Conjugated diene ionic liquid as well as preparation method and application thereof

Abstract

The invention discloses a conjugated diene ionic liquid, which is characterized in that the conjugated diene ionic liquid has a cation shown in a formula I: # imgabs0 #, R, R0, R1, R2 and R3 are independently selected from one of H, C1-C6 alkyl and phenyl; ra, Rb, Rc and Rd are independently selected from one of H and C1-C6 alkyl groups, and Ra, Rb, Rc and Rd are independently selected from one of H and C1-C6 alkyl groups; x, y and z are integers from 0 to 9. The ionic liquid has high polymerization reaction activity.

Description

Technical Field

[0001] The present application relates to a conjugated diene ionic liquid and a preparation method and application thereof, belonging to the field of petroleum additives. Background Art

[0002] Ionic liquids are molten salts that are liquid at or near room temperature and are composed of organic cations and organic or inorganic anions. Because the cations in their structure are generally large and asymmetric, it is difficult to form an ordered crystal structure, so they can move freely at or near room temperature and appear in liquid form. Since the first ionic liquid ethylammonium nitrate was disclosed in the last century, ionic liquids have experienced more than a hundred years of development, with an increasing number of types and increasingly rich functions, and have been applied to various fields to varying degrees.

[0003] In the field of drilling engineering, ionic liquids are mainly used as inhibitors for drilling fluids and as functional monomers for preparing polymer 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 liquids can be used as shale inhibitors. Reports on the use of ionic liquids as functional monomers for preparing polymer treatment agents for drilling fluids are more about applying them to the preparation of fluid loss reducers. For example, in 2018, in the article "High-temperature and high-calcium resistant fluid loss reducers containing ionic liquid segments" published in the journal "Drilling Fluids and Completion Fluids", it was reported that the terpolymerization of olefinic ionic liquid 1-vinyl-3-ethylimidazolium bromide (VeiBr) with 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and acrylamide (AM) was used to obtain a high-temperature and high-calcium resistant fluid loss reducer (PASV). The 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 a large side group cation, which not only increases the rigidity of the molecular chain, but also improves the adsorption of the molecular chain on the surface of clay particles, preventing Ca 2+ Na + The ion exchange adsorption reduced the Ca 2+The charge neutralization effect on clay promotes the dispersion of clay particles, which is conducive to the formation of a dense filter cake on the percolation surface and enhances the filtration and wall-building ability of the drilling fluid. Chinese patent CN 106749891B is an improvement on the molecular structure of the above-mentioned fluid loss reducer, that is, a cationic monomer containing a quaternary ammonium group is introduced into the molecular chain, thereby further improving its temperature and calcium resistance. The research on the introduction of ionic liquids as functional groups into polymer fluid loss reducers is reported in more detail in Chinese patent CN 113621104B. This patent uses alkenyl imidazole ionic liquids as functional monomers, copolymerizes them with alkenyl amides, alkenyl sulfonic acids, alkenyl siloxanes and alkenyl structural units with cyclic structures, and obtains a series of fluid loss reducers with ionic liquid segments. This type of fluid loss reducer can withstand temperatures of up to 200°C and has excellent salt and calcium resistance. By comparing the performance with the comparative example, it can be seen that the excellent fluid loss reduction effect of this type of fluid loss reducer is largely due to the introduction of ionic liquid segments into the molecule.

[0004] However, the copolymerization activity of alkenyl ionic liquids is generally low. After mixing them with other alkenyl functional monomers, it takes a long time to form free radicals under the same initiation conditions, which will inevitably affect the industrial production efficiency of such polymer products. Therefore, it is urgent to provide an alkenyl ionic liquid with high polymerization reaction activity, shorten the polymerization reaction time, and improve the polymerization reaction efficiency. Summary of the invention

[0005] According to the first aspect of the present application, a conjugated diene ionic liquid is provided, which aims to overcome the defects of the prior art, and the ionic liquid can be used to quickly prepare polymers containing ionic liquid segments, especially the polymer treatment agents for drilling fluid can be quickly prepared using the ionic liquid, including fluid loss reducers, inhibitors, plugging gels, tackifiers, plugging agents, etc.

[0006] The ionic liquid contains a diene structure, and 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 easier to open, and the polymerization activity increases. The benzene ring structure in the ionic liquid is conducive to improving the rigidity of the target polymer, can increase the spatial volume and steric hindrance of the polymer molecular chain, reduce the degree of thermal motion of the polymer molecules under high temperature conditions, and is conducive to improving the temperature resistance of the polymer molecules.

[0007] An ionic liquid of conjugated diene type having a cation represented by formula I:

[0008]

[0009] Among them, R, R0, R 1 , R 2 , R 3Independently selected from one of 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, C1-C6 alkyl;

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

[0012] Preferably, R, R0, R 1 , R 2 , R 3 Independently selected from one of 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 Independently selected from H, C1-C6 straight chain alkyl.

[0014] Preferably, R, R0, R 1 , R 2 , R 3 Independently selected from one of 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 Independently selected from H, C1-C4 straight chain alkyl.

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

[0017] According to one embodiment of the present 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 the present application, R, R0, R 1 , R 2 , R 3 Independently selected from one of H, methyl and phenyl.

[0019] According to one embodiment of the present application, R a , R b , R c , R d , R a , R b , R c , R d Independently selected from H or methyl.

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

[0021] According to the second aspect of the present application, a method for preparing an ionic liquid is provided, the method comprising: in the presence of a catalyst, subjecting an alkenyl compound represented by formula II-1 and a bisphenylimidazole compound represented by formula II-2 to a synthesis reaction to obtain a cation represented by formula I.

[0022] The method for preparing the above-mentioned ionic liquid comprises the following steps:

[0023] reacting a mixture containing an alkenyl compound, a bisphenylimidazole compound, a catalyst, and a solvent B to obtain the ionic liquid;

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

[0025]

[0026] The bisphenylimidazole compound has a cation represented by formula II-2:

[0027]

[0028] According to one embodiment of the present application, the anion in the bisphenylimidazole 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 the present application, the catalyst used in the preparation method provided in the present application only needs to be able to promote the coupling of the carbonyl group to the olefin.

[0030] According to one embodiment of the present 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 above-mentioned low-valent titanium, low-valent tungsten, low-valent molybdenum, low-valent zirconium, low-valent vanadium and low-valent niobium refer to the lowest valence state that metal ions can present. In nature, many metal ions have multiple valence states, and the so-called low-valent state can be understood as the second highest valence. The reaction used in this patent is the reaction of preparing the corresponding olefin by reducing and coupling carbonyl compounds, that is, McMurry coupling reaction, and the catalyst of this application is a conventional catalyst for 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 as the catalyst in the present application can be obtained by methods known in the art, taking 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, the method for preparing low-valent titanium comprises: dissolving a titanium-containing reagent and a reducing agent in a solvent A, and performing a reduction reaction.

[0035] Preferably, the method for preparing low-valent titanium further comprises: 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 the present 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, and the valence state of low-valent titanium generally varies with the reduction 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 the present 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 specifically includes: adding activated Zn, CuCl and solvent A into a reactor, then cooling and stirring, and then adding TiCl4 to perform 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 it needs to be cooled again after reflux; when the solvent A is DME, the reflux does not need to be heated, that is, the reflux is carried out at the cooling temperature of the previous step.

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

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

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

[0045] According to a specific embodiment of the present application, the method for preparing the ionic liquid comprises: before the synthesis reaction, dissolving the alkenyl compound and the bisphenylimidazole compound in a solvent B.

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

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

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

[0049] Optionally, the molar ratio of the alkenyl compound to the bisphenylimidazole 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 the two.

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

[0051] Temperature is -15-80℃;

[0052] The time is 2-10h.

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

[0054] According to one embodiment of the present application, the following steps are included:

[0055] S1, mixing the materials containing the alkenyl compound, the bisphenylimidazole compound and the solvent B to obtain solution I;

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

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

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

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

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

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

[0062] According to one embodiment of the present application, the quenching reagent is selected from at least one of alkali metal cyanide, amide, borane, K2CO3, LiAlH4 and NaBH.

[0063] According to one embodiment of the present 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 based on the molar amount of LiAlH4.

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

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

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

[0068] The preparation method of the ionic liquid monomer provided in the present application also includes a quenching reaction after the synthesis reaction proceeds to a certain extent. Because there are excess reactants in the synthesis reaction, when the reaction proceeds to a certain extent, the target product has been obtained, and if the excess reactants continue to exist, they will further react to generate undesirable products. The principle of quenching is to use another compound that is more likely to react with the excess compound to react with it, thereby removing it from the system.

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

[0070] The quenching reaction involved in the present application is, specifically, to add a quenching reagent after cooling the system, add 10 wt % NaOH solution after the first drop of water, and then add 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] The present application has no particular restrictions on the quenching agent, and conventional quenching agents such as alkali metal cyanide, amide, borane, K2CO3, LiAlH4 and NaBH can be selected. However, considering the stability of the product and the ease of handling, the present application prefers LiAlH4 as the quenching agent.

[0073] According to a preferred embodiment of the present 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 the present application, the mass ratio of the solvent B to the mass of the water added for the first time is 1:(50-100), and the dropping speed is controlled at 2-4 mL / min.

[0075] According to a preferred embodiment of the present application, the volume of the 10 wt % NaOH solution is the same as the volume of the water added dropwise for the first time, and there is no restriction on the adding speed, and the solution can be added all at once or dropwise.

[0076] According to a preferred embodiment of the present application, the mass of the water added again is 3 times the mass of the water added dropwise for the first time, and there is no restriction on the adding speed, and the water can be added all at once or dropwise.

[0077] In order to obtain a purified ionic liquid, the preparation method of the ionic liquid provided in the present application may further include: after quenching the reaction, adding a desiccant to the system, filtering, rinsing, collecting the filtrate, and distilling under reduced pressure to remove the solvent A and the rinsing agent to obtain a crude product of the ionic liquid. Finally, the crude product is recrystallized to remove unreacted raw materials, by-products, and residual catalysts.

[0078] According to a preferred embodiment of the present application, the mixed solution is dried with a desiccant, filtered, and then distilled under reduced pressure to remove the solvent to obtain a light yellow crude product.

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

[0080] The present application has no limitation on the filtering method, as long as the low-valent titanium can be filtered out, conventional filter aids may 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 the present application, diatomaceous earth filtration is used.

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

[0083] In order to obtain an ionic liquid with a higher purity, the preparation method of the ionic liquid provided in the present application further includes a deep purification operation, that is, recrystallizing the product obtained from the synthesis reaction.

[0084] According to a preferred embodiment of the present application, after reduced pressure distillation, acetonitrile is added to the crude product of the ionic liquid, and then toluene is added. After stirring evenly, the temperature is lowered to -28°C, and white crystals are precipitated. The crystals are filtered and rinsed with toluene to obtain a purified conjugated diene ionic liquid.

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

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

[0087] According to a third aspect of the present 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 liquid described above or the ionic liquid obtained by the preparation method described above.

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

[0091] The block ratio 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 synthesis of the polymer does not exceed 10%.

[0092] The present application does not particularly limit the polymerization method, and any of bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, reverse emulsion polymerization, melt polymerization, and interfacial polymerization can be used.

[0093] According to the specific implementation of the present application, solution polymerization is preferred. The present application lists specific operations in the text, which should not be understood by those skilled in the art as limiting the present invention.

[0094] According to the fourth aspect of the present application, a copolymer is provided for use in oilfield additives. The ionic liquid has a high polymerization activity and can be used to prepare a polymer containing an ionic liquid block. In particular, the ionic liquid can be used to quickly prepare a polymer treatment agent for drilling fluid, including a fluid loss reducer, an inhibitor, a plugging gel, a tackifier, a plugging agent, and the like.

[0095] Application of the above-mentioned copolymer in oilfield additives.

[0096] According to one embodiment of the present application, the copolymer is used in oil fields as a fluid loss reducer, an inhibitor, a plugging gel, a viscosity enhancer, and a plugging agent.

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

[0098] A drilling fluid, comprising a copolymer and an additive;

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

[0100] In the present application, there is no particular limitation on the above-mentioned drilling fluid system, and it can be various drilling fluid systems 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, solid-free drilling fluid system, oil-in-water drilling fluid system, silicate drilling fluid system. According to a specific embodiment of the present invention, the drilling fluid of the present invention can be a bentonite drilling fluid or a brine drilling fluid.

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

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

[0103] In the present application, there is no particular limitation on the content of the copolymer in the drilling fluid, and it 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 the drilling fluid.

[0104] In the present invention, there is no particular limitation on the preparation method of the drilling fluid, and a preparation method known to those skilled in the art may be used, which will not be described in detail in the present invention. The present invention lists specific operations in the text, which should not be understood by those skilled in the art as a limitation on the present invention.

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

[0106] In the present application, the term "alkyl" refers to a group formed by losing any hydrogen atom from an alkane compound molecule.

[0107] In the present application, the term "phenyl" refers to a group having a benzene ring as a functional group.

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

[0109] 1) The present application provides an ionic liquid of conjugated diene, which contains 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 easier to open, and the polymerization reaction activity increases; the benzene ring structure in the ionic liquid is beneficial to improving the rigidity of the target polymer, can increase the spatial volume and spatial steric hindrance of the polymer molecular chain, reduce the degree of thermal motion of the polymer molecules under high temperature conditions, and is beneficial to improving the temperature resistance of the polymer molecules.

[0110] 2) The application of an ionic liquid provided in the present application, wherein the ionic liquid monomer has a high polymerization reaction activity and can be used to prepare a polymer containing an ionic liquid block, and can be particularly used to efficiently prepare a polymer-type fluid loss reducer for drilling fluid containing an ionic liquid block. BRIEF DESCRIPTION OF THE DRAWINGS

[0111] Figure 1 The ionic liquid prepared in Example 1 of the present application 1 H NMR spectra.

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

[0113] Figure 3 The ionic liquid prepared in Example 3 of the present application 1 H NMR spectra.

[0114] Figure 4 The ionic liquid prepared in Example 4 of the present application 1 H NMR spectra.

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

[0116] Figure 6 The ionic liquid prepared in Example 6 of this application 1 H NMR spectra. DETAILED DESCRIPTION

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

[0118] Unless otherwise specified, the raw materials and catalysts in the examples of this application were purchased through commercial channels.

[0119] Unless otherwise specified, conventional test methods or test methods recommended by the instrument shall be used.

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

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

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

[0123]

[0124] R——yield of ionic liquid;

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

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

[0127] Calculation method of the reactivity ratio: According to 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 unit of Examples 1-16, the ratio of the two unit structures in the polymer is indirectly calculated, and the forward and reverse Fineman-Ross method is used to calculate the reactivity ratio of each group of monomers (the test method comes from: Li Qiulian, Ding Yaqin, Zhou Jinlan, et al. Design and practice of copolymerization monomer reactivity ratio determination experiment [J]. Polymer Bulletin, 2019, 11, 69-72.).

[0128] Drilling fluid testing procedure: adopt 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 into the reactor, the temperature was controlled to -10 °C, stirred, 75.8716 g (400 mmol) of TiCl4 was added, and refluxed for 3 h to obtain a low-valent titanium reducing agent.

[0131] 7.0091 g (100 mmol) of 2-methylacrolein (R, R 1 and R 2 For H, R 3 methyl) and 59.1222 g (150 mmol) of 1-(4-formylphenoxymethylenebenzyl)-3-methylimidazolium tetrafluoroborate (R0, R a , R b , R c ,,R d , R a , R b , R c and R d =H, x=y=1, z=0) (denoted as Y1) was dissolved in 400mL DME, mixed with a low-valent titanium reducing agent, and refluxed at -10°C for 4h. 0.003g (0.08mmol) LiAlH4 was added, 5mL water was uniformly added at a drop rate of 2.5mL / min, and then 5mL 10wt% NaOH solution was added, and then 15mL water was added again. Sufficient anhydrous Na2SO4 was added to the above system, filtered through diatomaceous earth, the filtrate was collected, and then rinsed with CH2Cl2, and the filtrate was collected. DME and CH2Cl2 were removed by vacuum distillation to obtain 31.47g of light yellow liquid. 4g acetonitrile was added, and then 80g toluene was added. After stirring evenly, the temperature was lowered to -28°C, and white crystals were precipitated. Filtered, the crystals were rinsed with toluene, and the purified conjugated diene ionic liquid (denoted as S1) was obtained with a yield of 60.35%.

[0132] The chemical reaction formula is as follows:

[0133]

[0134] The product obtained in Example 1 was characterized by nuclear magnetic resonance [(CD3)2SO, 25°C], and the nuclear magnetic resonance spectrum ( 1 H NMR) Figure 1 .according to 1 The H NMR analysis results were 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 into the reactor, the temperature was controlled to -5 °C, stirred, 94.8395 g (500 mmol) of TiiCl4 was added, and refluxed for 2.5 h to obtain a low-valent titanium reducing agent.

[0137] 11.2128 g (200 mmol) of acrolein (R, R 1 , R 2 and R 3 All are H) and 126.1273 g (320 mmol) of 1-(4-p-heptanoylphenoxydimethylenebenzyl)-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 500mL DME, mixed with a low-valent titanium reducing agent, and refluxed at -5°C for 5h. 0.0038g (0.1mmol) LiAlH4 was added, 10mL water was uniformly added at a drop rate of 4mL / min, 10mL 10wt% NaOH solution was added, and then 30mL water was added again. Sufficient amount of CaCl2 was added to the above system, filtered through diatomaceous earth, the filtrate was collected, and then rinsed with CH2Cl2, and the filtrate was collected. DME and CH2Cl2 were removed by vacuum distillation to obtain 86.75g of light yellow liquid. 10g acetonitrile was added, and then 200g toluene was added. After stirring evenly, the temperature was lowered to -28°C, and white crystals were precipitated. After filtering, the crystals were rinsed with toluene to obtain a purified conjugated diene ionic liquid (denoted as S2), with a yield of 57.96%.

[0138] The chemical reaction formula is as follows:

[0139]

[0140] The product obtained in Example 2 was characterized by NMR [(CD3)2SO, 25°C], and the NMR spectrum ( 1 H NMR) Figure 2 .according to 1 The H NMR analysis results were 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 into the reactor, the temperature was controlled to 0°C, stirred, 37.9358 g (200 mmol) of TiCl4 was added, and refluxed for 2 h to obtain a low-valent titanium reducing agent.

[0143] 14.0215 g (125 mmol) of 3,4-dimethyl-3-penten-2-one (R, R 1 , R 2 and R 3 methyl groups) and 101.689 g (200 mmol) of 1-(4-p-acetylphenoxydimethylenephenyldimethylene)-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 250mL DME, mixed with a low-valent titanium reducing agent, and refluxed at 0°C for 5h. 0.0047g (0.125mmol) LiAlH4 was added, 5mL of water was uniformly added at a drop rate of 2mL / min, and then 5mL of 10wt% NaOH solution was added, and then 15mL of water was added again. Sufficient MgSO4 was added to the above system, filtered through diatomaceous earth, the filtrate was collected, and then rinsed with CH2Cl2, and the filtrate was collected. DME and CH2Cl2 were removed by vacuum distillation to obtain 50g of light yellow liquid. 5g of acetonitrile was added, and then 200g of toluene was added. After stirring evenly, the temperature was lowered to -28°C, and white crystals were precipitated. Filtered, the crystals were rinsed with toluene, and the purified conjugated diene ionic liquid (denoted as S3) was obtained with a yield of 52.29%.

[0144] The chemical reaction formula is as follows:

[0145]

[0146] The product obtained in Example 3 was characterized by NMR [(CD3)2SO, 25°C], and the NMR spectrum ( 1 H NMR) Figure 3 .according to 1 The H NMR analysis results were 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, cooled to -8 °C and stirred, 66.3877 g (350 mmol) of TiCl4 was added, the temperature was raised to 74 °C and refluxed for 4 h, and 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 is methyl) and 75.6893 g (117.6 mmol) of 1-(4-formylphenoxydimethylbenzene)-3-propylimidazole bis(trifluoromethanesulfonyl)imide salt (R0 is H, R a , R b , R c , R d , R a , R b , R c and R d H, x=2, y=2, z=2) (denoted as Y4) 420mL THF, mixed into the low-valent titanium reducing agent, heated to 74°C under stirring, and refluxed for 7h. Add 0.0019g (0.0504mmol) LiAlH4, add 4.2mL water at a uniform rate of 3mL / min, then add 4.2mL 10wt% NaOH solution, and then add 12.6mL water again. Add enough CaSO4 to the above system, filter through diatomaceous earth, collect the filtrate, rinse with CH2Cl2, and collect the filtrate. Distill under reduced pressure to remove THF and CH2Cl2, and 47.5g of light yellow liquid is obtained. Add 4.75 g of acetonitrile and then 95 g of toluene, stir evenly and cool to -28°C, white crystals will precipitate, filter and rinse the crystals with toluene to obtain purified conjugated diene ionic liquid (denoted as S4) with a yield of 54.18%.

[0150] The chemical reaction formula is as follows:

[0151]

[0152] The product obtained in Example 4 was characterized by NMR [(CD3)2SO, 25°C], and the NMR spectrum ( 1 H NMR) Figure 4 .according to 1 The H NMR analysis results were 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, cooled to -10 °C and stirred, 113.8074 g (600 mmol) of TiCl4 was added, the temperature was raised to 66 °C and refluxed for 4 h, and then cooled to -10 °C again to obtain a low-valent titanium reducing agent.

[0155] 8.4118 g (100 mmol) of 3-methyl-3-butene-2-one (R 1 and R 2 For H, R and R 3 is methyl) and 92.8553 g (175 mmol) of 1-(4-p-hexanoylphenoxymethylenebenzyl)-3-methylimidazole diethyl phosphate (R0 is CH2CH2CH2CH2CH3, R a , R b , R c , R d , R a , R b , R c and R d =H, x=1, y=1, z=0) (denoted as Y5) 300mL THF, mixed into the low-valent titanium reducing agent, heated to 66°C under stirring, and refluxed for 8h. Add 0.0038g (0.1mmol) LiAlH4, uniformly add 5mL water at a dropping speed of 2.5mL / min, then add 5mL 10wt% NaOH solution, and then add 15mL water again. Add enough MgSO4 to the above system, filter through diatomaceous earth, collect the filtrate, rinse with CH2Cl2, and collect the filtrate. Distill under reduced pressure to remove THF and CH2Cl2, and obtain 40g of light yellow liquid. Add 8g acetonitrile, then add 80g toluene, stir evenly and cool to -28°C, white crystals will precipitate, filter, rinse the crystals with toluene, and obtain the purified conjugated diene ionic liquid (denoted as S5), with a yield of 49.57%.

[0156] The chemical reaction formula is as follows:

[0157]

[0158] The product obtained in Example 5 was characterized by NMR [(CD3)2SO, 25°C], and the NMR spectrum ( 1 H NMR) Figure 5 .according to 1 The H NMR analysis results were 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 into the reactor, cooled to 0 ° C, stirred, 102.4267 g (540 mmol) of TiCl4 was added, the temperature was raised to 76 ° C and refluxed for 2 h, and 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 is methyl) and 82.094 g (200 mmol) of 1-(4-formylphenoxymethylenephenyldimethylene)-3-methylimidazole lactate (R0 is H, R a ,,R b , R c , R d , R a , R b , R c and R d =H, x=1, y=2, z=0) (denoted as Y6) 400mL THF, mixed into the low-valent titanium reducing agent, heated to 76°C under stirring, and refluxed for 4h. Add 0.0023g (0.06mmol) LiAlH4, uniformly add 4mL water at a dropping speed of 2mL / min, then add 4mL 10wt% NaOH solution, and then add 12mL water again. Add enough anhydrous CaCl2 to the above system, filter through diatomaceous earth, collect the filtrate, rinse with CH2Cl2, and collect the filtrate. Distill under reduced pressure to remove THF and CH2Cl2, and obtain 42.81g of light yellow liquid. Add 5g acetonitrile, then add 120g toluene, stir evenly and cool to -28°C, white crystals precipitate, filter, rinse the crystals with toluene, and obtain the purified conjugated diene ionic liquid (denoted as S6), with a yield of 54.49%.

[0162] The chemical reaction formula is as follows:

[0163]

[0164] The product obtained in Example 6 was characterized by NMR [(CD3)2SO, 25°C], and the NMR spectrum ( 1 H NMR) Figure 6 .according to 1 The H NMR analysis results were 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, stirred, 5.9037 g (300 mmol) of TiCl4 was added, and 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 is methyl) and 128.321 g (240 mmol) of 1-(4-p-propionylphenoxymethylenebenzyl)-3-propylimidazole p-toluenesulfonate (R0 is CH2CH3, R a , R b , R c , R d , R a , R b , R c and R d =H, x=1, y=1, z=2) (denoted as Y7) was dissolved in 400 mL of DME, mixed into a low-valent titanium reducing agent, and refluxed at -8°C for 4 h. 0.0043 g (0.1125 mmol) of LiAlH4 was added, 6 mL of water was added dropwise at a rate of 2 mL / min, 6 mL of 10 wt% NaOH solution was added, and then 18 mL of water was added again. Sufficient amount of CaSO4 was added to the above system, filtered through diatomaceous earth, the filtrate was collected, and then rinsed with CH2Cl2, and the filtrate was collected. DME and CH2Cl2 were removed by vacuum distillation to obtain 57.59 g of light yellow liquid. 6 g of acetonitrile was added, and then 150 g of toluene was added. After stirring evenly, the temperature was lowered to -28°C, and white crystals were precipitated. After filtering, the crystals were rinsed with toluene to obtain a purified conjugated diene ionic liquid (denoted as S7) with a yield of 53.12%.

[0168] The chemical reaction formula is as follows:

[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, cooled to -2 °C and stirred, 75.8716 g (400 mmol) of TiCl4 was added, the temperature was raised to 69 °C and refluxed for 3.5 h, and then cooled to -2 °C again to obtain a low-valent titanium reducing agent.

[0172] 10.0942 g (120 mmol) of 3-penten-2-one (R 1 and R 3 For H, R 2 and R is methyl) and 101.1742 g (180 mmol) of 1-(4-p-butyrylphenoxymethylenebenzyl)-3-ethylimidazole lactate (R0 is CH2CH2CH3, R a , R b , R c , R d , R a , R b , R c and R d =H, x=y=z=1) (denoted as Y8) 480mL THF, mixed into the low-valent titanium reducing agent, heated to 69°C under stirring, and refluxed for 7.5h. Add 0.0036g (0.096mmol) LiAlH4, uniformly add 5mL water at a dropping speed of 2.5mL / min, then add 5mL 10wt% NaOH solution, and then add 15mL water again. Add enough MgSO4 to the above system, filter through diatomaceous earth, collect the filtrate, rinse with CH2Cl2, and collect the filtrate. Distill under reduced pressure to remove THF and CH2Cl2, and obtain 45.27g of light yellow liquid. Add 7.5g acetonitrile, then add 150g toluene, stir evenly and cool to -28°C, white crystals precipitate, filter, rinse the crystals with toluene, and obtain the purified conjugated diene ionic liquid (denoted as S8), with a yield of 61.17%.

[0173] The chemical reaction formula is as follows:

[0174]

[0175] Example 9

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

[0177] Example 10

[0178] The method of Example 1 was followed, except that 2-methylacrolein was replaced by 2-phenylacrolein, 1-(4-formylphenoxymethylenebenzyl)-3-methylimidazolium tetrafluoroborate was replaced by 1-(4-formylphenoxymethylenebenzyl)-3-methylimidazolium thiocyanate (denoted as Y10), and other conditions were the same as those of Example 1. The target product was denoted as S10, with a yield of 50.64%.

[0179] Embodiment 11

[0180] The method of Example 1 was followed, except that 2-methylacrolein was replaced by 3,3-diphenylacrolein, and other conditions were the same as those of Example 1, 1-(4-formylphenoxymethylenebenzyl)-3-methylimidazolium tetrafluoroborate was replaced by 1-(4-formylphenoxymethylenebenzyl)-3-methylimidazolium acetate (denoted as Y11), and 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-methylacrolein was replaced by 1,3-diphenyl-2-propenone, and other conditions were the same as in Example 1, 1-(4-formylphenoxymethylenebenzyl)-3-methylimidazolium tetrafluoroborate was replaced by 1-(4-formylphenoxymethylenebenzyl)-3-methylimidazolium aniline acetate (denoted as Y12), and 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 by phenylpropenone, 1-(4-formylphenoxydimethylenephenyldimethyl)-3-propylimidazole bis(trifluoromethanesulfonyl)imide salt was replaced by 1-(4-formylphenoxydimethylenephenyldimethyl)-3-propylimidazole dimethyl phosphate (denoted as Y13), and other conditions were the same as those of Example 4. The target product was denoted as S13, with a yield of 60.71%.

[0185] Embodiment 14

[0186] The method of Example 4 was followed, except that 3-methyl-2-butenal was replaced by 2-phenylacrolein, 1-(4-formylphenoxydimethylenephenyldimethyl)-3-propylimidazole bis(trifluoromethanesulfonyl)imide salt was replaced by 1-(4-formylphenoxydimethylenephenyldimethyl)-3-propylimidazole dicyanamide (denoted as Y14), and other conditions were the same as those of Example 4. The target product was denoted as S14 with a yield of 58.72%.

[0187] Embodiment 15

[0188] The method of Example 4 was followed, except that 3-methyl-2-butenal was replaced by 3,3-diphenylacrolein, 1-(4-formylphenoxydimethylenephenyldimethyl)-3-propylimidazole bis(trifluoromethanesulfonyl)imide salt was replaced by 1-(4-formylphenoxydimethylenephenyldimethyl)-3-propylimidazole trifluoroacetate (denoted as Y15), and other conditions were the same as those of Example 4. The target product was denoted as S15, with a yield of 52.43%.

[0189] Example 16

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

[0191] Test Example 1

[0192] This test example is used to compare the reactivity ratio.

[0193] In the reactor, different amounts of AM and S1-S16 (or Y1-Y16) were dissolved in 1,4-dioxane, the mass percentage concentration of the two monomers was controlled at 5.0%, 0.5% of the total mass of the two monomers was added to azobisisobutyronitrile (AIBN), and the reaction was started in a water bath at 60°C, and the reaction was terminated after 4 hours. The synthesized copolymer was precipitated with a large amount of anhydrous ethanol, filtered under reduced pressure, and dried in a vacuum drying oven to constant weight. Using (CD3)2SO as the solvent, the nuclear magnetic resonance hydrogen spectrum ( 1 HNMR). 1 In H 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 unit of Example 1-16. The reactivity ratio of each group of monomers was calculated by the forward and reverse Fineman-Ross method (the test method comes from: Li Qiulian, Ding Yaqin, Zhou Jinlan, et al. Design and practice of copolymerization 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] It can be seen from Table 1 that the reactivity ratios of S1-S16 are significantly higher than those of Y1-Y16, indicating that the ionic liquids with conjugated diene structures have higher polymerization activity.

[0197] Test Example 2

[0198] This test example is used to illustrate the preparation of the copolymer of the present invention.

[0199] Add 600 mL of N,N-dimethylformamide (DMF) into the reactor, and then add 60 g of AM, SSS, NVP, KH570, and ionic liquid (molar ratio of 25:10:4:2:1) in sequence, stir evenly, heat to 104°C, add 0.2 g of azoisobutylcyanamide (CABN) under nitrogen protection, and start the copolymerization reaction.

[0200] The copolymer products obtained after reaching the set copolymerization reaction time were taken out, and after reduced pressure distillation, they were immersed in anhydrous ethanol for 2 hours, precipitated, filtered, rinsed with acetone for 3 times, and vacuum dried to constant weight to obtain copolymers.

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

[0202] Drilling fluid preparation

[0203] Fresh water slurry: Add 400 mL of tap water to a high stirring cup, and quantitatively add 16 g of calcium bentonite and 0.8 g of Na2CO3 while stirring continuously. Stir for 20 minutes, stopping at least twice to scrape off the bentonite adhering to the container wall, and cure in a sealed container for 24 hours.

[0204] Saltwater-based slurry: Add 400 mL of tap water to a high-stirring cup, and quantitatively add 16 g of NaCl, 16 g of calcium bentonite, and 0.8 g of Na2CO3 while stirring continuously. Stir for 20 minutes, stopping at least twice to scrape off the bentonite adhering to the container wall, and cure in a sealed container for 24 hours.

[0205] 8 g of copolymers obtained by reaching different set copolymerization reaction times in P1-P16 (or P1'-P16') were weighed respectively as filtrate reducers, and then added into 400 mL of the above-mentioned freshwater-based slurry or saltwater-based slurry, fully stirred, and cured for 24 h under sealed conditions to obtain the corresponding drilling fluid test slurries to be tested (respectively recorded as Z1-Z16 and Z1'-Z16'), and each drilling fluid contained P1-P16 (or P1'-P16') obtained with different copolymerization reaction times.

[0206] Test method:

[0207] Adopt ZB / TE13004-90: Drilling Fluid Test Procedure.

[0208] Z1-Z16 (or Z1'-Z16') (each drilling fluid test slurry contains 8g of copolymers obtained with different copolymerization reaction times) were respectively placed in a high-temperature aging tank after high-speed stirring for 5min, and aged at 160℃ for 16h. 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 instrument. HTHP ), the test results are shown in Table 2 and Table 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] It can be seen from Table 1 and Table 2 that the freshwater drilling fluid and saltwater drilling fluid obtained by using P1-P16 as filtrate reducers have a FL of 0.5 h after the copolymerization time reaches 0.5 h. HTHP The value of no longer changes with the extension of the polymerization reaction time during the preparation of the fluid loss reducer, indicating that S1-S16 has completed the polymerization reaction with AM, SSS, NVP and KH570 within 0.5h, indicating that S1-S16 has a higher polymerization reaction activity. Compared with the freshwater drilling fluid and saltwater drilling fluid obtained by using P1'-P16' as a fluid loss reducer with the same polymerization reaction time, when the polymerization reaction time of the monomer is also about 0.5h, its F LHTHP With the extension of polymerization reaction time, the FL of freshwater drilling fluid and saltwater drilling fluid obtained by using P1'-P16' as filtrate reducer is HTHP The value of gradually decreased, indicating that Y1-Y16 did not complete the polymerization reaction with AM, SSS, NVP and KH570 during the longer polymerization reaction time. The above test results show that compared with Y1-Y16, S1-S16 with conjugated diene structure has higher polymerization activity.

[0216] The above are only a few embodiments of the present application and do not constitute any form of limitation to the present application. Although the present application is disclosed as above with preferred embodiments, it is not intended to limit the present application. Any technician familiar with the profession, without departing from the scope of the technical solution of the present application, using the technical content disclosed above to make slight changes or modifications are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. An ionic liquid of conjugated diene, characterized in that: Having a cation represented by formula I: Among them, R, R0, R 1 , R 2 , R 3 Independently selected from one of H, C1-C6 alkyl, and phenyl; R a , R b , R c , R d , R a , R b , R c , R d Independently selected from one of H and C1-C6 alkyl; x, y, z are integers from 0 to 9.

2. The ionic liquid according to claim 1, characterized in that 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; Preferably, R, R0, R 1 , R 2 , R 3 Independently selected from one of H, C1-C4 alkyl, and phenyl; Preferably, R a , R b , R c , R d , R a , R b , R c , R d Independently selected from H, C1-C4 alkyl; Preferably, R, R0, R 1 , R 2 , R 3 Independently selected from one of H, methyl, and phenyl; Preferably, R a , R b , R c , R d , R a , R b , R c , R d independently selected from H or methyl; Preferably, x and y are independently selected from 1 or 2, and z is an integer of 0-3.

3. The method for preparing the ionic liquid according to claim 1 or 2, characterized in that: The following steps are involved: reacting a mixture containing an alkenyl compound, a bisphenylimidazole compound, a catalyst, and a solvent B to obtain the ionic liquid; The alkenyl compound has a structure shown in Formula II-1: The bisphenylimidazole compound has a cation represented by formula II-2: The anion in the bisphenylimidazole 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.

4. The preparation method according to claim 3, characterized in that: 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; Preferably, the solvent B is selected from at least one of tetrahydrofuran and dimethyl ether; Preferably, the molar ratio of the alkenyl compound to the bisphenylimidazole compound is 1:1.4-1.8; Preferably, the concentration of the alkenyl compound in the solvent B is 0.2-0.5 mmol / mL; Preferably, the reaction conditions are as follows: Temperature is -15-80℃; Time is 2-10h; Preferably, when solvent B is tetrahydrofuran, the reaction temperature is 66-76°C; Preferably, when solvent B is dimethyl ether, the reaction temperature is -10-0°C.

5. The preparation method according to claim 3, characterized in that: The following steps are involved: S1, mixing materials containing the alkenyl compound, the bisphenylimidazole compound and the solvent B to obtain solution I; S2. Add the mixed solution containing the catalyst into the solution I, and stir and reflux to obtain the ionic liquid.

6. The preparation method according to any one of claims 3 to 5, characterized in that: After the reaction, a quenching reaction is also performed; Preferably, the quenching reaction comprises the following steps: First, a quenching agent is added to the mixture containing the ionic liquid, and then water is added dropwise, followed by 8wt%-12wt% NaOH solution, and finally water is added; Preferably, the quenching agent is selected from at least one of alkali metal cyanide, amide, borane, K2CO3, LiAlH4 and NaBH; Preferably, the molar amount of the quenching agent is 0.05%-0.1% of the molar amount of the alkenyl compound; Preferably, the volume ratio of the first dripping water to the volume of the solvent B is 1:50-100; the dripping speed is 2-4 mL / min; Preferably, the volume of the 8wt%-12wt% NaOH solution is the same as the volume of the water added dropwise for the first time; Preferably, the mass of the water added again is 2.8-3.2 times the mass of the water added dropwise for the first time.

7. A copolymer, characterized in that Obtained by copolymerization of ionic liquid and monomer; The ionic liquid is selected from the ionic liquid according to claim 1 or 2 or the ionic liquid obtained by the preparation method according to any one of claims 3 to 6.

8. The copolymer according to claim 7, characterized in that The monomer is selected from at least one of acrylamide, N-isopropylacrylamide, N,N'-methylenebisacrylamide, vinyl pyrrolidone, acrylic acid, sodium acrylate, acrylonitrile, sodium styrene sulfonate, 2-acrylamido-2-methylpropane sulfonic acid, dimethyldiallylammonium chloride and γ-methacryloxypropyltrimethoxysilane.

9. Use of the copolymer according to claim 7 or 8 in oil field additives; Preferably, the copolymer is used in oil fields as a fluid loss reducer, an inhibitor, a plugging gel, a viscosity enhancer, or a plugging agent.

10. A drilling fluid, characterized in that: Including copolymers, additives; The copolymer is selected from the copolymer described in claim 7 or 8.

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