactor.

[0052] 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.

[0053] The present invention also provides a special hydrogenated nitrile rubber for oil fields obtained by the preparation method.

[0054] Compared with the prior art, the present invention has at least the following advantages and beneficial effects:

[0055] (1) The macromolecular composite functional monomer prepared by the present invention is prepared by anionic polymerization of 2,4,6-trihydroxyphenyl allyl ether and 4-hydroxy-3-alkoxy-1-propenylbenzene. This monomer integrates alkoxy, polyhydroxy and ether groups on a macromolecular chain, fully utilizing the "aggregation effect" of macromolecules and the "group effect" of ether, polyhydroxy and alkoxy groups, and can effectively destroy the crystallinity of HNBR, and can prepare a special hydrogenated nitrile rubber for oil fields with a glass transition temperature Tg<-73°C of raw rubber, which can meet the requirements of oil well operation under low temperature conditions of -73°C.

[0056] (2) The macromolecular three-arm star-shaped composite functionalized grafting agent prepared by the present invention integrates the alkylstyrene homopolymer chain segment and the macromolecular composite functionalized long-chain monomer on a macromolecular chain, and fully utilizes the "aggregation effect" of the alkylbenzene in the alkylbenzene homopolymer and the "group effect" of the phenyl group in the macromolecular composite functionalized monomer to produce a certain "synergistic effect", thereby avoiding the destruction of the crystallinity of HNBR due to the macromolecular composite functionalized monomer, thereby causing the tear strength of HNBR to decrease, and at the same time, it can more effectively improve the tear strength of HNBR, and can prepare a special hydrogenated nitrile rubber for oil fields with a raw rubber tear strength of ≥71KN / m, which can meet the tear strength requirements of the stator rubber material of the submersible screw pump during oil well operation.

[0057] (3) The macromolecular three-arm star-shaped composite functionalized grafting agent prepared by the present invention increases the disorder of the HNBR molecular chain segment through the design of the three-arm star-shaped structure and the wide vinyl distribution in the BR chain segment. The widening of the molecular weight distribution ensures that HNBR can obtain good viscoelastic properties and greatly improves the compression permanent deformation resistance of HNBR. It can prepare special hydrogenated nitrile rubber for oil fields with a compression permanent deformation of raw rubber ≤15%, which can meet the compression resistance requirements of the stator rubber material of the submersible screw pump during oil well operation.

[0058] (4) The macromolecular three-arm star-shaped composite functionalized grafting agent prepared by the present invention can significantly improve the tear strength, compression permanent deformation resistance and lower the glass transition temperature (Tg) of HNBR with a low addition amount, and achieve a good "synergistic effect" in achieving a balanced relationship between the tear strength, compression resistance and cold resistance of HNBR.

[0059] (5) The preparation method of the special 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. BRIEF DESCRIPTION OF THE DRAWINGS

[0060] Figure 1 This is the infrared spectrum of the macromolecular three-arm star-shaped composite functionalized grafting agent in Example 1. DETAILED DESCRIPTION

[0061] 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.

[0062] (1) Source of raw materials:

[0063] Nitrile rubber 2907, acrylonitrile content 27% to 30%, PetroChina Lanzhou Petrochemical Company

[0064] 1,3-Butadiene, purity 99%, PetroChina Lanzhou Petrochemical Company

[0065] Styrene, purity 99%, PetroChina Lanzhou Petrochemical Company

[0066] 2,4,6-Tribromophenyl allyl ether, purity 98%, Hubei Shineng Chemical Technology Co., Ltd.

[0067] 4-Hydroxy-3-ethoxy-1-propenylbenzene, purity 99%, Shanghai Meixin Chemical Technology Co., Ltd.

[0068] p-Methylstyrene, purity 99%, Shandong No.1 Chemical Group Co., Ltd.

[0069] GrubbsⅠcatalyst, purity 99%, Hubei Xinyuhong Biopharmaceutical Technology Co., Ltd.

[0070] Dicumyl peroxide (DCP), Lanzhou Additive Factory

[0071] Other reagents are commercially available industrial products.

[0072] (2) Analytical testing methods:

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

[0074]

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

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

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

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

[0079] Infrared spectral analysis of samples: The functional group analysis of nano-silica before and after modification was performed using an infrared spectrometer from German Bruke Spectroscopy Instruments. The samples were dried in a vacuum oven at 100°C, pressed into tablets using potassium bromide, and the wave number range was 400-4000cm- 1 .

[0080] 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.

[0081] Tear strength: Execute the method in standard GB / T 529-2009.

[0082] Compression set: Execute the method in standard GB / T 7759.1-2015.

[0083] Example 1

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

[0085] 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%).

[0086] 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.

[0087] Preparation of macromolecular three-arm star-shaped composite functionalized grafting agent: In a 10L stainless steel polymerizer with a jacket, argon was passed through the system to replace it 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, 200mmol n-butyl lithium was added to start the reaction for 80min to form p-methylstyrene segments; then 500g 1,3-butadiene and 0.5g THF were added to the polymerizer in sequence, and after the temperature was raised to 60°C, the temperature was gradually raised from 60°C to 90°C within 40min of reaction time to form BR segments with wide vinyl distribution; then 50g macromolecular composite functionalized monomer and 1000g cyclohexane were mixed and stirred to dissolve for 80min, and then added to the polymerizer to react for 80min after complete dissolution; then the temperature was raised to 90°C, 65mmol 1,3,5-trichlorobenzene, coupling reaction for 80 minutes; finally, 20g 1,3-butadiene was added to the polymerization kettle for end-capping reaction for 30 minutes until no free monomers were present. The gel was wet-coagulated and dried to obtain a macromolecular three-arm star-shaped composite functionalized grafting agent (Mn was 7000, Mw / Mn was 9.26).

[0088] (2) Preparation of special 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 3% rubber solution by mass, and then the rubber solution was added to a 10L high-pressure reactor and nitrogen was introduced to remove the air in the reactor. Then, the nitrogen in the reactor was removed with hydrogen for 30 minutes, and then 0.02g of GrubbsⅠ catalyst xylene solution (mass concentration of 5%) was added under nitrogen protection. The hydrogen pressure in the pressurized reactor was 11MPa, the temperature was raised to 100℃, and after reacting for 9.0hr, the system was cooled, condensed, and vacuum dried to obtain HNBR rubber (hydrogenation degree HD=84.1%).

[0090] b Preparation of special hydrogenated nitrile rubber for oil fields: First, 200g of HNBR rubber was dissolved in chlorobenzene solution to prepare a 6% glue solution by mass, and then the glue solution was added to a 10L stainless steel reactor with a jacket, and nitrogen was introduced for replacement 3 times, and then 4.0g of a macromolecular three-arm star-shaped composite functionalized grafting agent was added to the reactor, stirred and mixed, and heated. When the temperature of the reactor reached 80°C, a mixed solution of 0.20g of DCP and 100g of chlorobenzene was added. After reacting for 10.0hr, it was flocculated with anhydrous ethanol, washed, and dried in a 70°C oven to constant weight to obtain a special hydrogenated nitrile rubber for oil fields (grafting rate 1.9%).

[0091] Example 2

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

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

[0094] b. Preparation of macromolecular composite 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.

[0095] Preparation of macromolecular three-arm star-shaped composite functionalized grafting agent: In a 10L stainless steel polymerizer with a jacket, argon was passed through the system to replace it three times, and 2200g cyclohexane, 1000g p-methylstyrene, and 4.0g THF were added to the polymerizer in sequence. After the temperature was raised to 52°C, 196mmol n-butyl lithium was added to start the reaction for 82min to form p-methylstyrene segments; then 520g 1,3-butadiene and 0.6g THF were added to the polymerizer in sequence. After the temperature was raised to 60°C, the temperature was gradually raised from 60°C to 90°C within 45min of reaction time to form BR segments with wide vinyl distribution; then 60g macromolecular composite functionalized monomer and 1200g cyclohexane were mixed and stirred to dissolve for 82min, until they were completely dissolved and added to the polymerizer to react for 82min; then the temperature was raised to 92°C, 62mmol n-butyl lithium was added to the polymerizer, and the reaction mixture was stirred to dissolve for 82min. 1,3,5-trichlorobenzene, coupling reaction for 82 minutes; finally, 30g 1,3-butadiene was added to the polymerization kettle for end-capping reaction for 32 minutes until no free monomer was present. The gel was wet-coagulated and dried to obtain a macromolecular three-arm star-shaped composite functionalized grafting agent (Mn was 7100, Mw / Mn was 9.41).

[0096] (2) Preparation of special hydrogenated nitrile rubber for oil fields:

[0097] a. Preparation of hydrogenated nitrile rubber (HNBR): Same as in Example 1.

[0098] b Preparation of special hydrogenated nitrile rubber for oil fields: First, 200g of HNBR rubber was dissolved in chlorobenzene solution to prepare a 6.6% 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 5.0g of a macromolecular three-arm star-shaped composite functionalized grafting agent was added to the reactor, stirred and mixed, and heated. When the temperature of the reactor reached 82°C, a mixture of 0.31g of DCP and 120g of chlorobenzene was added. After reacting for 10.4 hours, it was flocculated with anhydrous ethanol, washed, and dried in a 70°C oven to constant weight to obtain a special hydrogenated nitrile rubber for oil fields (grafting rate 2.3%).

[0099] Example 3

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

[0101] a Preparation of 2,4,6-trihydroxyphenyl allyl ether: same as Example 1.

[0102] 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.

[0103] Preparation of macromolecular three-arm star-shaped composite functionalized grafting agent: In a 10L stainless steel polymerizer with a jacket, argon was passed through the system to replace it 4 times, and 2400g cyclohexane, 1000g p-methylstyrene, and 4.0g THF were added to the polymerizer in sequence. After the temperature was raised to 54°C, 190mmol n-butyl lithium was added to start the reaction for 84min to form p-methylstyrene segments; then 540g 1,3-butadiene and 0.7g THF were added to the polymerizer in sequence, and after the temperature was raised to 60°C, the temperature was gradually raised from 60°C to 90°C within 50min reaction time to form BR segments with wide vinyl distribution; then 70g macromolecular composite functionalized monomer and 1400g cyclohexane were mixed and stirred to dissolve for 84min, until they were completely dissolved and added to the polymerizer to react for 84min; then the temperature was raised to 94°C, 59mmol n-butyl lithium was added to the polymerizer and the reaction mixture was stirred to dissolve for 84min. 1,3,5-trichlorobenzene, coupling reaction for 84 minutes; finally, 35g 1,3-butadiene was added to the polymerization kettle for end-capping reaction for 34 minutes until no free monomer was present. The gel was wet-coagulated and dried to obtain a macromolecular three-arm star-shaped composite functionalized grafting agent (Mn was 7400, Mw / Mn was 9.89).

[0104] (2) Preparation of special hydrogenated nitrile rubber for oil fields:

[0105] a. Preparation of hydrogenated nitrile rubber (HNBR): Same as in Example 1.

[0106] b Preparation of special hydrogenated nitrile rubber for oil fields: First, 200g of HNBR rubber was dissolved in chlorobenzene solution to prepare a 7.5% 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 4 times. Then 7.0g of a macromolecular three-arm star-shaped composite functionalized grafting agent was added to the reactor, stirred, mixed, and heated. When the temperature of the reactor reached 84°C, a mixture of 0.39g of DCP and 140g of chlorobenzene was added. After reacting for 10.9 hours, it was flocculated with anhydrous ethanol, washed, and dried in a 70°C oven to constant weight to obtain a special hydrogenated nitrile rubber for oil fields (grafting rate 2.8%).

[0107] Example 4

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

[0109] 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%).

[0110] 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.

[0111] Preparation of macromolecular three-arm star-shaped composite functionalized grafting agent: In a 10L stainless steel polymerizer with a jacket, argon was passed through the system to replace it 4 times, and 2600g cyclohexane, 1000g p-methylstyrene, and 4.5g THF were added to the polymerizer in sequence. After the temperature was raised to 56°C, 185mmol n-butyl lithium was added to start the reaction for 86min to form p-methylstyrene segments; then 560g 1,3-butadiene and 0.8g THF were added to the polymerizer in sequence. After the temperature was raised to 60°C, the temperature was gradually raised from 60°C to 90°C within 52min of reaction time to form BR segments with wide vinyl distribution; then 80g macromolecular composite functionalized monomer and 1600g cyclohexane were mixed and stirred to dissolve for 86min until they were completely dissolved and then added to the polymerizer to react for 86min; then the temperature was raised to 96°C and 56mmol n-butyl lithium was added to the polymerizer to react for 86min. 1,3,5-trichlorobenzene, coupling reaction for 86 minutes; finally, 40g 1,3-butadiene was added to the polymerization kettle for end-capping reaction for 34 minutes until no free monomer was present. The gel was wet-coagulated and dried to obtain a macromolecular three-arm star-shaped composite functionalized grafting agent (Mn was 7500, Mw / Mn was 10.21).

[0112] (2) Preparation of special hydrogenated nitrile rubber for oil fields:

[0113] 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%).

[0114] b Preparation of special hydrogenated nitrile rubber for oil fields: First, 200g of 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. Then 8.0g of a macromolecular three-arm star-shaped composite functionalized grafting agent was added to the reactor, stirred and mixed, and heated. When the temperature of the reactor reached 86°C, a mixture of 0.46g of DCP and 160g of chlorobenzene was added. After reacting for 11.4 hours, it was flocculated with anhydrous ethanol, washed, and dried in a 70°C oven to constant weight to obtain a special hydrogenated nitrile rubber for oil fields (grafting rate 3.1%).

[0115] Example 5

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

[0117] a Preparation of 2,4,6-trihydroxyphenyl allyl ether: same as Example 4.

[0118] 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.

[0119] Preparation of macromolecular three-arm star-shaped composite functionalized grafting agent: In a 10L stainless steel polymerizer with a jacket, argon was passed through the system to replace the system 5 times, and 2800g cyclohexane, 1000g p-methylstyrene, and 5.0g THF were added to the polymerizer in sequence. After the temperature was raised to 58°C, 181mmol n-butyl lithium was added to start the reaction for 88min to form p-methylstyrene segments; then 580g 1,3-butadiene and 0.9g THF were added to the polymerizer in sequence. After the temperature was raised to 60°C, the temperature was gradually raised from 60°C to 90°C within 56min of reaction time to form BR segments with wide vinyl distribution; then 90g macromolecular composite functionalized monomer and 1800g cyclohexane were mixed and stirred to dissolve for 88min until they were completely dissolved and then added to the polymerizer to react for 88min; then the temperature was raised to 98°C and 53mmol n-butyl lithium was added to the polymerizer to react for 88min. 1,3,5-trichlorobenzene, coupling reaction for 88 minutes; finally, 45g 1,3-butadiene was added to the polymerization kettle for end-capping reaction for 38 minutes until no free monomer was present. The gel was wet-coagulated and dried to obtain a macromolecular three-arm star-shaped composite functionalized grafting agent (Mn was 7800, Mw / Mn was 10.56).

[0120] (2) Preparation of special hydrogenated nitrile rubber for oil fields:

[0121] a Preparation of hydrogenated nitrile rubber (HNBR): same as Example 4.

[0122] b Preparation of special hydrogenated nitrile rubber for oil fields: First, 200g of 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. Then 9.0g of a macromolecular three-arm star-shaped composite functionalized grafting agent was added to the reactor, stirred and mixed, and heated. When the temperature of the reactor reached 86°C, a mixture of 0.52g of DCP and 180g of chlorobenzene was added. After reacting for 11.7 hours, it was flocculated with anhydrous ethanol, washed, and dried in a 70°C oven to constant weight to obtain a special hydrogenated nitrile rubber for oil fields (grafting rate 3.5%).

[0123] Example 6

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

[0125] a Preparation of 2,4,6-trihydroxyphenyl allyl ether: same as Example 4.

[0126] 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.

[0127] Preparation of macromolecular three-arm star-shaped composite functionalized grafting agent: In a 10L stainless steel polymerizer with a jacket, argon was passed through the system to replace the system 5 times, and 3200g cyclohexane, 1000g p-methylstyrene, and 6.0g THF were added to the polymerizer in sequence. After the temperature was raised to 60°C, 176mmol n-butyl lithium was added to start the reaction for 90min to form p-methylstyrene segments; then 600g 1,3-butadiene and 1.0g THF were added to the polymerizer in sequence. After the temperature was raised to 60°C, the temperature was gradually raised from 60°C to 90°C within 60min reaction time to form BR segments with wide vinyl distribution; then 100g macromolecular composite functionalized monomer and 2000g cyclohexane were mixed and stirred to dissolve for 90min, and then added to the polymerizer for reaction for 90min after complete dissolution; then the temperature was raised to 100°C, 49mmol 1,3,5-trichlorobenzene, coupling reaction for 90 minutes; finally, 50g 1,3-butadiene was added to the polymerization kettle for end-capping reaction for 40 minutes until no free monomers were present. The gel was wet-coagulated and dried to obtain a macromolecular three-arm star-shaped composite functionalized grafting agent (Mn was 8000, Mw / Mn was 10.92).

[0128] (2) Preparation of special hydrogenated nitrile rubber for oil fields:

[0129] a Preparation of hydrogenated nitrile rubber (HNBR): same as Example 4.

[0130] b Preparation of special hydrogenated nitrile rubber for oil fields: First, 200g of HNBR rubber was dissolved in chlorobenzene solution to prepare a 9.0% glue solution by mass, and then the glue solution was added to a 10L stainless steel reactor with a jacket, and nitrogen was introduced for replacement 5 times, and then 10.0g of a macromolecular three-arm star-shaped composite functionalized grafting agent was added to the reactor, stirred and mixed, and heated. When the temperature of the reactor reached 90°C, a mixed solution of 0.60g of DCP and 200g of chlorobenzene was added. After reacting for 12.0 hours, it was flocculated with anhydrous ethanol, washed, and dried in a 70°C oven to constant weight to obtain a special hydrogenated nitrile rubber for oil fields (grafting rate 3.7%).

[0131] Comparative Example 1

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

[0133] a Preparation of 2,4,6-trihydroxyphenyl allyl ether: same as Example 1.

[0134] b. Preparation of macromolecular composite functionalized monomer: Same as Example 1.

[0135] c Preparation of macromolecular three-arm star-shaped composite functionalized grafting agent: Other conditions are the same as those in Example 1, except that variable temperature polymerization is not used in the preparation of macromolecular three-arm star-shaped composite functionalized grafting agent, namely: in a 10L stainless steel polymerization kettle with a jacket, argon gas is passed through the system to replace the system three times, 2000g cyclohexane, 1000g p-methylstyrene, and 3.0g THF are added to the polymerization kettle in sequence, and after heating to 50°C, 200mmol n-butyl lithium is added to start the reaction for 80min to form p-methylstyrene segments; then 500g 1,3-butadiene and 0.5g THF are added to the polymerization kettle in sequence, the temperature is raised to 60°C, and the reaction is carried out for 40min to form BR segments; then 50g macromolecular composite functionalized monomer and 1000g cyclohexane are mixed and stirred to dissolve for 80min, until they are completely dissolved, and then added to the polymerization kettle to react for 80min; then the temperature is raised to 90°C, 65mmol n-butyl lithium is added 1,3,5-trichlorobenzene, coupling reaction for 80 minutes; finally, 20g 1,3-butadiene was added to the polymerization kettle for end-capping reaction for 30 minutes until no free monomer was present. The gel was wet-coagulated and dried to obtain a macromolecular three-arm star-shaped composite functionalized grafting agent a (Mn was 6900, Mw / Mn was 7.14).

[0136] (2) Preparation of special hydrogenated nitrile rubber for oil fields:

[0137] a. Preparation of hydrogenated nitrile rubber (HNBR): Same as in Example 1.

[0138] b Preparation of special hydrogenated nitrile rubber for oil fields: The other conditions are the same as those in Example 1, except that a macromolecular three-arm star-shaped composite functionalized grafting agent is not added during the preparation of the special hydrogenated nitrile rubber for oil fields, but a macromolecular three-arm star-shaped 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 form a 6% glue solution by mass, and then the glue solution is added to a 10L stainless steel reactor with a jacket, and nitrogen is introduced for replacement 3 times, and then 4.0 g of a macromolecular three-arm star-shaped composite functionalized grafting agent a is added to the reactor, stirred and mixed, and heated. When the reactor temperature reaches 80°C, a mixed solution of 0.20 g of DCP and 100 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 a special hydrogenated nitrile rubber for oil fields (grafting rate 1.8%).

[0139] Comparative Example 2

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

[0141] a Preparation of 2,4,6-trihydroxyphenyl allyl ether: same as Example 2.

[0142] b. Preparation of macromolecular composite functionalized monomer: same as Example 2.

[0143] c Preparation of macromolecular three-arm star-shaped composite functionalized grafting agent: The other conditions are the same as those in Example 2, except that 1,3-butadiene is not added during the preparation of the macromolecular three-arm star-shaped composite functionalized grafting agent, that is: in a 10L stainless steel polymerizer with a jacket, the system is replaced three times by passing argon gas, 2200g cyclohexane, 1000g p-methylstyrene, and 4.0g THF are added to the polymerizer in sequence, and after the temperature is raised to 52°C, 196mmol n-butyl lithium is added to start the reaction for 82min to form p-methylstyrene segments; then 0.6g THF is added to the polymerizer in sequence, and after the temperature is raised to 60°C, the temperature is gradually raised from 60°C to 90°C within a reaction time of 45min; then 60g macromolecular composite functionalized monomer and 1200g cyclohexane are mixed and stirred to dissolve for 82min, until they are completely dissolved and then added to the polymerizer for reaction for 82min; then the temperature is raised to 92°C, 62mmol n-butyl lithium is added 1,3,5-trichlorobenzene, coupling reaction for 82 minutes; finally, 30g 1,3-butadiene was added to the polymerization kettle for end-capping reaction for 32 minutes until no free monomer was present. The gel was wet-coagulated and dried to obtain a macromolecular three-arm star-shaped composite functionalized grafting agent b (Mn was 6200, Mw / Mn was 6.75).

[0144] (2) Preparation of special hydrogenated nitrile rubber for oil fields:

[0145] a Preparation of hydrogenated nitrile rubber (HNBR): same as in Example 2.

[0146] b Preparation of special hydrogenated nitrile rubber for oil fields: The other conditions are the same as those in Example 2, except that no macromolecular three-arm star-shaped composite functionalized grafting agent is added during the preparation of the special hydrogenated nitrile rubber for oil fields, but a macromolecular three-arm star-shaped composite functionalized grafting agent b is added in an amount of 5.0 g, namely: first, 200 g of HNBR rubber is dissolved in a chlorobenzene solution to form a glue solution with a mass fraction of 6.6%, 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 5.0 g of a macromolecular three-arm star-shaped composite functionalized grafting agent b is added to the reactor, stirred and mixed, and heated. When the reactor temperature reaches 82°C, a mixed solution of 0.31 g of DCP and 120 g of chlorobenzene is added, and after reacting for 10.4 hours, it is flocculated with anhydrous ethanol, washed, and dried in a 70°C oven to constant weight to obtain a special hydrogenated nitrile rubber for oil fields (grafting rate 2.0%).

[0147] Comparative Example 3

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

[0149] a Preparation of 2,4,6-trihydroxyphenyl allyl ether: same as Example 3.

[0150] b. Preparation of macromolecular composite functionalized monomer: same as Example 3.

[0151] c Preparation of macromolecular three-arm star-shaped composite functionalized grafting agent: Other conditions are the same as those in Example 3, except that p-methylstyrene is not added during the preparation of the macromolecular three-arm star-shaped composite functionalized grafting agent, that is: in a 10L stainless steel polymerizer with a jacket, the system is replaced 4 times by passing argon gas, 2400g cyclohexane and 4.0g THF are added to the polymerizer in sequence, and after the temperature is raised to 54°C, 190mmol n-butyl lithium is added to start the reaction for 84min; then 540g 1,3-butadiene and 0.7g THF are added to the polymerizer in sequence, and after the temperature is raised to 60°C, the temperature is gradually raised from 60°C to 90°C within a reaction time of 50min to form a BR segment with a wide vinyl distribution; then 70g macromolecular composite functionalized monomer and 1400g cyclohexane are mixed and stirred to dissolve for 84min, and then added to the polymerizer for reaction for 84min after complete dissolution; then the temperature is raised to 94°C, 59mmol n-butyl lithium is added 1,3,5-trichlorobenzene, coupling reaction for 84 minutes; finally, 35g 1,3-butadiene was added to the polymerization kettle for end-capping reaction for 34 minutes until no free monomer was present. The gel was wet-coagulated and dried to obtain a macromolecular three-arm star-shaped composite functionalized grafting agent c (Mn was 4600, Mw / Mn was 7.26).

[0152] (2) Preparation of special hydrogenated nitrile rubber for oil fields:

[0153] a. Preparation of hydrogenated nitrile rubber (HNBR): Same as Example 3.

[0154] b Preparation of special hydrogenated nitrile rubber for oil fields: The other conditions are the same as those in Example 3, except that a macromolecular three-arm star-shaped composite functionalized grafting agent is not added during the preparation of the special hydrogenated nitrile rubber for oil fields, but a macromolecular three-arm star-shaped composite functionalized grafting agent c is added in an amount of 7.0 g, namely: first, 200 g of HNBR rubber is dissolved in a chlorobenzene solution to form a glue solution with a mass fraction of 7.5%, 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 7.0 g of a macromolecular three-arm star-shaped composite functionalized grafting agent c is added to the reactor, stirred and mixed, and heated. When the reactor temperature reaches 84°C, a mixed solution of 0.39 g of DCP and 140 g of chlorobenzene is added, and after reacting for 10.9 hours, flocculation with anhydrous ethanol is performed, washing, and drying in a 70°C oven to constant weight to obtain a special hydrogenated nitrile rubber for oil fields (grafting rate 2.2%).

[0155] Comparative Example 4

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

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

[0158] b. Preparation of macromolecular composite functionalized monomer: same as Example 4.

[0159] c Preparation of macromolecular three-arm star-shaped composite functionalized grafting agent: The other conditions are the same as those in Example 4, except that p-methylstyrene is not added during the preparation of the macromolecular three-arm star-shaped composite functionalized grafting agent, but styrene is added in an amount of 1000 g, that is: in a 10L stainless steel polymerization kettle with a jacket, argon is passed through the system to replace 4 times, 2600g cyclohexane, 1000g styrene, and 4.5g THF are added to the polymerization kettle in sequence, and after the temperature is raised to 56°C, 185mmol n-butyl lithium is added to start the reaction for 86min to form styrene segments (PS); then 560g 1,3-butadiene, 0.8g THF, after heating to 60℃, within 52min reaction time, the temperature gradually increased from 60℃ to 90℃ to form a BR segment with a wide vinyl distribution; then 80g of the macromolecular composite functional monomer and 1600g of cyclohexane were mixed and stirred to dissolve for 86min, until completely dissolved and then added to the polymerization kettle to react for 86min; then the temperature was raised to 96℃, 56mmol 1,3,5-trichlorobenzene was added, and the coupling reaction was carried out for 86min; finally, 40g 1,3-butadiene was added to the polymerization kettle for end-capping reaction for 34min until no free monomer existed, and the colloid was wet condensed and dried to obtain a macromolecular three-arm star-shaped composite functional grafting agent d (Mn is 7100, Mw / Mn is 8.34).

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

[0161] a Preparation of hydrogenated nitrile rubber (HNBR): same as Example 4.

[0162] b Preparation of special hydrogenated nitrile rubber for oil fields: The other conditions are the same as those in Example 4, except that no macromolecular three-arm star-shaped composite functionalized grafting agent is added during the preparation of the special hydrogenated nitrile rubber for oil fields, but a macromolecular three-arm star-shaped composite functionalized grafting agent d is added in an amount of 8.0 g, namely: first, 200 g of HNBR rubber is dissolved in a chlorobenzene solution to form a 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 8.0 g of a macromolecular three-arm star-shaped composite functionalized grafting agent d is added to the reactor, stirred and mixed, and heated. When the reactor temperature reaches 86°C, a mixed solution of 0.46 g of DCP and 160 g of chlorobenzene is added, and after reacting for 11.4 hours, it is flocculated with anhydrous ethanol, washed, and dried in a 70°C oven to constant weight to obtain a special hydrogenated nitrile rubber for oil fields (grafting rate 2.9%).

[0163] Comparative Example 5

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

[0165] a Preparation of 2,4,6-trihydroxyphenyl allyl ether: same as Example 5.

[0166] b. Preparation of macromolecular composite functionalized monomer: same as Example 5.

[0167] c Preparation of macromolecular three-arm star-shaped composite functionalized grafting agent: The other conditions are the same as those in Example 5, except that the coupling agent 1,3,5-trichlorobenzene is not added during the preparation of the macromolecular three-arm star-shaped composite functionalized grafting agent, that is: in a 10L stainless steel polymerization kettle with a jacket, argon is passed through the system to replace 5 times, 2800g cyclohexane, 1000g p-methylstyrene, and 5.0g THF are added to the polymerization kettle in sequence, and after the temperature is raised to 58°C, 181mmol n-butyllithium is added to start the reaction for 88min to form p-methylstyrene segments; then 580g 1,3-butadiene, 0.9g THF, after heating to 60°C, within 56 minutes of reaction time, the temperature is gradually increased from 60°C to 90°C to form a BR segment with a wide vinyl distribution; then 90g of the macromolecular composite functional monomer and 1800g of cyclohexane are mixed and stirred to dissolve for 88 minutes, until they are completely dissolved and then added to the polymerization kettle to react for 88 minutes; finally, 45g of 1,3-butadiene is added to the polymerization kettle for end-capping reaction for 38 minutes until no free monomer exists, and the glue is wet-coagulated and dried to obtain a macromolecular three-arm star-shaped composite functional grafting agent e (Mn is 2700, Mw / Mn is 5.18).

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

[0169] a Preparation of hydrogenated nitrile rubber (HNBR): same as in Example 5.

[0170] b Preparation of special hydrogenated nitrile rubber for oil fields: The other conditions are the same as those in Example 5, except that no macromolecular three-arm star-shaped composite functionalized grafting agent is added during the preparation of the special hydrogenated nitrile rubber for oil fields, but a macromolecular three-arm star-shaped composite functionalized grafting agent e is added in an amount of 9.0 g, namely: first, 200 g of HNBR rubber is dissolved in a chlorobenzene solution to form a glue solution with a mass fraction of 8.1%, 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 macromolecular three-arm star-shaped composite functionalized grafting agent e is added to the reactor, stirred and mixed, and heated. When the reactor temperature reaches 86°C, a mixed solution of 0.52 g of DCP and 180 g of chlorobenzene is added, and after reacting for 11.7 hours, it is flocculated with anhydrous ethanol, washed, and dried in a 70°C oven to constant weight to obtain a special hydrogenated nitrile rubber for oil fields (grafting rate 3.2%).

[0171] Comparative Example 6

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

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

[0174] b. Preparation of macromolecular three-arm star-shaped composite functionalized grafting agent: The other conditions are the same as those in Example 6, except that in the preparation process of the macromolecular three-arm star-shaped composite functionalized grafting agent, no macromolecular composite functionalized monomer is added, but 2,4,6-trihydroxyphenyl allyl ether is added in an amount of 100 g, that is: in a 10L stainless steel polymerizer with a jacket, argon is passed through the system to replace 5 times, 3200 g of cyclohexane, 1000 g of p-methylstyrene, and 6.0 g of THF are added to the polymerizer in sequence, and after the temperature is raised to 60°C, 176 mmol of n-butyl lithium is added to start the reaction for 90 min to form p-methylstyrene segments; then 600 g of 1,3-butadiene, 1.0 g of THF, after heating to 60℃, within 60min reaction time, the temperature gradually increased from 60℃ to 90℃ to form a BR segment with a wide vinyl distribution; then 100g2,4,6-trihydroxyphenyl allyl ether and 2000gcyclohexane were mixed and stirred to dissolve for 90min, until completely dissolved and added to the polymerization kettle for reaction for 90min; then the temperature was raised to 100℃, 49mmol 1,3,5-trichlorobenzene was added, and the coupling reaction was carried out for 90min; finally, 50g1,3-butadiene was added to the polymerization kettle for end-capping reaction for 40min until no free monomer existed, and the glue was wet condensed and dried to obtain a macromolecular three-arm star-shaped composite functionalized grafting agent f (Mn is 6600, Mw / Mn is 6.21).

[0175] (2) Preparation of special hydrogenated nitrile rubber for oil fields:

[0176] a. Preparation of hydrogenated nitrile rubber (HNBR): Same as Example 6.

[0177] b Preparation of special hydrogenated nitrile rubber for oil fields: The other conditions are the same as those in Example 6, except that in the preparation process of special hydrogenated nitrile rubber for oil fields, no macromolecular three-arm star-shaped composite functionalized grafting agent is added, but a macromolecular three-arm star-shaped composite functionalized grafting agent f is added, and the addition amount is 10.0 g, that is: first, 200 g of HNBR rubber is dissolved in chlorobenzene solution to form a glue solution with a mass fraction of 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 three-arm star-shaped composite functionalized grafting agent f is added to the reactor, stirred and mixed, and heated. When the temperature of the reactor reaches 90°C, a mixed solution of 0.60 g of DCP and 200 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 a special hydrogenated nitrile rubber for oil fields (grafting rate 3.3%).

[0178] Table 1 Properties of special hydrogenated nitrile rubber for oil fields

[0179]

[0180]

[0181] It can be seen from Table 1 that the special hydrogenated nitrile rubber for oil field of the present invention has high tear strength, small compression permanent deformation and low glass transition temperature, and can be used as the rubber material of the stator of the submersible screw pump to meet the requirements of oil well operation under low temperature conditions of -73°C.

[0182] Figure 1 This is the infrared spectrum of the macromolecular three-arm star-shaped composite functionalized grafting agent in Example 1. Figure 1 It can be seen that the wave number is 3550~3480cm -1 The secondary contraction vibration absorption peak of hydroxyl group appears at 3100~2980cm -1 The asymmetric secondary contraction vibration double absorption peak of the benzene ring appears at 2900~2800cm -1 The secondary contraction vibration absorption peak of methyl (CH3) appears at 1650~1500cm -1 The secondary contraction vibration absorption peak of "carbon-carbon double bond" appears at 1200~1050cm -1 The secondary contraction vibration absorption peak of the ether group appears at 900~800cm -1 The secondary contraction vibration absorption peak of the para-substituted benzene ring appears at 700-600cm -1The secondary contraction vibration absorption peak of the ortho-substituted benzene ring appears at , indicating that the macromolecular composite functionalized grafting agent contains a benzene ring, a p-methylbenzene structure, an ortho-substituted structure of benzene, an ether group and an unsaturated structure.

[0183] 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 special hydrogenated nitrile rubber for oil fields, characterized in that: The steps include: (1) Preparation of macromolecular three-arm star-shaped composite functionalized grafting agent: a Preparation of 2,4,6-trihydroxyphenyl allyl ether: In a polymerization kettle, argon gas is introduced for replacement, deionized water, 2,4,6-tribromophenyl allyl ether, and NaOH aqueous solution are added to the polymerization kettle in sequence, stirred, mixed, heated, heated, reacted, and finally extracted, separated, washed, and dried to obtain 2,4,6-trihydroxyphenyl allyl ether; b. Preparation of macromolecular composite functional monomer: In a polymerization kettle, argon gas is introduced to replace the system, and a solvent, 4-hydroxy-3-alkoxy-1-propenylbenzene, 2,4,6-trihydroxyphenyl allyl ether, and a structure regulator are added to the polymerization kettle in sequence, and the temperature is raised, and then initiator 1 is added to the polymerization kettle for reaction; finally, 1,3-butadiene is added to the polymerization kettle for end-capping, and the reaction is continued until no free monomer exists. The gel solution is wet-coagulated and dried to obtain a macromolecular composite functional monomer; c Preparation of macromolecular three-arm star-shaped composite functionalized grafting agent In a polymerization kettle, argon is introduced to replace the system, and a solvent, p-alkylstyrene, and a first structural 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 1,3-butadiene and a second structural regulator are sequentially added to the polymerization kettle, the temperature is raised, and the reaction is a variable temperature polymerization. Within 40 to 60 minutes, the temperature gradually rises from 60°C to 90°C to form a BR segment with a wide vinyl distribution; then the macromolecular composite functionalized monomer and the solution are mixed and stirred to dissolve, and then added to the polymerization kettle until they are completely dissolved and reacted; the temperature is raised, and a coupling agent is added to carry out a coupling reaction; finally, 1,3-butadiene is added to the polymerization kettle for end-capping, and the reaction is carried out until there is no free monomer. After the reaction is completed, the reaction mixture after coupling is treated with water, and the glue solution is wet-coagulated and dried to obtain a macromolecular three-arm star-shaped composite functionalized grafting agent; (2) Preparation of special 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; b. Preparation of special hydrogenated nitrile rubber for oil field: HNBR rubber is dissolved in chlorobenzene solution to prepare a glue solution, and then the glue solution is added to a reactor, and an inert gas is introduced for replacement, and then a macromolecular three-arm star-shaped composite functionalized grafting agent is added to the reactor, stirred and mixed, heated, and a mixed solution of initiator 2 and chlorobenzene is added. After the reaction, flocculation, washing, and drying are performed to obtain a special hydrogenated nitrile rubber for oil field; The macromolecular three-arm star-shaped composite functionalized grafting agent has the following structure: Among them, R is a straight-chain alkyl group of C1 to C6; BR is a homopolymer segment of 1,3-butadiene with a wide vinyl distribution; B is end-capped 1,3-butadiene; n and m are the number of repeating units, and n≥1, m≥1 are positive integers; the number average molecular weight (Mn) of the macromolecular three-arm star-shaped composite functionalized grafting agent is 7000 to 8000, and the molecular weight distribution (Mw / Mn) is 9.26 to 10.

92.

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 0.1 to 0.3 parts based on 100 parts of the mass of the HNBR rubber.

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

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

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

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

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

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

12. The preparation method according to claim 1, characterized in that: In step (1) 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.

13. The preparation method according to claim 1, characterized in that: In step (1) c, during the formation of the BR segment with a wide vinyl distribution, the mass ratio of the solvent, p-alkylstyrene, the first structural regulator, 1,3-butadiene, and the second structural regulator is 200-300:100:0.3-0.6:50-60:0.05-0.1; During the end-capping process, the mass ratio of the macromolecular composite functionalized monomer, the solution, and 1,3-butadiene is 5-10:100-200:2-5.

14. 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.

15. 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%.

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

17. The preparation method according to claim 1, characterized in that: In step (2) b, the grafting rate of the special hydrogenated nitrile rubber for oil fields is 1.9% to 3.7%.

18. A special hydrogenated nitrile rubber for oil field obtained by the preparation method according to any one of claims 1 to 17.

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