Hydrophobic monomers, high molecular weight polymers, methods of making the same, and water-based drilling fluids and applications

Abstract

The application relates to the field of petroleum drilling aids, in particular to a hydrophobic monomer, a high-molecular polymer and a preparation method thereof, and a water-based drilling fluid and application, and provides the hydrophobic monomer with a structural formula shown in formula (I) and a preparation method thereof, on the basis of which a high-molecular polymer and a preparation method thereof are provided, and a water-based drilling fluid and application are provided. The high-molecular polymer provided by the application is used as a high-cutting agent for the water-based drilling fluid, can improve the dynamic cutting force of the drilling fluid while showing a lower tackifying effect, can be used as an ideal flow pattern regulator, has outstanding temperature resistance and salt resistance, has better weather resistance, and is environment-friendly.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of petroleum drilling aids, in particular to a hydrophobic monomer, a high molecular polymer, a preparation method thereof, a water-based drilling fluid and application. BACKGROUND

[0002] In drilling engineering, drilling fluid has the functions of cooling the drill bit, balancing the formation pressure and obtaining geological information, but the most important function is to carry the cuttings back to the ground to ensure the wellbore cleaning. In addition to the influence of drilling equipment, the rheological property of drilling fluid has a great influence on carrying cuttings. The yield point (YP) is the most important parameter to characterize the carrying capacity of drilling fluid. Simply put, YP is the attractive force between colloidal particles in the drilling fluid during circulation, that is, the network structure strength inside the drilling fluid under dynamic conditions. The higher the YP, the stronger the carrying capacity of the drilling fluid, and the more easily the cuttings at the bottom of the well are pushed to the ground.

[0003] At present, there are two ways to improve the YP of drilling fluid in drilling operation: one is to add bentonite (Na-MMT) to the drilling fluid, which is the most economical way, however, if the content of bentonite in the drilling fluid is high, it is easy to cause the negative effects such as bit balling, density fluctuation, solid content increase and drug consumption increase; the second is to add additives such as xanthan gum (XC), high-viscosity carboxymethyl cellulose (HV-CMC), high-viscosity anionic cellulose (PAC-HV) and other natural products, or polyacrylamide (PAM) and other artificially synthesized polymers, although the purpose of improving the YP of drilling fluid is achieved, but at the same time the viscosity of the drilling fluid also increases, and the over-high viscosity of the drilling fluid will have negative effects on the drilling speed, degassing effect, surge pressure, circulating pressure consumption and mud cake quality. In addition, the high salinity of deep well drilling and drilled strata puts higher requirements on the temperature resistance and salt resistance of the YP additives of drilling fluid, and the existing YP additives still have obvious deficiencies in this aspect.

[0004] Therefore, it is of great significance to provide a treatment agent which has obvious YP effect on drilling fluid, has no significant viscosity effect, and has good temperature resistance and salt resistance, to meet the needs of oil exploration and development. SUMMARY

[0005] The present application aims to solve the problems of the existing YP additives for water-based drilling fluid, such as poor YP effect, significant viscosity effect caused by YP, and insufficient temperature resistance and salt resistance, and provides a hydrophobic monomer, a high molecular polymer, a preparation method thereof and application, and a water-based drilling fluid.

[0006] In order to achieve the above-mentioned purpose, the first aspect of the present application provides a hydrophobic monomer, the structural formula of which is shown as formula (I):

[0007]

[0008] wherein t is a natural number of 0-10; R1, R2, R3, R4, R5 and R6 are each independently selected from one of —H, C1-C3 alkyl and a substituent M, and at least one of R1, R2, R3, R4, R5 and R6 is the substituent M;

[0009] the substituent M is wherein R0, R 00 and R 000 are each independently selected from —H or C1-C3 alkyl; and s is a natural number of 0-5.

[0010] The second aspect of the present application provides a preparation method of the hydrophobic monomer according to the first aspect, comprising:

[0011] (1) mixing an alkenyl cyclohexanol represented by formula (II), a cyclohexyl nitrile represented by formula (III) and a first solvent to obtain a mixed solution;

[0012]

[0013] (2) adding I2 to the mixed solution to perform a first reaction to obtain a pre-product solution;

[0014] (3) performing a second reaction on the pre-product solution in the presence of a second solvent to obtain a product system;

[0015] (4) performing separation treatment and drying on the product system to obtain the hydrophobic monomer;

[0016] wherein in formula (II), R1, R2, R3, R4, R5 and R6 are each independently selected from one of —H, C1-C3 alkyl and a substituent M, and at least one of R1, R2, R3, R4, R5 and R6 is the substituent M;

[0017] the substituent M is wherein R0, R 00 and R 000 are each independently selected from —H or C1-C3 alkyl; and s is a natural number of 0-5.

[0018] in formula (III), t is a natural number of 0-10.

[0019] The third aspect of the present application provides a high molecular polymer containing a structural unit A represented by formula (IV), a structural unit B represented by formula (V), a structural unit C represented by formula (VI) and a fourth structural unit D;

[0020]

[0021]

[0022] said fourth structural unit D is derived from a hydrophobic monomer according to the first aspect described above;

[0023] wherein,

[0024] the molar ratio of the structural unit A, the structural unit B, the structural unit C and the structural unit D is (30-50):(20-40):(5-10):(1-4);

[0025] in formula (IV), R 1 is selected from -H or C1-C6 alkyl;

[0026] R 2 is selected from wherein,

[0027] R a and R b are each independently selected from one of -H, C1-C6 alkyl, C1-C6 alkyl alcohol, C1-C8 alkyl ketone;

[0028] R c is selected from -H or C1-C6 alkyl;

[0029] R d is selected from one of -CH3, -CH2CH3, ;

[0030] in formula (V), R 3 is selected from -H or C1-C6 alkyl; R 4 is selected from -COOH or -COOA; wherein A is one of Na, K, Rb, Cs;

[0031] in formula (VI), X - is selected from BF4 - , PF6 - , SCN - , HSO3 - , CH3SO3 - , CF3SO3 - , CH3COO - , CF3COO - , Tf2N - , CH3OSO3 - , C2H5OSO3 - , p-TsO - , (CN)2N - , CH3CH(OH)COO - , C6H5NHCH2COO - , (CH3O)2PO2 -, (C2H5O)2PO2 - , F - , Cl - , Br - , I - , HCO3 - ; r is a natural number from 0 to 10;

[0032] R 5 and R 6 are each independently selected from -H or C1-C6 alkyl.

[0033] The fourth aspect of the present application provides a preparation method of the high molecular polymer of the third aspect, comprising:

[0034] (A) mixing an alkenyl amide represented by formula (IV'), an alkenyl carboxylic acid represented by formula (V'), an alkenyl ionic liquid represented by formula (VI') and a fourth monomer in a solvent a to obtain a mixture;

[0035] (B) polymerizing the mixture in the presence of an initiator and a molecular weight regulator to obtain a crude product;

[0036] (C) post-treating the crude product to obtain the high molecular polymer;

[0037]

[0038] The fourth monomer is the hydrophobic monomer of the first aspect.

[0039] wherein, R 1 -R 6 , X - , and the definition of r is the same as that in the third aspect.

[0040] The fifth aspect of the present application provides a water-based drilling fluid containing the high molecular polymer of the third aspect.

[0041] The sixth aspect of the present application provides an application of the water-based drilling fluid of the fifth aspect in oil drilling.

[0042] Through the above technical solution, the present application has the following beneficial effects:

[0043] (1) This invention provides a hydrophobic monomer and prepares a polymer based on the hydrophobic monomer. Specifically, it is a hydrophobic associative polymer. When the polymer is added to a water-based drilling fluid, the hydrophobic groups in the molecular chain associate and aggregate to form a continuous three-dimensional network structure in the slurry. This can significantly improve the shear force and dynamic plasticity ratio of the drilling fluid and optimize its rheological properties. The molecular weight of the polymer is controlled within a limited range, and the length of the molecular chain is small, resulting in a low viscosity effect while improving shear strength.

[0044] (2) The polymer provided by the present invention introduces a specific cyclic structure into the molecular chain, which makes the polymer have outstanding temperature resistance and salt resistance.

[0045] (3) The polymer provided by the present invention introduces structural units provided by imidazole ionic liquid into the molecular chain, which can further promote hydrophobic association between polymer molecules, enhance the tendency to form a three-dimensional network structure in the drilling fluid, and make it more conducive to obtaining the lifting effect. Attached Figure Description

[0046] Figure 1 The nuclear magnetic resonance spectrum of the hydrophobic monomer prepared in Example 1 of this invention ( 1 H-NMR);

[0047] Figure 2 The graph shows the change of dynamic plasticity ratio (YP / PV) with aging temperature for the polymer prepared in Example 10 of this invention, the polymers prepared in Comparative Examples 1-5, and the experimental slurries prepared with HV-CMC, PAC-HV, and XC under aging conditions of 16h. Detailed Implementation

[0048] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0049] The following provides a detailed description of specific embodiments of the present invention. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of the invention.

[0050] The first aspect of this invention provides a hydrophobic monomer, the structural formula of which is shown in formula (I):

[0051]

[0052] wherein t is a natural number from 0 to 10; R1, R2, R3, R4, R5 and R6 are each independently selected from -H, C1-C3 alkyl and a substituent M, and at least one of R1, R2, R3, R4, R5 and R6 is the substituent M;

[0053] The substituent M is wherein R0, R 00 and R 000 are each independently selected from -H or C1-C3 alkyl; and s is a natural number from 0 to 5.

[0054] According to the present application, the hydrophobic monomer, in addition to satisfying the above definition, further satisfies that t is a natural number from 0 to 5, preferably t = 0 or 1;

[0055] and / or one or two of R1, R2, R3, R4, R5 and R6 is the substituent M;

[0056] and / or R0, R 00 and R 000 are each independently selected from -H or -CH3; and s = 0 or 1.

[0057] According to some embodiments of the present application, the hydrophobic monomer can be a compound having a structure as shown in formula (1) to formula (13) below:

[0058]

[0059]

[0060]

[0061] According to the present application, the hydrophobic monomer is further preferably a compound having a structure as shown in formula (1), formula (2), formula (3), formula (4) or formula (8) above.

[0062] The second aspect of the present application provides a preparation method of the hydrophobic monomer of the first aspect above, comprising:

[0063] (1) mixing an alkenyl cyclohexanol shown in formula (II), a cyclohexyl nitrile shown in formula (III) and a first solvent to obtain a mixed solution;

[0064]

[0065] (2) adding I2 to the mixed solution to perform a first reaction to obtain a pre-product solution;

[0066] (3) performing a second reaction on the pre-product solution in the presence of a second solvent to obtain a product system;

[0067] (4) separating and drying the product system to obtain the hydrophobic monomer;

[0068] wherein, in formula (II), R1, R2, R3, R4, R5, and R6 are each independently selected from one of —H, C1-C3 alkyl, and a substituent M, and at least one of R1, R2, R3, R4, R5, and R6 is the substituent M;

[0069] the substituent M is wherein, R0, R 00 and R 000 are each independently selected from —H or C1-C3 alkyl; and s is a natural number from 0 to 5.

[0070] in formula (III), t is a natural number from 0 to 10.

[0071] According to the present application, in step (1), preferably, in formula (III) of the cyclohexyl nitrile, t is a natural number from 0 to 5, and further preferably t = 0 or 1;

[0072] and / or, in formula (II) of the alkenyl cyclohexanol, one or two of R1, R2, R3, R4, R5, and R6 are the substituent M;

[0073] and / or, in formula (II) of the alkenyl cyclohexanol, R0, R 00 and R 000 are each independently selected from —H or —CH3; and s = 0 or 1.

[0074] According to the present application, in step (1), the amount of the raw material monomers is such that the molar ratio of the cyclohexyl nitrile to the alkenyl cyclohexanol is (1.1-1.4):1.

[0075] According to the present application, in step (1), the amount of the first solvent is such that the concentration of the alkenyl cyclohexanol in the mixed solution is 5-8 wt%.

[0076] According to the present application, in step (1), the first solvent is selected from at least one of acetone, butanone, chloroform, dichloromethane, 1,1-dichloroethane, 1,2-dichloroethane, methyl ethyl ketone, tetrahydrofuran, petroleum ether, diethyl ether, ethyl acetate, benzene, toluene, xylene, cyclohexane, ethylene glycol dimethyl ether, nitromethane, 1,4-dioxane, pyridine, morpholine, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide, preferably at least one of benzene, toluene, xylene, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide, and further preferably at least one of benzene, toluene, and xylene.

[0077] According to the present application, in step (1), the mixing can be carried out in one step or in several steps, preferably in several steps, which can be specifically as follows: the alkenyl cyclohexanol is mixed with the first solvent to form a solution, and then the cyclohexyl nitrile is added and mixed until it is fully dissolved to obtain a uniform and stable mixed solution. The mixing is preferably carried out under stirring.

[0078] According to the present application, in step (2), the first reaction is carried out in an inert atmosphere, preferably an inert protective gas is introduced before the first reaction to remove oxygen from the reaction environment. In the present application, the inert protective gas can be nitrogen, helium, argon or other inert gases, preferably nitrogen.

[0079] According to the present application, in step (2), the molar ratio of I2 to cyclohexyl nitrile in the mixed solution is (2.5-25):100, preferably (4-20):100, and further preferably (8-12):100.

[0080] According to the present application, in step (2), the first reaction is a pre-reaction of the subsequent reaction steps, and the pre-product solution obtained is an intermediate product. The first reaction is preferably carried out under stirring, and the reaction conditions include: temperature of 40-80℃, preferably 55-65℃; time of 2-8h, preferably 4-6h.

[0081] According to the present application, in step (3), the second solvent is a mixed solution of one of tetrahydrofuran, ethylene glycol dimethyl ether, 1,4-dioxane, pyridine, morpholine, N,N-dimethylformamide, N,N-dimethylacetamide or dimethyl sulfoxide and water with a volume ratio of (10-5):1; and the volume ratio of the second solvent to the first solvent is (10-20):100.

[0082] According to the present application, in step (3), the pre-product solution is preferably first warmed to the required temperature for the second reaction, and then the second solvent is continuously added. After the addition of the second solvent is completed, the second reaction is carried out to obtain the product system.

[0083] According to the present application, in step (3), the second solvent is preferably added at a uniform speed, and the length of time for the addition is controlled to be 30-60min.

[0084] According to the present application, in step (3), the second reaction conditions include: temperature of 60-120℃, preferably 80-110℃; time of 2-8h, preferably 4-6h.

[0085] According to the present application, in step (4), the separation treatment, drying process can specifically include: subjecting the product system to reduced pressure distillation to separate and remove the first solvent, the second solvent, water and I2, then soaking in ethanol for 2-4 h, suction filtration, and separately washing with ethanol and acetone, and vacuum drying to constant weight to obtain the hydrophobic monomer.

[0086] The third aspect of the present application provides a high molecular polymer containing structural unit A shown in formula (IV), structural unit B shown in formula (V), structural unit C shown in formula (VI) and fourth structural unit D.

[0087]

[0088]

[0089] The fourth structural unit D is from the hydrophobic monomer of the first aspect described above;

[0090] wherein,

[0091] The molar ratio of the structural unit A, the structural unit B, the structural unit C and the fourth structural unit D is (20-60):(15-45):(4-12):(1-6);

[0092] In formula (IV), R 1 is selected from —H or C1-C6 alkyl;

[0093] R 2 is selected from wherein,

[0094] R a and R b are each independently selected from one of —H, C1-C6 alkyl, C1-C6 alkyl alcohol and C1-C8 alkyl ketone;

[0095] R c is selected from —H or C1-C6 alkyl;

[0096] R d is selected from —CH3, —CH2CH3, ;

[0097] In formula (V), R 3 is selected from —H or C1-C6 alkyl; R 4 is selected from —COOH or —COOA; wherein A is one of Na, K, Rb and Cs;

[0098] In formula (VI), X - is selected from BF4 - , PF6 - , SCN- HSO3 - CH3SO3 - CF3SO3 - CH3COO - CF3COO - Tf2N - CH3OSO3 - C2H5OSO3 - p-TsO - (CN)2N - CH3CH(OH)COO - C6H5NHCH2COO - (CH3O)2PO2 - (C2H5O)2PO2 - F - Cl - Br - I - HCO3 - r is a natural number from 0 to 10;

[0099] R 5 and R 6 are each independently selected from —H or C1-C6 alkyl.

[0100] According to the present application, the fourth structural unit D is derived from the hydrophobic monomer according to the aforementioned first aspect of the present application, in particular, is formed by opening one of the carbon-carbon double bonds in the substituent M in the hydrophobic monomer according to the aforementioned first aspect of the present application (structural formula as shown in formula (I)). When the hydrophobic monomer has multiple (e.g., 2, 3, 4, 5, or 6) substituents M in its structural formula, it should be understood that the fourth structural unit can be formed by opening one of the carbon-carbon double bonds, or can be formed by opening multiple carbon-carbon double bonds simultaneously.

[0101] According to the present application, in the high molecular polymer, the structural unit A shown in formula (IV), the structural unit B shown in formula (V), the structural unit C shown in formula (VI), and the fourth structural unit D meet the above definitions, preferably, in the structural unit A shown in formula (IV), R 1 is selected from —H, —CH3, —C2H5; for R 2 wherein R a and R b are each independently selected from —H, —CH3, —CH2CH3, —CH2OH, —CH2CH2OH, —CH2CH2OH, —CH2CH2CH2OH, c is selected from —H, —CH3, —CH2CH3, one of the following;

[0102] Preferably, in the structural unit B shown in formula (V), R 3 is selected from one of the following: -H, -CH3, -C2H5; in R 4 A in -COOA is selected from Na or K;

[0103] Preferably, in the structural unit C shown in formula (VI), r is a natural number from 0 to 5, further preferably r = 0 or 1; R 5 is selected from one of the following: -H, -CH3, -CH2CH3; R 6 is selected from one of the following: -H, -CH3, -CH2CH3, and -CH2CH2CH3;

[0104] Preferably, in the fourth structural unit D, t is a natural number from 0 to 5, further preferably t = 0 or 1;

[0105] and / or one or two of R1, R2, R3, R4, R5, and R6 are the substituent M;

[0106] and / or one or two of R0, R 00 and R 000 are each independently selected from -H or -CH3; s = 0 or 1.

[0107] According to the present application, preferably, the molar ratio of the structural unit A, the structural unit B, the structural unit C, and the fourth structural unit D is (30-50):(20-40):(5-10):(1-4).

[0108] According to the present application, the viscosity average molecular weight of the high molecular polymer is 2 x 10 4 -2.5 x 10 4 g / mol.

[0109] The high molecular polymer provided by the application is a hydrophobic associating polymer. Through specific molecular structure design, the hydrophobic groups in the molecular chain of the high molecular polymer can be aggregated by association after the high molecular polymer is dissolved in water. The behavior is similar to the clustering of surfactants. However, the clustering is constrained by the polymer molecules dissolved in water and does not form a significant micelle form. A continuous three-dimensional network structure can be formed. Application to a water-based drilling fluid forms such a three-dimensional network structure, which can play a positive role in improving the shear force of the drilling fluid, which is manifested as a significantly improved shear force and dynamic plasticity ratio. Limited by the molecular weight, the viscosity-increasing effect of the polymer is limited. While playing a role in increasing the shear force of the drilling fluid, the viscosity effect is low. It is an excellent low-viscosity-increasing shear force improver for water-based drilling fluid. In the molecular chain of the high molecular polymer, the specific ring structure provided by the hydrophobic monomer in the first aspect of the application is introduced. The hydrophobicity is better than that of a long alkyl chain, and the rigidity is also strong, which can hinder the curling of the molecular chain under high salinity conditions, thereby improving the salt resistance of the polymer. At the same time, the ring structure has a good steric effect, thereby increasing the resistance of the molecular chain to thermal motion under high temperature conditions, slowing down the desorption rate of the molecular chain under high temperature conditions, and thereby improving the temperature resistance of the polymer. In the molecular chain of the high molecular polymer, the structural unit shown as formula (VI) is also introduced, which can produce a strong dipole effect with water molecules, promote the ordered aggregation behavior of the polymer molecules in the water-based drilling fluid, that is, promote the hydrophobic association between molecules, and enhance the trend of forming a three-dimensional network structure in the drilling fluid, which is beneficial to obtaining further shear force increasing effect.

[0110] The fourth aspect of the application provides a preparation method of the high molecular polymer of the third aspect.

[0111] (A) mixing the alkenyl amide shown as formula (IV'), the alkenyl carboxylic acid shown as formula (V'), the alkenyl ionic liquid shown as formula (VI') and the fourth monomer in a solvent a to obtain a mixture;

[0112] (B) performing a polymerization reaction on the mixture in the presence of an initiator and a molecular weight regulator to obtain a crude product;

[0113] (C) performing post-treatment on the crude product to obtain the high molecular polymer;

[0114]

[0115] The fourth monomer is the hydrophobic monomer of the first aspect.

[0116] wherein, R 1 -R 6 , X - , and r are defined as the same as the definitions involved in the third aspect.

[0117] According to the present application, in step (A), the molar ratio of the alkenyl amide: alkenyl carboxylic acid: alkenyl ionic liquid: fourth monomer is preferably (20-60):(15-45):(4-12):(1-6), and further preferably (30-50):(20-40):(5-10):(1-4).

[0118] According to the present application, in step (A), the alkenyl ionic liquid represented by formula (VI’) is an imidazole ionic liquid.

[0119] According to the present application, in step (A), the amount of solvent a is such that the total concentration of the alkenyl amide, alkenyl carboxylic acid, alkenyl ionic liquid and fourth monomer in the mixture is 5-15 wt%.

[0120] According to the present application, in step (A), the solvent a is selected from at least one of acetone, butanone, chloroform, dichloromethane, 1,1-dichloroethane, 1,2-dichloroethane, methyl ethyl ketone, tetrahydrofuran, petroleum ether, diethyl ether, acetonitrile, ethyl acetate, benzene, toluene, m-xylene, cyclohexane, ethylene glycol dimethyl ether, nitromethane, 1,4-dioxane, pyridine, morpholine, 4-methyl-2-pentanone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide.

[0121] According to the present application, in step (A), the alkenyl amide, alkenyl carboxylic acid, alkenyl ionic liquid and fourth monomer are preferably sequentially added to the solvent a for mixing, and the resulting mixture is warmed to the required reaction temperature. The mixing is preferably carried out under stirring.

[0122] According to the present application, in step (B), each monomer undergoes radical polymerization under the action of an initiator, and the polymerization is carried out in an inert atmosphere, preferably by pre-injection of an inert gas such as nitrogen, helium or argon to achieve oxygen removal of the reaction environment, after which the initiator is added to the mixture, and the molecular weight regulator is continuously added, and after the addition of the molecular weight regulator is completed, the polymerization is carried out to obtain a crude product.

[0123] According to the present application, in step (B), the molecular weight regulator is preferably added at a uniform rate, and the length of time for addition is controlled to be 1-6 h.

[0124] According to the present application, in step (B), the weight ratio of the initiator:(alkenyl amide + alkenyl carboxylic acid + alkenyl ionic liquid + fourth monomer) is (0.2-2):100; and the molar ratio of the molecular weight regulator:(alkenyl amide + alkenyl carboxylic acid + alkenyl ionic liquid + fourth monomer) is (0.05-0.2):100.

[0125] According to the present application, in step (B), the conditions of the polymerization reaction include: temperature of 40-105℃, preferably 50-105℃; time of 9-30h, preferably 14-28h.

[0126] According to the present application, in step (B), the time of the polymerization reaction includes a first stage (the time of adding the molecular weight regulator) and a second stage (the time of continuing the reaction after the addition of the molecular weight regulator is completed), preferably, the first stage is 1-6h, and the second stage is 8-24h.

[0127] According to the present application, in step (B), the initiator is selected from at least one of azo initiators, organic peroxide initiators, inorganic peroxide initiators, and oil-soluble redox initiators, preferably azo initiators. Further, the azo initiator can be specifically selected from at least one of azobisimidozolinium hydrochloride, azoisobutyronitrile carbamoyl, azobis isobutyronitrile, azobis carboxyethyl-2-isobutyl amidine hydrate, azobisdimethyl N-2-hydroxybutyl acrylamide, azobiscyclohexyl carbonitrile, azobis isopentyl nitrile, azobis isoheptyl nitrile, azobis cyanovaleric acid, azobis isobutyl amidine hydrochloride, azobis isopropyl imidazole, azobis N-hydroxy isobutyl amidine hydrate, azobis N,N'-cyclobutyl isobutyl amidine hydrate, azobis dimethyl isobutyrate, 2,2'-azobis(N-cyclohexyl isobutyl amidine) hydrochloride.

[0128] According to the present application, in step (B), the molecular weight regulator is selected from at least one of isopropyl alcohol, mercaptopropionic acid, mercaptoacetic acid, mercaptoethanol, 1-mercapto-2-propanol, 3-mercapto-1-propanol, 2,3-dimercapto-1-propanol, and dodecyl mercaptan. The molecular weight regulator is preferably used in the form of a solution, and specifically, the molecular weight regulator can be formulated into a solution with a concentration of 0.2-0.6wt% by using a certain amount of the solvent a, and the type of the solvent a is preferably selected to be the same as that in step (A).

[0129] According to the present application, in step (C), the process of the post-treatment includes precipitation, washing, extraction, and vacuum drying in sequence. Specifically, after adding anhydrous ethanol to the crude product for precipitation, the product is filtered, the filtered product is washed with acetone, the washed product is extracted with a mixed solvent of glacial acetic acid and ethylene glycol, and finally vacuum dried to a constant weight to obtain a high molecular polymer product.

[0130] The fifth aspect of the present application provides a water-based drilling fluid containing the high molecular polymer of the third aspect.

[0131] According to the present application, the content of the high molecular polymer in the water-based drilling fluid is not particularly limited. In some embodiments of the present application, preferably, the content of the high molecular polymer in the water-based drilling fluid can be 0.05-10% w / v, i.e., the content of the high molecular polymer can be 0.05-10 g with respect to 100 mL of the water-based drilling fluid.

[0132] The sixth aspect of the present application provides the use of the water-based drilling fluid according to the fifth aspect in oil drilling.

[0133] The present application will be described in detail below by way of examples. In the following examples and comparative examples, unless otherwise specified, the methods are conventional methods; and the reagents and materials, unless otherwise specified, are commercially available.

[0134] In the following examples, the molar ratio of the structural units contained in the prepared high molecular polymer is calculated based on the amount of the raw materials.

[0135] Example 1

[0136] The preparation of the hydrophobic monomer is described in this example

[0137] Into a reactor equipped with a temperature control device, a reflux condenser and a constant pressure feeding device, 15.4253 g (0.1 mol) of 5-methyl-2-(2-methylvinyl)cyclohexanol and 200 g of toluene were added, and after being fully stirred to dissolve, 13.1 g (0.12 mol) of cyclohexylcarbonitrile was added, and after being fully stirred to completely dissolve, a mixed solution was obtained;

[0138] After nitrogen was bubbled for 30 min, 3.0457 g (0.012 mol) of I2 was added, and the temperature was raised to 60°C, and the reaction was continued for 4 h under stirring, to obtain a pre-product solution; the temperature was again raised to 100°C, and 20 mL of a mixed solution of 1,4-dioxane and 4 mL of water was added at a uniform speed through a dropping funnel within 40 min, and the reaction was continued for 4 h under stirring, to obtain a product system;

[0139] After the reaction was completed, toluene, 1,4-dioxane, water and I2 were removed by distillation under reduced pressure, and then soaked in ethanol for 2 h, and then suction filtered, and then washed with ethanol and acetone, and then vacuum dried to constant weight, to obtain the hydrophobic monomer (denoted as S1).

[0140] S1 was subjected to nuclear magnetic resonance characterization [(CD3)2SO, 25°C], and the nuclear magnetic resonance spectrum (1H NMR) was as shown in 1 Figure 1 which indicated that the prepared polymer S1 had the structural formula as shown in formula (1).

[0141] Example 2

[0142] ​Preparation of hydrophobic monomer is illustrated by this example

[0143] Into a reactor equipped with temperature control device, reflux condenser and constant pressure feeding device, 15.4253 g (0.1 mol) of 1-methyl-4-(1-methylethenyl)cyclohexanol and 180 g of benzene were added, and after being fully stirred to dissolve, 12.0089 g (0.11 mol) of cyclohexylcarbonitrile was added, and after being fully stirred to completely dissolve, a mixed solution was obtained;

[0144] After nitrogen was bubbled for 30 min, 3.3503 g (0.0132 mol) of I2 was added, and the temperature was raised to 55°C, and the reaction was continuously carried out for 6 h under stirring, to obtain a pre-product solution; the temperature was raised to 80°C again, and a mixed solution of 33.5 mL of pyridine and 6.5 mL of water was added at a constant speed through a dropping funnel within 60 min, and the reaction was continuously carried out for 6 h under stirring, to obtain a product system;

[0145] After the reaction was completed, benzene, pyridine, water and I2 were removed by distillation under reduced pressure, and then put into ethanol for soaking for 2 h, and then suction filtration, and then rinsing with ethanol and acetone respectively, and then vacuum drying to constant weight, to obtain a hydrophobic monomer (denoted as S2) having a structural formula as described in formula (2).

[0146] Example 3

[0147] Preparation of hydrophobic monomer is illustrated by this example

[0148] Into a reactor equipped with temperature control device, reflux condenser and constant pressure feeding device, 12.62 g (0.1 mol) of 1-vinylcyclohexanol and 200 g of toluene were added, and after being fully stirred to dissolve, 17.248 g (0.14 mol) of cyclohexylacetonitrile was added, and after being fully stirred to completely dissolve, a mixed solution was obtained;

[0149] After nitrogen was bubbled for 30 min, 2.8427 g (0.0112 mol) of I2 was added, and the temperature was raised to 60°C, and the reaction was continuously carried out for 5 h under stirring, to obtain a pre-product solution; the temperature was raised to 103°C again, and a mixed solution of 30 mL of N,N-dimethylformamide and 4 mL of water was added at a constant speed through a dropping funnel within 30 min, and the reaction was continuously carried out for 5 h under stirring, to obtain a product system;

[0150] After the reaction was completed, toluene, N,N-dimethylformamide, water and I2 were removed by distillation under reduced pressure, and then put into ethanol for soaking for 2 h, and then suction filtration, and then rinsing with ethanol and acetone respectively, and then vacuum drying to constant weight, to obtain a hydrophobic monomer (denoted as S3) having a structural formula as described in formula (3).

[0151] Example 4

[0152] Preparation of hydrophobic monomer is illustrated by this example

[0153] Into a reactor equipped with temperature control device, reflux condenser and constant pressure feeding device, 14.0226 g (0.1 mol) of 1-allylcyclohexanol and 250 g of xylene were added, and after being fully stirred to dissolve, 16.016 g (0.13 mol) of cyclohexylacetonitrile was added, and after being fully stirred to completely dissolve, a mixed solution was obtained;

[0154] After nitrogen was bubbled for 30 min, 3.6295 g (0.0143 mol) of I2 was added, and the temperature was raised to 65°C, and the reaction was continuously carried out under stirring for 4.5 h to obtain a pre-product solution; the temperature was raised to 110°C again, and a mixed solution of 31.5 mL of dimethyl sulfoxide and 3.5 mL of water was added at a constant speed through a dropping funnel within 50 min, and the reaction was continuously carried out under stirring for 6 h to obtain a product system;

[0155] After the reaction was completed, xylene, dimethyl sulfoxide, water and I2 were removed by distillation under reduced pressure, and then placed into ethanol for soaking for 2 h, suction filtration, washing with ethanol and acetone respectively, and vacuum drying to constant weight to obtain a hydrophobic monomer (denoted as S4) having a structural formula as described in formula (4).

[0156] Example 5

[0157] The preparation of a hydrophobic monomer is illustrated through this example

[0158] Into a reactor equipped with temperature control device, reflux condenser and constant pressure feeding device, 14.0226 g (0.1 mol) of 1-allylcyclohexanol and 250 g of xylene were added, and after being fully stirred to dissolve, 16.016 g (0.13 mol) of cyclohexylacetonitrile was added, and after being fully stirred to completely dissolve, a mixed solution was obtained;

[0159] After nitrogen was bubbled for 30 min, 3.6295 g (0.0143 mol) of I2 was added, and the temperature was raised to 65°C, and the reaction was continuously carried out under stirring for 4.5 h to obtain a pre-product solution; the temperature was raised to 110°C again, and a mixed solution of 31.5 mL of dimethyl sulfoxide and 3.5 mL of water was added at a constant speed through a dropping funnel within 50 min, and the reaction was continuously carried out under stirring for 6 h to obtain a product system;

[0160] After the reaction was completed, xylene, dimethyl sulfoxide, water and I2 were removed by distillation under reduced pressure, and then placed into ethanol for soaking for 2 h, suction filtration, washing with ethanol and acetone respectively, and vacuum drying to constant weight to obtain a hydrophobic monomer (denoted as S4) having a structural formula as described in formula (4).

[0161] Example 6

[0162] The preparation of a hydrophobic monomer is illustrated through this example

[0163] Into a reactor equipped with a temperature-controlling device, a reflux condenser and a constant-pressure feeding device, 18.2307 g (0.1 mol) of 2,6-dimethyl-4-(2-methylallyl)cyclohexanol and 250 g of dimethylbenzene were added, and after being fully stirred until dissolved, 16.4671 g (0.12 mol) of cyclohexylpropionitrile was added, and after being fully stirred until completely dissolved, a mixed solution was obtained;

[0164] After nitrogen was bubbled for 30 min, 3.0456 g (0.012 mol) of I2 was added, and the temperature was raised to 62°C, and the reaction was continuously carried out under stirring for 5.5 h to obtain a pre-product solution; the temperature was raised to 108°C again, and a mixed solution of 32 mL of dimethyl sulfoxide and 4 mL of water was added at a uniform speed through a dropping funnel within 50 min, and the reaction was continuously carried out under stirring for 5.5 h to obtain a product system;

[0165] After the reaction was completed, dimethylbenzene, dimethyl sulfoxide, water and I2 were removed by distillation under reduced pressure, and then placed into ethanol for immersion for 2 h, suction filtration, washing with ethanol and acetone respectively, and vacuum drying until a constant weight was obtained, to obtain a hydrophobic monomer (denoted as S7) having a structural formula as described in formula (7).

[0166] Example 7

[0167] The preparation of a hydrophobic monomer is illustrated through this example

[0168] Into a reactor equipped with a temperature-controlling device, a reflux condenser and a constant-pressure feeding device, 18.2307 g (0.1 mol) of 2,6-dimethyl-4-(2-methylallyl)cyclohexanol and 250 g of dimethylbenzene were added, and after being fully stirred until dissolved, 16.4671 g (0.12 mol) of cyclohexylpropionitrile was added, and after being fully stirred until completely dissolved, a mixed solution was obtained;

[0169] After nitrogen was bubbled for 30 min, 3.0456 g (0.012 mol) of I2 was added, and the temperature was raised to 62°C, and the reaction was continuously carried out under stirring for 5.5 h to obtain a pre-product solution; the temperature was raised to 108°C again, and a mixed solution of 32 mL of dimethyl sulfoxide and 4 mL of water was added at a uniform speed through a dropping funnel within 50 min, and the reaction was continuously carried out under stirring for 5.5 h to obtain a product system;

[0170] After the reaction was completed, dimethylbenzene, dimethyl sulfoxide, water and I2 were removed by distillation under reduced pressure, and then placed into ethanol for immersion for 2 h, suction filtration, washing with ethanol and acetone respectively, and vacuum drying until a constant weight was obtained, to obtain a hydrophobic monomer (denoted as S7) having a structural formula as described in formula (7).

[0171] Example 8

[0172] The preparation of a hydrophobic monomer is illustrated through this example

[0173] Into a reactor equipped with temperature control device, reflux condenser and constant pressure feeding device, 18.2307g (0.1mol) 2-propyl-4-(1-allyl)cyclohexanol and 220g of toluene were added, after fully stirred to dissolve, 14.7382g (0.135mol) 1-cyclohexylcarbonitrile was added, fully stirred to completely dissolve, to obtain a mixed solution;

[0174] After nitrogen was bubbled for 30min, 3.4263g (0.0135mol) I2 was added, the temperature was increased to 60℃, and the reaction was continuously stirred for 6h to obtain a pre-product solution; the temperature was increased to 102℃ again, and 35mL of a mixed solution of morpholine and 3.8mL of water was added at a constant speed through a dropping funnel within 50min, and the reaction was continuously stirred for 6h to obtain a product system;

[0175] After the reaction was completed, toluene, morpholine, water and I2 were removed by distillation under reduced pressure, and then soaked in ethanol for 2h, suction filtered, washed with ethanol and acetone respectively, and vacuum dried to constant weight to obtain a hydrophobic monomer (denoted as S8) with the structural formula of formula (8).

[0176] Example 9

[0177] The preparation of the hydrophobic monomer is illustrated by this example

[0178] Into a reactor equipped with temperature control device, reflux condenser and constant pressure feeding device, 18.0291g (0.1mol) 1,4-diallylcyclohexanol and 260g of toluene were added, after fully stirred to dissolve, 14.7839g (0.12mol) 1-cyclohexylcarbonitrile was added, fully stirred to completely dissolve, to obtain a mixed solution;

[0179] After nitrogen was bubbled for 30min, 3.4263g (0.0135mol) I2 was added, the temperature was increased to 60℃, and the reaction was continuously stirred for 6h to obtain a pre-product solution; the temperature was increased to 102℃ again, and 35mL of a mixed solution of morpholine and 3.8mL of water was added at a constant speed through a dropping funnel within 50min, and the reaction was continuously stirred for 6h to obtain a product system;

[0180] After the reaction was completed, toluene, morpholine, water and I2 were removed by distillation under reduced pressure, and then soaked in ethanol for 2h, suction filtered, washed with ethanol and acetone respectively, and vacuum dried to constant weight to obtain a hydrophobic monomer (denoted as S8) with the structural formula of formula (8).

[0181] Example 10

[0182] The preparation of the high molecular polymer is illustrated by this example

[0183] In a reactor equipped with temperature control device, reflux condenser and constant pressure feeding device, 21.3237 g (0.3 mol) of acrylamide, 37.6179 g (0.4 mol) of sodium acrylate, 29.6197 g (0.1 mol) of 1-ethenyl-3-butylimidazolium hexafluorophosphate and 10.537 g (0.04 mol) of the hydrophobic monomer S1 prepared in Example 1 were sequentially added into 520 mL of dimethyl sulfoxide for mixing and stirring, and the temperature was raised to 57°C;

[0184] After purging with N2 for 30 min, 0.5 g of azobisdimethylvaleronitrile was added into the above mixed solution, and 40 mL of N,N-dimethylformamide solution containing 0.08 g of isopropyl alcohol was uniformly added dropwise into the solution using a separatory funnel under stirring for 6 h, and the reaction was continued for 20 h to obtain a crude product.

[0185] After precipitation by adding 600 mL of anhydrous ethanol, the product was filtered, washed with acetone for 3 times, and then extracted with a Soxhlet extractor using a mixed solvent of glacial acetic acid and ethylene glycol (volume ratio of 3:2) as the extraction agent for 24 h, and dried under vacuum at 25°C to a constant weight to obtain a high molecular polymer (denoted as P1).

[0186] In P1, the molar ratio of the structural units the structural unit the structural unit and the fourth structural unit is 30:40:10:4.

[0187] It was tested that the viscosity-average relative molecular weight of P1 was 2.11 x 10 4 g / mol.

[0188] Example 11

[0189] The preparation of a high molecular polymer is described through this example

[0190] In a reactor equipped with temperature control device, reflux condenser and constant pressure feeding device, 67.6896 g (0.4 mol) of diacetone acrylamide, 21.6189 g (0.3 mol) of acrylic acid, 14.2274 g (0.07 mol) of 1-allyl-2,3-dimethylimidazolium dicyanamide and 7.9028 g (0.03 mol) of the hydrophobic monomer S1 prepared in Example 1 were sequentially added into 1050 mL of N,N-dimethylformamide for mixing and stirring, and the temperature was raised to 67°C;

[0191] After purging with N2 for 30 min, 0.5 g of azobisdimethylvaleronitrile was added into the above mixed solution, and 40 mL of N,N-dimethylformamide solution containing 0.08 g of isopropyl alcohol was uniformly added dropwise into the solution using a separatory funnel under stirring for 6 h, and the reaction was continued for 20 h to obtain a crude product.

[0192] After precipitation by adding 600 mL of anhydrous ethanol, the product is filtered, washed with acetone for 3 times respectively, and then extracted with a Soxhlet extractor for 24 h using a mixed solvent of glacial acetic acid and ethylene glycol with a volume ratio of 3:2 as the extraction agent. The product is dried to constant weight under vacuum at 25°C to obtain a high molecular polymer (denoted as P2).

[0193] In P2, the molar ratio of the structural units the structural unit the structural unit and the fourth structural unit is 40:30:7:3.

[0194] Tested, the viscosity average relative molecular weight of P2 is 2.05×10 4 g / mol.

[0195] Example 12

[0196] The preparation of a high molecular polymer is illustrated by this example

[0197] In a reactor equipped with a temperature control device, a reflux condenser device and a constant pressure feeding device, 86.606 g (0.5 mol) of N,N-bis(2-hydroxyethyl) methacrylamide, 44.0613 g (0.4 mol) of potassium acrylate, 24.5164 g (0.1 mol) of 1-allyl-3-butylimidazole bromide and 2.6343 g (0.01 mol) of the hydrophobic monomer S1 prepared in Example 1 are sequentially added to 1600 mL of tetrahydrofuran for mixing and stirring, and the temperature is raised to 56°C;

[0198] After N2 for 30 min, 2.0 g of azobisdimethylammonium hydrochloride is added to the above mixed solution, and 42 mL of tetrahydrofuran solution containing 0.248 g of 2,3-dimercapto-1-propanol is uniformly added dropwise using a separatory funnel under stirring for 6 h, and then the reaction is continued for 8 h to obtain a crude product;

[0199] After precipitation by adding 600 mL of anhydrous ethanol, the product is filtered, washed with acetone for 3 times respectively, and then extracted with a Soxhlet extractor for 24 h using a mixed solvent of glacial acetic acid and ethylene glycol with a volume ratio of 3:2 as the extraction agent. The product is dried to constant weight under vacuum at 25°C to obtain a high molecular polymer (denoted as P3).

[0200] In P3, the molar ratio of the structural units the structural unit the structural unit and the fourth structural unit is 50:40:10:1.

[0201] Tested, the viscosity average relative molecular weight of P3 is 2.00×104 g / mol.

[0202] Example 13

[0203] The preparation of a high molecular polymer is illustrated by this example

[0204] In a reactor equipped with temperature control device, reflux condenser and constant pressure feeding device, 25.5318 g (0.3 mol) of methacrylamide, 34.436 g (0.4 mol) of methacrylic acid, 18.6668 g (0.05 mol) of 1-allyl-3-methyl imidazolium acetate and 2.6343 g (0.01 mol) of the hydrophobic monomer S1 prepared in Example 1 were sequentially added into 800 mL of N,N-dimethylformamide for mixing and stirring and the temperature was raised to 64°C;

[0205] After purging with N2 for 30 min, 0.76 g of azobisisobutyronitrile was added into the above mixed solution, and 40 mL of N,N-dimethylformamide solution containing 0.08 g of 3-mercaptopropanol was uniformly added dropwise into the mixed solution using a separatory funnel under stirring for 6 h, and the reaction was continued for 12 h to obtain a crude product.

[0206] After precipitation by adding 600 mL of anhydrous ethanol and filtration, the product was washed with acetone for 3 times, respectively, and then extracted with a Soxhlet extractor using a mixed solvent of glacial acetic acid and ethylene glycol with a volume ratio of 3:2 as the extraction agent for 24 h, and dried under vacuum at 25°C to constant weight to obtain a high molecular polymer (denoted as P4).

[0207] The molar ratio of the structural units The structural unit The structural unit and the fourth structural unit is 30:40:5:1.

[0208] It was tested that the viscosity-average relative molecular weight of P4 was 2.22 x 10 4 g / mol.

[0209] Example 14

[0210] The preparation of a high molecular polymer is illustrated by this example

[0211] In a reactor equipped with temperature control device, reflux condenser and constant pressure feeding device, 25.5318 g (0.3 mol) of methacrylamide, 34.436 g (0.4 mol) of methacrylic acid, 18.6668 g (0.05 mol) of 1-allyl-3-methyl imidazolium acetate and 2.6343 g (0.01 mol) of the hydrophobic monomer S1 prepared in Example 1 were sequentially added into 800 mL of N,N-dimethylformamide for mixing and stirring and the temperature was raised to 64°C;

[0212] After 30 min of N2 flow, 1.0 g of azoisobutyronitrile carbamamide was added to the above mixed solution, and 30 mL of dimethyl sulfoxide solution containing 0.11 g of 1-mercapto-2-propanol was uniformly added dropwise using a separatory funnel under stirring for 1 h, and the reaction was continued for 15 h to obtain a crude product;

[0213] After precipitation by adding 600 mL of anhydrous ethanol and filtration, the product was washed with acetone three times, respectively, and then extracted with a Soxhlet extractor using a mixed solvent of glacial acetic acid and ethylene glycol at a volume ratio of 3:2 as an extraction agent for 24 h. After drying to constant weight under vacuum at 25 °C, a high molecular polymer (denoted as P5) was obtained.

[0214] In P5, the molar ratio of the structural units and the fourth structural unit is 45:25:8:3.

[0215] It was tested that the viscosity-average relative molecular weight of P5 was 2.17 x 10 4 g / mol.

[0216] Example 15

[0217] The preparation of a high molecular polymer is described through this example

[0218] In a reactor equipped with a temperature control device, a reflux condenser device, and a constant pressure feeding device, 38.7477 g (0.3 mol) of N-(2-hydroxypropyl) acrylamide, 24.8361 g (0.2 mol) of potassium methacrylate, 43.1368 g (0.1 mol) of 1-vinyl-3-ethylimidazole bis(trifluoromethanesulfonyl) imide salt, and 2.6343 g (0.01 mol) of the hydrophobic monomer S1 prepared in Example 1 were sequentially added to 1200 mL of dimethyl sulfoxide for mixing, stirring, and heating to 92 °C;

[0219] After 30 min of N2 flow, 0.95 g of 2,2'-azobis(N-cyclohexyl isobutyl amidine) hydrochloride was added to the above mixed solution, and 40 mL of dimethyl sulfoxide solution containing 0.2 g of dodecyl mercaptan was uniformly added dropwise using a separatory funnel under stirring for 2 h, and the reaction was continued for 17.5 h to obtain a crude product.

[0220] After precipitation by adding 600 mL of anhydrous ethanol and filtration, the product was washed with acetone three times, respectively, and then extracted with a Soxhlet extractor using a mixed solvent of glacial acetic acid and ethylene glycol at a volume ratio of 3:2 as an extraction agent for 24 h. After drying to constant weight under vacuum at 25 °C, a high molecular polymer (denoted as P6) was obtained.

[0221] ​​P6, the molar ratio of the structural units the structural units the structural units and the fourth structural units is 30:20:10:1.

[0222] The viscosity-average relative molecular weight of P6 is 2.10 x 10 4 g / mol.

[0223] Example 16

[0224] The preparation of a high-molecular polymer is illustrated by this example

[0225] In a reactor equipped with a temperature control device, a reflux condenser and a constant-pressure feeding device, 44.5155 g (0.35 mol) of N, N-diethylacrylamide, 25.2221 g (0.35 mol) of acrylic acid, 11.8933 g (0.06 mol) of 1-vinyl-3-methylimidazole lactate and 10.537 g (0.04 mol) of the hydrophobic monomer S2 prepared in Example 2 were sequentially added to 1200 mL of dimethyl sulfoxide for mixing and stirring and the temperature was raised to 72°C;

[0226] After purging with N2 for 30 min, 0.2 g of benzoyl peroxide was added to the above mixed solution, and 40 mL of a dimethyl sulfoxide solution containing 0.125 g of mercaptoethanol was uniformly added dropwise using a separatory funnel under stirring for 3 h, and the reaction was continued for 12 h to obtain a crude product;

[0227] After precipitation by adding 600 mL of anhydrous ethanol and filtration, the product was washed with acetone for 3 times, respectively, and then extracted with a Soxhlet extractor using a mixed solvent of glacial acetic acid-ethylene glycol with a volume ratio of 3:2 as the extraction agent for 24 h, and dried under vacuum at 25°C to a constant weight to obtain a high-molecular polymer (denoted as P7).

[0228] P7, the molar ratio of the structural units the structural units the structural units and the fourth structural units is 35:35:6:4.

[0229] The viscosity-average relative molecular weight of P7 is 2.09 x 10 4 g / mol.

[0230] Example 17

[0231] The preparation of a high-molecular polymer is illustrated by this example

[0232] In a reactor equipped with temperature control device, reflux condenser and constant pressure feeding device, 39.6532 g (0.4 mol) of N-vinyl-N-methylacetamide, 27.018 g (0.25 mol) of sodium methacrylate, 14.7194 g (0.07 mol) of 1-propenyl-3-propylimidazole acetate and 5.2685 g (0.02 mol) of the hydrophobic monomer S2 prepared in Example 2 were sequentially added into 1200 mL of N,N-dimethylformamide for mixing and stirring and heating to 44°C;

[0233] After purging with N2 for 30 min, 0.75 g of azobisdimethylvaleronitrile was added into the above mixed solution, and 35 mL of N,N-dimethylformamide solution containing 0.14 g of mercaptopropionic acid was uniformly added dropwise into the mixed solution using a separatory funnel under stirring for 4 h, and the reaction was continued for 22 h to obtain a crude product.

[0234] After adding 600 mL of anhydrous ethanol for precipitation and filtration, the product was washed with acetone for 3 times, respectively, and then extracted with a Soxhlet extractor using a mixed solvent of glacial acetic acid and ethylene glycol with a volume ratio of 3:2 as the extraction agent for 24 h, and dried under vacuum at 25°C to constant weight to obtain a high molecular polymer (denoted as P8).

[0235] The molar ratio of the structural units The structural unit The structural unit and the fourth structural unit is 40:25:7:2.

[0236] It was tested that the viscosity-average relative molecular weight of P8 was 2.15 x 10 4 g / mol.

[0237] Example 18

[0238] The preparation of a high molecular polymer is illustrated by this example

[0239] In a reactor equipped with temperature control device, reflux condenser and constant pressure feeding device, 50.5525 g (0.5 mol) of N-hydroxymethyl acrylamide, 37.6179 g (0.4 mol) of sodium acrylate, 18.6668 g (0.05 mol) of 1-allyl-3-methyl imidazole anilino acetate and 9.9759 g (0.04 mol) of the hydrophobic monomer S3 prepared in Example 3 were sequentially added into 1800 mL of 1,4-dioxane for mixing and stirring and heating to 69°C;

[0240] After 30 min of N2 flow, 0.8 g of azobisdimethylvaleric acid was added to the above mixed solution, and 40 mL of N,N-dimethylacetamide solution containing 0.12 g of dodecyl mercaptan was added dropwise uniformly using a separatory funnel under stirring within 4 h, and the reaction was continued for 18 h to obtain a crude product;

[0241] After precipitation by adding 600 mL of anhydrous ethanol and filtration, the product was washed with acetone three times in succession, and then extracted with a Soxhlet extractor using a mixed solvent of glacial acetic acid and ethylene glycol in a volume ratio of 3:2 as an extraction agent for 24 h. After drying to constant weight under vacuum at 25°C, a high molecular polymer (denoted as P9) was obtained.

[0242] In P9, the molar ratio of the structural units the structural unit the structural unit and the fourth structural unit is 50:40:5:4.

[0243] It was tested that the viscosity-average relative molecular weight of P9 was 2.03 x 10 4 g / mol.

[0244] Example 19

[0245] The preparation of a high molecular polymer is described through this example

[0246] In a reactor equipped with a temperature control device, a reflux condenser device and a constant pressure feeding device, 53.6613 g (0.38 mol) of N,N-diethyl methacrylamide, 39.7377 g (0.32 mol) of potassium methacrylate, 20.7205 g (0.075 mol) of 1-vinyl-3-butylimidazole dimethyl phosphate salt and 7.4819 g (0.03 mol) of the hydrophobic monomer S3 prepared in Example 3 were sequentially added to 2000 mL of N,N-dimethylacetamide for mixing, stirring and heating to 61°C;

[0247] After 30 min of N2 flow, 0.8 g of azobisdimethylvaleric acid was added to the above mixed solution, and 40 mL of N,N-dimethylacetamide solution containing 0.12 g of dodecyl mercaptan was added dropwise uniformly using a separatory funnel under stirring within 4 h, and the reaction was continued for 18 h to obtain a crude product;

[0248] After precipitation by adding 600 mL of anhydrous ethanol and filtration, the product was washed with acetone three times in succession, and then extracted with a Soxhlet extractor using a mixed solvent of glacial acetic acid and ethylene glycol in a volume ratio of 3:2 as an extraction agent for 24 h. After drying to constant weight under vacuum at 25°C, a high molecular polymer (denoted as P9) was obtained.

[0249] In P10, the molar ratio of the structural units the structural unit Structural unit and fourth structural unit at a molar ratio of 38:32:7.5:3.

[0250] The viscosity-average relative molecular weight of P10 is 2.19 x 10 4 g / mol.

[0251] Example 20

[0252] This example illustrates the preparation of a high molecular polymer

[0253] In a reactor equipped with a temperature control device, a reflux condenser and a constant pressure feeding device, 57.566 g (0.5 mol) of N-hydroxyethyl acrylamide, 18.809 g (0.2 mol) of sodium acrylate, 13.6121 g (0.05 mol) of 1-ethenyl-3-ethyl imidazole trifluoromethanesulfonate and 2.6325 g (0.01 mol) of the hydrophobic monomer S4 prepared in Example 4 were sequentially added to 800 mL of dimethyl sulfoxide for mixing and stirring and the temperature was raised to 86°C;

[0254] After purging with N2 for 30 min, 0.75 g of azobisdimethyl N-2-hydroxybutyl acrylamide was added to the above mixed solution, and 40 mL of a dimethyl sulfoxide solution containing 0.14 g of 2,3-dimercapto-1-propanol was uniformly added dropwise using a separatory funnel under stirring for 3 h, and the reaction was continued for 20 h to obtain a crude product;

[0255] After precipitation by adding 600 mL of anhydrous ethanol and filtration, the product was washed with acetone for 3 times, respectively, and then extracted with a Soxhlet extractor using a mixed solvent of glacial acetic acid-ethylene glycol at a volume ratio of 3:2 as the extraction agent for 24 h, and dried under vacuum at 25°C to a constant weight to obtain a high molecular polymer (denoted as P11).

[0256] In P11, the molar ratio of the structural unit the structural unit the structural unit and the fourth structural unit is 50:20:5:1.

[0257] The viscosity-average relative molecular weight of P11 is 2.18 x 10 4 g / mol.

[0258] Example 21

[0259] This example illustrates the preparation of a high molecular polymer

[0260] In a reactor equipped with temperature control device, reflux condenser and constant pressure feeding device, 34.0424 g (0.4 mol) of N-vinylacetamide, 33.046 g (0.3 mol) of potassium acrylate, 16.7449 g (0.08 mol) of 1-allyl-3-propylimidazole thiocyanate and 7.8974 g (0.03 mol) of the hydrophobic monomer S4 prepared in Example 4 were sequentially added into 1200 mL of N,N-dimethylacetamide for mixing and stirring, and heated to 104°C;

[0261] After purging with N2 for 30 min, 1.6 g of azobis isobutyl cyanocarbamide was added into the above mixed solution, and 40 mL of N,N-dimethylacetamide solution containing 0.15 g of dodecyl mercaptan was uniformly added dropwise using a separatory funnel under stirring for 2 h, and the reaction was continued for 16 h to obtain a crude product;

[0262] After precipitation by adding 600 mL of anhydrous ethanol and filtration, the product was washed with acetone for 3 times, respectively, and then extracted with a Soxhlet extractor using a mixed solvent of glacial acetic acid and ethylene glycol with a volume ratio of 3:2 as the extraction agent for 24 h, and dried under vacuum at 25°C to constant weight to obtain a high molecular polymer (denoted as P12).

[0263] In P12, the molar ratio of the structural units the structural unit the structural unit and the fourth structural unit is 40:30:8:3.

[0264] It was tested that the viscosity-average relative molecular weight of P12 was 2.00 x 10 4 g / mol.

[0265] Example 22

[0266] The preparation of a high molecular polymer is illustrated by this example

[0267] In a reactor equipped with temperature control device, reflux condenser and constant pressure feeding device, 40.2962 g (0.35 mol) of N-hydroxyethyl acrylamide, 49.6721 g (0.4 mol) of potassium methacrylate, 10.1625 g (0.05 mol) of 1-allyl-2,3-dimethylimidazole dicyanamide salt and 5.8296 g (0.02 mol) of the hydrophobic monomer S5 prepared in Example 5 were sequentially added into 1200 mL of N,N-dimethylacetamide for mixing and stirring, and heated to 88°C;

[0268] After 30 min of N2 flow, 1.2 g of azobiscyclohexylcarbonitrile was added to the above mixed solution, and 50 mL of N,N-dimethylacetamide solution containing 0.3 g of dodecyl mercaptan was added dropwise uniformly using a separatory funnel under stirring within 2 h, and the reaction was continued for 16 h to obtain a crude product;

[0269] After precipitation by adding 600 mL of anhydrous ethanol and filtration, the product was washed with acetone for 3 times, respectively, and then extracted with a Soxhlet extractor using a mixed solvent of glacial acetic acid-ethylene glycol with a volume ratio of 3:2 as an extraction agent for 24 h, and dried to constant weight under vacuum at 25°C to obtain a high molecular polymer (denoted as P13).

[0270] In P13, the molar ratio of the structural units the structural unit the structural unit and the fourth structural unit is 35:40:5:2.

[0271] It was tested that the viscosity-average relative molecular weight of P13 was 2.02×10 4 g / mol.

[0272] Example 23

[0273] The preparation of a high molecular polymer is illustrated by this example

[0274] In a reactor equipped with a temperature control device, a reflux condenser device and a constant pressure feeding device, 29.7399 g (0.3 mol) of N,N-dimethylacrylamide, 27.5383 g (0.25 mol) of potassium acrylate, 13.8755 g (0.07 mol) of 1-vinyl-3-methylimidazolium lactate and 10.8484 g (0.03 mol) of the hydrophobic monomer S6 prepared in Example 6 were sequentially added to 1200 mL of N,N-dimethylformamide for mixing, stirring and heating to 67°C;

[0275] After 30 min of N2 flow, 1.2 g of azobiscyclohexylcarbonitrile was added to the above mixed solution, and 50 mL of N,N-dimethylacetamide solution containing 0.3 g of dodecyl mercaptan was added dropwise uniformly using a separatory funnel under stirring within 2 h, and the reaction was continued for 16 h to obtain a crude product;

[0276] After precipitation by adding 600 mL of anhydrous ethanol and filtration, the product was washed with acetone for 3 times, respectively, and then extracted with a Soxhlet extractor using a mixed solvent of glacial acetic acid-ethylene glycol with a volume ratio of 3:2 as an extraction agent for 24 h, and dried to constant weight under vacuum at 25°C to obtain a high molecular polymer (denoted as P13).

[0277] In P14, the molar ratio of the structural units the structural unit Structural unit and fourth structural unit at a molar ratio of 30:25:7:3.

[0278] P14 was tested to have a viscosity-average relative molecular weight of 2.05 x 10 4 g / mol.

[0279] Example 24

[0280] The method of Example 23 was followed, except that the hydrophobic monomer S6 was replaced with the same molar amount of the hydrophobic monomer S7 prepared in Example 7, and other conditions were the same as in Example 23. A polymer was obtained (denoted as P15).

[0281] In P15, the structural unit structural unit structural unit and fourth structural unit at a molar ratio of 30:25:7:3.

[0282] P15 was tested to have a viscosity-average relative molecular weight of 2.15 x 10 4 g / mol.

[0283] Example 25

[0284] The method of Example 23 was followed, except that the hydrophobic monomer S6 was replaced with the same molar amount of the hydrophobic monomer S8 prepared in Example 8, and other conditions were the same as in Example 23. A polymer was obtained (denoted as P16).

[0285] In P16, the structural unit structural unit structural unit and fourth structural unit at a molar ratio of 30:25:7:3.

[0286] P16 was tested to have a viscosity-average relative molecular weight of 2.11 x 10 4 g / mol.

[0287] Example 26

[0288] The method of Example 23 was followed, except that the hydrophobic monomer S6 was replaced with the same molar amount of the hydrophobic monomer S9 prepared in Example 9, and 1-vinyl-3-methylimidazole lactate was replaced with the same molar amount of 1-propenyl-2,3-dimethylimidazole p-toluenesulfonate. Other conditions were the same as in Example 23. A polymer was obtained (denoted as P17).

[0289] In P17, the structural unit structural unit structural unit and a fourth structural unit in a molar ratio of 30:25:7:3.

[0290] P17 was tested and had a viscosity average relative molecular mass of 2.17 x 10 4 g / mol.

[0291] Comparative Example 1

[0292] The procedure of Example 10 was followed except that no 1 -vinyl-3-butyl imidazolium hexafluorophosphate was added. The other conditions were the same as in Example 10. A polymer was obtained (denoted D1).

[0293] D1 was tested and had a viscosity average relative molecular mass of 2.12 x 10 4 g / mol.

[0294] Comparative Example 2

[0295] The procedure of Example 10 was followed except that 1 -vinyl-3-butyl imidazolium hexafluorophosphate was replaced by the same molar amount of 1 -vinyl imidazole. The other conditions were the same as in Example 10. A polymer was obtained (denoted D2).

[0296] D2 was tested and had a viscosity average relative molecular mass of 2.04 x 10 4 g / mol.

[0297] Comparative Example 3

[0298] The procedure of Example 10 was followed except that no hydrophobic monomer S1 was added. The other conditions were the same as in Example 10. A polymer was obtained (denoted D3).

[0299] D3 was tested and had a viscosity average relative molecular mass of 2.10 x 10 4 g / mol.

[0300] Comparative Example 4

[0301] The procedure of Example 10 was followed except that hydrophobic monomer S1 was replaced by the same molar amount of octadecyl acrylamide. The other conditions were the same as in Example 10. A polymer was obtained (denoted D4).

[0302] D4 was tested and had a viscosity average relative molecular mass of 2.10 x 10 4 g / mol.

[0303] Comparative Example 5

[0304] The procedure of Example 10 was followed except that hydrophobic monomer S1 was replaced by the same molar amount of p-methyl styrene. The other conditions were the same as in Example 10. A polymer was obtained (denoted D5).

[0305] The viscosity-average relative molecular weight of D5 was 2.07 x 10 4 g / mol.

[0306] Test Example

[0307] The polymers P1-P17, D1-D5 prepared according to Examples 10-26, Comparative Examples 1-5, and conventional tackifiers carboxymethyl cellulose sodium salt (HV-CMC), polyanionic cellulose (PAC-HV), and xanthan gum (XC) were tested to evaluate the rheology adjustment performance, temperature resistance, salt resistance, weather resistance, biological toxicity, and biodegradability of the above products.

[0308] 1. Evaluation of rheology adjustment performance

[0309] 16.0 g of sodium-based bentonite was added to 400 mL of deionized water, stirred at a speed of 800 rpm for 2 h, and then allowed to stand for 24 h to obtain base slurry A;

[0310] P1-P17, D1-D5, conventional tackifiers HV-CMC, PAC-HV, and XC were added to base slurry A at an addition amount of 1% (i.e., 1 g per 100 mL of base slurry A), and after stirring, the obtained experimental slurries were aged at different aging temperatures for a certain period of time. The rheological parameters of the different experimental slurries, apparent viscosity (AV), plastic viscosity (PV), and yield point (YP), were determined according to the test procedure specified in GB / T 16783.1-2014 “Petroleum and Natural Gas Industries-Drilling Fluids-Field Testing-Part 1: Water-Based Drilling Fluids”, and the dynamic plasticity ratio (YP / PV) was calculated.

[0311] Among them, HV-CMC meets the Q / SH 0038-2007 standard (viscometer 600 r / min reading value, deionized water: 32, salt water: 31, saturated salt water: 30), PAC-HV meets the Q / SH CG 106-2017 standard (apparent viscosity (AV): 50.5 mPa·s), and XC meets the GB / T 5005-2010 standard (direct-reading viscometer 300 r / min reading value: 56).

[0312] The test results of aging temperature 120°C and aging time 16 h are shown in Table 1.

[0313] Table 1

[0314]

[0315]

[0316] As shown in Table 1, the YP / PV values ​​of Examples 10-26 are comparable and all greater than 0.42 Pa / mPa·s, exhibiting good shearing effect. Meanwhile, the AV values ​​are all below 28.0 mPa·s, indicating no significant viscosity effect. Comparing the YP / PV values ​​of Example 10 with Comparative Examples 1 and 2, the imidazole ionic liquid block introduced into the polymer molecular chain has a positive impact on improving the shearing effect of the polymer. Comparing the YP / PV values ​​of Example 10 with Comparative Examples 3, 4, and 5, the structural unit provided by the hydrophobic monomer containing dicyclohexyl groups in the polymer can significantly improve the shearing effect of the polymer, and the effect is stronger than that of long-chain hydrophobic monomers and phenyl hydrophobic monomers. Conventional thickeners, such as HV-CMC, PAC-HV, and XC, have weaker shearing effects. This may be because high temperature promotes the thermal degradation of the molecular chain of natural modified thickeners, thereby destroying their three-dimensional spatial network structure in the drilling fluid to a certain extent, resulting in poor shearing effect.

[0317] 2. Evaluation of temperature resistance

[0318] Base slurry A and experimental slurry were prepared according to the methods and parameters described in the above rheological performance evaluation, and aged and rheological parameters were tested using the same method. The YP / PV test results for the polymer prepared in Example 10, the polymers prepared in Comparative Examples 1-5, and the experimental slurries prepared using HV-CMC, PAC-HV, and XC at aging times of 16 hours and aging temperatures of 60℃, 70℃, 80℃, 90℃, 100℃, 110℃, 120℃, 130℃, 140℃, 150℃, 160℃, 170℃, and 180℃ are shown below. Figure 2 .

[0319] Depend on Figure 2It can be seen that with the increase of temperature, the YP / PV value of each experimental slurry gradually decreases, indicating that high temperature weakens the structural force of the three-dimensional spatial network structure formed by the polymer in the experimental slurry, thereby negatively affecting the thinning effect of the experimental slurry. When the aging temperature is increased to 150°C, the YP / PV value of Example 10 is 0.50 Pa / mPa·s, and when the aging temperature is increased to 160°C, the YP / PV value of Example 10 is still as high as 0.47 Pa / mPa·s, showing good thinning ability. Comparing the YP / PV values of Example 10 with those of Comparative Examples 1 and 2, the YP / PV value of Example 10 is always greater than those of Comparative Examples 1 and 2 under each temperature condition, and the test results show that compared with the introduction of imidazole non-ionic monomers into the polymer molecular chain, the introduction of imidazole ionic monomers into the polymer molecular chain can effectively improve the temperature resistance of the thinning agent; comparing the YP / PV values of Example 10 with those of Comparative Examples 3, 4 and 5, the YP / PV value of Example 10 is always greater than those of Comparative Examples 3, 4 and 5 under each temperature condition, and the test results show that compared with the introduction of long carbon chain hydrophobic monomers and phenyl hydrophobic monomers into the polymer molecular chain, the introduction of hydrophobic monomers containing bicyclohexyl into the polymer molecular chain can effectively improve the temperature resistance; comparing Example 10 with HV-CMC, PAC-HV and XC, except that the YP / PV value of XC is higher when the temperature is not higher than 90°C, the YP / PV value of Example 10 is always greater than those of HV-CMC, PAC-HV and XC under other temperature conditions, and compared with conventional drilling fluid treatment agents with thinning effect, Example 10 shows good temperature resistance.

[0320] 3. Salt resistance evaluation

[0321] The salt water base slurry and the salt water experimental slurry (using different concentrations of NaCl aqueous solution to replace deionized water) were prepared according to the method and parameters in the rheological property adjustment performance evaluation, and the same method was used for aging and testing the rheological parameters. Among them, the YP / PV test results of the salt water experimental slurries prepared by the polymers of Example 10, Comparative Examples 1-5 and HV-CMC, PAC-HV and XC under the conditions of aging time of 16 h and aging temperature of 120°C are shown in Table 2.

[0322] Table 2

[0323]

[0324]

[0325] As can be seen from Table 2, with the increase of the concentration of NaCl, the YP / PV values of the experimental slurries as a whole showed a downward trend. In comparison, the YP / PV values of Example 10 were less affected by the concentration of NaCl, showing strong salt resistance.

[0326] 4. Evaluation of weathering performance

[0327] The base slurry A and the experimental slurries were prepared according to the method and parameters in the above rheological property evaluation, and were aged and tested for rheological parameters in the same way. Among them, the experimental slurries prepared by using the polymer of Example 10, the polymers of Comparative Examples 1-5, and HV-CMC, PAC-HV, XC were tested for YP / PV at an aging temperature of 120℃ and aging times of 16h, 24h, 32h, 40h and 48h, respectively. The test results are shown in Table 3.

[0328] Table 3

[0329]

[0330]

[0331] As can be seen from Table 3, with the extension of the aging time, the YP / PV values of the experimental slurries as a whole showed a downward trend. In comparison, the YP / PV values of Example 10 were less affected by the aging time, and its YP / PV value remained at 0.56 Pa / mPa·s when the aging time was as long as 40h, showing good weather resistance.

[0332] 5. Evaluation of biological toxicity and biodegradability

[0333] The polymers P1-P17 and D1-D5 prepared by Examples 10-26 and Comparative Examples 1-5 were evaluated for biological toxicity and biodegradability according to the biological toxicity and organic pollutant biodegradability classification standards approved by the U.S. Environmental Protection Agency (EPA) and the biological toxicity evaluation method of drilling fluid (fairy shrimp biological detection method). The results are shown in Table 4. Among them,

[0334] Biological toxicity classification standards: EC 50 ≤1, highly toxic; 1 50 ≤100, high toxicity; 100 50 ≤1000, moderate toxicity; 1000 50 ≤10000, slightly toxic; 10000 50 ≤30000, non-toxic; EC 50 > 30000, recommended discharge standard;

[0335] Biodegradability evaluation index (Y) = (biochemical oxygen consumption (BOD) / chemical oxygen consumption (COD)) x 100; wherein, Y≥25.0, easy to degrade; 15.0≤Y<25.0, more easily degradable; 5≤Y<15.0, degradable; Y<5.0, difficult to degrade.

[0336] Table 4

[0337]

[0338]

[0339] As can be seen from Table 4, the EC of Examples 10-26 50 are all higher than 30000 mg / L, reaching the recommended discharge standard; the Y value range meets 15.0≤Y<25.0, reaching the more easily degradable standard, and is more friendly to the environment.

[0340] The preferred embodiments of the present application are described in detail above, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be considered as disclosed by the present application, and all fall within the protection scope of the present application.

Claims

1. A hydrophobic monomer characterized in that, The hydrophobic monomer is a compound with a structure shown in formula (1) to formula (13); 2. A method for preparing a hydrophobic monomer, characterized by, The preparation method comprises: (1) mixing an alkenyl cyclohexanol shown in formula (II), a cyclohexyl nitrile shown in formula (III) and a first solvent to obtain a mixed solution; (2) adding I2 in the mixed solution to perform a first reaction to obtain a pre-product solution; (3) performing a second reaction on the pre-product solution in the presence of a second solvent to obtain a product system; (4) performing separation treatment and drying on the product system to obtain the hydrophobic monomer. In formula (II), R1, R2, R3, R4, R5 and R6 are each independently selected from one of --H, C1-C3 alkyl and a substituent M, and at least one of R1, R2, R3, R4, R5 and R6 is the substituent M. The substituent M is wherein R0, R 00 and R 000 each independently is selected from -H or C1-C3 alkyl; s is a natural number from 0 to 5; In formula (III), t is a natural number of 0-10.

3. The method of making according to claim 2, wherein, t is a natural number of 0-5; and / or, one or two of R1, R2, R3, R4, R5 and R6 is the substituent M; and / or, R0, R 00 and R 000 each independently selected from -H or -CH3; s = 0 or 1.

4. The production method according to claim 3, wherein t = 0 or 1.

5. The production process according to any one of claims 2 to 4, wherein In step (1), the first solvent is selected from at least one of acetone, butanone, chloroform, dichloromethane, 1,1-dichloroethane, 1,2-dichloroethane, methyl ethyl ketone, tetrahydrofuran, petroleum ether, diethyl ether, ethyl acetate, benzene, toluene, xylene, cyclohexane, ethylene glycol dimethyl ether, nitromethane, 1,4-dioxane, pyridine, morpholine, N,N-dimethylformamide, N,N-dimethylacetamide and dimethyl sulfoxide; and / or, the molar ratio of the cyclohexyl nitrile to the alkenyl cyclohexanol is (1.1-1.4):1; and / or, the concentration of the alkenyl cyclohexanol in the mixed solution is 5-8wt%.

6. The production method according to claim 5, wherein The first solvent is selected from at least one of benzene, toluene, xylene, N,N-dimethylformamide, N,N-dimethylacetamide and dimethyl sulfoxide.

7. The production method according to claim 6, wherein The first solvent is selected from at least one of benzene, toluene and xylene.

8. The method of making according to any one of claims 2-4, wherein, In step (2), the molar ratio of I2 to the cyclohexyl nitrile is (2.5-25):

100.

9. The production method according to claim 8, wherein, In step (2), the molar ratio of I2 to the cyclohexyl nitrile is (4-20):

100.

10. The production method according to claim 9, wherein In step (2), the molar ratio of I2 to the cyclohexyl nitrile is (8-12):

100.

11. The method of making according to any one of claims 2-4, wherein, In step (2), the conditions of the first reaction include: the temperature is 40-80℃; and the time is 2-8h.

12. The method of making according to claim 11, wherein, In step (2), the conditions of the first reaction include: the temperature is 55-65℃; and the time is 4-6h.

13. The method of making according to any one of claims 2-4, wherein, In step (3), the second solvent is a mixed solution formed by one of tetrahydrofuran, ethylene glycol dimethyl ether, 1,4-dioxane, pyridine, morpholine, N,N-dimethylformamide, N,N-dimethylacetamide or dimethyl sulfoxide and water in a volume ratio of (10-5):1; and / or, the volume ratio of the second solvent to the first solvent is (10-20):

100.

14. The method of making according to any one of claims 2-4, wherein, In step (3), the conditions of the second reaction include: the temperature is 60-120℃; and the time is 2-8h.

15. The method of manufacturing according to claim 14, wherein, In step (3), the conditions of the second reaction include: the temperature is 80-110℃; and the time is 4-6h.

16. A high molecular polymer comprising structural unit A shown in formula (IV), structural unit B shown in formula (V), structural unit C shown in formula (VI) and a fourth structural unit D; the fourth structural unit D is from a hydrophobic monomer; wherein, the molar ratio of the structural unit A, the structural unit B, the structural unit C and the fourth structural unit D is (20-60):(15-45):(4-12):(1-6); In formula (IV), R 1 is selected from -H or C1-C6alkyl; R 2 selected from wherein, R a and R b each independently is selected from one of -H, C1-C6 alkyl, C1-C6 alkyl alcohol, C1-C8 alkyl ketone; R c selected from -H or C1-C6alkyl; R d selected from -CH3, -CH2CH3, one of -CH3, -CH2CH3, In formula (V), R 3 selected from -H or C1-C6 alkyl; R 4 selected from -COOH or -COOA; wherein, A is one of Na, K, Rb, Cs; In formula (VI), X - is selected from the group consisting of BF4 - , PF6 - , SCN - , HSO3 - , CH3SO3 - , CF3SO3 - , CH3COO - , CF3COO - , Tf2N - , CH3OSO3 - , C2H5OSO3 - , p-TsO - , (CN)2N - , CH3CH(OH)COO - , C6H5NHCH2COO - , (CH3O)2PO2 - , (C2H5O)2PO2 - , F - , Cl - , Br - , I - , HCO3 - ; r is a natural number from 0 to 10. R 5 and R 6 each independently is selected from -H or C1-C6alkyl; wherein, the structural formula of the hydrophobic monomer is shown in formula (I): wherein, t is a natural number of 0-10; R1, R2, R3, R4, R5 and R6 are each independently selected from -H, C1-C3 alkyl and a substituent M, and at least one of R1, R2, R3, R4, R5 and R6 is the substituent M; The substituent M is wherein R0, R 00 and R 000 each independently is selected from -H or C1-C3 alkyl; s is a natural number from 0 to 5.

17. The high molecular polymer of claim 16, wherein, In formula (IV), R 1 is selected from one of -H, -CH3, -C2H5; R a and R b are each independently selected from -H, -CH3, -CH2CH3, -CH2OH, -CH2CH2OH, is selected from one of -H, -CH3, -CH2CH3; R c is selected from one of -H, -CH3, -CH2CH3, ​ In formula (V), R 3 one selected from -H, -CH3, -C2H5; A is Na or K; In formula (VI), r is a natural number of 0-5; R 5 is selected from one of -H, -CH3, -CH2CH3; R 6 is selected from one of -H, -CH3, -CH2CH3, and -CH2CH2CH3.

18. The high molecular polymer of claim 17, wherein, in formula (VI), r = 0 or 1.

19. The high molecular polymer of any one of claims 16-18, wherein, in formula (I), t is a natural number of 0-5; and / or, one or two of R1, R2, R3, R4, R5 and R6 is the substituent M; and / or, R0, R 00 and R 000 each independently selected from -H or -CH3; s = 0 or 1.

20. The high molecular polymer of claim 19, wherein, in formula (I), t = 0 or 1.

21. The high molecular polymer of any one of claims 16-18, wherein, the hydrophobic monomer is the hydrophobic monomer of claim 1.

22. The high molecular polymer of any one of claims 16-18 and 20, wherein, The viscosity average molecular weight of the high molecular polymer is 2 x 10 4 -2.5 x 10 4 g / mol.

23. The high molecular polymer of claim 19, wherein, The viscosity average molecular weight of the high molecular polymer is 2 x 10 4 -2.5 x 10 4 g / mol.

24. The high molecular polymer of claim 21, wherein, The viscosity average molecular weight of the high molecular polymer is 2 x 10 4 -2.5 x 10 4 g / mol.

25. A method for preparing the high molecular polymer of any one of claims 16-24, comprising: (A) mixing an alkenyl amide shown in formula (IV'), an alkenyl carboxylic acid shown in formula (V'), an alkenyl ionic liquid shown in formula (VI') and a fourth monomer in a solvent a to obtain a mixture; (B) polymerizing the mixture in the presence of an initiator and a molecular weight regulator to obtain a crude product; (C) post-treating the crude product to obtain the high molecular polymer; wherein R 1 -R 6 , X - , r are defined as in any one of claims 16-24. the fourth monomer is a hydrophobic monomer, and the structural formula of the hydrophobic monomer is shown in formula (I): wherein, t is a natural number of 0-10; R1, R2, R3, R4, R5 and R6 are each independently selected from -H, C1-C3 alkyl and a substituent M, and at least one of R1, R2, R3, R4, R5 and R6 is the substituent M; The substituent M is wherein R0, R 00 and R 000 each independently is selected from -H or C1-C3 alkyl; s is a natural number from 0 to 5.

26. The method of manufacturing according to claim 25, wherein, in formula (I), t is a natural number of 0-5; and / or, one or two of R1, R2, R3, R4, R5 and R6 is the substituent M; and / or, R0, R 00 and R 000 each independently selected from -H or -CH3; s = 0 or 1.

27. The method of manufacturing according to claim 26, wherein, in formula (I), t = 0 or 1.

28. The method of manufacturing according to claim 25, wherein, the hydrophobic monomer is the hydrophobic monomer of claim 1.

29. The method of making according to any one of claims 25-28, wherein, in step (A), the molar ratio of the alkenyl amide: the alkenyl carboxylic acid: the alkenyl ionic liquid: the fourth monomer is (20-60):(15-45):(4-12):(1-6); and / or, the total concentration of the alkenyl amide, the alkenyl carboxylic acid, the alkenyl ionic liquid and the fourth monomer in the mixture is 5-15 wt%.

30. The method of making according to any one of claims 25-28, wherein, in step (A), the solvent a is selected from at least one of acetone, butanone, chloroform, dichloromethane, 1,1-dichloroethane, 1,2-dichloroethane, methyl ethyl ketone, tetrahydrofuran, petroleum ether, diethyl ether, acetonitrile, ethyl acetate, benzene, toluene, m-xylene, cyclohexane, ethylene glycol dimethyl ether, nitromethane, 1,4-dioxane, pyridine, morpholine, 4-methyl-2-pentanone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide.

31. The method of making according to any one of claims 25-28, wherein, In step (B), the initiator is at least one selected from the group consisting of azo-based initiators, organic peroxide-based initiators, inorganic peroxide-based initiators, and oil-soluble redox-based initiators; And / or, the molecular weight regulator is at least one selected from the group consisting of isopropyl alcohol, mercaptopropionic acid, mercaptoacetic acid, mercaptoethanol, 1-mercapto-2-propanol, 3-mercaptopropyl alcohol, 2,3-dimercapto-1-propanol, and dodecyl mercaptan.

32. The method of manufacturing according to claim 31, wherein, In step (B), the initiator is an azo-based initiator.

33. The method of making according to any one of claims 25-28, wherein, In step (B), the weight ratio of the initiator to (alkenyl amide + alkenyl carboxylic acid + alkenyl ionic liquid + fourth monomer) is (0.2-2):

100. The molar ratio of the molecular weight regulator to (alkenyl amide + alkenyl carboxylic acid + alkenyl ionic liquid + fourth monomer) is (0.05-0.2):

100.

34. The method of making according to any one of claims 25-28, wherein, In step (B), the conditions of the polymerization reaction include a temperature of 40-105℃ and a time of 9-30h.

35. The method of manufacturing according to claim 34, wherein, In step (B), the conditions of the polymerization reaction include a temperature of 50-105℃ and a time of 14-28h.

36. A water-based drilling fluid containing the high molecular polymer of any one of claims 16-24.

37. Use of the water-based drilling fluid of claim 36 in oil drilling.

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