A hydrogenated nitrile rubber for oil field use with low temperature resistance and a method for preparing the same

Abstract

The application discloses a hydrogenated butyl nitrile rubber for oil fields with deformation resistance and low temperature and a preparation method thereof, and the preparation method comprises the following steps: (1) preparing a macromolecular long branched chain linking agent, and (2) preparing the hydrogenated butyl nitrile rubber for oil fields with deformation resistance and low temperature. 12 The macromolecular long branched chain linking agent has the following structure: wherein PS is a styrene homopolymer segment, BR is a 1,3-butadiene homopolymer segment, R is a linear alkyl group with C6-C The number average molecular weight (Mn) of the macromolecular long chain linking agent is 6000-7000. The preparation method of the hydrogenated butyl nitrile rubber for oil fields with deformation resistance and low temperature has the characteristics of green environmental protection, efficient and stable modification effect, low modifier consumption, easily available raw materials on the market, and suitability for industrial production.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of rubber, and particularly relates to a macromolecular long-chain branched modifier modified deformation-resistant and low-temperature grade hydrogenated nitrile rubber for oil fields and a preparation method thereof. BACKGROUND

[0002] Hydrogenated nitrile rubber (HNBR for short) is prepared by selectively hydrogenating carbon-carbon double bonds in nitrile rubber, so that 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, and is widely used in petroleum 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 (NBR for short) is a highly ordered polyethylene structure, which is very easy to form a crystalline structure, and also causes the increase of Tg, so that the low temperature 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 the oil drilling equipment faces the application environment under low temperature conditions, and the low temperature resistance of the rubber sealing material is extremely high.

[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, which contains epoxy groups on the rubber main chain, 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 the 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 1.05-3.25 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 raw material; the HNBR / PNB block copolymer is obtained by modifying NBR or HNBR through olefin metathesis reaction with norbornene monomer as 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 low-temperature resistance, having 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 5℃ compression cold resistance coefficient of ≥0.16. CN 105754164 A discloses a low-temperature resistant rubber material, although the low-temperature resistance of the material is improved, the addition of plasticizer dioctyl phthalate (DOP) causes the mechanical properties and oil resistance of the material to decrease, and DOP is not environmentally friendly and is easy to precipitate. Zhang Dongheng et al. disclose that the low-temperature performance of HNBR can be improved by blending ethylene-propylene rubber (EPDM) with HNBR, and when the EPDM addition amount is 15%, the Tg decreases by 3℃; but further increasing the EPDM amount, 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 in the prior art, the present application provides a preparation method of hydrogenated nitrile rubber for oil field use in deformation resistance and low temperature, which has a tear strength of ≥42KN / m, a compression permanent deformation resistance of ≤26%, and a glass transition temperature Tg of <-57℃, and can meet the requirements of deformation resistance and low temperature in the range of -57℃ to 59℃. The present application first prepares a block copolymer by distributed synthesis through an anionic polymerization method, and then prepares a macromolecular long-chain grafting agent with radical reactivity by reacting with a long-chain α-olefin and ethylene under the action of a nickel-based complex catalyst. Finally, the macromolecular long-chain grafting agent is grafted to the main chain of the hydrogenated nitrile rubber to prepare the hydrogenated nitrile rubber for oil field use in deformation resistance and low temperature. The method not only solves the problem of easy crystallization of the hydrogenated nitrile rubber, but also avoids the problem of mechanical property reduction caused by the reduction of crystallinity, so that the hydrogenated nitrile rubber not only shows very excellent low temperature resistance, but also maintains sufficient mechanical properties and deformation resistance, and realizes the balance among the low temperature resistance, mechanical properties and deformation resistance of the hydrogenated nitrile rubber. It is very suitable for oil well operation under the working conditions of -57℃, tear strength ≥42KN / m and compression permanent deformation resistance ≤26%.

[0008] Unless otherwise specified, the "parts" in the present 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 present application provides a preparation method of hydrogenated nitrile rubber for oil field use in deformation resistance and low temperature, which comprises the following steps:

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

[0011] a. Preparation of –BR-PS-block copolymer: In a polymerization kettle, the system is replaced by argon, and then solvent, 1,3-butadiene, structure regulator, initiator 1 are sequentially added into the polymerization kettle, heated, reacted to form BR segment, then styrene, structure regulator are sequentially added into the polymerization kettle, heated, reacted until no free monomer exists, and then the glue solution is subjected to wet coagulation and drying to obtain –BR-PS-block copolymer;

[0012] b. Preparation of macromolecular long-chain grafting agent: In a reaction kettle, the system is replaced by inert gas, and then solvent is added, heated, and then alkylaluminoxane cocatalyst is added under stirring, and then –BR-PS-block copolymer and solution are mixed and dissolved under stirring, and then long-chain α-olefin and nickel-based complex catalyst are added into the reaction kettle, at which time ethylene is introduced, and then reacted; after the reaction is completed, centrifugal separation and drying are performed to obtain the macromolecular long-chain grafting agent;

[0013] (2) Preparation of hydrogenated nitrile rubber for oil field use in deformation resistance and low temperature:

[0014] Preparation of hydrogenated nitrile rubber (HNBR): the nitrile rubber is dissolved in chlorobenzene solution to form a glue solution, then the glue solution is added into a reaction kettle, inert gas is introduced to replace the air in the reaction kettle, then the inert gas in the reaction kettle is replaced by hydrogen gas, under the protection of nitrogen, 0.02-0.1 parts of Grubbs I catalyst is added into xylene solution, pressure is applied, temperature is raised, reaction is carried out, the system is cooled, coagulation is carried out, and drying is carried out to obtain HNBR rubber;

[0015] Preparation of hydrogenated nitrile rubber for oil field resistant to deformation and low temperature: the HNBR rubber is dissolved in chlorobenzene solution to form a glue solution, then the glue solution is added into a reaction kettle, inert gas is introduced to replace the air in the reaction kettle, then a macromolecular long branched chain grafting agent is added into the reaction kettle, stirring, mixing and heating are carried out, a mixed solution of initiator 2 and chlorobenzene is added, reaction, flocculation, washing and drying are carried out to obtain hydrogenated nitrile rubber for oil field resistant to deformation and low temperature;

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

[0017]

[0018] Wherein, PS is a styrene homopolymer segment, BR is a 1,3-butadiene homopolymer segment, R is a C6-C 12 alkyl straight chain; m and n 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 long chain grafting agent is 6000-7000.

[0019] The long chain alpha-olefin in the application is a C6-C 12 alkyl straight chain, which can be selected from one of 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene and 1-dodecene, and is preferably 1-octene.

[0020] The nickel-based complex catalyst in the application is selected from one of chlorinated (1-naphthyl)〔8-(diphenyl phosphine) quinoline〕nickel, trans-brominated phenyl (di(triphenyl phosphine)) nickel and 2,5-diformyl pyrrole nickel dibromide, and is preferably trans-brominated phenyl (di(triphenyl phosphine)) nickel.

[0021] The alkyl aluminum oxyalkane cocatalyst in the application is selected from one of methyl aluminum oxyalkane (MAO) and ethyl aluminum oxyalkane (EAO), and is preferably methyl aluminum oxyalkane.

[0022] The initiator 1 described in the present application is a hydrocarbon monolithium compound, that is, 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, naphthyl lithium, cyclohexyllithium, dodecyl lithium, preferably n-butyllithium. The amount of organic lithium added is determined by the molecular weight of the designed polymer.

[0023] The initiator 2 described in the present application is an organic peroxide selected from one of diacetyl peroxide, diisobutyryl peroxide, cumene hydroperoxide, dicumyl peroxide (DCP) and dibenzoyl peroxide, preferably dicumyl peroxide (DCP), and the amount of addition is 0.0-0.2 parts, preferably 0.1-0.15 parts, based on 100 parts of the mass of HNBR rubber.

[0024] The nitrile butadiene rubber described in the present application is copolymerized by emulsion polymerization of 1,3-butadiene and acrylonitrile. The acrylonitrile content of the nitrile butadiene rubber is 20wt%-42wt%, preferably 22wt%-35wt%.

[0025] The structure regulator described in the present application is a polar organic compound that produces a solvation effect in the polymerization system, which can regulate the reactivity ratio of styrene and 1,3-butadiene, so that the two are randomly copolymerized. 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), triethylamine, preferably tetrahydrofuran (THF).

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

[0027] In a of step (1) of the present application, during the formation of the BR segment, the mass ratio of the solvent, 1,3-butadiene and structure regulator is 400-500:100:0.5-1.0, and the temperature is raised to 50-60℃; the reaction time is 60-70min.

[0028] In a of step (1) of the present application, during the formation of the –BR-PS- block copolymer, the amount of styrene added is 40-60 parts, the amount of structure regulator added is 1.0-1.5 parts, and the temperature is raised to 70-80℃, based on 100 parts of the mass of 1,3-butadiene; the reaction time is 80-90min.

[0029] In the b of step (1) of the present application, the mass ratio of the solvent, the alkyl aluminum oxane cocatalyst, the BR-PS-block copolymer, the solvent, the long-chain alpha-olefin, the nickel-based complex catalyst is 300-400:20-30:2.0-4.0:100-200:8-15:1.

[0030] In the b of step (1) of the present application, the temperature is raised to 80-90 DEG C; the stirring speed is 700-800 rpm; the time of continuous stirring is 20-30 min; the time of stirring dissolution is 40-60 min; the reaction pressure is 15-20 MPa, and the time is 6.0-7.0 hr.

[0031] In the a of step (2) of the present application, the mass ratio of the butyl nitrile rubber and the Grubbs I catalyst is 100:0.02-0.1.

[0032] In the a of step (2) of the present application, the mass fraction of butyl nitrile rubber in the glue solution is 3%-6%.

[0033] In the a of step (2) of the present application, the mass concentration of Grubbs I catalyst in the xylene solution of Grubbs I catalyst is 5%-10%.

[0034] In the a of step (2) of the present application, the pressure is raised to 11-14 MPa; the temperature is raised to 100-120 DEG C; and the reaction time is 9-11 hr.

[0035] In the a of step (2) of the present application, the hydrogenation degree HD of the HNBR rubber is less than 90%.

[0036] In the b of step (2) of the present application, the mass ratio of the HNBR rubber, the macromolecular long-chain branch linking agent and the chlorobenzene is 100:2-4:100-200.

[0037] In the b of step (2) of the present application, the mass fraction of HNBR rubber in the glue solution is 6%-9%.

[0038] In the b of step (2) of the present application, the temperature is raised to 80-90 DEG C; and the reaction time is 9.0-10.0 hr.

[0039] In the b of step (2) of the present application, the grafting rate of the deformation-resistant, low-temperature grade hydrogenated butyl nitrile rubber for oil field is 1.8%-3.2%.

[0040] The polymerization reactions of 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 element group 0 in the periodic table except radon, and preferably nitrogen.

[0041] The reaction kettle according to the present application can be a loop reactor or a tank reactor, and is preferably a tank reactor.

[0042] The pressurization in step (2)a 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 is within the conventional range in the prior art, and is not particularly limited in the present application.

[0043] The present application also provides a low-temperature and deformation-resistant hydrogenated nitrile rubber for oil field prepared by the above preparation method.

[0044] Compared with the prior art, the present application has at least the following advantages and beneficial effects:

[0045] (1) The macromolecular long-chain branch grafting agent prepared by the present application is prepared into a -BR-PS-block copolymer by distributed synthesis through an anionic polymerization method, and then a long-chain alpha-olefin is combined into a macromolecular long-chain branch through coordination polymerization, and the ethylene is activated to make it have radical reaction activity, which can be grafted onto the hydrogenated nitrile rubber to form a long-chain branched structure containing benzene rings and unsaturated double bonds on the main chain structure of the hydrogenated nitrile rubber. This structure organically combines the long-chain branched structure, benzene ring and unsaturated double bond structure in one macromolecular chain, which reduces the crystallinity of HNBR and improves the viscoelasticity, and at the same time avoids the decrease of the mechanical properties of HNBR, achieves a good "synergistic effect" in achieving the balance among low-temperature resistance, deformation resistance and tear resistance, and can prepare a low-temperature and deformation-resistant hydrogenated nitrile rubber for oil field with a tear strength of raw rubber ≥ 42 KN / m, a compression permanent set resistance ≤ 26%, and a glass transition temperature Tg <-57℃.

[0046] (2) The low-temperature and deformation-resistant hydrogenated nitrile rubber for oil field prepared by the present application can greatly reduce the glass transition temperature (Tg) of HNBR while significantly improving the compression permanent set resistance and tear strength of HNBR with a low addition amount under the condition of ensuring a certain hydrogenation degree, and is suitable for oil well operation under low-temperature working conditions of -57℃.

[0047] (3) The preparation method of the low-temperature and deformation-resistant hydrogenated nitrile rubber for oil field has the characteristics of green environmental protection, high and stable modification effect, low amount of modifier, easy availability of raw materials on the market, and suitability for industrial production. DETAILED DESCRIPTION

[0048] The following examples and comparative examples illustrate the inventive effects of the present invention, but the scope of protection of the present invention is not limited to these examples and comparative examples. The raw materials used in the examples are all industrial grade, purified before use, and have no other special requirements. The "parts" mentioned in the examples and comparative examples refer to parts by weight.

[0049] (1) Source of raw materials:

[0050]

[0051] (2) Analysis and testing methods:

[0052] 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:

[0053]

[0054] 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).

[0055] Molecular weight determination: Molecular weight was determined using a Waters 2414 gel permeation chromatography (GPC) system (Waters, Inc., USA). A polystyrene standard was used as the calibration curve. The mobile phase was tetrahydrofuran, the column temperature was 40℃, the sample concentration was 1 mg / mL, the injection volume was 50 μL, the elution time was 40 min, and the flow rate was 1 mL / min. -1 .

[0056] 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:

[0057] Degree of hydrogenation (HD%) = 1 - Degree of unsaturation (U)

[0058] Measurement of glass transition temperature Tg: The glass transition temperature of the product was measured by DSC. The instrument model was DSC1, the company was Mettler Company, Switzerland, the temperature range was -80-80℃, and the temperature rising rate was 10℃ / min.

[0059] Compression set: The method in standard GB / T 7759.1-2015 was performed.

[0060] Tear strength: The method in standard GB / T 529-2009 was performed.

[0061] Example 1

[0062] (1) Preparation of macromolecular long-branching linking agent:

[0063] a Preparation of BR-PS copolymer: In a 10L jacketed stainless steel polymerization kettle, the system was replaced by argon for 3 times, 2000g cyclohexane, 500g 1,3-butadiene, 2.5g THF, 192mmol n-butyllithium were sequentially added into the polymerization kettle, the temperature was raised to 50℃, and the reaction was carried out for 60min to form BR segment; then 200g styrene, 5.0g THF were sequentially added into the polymerization kettle, the temperature was raised to 70℃, and the reaction was carried out for 80min until no free monomer existed, the glue liquid was prepared by wet coagulation and drying to obtain BR-PS copolymer.

[0064] b Preparation of macromolecular long-branching linking agent: first, the 10L high-pressure reaction kettle was replaced by nitrogen for 3 times, 3000g cyclohexane was added, the temperature was raised to 80℃, and then 200g methylaluminoxane cocatalyst was added by gradually dropping under the condition of uniform stirring at a speed of 700rpm, the stirring was continued for 20min under the protection of nitrogen, then 20g

[0065] After the BR-PS copolymer and 1000g cyclohexane were mixed and stirred for 40min, 80g 1-octene and 10g trans-brominated phenyl(bis(triphenylphosphine)) nickel main catalyst were added into the high-pressure reaction kettle, ethylene was introduced, the pressure was maintained at 15MPa, and the reaction was carried out for 6.0hr; after the reaction was completed, the macromolecular long-branching linking agent (the number average molecular weight Mn was 6000) was prepared by centrifugal separation, drying.

[0066] (2) Preparation of hydrogenated nitrile rubber for oil field with deformation resistance and low temperature resistance:

[0067] 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 3%, which was then added to a 10 L high-pressure reaction kettle. Nitrogen was introduced to remove air in the reaction kettle. Then, 0.02 g of Grubbs I catalyst solution in xylene (mass concentration of 5%) was added under nitrogen protection after nitrogen in the reaction kettle was replaced by hydrogen for 30 min. 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%).

[0068] Preparation of hydrogenated nitrile rubber for deformation-resistant and low-temperature oilfield use: 200 g of HNBR rubber was first dissolved in chlorobenzene solution to prepare a glue solution with a mass fraction of 6%, which was then added to a 10 L stainless steel reaction kettle with a jacket. Nitrogen was introduced to replace 3 times, and then 4.0 g of a macromolecular long-branching grafting agent was added to the reaction kettle. After stirring, mixing, and heating, 0.20 g of DCP and 200 g of chlorobenzene were added when the temperature of the reaction kettle reached 80°C. After 9.0 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 hydrogenated nitrile rubber for deformation-resistant and low-temperature oilfield use (grafting rate 1.8%). Sample analysis: standard samples were prepared, and the performance was tested as shown in Table 1.

[0069] Example 2

[0070] (1) Preparation of macromolecular long-branching grafting agent:

[0071] Preparation of -BR-PS-copolymer: argon was introduced into a 10 L stainless steel polymerization kettle with a jacket to replace the system 3 times. 2100 g of cyclohexane, 500 g of 1,3-butadiene, 3.0 g of THF, and 203 mmol of n-butyllithium were sequentially added to the polymerization kettle. The temperature was increased to 52°C, and the reaction was carried out for 62 min to form BR segments. Then, 220 g of styrene and 5.5 g of THF were sequentially added to the polymerization kettle. The temperature was increased to 72°C, and the reaction was carried out for 82 min until no free monomer was present. The glue solution was coagulated by wet method and dried to obtain -BR-PS-copolymer.

[0072] Preparation of macromolecular long-branching grafting agent: 3200 g of cyclohexane was first introduced into a 10 L high-pressure reaction kettle and heated to 82°C. Then, 220 g of methylaluminoxane catalyst was gradually added under uniform stirring at a speed of 720 rpm. The system was continuously stirred for 22 min under nitrogen protection. Subsequently, 25 g of

[0073] - BR-PS-copolymer and 1200 g cyclohexane were mixed and stirred for 45 min, then 90 g 1-octene and 10 g trans-brominated benzyl(triphenylphosphine) nickel procatalyst were added into a high-pressure reactor, ethylene was introduced, the pressure was maintained at 16 MPa, and the reaction was carried out for 6.2 hr; after the reaction was completed, the macromolecular long-branching linking agent (number average molecular weight Mn = 6100) was obtained by centrifugal separation, drying, and preparation.

[0074] (2) Preparation of a deformation-resistant and low-temperature hydrogenated nitrile rubber for oil fields:

[0075] 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%, and then the glue solution was added to a 10 L high-pressure reactor, nitrogen was introduced to remove air in the reactor, then hydrogen was introduced to remove nitrogen in the reactor for 32 min, and then 0.03 g of Grubbs I catalyst in xylene solution (mass concentration of 6%) was added under nitrogen protection, the hydrogen pressure in the reactor was increased to 12 MPa, the temperature was increased to 105°C, and the reaction was carried out for 9.5 hr; after the system was cooled, coagulation and vacuum drying were carried out to obtain HNBR rubber (hydrogenation degree HD = 85.7%).

[0076] b Preparation of a deformation-resistant and low-temperature 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 6.5%, and then the glue solution was added to a 10 L stainless steel reactor with a jacket, nitrogen was introduced to replace 3 times, and then 4.5 g of macromolecular long-branching linking agent was added to the reactor, stirred and mixed, heated, and when the temperature of the reactor reached 82°C, 0.22 g of DCP and 260 g of a mixture of chlorobenzene were added, and the reaction was carried out for 9.2 hr; after flocculation with anhydrous ethanol, washing, and drying in a 70°C oven to constant weight, a deformation-resistant and low-temperature hydrogenated nitrile rubber for oil fields was obtained (grafting rate 2.1%). Sample analysis: standard samples were prepared, and the performance was tested as shown in Table 1.

[0077] Example 3

[0078] (1) Preparation of a macromolecular long-branching linking agent:

[0079] a Preparation of BR-PS-copolymer: argon was introduced into a 10 L stainless steel polymerization kettle with a jacket to replace the system 4 times, 2200 g of cyclohexane, 500 g of 1,3-butadiene, 3.5 g of THF, and 211 mmol of n-butyllithium were sequentially added to the polymerization kettle, the temperature was increased to 54°C, and the reaction was carried out for 65 min to form BR segments; then 240 g of styrene and 6.0 g of THF were sequentially added to the polymerization kettle, the temperature was increased to 74°C, and the reaction was carried out for 84 min until no free monomer was present; the glue solution was coagulated by wet method and dried to obtain BR-PS-copolymer.

[0080] Preparation of macromolecular long-branching linking agent: first, 3400 g of cyclohexane was added into a 10 L autoclave, and the temperature was raised to 84°C. Then, 240 g of methylaluminoxane co-catalyst was added dropwise under uniform stirring at a speed of 740 rpm. The stirring was continued for 24 min under nitrogen protection. Subsequently, 30 g of

[0081] BR-PS-copolymer and 1500 g of cyclohexane were mixed and stirred for 50 min, and then 110 g of 1-octene and 10 g of trans-bromophenyl(bis(triphenylphosphine)) nickel primary catalyst were added into the autoclave. Ethylene was introduced, and the pressure was maintained at 17 MPa for 6.4 hr. After the reaction was completed, macromolecular long-branching linking agent (with a number average molecular weight Mn of 6300) was obtained by centrifugal separation, drying, and the like.

[0082] (2) Preparation of hydrogenated nitrile rubber for oil field resistant to deformation and low temperature:

[0083] Preparation of hydrogenated nitrile rubber (HNBR): first, 100 g of nitrile rubber 2907 was dissolved in chlorobenzene solution to prepare a glue solution with a mass fraction of 4%. Then, the glue solution was added into a 10 L autoclave, and nitrogen was introduced to remove air in the autoclave. Then, hydrogen was introduced to remove nitrogen in the autoclave for 34 min. Subsequently, 0.05 g of Grubbs I catalyst was added into xylene solution (with a mass concentration of 7%) under nitrogen protection. The hydrogen pressure in the autoclave was increased to 12 MPa, and the temperature was raised to 110°C. After 10 hr of reaction, the system was cooled, coagulated, and dried in vacuum to obtain HNBR rubber (with a hydrogenation degree HD of 86.2%).

[0084] Preparation of hydrogenated nitrile rubber for oil field resistant to deformation and low temperature: first, 200 g of HNBR rubber was dissolved in chlorobenzene solution to prepare a glue solution with a mass fraction of 7.0%. Then, the glue solution was added into a 10 L stainless steel autoclave with a jacket, and nitrogen was introduced for 4 times. Subsequently, 5.0 g of macromolecular long-branching linking agent was added into the autoclave, and the mixture was stirred and heated. When the temperature of the autoclave reached 84°C, 0.24 g of DCP and 280 g of chlorobenzene were added. After 9.4 hr of reaction, the mixture was flocculated with anhydrous ethanol, washed, and dried in a 70°C oven until the weight was constant to obtain hydrogenated nitrile rubber for oil field resistant to deformation and low temperature (with a grafting rate of 2.4%). The sample was analyzed to prepare a standard sample, and the performance was tested, as shown in Table 1.

[0085] Example 4

[0086] (1) Preparation of macromolecular long-branching linking agent:

[0087] Preparation of -BR-PS-copolymer: In a 10L jacketed stainless steel polymerization kettle, the system was replaced by argon for 4 times, 2300g cyclohexane, 500g 1,3-butadiene, 4.0g THF, 219mmol n-butyllithium were added into the polymerization kettle in turn, heated to 56℃, and reacted for 67min to form BR segment; then 260g styrene, 6.5g THF were added into the polymerization kettle in turn, heated to 76℃, and reacted for 85min until no free monomer existed, the glue liquid was prepared by wet coagulation and drying to obtain -BR-PS-copolymer.

[0088] Preparation of macromolecular long-branching linking agent: first, the 10L high-pressure reaction kettle was replaced by nitrogen for 4 times, 3600g cyclohexane was added, heated to 85℃, and then 260g methylaluminoxane cocatalyst was added dropwise under uniform stirring at a speed of 760rpm, and continued to stir for 26min under nitrogen protection, then 34g

[0089] The -BR-PS-copolymer and 1700g cyclohexane were mixed and stirred to dissolve for 53min, then 120g 1-octene and 10g trans-brominated phenyl(bis(triphenylphosphine))nickel main catalyst were added into the high-pressure reaction kettle, ethylene was introduced, and the pressure was maintained at 18MPa for 6.6hr; after the reaction was completed, the macromolecular long-branching linking agent (number average molecular weight Mn=6600) was prepared by centrifugal separation, drying.

[0090] (2) Preparation of hydrogenated nitrile rubber for oil field resistant to deformation and low temperature:

[0091] Preparation of hydrogenated nitrile rubber (HNBR): first, 100g nitrile rubber 2907 was dissolved in chlorobenzene solution to prepare a glue liquid with a mass fraction of 4.5%, then the glue liquid was added into a 10L high-pressure reaction kettle, nitrogen was introduced to remove air in the reaction kettle, then hydrogen was used to remove nitrogen in the reaction kettle for 36min, then 0.07g Grubbs I catalyst in xylene solution (mass concentration 8%) was added under nitrogen protection, the hydrogen pressure in the reaction kettle was increased to 12MPa, and the temperature was increased to 113℃, and reacted for 10hr, then the system was cooled, coagulated, and vacuum dried to obtain HNBR rubber (hydrogenation degree HD=87.1%).

[0092] bPreparation of hydrogenated nitrile rubber for oil field with deformation resistance and low temperature: first, 200g HNBR rubber was dissolved in chlorobenzene solution, configured into a glue solution with mass fraction of 7.5%, then the glue solution was added to a 10L stainless steel reactor with jacket, replaced 4 times by nitrogen, then 6.0g macromolecular long branched grafting agent was added to the reactor, mixed and heated, when the temperature of the reactor reached 86℃, 0.26g DCP and 320g mixed solution of chlorobenzene were added, after 9.6hr reaction, flocculation with anhydrous ethanol, washing, drying in 70℃ oven until constant weight, hydrogenated nitrile rubber for oil field with deformation resistance and low temperature (grafting rate 2.7%) was obtained. Sample analysis: standard sample was prepared, and the performance was tested as shown in Table 1.

[0093] Example 5

[0094] (1) Preparation of macromolecular long branched grafting agent:

[0095] aPreparation of BR-PS-copolymer: in a 10L stainless steel polymerization kettle with jacket, the system was replaced 5 times by argon, 2400g cyclohexane, 500g 1,3-butadiene, 4.5g THF, 224mmol n-butyllithium were sequentially added to the polymerization kettle, heated to 58℃, and reacted for 69min to form BR segments; then 280g styrene and 6.8g THF were sequentially added to the polymerization kettle, heated to 78℃, and reacted for 87min until no free monomer was present, the glue solution was prepared by wet coagulation and drying to obtain BR-PS-copolymer.

[0096] bPreparation of macromolecular long branched grafting agent: first, 3800g cyclohexane was added to a 10L high-pressure reaction kettle, heated to 87℃, and then 280g methylaluminoxane cocatalyst was gradually added under uniform stirring at a speed of 780rpm, and stirring was continued for 28min under nitrogen protection, then 36g

[0097] BR-PS-copolymer and 1700g cyclohexane were mixed and dissolved under stirring for 57min, then 140g 1-octene and 10g trans-brominated phenyl(bis(triphenylphosphine)) nickel main catalyst were added to the high-pressure reaction kettle, ethylene was introduced, and the pressure was maintained at 19MPa for 6.8hr; after the reaction was completed, centrifugal separation, drying, and macromolecular long branched grafting agent (number average molecular weight Mn6800) was prepared.

[0098] (2) Preparation of hydrogenated nitrile rubber for oil field with deformation resistance and low temperature:

[0099] 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 5.0%, 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 0.09 g of Grubbs I catalyst solution in xylene (mass concentration of 9%) was added under nitrogen protection after 38 min of hydrogen pressure increase in the reaction kettle, the hydrogen pressure was 13 MPa, the temperature was increased to 117 ℃, and the reaction was carried out for 11 h. After the system was cooled, coagulation and vacuum drying were carried out to obtain HNBR rubber (hydrogenation degree HD = 88.3%).

[0100] Preparation of hydrogenated nitrile rubber for oil field resistant to deformation and low temperature: 200 g of HNBR rubber was first dissolved in chlorobenzene solution to prepare a glue solution with a mass fraction of 8.0%, and then the glue solution was added to a 10 L stainless steel reaction kettle with a jacket, nitrogen was introduced to replace 5 times, and then 7.0 g of macromolecular long branch linking agent was added to the reaction kettle, stirred and mixed, heated, and when the temperature of the reaction kettle reached 89 ℃, 0.29 g of DCP and 360 g of chlorobenzene mixture were added. After 9.8 h of reaction, the system was coagulated with anhydrous ethanol, washed, and dried in a 70 ℃ oven to constant weight to obtain hydrogenated nitrile rubber for oil field resistant to deformation and low temperature (grafting rate 3.1%). Sample analysis: standard samples were prepared, and the performance was tested as shown in Table 1.

[0101] Example 6

[0102] (1) Preparation of macromolecular long branch linking agent:

[0103] Preparation of -BR-PS-copolymer: in a 10 L stainless steel polymerization kettle with a jacket, the system was replaced 5 times with argon, 2500 g of cyclohexane, 500 g of 1,3-butadiene, 5.0 g of THF, and 245 mmol of n-butyllithium were sequentially added to the polymerization kettle, and the temperature was increased to 60 ℃. After 70 min of reaction, BR segments were formed. Then 300 g of styrene and 7.5 g of THF were sequentially added to the polymerization kettle, and the temperature was increased to 80 ℃. After 90 min of reaction until no free monomer was present, the glue solution was coagulated by wet method and dried to obtain -BR-PS-copolymer.

[0104] Preparation of macromolecular long branch linking agent: first, 4000 g of cyclohexane was added to a 10 L high-pressure reaction kettle, and the temperature was increased to 90 ℃. Under uniform stirring at a speed of 800 rpm, 300 g of methylaluminoxane catalyst was gradually added dropwise, and the stirring was continued for 30 min under nitrogen protection. Then 40 g of

[0105] BR-PS-copolymer and 2000g cyclohexane were mixed and stirred to dissolve for 60 min, then 150g 1-hexene and 10g trans-brominated nickel phenyl(bis(triphenylphosphine)) were added into a high-pressure reactor, ethylene was introduced, and the pressure was maintained at 20 MPa for 7.0 hr; after the reaction was completed, centrifugal separation, drying, and preparation of macromolecular long-branching linking agent (number average molecular weight Mn of 7000) were performed.

[0106] (2) Preparation of hydrogenated nitrile rubber for oil field resistant to deformation and low temperature:

[0107] a Preparation of hydrogenated nitrile rubber (HNBR): 100g nitrile rubber 2907 was first dissolved in chlorobenzene solution to prepare a glue solution with a mass fraction of 6.0%, then the glue solution was added to a 10L high-pressure reactor, nitrogen was introduced to remove air in the reactor, then hydrogen was used to remove nitrogen in the reactor for 40 min, then 0.1g Grubbs I catalyst solution in xylene (mass concentration of 10%) was added under nitrogen protection, the hydrogen pressure in the reactor was increased to 14 MPa, and the temperature was increased to 120°C, and the reaction was carried out for 11 hr; after the reaction was completed, the system was cooled, coagulated, and vacuum dried to obtain HNBR rubber (hydrogenation degree HD = 89.4%).

[0108] b Preparation of hydrogenated nitrile rubber for oil field resistant to deformation and low temperature: 200g HNBR rubber was first dissolved in chlorobenzene solution to prepare a glue solution with a mass fraction of 9.0%, then the glue solution was added to a 10L stainless steel reactor with a jacket, nitrogen was introduced to replace 5 times, then 8.0g macromolecular long-branching linking agent was added to the reactor, and the mixture was stirred and heated; when the temperature of the reactor reached 90°C, 0.30g BPO and 400g chlorobenzene were added, and the reaction was carried out for 10.0 hr; after the reaction was completed, the product was flocculated with anhydrous ethanol, washed, and dried in a 70°C oven to constant weight to obtain hydrogenated nitrile rubber for oil field resistant to deformation and low temperature (grafting rate of 3.2%); sample analysis: standard samples were prepared, and the performance was tested as shown in Table 1.

[0109] Comparative Example 1

[0110] (1) Preparation of macromolecular long-branching linking agent:

[0111] a Preparation of BR-PS-copolymer: same as Example 1.

[0112] Preparation of macromolecular long-branching linking agent: other conditions are the same as example 1, the difference is that the amount of macromolecular long-branching linking agent - BR-PS-copolymer is 10 g, that is: first replace 3 times with nitrogen in 10 L autoclave, add 3000 g of cyclohexane, heat to 80 ℃, then add 200 g of methylaluminoxane cocatalyst under uniform stirring at a speed of 700 rpm, continue to stir for 20 min under nitrogen protection, then add 10 g of -BR-PS-copolymer and 1000 g of cyclohexane after stirring and dissolving for 40 min, add 80 g of 1-octene and 10 g of trans-bromophenyl(bis(triphenylphosphine))nickel primary catalyst, and then add ethylene into the autoclave, keep the pressure at 15 MPa for 6.0 hr; after the reaction is completed, centrifugal separation, drying, and macromolecular long-branching linking agent a (number average molecular weight Mn is 5200) is prepared.

[0113] (2) Preparation of deformation-resistant and low-temperature grade hydrogenated nitrile rubber for oil field:

[0114] a Preparation of hydrogenated nitrile rubber (HNBR): same as example 1.

[0115] b Preparation of deformation-resistant and low-temperature grade hydrogenated nitrile rubber for oil field: other conditions are the same as example 1, the difference is that no macromolecular long-branching linking agent is added in the preparation process of deformation-resistant and low-temperature grade hydrogenated nitrile rubber for oil field, but macromolecular long-branching linking agent a is added, and the amount is 4.0 g, that is: first dissolve 200 g of HNBR rubber in chlorobenzene solution to prepare a glue solution with a mass fraction of 6%, then add the glue solution into a 10 L stainless steel reaction kettle with a jacket, replace 3 times with nitrogen, then add 4.0 g of macromolecular long-branching linking agent a into the reaction kettle, stir and mix, heat, and when the temperature of the reaction kettle reaches 80 ℃, add 0.20 g of DCP and 200 g of chlorobenzene mixture, react for 9.0 hr, then flocculate with anhydrous ethanol, wash, and dry in a 70 ℃ oven until the weight is constant to obtain deformation-resistant and low-temperature grade hydrogenated nitrile rubber for oil field (grafting rate 1.6%). Sample analysis: standard samples are prepared, and the performance is tested as shown in Table 1.

[0116] Comparative example 2

[0117] (1) Preparation of macromolecular long-branching linking agent:

[0118] a Preparation of -BR-PS-copolymer: other conditions are the same as example 2, the difference is that

[0119] Preparation of -BR-PS-copolymer: The preparation process of -BR-PS-copolymer is as follows: the system is replaced by argon for 3 times in a 10L stainless steel polymerization kettle with jacket, 2100g cyclohexane, 500g 1,3-butadiene, 3.0g THF, 203mmol n-butyllithium are sequentially added into the polymerization kettle, the temperature is raised to 52°C, and the reaction is carried out for 62min until no free monomer exists. The glue solution is prepared by wet coagulation and drying to obtain -BR-homopolymer.

[0120] Preparation of macromolecular long branch linking agent b: the preparation process of macromolecular long branch linking agent b is as follows: the system is replaced by nitrogen for 3 times in a 10L high-pressure reaction kettle, 3200g cyclohexane is added, the temperature is raised to 82°C, and then 220g methylaluminoxane cocatalyst is added by dropwise adding under the condition of uniform stirring at a speed of 720rpm. The stirring is continued for 22min under the protection of nitrogen gas. Then, 25g -BR-copolymer and 1200g cyclohexane are mixed and stirred to dissolve for 45min, and then 90g 1-octene and 10g trans-bromophenyl(bis(triphenylphosphine))nickel are added into the high-pressure reaction kettle. Ethylene is introduced, the pressure is kept at 16MPa, and the reaction is carried out for 6.2hr. After the reaction is completed, the macromolecular long branch linking agent b (the number average molecular weight Mn is 5500) is obtained by centrifugal separation, drying, and the like.

[0121] (2) Preparation of hydrogenated nitrile rubber for oil field with deformation resistance and low temperature resistance:

[0122] Preparation of hydrogenated nitrile rubber (HNBR): the same as example 2.

[0123] Preparation of hydrogenated nitrile rubber for oil field with deformation resistance and low temperature resistance: the preparation process of hydrogenated nitrile rubber for oil field with deformation resistance and low temperature resistance is as follows: 200g HNBR rubber is dissolved in chlorobenzene solution to prepare a glue solution with a mass fraction of 6.5%, and then the glue solution is added into a 10L stainless steel reaction kettle with jacket. The system is replaced by nitrogen for 3 times, and then 4.5g macromolecular long branch linking agent b is added into the reaction kettle. The stirring, mixing, and heating are carried out, 0.22g DCP and 260g mixed solution of chlorobenzene are added when the temperature of the reaction kettle reaches 82°C, the reaction is carried out for 9.2hr, and then the hydrogenated nitrile rubber for oil field with deformation resistance and low temperature resistance (the grafting rate is 1.9%) is obtained by flocculation with anhydrous ethanol, washing, and drying to constant weight in a 70°C oven. The sample analysis is carried out: the standard sample is prepared, and the performance is tested and shown in table 1.

[0124] Comparative example 3

[0125] (1) Preparation of macromolecular long-branching linking agent:

[0126] a Preparation of -BR-PS-copolymer: other conditions are the same as in Example 3, except that

[0127] -PS-homopolymer is prepared in a 10L jacketed stainless steel polymerization kettle by replacing the system with argon for 4 times, sequentially adding 2200g cyclohexane, 240g styrene, 6.0g THF into the polymerization kettle, heating to 74℃, and reacting for 84min until no free monomer exists, and then the gel is prepared by wet coagulation and drying.

[0128] b Preparation of macromolecular long-branching linking agent: other conditions are the same as in Example 3, except that -BR-PS-copolymer is not added in the preparation process of macromolecular long-branching linking agent, but -PS-homopolymer is added in an amount of 30g, i.e. first replace the system with nitrogen for 4 times in a 10L high-pressure reaction kettle, add 3400g cyclohexane, heat to 84℃, then gradually add 240g methylaluminoxane co-catalyst under uniform stirring at a speed of 740rpm, continue to stir for 24min under nitrogen protection, then mix 30g -PS-homopolymer and 1500g cyclohexane, stir and dissolve for 50min, then add 110g 1-octene and 10g trans-bromophenyl(di(triphenylphosphine))nickel main catalyst into the high-pressure reaction kettle, introduce ethylene, maintain the pressure at 17MPa, and react for 6.4hr; after the reaction is completed, centrifugal separation, drying, and macromolecular long-branching linking agent c (number average molecular weight Mn is 3300) is prepared.

[0129] (2) Preparation of shape deformation resistant, low temperature grade hydrogenated nitrile rubber for oil field:

[0130] a Preparation of hydrogenated nitrile rubber (HNBR): same as in Example 3.

[0131] b Preparation of hydrogenated nitrile rubber for oil field of deformation resistance and low temperature grade: other conditions are the same as example 3, the difference is that the hydrogenated nitrile rubber for oil field of deformation resistance and low temperature grade is prepared without adding macromolecular long branch linking agent, but adding macromolecular long branch linking agent c, the amount is 5.0g, namely: first, 200g HNBR rubber is dissolved in chlorobenzene solution, and the glue liquid with mass fraction of 7.0% is configured, then the glue liquid is added to the 10L stainless steel reaction kettle with jacket, and nitrogen is blown in to replace 4 times, then 5.0g macromolecular long branch linking agent c is added to the reaction kettle, stirring, heating, when the temperature of the reaction kettle reaches 84℃, 0.24g DCP and 280g mixed solution of chlorobenzene are added, after 9.4hr of reaction, the product is flocculated with anhydrous ethanol, washed, dried in 70℃ oven until constant weight, and the hydrogenated nitrile rubber for oil field of deformation resistance and low temperature grade (grafting rate 2.2%) is obtained. Sample analysis: standard test sample is prepared, and the performance is tested and shown in table 1.

[0132] Comparative example 4

[0133] (1) Preparation of macromolecular long branch linking agent:

[0134] a Preparation of –BR-PS-copolymer: other conditions are the same as example 4, the difference is that

[0135] –BR-PS-copolymer is prepared by adding 1,3-butadiene and styrene together instead of adding them step by step, namely: in the 10L stainless steel polymerization kettle with jacket, the system is replaced 4 times by blowing argon, 2300g cyclohexane, 500g 1,3-butadiene, 260g styrene, 4.0g THF, 219mmol n-butyllithium are added to the polymerization kettle in turn, the temperature is raised to 56℃, and the reaction is carried out for 67min until there is no free monomer, then the glue liquid is condensed by wet method, dried, and the –SBR-block copolymer is prepared.

[0136] b Preparation of macromolecular long branch linking agent: other conditions are the same as example 4, the difference is that the macromolecular long branch linking agent is prepared without adding –BR-PS-copolymer, but adding –SBR-block copolymer, the amount is 34g, namely: first, the 10L high pressure reaction kettle is replaced 4 times by blowing nitrogen, 3600g cyclohexane is added, the temperature is raised to 85℃, then 260g methylaluminoxane catalyst is added dropwise under uniform stirring at the speed of 760rpm, the stirring is continued under nitrogen protection for 26min, then 34g

[0137] - SBR-block copolymer and 1700 g of cyclohexane were mixed and stirred for 53 min, then 120 g of 1-octene and 10 g of trans-bromophenyl (bis(triphenylphosphine)) nickel procatalyst were added into a high-pressure reactor, ethylene was introduced, the pressure was maintained at 18 MPa, and the reaction was carried out for 6.6 hr; after the reaction was completed, centrifugal separation, drying, and preparation were carried out to obtain macromolecular long-chain branch linker d (the number average molecular weight Mn was 6400).

[0138] (2) Preparation of a deformation-resistant and low-temperature grade hydrogenated nitrile rubber for oilfields:

[0139] a Preparation of hydrogenated nitrile rubber (HNBR): same as in Example 4.

[0140] b Preparation of a deformation-resistant and low-temperature grade hydrogenated nitrile rubber for oilfields: other conditions were the same as in Example 4, except that in the preparation of the deformation-resistant and low-temperature grade hydrogenated nitrile rubber for oilfields, the macromolecular long-chain branch linker was not added, but macromolecular long-chain branch linker d was added, and the amount was 6.0 g, that is, first, 200 g of HNBR rubber was dissolved in a chlorobenzene solution to prepare a glue solution with a mass fraction of 7.5%, then the glue solution was added to a 10 L stainless steel reactor with a jacket, nitrogen was introduced for replacement for 4 times, then 6.0 g of macromolecular long-chain branch linker d was added to the reactor, stirring and mixing, heating, when the temperature of the reactor reached 86°C, 0.26 g of DCP and 320 g of a mixture of chlorobenzene were added, the reaction was carried out for 9.6 hr, then flocculation was carried out with anhydrous ethanol, washing, drying in a 70°C oven until the weight was constant, to obtain a deformation-resistant and low-temperature grade hydrogenated nitrile rubber for oilfields (grafting rate 2.6%). Sample analysis: standard samples were prepared, and the performance was tested, as shown in Table 1.

[0141] Comparative Example 5

[0142] (1) Preparation of a macromolecular long-chain branch linker:

[0143] Other conditions were the same as in Example 5, except that in the preparation of the macromolecular long-chain branch linker, the -BR-PS-copolymer was not added, but styrene was added, and the amount was 36 g, that is, first, nitrogen was introduced for replacement for 4 times in a 10 L high-pressure reactor, 3800 g of cyclohexane was added, the temperature was raised to 87°C, then 280 g of methylaluminoxane cocatalyst was gradually added dropwise under uniform stirring at a speed of 780 rpm, stirring was continued under nitrogen protection for 28 min, then 36 g of styrene and 1700 g of cyclohexane were mixed and stirred for 57 min, then 140 g of 1-octene and 10 g of trans-bromophenyl (bis(triphenylphosphine)) nickel procatalyst were added into the high-pressure reactor, ethylene was introduced, the pressure was maintained at 19 MPa, and the reaction was carried out for 6.8 hr; after the reaction was completed, centrifugal separation, drying, and preparation were carried out to obtain macromolecular long-chain branch linker e (the number average molecular weight Mn was 3800).

[0144] (2) Preparation of hydrogenated nitrile rubber for oil field of deformation resistance and low temperature grade:

[0145] a Preparation of hydrogenated nitrile rubber (HNBR): same as example 5.

[0146] b Preparation of hydrogenated nitrile rubber for oil field of deformation resistance and low temperature grade: other conditions are same as example 5, the difference is that the macromolecular long-branching chain grafting agent is not added in the preparation process of hydrogenated nitrile rubber for oil field of deformation resistance and low temperature grade, but macromolecular long-branching chain grafting agent e is added, the amount is 7.0g, namely: first, 200g HNBR rubber is dissolved in chlorobenzene solution, and a glue solution with a mass fraction of 8.0% is configured, then the glue solution is added to a 10L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace 5 times, then 7.0g macromolecular long-branching chain grafting agent e is added to the reaction kettle, stirring, heating, when the temperature of the reaction kettle reaches 89℃, 0.29g DCP and 360g mixed solution of chlorobenzene are added, after 9.8hr of reaction, flocculation with anhydrous ethanol, washing, drying in a 70℃ oven until constant weight, hydrogenated nitrile rubber for oil field of deformation resistance and low temperature grade (grafting rate 3.0%) is obtained. Sample analysis: standard test samples are prepared, and the performance is tested as shown in table 1.

[0147] Comparative example 6

[0148] (1) Preparation of macromolecular long-branching chain grafting agent:

[0149] a Preparation of –BR-PS-copolymer: same as example 6.

[0150] b Preparation of macromolecular long-branching chain grafting agent: other conditions are same as example 6, the difference is that 1-hexene is not added in the preparation process of macromolecular long-branching chain grafting agent, but 1-butene is added, the amount is 150g, namely: first, nitrogen is introduced to replace 5 times in a 10L high-pressure reaction kettle, 4000g cyclohexane is added, after heating to 90℃, 300g methylaluminoxane co-catalyst is added dropwise under uniform stirring at a speed of 800rpm, stirring is continued for 30min under nitrogen protection, then 40g –BR-PS-copolymer and 2000g cyclohexane are mixed and dissolved for 60min, then 150g 1-butene and 10g trans-bromophenyl (di(triphenylphosphine)) nickel main catalyst are added to the high-pressure reaction kettle, ethylene is introduced, the pressure is maintained at 20MPa, and the reaction is carried out for 7.0hr; after the reaction is completed, centrifugal separation, drying, and macromolecular long-branching chain grafting agent f (number average molecular weight Mn is 6500) is prepared.

[0151] (2) Preparation of hydrogenated nitrile rubber for oil field of deformation resistance and low temperature grade:

[0152] a Preparation of hydrogenated nitrile rubber (HNBR): same as example 6.

[0153] b Preparation of hydrogenated nitrile rubber for low temperature and deformation resistant oil field: other conditions are the same as example 6, the difference is that the macromolecular long branch linking agent is not added in the preparation process of hydrogenated nitrile rubber for low temperature and deformation resistant oil field, but macromolecular long branch linking agent f is added, the amount is 8.0g, namely: first, 200g HNBR rubber is dissolved in chlorobenzene solution, and the glue liquid with mass fraction of 9.0% is configured, then the glue liquid is added to the 10L stainless steel reaction kettle with jacket, nitrogen is replaced for 5 times, then 8.0g macromolecular long branch linking agent f is added to the reaction kettle, stirring, heating, when the temperature of the reaction kettle reaches 90℃, 0.30g BPO and 400g chlorobenzene mixture are added, after 10.0hr reaction, flocculation with anhydrous ethanol, washing, drying in 70℃ oven to constant weight, hydrogenated nitrile rubber for low temperature and deformation resistant oil field (grafting rate 3.2%) is obtained. Sampling analysis: standard test sample is prepared, and the performance is tested and seen in table 1.

[0154] Table 1 Performance of hydrogenated nitrile rubber for low temperature and deformation resistant oil field

[0155]

[0156]

[0157] From table 1, it can be seen that the hydrogenated nitrile rubber for low temperature and deformation resistant oil field of the application has high tear strength, small compression permanent deformation and low glass transition temperature, and is suitable for oil well operation under low temperature working condition of-57℃ working temperature.

[0158] Of course, the present application can also 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 should belong to the protection scope of the present application.

Claims

1. A method for preparing a deformation-resistant, low-temperature-grade hydrogenated nitrile butadiene rubber for oilfield use, characterized in that, Includes the following steps: (1) Preparation of macromolecular long-branched linking agents: Preparation of α-BR-PS- copolymer: Argon gas was introduced into the polymerization reactor to replace the system. Solvent, 1,3-butadiene, structure modifier, and initiator 1 were added to the polymerization reactor in sequence. The temperature was raised and the reaction was carried out to form BR segments. Then styrene and structure modifier were added to the polymerization reactor in sequence. The temperature was raised and the reaction was carried out until no free monomers were present. The glue solution was wet coagulated and dried to obtain α-BR-PS-block copolymer. Preparation of macromolecular long-branched linking agent: An inert gas is introduced into the reactor for purging, a solvent is added, the temperature is raised, and an alkylaluminoxane co-catalyst is added under stirring. Stirring continues under inert gas protection. Then, the BR-PS-block copolymer and solution are mixed and stirred until completely dissolved. This is then added to the reactor along with a long-chain α-olefin and a nickel-based complexing catalyst. Ethylene is then introduced, and the reaction proceeds. After the reaction is complete, the mixture is centrifuged and dried to obtain the macromolecular long-branched linking agent. The mass ratio of the solvent, alkylaluminoxane co-catalyst, BR-PS-block copolymer, solution, long-chain α-olefin, and nickel-based complexing catalyst is 300~400:20~30:2.0~4.0:100~200:8~15:

1. The long-chain α-olefin is selected from one of 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, and 1-dodecene. (2) Preparation of deformation-resistant, low-temperature grade hydrogenated nitrile butadiene rubber for oilfield use: Preparation of hydrogenated nitrile butadiene rubber (HNBR): Nitrile butadiene rubber is dissolved in chlorobenzene solution to prepare a rubber solution. The rubber solution is then added to a reaction vessel, and an inert gas is introduced to remove air from the reaction vessel. After removing the inert gas from the reaction vessel with hydrogen, 0.02~0.1 parts of xylene solution containing Grubbs I catalyst are added under nitrogen protection. The system is pressurized, heated, and reacted. The system is then cooled, condensed, and dried to obtain HNBR rubber. b. Preparation of deformation-resistant, low-temperature grade 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 long-branched linking agent is then added to the reaction vessel, stirred and mixed, heated, and a mixture of initiator 2 and chlorobenzene is added. The reaction proceeds, followed by flocculation, washing, and drying to obtain deformation-resistant, low-temperature grade hydrogenated nitrile butadiene rubber for oilfields. The number-average molecular weight (Mn) of the macromolecular long-branched linker is 6000~7000.

2. The preparation method according to claim 1, characterized in that, The nickel-based complexing catalyst is selected from one of (1-naphthyl)[8-(diphenylphosphino)quinoline]nickel chloride, trans-phenyl bromide (di(triphenylphosphine))nickel, and 2,5-dicarboxypyrrole nickel dibromide.

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

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, and its addition amount is 0.0~0.2 parts based on 100 parts 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, and 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), diethyl 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, during the formation of the BR segment, the mass ratio of solvent, 1,3-butadiene, and structure modifier is 400~500:100:0.5~1.

0.

10. The preparation method according to claim 1, characterized in that, In step (1)a, based on 100 parts by mass of 1,3-butadiene, the amount of styrene added during the formation of the –BR-PS-block copolymer is 40-60 parts, and the amount of the structure modifier added is 1.0-1.5 parts.

11. The preparation method according to claim 1, characterized in that, In step (2)a, the mass ratio of the nitrile rubber to the Grubbs I catalyst is 100:0.02~0.

1.

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

13. The preparation method according to claim 1, characterized in that, The mass ratio of the HNBR rubber, the macromolecular long-branched linker, and the chlorobenzene is 100:2~4:100~200.

14. The preparation method according to claim 1, characterized in that, In step (2)b, the grafting rate of the deformation-resistant, low-temperature grade hydrogenated nitrile butadiene rubber for oilfield use is 1.8% to 3.2%.

15. A deformation-resistant, low-temperature grade hydrogenated nitrile butadiene rubber for oilfield use obtained by the preparation method according to any one of claims 1-14.

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