Low-temperature-resistant hydrogenated nitrile rubber for oil field and preparation method thereof

Abstract

The application discloses a low-temperature-resistant hydrogenated butyl nitrile rubber for oil fields and a preparation method thereof, and the preparation method comprises the following steps: preparing a reactive macromolecular long-chain linking branching agent, preparing long-chain branched butyl nitrile rubber, and preparing the low-temperature-resistant hydrogenated butyl nitrile rubber for oil fields, wherein the reactive macromolecular long-chain linking branching agent has the following structure: wherein R is a linear alkyl group with 6-12 carbon atoms; 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; and the number average molecular weight (Mn) of the reactive macromolecular long-chain linking branching agent is 4000-6000. The preparation method of the low-temperature-resistant hydrogenated butyl nitrile rubber for oil fields has the characteristics of green environmental protection, efficient and stable modification effect, low addition ratio, easy availability of 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 low-temperature-resistant hydrogenated nitrile rubber and a preparation method thereof. BACKGROUND

[0002] Hydrogenated nitrile rubber (HNBR) 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) 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 rubber sealing materials 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 compression cold-resistant special hydrogenated nitrile rubber 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 45℃ 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 low-temperature hydrogenated butyronitrile rubber with hydrogenation degree of more than 96% and glass transition temperature Tg of raw rubber of less than -49 DEG C, which can meet the use requirement in the range of -49 DEG C to -53 DEG C. The method comprises the following steps: firstly, using coordination polymerization, long-chain alpha-olefin monomer is reacted with ethylene under the action of nickel-based complex catalyst to prepare a reactive macromolecular long-chain grafting agent with radical reaction activity; then, the reactive macromolecular long-chain grafting agent is grafted to the main chain of butyronitrile rubber to prepare long-chain branched butyronitrile rubber; finally, the long-chain branched butyronitrile rubber is subjected to hydrogenation reaction to prepare low-temperature resistant hydrogenated butyronitrile rubber for oil field. The method solves the problem that butyronitrile rubber is easy to crystallize in the hydrogenation process, thereby causing the glass transition temperature Tg to increase, and makes the hydrogenated butyronitrile rubber show very excellent low-temperature resistance, which is very suitable for oil well operation under low-temperature working condition of -49 DEG C.

[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 low-temperature resistant hydrogenated butyronitrile rubber for oil field, which comprises the following steps:

[0010] (1) Firstly, inert gas is introduced into a reaction kettle for replacement, a solvent is added, and the temperature is raised. Under stirring, an alkyl aluminum oxide cocatalyst is added, and then the nickel-based complex catalyst and long-chain alpha-olefin are added under the protection of inert gas. Ethylene is introduced, and the reaction is started. After the reaction is completed, centrifugal separation and drying are carried out to obtain a reactive macromolecular long-chain grafting agent;

[0011] (2) Butyronitrile rubber is dissolved in chlorobenzene solution to prepare a glue solution, and then the glue solution is added into the reaction kettle. Nitrogen is introduced for replacement, and then the reactive macromolecular long-chain grafting agent is added into the reaction kettle. After stirring and mixing, heating is carried out. Then, an initiator and a mixed solution of chlorobenzene are added. After the reaction is completed, flocculation, washing and drying are carried out to obtain long-chain branched butyronitrile rubber;

[0012] (3) The long-chain branched butyronitrile rubber is dissolved in a solvent to prepare a glue solution, which is then added into the reaction kettle. Inert gas is introduced to remove air in the reaction kettle. Then, hydrogen is used to remove the inert gas in the reaction kettle. Under the protection of nitrogen, a dimethylbenzene solution of Grubbs II catalyst is added. After pressure and temperature rising, reaction, temperature dropping, coagulation and drying are carried out to obtain low-temperature resistant hydrogenated butyronitrile rubber for oil field;

[0013] The reactive macromolecular long-chain grafting agent has the following structure:

[0014]

[0015] In the formula, R is C6-C30, n is 1-10, and m is 1-10.12 a straight-chain alkyl; 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 reactive macromolecular long-chain linking agent is 4000-6000.

[0016] The long-chain α-olefin according to the present application is a C6-C12 straight-chain olefin, 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.

[0017] The nickel-based complex catalyst according to the present application is selected from one of chloro(1-naphthyl)〔8-(diphenylphosphino)quinoline〕nickel, trans-phenyl(bis(triphenylphosphine))nickel bromide and 2,5-diformylpyrrole nickel dibromide, and is preferably trans-phenyl(bis(triphenylphosphine))nickel bromide.

[0018] The alkylaluminoxane cocatalyst according to the present application is selected from one of methylaluminoxane (MAO) and ethylaluminoxane (EAO), and is preferably methylaluminoxane.

[0019] In step (1) of the present application, the mass ratio of the solvent, the alkylaluminoxane cocatalyst, the long-chain α-olefin and the nickel-based complex catalyst is 300-500:10-20:20-30:1.

[0020] In step (1), the temperature is raised to 70-90°C, the rotation speed is 500-700 rpm, and the time for continuing stirring is 15-30 min.

[0021] In step (1), the reaction pressure is 10-15 MPa, and the reaction time is 3.0-6.0 hr.

[0022] The initiator according to the present application is an organic peroxide selected from one of diacetyl peroxide, diisobutyryl peroxide, cumene hydroperoxide, dicumyl peroxide (DCP) and dibenzoyl peroxide, and is preferably dicumyl peroxide (DCP). The amount of the initiator added is 0.01-0.1 parts, preferably 0.03-0.05 parts, based on 100 parts of the mass of the nitrile rubber.

[0023] The nitrile rubber according to the present application is obtained by copolymerization of 1,3-butadiene and acrylonitrile through emulsion polymerization, and the acrylonitrile content of the nitrile rubber is 20wt%-42wt%, preferably 22wt%-35wt%.

[0024] In step (2) of the present application, the mass fraction of the glue solution is 5%-7%.

[0025] In step (2) of the present application, the mass ratio of the reactive macromolecular long chain linking agent, chlorobenzene and butyl nitrile rubber is 5-7: 50-100: 100.

[0026] In step (2) of the present application, the grafting rate of the long chain branched butyl nitrile rubber is 3.8%-4.9%.

[0027] In step (2) of the present application, the heating is to 70-80℃, and the reaction time is 6.0-7.0 hr.

[0028] The solvent of the present application can be selected from one of cyclohexane, carbon disulfide (CS2), nitrobenzene, petroleum ether, tetrachloroethane, toluene, xylene, preferably xylene.

[0029] In step (3) of the present application, the mass ratio of the long chain branched butyl nitrile rubber and Grubbs II catalyst is 100: 0.1-0.5.

[0030] In step (3) of the present application, the mass fraction of the glue solution is 3%-10%, and the mass concentration of the xylene solution of Grubbs II catalyst is 5%-10%.

[0031] In step (3) of the present application, the pressure is increased to 6-10 MPa, the temperature is increased to 80-110℃, and the reaction time is 8-10 hr.

[0032] The polymerization reaction of the present application is carried out in an oxygen-free, water-free and inert gas environment. The inert gas is nitrogen or a gas of element group 0 in the periodic table except radon, preferably nitrogen.

[0033] The reaction kettle of the present application can be a loop reactor or a tank reactor, preferably a tank reactor.

[0034] The pressurization in step (3) of the present application is achieved by adding hydrogen. 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.

[0035] The present application also provides a low-temperature-resistant hydrogenated butyl nitrile rubber for oil field prepared by the above preparation method.

[0036] Compared with the prior art, the present application has at least the following advantages and beneficial effects:

[0037] (1) The prepared reactive macromolecular long chain branch linking agent is composed of long chain alpha-olefin into a macromolecular chain by coordination polymerization, and has free radical reactivity after activation treatment by ethylene, so that it can be grafted onto the butyl nitrile rubber to form long chain branched structure on the main chain structure of butyl nitrile rubber. This structure can significantly destroy the highly saturated carbon hydrogen structure of HNBR at a low addition amount, effectively reduce the crystallinity of HNBR, greatly reduce the glass transition temperature (Tg) of hydrogenated butyl nitrile rubber, and can prepare low temperature grade hydrogenated butyl nitrile rubber with Tg<-49℃.

[0038] (2) The prepared long chain branched butyl nitrile rubber fully utilizes the "structure stacking effect" of long branched chain under the premise of ensuring hydrogenation degree, greatly improves the low temperature resistance modification effect, and can meet the use requirements of oil drilling equipment for rubber sealing materials under the condition of-49℃ to-53℃ minimum temperature.

[0039] (3) The preparation method of the low temperature resistant hydrogenated butyl nitrile rubber for oil field has the characteristics of green environmental protection, high and stable modification effect, low addition ratio, easy-to-buy raw materials, and is suitable for industrial production. DETAILED DESCRIPTION

[0040] The following examples and comparative examples are used 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.

[0041] (1) Raw material sources:

[0042]

[0043] (2) Analysis test method:

[0044] Determination of grafting rate: about 4g of sample was taken from a three-necked bottle into a weighing bottle, 2-3 drops of hydroquinone solution was added after weighing, and then dried to constant weight. Then the above sample was placed in a soxhlet fat extractor, extracted with toluene at 90℃ water bath for 24h, and then dried to constant weight. The monomer grafting rate was calculated according to the following formula:

[0045]

[0046] In the formula, m0 is the total mass of the rubber slurry (g); m is the mass of the sample after reaction (g); m m is the total mass of monomer in the reactant (g); m NBR is the mass of butyl nitrile rubber in the sample (g); m1 is the mass of the sample after extraction (g).

[0047] 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 .

[0048] 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:

[0049] Degree of hydrogenation (HD%) = 1 - Degree of unsaturation (U)

[0050] Determination of glass transition temperature (Tg): The glass transition temperature of the product was measured using DSC. The instrument model was DSC1, manufactured by Mettler AG, Switzerland. The heating range was -80 to 80 °C, and the heating rate was 10 °C / min.

[0051] Example 1

[0052] (1) Preparation of reactive macromolecular long-linked branching agents:

[0053] First, nitrogen was purged twice in a 10L high-pressure reactor. Then, 3000g of xylene was added, and the temperature was raised to 70℃. 100g of methylaluminoxane co-catalyst was added dropwise under uniform stirring at 500rpm. Stirring was continued for 15min under nitrogen protection. Then, 10g of trans-bromophenyl(di(triphenylphosphine))nickel main catalyst and 200g of 1-octene were added, and ethylene was introduced. The pressure was maintained at 10MPa, and the reaction was carried out for 3.0hr. After the reaction was completed, the reactive macromolecular long-linked branching agent (number average molecular weight Mn of 4100) was obtained by centrifugation, drying, and separation.

[0054] (2) Preparation of long-chain branched nitrile butadiene rubber:

[0055] Firstly, 200 g of nitrile rubber 2707 was dissolved in chlorobenzene solution to prepare a glue solution with a mass fraction of 5%, and then the glue solution was added to a 10 L stainless steel reaction kettle with a jacket, replaced with nitrogen gas for 3 times, and then 10 g of reactive macromolecular long chain branching agent was added to the reaction kettle, stirred and heated. When the temperature of the reaction kettle reached 70°C, 0.06 g of DCP and 100 g of chlorobenzene mixture were added, and after 6.0 hr of reaction, the product was flocculated with anhydrous ethanol, washed, and dried in a 70°C oven until the weight was constant, to obtain long-chain branched nitrile rubber (grafting rate 3.8%).

[0056] (3) Preparation of low-temperature-resistant hydrogenated nitrile rubber for oil field:

[0057] Firstly, 100 g of long-chain branched nitrile rubber was dissolved in xylene to prepare a glue solution with a mass fraction of 3%, and then added to a 10 L high-pressure reaction kettle to remove air in the reaction kettle by nitrogen gas. After 30 min of nitrogen gas removal, 0.1 g of Grubbs II catalyst in xylene solution (mass concentration 5%) was added under nitrogen protection, the hydrogen pressure in the reaction kettle was increased to 6 MPa, and the temperature was increased to 80°C. After 8.0 hr of reaction, the system was cooled, coagulated, and vacuum dried to obtain low-temperature-resistant hydrogenated nitrile rubber for oil field. Sample analysis: standard test samples were prepared, and the performance was tested as shown in Table 1.

[0058] Example 2

[0059] (1) Preparation of reactive macromolecular long chain branching agent:

[0060] Firstly, 3500 g of xylene was added to a 10 L high-pressure reaction kettle, and the temperature was increased to 75°C. Under uniform stirring at a speed of 550 rpm, 120 g of methylaluminoxane co-catalyst was gradually added dropwise, and the stirring was continued for 20 min under nitrogen gas protection. Then, 10 g of trans-bromophenyl (bis(triphenylphosphine)) nickel main catalyst and 220 g of 1-octene were added, and ethylene was introduced, keeping the pressure at 11 MPa for 3.5 hr. After the reaction was completed, the product was separated by centrifugation, dried, and obtained as a reactive macromolecular long chain branching agent (number average molecular weight Mn4600).

[0061] (2) Preparation of long-chain branched nitrile rubber:

[0062] Firstly, 200 g of nitrile rubber 2707 was dissolved in chlorobenzene solution to prepare a glue solution with a mass fraction of 5.5%, and then the glue solution was added to a 10 L stainless steel reaction kettle with a jacket, and replaced with nitrogen gas for 3 times. Then 11 g of reactive macromolecular long chain branching agent was added to the reaction kettle, and stirred and heated. When the temperature of the reaction kettle reached 72°C, 0.07 g of DCP and 120 g of a mixture of chlorobenzene were added. After 6.2 hours of reaction, the product was flocculated with anhydrous ethanol, washed, and dried in a 70°C oven until the weight was constant, to obtain long-chain branched nitrile rubber (grafting rate 4.1%).

[0063] (3) Preparation of low-temperature-resistant hydrogenated nitrile rubber for oil field:

[0064] Firstly, 100 g of long-chain branched nitrile rubber was dissolved in xylene to prepare a glue solution with a mass fraction of 5%. Then, the glue solution was added to a 10 L high-pressure reaction kettle, and nitrogen was introduced to remove air in the reaction kettle. Then, the nitrogen in the reaction kettle was replaced with hydrogen for 32 min. Then, 0.2 g of Grubbs II catalyst in xylene solution (mass concentration 6%) was added under nitrogen protection. The hydrogen pressure in the reaction kettle was increased to 7 MPa, and the temperature was increased to 90°C. After 8.5 hours of reaction, the system was cooled, coagulated, and vacuum dried to obtain low-temperature-resistant hydrogenated nitrile rubber for oil field. Sample analysis: standard test samples were prepared, and the performance was tested as shown in Table 1.

[0065] Example 3

[0066] (1) Preparation of reactive macromolecular long chain branching agent:

[0067] Firstly, 4000 g of xylene was added to a 10 L high-pressure reaction kettle, and the temperature was increased to 80°C. Then, 140 g of methylaluminoxane co-catalyst was added dropwise under uniform stirring at a speed of 600 rpm. After 23 min of stirring under nitrogen protection, 10 g of trans-bromophenyl (bis(triphenylphosphine)) nickel main catalyst and 240 g of 1-octene were added, and ethylene was introduced. The pressure was maintained at 12 MPa, and the reaction was carried out for 4.0 hours. After the reaction was completed, the product was separated by centrifugation, dried, and obtained as a reactive macromolecular long chain branching agent (number average molecular weight Mn 5100).

[0068] (2) Preparation of long-chain branched nitrile rubber:

[0069] Firstly, 200 g of nitrile rubber 2707 was dissolved in chlorobenzene solution to prepare a glue solution with a mass fraction of 6.0%, and then the glue solution was added to a 10 L stainless steel reaction kettle with a jacket, and replaced with nitrogen gas for 4 times. Then 12 g of reactive macromolecular long chain branching agent was added to the reaction kettle, and stirred and heated. When the temperature of the reaction kettle reached 74°C, 0.08 g of DCP and 140 g of a mixture of chlorobenzene were added. After 6.4 hours of reaction, the product was flocculated with anhydrous ethanol, washed, and dried in a 70°C oven until the weight was constant, to obtain long-chain branched nitrile rubber (grafting rate 4.3%).

[0070] (3) Preparation of low-temperature-resistant hydrogenated nitrile rubber for oil field:

[0071] Firstly, 100 g of long-chain branched nitrile rubber was dissolved in xylene to prepare a glue solution with a mass fraction of 5%, and then added to a 10 L high-pressure reaction kettle. Nitrogen was introduced to remove air in the reaction kettle, and then hydrogen was introduced to remove nitrogen in the reaction kettle for 35 min. Under nitrogen protection, 0.3 g of Grubbs II catalyst in xylene solution (mass concentration 7%) was added. The hydrogen pressure in the reaction kettle was increased to 8 MPa, and the temperature was increased to 95°C. After 9.0 hours of reaction, the system was cooled, coagulated, and vacuum dried to obtain low-temperature-resistant hydrogenated nitrile rubber for oil field. Sample analysis: standard test samples were prepared, and the performance was tested as shown in Table 1.

[0072] Example 4

[0073] (1) Preparation of reactive macromolecular long chain branching agent:

[0074] Firstly, 4300 g of xylene was added to a 10 L high-pressure reaction kettle, and the temperature was increased to 83°C. Under uniform stirring at a speed of 620 rpm, 160 g of methylaluminoxane co-catalyst was gradually added dropwise. After stirring for 25 min under nitrogen protection, 10 g of trans-bromophenyl (bis(triphenylphosphine)) nickel main catalyst and 260 g of 1-octene were added, and ethylene was introduced. The pressure was maintained at 13 MPa, and the reaction was carried out for 4.4 hours. After the reaction was completed, the product was separated by centrifugation, dried, and prepared into a reactive macromolecular long chain branching agent (number average molecular weight Mn5400).

[0075] (2) Preparation of long-chain branched nitrile rubber:

[0076] Firstly, 200 g of nitrile rubber 2707 was dissolved in chlorobenzene solution to prepare a glue solution with a mass fraction of 6.4%, and then the glue solution was added to a 10 L stainless steel reaction kettle with a jacket, and replaced with nitrogen gas for 4 times. Then 12.5 g of reactive macromolecular long chain branching agent was added to the reaction kettle, and stirred, mixed and heated. When the temperature of the reaction kettle reached 76°C, 0.085 g of DCP and 170 g of chlorobenzene mixture were added. After 6.6 hours of reaction, the product was flocculated with anhydrous ethanol, washed, and dried in a 70°C oven until the weight was constant, to obtain long-chain branched nitrile rubber (grafting rate 4.4%).

[0077] (3) Preparation of low-temperature-resistant hydrogenated nitrile rubber for oil field:

[0078] Firstly, 100 g of long-chain branched nitrile rubber was dissolved in xylene to prepare a glue solution with a mass fraction of 6%. Then, the glue solution was added to a 10 L high-pressure reaction kettle, and nitrogen was introduced to remove air in the reaction kettle. Then, the nitrogen in the reaction kettle was replaced with hydrogen for 37 min. Then, 0.35 g of Grubbs II catalyst in xylene solution (mass concentration 8%) was added under nitrogen protection. The hydrogen pressure in the reaction kettle was increased to 8.5 MPa, and the temperature was increased to 100°C. After 9.3 hours of reaction, the system was cooled, coagulated, and vacuum dried to obtain low-temperature-resistant hydrogenated nitrile rubber for oil field. Sample analysis: standard test samples were prepared, and the performance was tested as shown in Table 1.

[0079] Example 5

[0080] (1) Preparation of reactive macromolecular long chain branching agent:

[0081] Firstly, 4600 g of xylene was added to a 10 L high-pressure reaction kettle, and the temperature was increased to 87°C. Then, 180 g of methylaluminoxane co-catalyst was added under uniform stirring at a speed of 660 rpm. After 28 min of stirring under nitrogen protection, 10 g of trans-bromophenyl (bis(triphenylphosphine)) nickel main catalyst and 280 g of 1-octene were added, and ethylene was introduced. The pressure was maintained at 14 MPa, and the reaction was carried out for 4.6 hours. After the reaction was completed, the product was separated by centrifugation, dried, and obtained as a reactive macromolecular long chain branching agent (number average molecular weight Mn 5600).

[0082] (2) Preparation of long-chain branched nitrile rubber:

[0083] Firstly, 200 g of nitrile rubber 2707 was dissolved in chlorobenzene solution to prepare a glue solution with a mass fraction of 6.6%, and then the glue solution was added to a 10 L stainless steel reaction kettle with a jacket, and replaced with nitrogen gas for 5 times. Then 13 g of reactive macromolecular long chain branching agent was added to the reaction kettle, and stirred and heated. When the temperature of the reaction kettle reached 78℃, 0.09 g of DCP and 180 g of chlorobenzene mixture were added. After 6.8 hours of reaction, the product was flocculated with anhydrous ethanol, washed, and dried in a 70℃ oven until the weight was constant, to obtain long-chain branched nitrile rubber (grafting rate 4.6%).

[0084] (3) Preparation of low-temperature-resistant hydrogenated nitrile rubber for oil field:

[0085] Firstly, 100 g of long-chain branched nitrile rubber was dissolved in xylene to prepare a glue solution with a mass fraction of 8%, and then added to a 10 L high-pressure reaction kettle. Nitrogen was introduced to remove air in the reaction kettle, and then hydrogen was introduced to remove nitrogen in the reaction kettle for 38 min. Under nitrogen protection, 0.4 g of Grubbs II catalyst solution in xylene (mass concentration 9%) was added. The hydrogen pressure in the reaction kettle was increased to 9 MPa, and the temperature was increased to 105℃. After 9.6 hours of reaction, the system was cooled, coagulated, and vacuum dried to obtain low-temperature-resistant hydrogenated nitrile rubber for oil field. Sample analysis: standard test samples were prepared, and the performance was tested as shown in Table 1.

[0086] Example 6

[0087] (1) Preparation of reactive macromolecular long chain branching agent:

[0088] Firstly, 5000 g of xylene was added to a 10 L high-pressure reaction kettle, and the temperature was increased to 90℃. Under uniform stirring at a speed of 700 rpm, 200 g of methylaluminoxane co-catalyst was gradually added dropwise, and then 10 g of trans-bromophenyl (bis(triphenylphosphine)) nickel main catalyst and 300 g of 1-octene were added under nitrogen protection. The pressure was maintained at 15 MPa, and the reaction was carried out for 6.0 hours. After the reaction was completed, the product was separated by centrifugation, dried, and obtained as a reactive macromolecular long chain branching agent (number average molecular weight Mn 6000).

[0089] (2) Preparation of long-chain branched nitrile rubber:

[0090] Firstly, 200 g of nitrile rubber 2707 was dissolved in chlorobenzene solution to prepare a glue solution with a mass fraction of 7.0%, and then the glue solution was added to a 10 L stainless steel reaction kettle with a jacket, and replaced with nitrogen gas for 5 times. Then, 14 g of reactive macromolecular long chain branching agent was added to the reaction kettle, and stirred, mixed and heated. When the temperature of the reaction kettle reached 80°C, 0.1 g of DCP and 200 g of chlorobenzene mixture were added. After 7.0 hr of reaction, the product was flocculated with anhydrous ethanol, washed, and dried in a 70°C oven until the weight was constant, to obtain long-chain branched nitrile rubber (grafting rate 4.9%).

[0091] (3) Preparation of low-temperature-resistant hydrogenated nitrile rubber for oil field:

[0092] Firstly, 100 g of long-chain branched nitrile rubber was dissolved in xylene to prepare a glue solution with a mass fraction of 10%, and then added to a 10 L high-pressure reaction kettle. Nitrogen was introduced to remove air in the reaction kettle, and then hydrogen was introduced to remove nitrogen in the reaction kettle for 40 min. Under nitrogen protection, 0.5 g of Grubbs II catalyst solution in xylene (mass concentration 10%) was added. The hydrogen pressure in the reaction kettle was increased to 10 MPa, and the temperature was increased to 110°C. After 10.0 hr of reaction, the system was cooled, coagulated, and vacuum dried to obtain low-temperature-resistant hydrogenated nitrile rubber for oil field. Sample analysis: standard test samples were prepared, and the performance was tested as shown in Table 1.

[0093] Example 7

[0094] (1) Preparation of reactive macromolecular long chain branching agent:

[0095] Firstly, 5000 g of xylene was added to a 10 L high-pressure reaction kettle, and the temperature was increased to 90°C. Under uniform stirring at a speed of 700 rpm, 200 g of ethyl aluminum oxane cocatalyst was gradually added dropwise, and then 10 g of 2,5-diformylpyrrole nickel dibromide main catalyst and 300 g of 1-hexene were added under nitrogen protection. The pressure was maintained at 15 MPa, and the reaction was carried out for 6.0 hr. After the reaction was completed, the product was separated by centrifugation, dried, and obtained as a reactive macromolecular long chain branching agent (number average molecular weight Mn 5700).

[0096] (2) Preparation of long-chain branched nitrile rubber:

[0097] Firstly, 200 g of nitrile rubber 2707 was dissolved in chlorobenzene solution to prepare a glue solution with a mass fraction of 7.0%, and then the glue solution was added to a 10 L stainless steel reaction kettle with a jacket, and replaced with nitrogen gas for 5 times. Then, 14 g of reactive macromolecular long chain branch linker was added to the reaction kettle, and stirred and heated. When the temperature of the reaction kettle reached 80℃, a mixture of 0.2 g of diacetyl peroxide and 200 g of chlorobenzene was added. After 7.0 hr of reaction, the product was flocculated with anhydrous ethanol, washed, and dried in a 70℃ oven until the weight was constant, to obtain long-chain branched nitrile rubber (grafting rate 4.7%).

[0098] (3) Preparation of low-temperature-resistant hydrogenated nitrile rubber for oil field:

[0099] Firstly, 100 g of long-chain branched nitrile rubber was dissolved in xylene to prepare a glue solution with a mass fraction of 10%, and then added to a 10 L high-pressure reaction kettle. Nitrogen was introduced to remove air in the reaction kettle, and then hydrogen was introduced to remove nitrogen in the reaction kettle for 40 min. Then, 0.5 g of Grubbs II catalyst in xylene solution (mass concentration 10%) was added under nitrogen protection. The hydrogen pressure in the reaction kettle was increased to 10 MPa, and the temperature was increased to 110℃. After 10.0 hr of reaction, the system was cooled, coagulated, and vacuum dried to obtain low-temperature-resistant hydrogenated nitrile rubber for oil field. Sample analysis: standard samples were prepared, and the performance was tested as shown in Table 1.

[0100] Comparative Example 1

[0101] (1) Preparation of reactive macromolecular long chain branch linker:

[0102] The other conditions were the same as in Example 1, except that the amount of trans-bromophenyl (di(triphenylphosphine)) nickel main catalyst added in the preparation process of the reactive macromolecular long chain branch linker was 5 g, i.e.: first, nitrogen was introduced into a 10 L high-pressure reaction kettle for 2 times, 3000 g of xylene was added, and the temperature was increased to 70℃. Then, 100 g of methylaluminoxane cocatalyst was added dropwise under uniform stirring at a speed of 500 rpm, and stirring was continued for 15 min under nitrogen protection. Then, 5 g of trans-bromophenyl (di(triphenylphosphine)) nickel main catalyst and 200 g of 1-octene were added, and ethylene was introduced, and the pressure was maintained at 10 MPa for 3.0 hr of reaction; after the reaction was completed, centrifugal separation, drying, and preparation of the reactive macromolecular long chain branch linker a (number average molecular weight Mn 2600) were performed.

[0103] (2) Preparation of long-chain branched nitrile rubber:

[0104] The other conditions are the same as in Example 1, except that no reactive macromolecular long-chain branching agent is added in the preparation process of the long-chain branched nitrile rubber, but a reactive macromolecular long-chain branching agent a is added, and the amount is 10 g, that is, first 200 g of nitrile rubber 2707 is dissolved in chlorobenzene solution to prepare a glue solution with a mass fraction of 5%, then the glue solution is added to a 10 L stainless steel reaction kettle with a jacket, and the reaction kettle is replaced with nitrogen gas for 3 times, then 10 g of reactive macromolecular long-chain branching agent a is added to the reaction kettle, and stirring, mixing and heating are carried out, 0.06 g of DCP and 100 g of a mixture of chlorobenzene are added when the temperature of the reaction kettle reaches 70°C, and after 6.0 hr of reaction, the product is flocculated with anhydrous ethanol, washed, dried in a 70°C oven until the weight is constant, and long-chain branched nitrile rubber a (grafting rate 3.5%) is obtained.

[0105] (3) Preparation of low-temperature-resistant hydrogenated nitrile rubber for oil field:

[0106] The other conditions are the same as in Example 1, except that no long-chain branched nitrile rubber is added in the preparation process of the low-temperature-resistant hydrogenated nitrile rubber for oil field, but long-chain branched nitrile rubber a is added, and the amount is 100 g, that is, first 100 g of long-chain branched nitrile rubber a is dissolved in xylene to prepare a glue solution with a mass fraction of 3%, then it is added to a 10 L high-pressure reaction kettle, nitrogen gas is introduced to remove air in the reaction kettle, then hydrogen gas is used to remove nitrogen gas in the reaction kettle for 30 min, then 0.1 g of Grubbs II catalyst in xylene solution (mass concentration 5%) is added under nitrogen protection, the hydrogen pressure in the pressurized reaction kettle is 6 MPa, the temperature is raised to 80°C, and after 8.0 hr of reaction, the system is cooled, coagulated and vacuum dried to obtain the low-temperature-resistant hydrogenated nitrile rubber for oil field. Sample analysis: standard test samples are prepared, and the performance is tested as shown in Table 1.

[0107] Comparative Example 2

[0108] (1) Preparation of reactive macromolecular long-chain branching agent:

[0109] The other conditions are the same as in Example 2, except that no 1-octene is added in the preparation process of the reactive macromolecular long-chain branching agent, but 1-butene is added, and the amount is 220 g, that is, first nitrogen gas is introduced into a 10 L high-pressure reaction kettle for 2 times, 3500 g of xylene is added, the temperature is raised to 75°C, then 120 g of methylaluminoxane co-catalyst is added dropwise under uniform stirring at a speed of 550 rpm, stirring is continued for 20 min under nitrogen protection, then 10 g of trans-bromophenyl (bis(triphenylphosphine)) nickel main catalyst and 220 g of 1-butene are added, and ethylene is introduced, and the pressure is maintained at 11 MPa for 3.5 hr; after the reaction is completed, centrifugal separation, drying and preparation are carried out to obtain the reactive macromolecular long-chain branching agent b (number average molecular weight Mn is 3900).

[0110] (2) Preparation of long-chain branched nitrile rubber:

[0111] The other conditions were the same as in Example 2, except that no reactive macromolecular long-chain branching agent was added in the preparation of the long-chain branched nitrile rubber, but a reactive macromolecular long-chain branching agent b was added, and the amount was 11 g, that is, first 200 g of nitrile rubber 2707 was dissolved in a chlorobenzene solution to prepare a glue solution with a mass fraction of 5.5%, then the glue solution was added to a 10 L stainless steel reaction kettle with a jacket, and the reaction kettle was replaced with nitrogen gas for 3 times, then 11 g of reactive macromolecular long-chain branching agent b was added to the reaction kettle, and the mixture was stirred and heated, and when the temperature of the reaction kettle reached 72°C, 0.07 g of DCP and 120 g of a mixture of chlorobenzene were added, and after 6.2 hr of reaction, the product was flocculated with anhydrous ethanol, washed, and dried in a 70°C oven to constant weight to obtain long-chain branched nitrile rubber b (grafting rate 4.2%).

[0112] (3) Preparation of low-temperature-resistant hydrogenated nitrile rubber for oil fields:

[0113] The other conditions were the same as in Example 2, except that no long-chain branched nitrile rubber was added in the preparation of the low-temperature-resistant hydrogenated nitrile rubber for oil fields, but long-chain branched nitrile rubber b was added, and the amount was 100 g, that is, first 100 g of long-chain branched nitrile rubber b was dissolved in xylene to prepare a glue solution with a mass fraction of 5%, then it was added to a 10 L high-pressure reaction kettle, and nitrogen gas was introduced to remove the air in the reaction kettle, then the nitrogen gas in the reaction kettle was replaced with hydrogen gas for 32 min, then 0.2 g of Grubbs II catalyst in xylene solution (mass concentration 6%) was added under nitrogen protection, the hydrogen pressure in the reaction kettle was increased to 7 MPa, and the temperature was increased to 90°C, and after 8.5 hr of reaction, the system was cooled, coagulated, and vacuum dried to obtain the low-temperature-resistant hydrogenated nitrile rubber for oil fields. Sample analysis: standard test samples were prepared, and the tested properties are shown in Table 1.

[0114] Comparative Example 3

[0115] (1) Preparation of reactive macromolecular long-chain branching agent:

[0116] The other conditions are the same as in Example 3, except that the preparation process of the reactive macromolecular long chain linking agent is carried out by passing in ethylene, and the pressure is not kept at 12 MPa, but at 4 MPa, that is: first, replace 2 times with nitrogen in a 10 L high-pressure reactor, add 4000 g of dimethylbenzene, heat to 80°C, then gradually add 140 g of methylaluminoxane co-catalyst under uniform stirring at a speed of 600 rpm, continue to stir for 23 min under nitrogen protection, then add 10 g of trans-bromophenyl (di(triphenylphosphine)) nickel main catalyst and 240 g of 1-octene and pass in ethylene, keep the pressure at 4 MPa for 4.0 hr; after the reaction is completed, centrifugal separation, drying, and the reactive macromolecular long chain linking agent c (number average molecular weight Mn is 4900) is prepared.

[0117] (2) Preparation of long-chain branched nitrile rubber:

[0118] The other conditions are the same as in Example 3, except that the preparation process of the long-chain branched nitrile rubber is not added with the reactive macromolecular long chain linking agent, but with the reactive macromolecular long chain linking agent c, and the amount of addition is 12 g, that is: first, 200 g of nitrile rubber 2707 is dissolved in chlorobenzene solution to prepare a glue solution with a mass fraction of 6.0%, then the glue solution is added to a 10 L stainless steel reactor with a jacket, and the reactor is replaced with nitrogen gas 4 times, then 12 g of the reactive macromolecular long chain linking agent c is added to the reactor, stirred and mixed, heated, and when the temperature of the reactor reaches 74°C, 0.08 g of DCP and 140 g of a mixture of chlorobenzene are added, and after 6.4 hr of reaction, the system is flocculated with anhydrous ethanol, washed, and dried in a 70°C oven to constant weight to obtain the long-chain branched nitrile rubber c (grafting rate 1.2%).

[0119] (3) Preparation of low-temperature resistant hydrogenated nitrile rubber for oil field:

[0120] The other conditions are the same as in Example 3, except that the preparation process of the low-temperature resistant hydrogenated nitrile rubber for oil field is not added with the long-chain branched nitrile rubber, but with the long-chain branched nitrile rubber c, and the amount of addition is 100 g, that is: first, 100 g of long-chain branched nitrile rubber c is dissolved in dimethylbenzene to prepare a glue solution with a mass fraction of 5%, then the glue solution is added to a 10 L high-pressure reactor, and the reactor is replaced with nitrogen gas to remove the air in the reactor, then the nitrogen gas in the reactor is replaced with hydrogen gas for 35 min, then 0.3 g of Grubbs II catalyst in dimethylbenzene solution (mass concentration 7%) is added under nitrogen protection, the hydrogen pressure in the reactor is increased to 8 MPa, and the temperature is increased to 95°C, and after 9.0 hr of reaction, the system is cooled, coagulated, and vacuum dried to obtain the low-temperature resistant hydrogenated nitrile rubber for oil field. Sample analysis: standard test samples are prepared, and the performance is tested as shown in Table 1.

[0121] Comparative Example 4

[0122] (1) Preparation of long-chain branched butadiene-acrylonitrile rubber:

[0123] (2) Preparation of long-chain branched butadiene-acrylonitrile rubber:

[0124] The other conditions are the same as in Example 4, except that the amount of the long-chain branched butadiene-acrylonitrile rubber prepared in the process is 6.0 g, i.e., first 200 g of butadiene-acrylonitrile rubber 2707 is dissolved in chlorobenzene solution to prepare a glue solution with a mass fraction of 6.4%, and then the glue solution is added to a 10 L jacketed stainless steel reactor, which is replaced with nitrogen gas for 4 times, and then 6.0 g of the long-chain branched butadiene-acrylonitrile rubber is added to the reactor, which is stirred, mixed and heated, and when the temperature of the reactor reaches 76°C, 0.085 g of DCP and 170 g of a mixture of chlorobenzene are added, and after 6.6 hr of reaction, the product is flocculated with anhydrous ethanol, washed, and dried in a 70°C oven to constant weight to obtain long-chain branched butadiene-acrylonitrile rubber d (grafting rate 2.7%).

[0125] (3) Preparation of low-temperature-resistant hydrogenated butadiene-acrylonitrile rubber for oil fields:

[0126] The other conditions are the same as in Example 4, except that the long-chain branched butadiene-acrylonitrile rubber is not added in the preparation process of the low-temperature-resistant hydrogenated butadiene-acrylonitrile rubber for oil fields, but 100 g of long-chain branched butadiene-acrylonitrile rubber d is added, i.e., first 100 g of long-chain branched butadiene-acrylonitrile rubber d is dissolved in xylene to prepare a glue solution with a mass fraction of 6%, and then added to a 10 L high-pressure reactor, and nitrogen gas is introduced to remove the air in the reactor, and then hydrogen gas is introduced to remove the nitrogen gas in the reactor for 37 min, and then 0.35 g of Grubbs II catalyst in xylene solution (mass concentration 8%) is added under nitrogen protection, and the hydrogen pressure in the reactor is increased to 8.5 MPa, and the temperature is increased to 100°C, and after 9.3 hr of reaction, the system is cooled, coagulated, and vacuum dried to obtain the low-temperature-resistant hydrogenated butadiene-acrylonitrile rubber for oil fields. Sample analysis: standard test samples are prepared, and the tested properties are shown in Table 1.

[0127] Comparative Example 5

[0128] (1) Preparation of long-chain branched butadiene-acrylonitrile rubber:

[0129] The other conditions are the same as in Example 5, except that no reactive macromolecular long-chain branching agent is added in the preparation of the long-chain branched nitrile rubber, but a small molecule monomer 1-octene is added, and the amount is 13 g, that is, first 200 g of nitrile rubber 2707 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 the reaction kettle is replaced with nitrogen gas for 5 times, then 13 g of 1-octene is added to the reaction kettle, and the mixture is stirred and heated, and when the temperature of the reaction kettle reaches 78°C, a mixture of 0.09 g of DCP and 180 g of chlorobenzene is added, and after 6.8 hours of reaction, the product is flocculated with anhydrous ethanol, washed, and dried in a 70°C oven until the weight is constant to obtain long-chain branched nitrile rubber e (grafting rate 4.8%).

[0130] (2) Preparation of low-temperature-resistant hydrogenated nitrile rubber for oil field:

[0131] The other conditions are the same as in Example 5, except that no long-chain branched nitrile rubber is added in the preparation of the low-temperature-resistant hydrogenated nitrile rubber for oil field, but long-chain branched nitrile rubber e is added, and the amount is 100 g, that is, first 100 g of long-chain branched nitrile rubber e is dissolved in xylene to prepare a glue solution with a mass fraction of 8%, then it is added to a 10 L high-pressure reaction kettle, nitrogen gas is introduced to remove air in the reaction kettle, then 38 min after the nitrogen gas in the reaction kettle is replaced with hydrogen gas, 0.4 g of Grubbs II catalyst in xylene solution (mass concentration 9%) is added under nitrogen protection, the hydrogen pressure in the pressurized reaction kettle is 9 MPa, the temperature is raised to 105°C, and after 9.6 hours of reaction, the system is cooled, coagulated, and vacuum dried to obtain the low-temperature-resistant hydrogenated nitrile rubber for oil field. Sample analysis: standard test samples are prepared, and the tested properties are shown in Table 1.

[0132] Comparative Example 6

[0133] (1) Preparation of reactive macromolecular long-chain branching agent: same as in Example 6.

[0134] (2) Preparation of long-chain branched nitrile rubber:

[0135] The other conditions are the same as in Example 6, except that the amount of DCP added in the preparation of the long-chain branched nitrile rubber is 0.01 g, that is, first 200 g of nitrile rubber 2707 is dissolved in chlorobenzene solution to prepare a glue solution with a mass fraction of 7.0%, then the glue solution is added to a 10 L stainless steel reaction kettle with a jacket, and the reaction kettle is replaced with nitrogen gas for 5 times, then 14 g of reactive macromolecular long-chain branching agent is added to the reaction kettle, and the mixture is stirred and heated, and when the temperature of the reaction kettle reaches 80°C, a mixture of 0.01 g of DCP and 200 g of chlorobenzene is added, and after 7.0 hours of reaction, the product is flocculated with anhydrous ethanol, washed, and dried in a 70°C oven until the weight is constant to obtain long-chain branched nitrile rubber f (grafting rate 3.2%).

[0136] (3) Preparation of the low-temperature-resistant hydrogenated nitrile rubber for oil field:

[0137] The other conditions are the same as in Example 6, except that in the preparation of the low-temperature-resistant hydrogenated nitrile rubber for oil field, the long-chain branched nitrile rubber is not added, but the long-chain branched nitrile rubber f is added, and the amount of addition is 100 g, that is, first, 100 g of long-chain branched nitrile rubber f is dissolved in xylene to prepare a glue solution with a mass fraction of 10%, and then it is added to a 10L high-pressure reaction kettle, nitrogen is introduced to remove the air in the reaction kettle, then the nitrogen in the reaction kettle is replaced with hydrogen for 40 min, and then 0.5 g of Grubbs II catalyst solution in xylene (mass concentration of 10%) is added under nitrogen protection, the hydrogen pressure in the reaction kettle is increased to 10 MPa, the temperature is increased to 110°C, and the reaction is carried out for 10.0 hr, then the system is cooled, coagulated, and vacuum dried to obtain the low-temperature-resistant hydrogenated nitrile rubber for oil field. Sample analysis: standard test samples are prepared, and the tested properties are shown in Table 1.

[0138] Comparative Example 7

[0139] (1) Preparation of the long-chain branched nitrile rubber:

[0140] The other conditions are the same as in Example 7, except that in the preparation of the long-chain branched nitrile rubber, the reactive macromolecular long-chain branching agent is not added, but the small molecule monomer 1-hexene is added, and the amount of addition is 14 g, that is, first, 200 g of nitrile rubber 2707 is dissolved in chlorobenzene solution to prepare a glue solution with a mass fraction of 7.0%, then the glue solution is added to a 10L stainless steel reaction kettle with a jacket, and the reaction kettle is replaced with nitrogen gas for 5 times, then 14 g of 1-hexene is added to the reaction kettle, and the mixture is stirred and heated, when the temperature of the reaction kettle reaches 80°C, 0.2 g of diacetyl peroxide and 200 g of chlorobenzene are added, the reaction is carried out for 7.0 hr, then it is flocculated with anhydrous ethanol, washed, and dried in a 70°C oven to constant weight to obtain the long-chain branched nitrile rubber g (grafting rate of 5.0%).

[0141] (2) Preparation of the low-temperature-resistant hydrogenated nitrile rubber for oil field:

[0142] The other conditions are the same as those in Example 7, except that the long-chain branched nitrile rubber g is added instead of the long-chain branched nitrile rubber in the preparation process of the low-temperature-resistant hydrogenated nitrile rubber for oil field, and the amount of the long-chain branched nitrile rubber g added is 100 g, that is, first, 100 g of the long-chain branched nitrile rubber g is dissolved in xylene to prepare a glue solution with a mass fraction of 10%, and then the glue solution is added to a 10 L high-pressure reaction kettle, nitrogen is introduced to remove the air in the reaction kettle, then the nitrogen in the reaction kettle is replaced with hydrogen for 40 min, and then 0.5 g of a xylene solution of Grubbs II catalyst (with a mass concentration of 10%) is added under the protection of nitrogen, the hydrogen pressure in the reaction kettle is increased to 10 MPa, the temperature is increased to 110°C, and the reaction is carried out for 10.0 hr, after which the system is cooled, coagulated, and vacuum dried to obtain the low-temperature-resistant hydrogenated nitrile rubber for oil field. Sampling analysis: standard test samples are prepared, and the performance is tested and shown in Table 1.

[0143] Table 1 Performance of the low-temperature-resistant hydrogenated nitrile rubber for oil field

[0144]

[0145] As shown in Table 1, the low-temperature-resistant hydrogenated nitrile rubber for oil field has a low glass transition temperature and is suitable for oil well operation under low-temperature working conditions with a working temperature of -49°C.

[0146] 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 should all belong to the protection scope of the present application.

Claims

1. A process for the production of a low temperature resistant hydrogenated nitrile rubber for oil field use, characterized by, It comprises the following steps: (1) first, inert gas is introduced into the reaction kettle to replace the air, a solvent is added, and the temperature is raised, then an alkyl aluminoxane cocatalyst is added under stirring, the stirring is continued under the protection of inert gas, then a nickel-based complex catalyst and a long-chain alpha-olefin are added, and ethylene is introduced to start the reaction; after the reaction is completed, centrifugal separation and drying are carried out to obtain a reactive macromolecular long-chain branching agent; the long-chain alpha-olefin is selected from one of 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene and 1-dodecene; (2) the nitrile rubber is dissolved in a chlorobenzene solution to prepare a glue solution, then the glue solution is added into the reaction kettle, nitrogen is introduced to replace the air, then the reactive macromolecular long-chain branching agent is added into the reaction kettle, stirring and heating are carried out, then a mixture of an initiator and chlorobenzene is added, and the reaction is carried out, after the reaction is completed, flocculation, washing and drying are carried out to obtain a long-chain branched nitrile rubber; the grafting rate of the long-chain branched nitrile rubber is 3.8% to 4.9%; (3) the long-chain branched nitrile rubber is dissolved in a solvent to prepare a glue solution, then the glue solution is added into the reaction kettle, inert gas is introduced to remove the air in the reaction kettle, then hydrogen is introduced to remove the inert gas in the reaction kettle, a Grubbs II catalyst solution in xylene is added under the protection of nitrogen, pressure is applied and the temperature is raised, the reaction is carried out, the temperature is lowered, and the product is condensed and dried to obtain a low-temperature-resistant hydrogenated nitrile rubber for oil field use; The number average molecular weight Mn of the reactive macromolecular long-chain branching agent is 4000 to 6000.

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

3. The preparation method according to claim 1, characterized in that, The alkyl aluminoxane cocatalyst is selected from one of methyl aluminoxane (MAO) and ethyl aluminoxane (EAO).

4. The method of claim 1, wherein, In step (1), the mass ratio of the solvent, the alkyl aluminoxane cocatalyst, the long-chain alpha-olefin and the nickel-based complex catalyst is 300 to 500: 10 to 20: 20 to 30:

1.

5. The preparation method according to claim 1, characterized in that, The initiator is selected from one of diacetyl peroxide, diisobutyryl peroxide, cumene hydroperoxide, dicumyl peroxide (DCP) and dibenzoyl peroxide, and the amount of the initiator added is 0.01 to 0.1 parts based on 100 parts of the nitrile rubber.

6. The method of claim 1, wherein, The nitrile rubber is prepared by emulsion polymerization of 1,3-butadiene and acrylonitrile, and the acrylonitrile content of the nitrile rubber is 20wt% to 42wt%.

7. The preparation method according to claim 1, characterized in that, In step (2), the mass ratio of the reactive macromolecular long-chain branching agent, chlorobenzene and nitrile rubber is 5 to 7: 50 to 100:

100.

8. The method of claim 1, wherein, The solvent is selected from one of cyclohexane, carbon disulfide (CS2), nitrobenzene, petroleum ether, tetrachloroethane, toluene and xylene.

9. The method of claim 1, wherein, In step (3), the mass ratio of the long-chain branched nitrile rubber and the Grubbs II catalyst is 100: 0.1 to 0.

5.

10. A low-temperature-resistant hydrogenated nitrile rubber for oil field use prepared by the preparation method of any one of claims 1 to 9.

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