Special hydrogenated butyronitrile rubber for oil field and its preparation method

Abstract

The application discloses a special hydrogenated butyl nitrile rubber for oil fields and a preparation method thereof, and the preparation method comprises the following steps: (1) preparing a macromolecular three-arm star-shaped composite functionalized grafting agent, and (2) preparing the special hydrogenated butyl nitrile rubber for oil fields; the macromolecular three-arm star-shaped composite functionalized grafting agent has the following structure: wherein R is a linear alkyl group with 1-6 carbon atoms; BR is a homopolymer segment of 1,3-butadiene with wide vinyl distribution; B is a capped 1,3-butadiene; n and m are the number of repeating units, and n is a positive integer greater than or equal to 1, and m is a positive integer greater than or equal to 1; the number average molecular weight (Mn) of the macromolecular three-arm star-shaped composite functionalized grafting agent is 7000-8000, and the molecular weight distribution (Mw / Mn) is 9.26-10.92. The preparation method of the special hydrogenated butyl nitrile rubber for oil fields has the characteristics of green environmental protection, efficient modification effect, low modifier consumption, easy availability of raw materials on the market and suitability for industrial production.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of rubber, and particularly relates to a macromolecular three-arm star-shaped composite functionalized grafting agent and a preparation method of a special hydrogenated nitrile rubber for oil fields. BACKGROUND

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

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

[0004] There are many patent literatures about the preparation method of low-temperature-resistant hydrogenated nitrile rubber in the prior art. For example:

[0005] CN 106349410 B discloses a special hydrogenated nitrile rubber with compression cold resistance and a preparation method thereof. The rubber main chain contains epoxy groups, and part of the epoxy groups are further connected with ester side groups. The ester side groups are generated by ring-opening reaction of C6-C24 acid anhydride and the epoxy groups. The preparation method comprises introducing epoxy groups into the rubber molecular main chain, and then introducing ester groups by reacting part of the epoxy groups with acid anhydride under the action of a catalyst 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. The number average molecular weight of the copolymer is 1.05-3.25 x 10 5 , and the weight average molecular weight is 3.02-9.32 x 10 5polydispersity coefficient is 2.0-2.7; the hydrogenation degree of the low-temperature grade hydrogenated butyl nitrile rubber raw rubber is above 90%, and the glass transition temperature is -38℃ to -42℃. CN 112592461 B discloses a modified hydrogenated butyl nitrile rubber material with the characteristics of low-temperature resistance and high damping, and a preparation method and application thereof. The modified hydrogenated butyl nitrile rubber material is prepared by using an HNBR / PNB block copolymer as a raw material; the HNBR / PNB block copolymer is obtained by modifying NBR or HNBR through olefin metathesis reaction with norbornene monomer as a modifier. CN 115594898 A discloses a low-temperature resistant hydrogenated butyl nitrile rubber compound and a banburying preparation method thereof, mainly blending, banburying hydrogenated butyl nitrile rubber, plasticizer and hardness regulator, finally obtaining a hydrogenated butyl nitrile rubber compound with a Shore A hardness of 67±5, a tensile strength of ≥14 MPa, an elongation at break of ≥180%, a compression set of ≤35%, and a 45℃ compression cold resistance coefficient of ≥0.16. CN 105754164 A discloses a low-temperature resistant rubber material, although the material has improved low-temperature resistance, but the addition of plasticizer dioctyl phthalate (DOP) has reduced the mechanical properties and oil resistance of the material, and DOP is not environmentally friendly and can be precipitated. Zhang Dongheng et al. disclosed that the low-temperature resistance of HNBR can be improved by blending ethylene-propylene rubber (EPDM) with HNBR, and when the addition amount of EPDM is 15%, the Tg decreases by 3℃; but further increasing the amount of EPDM, the Tg of the blended rubber does not decrease any more (Synthetic Rubber Industry, 2002, 25(1): )。

[0006] In the above prior art, although the low-temperature resistance of hydrogenated butyl nitrile rubber can be improved to some extent by adding small molecule modifiers, copolymerization and blending methods, these methods still have certain limitations, and the preparation methods have the problems of complex process, difficult actual operation, large addition amount, high cost, and unobvious modification effect. SUMMARY

[0007] In order to solve the problems existing in the prior art, the application provides a preparation method of special hydrogenated nitrile rubber for oil fields, which has a tear strength of rubber of ≥71KN / m, a compression set resistance of ≤15%, and a glass transition temperature Tg of <-73℃. The application first performs a hydrolysis reaction on 2,4,6-tribromophenyl allyl ether to synthesize 2,4,6-trihydroxyphenyl allyl ether, and then prepares a macromolecular complex functional monomer from the 2,4,6-trihydroxyphenyl allyl ether and 4-hydroxy-3-alkoxy-1-propenylbenzene. Secondly, the macromolecular complex functional monomer is prepared into a macromolecular three-arm star-shaped complex functional grafting agent with a wide ethylene group distribution through temperature change polymerization and coupling reaction from p-alkylstyrene and 1,3-butadiene. The grafting agent gives the hydrogenated nitrile rubber very excellent tear strength, deformation resistance and cold resistance, realizes the balance among the mechanical properties, deformation resistance and cold resistance of the hydrogenated nitrile rubber, and is very suitable for the rubber material of the stator of a submersible screw pump for oil well operation under low temperature conditions.

[0008] Unless otherwise specified, the "parts" in the application refer to mass parts, the "%" refers to mass percentage, and the "ratio" refers to mass ratio.

[0009] In order to achieve the above-mentioned purpose, the application provides a preparation method of special hydrogenated nitrile rubber for oil fields, which comprises the following steps:

[0010] (1) Preparation of the macromolecular three-arm star-shaped complex functional grafting agent:

[0011] a Preparation of 2,4,6-trihydroxyphenyl allyl ether: in a polymerization kettle, argon is introduced to replace the system, deionized water, 2,4,6-tribromophenyl allyl ether and NaOH aqueous solution are sequentially added into the polymerization kettle, stirring, mixing, heating, temperature rising, reaction, and finally extraction, separation, washing and drying to obtain 2,4,6-trihydroxyphenyl allyl ether;

[0012] b Preparation of the macromolecular complex functional monomer: in a polymerization kettle, argon is introduced to replace the system, a solvent, 4-hydroxy-3-alkoxy-1-propenylbenzene, 2,4,6-trihydroxyphenyl allyl ether and a structure regulator are sequentially added into the polymerization kettle, temperature rising, and then an initiator 1 is added into the polymerization kettle for reaction; finally, 1,3-butadiene is added into the polymerization kettle for end-capping, and the reaction is continued until no free monomer exists; the glue solution is subjected to wet coagulation and drying to obtain the macromolecular complex functional monomer;

[0013] Preparation of macromolecular three-arm star-shaped complex functionalized grafting agent in a polymerization kettle, the system is replaced by argon, the polymerization kettle is sequentially added with a solvent, p-alkyl styrene, a first structure regulator, heated, initiator 1 is added, reacted, p-alkyl styrene homopolymer segments are formed; then 1,3-butadiene and a second structure regulator are sequentially added into the polymerization kettle, heated, and reacted by temperature swing polymerization, the temperature is gradually increased from 60 to 90 degrees Celsius within 40 to 60 minutes, and BR segments with wide ethylene group distribution are formed; then the macromolecular complex functionalized monomer and the solution are mixed and stirred until completely dissolved, and then added into the polymerization kettle, reacted, heated, and coupled by adding a coupling agent; finally, 1,3-butadiene is added into the polymerization kettle for end-capping, and the reaction is continued until no free monomer exists; after the reaction is completed, the coupled reaction mixture is treated with water, the glue solution is coagulated by a wet method, dried, and the macromolecular three-arm star-shaped complex functionalized grafting agent is obtained;

[0014] (2) Preparation of special hydrogenated nitrile rubber for oil field:

[0015] a Preparation of hydrogenated nitrile rubber (HNBR): the nitrile rubber is dissolved in a chlorobenzene solution to configure a glue solution, the glue solution is added into a reaction kettle, inert gas is introduced to remove air in the reaction kettle, then the inert gas in the reaction kettle is removed by hydrogen, and a dimethylbenzene solution of Grubbs I catalyst is added under the protection of nitrogen, pressurized, heated, and reacted, and then the system is cooled, coagulated, and vacuum dried to obtain the HNBR rubber;

[0016] b Preparation of special hydrogenated nitrile rubber for oil field: the HNBR rubber is dissolved in a chlorobenzene solution to configure a glue solution, the glue solution is added into a reaction kettle, inert gas is introduced to replace, and then a macromolecular three-arm star-shaped complex functionalized grafting agent is added into the reaction kettle, stirred, mixed, heated, a mixed solution of initiator 2 and chlorobenzene is added, reacted, flocculated, washed, and dried to obtain the special hydrogenated nitrile rubber for oil field;

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

[0018]

[0019] wherein, R is a linear alkyl group with 1 to 6 carbon atoms; BR is a 1,3-butadiene homopolymer segment with wide ethylene group distribution; B is an end-capped 1,3-butadiene; n and m are the number of repeating units, n is a positive integer greater than or equal to 1, and m is a positive integer greater than or equal to 1; the number average molecular weight (Mn) of the macromolecular three-arm star-shaped complex functionalized grafting agent is 7000 to 8000, and the molecular weight distribution (Mw / Mn) is 9.26 to 10.92.

[0020] The p-alkylstyrene is an aryl ethylene compound selected from one of p-methylstyrene, p-ethylstyrene, p-propylstyrene, p-butylstyrene, p-pentylstyrene and p-hexylstyrene, and preferably p-methylstyrene.

[0021] The 4-hydroxy-3-alkoxy-1-propenyl benzene is an unsaturated organic compound selected from one of 4-hydroxy-3-methoxy-1-propenyl benzene, 4-hydroxy-3-ethoxy-1-propenyl benzene, 4-hydroxy-3-propoxy-1-propenyl benzene, 4-hydroxy-3-butoxy-1-propenyl benzene, 4-hydroxy-3-pentoxy-1-propenyl benzene and 4-hydroxy-3-hexyloxy-1-propenyl benzene, and preferably 4-hydroxy-3-ethoxy-1-propenyl benzene.

[0022] The initiator 1 is a hydrocarbon monolithium compound, i.e. RLi, wherein R is a saturated aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or a complex group of the above groups, containing 1-20 carbon atoms. The hydrocarbon monolithium compound is selected from one of n-butyllithium, sec-butyllithium, methylbutyllithium, phenylbutyllithium, naphthyllithium, cyclohexyllithium and dodecyl lithium, and preferably n-butyllithium. The amount of the organolithium is determined by the molecular weight of the designed polymer.

[0023] The initiator 2 is an organic peroxide selected from one of diacetyl peroxide, diisobutyryl peroxide, cumene hydroperoxide, dicumyl peroxide (DCP) and dibenzoyl peroxide (BPO), and preferably DCP. The amount of the initiator 2 is 0.1-0.3 parts based on 100 parts of the HNBR rubber.

[0024] The coupling agent is one of 1,3,5-trichlorobenzene and 1,3,5-tribromobenzene, and preferably 1,3,5-trichlorobenzene. The amount of the coupling agent is determined by the amount of the initiator 1. The star-shaped polymer with a hetero-arm structure is formed by gradually polymerizing through an excess amount of the coupling agent. The molar ratio of the total amount of the initiator 1 to the coupling agent is 3.0-4.0.

[0025] The nitrile butadiene rubber is copolymerized by emulsion polymerization of 1,3-butadiene and acrylonitrile. The acrylonitrile content of the nitrile butadiene rubber is 20wt%-42wt%, and preferably 22wt%-35wt%.

[0026] The structure regulator is a polar organic compound which produces a solvation effect in a polymerization system, can regulate the reactivity ratio of the alkylstyrene and 1,3-butadiene, and makes the two random copolymerize. The polar organic compound is selected from one of diethylene glycol dimethyl ether (2G), tetrahydrofuran (THF), diethyl ether, ethyl methyl ether, anisole, diphenyl ether, ethylene glycol dimethyl ether (DME), and triethylamine, and preferably tetrahydrofuran (THF).

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

[0028] In a of step (1) a, the mass ratio of the deionized water, 2,4,6-tribromophenyl allyl ether, and NaOH aqueous solution is 300-400:100:20-30.

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

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

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

[0032] In b of step (1), the mass ratio of the solvent, 4-hydroxy-3-alkyloxy-1-propenyl benzene, 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 b of step (1), the temperature is raised to 70-80°C; the reaction time after adding the initiator 1 is 90-100 min; and the reaction time for end-capping by adding 1,3-butadiene is 30-40 min.

[0034] In c of step (1), in the formation process of the BR chain segment with a wide ethylene group distribution, the mass ratio of the solvent, p-alkylstyrene, the first structure regulator, 1,3-butadiene, and the second structure regulator is 200-300:100:0.3-0.6:50-60:0.05-0.1.

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

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

[0037] In step (1)c of the present application, the stirring and dissolving time is 80-90 min.

[0038] In step (1)c of the present application, the reaction time after adding the macromolecular complex functional monomer and solution is 80-90 min.

[0039] In step (1)c of the present application, the temperature is raised to 90-100 DEG C before adding the coupling agent; the coupling reaction time after adding the coupling agent is 80-90 min.

[0040] In step (1)c of the present application, the reaction time for end-capping with 1,3-butadiene is 30-40 min.

[0041] In step (2)a of the present application, the mass ratio of the nitrile rubber and Grubbs I catalyst is 100:0.02-0.1.

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

[0043] In step (2)a of the present application, the mass concentration of Grubbs I catalyst in the xylene solution of Grubbs I catalyst is 5%-10%.

[0044] In step (2)a of the present application, the pressure is raised to 11-14 MP; the temperature is raised to 100-120 DEG C, and the reaction time is 9-11 hr.

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

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

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

[0048] In step (2)b of the present application, the temperature is raised to 80-90 DEG C; the reaction time is 10.0-12.0 hr.

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

[0050] The polymerization reactions described in the present application are all carried out in an oxygen-free, water-free and inert gas environment. The inert gas is nitrogen or a gas of the group 0 elements of the periodic table except radon, preferably nitrogen.

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

[0052] The pressurization in a of step (2) of the present application is achieved by adding hydrogen, and the amount of hydrogen added is well known to those skilled in the art, and the amount of hydrogen added conforms to the conventional addition range in the prior art, and the present application does not make special limitations.

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

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

[0055] (1) The macromolecular complex functional monomer prepared by the present application is prepared by anionic polymerization of 2,4,6-trihydroxyphenyl allyl ether and 4-hydroxy-3-alkoxy-1-propenyl benzene. This monomer integrates alkoxyl, polyhydroxyl and ether group on a macromolecular chain, fully utilizes the "accumulation effect" of the macromolecule, the "group effect" of the ether group, the polyhydroxyl and the alkoxyl, can effectively destroy the crystallinity of HNBR, and can prepare a special hydrogenated nitrile rubber for oil field with a glass transition temperature Tg of the raw rubber <-73℃, which can meet the requirements of oil well operation under low temperature working conditions of -73℃.

[0056] (2) The macromolecular three-arm star-shaped complex functional grafting agent prepared by the present application integrates the p-alkylstyrene homopolymer segment and the macromolecular complex functional long-chain monomer on a macromolecular chain, fully utilizes the "accumulation effect" of the p-alkylbenzene in the p-alkylbenzene homopolymer and the "group effect" of the phenyl in the macromolecular complex functional monomer, produces a certain "synergistic effect", avoids the decrease of the tear strength of HNBR due to the destruction of the crystallinity of HNBR by the macromolecular complex functional monomer, and can more effectively improve the tear strength of HNBR, can prepare a special hydrogenated nitrile rubber for oil field with a tear strength of the raw rubber ≥71KN / m, and can meet the requirements of the tear strength of the submersible screw pump stator rubber material during oil well operation.

[0057] (3) The macromolecular three-arm star-shaped composite functionalized grafting agent prepared by the present application increases the disorder of HNBR molecular segments and widens the molecular weight distribution through the design of the three-arm star-shaped structure and the wide ethylene group distribution in the BR segment, so that the HNBR can obtain good viscoelastic properties, and the compression set resistance of the HNBR is greatly improved, the special hydrogenated nitrile rubber for oil field with a compression set of the raw rubber ≤ 15% can be prepared, and the requirement of the compression resistance of the submersible screw pump stator rubber material in the oil well operation can be met.

[0058] (4) The macromolecular three-arm star-shaped composite functionalized grafting agent prepared by the present application can significantly improve the tear strength, compression set resistance and glass transition temperature (Tg) of the HNBR at a low addition amount, and a good "synergistic effect" is achieved in realizing the balance among the tear strength, compression resistance and cold resistance of the HNBR.

[0059] (5) The preparation method of the special hydrogenated nitrile rubber for oil field has the characteristics of green environmental protection, high modification effect, low modifier dosage, easy availability of raw materials on the market and suitability for industrial production. BRIEF DESCRIPTION OF DRAWINGS

[0060] Figure 1 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 inventive effect of the present application, but the protection scope of the present application is not limited to these examples and comparative examples. The raw materials used in the examples are all industrial grade, which are used after purification, without other special requirements. The "parts" in the examples and comparative examples refer to mass parts.

[0062] (1) Raw material sources:

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

[0064] 1,3-butadiene, purity 99%, China Petroleum Lanzhou Petrochemical Company

[0065] Styrene, purity 99%, China Petroleum Lanzhou Petrochemical Company

[0066] 2,4,6-tribromophenyl allyl ether, purity 98%, Hubei Shennei 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 Yihao Chemical Group Co., Ltd.

[0069] Grubbs I catalyst, 99% purity, Hubei Xinyuhong Biomedical Technology Co., Ltd.

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

[0071] All other reagents are commercially available industrial products.

[0072] (2) Analysis and testing methods:

[0073] Grafting rate determination: Approximately 4g of sample was pipetted from a three-necked flask into a weighing bottle. After weighing, 2-3 drops of hydroquinone solution were added, and the sample was dried to constant weight. The sample was then placed in a Soxhlet extractor and extracted with toluene in a 90°C water bath for 24 hours, followed by drying to constant weight. The monomer grafting rate was calculated using the following formula:

[0074]

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

[0076] Molecular weight and distribution determination: Molecular weight and distribution were determined using a Waters 2414 gel permeation chromatography (GPC) system (Waters, Inc., USA). A polystyrene standard was used as the calibration curve. The mobile phase was tetrahydrofuran, the column temperature was 40℃, the sample concentration was 1 mg / mL, the injection volume was 50 μL, the elution time was 40 min, and the flow rate was 1 mL / min. -1 .

[0077] Determination of HNBR hydrogenation degree: using nuclear magnetic resonance hydrogen spectroscopy (NMR spectroscopy). 1 The degree of hydrogenation of hydrogenated nitrile butadiene rubber (NMR) is calculated using the following main methods: 1. The product is completely dissolved in deuterated chloroform to prepare a 1H NMR sample; 2. The 1H NMR spectrum is measured and analyzed: The degree of hydrogenation of hydrogenated nitrile butadiene rubber is determined by 1H NMR spectroscopy and calculated using the following methods: characteristic proton peak of 1,4-C=C-: 5.4 ppm, characteristic proton peak of 1,2-C=C-: 5.0 ppm, characteristic proton peak of saturated hydrocarbons: 1.25 ppm, characteristic proton peak of cyano-linked groups: 2.5 ppm. The formula for calculating the degree of hydrogenation is as follows:

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

[0079] Sample infrared spectrum analysis: The infrared spectrometer of German Bruke Spectrometer Instrument Co., Ltd. was used to analyze the functional groups of the samples before and after modification. The samples were dried in a vacuum oven at 100℃, and potassium bromide was used for tabletting. The wave number range was 400-4000cm- 1 .

[0080] Determination of glass transition temperature Tg: DSC was used to measure the glass transition temperature of the product. The instrument model is DSC1, the company is Mettler Company of Switzerland, the temperature range is-80-80℃, and the temperature rising rate is 10℃ / min.

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

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

[0083] Example 1

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

[0085] a Preparation of 2,4,6-trihydroxyphenyl allyl ether: first, replace the system with argon for 3 times in a 5L jacketed stainless steel polymerization kettle, and then add 1500 deionized water, 500g 2,4,6-tribromophenyl allyl ether and 100g 10% mass concentration NaOH aqueous solution into the polymerization kettle in sequence, stir, mix, heat, and raise the temperature to 130℃. After 6.0hr of reaction, finally extract, separate, wash and dry to obtain 2,4,6-trihydroxyphenyl allyl ether (yield 80%).

[0086] b Preparation of macromolecular composite functional monomer: replace the system with argon for 3 times in a 10L jacketed stainless steel polymerization kettle, and then add 2000g cyclohexane, 300g 4-hydroxy-3-alkoxy-1-propenyl benzene, 700g 2,4,6-trihydroxyphenyl allyl ether and 3.0g THF into the polymerization kettle in sequence, raise the temperature to 70℃, and then add 320mmol n-butyllithium into the polymerization kettle for 90min. Finally, add 20g 1,3-butadiene into the polymerization kettle for end-capping, and react for 30min until no free monomer exists. The glue solution is prepared into macromolecular composite functional monomer by wet coagulation and drying.

[0087] Preparation of the macromolecular three-arm star-shaped complex functionalized grafting agent: In a 10 L jacketed stainless steel polymerization kettle, the system was replaced three times by argon. 2000 g of cyclohexane, 1000 g of p-methylstyrene, and 3.0 g of THF were sequentially added to the polymerization kettle. After being heated to 50°C, 200 mmol of n-butyllithium was added to start the reaction for 80 min to form the p-methylstyrene segment. Then 500 g of 1,3-butadiene and 0.5 g of THF were sequentially added to the polymerization kettle. After being heated to 60°C, the temperature was gradually increased from 60°C to 90°C within 40 min to form the BR segment with a wide ethylene group distribution. Then 50 g of macromolecular complex functionalized monomer and 1000 g of cyclohexane were mixed and stirred to dissolve for 80 min. After complete dissolution, the mixture was added to the polymerization kettle for reaction for 80 min. Subsequently, the temperature was increased to 90°C, and 65 mmol of 1,3,5-trichlorobenzene was added for coupling reaction for 80 min. Finally, 20 g of 1,3-butadiene was added to the polymerization kettle for end-capping reaction for 30 min until no free monomer was present. The glue solution was coagulated by wet method, dried, and the macromolecular three-arm star-shaped complex functionalized grafting agent (Mn of 7000 and Mw / Mn of 9.26) was prepared.

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

[0089] a Preparation of hydrogenated nitrile rubber (HNBR): 100 g of nitrile rubber 2907 was first dissolved in a chlorobenzene solution to prepare a glue solution with a mass fraction of 3%. The glue solution was then added to a 10 L high-pressure reaction kettle, and nitrogen was introduced to remove air in the reaction kettle. After 30 min of hydrogen replacement of nitrogen in the reaction kettle under nitrogen protection, 0.02 g of Grubbs I catalyst in xylene solution (mass concentration of 5%) was added. The hydrogen pressure in the reaction kettle was increased to 11 MPa, and the temperature was increased to 100°C. After 9.0 hr of reaction, the system was cooled, coagulated, and vacuum dried to obtain HNBR rubber (hydrogenation degree HD = 84.1%).

[0090] b Preparation of a special hydrogenated nitrile rubber for oil fields: 200 g of HNBR rubber was first dissolved in a chlorobenzene solution to prepare a glue solution with a mass fraction of 6%. The glue solution was then added to a 10 L jacketed stainless steel reaction kettle, and nitrogen was introduced to replace three times. Then 4.0 g of macromolecular three-arm star-shaped complex functionalized grafting agent was added to the reaction kettle, and the mixture was stirred and heated. When the temperature of the reaction kettle reached 80°C, 0.20 g of DCP and 100 g of chlorobenzene were added. After 10.0 hr of reaction, the system was coagulated with anhydrous ethanol, washed, and dried in a 70°C oven until the weight was constant 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 complex functionalized grafting agent:

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

[0094] b Preparation of macromolecular complex functionalized monomer: in a 10L jacketed stainless steel polymerization kettle, the system was replaced 3 times by argon, 2200g cyclohexane, 320g 4-hydroxy-3-alkoxy-1-propenylbenzene, 680g 2,4,6-trihydroxyphenyl allyl ether, 3.5g THF were sequentially added to the polymerization kettle, the temperature was raised to 72℃, then 316mmol n-butyllithium was added to the polymerization kettle and reacted for 92min; finally, 30g 1,3-butadiene was added to the polymerization kettle for end-capping, and reacted for 32min until no free monomer was present, the glue solution was prepared by wet coagulation and drying to obtain the macromolecular complex functionalized monomer.

[0095] c Preparation of macromolecular three-arm star-shaped complex functionalized grafting agent: in a 10L jacketed stainless steel polymerization kettle, the system was replaced 3 times by argon, 2200g cyclohexane, 1000g p-methylstyrene, 4.0g THF were sequentially added to the polymerization kettle, the temperature was raised to 52℃, then 196mmol n-butyllithium was added to start the reaction for 82min to form p-methylstyrene segments; then 520g 1,3-butadiene and 0.6g THF were sequentially added to the polymerization kettle, the temperature was raised to 60℃, and within 45min, the temperature was gradually raised from 60℃ to 90℃ to form a wide ethylene group distribution BR segment; then 60g macromolecular complex functionalized monomer and 1200g cyclohexane were mixed and stirred to dissolve for 82min, and then added to the polymerization kettle to react for 82min after complete dissolution; then the temperature was raised to 92℃, and 62mmol 1,3,5-trichlorobenzene was added to couple for 82min; finally, 30g 1,3-butadiene was added to the polymerization kettle for end-capping reaction for 32min until no free monomer was present, the glue solution was prepared by wet coagulation and drying to obtain the macromolecular three-arm star-shaped complex functionalized grafting agent (Mn 7100, Mw / Mn 9.41).

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

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

[0098] Preparation of special hydrogenated nitrile rubber for oil field: first, 200g HNBR rubber was dissolved in chlorobenzene solution, and a glue solution with a mass fraction of 6.6% was prepared, then the glue solution was added to a 10L stainless steel reaction kettle with a jacket, and nitrogen was introduced to replace 3 times, then 5.0g of macromolecular three-arm star-shaped complex functionalized grafting agent was added to the reaction kettle, stirred and mixed, heated, and when the temperature of the reaction kettle reached 82℃, 0.31g of DCP and 120g of chlorobenzene mixture were added, and after 10.4hr of reaction, the product was flocculated with anhydrous ethanol, washed, dried in a 70℃ oven until constant weight, and special hydrogenated nitrile rubber for oil field (grafting rate 2.3%) was obtained.

[0099] Example 3

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

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

[0102] b Preparation of macromolecular complex functionalized monomer: in a 10L stainless steel polymerization kettle with a jacket, the system was replaced 4 times with argon, 2400g of cyclohexane, 340g of 4-hydroxy-3-alkoxy-1-propenyl benzene, 660g of 2,4,6-trihydroxyphenyl allyl ether, 4.0g of THF were added to the polymerization kettle in turn, the temperature was raised to 74℃, then 309mmol of n-butyllithium was added to the polymerization kettle and reacted for 94min; finally, 35g of 1,3-butadiene was added to the polymerization kettle for end-capping, and the reaction was carried out for 34min until no free monomer was present, then the glue solution was prepared by wet agglomeration and drying to obtain macromolecular complex functionalized monomer.

[0103] Preparation of macromolecular three-arm star-shaped complex functionalized grafting agent: In a 10 L jacketed stainless steel polymerization kettle, the system was replaced 4 times by argon, 2400 g of cyclohexane, 1000 g of p-methylstyrene, and 4.0 g of THF were sequentially added to the polymerization kettle, and after being heated to 54°C, 190 mmol of n-butyllithium was added to start the reaction for 84 min to form a p-methylstyrene segment; then 540 g of 1,3-butadiene and 0.7 g of THF were sequentially added to the polymerization kettle, and after being heated to 60°C, the temperature was gradually increased from 60°C to 90°C within 50 min to form a BR segment with a wide ethylene group distribution; then 70 g of macromolecular complex functionalized monomer and 1400 g of cyclohexane were mixed and stirred to dissolve for 84 min, and after complete dissolution, they were added to the polymerization kettle for reaction for 84 min; then after being heated to 94°C, 59 mmol of 1,3,5-trichlorobenzene was added for coupling reaction for 84 min; finally, 35 g of 1,3-butadiene was added to the polymerization kettle for end-capping reaction for 34 min until no free monomer was present, and the glue solution was coagulated by wet method and dried to obtain a macromolecular three-arm star-shaped complex functionalized grafting agent (Mn of 7400 and Mw / Mn of 9.89).

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

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

[0106] b Preparation of special hydrogenated nitrile rubber for oil field: first, 200 g of HNBR rubber was dissolved in chlorobenzene solution to prepare a glue solution with a mass fraction of 7.5%, and then the glue solution was added to a 10 L jacketed stainless steel reaction kettle, which was replaced 4 times by nitrogen, and then 7.0 g of macromolecular three-arm star-shaped complex functionalized grafting agent was added to the reaction kettle, which was stirred, mixed, and heated, and when the temperature of the reaction kettle reached 84°C, 0.39 g of DCP and 140 g of a mixture of chlorobenzene were added, and after reaction for 10.9 hr, the product was flocculated with anhydrous ethanol, washed, and dried in a 70°C oven until the weight was constant to obtain special hydrogenated nitrile rubber for oil field (grafting rate 2.8%).

[0107] Example 4

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

[0109] Preparation of 2,4,6-trihydroxyphenyl allyl ether: first, the system was replaced by argon for 4 times in a 5L jacketed stainless steel polymerization kettle, 2000 deionized water, 500g 2,4,6-tribromophenyl allyl ether, 150g 20% mass concentration NaOH aqueous solution were sequentially added into the polymerization kettle, stirred, mixed, heated, and the temperature was raised to 140℃, after 8.0 hours of reaction, finally extracted, separated, washed, and dried to obtain 2,4,6-trihydroxyphenyl allyl ether (the yield was 83%).

[0110] b Preparation of macromolecular complex functional monomer: the system was replaced by argon for 4 times in a 10L jacketed stainless steel polymerization kettle, 2600g cyclohexane, 350g 4-hydroxy-3-alkoxy-1-propenylbenzene, 650g 2,4,6-trihydroxyphenyl allyl ether, 4.3g THF were sequentially added into the polymerization kettle, the temperature was raised to 76℃, then 303mmol n-butyllithium was added into the polymerization kettle for 96min reaction; finally, 40g 1,3-butadiene was added into the polymerization kettle for end-capping reaction for 36min until no free monomer existed, the glue liquid was prepared into a macromolecular complex functional monomer by wet coagulation and drying.

[0111] c Preparation of macromolecular three-arm star-shaped complex functional grafting agent: the system was replaced by argon for 4 times in a 10L jacketed stainless steel polymerization kettle, 2600g cyclohexane, 1000g p-methylstyrene, 4.5g THF were sequentially added into the polymerization kettle, the temperature was raised to 56℃, then 185mmol n-butyllithium was added to start the reaction for 86min to form p-methylstyrene segments; then 560g 1,3-butadiene and 0.8g THF were sequentially added into the polymerization kettle, the temperature was raised to 60℃, and the temperature was gradually raised from 60℃ to 90℃ within 52min reaction time to form BR segments with wide ethylene group distribution; then 80g macromolecular complex functional monomer and 1600g cyclohexane were mixed and stirred to dissolve for 86min, and then added into the polymerization kettle for 86min reaction after completely dissolved; then the temperature was raised to 96℃, 56mmol 1,3,5-trichlorobenzene was added for 86min coupling reaction; finally, 40g 1,3-butadiene was added into the polymerization kettle for end-capping reaction for 34min until no free monomer existed, the glue liquid was prepared into a macromolecular three-arm star-shaped complex functional grafting agent (Mn was 7500, Mw / Mn was 10.21) by wet coagulation and drying.

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

[0113] Preparation of hydrogenated nitrile rubber (HNBR) : 100 g of nitrile rubber 2907 was first dissolved in chlorobenzene solution to prepare a glue solution with a mass fraction of 4.5%, and then the glue solution was added to a 10 L high-pressure reaction kettle, nitrogen was introduced to remove air in the reaction kettle, then 0.07 g of Grubbs I catalyst solution in xylene (mass concentration of 8%) was added under nitrogen protection after 36 min of hydrogen gas displacement in the reaction kettle, the hydrogen pressure in the reaction kettle was increased to 12 MPa, the temperature was increased to 113 ℃, and the reaction was carried out for 10 h. After the system was cooled, coagulation and vacuum drying were carried out to obtain HNBR rubber (hydrogenation degree HD = 87.1%).

[0114] Preparation of special hydrogenated nitrile rubber for oil field: 200 g of HNBR rubber was first 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 10 L stainless steel reaction kettle with a jacket, nitrogen was introduced to replace 4 times, and then 8.0 g of macromolecular three-arm star-shaped composite functionalized grafting agent was added to the reaction kettle, stirred and mixed, heated, and when the temperature of the reaction kettle reached 86 ℃, 0.46 g of DCP and 160 g of chlorobenzene mixture were added. After 11.4 h of reaction, the system was coagulated with anhydrous ethanol, washed, and dried in a 70 ℃ oven to constant weight to obtain special hydrogenated nitrile rubber for oil field (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 functionalized monomer: in a 10 L stainless steel polymerization kettle with a jacket, the system was replaced 5 times with argon, 2800 g of cyclohexane, 370 g of 4-hydroxy-3-alkoxy-1-propenylbenzene, 630 g of 2,4,6-trihydroxyphenyl allyl ether, 4.8 g of THF were added to the polymerization kettle in turn, the temperature was increased to 78 ℃, then 297 mmol of n-butyllithium was added to the polymerization kettle and reacted for 98 min, and finally 45 g of 1,3-butadiene was added to the polymerization kettle for end-capping, and the reaction was carried out for 38 min until no free monomer was present. The glue solution was coagulated by wet method, dried, and macromolecular composite functionalized monomer was prepared.

[0119] Preparation of macromolecular three-arm star-shaped complex functionalized grafting agent: In a 10 L jacketed stainless steel polymerization kettle, the system was replaced 5 times by argon, 2800 g of cyclohexane, 1000 g of p-methylstyrene, and 5.0 g of THF were sequentially added into the polymerization kettle, the temperature was raised to 58°C, then 181 mmol of n-butyllithium was added to start the reaction for 88 min to form the p-methylstyrene segment; then 580 g of 1,3-butadiene and 0.9 g of THF were sequentially added into the polymerization kettle, the temperature was raised to 60°C, and the temperature was gradually raised from 60°C to 90°C within 56 min to form the BR segment with a wide ethylene group distribution; then 90 g of macromolecular complex functionalized monomer and 1800 g of cyclohexane were mixed and stirred to dissolve for 88 min, and then added into the polymerization kettle to react for 88 min after complete dissolution; then the temperature was raised to 98°C, 53 mmol of 1,3,5-trichlorobenzene was added, and the coupling reaction was carried out for 88 min; finally, 45 g of 1,3-butadiene was added into the polymerization kettle to carry out the end-capping reaction for 38 min until no free monomer existed, the glue solution was coagulated by wet method and dried to obtain the macromolecular three-arm star-shaped complex functionalized grafting agent (Mn is 7800, and Mw / Mn is 10.56).

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

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

[0122] b Preparation of special hydrogenated nitrile rubber for oil field: first, 200 g of HNBR rubber was dissolved in chlorobenzene solution to prepare a glue solution with a mass fraction of 8.1%, then the glue solution was added into a 10 L jacketed stainless steel reaction kettle, nitrogen was introduced to replace 4 times, then 9.0 g of macromolecular three-arm star-shaped complex functionalized grafting agent was added into the reaction kettle, stirring, mixing and heating, 0.52 g of DCP and 180 g of chlorobenzene mixture were added when the temperature of the reaction kettle reached 86°C, and the reaction was carried out for 11.7 hr, then the product was coagulated by anhydrous ethanol, washed, and dried in a 70°C oven until the weight was constant to obtain the special hydrogenated nitrile rubber for oil field (grafting rate 3.5%).

[0123] Example 6

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

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

[0126] Preparation of macromolecular complex functional monomer: In a 10L jacketed stainless steel polymerization kettle, the system was replaced by argon for 5 times, 3000g cyclohexane, 400g 4-hydroxy-3-alkoxy-1-propenyl benzene, 600g 2,4,6-trihydroxyphenyl allyl ether, 5.0g THF were added into the polymerization kettle, heated to 80℃, then 289mmol n-butyllithium was added into the polymerization kettle for 100min; finally, 50g 1,3-butadiene was added into the polymerization kettle for end-capping, reacted for 40min until no free monomer existed, the glue solution was prepared by wet coagulation and drying to obtain macromolecular complex functional monomer.

[0127] Preparation of macromolecular three-arm star complex functional grafting agent: In a 10L jacketed stainless steel polymerization kettle, the system was replaced by argon for 5 times, 3200g cyclohexane, 1000g p-methyl styrene, 6.0g THF were added into the polymerization kettle, heated to 60℃, then 176mmol n-butyllithium was added for 90min to form p-methyl styrene segment; then 600g 1,3-butadiene, 1.0g THF were added into the polymerization kettle, heated to 60℃, the temperature was gradually increased from 60℃ to 90℃ within 60min to form BR segment with wide ethylene group distribution; then 100g macromolecular complex functional monomer and 2000g cyclohexane were mixed and stirred for 90min until completely dissolved, then added into the polymerization kettle for 90min; then heated to 100℃, added 49mmol 1,3,5-trichlorobenzene for coupling reaction for 90min; finally, 50g 1,3-butadiene was added into the polymerization kettle for end-capping for 40min until no free monomer existed, the glue solution was prepared by wet coagulation and drying to obtain macromolecular three-arm star complex functional grafting agent (Mn 8000, Mw / Mn 10.92).

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

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

[0130] b Preparation of special hydrogenated nitrile rubber for oil field: first, 200g HNBR rubber was dissolved in chlorobenzene solution to prepare glue solution with mass fraction of 9.0%, then the glue solution was added into a 10L jacketed stainless steel reaction kettle, replaced by nitrogen for 5 times, then 10.0g macromolecular three-arm star complex functional grafting agent was added into the reaction kettle, stirred and mixed, heated, when the temperature of the reaction kettle reached 90℃, 0.60g DCP and 200g chlorobenzene mixture were added, reacted for 12.0hr, then flocculated with anhydrous ethanol, washed, dried in 70℃ oven until constant weight to obtain special hydrogenated nitrile rubber for oil field (grafting rate 3.7%).

[0131] Comparative Example 1

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

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

[0134] b Preparation of macromolecular complex functionalized monomer: same as Example 1.

[0135] c Preparation of macromolecular three-arm star-shaped complex functionalized grafting agent: other conditions are the same as Example 1, the difference is that the macromolecular three-arm star-shaped complex functionalized grafting agent is prepared without using temperature swing polymerization method, that is: in a 10L jacketed stainless steel polymerization kettle, the system is replaced 3 times by argon, 2000g of cyclohexane, 1000g of p-methylstyrene, 3.0g of THF are sequentially added into the polymerization kettle, after heating to 50℃, 200mmol of n-butyllithium is added to start the reaction for 80min to form p-methylstyrene segment; then 500g of 1,3-butadiene and 0.5g of THF are sequentially added into the polymerization kettle, and the temperature is raised to 60℃ for 40min to form BR segment; then 50g of macromolecular complex functionalized monomer and 1000g of cyclohexane are mixed and stirred to dissolve for 80min, until completely dissolved, then added into the polymerization kettle for 80min; then the temperature is raised to 90℃, 65mmol of 1,3,5-trichlorobenzene is added for coupling reaction for 80min; finally, 20g of 1,3-butadiene is added into the polymerization kettle for end-capping reaction for 30min until no free monomer exists, the glue solution is wet coagulated and dried to obtain the macromolecular three-arm star-shaped complex functionalized grafting agent a (Mn is 6900, Mw / Mn is 7.14).

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

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

[0138] b Preparation of special hydrogenated nitrile rubber for oil field: the conditions are the same as those in Example 1, except that no macromolecular three-arm star-shaped complex functionalized grafting agent is added in the preparation process of the special hydrogenated nitrile rubber for oil field, but macromolecular three-arm star-shaped complex functionalized grafting agent a is added, and the amount is 4.0 g, that is, first, 200 g of HNBR rubber is dissolved in chlorobenzene solution to prepare a glue solution with a mass fraction of 6%, then the glue solution is added to a 10 L stainless steel reaction kettle with a jacket, and nitrogen is blown in to replace 3 times, then 4.0 g of macromolecular three-arm star-shaped complex functionalized grafting agent a is added to the reaction kettle, and stirring, mixing and heating are carried out, 0.20 g of DCP and 100 g of chlorobenzene are added when the temperature of the reaction kettle reaches 80°C, and the mixture is reacted for 10.0 hours, then flocculated with anhydrous ethanol, washed, dried in a 70°C oven until the weight is constant, and the special hydrogenated nitrile rubber for oil field (grafting rate 1.8%) is obtained.

[0139] Comparative Example 2

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

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

[0142] b Preparation of macromolecular complex functionalized monomer: the same as in Example 2.

[0143] c Preparation of macromolecular three-arm star-shaped complex functionalized grafting agent: the conditions are the same as those in Example 2, except that no 1,3-butadiene is added in the preparation process of the macromolecular three-arm star-shaped complex functionalized grafting agent, that is, in a 10 L stainless steel polymerization kettle with a jacket, the system is replaced 3 times with argon, 2200 g of cyclohexane, 1000 g of p-methylstyrene, 4.0 g of THF are sequentially added to the polymerization kettle, the temperature is raised to 52°C, then 196 mmol of n-butyllithium is added to start the reaction for 82 min to form a p-methylstyrene segment, then 0.6 g of THF is sequentially added to the polymerization kettle, the temperature is raised to 60°C, and the temperature is gradually raised from 60°C to 90°C in 45 min, then 60 g of macromolecular complex functionalized monomer and 1200 g of cyclohexane are mixed and dissolved for 82 min, then added to the polymerization kettle for reaction for 82 min, then the temperature is raised to 92°C, 62 mmol of 1,3,5-trichlorobenzene is added for coupling reaction for 82 min, and finally 30 g of 1,3-butadiene is added to the polymerization kettle for end-capping reaction for 32 min until no free monomer exists, then the glue solution is flocculated by wet method, dried, and the macromolecular three-arm star-shaped complex functionalized grafting agent b (Mn is 6200, Mw / Mn is 6.75) is prepared.

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

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

[0146] b Preparation of special hydrogenated nitrile rubber for oil field: other conditions are same as example 2, the difference is that the macromolecular three-arm star-shaped complex functionalized grafting agent is not added in the preparation process of special hydrogenated nitrile rubber for oil field, but the macromolecular three-arm star-shaped complex functionalized grafting agent b is added, and the amount is 5.0 g, that is, first 200 g of HNBR rubber is dissolved in chlorobenzene solution to prepare a glue solution with a mass fraction of 6.6%, then the glue solution is added to a 10 L stainless steel reaction kettle with a jacket, and nitrogen is blown in to replace 3 times, then 5.0 g of macromolecular three-arm star-shaped complex functionalized grafting agent b is added to the reaction kettle, and stirring, mixing and heating are carried out, 0.31 g of DCP and 120 g of chlorobenzene mixture are added when the temperature of the reaction kettle reaches 82℃, and after 10.4 hr of reaction, the product is flocculated with anhydrous ethanol, washed, dried in a 70℃ oven until the weight is constant, and the special hydrogenated nitrile rubber for oil field (grafting rate 2.0%) is obtained.

[0147] Comparative example 3

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

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

[0150] b Preparation of macromolecular complex functionalized monomer: same as example 3.

[0151] Preparation of the macromolecular three-armed star-shaped complex functionalized grafting agent c: other conditions are the same as those in Example 3, except that no p-methylstyrene is added in the preparation of the macromolecular three-armed star-shaped complex functionalized grafting agent, i.e. in a 10 L stainless steel polymerization kettle with a jacket, the system is replaced 4 times by argon, 2400 g of cyclohexane and 4.0 g of THF are sequentially added to the polymerization kettle, after being heated to 54°C, 190 mmol of n-butyllithium is added to start the reaction for 84 min; then 540 g of 1,3-butadiene and 0.7 g of THF are sequentially added to the polymerization kettle, after being heated to 60°C, the temperature is gradually increased from 60°C to 90°C within 50 min of reaction time to form a wide ethylene group distribution BR segment; then 70 g of macromolecular complex functionalized monomer and 1400 g of cyclohexane are mixed and stirred to dissolve for 84 min, and then added to the polymerization kettle to react for 84 min after complete dissolution; subsequently, after being heated to 94°C, 59 mmol of 1,3,5-trichlorobenzene is added for coupling reaction for 84 min; finally, 35 g of 1,3-butadiene is added to the polymerization kettle for end-capping reaction for 34 min until no free monomer exists, and the glue solution is prepared into a macromolecular three-armed star-shaped complex functionalized grafting agent c (Mn is 4600, Mw / Mn is 7.26) by wet coagulation and drying.

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

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

[0154] b Preparation of a special hydrogenated nitrile rubber for oil field: other conditions are the same as those in Example 3, except that no macromolecular three-armed star-shaped complex functionalized grafting agent is added in the preparation of the special hydrogenated nitrile rubber for oil field, but the macromolecular three-armed star-shaped complex functionalized grafting agent c is added, and the amount is 7.0 g, i.e. first 200 g of HNBR rubber is dissolved in chlorobenzene solution to prepare a glue solution with a mass fraction of 7.5%, then the glue solution is added to a 10 L stainless steel reaction kettle with a jacket, and the system is replaced 4 times by nitrogen, then 7.0 g of macromolecular three-armed star-shaped complex functionalized grafting agent c is added to the reaction kettle, and stirring, mixing and heating are performed, and when the temperature of the reaction kettle reaches 84°C, 0.39 g of DCP and 140 g of a mixture of chlorobenzene are added, and after 10.9 hr of reaction, the product is flocculated with anhydrous ethanol, washed, and dried in a 70°C oven until the weight is constant to obtain a special hydrogenated nitrile rubber for oil field (grafting rate 2.2%).

[0155] Comparative Example 4

[0156] (1) Preparation of a macromolecular three-armed star-shaped complex functionalized grafting agent:

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

[0158] b Preparation of macromolecular complex functional monomer: same as example 4.

[0159] c Preparation of macromolecular three-arm star complex functional grafting agent: other conditions are the same as example 4, the difference is that in the preparation of macromolecular three-arm star complex functional grafting agent, instead of p-methyl styrene, styrene is added, the amount is 1000g, namely: in a 10L jacketed stainless steel polymerization kettle, the system is replaced 4 times by argon, 2600g cyclohexane, 1000g styrene, 4.5g THF are sequentially added into the polymerization kettle, after heating to 56℃, 185mmol n-butyllithium is added to start the reaction for 86min, forming styrene segment (PS); then 560g 1,3-butadiene, 0.8g THF are sequentially added into the polymerization kettle, after heating to 60℃, the temperature is gradually increased from 60℃ to 90℃ in 52min reaction time, forming BR segment with wide ethylene group distribution; then 80g macromolecular complex functional monomer and 1600g cyclohexane are mixed and stirred to dissolve for 86min, until completely dissolved, then added into the polymerization kettle for reaction for 86min; then after heating to 96℃, 56mmol 1,3,5-trichlorobenzene is added for coupling reaction for 86min; finally, 40g 1,3-butadiene is added into the polymerization kettle for end-capping reaction for 34min until no free monomer exists, the glue solution is coagulated by wet method, dried, and the macromolecular three-arm star complex functional grafting agent d (Mn is 7100, Mw / Mn is 8.34) is prepared.

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

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

[0162] b Preparation of special hydrogenated nitrile rubber for oil field: other conditions are the same as example 4, the difference is that in the preparation of special hydrogenated nitrile rubber for oil field, instead of macromolecular three-arm star complex functional grafting agent, macromolecular three-arm star complex functional grafting agent d is added, the amount is 8.0g, namely: first, 200g HNBR rubber is dissolved in chlorobenzene solution to prepare glue solution with mass fraction of 8.1%, then the glue solution is added into a 10L jacketed stainless steel reaction kettle, replaced 4 times by nitrogen, then 8.0g macromolecular three-arm star complex functional grafting agent d is added into the reaction kettle, stirred and mixed, heated, when the temperature of the reaction kettle reaches 86℃, 0.46g DCP and 160g mixed solution of chlorobenzene are added, after reaction for 11.4hr, flocculated with anhydrous ethanol, washed, dried in 70℃ oven until constant weight, and the special hydrogenated nitrile rubber for oil field (grafting rate 2.9%) is obtained.

[0163] Comparative example 5

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

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

[0166] b Preparation of macromolecular complex functionalized monomer: same as example 5.

[0167] c Preparation of macromolecular three-arm star-shaped complex functionalized grafting agent: other conditions are the same as example 5, the difference is that no coupling agent 1,3,5-trichlorobenzene is added in the preparation process of macromolecular three-arm star-shaped complex functionalized grafting agent, that is: in a 10L jacketed stainless steel polymerization kettle, the system is replaced 5 times by argon, 2800g cyclohexane, 1000g p-methylstyrene, 5.0g THF are sequentially added into the polymerization kettle, after heating to 58℃, 181mmol n-butyllithium is added to start the reaction for 88min to form p-methylstyrene segment; then 580g 1,3-butadiene, 0.9g THF are sequentially added into the polymerization kettle, after heating to 60℃, the temperature is gradually increased from 60℃ to 90℃ within 56min reaction time to form a wide ethylene group distribution BR segment; then 90g macromolecular complex functionalized monomer and 1800g cyclohexane are mixed and stirred to dissolve for 88min, until completely dissolved, then added into the polymerization kettle to react for 88min; finally, 45g 1,3-butadiene is added into the polymerization kettle to carry out end-capping reaction for 38min until no free monomer exists, the glue solution is wet coagulated, dried to obtain macromolecular three-arm star-shaped complex functionalized grafting agent e (Mn is 2700, Mw / Mn is 5.18).

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

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

[0170] b Preparation of special hydrogenated nitrile rubber for oil field: the other conditions are the same as example 5, the difference is that the macromolecular three-arm star-shaped composite functionalized grafting agent is not added in the preparation process of the special hydrogenated nitrile rubber for oil field, but the macromolecular three-arm star-shaped composite functionalized grafting agent e is added, the amount is 9.0g, that is: first, 200g HNBR rubber is dissolved in chlorobenzene solution, and the glue liquid with a mass fraction of 8.1% is configured, then the glue liquid is added to the 10L stainless steel reaction kettle with jacket, nitrogen is introduced to replace 4 times, then 9.0g macromolecular three-arm star-shaped composite functionalized grafting agent e is added to the reaction kettle, stirring, heating, when the temperature of the reaction kettle reaches 86℃, 0.52g DCP and 180g chlorobenzene mixture are added, after 11.7hr reaction, the glue liquid is flocculated with anhydrous ethanol, washed, dried in 70℃ oven until constant weight, to obtain the special hydrogenated nitrile rubber for oil field (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: the same as example 6.

[0174] b Preparation of macromolecular three-arm star-shaped composite functionalized grafting agent: the other conditions are the same as example 6, the difference is that the macromolecular composite functionalized monomer is not added in the preparation process of the macromolecular three-arm star-shaped composite functionalized grafting agent, but 2,4,6-trihydroxyphenyl allyl ether is added, the amount is 100g, that is: in the 10L stainless steel polymerization kettle with jacket, the system is replaced 5 times by argon, 3200g cyclohexane, 1000g p-methylstyrene, 6.0g THF are added into the polymerization kettle in turn, after heating to 60℃, 176mmol n-butyllithium is added to start the reaction for 90min to form p-methylstyrene segment; then 600g 1,3-butadiene and 1.0g THF are added into the polymerization kettle in turn, after heating to 60℃, the temperature is gradually increased from 60℃ to 90℃ within 60min reaction time to form BR segment with wide ethylene group distribution; then 100g 2,4,6-trihydroxyphenyl allyl ether and 2000g cyclohexane are mixed and dissolved for 90min, then added to the polymerization kettle to react for 90min; then after heating to 100℃, 49mmol 1,3,5-trichlorobenzene is added to couple for 90min; finally, 50g 1,3-butadiene is added to the polymerization kettle to cap for 40min until no free monomer exists, the glue liquid is flocculated by wet method, dried, to obtain the 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 field:

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

[0177] b Preparation of special hydrogenated nitrile rubber for oil field: other conditions are same as example 6, the difference is that the macromolecular three-arm star-shaped complex functionalized grafting agent is not added in the preparation process of the special hydrogenated nitrile rubber for oil field, but the macromolecular three-arm star-shaped complex functionalized grafting agent f is added, and the amount is 10.0 g, namely: first, 200 g of HNBR rubber is dissolved in chlorobenzene solution to configure a glue solution with a mass fraction of 9.0%, then the glue solution is added to a 10 L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace 5 times, then 10.0 g of macromolecular three-arm star-shaped complex functionalized grafting agent f is added to the reaction kettle, stirring, heating, when the temperature of the reaction kettle reaches 90℃, 0.60 g of DCP and 200 g of chlorobenzene mixture are added, after 12.0 hr of reaction, flocculation with anhydrous ethanol, washing, drying in a 70℃ oven until constant weight, to obtain the special hydrogenated nitrile rubber for oil field (grafting rate 3.3%).

[0178] Table 1 Performance of special hydrogenated nitrile rubber for oil field

[0179]

[0180]

[0181] From table 1, it can be seen that the special hydrogenated nitrile rubber for oil field of the present application has high tear strength, small compression permanent deformation and low glass transition temperature, and can meet the oil well operation under the working temperature of-73℃ low temperature condition when used as the rubber material of submersible screw pump stator.

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

[0183] Of course, the present application can have other various embodiments, and those skilled in the art can make various corresponding changes and modifications according to the present application without departing from the spirit and essence of the present application, but these corresponding changes and modifications shall all belong to the protection scope of the present application.

Claims

1. A method for preparing a special hydrogenated nitrile butadiene rubber for oil fields, characterized in that, Includes the following steps: (1) Preparation of macromolecular three-arm star-shaped composite functionalized grafting agent: Preparation of 2,4,6-trihydroxyphenylallyl ether: Argon gas was introduced into the polymerization reactor for purging. Deionized water, 2,4,6-tribromophenylallyl ether, and NaOH aqueous solution were added sequentially to the polymerization reactor. The mixture was stirred, mixed, heated, and allowed to react. Finally, the mixture was extracted, separated, washed, and dried to obtain 2,4,6-trihydroxyphenylallyl ether. The mass ratio of the deionized water, 2,4,6-tribromophenylallyl ether, and NaOH aqueous solution was 300~400:100:20~30. b. Preparation of macromolecular composite functionalized monomers: In a polymerization reactor, argon gas is introduced to purge the system. Solvent, 4-hydroxy-3-alkoxy-1-propenylbenzene, 2,4,6-trihydroxyphenylallyl ether, and structure modifier are added sequentially to the polymerization reactor. The temperature is raised, and initiator 1 is added to the polymerization reactor for reaction. Finally, 1,3-butadiene is added to the polymerization reactor for end-capping. The reaction continues until no free monomers are present. The solution is wet-coagulated and dried to obtain macromolecular composite functionalized monomers. The mass ratio of the solvent, 4-hydroxy-3-alkoxy-1-propenylbenzene, 2,4,6-trihydroxyphenylallyl ether, structure modifier, and 1,3-butadiene is 200~300:30~40:60~70:0.3~0.5:2~5. Preparation of macromolecular three-armed star-shaped composite functionalized grafting agent: In a polymerization reactor, argon gas is introduced to purge the system. Solvent, p-alkylstyrene, and a first structure modifier are added sequentially to the reactor. The temperature is raised, and initiator 1 is added to react and form p-alkylstyrene homopolymer segments. Then, 1,3-butadiene and a second structure modifier are added sequentially to the reactor. The temperature is raised, and the reaction is a temperature-switched polymerization, with the temperature gradually increased from 60℃ to 90℃ over 40-60 minutes to form BR segments with a wide vinyl distribution. Then, the macromolecular composite functionalized monomer is mixed with the solution and stirred until completely dissolved before being added to the polymerization reactor for reaction. The temperature is raised, and a coupling agent is added to carry out the coupling reaction. Finally, 1,3-butadiene is added to the reactor for end-capping, and the reaction continues until no... Until the presence of free monomers, after the reaction is complete, the coupled reaction mixture is treated with water, and the gel is wet-coagulated and dried to obtain a macromolecular three-arm star-shaped composite functionalized grafting agent; the coupling agent is one of 1,3,5-trichlorobenzene and 1,3,5-tribromobenzene; in the formation of the broad vinyl-distributed BR segments, the mass ratio of the solvent, p-alkylstyrene, primary structure modifier, 1,3-butadiene, and secondary structure modifier is 200~300:100:0.3~0.6:50~60:0.05~0.1; in the end-capping process, the mass ratio of the macromolecular composite functionalized monomer, solution, and 1,3-butadiene is 5~10:100~200:2~5; (2) Preparation of special hydrogenated nitrile butadiene rubber for oil fields: Preparation of hydrogenated nitrile butadiene rubber (HNBR): Nitrile butadiene rubber is dissolved in chlorobenzene solution to prepare a rubber solution. The rubber solution is then added to a reaction vessel, and an inert gas is introduced to remove the air from the reaction vessel. After the inert gas in the reaction vessel is removed by hydrogen, a xylene solution of Grubbs I catalyst is added under nitrogen protection. The pressure is increased and the temperature is raised. After the reaction, the system is cooled, condensed, and vacuum dried to obtain HNBR rubber. b. Preparation of special hydrogenated nitrile butadiene rubber for oilfields: HNBR rubber is dissolved in chlorobenzene solution to prepare a rubber solution. The rubber solution is then added to a reaction vessel, and an inert gas is introduced for purging. A macromolecular three-arm star-shaped composite functionalized grafting agent is then added to the reaction vessel. The mixture is stirred, heated, and a mixture of initiator 2 and chlorobenzene is added. After the reaction, the mixture is flocculated, washed, and dried to obtain special hydrogenated nitrile butadiene rubber for oilfields. The macromolecular three-armed star-shaped composite functionalized grafting agent has the following structure: Wherein, R is a C1-C6 straight-chain alkyl group; BR is a homopolymer segment of 1,3-butadiene with a broad vinyl distribution; B is a capped 1,3-butadiene; n and m are the number of repeating units, n≥1 and m≥1 being positive integers; the number average molecular weight (Mn) of the macromolecular three-arm star-shaped composite functionalized grafting agent is 7000~8000, and the molecular weight distribution (Mw / Mn) is 9.26~10.

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-pentoxy-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-butyllithium, sec-butyllithium, methylbutyllithium, phenylbutyllithium, naphthalenelithium, cyclohexyllithium, and dodecyllithium.

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, diisobutyryl peroxide (DCP), and benzoyl peroxide (BPO), and its addition amount is 0.1 to 0.3 parts based on 100 parts by weight of HNBR rubber.

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

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

8. 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.

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

10. 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.

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

12. 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.

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

14. A special hydrogenated nitrile butadiene rubber for oil fields obtained by the preparation method according to any one of claims 1-13.

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