Conjugated diene-based ionic liquids, methods for their preparation and use

Abstract

The application discloses a conjugated diene ionic liquid, characterized by having a cation shown in formula I: wherein R, R0, R 1 , R 2 , R 3 are independently selected from one of H, C1-C6 alkyl, phenyl; R a , R b , R c , R d , R a , R b , R c , R d are independently selected from one of H, C1-C6 alkyl; x, y, z are integers from 0 to 9. The ionic liquid has high polymerization reactivity.

Description

Technical Field

[0001] This application relates to a conjugated diene-based ionic liquid, its preparation method, and its application, belonging to the field of petroleum additives. Background Technology

[0002] Ionic liquids are molten salts that exist in a liquid state at or near room temperature, composed of organic cations and organic or inorganic anions. Because the cations in their structure are generally large and asymmetrical, they are difficult to form ordered crystal structures, allowing them to move freely at or near room temperature, thus exhibiting a liquid state. Since the first ionic liquid, ethylammonium nitrate, was disclosed in the last century, ionic liquids have undergone more than a hundred years of development, with a gradual increase in types and functions, finding applications to varying degrees in different fields.

[0003] In the field of drilling engineering, ionic liquids are mainly used as inhibitors in drilling fluids and as functionalized monomers for preparing polymeric treatment agents for drilling fluids. For example, in 2008, the article "Performance evaluation of ionic liquids as a clay stabilizer and shale inhibitor" reported that quaternary ammonium methyl sulfate ionic liquid could be used as a shale inhibitor. Reports on using ionic liquids as functional monomers for preparing polymeric treatment agents for drilling fluids are more focused on their application in the preparation of filtration loss reducers. For instance, in 2018, the article "High-Temperature and High-Calcium Filtration Loss Reducer Containing Ionic Liquid Segments" published in the journal *Drilling Fluids & Completion Fluids* reported the use of alkenyl ionic liquid 1-vinyl-3-ethylimidazolium bromide (VeiBr) in a ternary copolymerization with 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and acrylamide (AM) to obtain a high-temperature and high-calcium filtration loss reducer (PASV). Performance evaluation results show that the higher the proportion of ionic liquid segments in the PASV molecular chain, the better the filtration loss reduction effect of PASV. This is mainly because the ionic liquid has large side group cations, which not only increase the rigidity of the molecular chain but also improve the adsorption of the molecular chain on the surface of clay particles, thus preventing Ca from being absorbed. 2+ Na on the surface of bentonite + Ion exchange adsorption reduced Ca 2+The charge neutralization effect on clay promotes the dispersion of clay particles, which is beneficial for forming a dense filter cake on the filtration surface and enhances the filtration and wall-building ability of drilling fluid. Chinese patent CN 106749891B improves upon the molecular structure of the aforementioned filtration reducer by introducing a cationic monomer containing a quaternary ammonium group into the molecular chain, thereby further improving its temperature and calcium resistance. Research on the introduction of ionic liquids as functional groups into polymer-based filtration reducers is reported in more detail in Chinese patent CN 113621104B. This patent uses alkenyl imidazole ionic liquids as functional monomers, copolymerizing them with alkenyl amides, alkenyl sulfonic acids, alkenyl siloxanes, and alkenyl structural units with cyclic structures to obtain a series of filtration reducers with ionic liquid segments. These filtration reducers can withstand temperatures up to 200℃ and have excellent salt and calcium resistance. Performance comparisons with comparative examples show that the excellent filtration reduction effect of these filtration reducers is largely due to the introduction of ionic liquid segments into the molecule.

[0004] However, alkenyl ionic liquids generally exhibit low copolymerization activity. When mixed with other alkenyl functional monomers, they require a long time to form free radicals under the same initiation conditions, which inevitably affects the industrial production efficiency of such polymer products. Therefore, there is an urgent need to provide an alkenyl ionic liquid with higher polymerization reactivity to shorten the polymerization reaction time and improve polymerization efficiency. Summary of the Invention

[0005] According to the first aspect of this application, a conjugated diene-based ionic liquid is provided, which aims to overcome the deficiencies of the prior art. This type of ionic liquid can be used to rapidly prepare polymers containing ionic liquid segments. In particular, this type of ionic liquid can be used to rapidly prepare polymer-based treatment agents for drilling fluids, including filtration loss reducers, inhibitors, plugging gels, thickeners, and sealing agents.

[0006] This ionic liquid contains a diene structure. The conjugation effect disperses the electron cloud on the double bonds, making the bond length more even, increasing the molecular refractive index, decreasing the internal energy, and making the double bonds easier to open, thus increasing the polymerization reactivity. The benzene ring structure in the ionic liquid helps to improve the rigidity of the target polymer, increasing the spatial volume and steric hindrance of the polymer molecular chain, reducing the thermal motion of the polymer molecules under high-temperature conditions, and improving the temperature resistance of the polymer molecules.

[0007] An ionic liquid of the conjugated diene type, having a cation as shown in Formula I:

[0008]

[0009] Among them, R, R0, R 1 R 2 R 3Independently selected from H, C1-C6 alkyl, and phenyl;

[0010] R a R b R c R d R a R b R c R d Independently selected from H and C1-C6 alkyl groups;

[0011] x, y, and z are integers from 0 to 9.

[0012] Preferably, R, R0, R 1 R 2 R 3 It is independently selected from H, C1-C6 straight-chain alkyl, and phenyl.

[0013] Preferably, R a R b R c R d R a R b R c R d It is independently selected from H and C1-C6 straight-chain alkyl groups.

[0014] Preferably, R, R0, R 1 R 2 R 3 It is independently selected from H, C1-C4 straight-chain alkyl, and phenyl.

[0015] Preferably, R a R b R c R d R a R b R c R d It is independently selected from H and C1-C4 straight-chain alkyl groups.

[0016] Optionally, x, y, and z are independently selected from any value of 0, 1, 2, 3, 4, 5, 6, 7, 8, and 9 or a range of values ​​between any two.

[0017] According to one embodiment of this application, the anion in the ionic liquid 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 - One of them.

[0018] According to one embodiment of this application, R, R0, R 1 R 2 R 3 It is independently selected from one of H, methyl, and phenyl.

[0019] According to one embodiment of this application, R a R b R c R d R a R b R c R d It is independently selected from H or methyl.

[0020] According to one embodiment of this application, x and y are independently selected from 1 or 2, and z is an integer from 0 to 3.

[0021] According to a second aspect of this application, a method for preparing an ionic liquid is provided, the method comprising: in the presence of a catalyst, reacting an alkenyl compound represented by Formula II-1 and a diphenylimidazolium compound represented by Formula II-2 to obtain a cation represented by Formula I.

[0022] The method for preparing the ionic liquid described above includes the following steps:

[0023] The ionic liquid is obtained by reacting a mixture containing an alkenyl compound, a diphenylimidazolium compound, a catalyst, and solvent B.

[0024] The alkenyl compound has the structure shown in Formula II-1:

[0025]

[0026] The diphenylimidazolium compound has the cation shown in Formula II-2:

[0027]

[0028] According to one embodiment of this application, the anion in the diphenylimidazolium compound 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 - One of them.

[0029] According to one embodiment of this application, the catalyst used in the preparation method provided in this application only needs to be able to promote the coupling of carbonyl groups into olefins.

[0030] According to one embodiment of this application, the catalyst is selected from at least one of low-valent titanium, low-valent tungsten, low-valent molybdenum, low-valent zirconium, low-valent vanadium, and low-valent niobium.

[0031] The aforementioned low-valence titanium, low-valence tungsten, low-valence molybdenum, low-valence zirconium, low-valence vanadium, and low-valence niobium refer to the lowest valence states that metal ions can exhibit. In nature, many metal ions have multiple valence states; the so-called low valence state can be understood as the second highest valence state. The reaction utilized in this patent is the reaction of preparing the corresponding olefin by reducing and coupling carbonyl compounds, namely the McMurry coupling reaction. The catalyst in this application is a conventional catalyst for the McMurry coupling reaction.

[0032] The low-valent titanium, low-valent tungsten, low-valent molybdenum, low-valent zirconium, low-valent vanadium, and low-valent niobium used in the catalyst of this application can be obtained by methods known in the art, using the preparation of low-valent titanium as an example.

[0033] According to a preferred embodiment of the present invention, the catalyst is low-valent titanium.

[0034] According to a preferred embodiment of the present invention, for example, a method for preparing low-valent titanium includes: dissolving a titanium-containing reagent and a reducing agent in solvent A to carry out a reduction reaction.

[0035] Preferably, the method for preparing low-valent titanium further includes: the reduction reaction is carried out under a protective atmosphere, wherein the protective atmosphere is nitrogen and / or argon.

[0036] According to one embodiment of this application, the titanium-containing reagent is selected from at least one of TiCl3, TiCl4, or commercial titanium powder; the reducing agent is selected from at least one of K, Li, Na, Zn+CuCl, LiAlH4, Mg, Mg+Hg, Li+Hg, and chlorosilane. The valence state of low-valence titanium generally varies with the reducing activity of the reducing agent and the molar ratio of the reducing agent to TiCl3, TiCl4, and commercial titanium powder.

[0037] According to one embodiment of this application, solvent A is tetrahydrofuran (THF) and / or dimethyl ether (DME).

[0038] According to a preferred embodiment of the present invention, the titanium-containing reagent is TiCl4; the reducing agent is Zn and CuCl; and the solvent A is one of THF and DME.

[0039] Preferably, the concentration of TiCl4 in solvent A is 0.2-0.6 mmol / mL, the concentration of Zn in solvent A is 0.3-0.7 mmol / mL, and the concentration of CuCl in solvent A is 0.03-0.08 mmol / mL.

[0040] According to a specific embodiment of the present invention, the method for preparing low-valent titanium further includes: adding activated Zn, CuCl and solvent A to a reactor, then cooling and stirring, and then adding TiCl4 to carry out the reduction reaction in a reflux manner to obtain low-valent titanium.

[0041] According to a preferred embodiment of the present invention, when the solvent A is THF, the reflux temperature is 66°C to 76°C, and cooling is required again after reflux; when the solvent A is DME, reflux does not require heating, that is, reflux is performed at the cooling temperature of the previous step.

[0042] Preferably, the particle size of the Zn is at least 400 mesh, more preferably 400-800 mesh.

[0043] Preferably, the cooling temperature is -10 to 0°C, and the reflux time is 2 to 4 hours.

[0044] According to one embodiment of this application, the solvent B is selected from at least one of tetrahydrofuran and dimethyl ether.

[0045] According to one specific embodiment of this application, the method for preparing the ionic liquid includes: dissolving the alkenyl compound and the diphenylimidazolium compound in solvent B before the synthesis reaction.

[0046] According to a specific embodiment of this application, the preparation method of the ionic liquid includes: dissolving an alkenyl compound and a diphenylimidazolium compound in solvent B, then mixing them into a low-valent titanium reagent, and carrying out the synthesis reaction under stirring conditions in a reflux manner.

[0047] Preferably, solvent B is the same as solvent A, and the volume ratio is 1:(2-4).

[0048] According to one embodiment of this application, the molar ratio of the alkenyl compound and the diphenylimidazolium compound is 1:(1.4-1.8).

[0049] Optionally, the molar ratio of the alkenyl compound and the diphenylimidazolium compound is independently selected from any value of 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8 or any range between both.

[0050] According to one embodiment of this application, the reaction conditions are as follows:

[0051] Temperature range: -15 to 80℃;

[0052] The time is 2-10 hours.

[0053] Preferably, the temperature of the synthesis reaction is -10 to 0°C or 66 to 76°C; the time of the synthesis reaction is 2 to 10 hours; more preferably 4 to 8 hours. Wherein, when solvent B is THF, the temperature of the synthesis reaction is 66 to 76°C; when solvent B is DME, the temperature of the synthesis reaction is -10 to 0°C.

[0054] According to one embodiment of this application, the steps include:

[0055] S1. Mix the materials containing the alkenyl compound, the diphenylimidazolium compound, and the solvent B to obtain solution I;

[0056] S2. Add the mixture containing the catalyst to solution I, and stir and reflux to obtain the ionic liquid.

[0057] According to one embodiment of this application, in step S1, the concentration of the alkenyl compound in solvent B is 0.2-0.5 mmol / mL.

[0058] According to one embodiment of this application, after the reaction, a quenching reaction is also performed.

[0059] According to one embodiment of this application, the quenching reaction includes the following steps:

[0060] First, add the quenching reagent to the mixture containing the ionic liquid, then add water dropwise, followed by 8wt%-12wt% NaOH solution, and finally add more water.

[0061] Preferably, a 10wt% NaOH solution is used.

[0062] According to one embodiment of this application, the quenching agent is selected from at least one of alkali metal cyanides, ammonia compounds, boranes, K2CO3, LiAlH4, and NaBH.

[0063] According to one embodiment of this application, the molar amount of the quenching agent is 0.05%-0.1% of the molar amount of the alkenyl compound;

[0064] The molar amount of the quenching reagent is expressed as the molar amount of LiAlH4.

[0065] According to one embodiment of this application, the volume ratio of the first added water to the volume of the solvent B is 1:50-100; the dropping rate is 2-4 mL / min.

[0066] According to one embodiment of this application, the volume of the 8wt%-12wt% NaOH solution is the same as the volume of water added dropwise for the first time.

[0067] According to one embodiment of this application, the mass of water added again is 2.8-3.2 times the mass of water added the first time.

[0068] The method for preparing ionic liquid monomers provided in this application further includes a quenching reaction after the synthesis reaction has proceeded to a certain extent. Because the synthesis reaction involves excess reactants, if the excess reactants continue to exist after the target product has been obtained, they will further react to generate undesirable products. The principle of quenching is to react the excess compound with another compound that is more readily reactive, thereby removing it from the system.

[0069] To avoid impurities in the product, this application preferably performs a quenching reaction after the synthesis reaction has proceeded to a certain extent, that is, after the alkenyl compound has completely reacted.

[0070] The quenching reaction involved in this application specifically involves adding a quenching reagent after cooling the system, adding water dropwise for the first time, then adding 10wt% NaOH solution, and then adding water again.

[0071] According to a preferred embodiment of the present invention, when the solvent is THF, the quenching temperature can be room temperature or the original reaction temperature of 66-76°C. There is no limitation on the quenching temperature.

[0072] This application does not impose any particular restrictions on the quenching reagent; conventional quenching reagents such as alkali metal cyanides, ammonides, boranes, K₂CO₃, LiAlH₄, and NaBH₄ can be selected. However, considering the stability of the product and the ease of processing, this application prefers LiAlH₄ as the quenching reagent.

[0073] According to a preferred embodiment of this application, the molar amount of LiAlH4 is 0.05%-0.1% of the molar amount of the alkenyl compound.

[0074] According to a preferred embodiment of this application, the volume ratio of water to solvent B in the first drop is 1:(50-100), and the dropping speed is controlled at 2-4 mL / min.

[0075] According to a preferred embodiment of this application, the volume of the 10wt% NaOH solution is the same as the volume of the water added in the first drop, and there is no limitation on the addition rate; it can be added all at once or drop by drop.

[0076] According to a preferred embodiment of this application, the mass of water added again is three times the mass of water added in the first dripping. There is no limit to the addition speed; it can be added all at once or drop by drop.

[0077] To obtain a purified ionic liquid, the method for preparing the ionic liquid provided in this application may further include: after quenching the reaction, adding a drying agent to the system, filtering, rinsing, collecting the filtrate, and distilling under reduced pressure to remove solvent A and rinsing reagent, thereby obtaining a crude ionic liquid product. Finally, recrystallizing the crude product to remove unreacted raw materials, byproducts, and residual catalyst.

[0078] According to a preferred embodiment of this application, the mixture is dried with a desiccant, filtered, and then distilled under reduced pressure to remove the solvent, yielding a pale yellow crude product.

[0079] According to a preferred embodiment of this application, the desiccant is preferably an inorganic neutral desiccant, such as one or more of MgSO4, Na2SO4, CaSO4, and CaCl2.

[0080] This application does not restrict the filtration method, as long as it can filter out low-priced titanium. Conventional filter aids can be added, such as alumina filter aid, diatomaceous earth filter aid, charcoal powder filter aid, activated carbon filter aid, and perlite filter aid.

[0081] According to a preferred embodiment of this application, diatomaceous earth filtration is used.

[0082] In order to collect as much product as possible, this application also preferably performs rinsing after filtration and collection of filtrate. The rinsing solvent can be selected from conventional rinsing reagents, preferably CH2Cl2. After rinsing, the rinsing liquid is mixed with the filtrate to obtain a mixture, which is the crude product of ionic liquid.

[0083] To obtain ionic liquids with higher purity, the preparation method of the ionic liquid provided in this application further includes a deep purification operation, namely, recrystallizing the product obtained from the synthesis reaction.

[0084] According to a preferred embodiment of this application, after vacuum distillation, acetonitrile is added to the crude product of the ionic liquid, followed by toluene. After stirring evenly, the mixture is cooled to -28°C, and white crystals precipitate out. The crystals are then filtered and rinsed with toluene to obtain the purified conjugated diene ionic liquid.

[0085] According to a preferred embodiment of this application, the mass ratio of acetonitrile to crude ionic liquid is 1:(5-10).

[0086] According to a preferred embodiment of this application, the mass ratio of toluene to crude ionic liquid is (2-4):1.

[0087] According to a third aspect of this application, a copolymer is provided.

[0088] A copolymer obtained by copolymerizing an ionic liquid with a monomer;

[0089] The ionic liquid is selected from the ionic liquids described above or the ionic liquids prepared by the methods described above.

[0090] According to one embodiment of this application, the monomer is selected from at least one of acrylamide (AM), N-isopropylacrylamide (NIPAM), N,N'-methylenebisacrylamide (BIS), vinylpyrrolidone (NVP), acrylic acid (AA), sodium acrylate (AAS), acrylonitrile (CN), sodium styrene sulfonate (SSS), 2-acrylamido-2-methylpropanesulfonic acid (AMPS), dimethyl diallyl ammonium chloride (DMDAAC), and γ-methacryloyloxypropyltrimethoxysilane (KH570).

[0091] The block proportion of the ionic liquid in the polymer, or the ratio between the ionic liquid and other monomers, depends on the purpose of the specific polymer to be synthesized. Generally, the percentage (molar ratio) of the ionic liquid in all monomers involved in the polymer synthesis does not exceed 10%.

[0092] This application does not specifically limit the polymerization method; any one of bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, reverse emulsion polymerization, melt polymerization, and interfacial polymerization may be used.

[0093] According to the specific embodiments of this application, solution polymerization is preferred. Specific operations are listed in this application, and those skilled in the art should not understand them as limitations on the present invention.

[0094] According to a fourth aspect of this application, an application of a copolymer in oilfield additives is provided. This ionic liquid exhibits high polymerization reactivity and can be used to prepare polymers containing ionic liquid blocks. In particular, this type of ionic liquid can be used to rapidly prepare polymer-based treatment agents for drilling fluids, including filtration reducers, inhibitors, plugging gels, thickeners, and sealing agents.

[0095] The application of the copolymers described above in oilfield additives.

[0096] According to one embodiment of this application, the copolymer is used in oil fields as a filtration loss reducer, inhibitor, plugging gel, thickener, and sealing agent.

[0097] According to the fifth aspect of this application, a drilling fluid is provided.

[0098] A drilling fluid comprising copolymers and additives;

[0099] The copolymer is selected from the copolymers described above.

[0100] In this application, there is no particular limitation on the above-mentioned drilling fluid system, which can be any drilling fluid system known in the art, such as bentonite drilling fluid system, potassium amine-based drilling fluid system, polymer strong inhibition drilling fluid system, polyol drilling fluid system, sulfonated drilling fluid system, polysulfonated drilling fluid system, brine drilling fluid system, composite salt drilling fluid system, seawater drilling fluid system, calcium chloride drilling fluid system, solids-free drilling fluid system, water-in-oil drilling fluid system, and silicate drilling fluid system. According to a specific embodiment of the present invention, the drilling fluid of the present invention can be bentonite drilling fluid or brine drilling fluid.

[0101] Preferably, the water-based drilling fluid also contains additives.

[0102] Preferably, the additives include bentonite and Na2CO3.

[0103] In this application, the content of the copolymer in the drilling fluid is not particularly limited and can be appropriately adjusted according to the formation conditions. For example, the content of the copolymer can be 0.2wt%-2.0wt% based on the total amount of drilling fluid.

[0104] In this invention, there are no particular limitations on the preparation method of the drilling fluid. Preparation methods well known to those skilled in the art can be used, and will not be described in detail here. Specific operations are listed in this article, and those skilled in the art should not understand them as limitations on this invention.

[0105] In this application, C1-C6, etc., all refer to the number of carbon atoms contained in the group.

[0106] In this application, the term "alkyl" refers to a group formed by the loss of any one hydrogen atom from an alkane molecule.

[0107] In this application, the term "phenyl" refers to a group with a benzene ring as its functional group.

[0108] In this application, the term "methyl" refers to an electrically neutral monovalent group remaining after removing a hydrogen atom from a methane molecule. The beneficial effects of this application include:

[0109] 1) The present application provides a conjugated diene-based ionic liquid containing a diene structure. The conjugation effect disperses the electron cloud on the double bond of the molecule, the bond length tends to be averaged, the molecular refractive index increases, the internal energy decreases, the double bond is more easily opened, and the polymerization reaction activity increases. The benzene ring structure in the ionic liquid is beneficial to improving the rigidity of the target polymer, which can increase the spatial volume and steric hindrance of the polymer molecular chain, reduce the degree of thermal motion of the polymer molecule under high temperature conditions, and is beneficial to improving the temperature resistance of the polymer molecule.

[0110] 2) The application of the ionic liquid provided in this application is that the ionic liquid monomer has high polymerization reactivity and can be used to prepare polymers containing ionic liquid blocks, especially for the efficient preparation of polymer-type filtration reducers for drilling fluids containing ionic liquid blocks. Attached Figure Description

[0111] Figure 1 The ionic liquid prepared in Example 1 of this application 1 H NMR spectrum.

[0112] Figure 2 The ionic liquid prepared in Example 2 of this application 1 H NMR spectrum.

[0113] Figure 3 The ionic liquid prepared in Example 3 of this application 1 H NMR spectrum.

[0114] Figure 4 The ionic liquid prepared in Example 4 of this application 1 H NMR spectrum.

[0115] Figure 5 The ionic liquid prepared in Example 5 of this application 1 H NMR spectrum.

[0116] Figure 6 The ionic liquid prepared in Example 6 of this application 1 H NMR spectrum. Detailed Implementation

[0117] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.

[0118] Unless otherwise specified, the raw materials and catalysts used in the embodiments of this application were all purchased commercially.

[0119] Unless otherwise specified, use conventional testing methods or the testing methods recommended by the instrument.

[0120] The analysis method in the embodiments of this application is as follows:

[0121] Nuclear magnetic resonance analysis was performed using an Avance III-800MHz (Bruker, Switzerland).

[0122] In the embodiments of this application, the ionic liquid yield (R) is calculated as follows:

[0123]

[0124] R – Yield of the ionic liquid;

[0125] H0 — The theoretical mass of the ionic liquid;

[0126] H1 — Measured mass of the ionic liquid (mass of the ionic liquid after recrystallization):

[0127] Method for calculating the reactivity ratio: Based on the ratio of the proton peak area on the amide group in the acrylamide structural unit to the proton peak area on the benzene ring in the structural units of Examples 1-16, the ratio of the two structural units in the polymer is indirectly calculated. The reactivity ratio of each monomer group is calculated by the forward and reverse Fineman-Ross method (test method from: Li Qiulian, Ding Yaqin, Zhou Jinlan, et al. Design and practice of copolymerization reaction monomer reactivity ratio determination experiment [J]. Polymer Bulletin, 2019, 11, 69-72.).

[0128] Drilling fluid testing procedure: ZB / TE13004-90.

[0129] Example 1

[0130] Under nitrogen protection, 32.69 g (500 mmol) of 600-mesh activated Zn powder, 5.94 g (60 mmol) of CuCl and 1000 mL of DME were added to the reactor. The temperature was controlled to -10 °C, and the mixture was stirred. Then, 75.8716 g (400 mmol) of TiCl4 was added and the mixture was refluxed for 3 h to obtain a low-valent titanium reducing agent.

[0131] 7.0091g ​​(100mmol) of 2-methylpropenal (R, R) 1 and R 2 For H, R 3 (Methyl) and 59.1222g (150mmol) 1-(4-p-formylphenoxymethylenebenzyl)-3-methylimidazolium tetrafluoroborate (R0, R) a R b R c 、、R d R a R b R c and R d A solution of H (x = y = 1, z = 0) (denoted as Y1) was dissolved in 400 mL of DME and mixed with a low-valent titanium reducing agent. The solution was refluxed at -10 °C for 4 h. 0.003 g (0.08 mmol) of LiAlH4 was added, followed by 5 mL of water at a constant dropping rate of 2.5 mL / min. Then, 5 mL of 10 wt% NaOH solution was added, followed by another 15 mL of water. Sufficient anhydrous Na2SO4 was added to the above system, and the mixture was filtered through diatomaceous earth. The filtrate was collected and rinsed with CH2Cl2, and the filtrate was collected again. The mixture was then distilled under reduced pressure to remove DME and CH2Cl2, yielding 31.47 g of a pale yellow liquid. 4 g of acetonitrile was added, followed by 80 g of toluene. After stirring thoroughly, the mixture was cooled to -28 °C, resulting in the precipitation of white crystals. The crystals were filtered and rinsed with toluene to obtain the purified conjugated diene ionic liquid (denoted as S1) with a yield of 60.35%.

[0132] The chemical reaction formula is shown below:

[0133]

[0134] The product obtained in Example 1 was characterized by nuclear magnetic resonance [(CD3)2SO, 25°C], and its nuclear magnetic resonance spectrum ( 1 H NMR) such as Figure 1 .according to 1 The H NMR analysis results are consistent with the molecular structure of the target product.

[0135] Example 2

[0136] Under argon protection, 19.614 g (300 mmol) of 800-mesh activated Zn powder, 4.95 g (50 mmol) of CuCl and 1000 mL of DME were added to the reactor. The temperature was controlled at -5 °C, and the mixture was stirred. Then, 94.8395 g (500 mmol) of TiiCl4 was added and the mixture was refluxed for 2.5 h to obtain a low-valent titanium reducing agent.

[0137] 11.2128g (200mmol) of acrolein (R, R) 1 R 2 and R 3 Both are H) and 126.1273g (320mmol) 1-(4-p-heptanylphenoxydimethylbenzyl)-3-butylimidazolium bromide (R0 is CH2CH2CH2CH2CH2CH3, R a R b R c R d R a R b R c and R d H (x=2, y=1, z=3) (denoted as Y2) was dissolved in 500 mL of DME and mixed with a low-valent titanium reducing agent. The mixture was refluxed at -5 °C for 5 h. 0.0038 g (0.1 mmol) of LiAlH4 was added, followed by 10 mL of water at a constant dropping rate of 4 mL / min, then 10 mL of 10 wt% NaOH solution was added, and then another 30 mL of water was added. Sufficient CaCl2 was added to the above system, and the mixture was filtered through diatomaceous earth. The filtrate was collected and rinsed with CH2Cl2, and the filtrate was collected again. The mixture was then distilled under reduced pressure to remove DME and CH2Cl2, yielding 86.75 g of a pale yellow liquid. 10 g of acetonitrile was added, followed by 200 g of toluene. After stirring evenly, the mixture was cooled to -28 °C, and white crystals precipitated. The crystals were filtered and rinsed with toluene to obtain the purified conjugated diene ionic liquid (denoted as S2) with a yield of 57.96%.

[0138] The chemical reaction formula is shown below:

[0139]

[0140] The product obtained in Example 2 was characterized by nuclear magnetic resonance [(CD3)2SO, 25°C], and its nuclear magnetic resonance spectrum ( 1 H NMR) such as Figure 2 .according to 1 The H NMR analysis results are consistent with the molecular structure of the target product.

[0141] Example 3

[0142] Under argon protection, 45.766 g (700 mmol) of 400-mesh activated Zn powder, 7.92 g (80 mmol) of CuCl and 1000 mL of DME were added to the reactor. The temperature was controlled to 0 °C, stirred, and 37.9358 g (200 mmol) of TiCl4 was added. The mixture was refluxed for 2 h to obtain a low-valent titanium reducing agent.

[0143] 14.0215g (125mmol) of 3,4-dimethyl-3-penten-2-one (R, R) 1 R 2 and R 3 All are methyl) and 101.689 g (200 mmol) 1-(4-p-acetylphenoxydimethylphenyldimethyl)-3-ethylimidazolium hexafluorophosphate (R0 is methyl, R a R b R c R d R a R b R c and R d H, x=2, y=2, z=1 (denoted as Y3) was dissolved in 250 mL of DME and mixed with low-valent titanium reducing agent. The mixture was refluxed at 0 °C for 5 h. 0.0047 g (0.125 mmol) of LiAlH4 was added, followed by 5 mL of water at a constant dropping rate of 2 mL / min, then 5 mL of 10 wt% NaOH solution was added, and then another 15 mL of water was added. Sufficient MgSO4 was added to the above system, and the mixture was filtered through diatomaceous earth. The filtrate was collected and rinsed with CH2Cl2, and the filtrate was collected again. The mixture was then distilled under reduced pressure to remove DME and CH2Cl2, yielding 50 g of a pale yellow liquid. 5 g of acetonitrile was added, followed by 200 g of toluene. After stirring evenly, the mixture was cooled to -28 °C, and white crystals precipitated. The crystals were filtered and rinsed with toluene to obtain the purified conjugated diene ionic liquid (denoted as S3) with a yield of 52.29%.

[0144] The chemical reaction formula is shown below:

[0145]

[0146] The product obtained in Example 3 was characterized by nuclear magnetic resonance [(CD3)2SO, 25°C], and its nuclear magnetic resonance spectrum ( 1 H NMR) such as Figure 3 .according to 1 The H NMR analysis results are consistent with the molecular structure of the target product.

[0147] Example 4

[0148] Under nitrogen protection, 26.152 g (400 mmol) of 500-mesh activated Zn powder, 2.97 g (30 mmol) of CuCl and 1000 mL of THF were added to the reactor. The mixture was cooled to -8 °C and stirred. Then, 66.3877 g (350 mmol) of TiCl4 was added, and the mixture was heated to 74 °C and refluxed for 4 h. The mixture was then cooled to -8 °C again to obtain a low-valent titanium reducing agent.

[0149] 7.0659 g (84 mmol) of 3-methyl-2-butenal (R and R) 3 For H, R 1 and R 2 (Methyl) and 75.6893 g (117.6 mmol) 1-(4-p-formylphenoxydimethylenephenyldimethyl)-3-propylimidazolium bis(trifluoromethanesulfonyl)imine salt (R0 is H, R a R b R c R d R a R b R c and R d 420 mL of THF (H, x = 2, y = 2, z = 2, denoted as Y4) was mixed into a low-valent titanium reducing agent and heated to 74 °C under stirring, then refluxed for 7 h. 0.0019 g (0.0504 mmol) of LiAlH4 was added, followed by 4.2 mL of water at a constant dropping rate of 3 mL / min, then 4.2 mL of 10 wt% NaOH solution, and finally 12.6 mL of water. Sufficient CaSO4 was added to the above system, and the mixture was filtered through diatomaceous earth. The filtrate was collected, rinsed with CH2Cl2, and the filtrate was collected again. The mixture was then distilled under reduced pressure to remove THF and CH2Cl2, yielding 47.5 g of a pale yellow liquid. Add 4.75g of acetonitrile, then add 95g of toluene, stir well, and cool to -28℃. White crystals will precipitate. Filter and rinse the crystals with toluene to obtain the purified conjugated diene ionic liquid (denoted as S4) with a yield of 54.18%.

[0150] The chemical reaction formula is shown below:

[0151]

[0152] The product obtained in Example 4 was characterized by nuclear magnetic resonance [(CD3)2SO, 25°C], and its nuclear magnetic resonance spectrum ( 1 H NMR) such as Figure 4 .according to 1 The H NMR analysis results are consistent with the molecular structure of the target product.

[0153] Example 5

[0154] Under nitrogen protection, 39.228 g (600 mmol) of 700-mesh activated Zn powder, 3.96 g (40 mmol) of CuCl and 1000 mL of THF were added to the reactor. The mixture was cooled to -10 °C and stirred. Then, 113.8074 g (600 mmol) of TiCl4 was added, and the mixture was heated to 66 °C and refluxed for 4 h. The mixture was then cooled to -10 °C again to obtain a low-valent titanium reducing agent.

[0155] 8.4118 g (100 mmol) of 3-methyl-3-buten-2-one (R 1 and R 2 For H, R and R 3 (Methyl) and 92.8553 g (175 mmol) of 1-(4-p-hexanoylphenoxymethylenebenzyl)-3-methylimidazolium phosphate diethyl ester salt (R0 is CH2CH2CH2CH2CH3, R a R b R c R d R a R b R c and R d 300 mL of THF (H, x = 1, y = 1, z = 0) (denoted as Y5) was mixed with a low-valent titanium reducing agent and heated to 66 °C under stirring, then refluxed for 8 h. 0.0038 g (0.1 mmol) of LiAlH4 was added, followed by 5 mL of water at a constant dropping rate of 2.5 mL / min, then 5 mL of 10 wt% NaOH solution, and finally 15 mL of water. Sufficient MgSO4 was added to the above system, filtered through diatomaceous earth, and the filtrate was collected and rinsed with CH2Cl2. The filtrate was then collected again. The system was distilled under reduced pressure to remove THF and CH2Cl2, yielding 40 g of a pale yellow liquid. 8 g of acetonitrile was added, followed by 80 g of toluene. After stirring thoroughly, the mixture was cooled to -28 °C, resulting in the precipitation of white crystals. These crystals were filtered and rinsed with toluene to obtain the purified conjugated diene ionic liquid (denoted as S5) with a yield of 49.57%.

[0156] The chemical reaction formula is shown below:

[0157]

[0158] The product obtained in Example 5 was characterized by nuclear magnetic resonance [(CD3)2SO, 25°C], and its nuclear magnetic resonance spectrum ( 1 H NMR) such as Figure 5 .according to 1 The H NMR analysis results are consistent with the molecular structure of the target product.

[0159] Example 6

[0160] Under argon protection, 37.9204 g (580 mmol) of 800-mesh activated Zn powder, 4.752 g (48 mmol) of CuCl and 1000 mL of THF were added to the reactor. The mixture was cooled to 0 °C and stirred. Then, 102.4267 g (540 mmol) of TiCl4 was added, and the mixture was heated to 76 °C and refluxed for 2 h. The mixture was then cooled to 0 °C again to obtain a low-valent titanium reducing agent.

[0161] 11.7774 g (120 mmol) of 3-methyl-3-penten-2-one (R 1 For H, R 2 R and R 3 (Methyl) and 82.094 g (200 mmol) 1-(4-p-formylphenoxymethylenephenyldimethyl)-3-methylimidazolium lactate (R0 is H, R a 、、R b R c R d R a R b R c and R d 400 mL of THF (H, x = 1, y = 2, z = 0) (denoted as Y6) was mixed with a low-valent titanium reducing agent and heated to 76 °C under stirring, then refluxed for 4 h. 0.0023 g (0.06 mmol) of LiAlH4 was added, followed by 4 mL of water at a constant dropping rate of 2 mL / min, then 4 mL of 10 wt% NaOH solution, and finally 12 mL of water. Sufficient anhydrous CaCl2 was added to the above system, filtered through diatomaceous earth, and the filtrate was collected and rinsed with CH2Cl2. The filtrate was then collected again. The system was distilled under reduced pressure to remove THF and CH2Cl2, yielding 42.81 g of a pale yellow liquid. 5 g of acetonitrile was added, followed by 120 g of toluene. After stirring thoroughly, the mixture was cooled to -28 °C, resulting in the precipitation of white crystals. These crystals were filtered and rinsed with toluene to obtain the purified conjugated diene ionic liquid (denoted as S6) with a yield of 54.49%.

[0162] The chemical reaction formula is shown below:

[0163]

[0164] The product obtained in Example 6 was characterized by nuclear magnetic resonance [(CD3)2SO, 25°C], and its nuclear magnetic resonance spectrum ( 1 H NMR) such as Figure 6 .according to 1 The H NMR analysis results are consistent with the molecular structure of the target product.

[0165] Example 7

[0166] Under argon protection, 23.5368 g (360 mmol) of 500-mesh activated Zn powder, 3.168 g (32 mmol) of CuCl and 1000 mL of DME were added to the reactor, the temperature was controlled to -8 °C, and the mixture was stirred. Then, 5.9037 g (300 mmol) of TiCl4 was added and the mixture was refluxed for 4 h to obtain a low-valent titanium reducing agent.

[0167] 14.7218 g (150 mmol) of 2,3-dimethyl-2-butenal (R is H, R 1 R 2 and R 3 (Methyl) and 128.321 g (240 mmol) 1-(4-p-propionylphenoxymethylenebenzyl)-3-propylimidazolium p-toluenesulfonate (R0 is CH2CH3, R a R b R c R d R a R b R c and R d A solution of H (x=1, y=1, z=2) (denoted as Y7) was dissolved in 400 mL of DME and mixed with a low-valent titanium reducing agent. The solution was refluxed at -8 °C for 4 h. 0.0043 g (0.1125 mmol) of LiAlH4 was added, followed by 6 mL of water at a constant dropping rate of 2 mL / min. Then, 6 mL of 10 wt% NaOH solution was added, followed by another 18 mL of water. Sufficient CaSO4 was added to the above system, and the mixture was filtered through diatomaceous earth. The filtrate was collected and rinsed with CH2Cl2. The filtrate was then collected again. The mixture was distilled under reduced pressure to remove DME and CH2Cl2, yielding 57.59 g of a pale yellow liquid. 6 g of acetonitrile was added, followed by 150 g of toluene. After stirring thoroughly, the mixture was cooled to -28 °C, resulting in the precipitation of white crystals. These crystals were filtered and rinsed with toluene to obtain the purified conjugated diene ionic liquid (denoted as S7) with a yield of 53.12%.

[0168] The chemical reaction formula is shown below:

[0169]

[0170] Example 8

[0171] Under argon protection, 26.152 g (400 mmol) of 600-mesh activated Zn powder, 4.95 g (50 mmol) of CuCl and 1000 mL of THF were added to the reactor. The mixture was cooled to -2 °C and stirred. Then, 75.8716 g (400 mmol) of TiCl4 was added, and the mixture was heated to 69 °C and refluxed for 3.5 h. The mixture was then cooled to -2 °C again to obtain a low-valent titanium reducing agent.

[0172] 10.0942g (120mmol) of 3-penten-2-one (R 1 and R 3 For H, R 2 (and R is methyl) and 101.1742 g (180 mmol) 1-(4-p-butyrylphenoxymethylenebenzyl)-3-ethylimidazolium lactate (R0 is CH2CH2CH3, R a R b R c R d R a R b R c and R d 480 mL of THF (H, x = y = z = 1) (denoted as Y8) was mixed with a low-valent titanium reducing agent and heated to 69 °C under stirring, then refluxed for 7.5 h. 0.0036 g (0.096 mmol) of LiAlH4 was added, followed by 5 mL of water at a constant dropping rate of 2.5 mL / min, then 5 mL of 10 wt% NaOH solution, and finally 15 mL of water. Sufficient MgSO4 was added to the above system, filtered through diatomaceous earth, and the filtrate was collected and rinsed with CH2Cl2. The filtrate was then collected again. The system was distilled under reduced pressure to remove THF and CH2Cl2, yielding 45.27 g of a pale yellow liquid. 7.5 g of acetonitrile was added, followed by 150 g of toluene. After stirring thoroughly, the mixture was cooled to -28 °C, resulting in the precipitation of white crystals. These crystals were filtered and rinsed with toluene to obtain the purified conjugated diene ionic liquid (denoted as S8) with a yield of 61.17%.

[0173] The chemical reaction formula is shown below:

[0174]

[0175] Example 9

[0176] The method of Example 1 was followed, except that 2-methylpropenal was replaced with phenylpropenone, and 1-(4-p-formylphenoxymethylenebenzyl)-3-methylimidazolium tetrafluoroborate was replaced with 1-(4-p-formylphenoxymethylenebenzyl)-3-methylimidazolium chloride (denoted as Y9). Other conditions were the same as in Example 1. The target product was denoted as S9, and the yield was 57.10%.

[0177] Example 10

[0178] The method of Example 1 was followed, except that 2-methylpropenal was replaced with 2-phenylpropenal, and 1-(4-p-formylphenoxymethylenebenzyl)-3-methylimidazolium tetrafluoroborate was replaced with 1-(4-p-formylphenoxymethylenebenzyl)-3-methylimidazolium thiocyanate (denoted as Y10). Other conditions were the same as in Example 1. The target product was denoted as S10, and the yield was 50.64%.

[0179] Example 11

[0180] The method of Example 1 was followed, except that 2-methylpropenal was replaced with 3,3-diphenylpropenal, and the other conditions were the same as in Example 1. 1-(4-p-formylphenoxymethylenebenzyl)-3-methylimidazolium tetrafluoroborate was replaced with 1-(4-p-formylphenoxymethylenebenzyl)-3-methylimidazolium acetate (denoted as Y11). The target product was denoted as S11, with a yield of 51.89%.

[0181] Example 12

[0182] The method of Example 1 was followed, except that 2-methylpropenal was replaced with 1,3-diphenyl-2-propenone, and the other conditions were the same as in Example 1. 1-(4-p-formylphenoxymethylenebenzyl)-3-methylimidazolium tetrafluoroborate was replaced with 1-(4-p-formylphenoxymethylenebenzyl)-3-methylimidazolium aniline acetate (denoted as Y12). The target product was denoted as S12, with a yield of 55.24%.

[0183] Example 13

[0184] The method of Example 4 was followed, except that 3-methyl-2-butenal was replaced with phenylpropenone, and 1-(4-p-formylphenoxydimethylenephenyldimethyl)-3-propylimidazolium bis(trifluoromethanesulfonyl)imine salt was replaced with 1-(4-p-formylphenoxydimethylenephenyldimethyl)-3-propylimidazolium dimethyl phosphate salt (denoted as Y13). Other conditions were the same as in Example 4. The target product was denoted as S13, and the yield was 60.71%.

[0185] Example 14

[0186] The method of Example 4 was followed, except that 3-methyl-2-butenal was replaced with 2-phenylpropenal, and 1-(4-p-formylphenoxydimethylenephenyldimethyl)-3-propylimidazolium bis(trifluoromethanesulfonyl)imine salt was replaced with 1-(4-p-formylphenoxydimethylenephenyldimethyl)-3-propylimidazolium dicyandiamide salt (denoted as Y14). Other conditions were the same as in Example 4. The target product was denoted as S14, and the yield was 58.72%.

[0187] Example 15

[0188] The method of Example 4 was followed, except that 3-methyl-2-butenal was replaced with 3,3-diphenylpropenal, and 1-(4-p-formylphenoxydimethylenephenyldimethyl)-3-propylimidazolium bis(trifluoromethanesulfonyl)imine salt was replaced with 1-(4-p-formylphenoxydimethylenephenyldimethyl)-3-propylimidazolium trifluoroacetate salt (denoted as Y15). Other conditions were the same as in Example 4. The target product was denoted as S15, and the yield was 52.43%.

[0189] Example 16

[0190] The method of Example 4 was followed, except that 3-methyl-2-butenal was replaced with 1,3-diphenyl-2-propenone, and 1-(4-p-formylphenoxydimethylenephenyldimethyl)-3-propylimidazolium bis(trifluoromethanesulfonyl)imine salt was replaced with 1-(4-p-formylphenoxydimethylenephenyldimethyl)-3-propylimidazolium thiocyanate (denoted as Y16). Other conditions were the same as in Example 4. The target product was denoted as S16, and the yield was 52.95%.

[0191] Test Example 1

[0192] This test case is used to compare the magnitude of the reactivity ratio.

[0193] In a reactor, different amounts of AM and S1-S16 (or Y1-Y16) were dissolved in 1,4-dioxane, with the mass percentage concentration of the two monomers controlled at 5.0%. Azobisisobutyronitrile (AIBN) at 0.5% of the total mass of the two monomers was added, and the reaction was initiated in a 60°C water bath and terminated after 4 hours. The synthesized copolymer was precipitated with a large amount of anhydrous ethanol, filtered under reduced pressure, and dried to constant weight in a vacuum drying oven. The proton nuclear magnetic resonance spectrum was determined using (CD3)2SO4 as the solvent. 1 HNMR). In 1 In 1H NMR, the ratio of the two unit structures in the polymer was indirectly calculated based on the ratio of the proton peak area on the amide group in the acrylamide structural unit to the proton peak area on the benzene ring in the structural units of Examples 1-16. The reactivity ratio of each monomer group was calculated using the forward and reverse Fineman-Ross methods (test method from: Li Qiulian, Ding Yaqin, Zhou Jinlan, et al. Design and practice of copolymerization reaction monomer reactivity ratio determination experiment [J]. Polymer Bulletin, 2019, 11, 69-72.). The test results are shown in Table 1.

[0194] Table 1. Test results of monomer reactivity ratio

[0195] test group AM Y AM S Group 1 2.8719 0.1192 2.6800 0.2386 Group 2 2.7988 0.1072 2.7540 0.2319 Group 3 2.9014 0.1204 2.6904 0.2471 Group 4 2.8000 0.1108 2.7610 0.2227 Group 5 2.8724 0.1291 2.7713 0.2500 Group 6 2.7503 0.1267 2.6959 0.2477 Group 7 2.6517 0.1340 2.6298 0.2353 Group 8 2.7894 0.1135 2.7014 0.2248 Group 9 2.8530 0.1317 2.8116 0.2314 Group 10 2.7617 0.1008 2.8249 0.2615 Group 11 2.8905 0.1221 2.8544 0.2428 Group 12 2.8335 0.1142 2.7380 0.2379 Group 13 2.7761 0.1207 2.7719 0.2368 Group 14 2.7683 0.1199 2.7450 0.2294 Group 15 2.6544 0.1286 2.7117 0.2250 Group 16 2.7480 0.1295 2.7826 0.2437

[0196] As can be seen from Table 1, the polymerization reactivity of S1-S16 is significantly higher than that of Y1-Y16, indicating that ionic liquids with conjugated diene structures have higher polymerization reactivity.

[0197] Test Example 2

[0198] This test example illustrates the preparation of the copolymer of the present invention.

[0199] Add 600 mL of N,N-dimethylformamide (DMF) to the reactor, followed by AM, SSS, NVP, KH570, and 60 g of ionic liquid (molar ratio 25:10:4:2:1). Stir until homogeneous, heat to 104 °C, and add 0.2 g of azoisobutyl cyanoformamide (CABN) under nitrogen protection to begin the copolymerization reaction.

[0200] The copolymers obtained after different copolymerization reaction times were taken out, distilled under reduced pressure, soaked in anhydrous ethanol for 2 hours, precipitated, filtered, rinsed with acetone 3 times, and dried under vacuum to constant weight to obtain the copolymer.

[0201] The ionic monomers used in the preparation of copolymers P1-P16 are S1-S16, and the ionic monomers used in the preparation of copolymers P1'-P16' are Y1-Y16.

[0202] Drilling fluid preparation

[0203] Freshwater-based slurry: Add 400 mL of tap water to a high-speed stirring cup, and add 16 g of calcium bentonite and 0.8 g of Na2CO3 in a measured amount while stirring continuously. Stir for 20 min, stopping at least twice during this period to scrape off the bentonite adhering to the container wall, and cure in a sealed container for 24 h.

[0204] Salt-based slurry: Add 400 mL of tap water to a high-speed stirring cup, and add 16 g NaCl, 16 g calcium bentonite, and 0.8 g Na2CO3 in a measured amount while stirring continuously. Stir for 20 min, stopping at least twice during this period to scrape off the bentonite adhering to the container wall, and cure in a sealed container for 24 h.

[0205] 8g of copolymers obtained from P1-P16 (or P1'-P16') at different set copolymerization reaction times were weighed out as filtration loss reducers and added to 400mL of the above-mentioned fresh water-based slurry or brine-based slurry. The mixture was stirred thoroughly and cured under sealed conditions for 24h to obtain the corresponding drilling fluid test slurries (denoted as Z1-Z16 and Z1'-Z16', respectively). Each drilling fluid contained P1-P16 (or P1'-P16') obtained at different copolymerization reaction times.

[0206] Test method:

[0207] ZB / TE13004-90: Drilling Fluid Testing Procedure was adopted.

[0208] Z1-Z16 (or Z1'-Z16') (each sample of drilling fluid test slurry contained 8g of copolymer obtained by different copolymerization reaction times) were respectively placed into a high-temperature aging tank after being stirred at high speed for 5 minutes, and aged at 160℃ for 16 hours. The high-temperature and high-pressure filtration loss (FL) of the drilling fluid test slurry was measured using a high-temperature and high-pressure filtration loss meter. HTHP The test results are shown in Tables 2 and 3.

[0209] Table 2. FL of Freshwater Drilling Fluid HTHP Measurement results

[0210]

[0211]

[0212] Table 3. FL of brine drilling fluid HTHP Measurement results

[0213]

[0214]

[0215] As can be seen from Tables 1 and 2, the FL of freshwater drilling fluid and brine drilling fluid obtained by using P1-P16 as filtration loss reducers decreased after a copolymerization reaction time of 0.5 h. HTHP The value no longer changed with the extension of the polymerization reaction time during the synthesis of the filtration loss reducer, indicating that S1-S16 had completed the polymerization reaction with AM, SSS, NVP, and KH570 within 0.5 h, demonstrating that S1-S16 has high polymerization reactivity. Compared with the same polymerization reaction time, the F-value of freshwater drilling fluid and brine drilling fluid obtained using P1'-P16' as the filtration loss reducer, when the polymerization reaction time of this monomer was also approximately 0.5 h, was significantly higher. LHTHP Slightly larger. With increasing polymerization time, the FL of freshwater drilling fluid and brine drilling fluid obtained using P1'-P16' as filtration loss reducers decreases. HTHP The gradually decreasing value indicates that Y1-Y16 did not complete the polymerization reaction with AM, SSS, NVP, and KH570 within a longer polymerization reaction time. These test results demonstrate that S1-S16, with its conjugated diene structure, exhibits higher polymerization reactivity compared to Y1-Y16.

[0216] The above description is merely a few embodiments of this application and is not intended to limit this application in any way. Although this application discloses preferred embodiments as described above, it is not intended to limit this application. Any changes or modifications made by those skilled in the art without departing from the scope of the technical solution of this application using the disclosed technical content are equivalent to equivalent implementation cases and all fall within the scope of the technical solution.

Claims

1. An ionic liquid of a conjugated diene, characterized by, a cation represented by Formula I: Formula I; wherein R, R0, R 1 , R 2 , R 3 are independently selected from one of H, C1-C6 alkyl, phenyl; R a , R b , R c , R d , R a , R b , R c , R d is independently selected from one of H, C1-C6alkyl; x, y, z are independently an integer from 0 to 6; the anion in the ionic liquid is selected from one 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 - .

2. The ionic liquid of claim 1, wherein, R, R0, R 1 , R 2 , R 3 are independently selected from one of H, C1-C4 alkyl, phenyl.

3. The ionic liquid according to claim 1 or 2, characterized in that R a , R b , R c , R d , R a , R b , R c , R d is independently selected from one of H, C1-C4alkyl.

4. The ionic liquid according to claim 1 or 2, characterized in that, R, R0, R 1 , R 2 , R 3 are independently selected from one of H, methyl, phenyl.

5. The ionic liquid according to claim 1 or 2, characterized in that, R a , R b , R c , R d , R a , R b , R c , R d is independently selected from H or methyl.

6. The ionic liquid according to claim 1 or 2, characterized in that, x, y are independently selected from 1 or 2, and z is an integer from 0 to 3.

7. Process for the preparation of the ionic liquid according to any one of claims 1 to 6, characterized in that, comprising the following steps: a mixture containing an alkenyl compound, a bis-phenylimidazole compound, a catalyst, a solvent B is reacted to obtain the ionic liquid; the alkenyl compound has a structure represented by Formula II-1: Formula II-1; the bis-phenylimidazole compound has a cation represented by Formula II-2: Formula II-2; the anion in the bisphenylimidazole compound 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 - .

8. The method of claim 7, wherein, the catalyst is selected from at least one of titanium suboxide, tungsten suboxide, molybdenum suboxide, zirconium suboxide, vanadium suboxide and niobium suboxide.

9. The production method according to claim 7 or 8, characterized by, the solvent B is selected from at least one of tetrahydrofuran and dimethyl ether.

10. The production method according to claim 7 or 8, characterized by, the molar ratio of the alkenyl compound to the bis-phenylimidazole compound is 1:1.4-1.

8.

11. The production method according to claim 7 or 8, characterized by, the concentration of the alkenyl compound in the solvent B is 0.2-0.5 mmol / mL.

12. The production method according to claim 7 or 8, characterized by, the reaction conditions are as follows: the temperature is -15-80 ℃; the time is 2-10 h.

13. The method of claim 12, wherein, when the solvent B is tetrahydrofuran, the reaction temperature is 66-76 ℃.

14. The method of claim 12, wherein, when the solvent B is dimethyl ether, the reaction temperature is -10-0 ℃.

15. The method of manufacturing according to claim 7 or 8, wherein, comprising the following steps: S1, mixing materials containing the alkenyl compound, the bis-phenylimidazole compound and the solvent B to obtain solution I; S2, adding a mixture containing the catalyst to the solution I, and stirring to reflux to obtain the ionic liquid.

16. The method of claim 7 or 8, wherein, After the reaction, a quenching reaction is further performed.

17. The method of claim 16, wherein, the quenching reaction comprises the following steps: firstly adding a quenching reagent to a mixture containing the ionic liquid, then adding water dropwise, followed by adding an 8wt%-12wt% NaOH solution, and finally adding water.

18. The method of claim 17, wherein, the quenching reagent is selected from at least one of alkali metal cyanide, amide, borane, K2CO3, LiAlH4 and NaBH.

19. The method of claim 17, wherein, the molar amount of the quenching reagent is 0.05%-0.1% of the molar amount of the alkenyl compound.

20. The method of claim 17, wherein, the volume ratio of the first water dropwise to the volume of the solvent B is 1:50-100, and the dropwise speed is 2-4 mL / min.

21. The method of claim 17, wherein, the volume of the 8wt%-12wt% NaOH solution is the same as that of the first water dropwise.

22. The method of claim 17, wherein, the mass of the water added again is 2.8-3.2 times of the mass of the first water dropwise.

23. A copolymer, characterized in that, obtained by copolymerization of the ionic liquid and a monomer; the ionic liquid is selected from the ionic liquid of any one of claims 1-6 or the ionic liquid obtained by the preparation method of any one of claims 7-22.

24. The copolymer of claim 23, wherein, the monomer is selected from at least one of acrylamide, N-isopropyl acrylamide, N,N'-methylene bisacrylamide, vinyl pyrrolidone, acrylic acid, sodium acrylate, acrylonitrile, sodium styrene sulfonate, 2-acrylamido-2-methylpropane sulfonic acid, dimethyldiallyl ammonium chloride and γ-methacryloyloxypropyl trimethoxysilane.

25. Use of the copolymer of claim 23 or 24 in oil field additives.

26. The use according to claim 25, characterized in that, the copolymer is used in oil fields as a fluid loss additive, an inhibitor, a plugging gel, a viscosity enhancer and a plugging agent.

27. A drilling fluid, characterized by, comprising a copolymer and an additive; the copolymer is selected from the copolymer of claim 23 or 24.

Images