Sulfonic acid monomer, preparation method and application thereof, copolymer and application thereof, and drilling fluid

Abstract

The present invention relates to the field of oilfield additives, and discloses a sulfonic acid monomer, a preparation method and application thereof, a copolymer and application thereof, and a drilling fluid. The sulfonic acid monomer has a structure shown in formula (I-1), wherein R, R0, and R 1 、R 2 、R 3 Each of R1, R2, R3, R4, and R5 is independently H or a C1-C6 alkyl group; at least one of R1, R2, R3, R4, and R5 is SO3H, SO3Na, or SO3K, and the others are independently H or a C1-C6 alkyl group; and t is a natural number ranging from 0 to 9. The sulfonic acid monomer has high polymerization activity, and the polymer prepared using the sulfonic acid monomer has good temperature and salt resistance.

Description

Technical Field

[0001] The present invention relates to the field of petroleum additives, in particular to a sulfonic acid monomer, a preparation method and application thereof, a copolymer and application thereof, and a drilling fluid. Background Art

[0002] Oilfield additives are fine chemical products widely used in the petroleum industry in the exploration and development of oil and gas fields, as well as in the extraction and transportation of oil and gas. With the increasing variety of oil products being developed, the demand for oilfield additives is also rising. The country is vigorously striving to improve oil field production rates and the quality of produced oil products, requiring a large amount of oilfield additives in this process.

[0003] Among oilfield chemical additives, polymers derived from the copolymerization of olefinic monomers are widely used. This is particularly true in drilling operations, where the performance of many chemical working fluids (such as drilling fluids, cement slurries, and fracturing fluids) relies heavily on synthetic polymers with superior temperature and salt tolerance, given the high temperatures, high pressures, and high salinity of the formations. Among these synthetic polymers, sulfonate copolymers containing 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 2-acryloyloxy-2-methylpropanesulfonic acid (AOPS), sodium methyl propenesulfonate (SMAS), and sodium styrenesulfonate (SSS) have been the most extensively studied. Sulfonate copolymers using AMPS as a reactive monomer are particularly widely studied and applied. AMPS contains salt-sensitive -SO3 groups, which impart excellent temperature and salt tolerance to copolymers prepared using AMPS. However, the copolymerization reaction involving AMPS is generally slow, leading to the widespread use of sodium isoprenesulfonate, a sulfonic acid monomer with a conjugated diene structure. The monomer has high copolymerization activity, and the copolymerization reaction time generally does not exceed 1 hour. It can even undergo explosion polymerization with olefin monomers at extremely low initiator content.

[0004] However, the monomer still has low polymerization activity and the polymer obtained by polymerization has unsatisfactory temperature and salt resistance. Therefore, there is an urgent need to provide a sulfonic acid monomer with high polymerization activity, and the polymer obtained by polymerization of the sulfonic acid monomer has good temperature and salt resistance. Summary of the Invention

[0005] The purpose of the present invention is to overcome the problems in the prior art that sulfonic acid monomers have low polymerization reaction activity and the resulting polymers have poor temperature and salt resistance during production and practical applications, and to provide a sulfonic acid monomer, a preparation method and application thereof, a copolymer and application thereof, and a drilling fluid. The sulfonic acid monomer has good polymerization activity, and the polymer prepared using the monomer has good temperature and salt resistance.

[0006] In order to achieve the above-mentioned object, the first aspect of the present invention provides a sulfonic acid monomer having a structure shown in formula (I-1),

[0007]

[0008] Among them, R, R0, R 1 、R 2 、R 3 Each is independently H or C1-C6 alkyl; at least one of R1, R2, R3, R4 and R5 is SO3H, SO3Na or SO3K, and the others are each independently H or C1-C6 alkyl; t is a natural number of 0-9.

[0009] The second aspect of the present invention provides a method for preparing the sulfonic acid monomer, which comprises: in the presence of a catalyst, subjecting an alkenyl compound represented by formula (II-1) and a phenyl compound represented by formula (II-2) to a synthesis reaction to obtain a sulfonic acid monomer represented by formula (I-1);

[0010]

[0011]

[0012] Among them, R, R 1 、R 2 、R 3 The definitions of R0, R1, R2, R3, R4, R5 and t are the same as those above.

[0013] The third aspect of the present invention provides a sulfonic acid monomer prepared by the preparation method provided by the present invention.

[0014] A fourth aspect of the present invention provides a use of the sulfonic acid monomer provided by the present invention in an oilfield additive.

[0015] The fifth aspect of the present invention provides a copolymer comprising structural units derived from the sulfonic acid monomer provided by the present invention.

[0016] The sixth aspect of the present invention provides an application of the copolymer provided by the present invention as a fluid loss reducer, a viscosity enhancer, a viscosity reducer, a shear enhancer, or an inhibitor.

[0017] A seventh aspect of the present invention provides a drilling fluid, which contains the copolymer provided by the present invention.

[0018] The beneficial effects of the present invention are:

[0019] (1) The sulfonic acid monomer provided by the present invention introduces a benzene ring structure, so the monomer not only improves the water solubility of the polymer molecule, but also has a weaker sensitivity to metal ions; the introduced benzene ring structure also gives the monomer stronger rigidity. In addition, due to the steric effect of the benzene ring structure, the degree of thermal motion of the molecular chain under high temperature conditions is also reduced. Comparison of high temperature and high pressure fluid loss (FL) measured in salt water-based slurry and fresh water-based slurry HTHP ) It can be seen that the copolymer obtained from the sulfonic acid monomer provided by the present invention, when used as a fluid loss control agent in drilling fluid, exhibits better fluid loss control and temperature and salt resistance than sodium isoprene sulfonate. The sulfonic acid monomer provided by the present invention simultaneously introduces a sulfonic acid group and a benzene ring structure, which work together synergistically to significantly improve the temperature and salt resistance of the polymer molecule.

[0020] (2) The sulfonic acid monomer provided by the present invention also contains a conjugated diene structure, which can cooperate with the sulfonic acid group and benzene ring structure contained therein to enhance the polymerization reaction activity of the monomer and increase the polymerization reaction speed. The sulfonic acid monomer provided by the present invention is used as a raw material to further obtain a fluid loss reducer. After the polymerization reaction time reaches 0.5h, its FL HTHP The value of no longer changes with the extension of the polymerization reaction time, indicating that the monomer has completed the polymerization reaction within 0.5 h and has a high polymerization reaction activity, which is equivalent to that of sodium isoprene sulfonate. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 is the magnetic resonance spectrum of the sulfonic acid monomer obtained in Example 1 ( 1 H NMR) spectra;

[0022] Figure 2 is the magnetic resonance spectrum of the sulfonic acid monomer obtained in Example 2 ( 1 H NMR) spectrum. DETAILED DESCRIPTION

[0023] The following is combined with Figure 1-2 The specific embodiments of the present invention are described in detail. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present invention and are not used to limit the present invention.

[0024] The endpoints of the ranges and any values ​​disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoints of each range, the endpoints of each range and individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered to be specifically disclosed herein.

[0025] The first aspect of the present invention provides a sulfonic acid monomer, wherein the sulfonic acid monomer has a structure shown in formula (I-1),

[0026]

[0027] Among them, R, R0, R 1 、R 2 、R 3 Each is independently H or C1-C6 alkyl; at least one of R1, R2, R3, R4 and R5 is SO3H, SO3Na or SO3K, and the others are each independently H or C1-C6 alkyl; t is a natural number of 0-9.

[0028] According to the present invention, preferably, R, R 1 、R 2 、R 3 Each is independently H or CH3, R0 is H, CH3, C2H5, CH(CH3)2 or C(CH3)3; at least one of R1, R2, R3, R4 and R5 is SO3H, SO3Na or SO3K, and the rest are H; t is a natural number of 0-6; more preferably, t is 0, 1 or 2.

[0029] According to a specific embodiment of the present invention, the monomer is selected from the following compounds:

[0030]

[0031] The second aspect of the present invention provides a method for preparing the sulfonic acid monomer, wherein the method comprises: in the presence of a catalyst, performing a synthesis reaction on an alkenyl compound represented by formula (II-1) and a phenyl compound represented by formula (II-2) to obtain a sulfonic acid monomer represented by formula (I-1),

[0032]

[0033] Among them, R, R 1 、R 2 、R 3 The definitions of R0, R1, R2, R3, R4, R5 and t are the same as those above.

[0034] The catalyst used in the preparation method provided by the present invention can be any catalyst that can promote the coupling of carbonyl groups to olefins, and can be, for example, at least one of low-valent titanium, low-valent tungsten, low-valent molybdenum, low-valent zirconium, low-valent vanadium and low-valent niobium.

[0035] 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 the present invention can be obtained by methods known in the art, taking the preparation of low-valent titanium as an example.

[0036] According to a preferred embodiment of the present invention, the catalyst is low-valent titanium.

[0037] According to a preferred embodiment of the present invention, for example, the method for preparing low-valent titanium includes: dissolving a titanium-containing reagent and a reducing agent in a solvent A, and performing a reduction reaction.

[0038] 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.

[0039] According to the present invention, the titanium-containing reagent is selected from at least one of titanium trichloride, titanium tetrachloride 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 reducing activity of the reducing agent and the molar ratio of the reducing agent to titanium trichloride, titanium tetrachloride and commercial titanium powder.

[0040] According to the present invention, solvent A is tetrahydrofuran (THF) and / or dimethyl ether (DEM).

[0041] According to a preferred embodiment of the present invention, the titanium-containing reagent is titanium tetrachloride; the reducing agent is Zn and CuCl; and the solvent A is one of tetrahydrofuran (THF) and dimethyl ether (DME).

[0042] Preferably, the concentration of titanium tetrachloride in solvent A is 0.2-0.7 mmol / mL, the concentration of Zn in solvent A is 0.3-0.8 mmol / mL, and the concentration of CuCl in solvent A is 0.02-0.06 mmol / mL.

[0043] According to a specific embodiment of the present invention, the preparation method of low-valent titanium further specifically includes: adding activated Zn, CuCl and solvent A into a reactor, then cooling and stirring, and then adding TiCl4, and performing the reduction reaction in a reflux manner to obtain low-valent titanium.

[0044] According to a preferred embodiment of the present invention, when the solvent A is THF, the reflux temperature is 66°C to 72°C, and the reflux needs to be cooled again after the 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.

[0045] Preferably, the particle size of the Zn is at least 200 mesh, more preferably 200-600 mesh.

[0046] Preferably, the cooling temperature is -10°C to 0°C, and the reflux time is 2-4 hours.

[0047] According to a preferred embodiment of the present invention, the molar ratio of the alkenyl compound to the phenyl compound in the synthesis reaction is 1:(1.2-1.6).

[0048] According to a specific embodiment of the present invention, the method for preparing the sulfonic acid monomer comprises: before the synthesis reaction, dissolving the alkenyl compound and the phenyl compound in solvent B.

[0049] According to a specific embodiment of the present invention, the preparation method of the sulfonic acid monomer includes: dissolving an alkenyl compound and a phenyl 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.

[0050] Preferably, the solvent B is the same as the solvent A, and the volume ratio is 1:(2.5-5).

[0051] Preferably, the concentration of the alkenyl compound in the solvent B is 0.2-0.5 mmol / mL.

[0052] Preferably, the synthesis reaction temperature is -10°C to 0°C or 66°C to 72°C; the synthesis reaction time is 2-8 hours, more preferably 3-6 hours. When solvent B is THF, the synthesis reaction temperature is 66°C to 72°C; when solvent B is DME, the synthesis reaction temperature is -10°C to 0°C.

[0053] The monomer preparation method provided herein may further include a quenching reaction after the synthesis reaction proceeds to a certain extent. This is because excess reactants are present in the synthesis reaction. Once the desired product has been obtained, the excess reactants may react further to form undesirable products. The principle of quenching is to remove the excess compound from the system by reacting it with another compound that is more reactive with it.

[0054] In order to avoid the presence of impurities in the product, the present invention preferably performs a quenching reaction after the synthesis reaction has proceeded to a certain extent, that is, after the reaction of the alkenyl compound is complete. The present invention does not particularly limit the quenching agent, and conventional quenching agents such as alkali metal cyanides, amides, borane, potassium carbonate, lithium aluminum hydride, and sodium borohydride can be selected. However, considering the stability of the product and the difficulty of handling, potassium carbonate (K2CO3) is preferably used as the quenching agent in the present invention.

[0055] According to a preferred embodiment of the present invention, the concentration of the potassium carbonate solution is 5wt%-20wt%, preferably 8wt%-12wt%, and the volume ratio of the K2CO3 solution to the solvent B is 1:(8-16).

[0056] In order to obtain a solid monomer, the method for preparing the monomer provided by the present invention may further comprise: filtering after quenching the reaction, removing the catalyst, collecting the filtrate; and drying and removing the solvent.

[0057] The present invention has no limitation on the filtering method, as long as low-valent titanium can be filtered out, and conventional filter aids such as diatomaceous earth filter aid, charcoal powder filter aid, activated carbon filter aid, and perlite filter aid can be added.

[0058] According to a preferred embodiment of the present invention, diatomaceous earth filtration is used.

[0059] In order to collect as much product as possible, the present invention 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.

[0060] The present invention has no limitation on the method for obtaining the monomer solid, including the drying agent used and the method for removing the solvent, as long as a solid product can be obtained.

[0061] According to a preferred embodiment of the present invention, 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; the desiccant is preferably an inorganic neutral desiccant, such as one or more of MgSO4, anhydrous Na2SO4, CaSO4, and CaCl2.

[0062] In order to obtain a high-purity monomer solid, the preparation method of the sulfonic acid monomer provided by the present invention may further include: purification, purifying the crude product obtained from the synthesis reaction.

[0063] According to the present invention, recrystallization is used for purification. The present invention has no limitation on the solvent for recrystallization. Considering the polarity and solubility of the solvent, the present invention preferably uses methanol or ethanol to recrystallize the crude product to obtain a white frosty powder, which is the sulfonic acid monomer of the conjugated diene.

[0064] The third aspect of the present invention provides a sulfonic acid monomer prepared by the preparation method provided by the present invention.

[0065] A fourth aspect of the present invention provides a use of the sulfonic acid monomer provided by the present invention in an oilfield additive.

[0066] According to a fifth aspect of the present invention, there is provided a copolymer comprising structural units derived from the sulfonic acid monomer of the present invention.

[0067] The present invention has no particular limitation on the type of the copolymer, which is obtained by polymerizing the sulfonic acid monomer of the present invention alone or with other monomers.

[0068] Preferably, the other monomers may be selected from, but not limited to, one or more of acrylamide, N-isopropylacrylamide, vinyl pyrrolidone, acrylic acid, sodium acrylate, acrylonitrile, 2-acrylamido-2-methylpropanesulfonic acid, dimethyldiallylammonium chloride, and γ-methacryloyloxypropyltrimethoxysilane. For example, the copolymer may be a terpolymer, which may be obtained by polymerizing monomers acrylamide (AM), vinyl pyrrolidone (NVP), and the sulfonic acid monomer provided by the present invention in a molar ratio of (1-10): (1-3): (1-3). The weight average molecular weight of the copolymer may be 1.5×10 5 -2.5×10 5 g / mol.

[0069] The present invention does not particularly limit the polymerization method, and any of solution polymerization, gas phase polymerization, and bulk polymerization can be used. According to the specific embodiment of the present invention, solution polymerization is preferred. The present invention lists specific operations in the text, which should not be understood by those skilled in the art as limiting the present invention.

[0070] The sixth aspect of the present invention provides an application of the copolymer provided by the present invention as a fluid loss reducer, a viscosity enhancer, a viscosity reducer, a shear enhancer, or an inhibitor.

[0071] A seventh aspect of the present invention provides a drilling fluid, which contains the copolymer provided by the present invention.

[0072] In the present invention, there is no particular limitation on the drilling fluid system, and it may be any drilling fluid system known in the art. According to a specific embodiment of the present invention, the drilling fluid of the present invention may be a water-based drilling fluid or a salt-based drilling fluid.

[0073] Preferably, the water-based drilling fluid further contains additives.

[0074] Preferably, the additives include bentonite and sodium carbonate.

[0075] In the present invention, 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 0.2 wt%-2.0 wt% based on the total amount of the drilling fluid.

[0076] In the present invention, there is no particular limitation on the preparation method of the drilling fluid, and a preparation method well known to those skilled in the art can be adopted, which will not be described in detail herein. The present invention lists specific operations herein, which should not be understood by those skilled in the art as limiting the present invention.

[0077] Example 1

[0078] Under argon protection, 16.345 g (250 mmol) of 200 mesh activated Zn powder, 1.98 g (20 mmol) of CuCl and 500 mL of THF were added to the reactor, cooled to -5 ° C, stirred, 37.9358 g (200 mmol) of TiCl4 was added, the temperature was raised to 68 ° C and refluxed for 2.5 h, and then cooled to -5 ° C again to obtain a low-valent titanium reducing agent.

[0079] Dissolve 4.2055 g (60 mmol) of methyl vinyl ketone and 18.7347 g (90 mmol) of sodium benzaldehyde-2-sulfonate in 200 mL of THF, add a low-valent titanium reducing agent, and heat to 68°C with stirring. Reflux for 5 h. Add 20 mL of a 10.0 wt% KCO solution, filter through celite, collect the filtrate, rinse with CHCl, and combine the rinse with the filtrate to obtain a mixed solution. Add a sufficient amount of NaSO, filter, and remove the THF by vacuum distillation to obtain a pale yellow crude product.

[0080] The crude product was recrystallized from methanol to obtain a white frosty powder, which was the target product with a yield of 72.5%.

[0081] The product obtained in Example 1 was characterized by nuclear magnetic resonance [(CD3)2SO, 25 ° C], magnetic resonance spectrum ( 1 H NMR) Figure 1 .according to 1 H NMR analysis shows that the target product is a sulfonic acid monomer of a conjugated diene having the structure represented by formula (I-1) of the present invention, wherein: R 1 、R 2 、R 3 , R0, R2, R3, R4 and R5 are H, R is CH3, R1 is SO3Na, t=0, as shown in the following formula:

[0082]

[0083] Example 2

[0084] Under nitrogen protection, 15.6912 g (240 mmol) of 400 mesh activated Zn powder, 1.584 g (16 mmol) of CuCl and 800 mL of DME were added to the reactor, the temperature was controlled to -10°C, stirred, 30.3486 g (160 mmol) of TiCl4 was added, and refluxed for 2 h to obtain a low-valent titanium reducing agent.

[0085] Dissolve 7.0091 g (100 mmol) of 2-butenal and 37.2242 g (120 mmol) of sodium benzaldehyde-2,4-disulfonate in 200 mL of dimethylbenzene (DME), add a low-valent titanium reducing agent, and reflux for 3 hours. Add 20 mL of a 10.0 wt% K₂CO₃ solution, filter through diatomaceous earth, collect the filtrate, rinse with CH₂Cl₂, and combine the rinse and filtrate to obtain a mixed solution. Add a sufficient amount of MgSO₄ to the mixed solution, filter, and remove the DME by vacuum distillation to obtain a pale yellow crude product.

[0086] The crude product was recrystallized from ethanol to obtain a white frosty powder, which was the target product with a yield of 76.9%.

[0087] The product obtained in Example 2 was characterized by nuclear magnetic resonance [(CD3)2SO, 25 ° C], magnetic resonance spectrum ( 1 H NMR) Figure 2 .according to 1 H NMR analysis shows that the target product is a sulfonic acid monomer of a conjugated diene having the structure represented by formula (I-1) of the present invention, wherein: R 1 CH3, R 2 、R 3 , R, R0, R2, R4 and R5 are H, R1 and R3 are SO3Na, t=0, as shown in the following formula:

[0088]

[0089] Example 3

[0090] Under nitrogen protection, 15.6912 g (240 mmol) of 600 mesh activated Zn powder, 1.584 g (16 mmol) of CuCl and 800 mL of DME were added to the reactor, the temperature was controlled to -10°C, stirred, 30.3486 g (160 mmol) of TiCl4 was added, and refluxed for 2 h to obtain a low-valent titanium reducing agent.

[0091] Dissolve 7.0091 g (100 mmol) of methacrolein and 27.3914 g (120 mmol) of 4-(4-sulfonatophenyl)-2-butanone in 200 mL of dimethylbenzene (DME), add a low-valent titanium reducing agent, and reflux for 3 hours. Add 20 mL of a 10.0 wt% KCO solution, filter through celite, collect the filtrate, rinse with CHCl, and combine the rinse with the filtrate to obtain a mixed solution. Add a sufficient amount of MgSO, filter, and remove the DME by vacuum distillation to obtain a pale yellow crude product.

[0092] The crude product was recrystallized from methanol to obtain a white frosty powder, which was the target product with a yield of 71.4%.

[0093] The product obtained in Example 3 was characterized by nuclear magnetic resonance [(CD3)2SO, 25°C]. 1 H NMR analysis shows that the target product is a sulfonic acid monomer of a conjugated diene having the structure represented by formula (I-1) of the present invention, wherein: R 1 and R0 is CH3, R 2 、R 3 , R, R1, R2, R4 and R5 are H, R3 is SO3H, t=2, as shown in the following formula:

[0094]

[0095] Example 4

[0096] Under nitrogen protection, 19.614 g (300 mmol) of 500 mesh activated Zn powder, 2.97 g (30 mmol) of CuCl and 500 mL of THF were added to the reactor, cooled to -10 ° C, stirred, 47.4198 g (250 mmol) of TiCl4 was added, the temperature was raised to 72 ° C and refluxed for 2 h, and then cooled to -10 ° C again to obtain a low-valent titanium reducing agent.

[0097] Dissolve 2.103 g (25 mmol) of 3-methyl-2-butenal and 11.7717 g (40 mmol) of 3,5-disulfonic acid phenylacetone in 125 mL of THF, add a low-valent titanium reducing agent, and heat to 72°C with stirring. Reflux for 3 hours. Add 15 mL of a 12.0 wt% KCO solution, filter through celite, collect the filtrate, rinse with CHCl, and combine the rinse and filtrate to obtain a mixed solution. Add sufficient CaCl, filter, and remove the THF by vacuum distillation to obtain a pale yellow crude product.

[0098] The crude product was recrystallized from methanol to obtain a white frosty powder, which was the target product with a yield of 75.6%.

[0099] The product obtained in Example 4 was characterized by nuclear magnetic resonance [(CD3)2SO, 25°C]. 1 H NMR analysis shows that the target product is a sulfonic acid monomer of a conjugated diene having the structure represented by formula (I-1) of the present invention, wherein: R 1 、R 2 and R0 is CH3, R 3 , R, R1, R3 and R5 are H, R2 and R4 are SO3H, t=1, as shown in the following formula:

[0100]

[0101] Example 5

[0102] Under argon protection, 19.614 g (300 mmol) of 400 mesh activated Zn powder, 2.97 g (30 mmol) of CuCl and 600 mL of THF were added to the reactor, cooled to 0 ° C, stirred, 79.6652 g (420 mmol) of TiCl4 was added, the temperature was raised to 68 ° C and refluxed for 4 h, and then cooled to 0 ° C again to obtain a low-valent titanium reducing agent.

[0103] Dissolve 2.6911 g (48 mmol) of acrolein and 17.1575 g (72 mmol) of potassium acetophenone-2-sulfonate in 120 mL of THF, add a low-valent titanium reducing agent, and heat to 68°C with stirring. Reflux for 6 hours. Add 75 mL of an 8.0 wt% KCO solution, filter through celite, collect the filtrate, rinse with CHCl, and combine the rinse with the filtrate to obtain a mixed solution. Add a sufficient amount of NaSO, filter, and remove the THF by vacuum distillation to obtain a pale yellow crude product.

[0104] The crude product was recrystallized from methanol to obtain a white frosty powder, which was the target product with a yield of 78.3%.

[0105] The product obtained in Example 5 was characterized by nuclear magnetic resonance [(CD3)2SO, 25°C]. 1 H NMR analysis shows that the target product is a sulfonic acid monomer of a conjugated diene having the structure shown in formula (I-1) of the present invention, wherein: R0 is CH3, R 1 、R 2 、R 3 , R, R2, R3, R4 and R5 are H, R1 is SO3K, t=0, as shown in the following formula:

[0106]

[0107] Example 6

[0108] Under argon protection, 20.9216 g (320 mmol) of 500 mesh activated Zn powder, 2.376 g (24 mmol) of CuCl and 800 mL of THF were added to the reactor, cooled to -4 ° C and stirred, 45.523 g (240 mmol) of TiCl4 was added, the temperature was raised to 70 ° C and refluxed for 3.5 h, and then cooled to -4 ° C again to obtain a low-valent titanium reducing agent.

[0109] Dissolve 6.2813 g (64 mmol) of 4-methyl-3-penten-2-one and 23.2597 g (96 mmol) of 2,2-dimethyl-(4-sulfonatophenyl)-1-propanone in 320 mL of THF, add a low-valent titanium reducing agent, and heat to 70°C with stirring, reflux for 5 hours. Add 20 mL of a 12.0 wt% KCO solution, filter through celite, collect the filtrate, rinse with CHCl, and combine the rinse and filtrate to obtain a mixed solution. Add a sufficient amount of NaSO, filter, and remove the THF by vacuum distillation to obtain a pale yellow crude product.

[0110] The crude product was recrystallized from methanol to obtain a white frosty powder, which was the target product with a yield of 72.7%.

[0111] The product obtained in Example 6 was characterized by nuclear magnetic resonance [(CD3)2SO, 25°C]. 1 H NMR analysis shows that the target product is a sulfonic acid monomer of a conjugated diene having the structure represented by formula (I-1) of the present invention, wherein: R 1 、R 2 and R is CH3, R 3 , R1, R2, R4 and R5 are H, R3 is SO3H, R0 is C(CH3)3, t=0, as shown in the following formula:

[0112]

[0113] Example 7

[0114] Under nitrogen protection, 52.304 g (800 mmol) of 200 mesh activated Zn powder, 3.96 g (40 mmol) of CuCl and 1000 mL of DME were added to the reactor, the temperature was controlled to 0°C, and the mixture was stirred. 75.8716 g (400 mmol) of TiCl4 was added and refluxed for 4 h to obtain a low-valent titanium reducing agent.

[0115] Dissolve 12.6681 g (125 mmol) of 3-methyl-3-penten-2-one and 39.9459 g (175 mmol) of 2-methyl-1-(2-sulfonatophenyl)-1-propanone in 250 mL of dimethylbenzene (DME), add a low-valent titanium reducing agent, and reflux for 4 hours. Add 25 mL of a 10.0 wt% KCO solution, filter through celite, collect the filtrate, rinse with CHCl, and combine the rinse with the filtrate to obtain a mixed solution. Add a sufficient amount of CaSO, filter, and remove the DME by vacuum distillation to obtain a pale yellow crude product.

[0116] The crude product was recrystallized from methanol to obtain a white frosty powder, which was the target product with a yield of 75.0%.

[0117] The product obtained in Example 7 was characterized by nuclear magnetic resonance [(CD3)2SO, 25°C]. 1 H NMR analysis shows that the target product is a sulfonic acid monomer of a conjugated diene having the structure represented by formula (I-1) of the present invention, wherein: R 1 、R 3 and R is CH3, R 2 , R2, R3, R4 and R5 are H, R1 is SO3H, R0 is CH(CH3)2, t=0, as shown in the following formula:

[0118]

[0119] Example 8

[0120] Under argon protection, 19.614 g (300 mmol) of 600 mesh activated Zn powder, 4.455 g (45 mmol) of CuCl and 750 mL of DME were added to the reactor, the temperature was controlled to -6°C, stirred, 30.3486 g (160 mmol) of TiCl4 was added, and refluxed for 4 h to obtain a low-valent titanium reducing agent.

[0121] Dissolve 10.0955 g (90 mmol) of 3,4-dimethyl-2-pentanone and 36.1028 g (112 mmol) of 1-(2,4-disulfonic acid phenyl)-3-pentanone in 300 mL of dimethylbenzene (DME), add the mixture to a low-valent titanium reducing agent, and reflux for 3 hours. Add 30 mL of a 10.0 wt% KCO solution, filter through diatomaceous earth, collect the filtrate, rinse with CHCl, and combine the rinse with the filtrate to obtain a mixed solution. Add sufficient CaCl, filter, and remove the DME by vacuum distillation to obtain a pale yellow crude product.

[0122] The crude product was recrystallized from ethanol to obtain a white frosty powder, which was the target product with a yield of 73.8%.

[0123] The product obtained in Example 8 was characterized by nuclear magnetic resonance [(CD3)2SO, 25°C]. 1 H NMR analysis shows that the target product is a sulfonic acid monomer of a conjugated diene having the structure represented by formula (I-1) of the present invention, wherein: R 1 、R 2 、R 3 and R is CH3, R2, R4 and R5 are H, R1 and R3 are SO3H, R0 is C2H5, t=2, as shown in the following formula:

[0124]

[0125] Example 9

[0126] The method of Example 8 was followed, except that the molar amount of 1-(2,4-disulfonic acid phenyl)-3-pentanone was 160 mmol. Other conditions were the same as those of Example 8, and the yield of the target product was 45.8%.

[0127] The obtained product was characterized by nuclear magnetic resonance [(CD3)2SO, 25℃], according to 1 H NMR analysis showed that the structure of the target product was the same as that of Example 8.

[0128] Example 10

[0129] The method of Example 8 was followed, except that the temperature was controlled at 5° C. Other conditions were the same as those of Example 8, and the yield of the target product was 40.1%.

[0130] The obtained product was characterized by nuclear magnetic resonance [(CD3)2SO, 25℃], according to 1 H NMR analysis showed that the structure of the target product was the same as that of Example 8.

[0131] Example 11

[0132] The method of Example 6 was followed, except that the heating temperature in the step of preparing low-valent titanium was 80° C. Other conditions were the same as those of Example 6, and the yield of the target product was 24.6%.

[0133] The obtained product was characterized by nuclear magnetic resonance [(CD3)2SO, 25℃], according to 1 H NMR analysis showed that the structure of the target product was the same as that in Example 6.

[0134] Example 12

[0135] The method of Example 6 was followed, except that the reflux time in the step of preparing low-valent titanium was 1 hour. Other conditions were the same as those of Example 6, and the yield of the target product was 34.8%.

[0136] The obtained product was characterized by nuclear magnetic resonance [(CD3)2SO, 25℃], according to 1 H NMR analysis showed that the structure of the target product was the same as that in Example 6.

[0137] Example 13

[0138] The method of Example 6 was followed, except that the particle size of the activated Zn powder in the step of preparing low-valent titanium was 100 mesh. Other conditions were the same as those of Example 6, and the yield of the target product was 23.7%.

[0139] The obtained product was characterized by nuclear magnetic resonance [(CD3)2SO, 25℃], according to 1 H NMR analysis showed that the structure of the target product was the same as that in Example 6.

[0140] Preparation Example 1-18

[0141] This preparation example is used to illustrate the preparation of the copolymer of the present invention.

[0142] Add 400 mL of distilled water to the reactor, and then add 60 g of AM, vinyl pyrrolidone (NVP), and sulfonic acid monomer (molar ratio: 3:1:1) in sequence. Adjust the pH of the solution to 8.0 with 10 wt% NaOH, raise the temperature to 45 ° C, and add 0.2 g of (NH4)2S2O8 under nitrogen protection to start the copolymerization reaction.

[0143] The copolymer products obtained after reaching the set copolymerization reaction time were taken out, vacuum dried at 60°C to constant weight, and then immersed in 350 mL of anhydrous ethanol for 2 hours, precipitated, filtered, and rinsed with acetone three times. The product was then extracted with a Soxhlet extractor using a mixed solvent of glacial acetic acid and ethylene glycol with a volume ratio of 3:2 as an extractant for 4 hours. After the product was taken out, it was vacuum dried at 25°C to constant weight to obtain copolymer 1-18 with a weight average molecular weight of 1.5×10 5 -2.5×10 5 g / mol.

[0144] The sulfonic acid monomers of Preparation Examples 1-13 are the sulfonic acid monomers of conjugated dienes prepared in Examples 1-13; and the sulfonic acid monomers of Preparation Examples 14-18 are sodium isoprene sulfonate, AMPS, AOPS, SSS and SMAS.

[0145] Test Example 1 Evaluation of the Temperature Resistance of Fluid Loss Control Products

[0146] 1. Preparation of drilling fluid

[0147] Freshwater slurry: Add 400 mL of tap water to a high-stirring beaker. While stirring continuously, quantitatively add 16.0 g of calcium bentonite and 0.8 g of Na2CO3. Stir for 20 minutes, stopping at least twice to scrape off any bentonite adhering to the container walls. Cure in a sealed container for 24 hours.

[0148] 8 g of the copolymers obtained in Preparation Examples 1-18 with different set copolymerization reaction times were respectively weighed as fluid loss reducers and added to 400 mL of the above-mentioned fresh water-based slurry. The mixture was fully stirred and cured under sealed conditions for 24 h to obtain drilling fluids 1-18. Each drilling fluid contained a copolymer obtained with a different copolymerization reaction time, as shown in Table 1.

[0149] 2. Test method:

[0150] Adopt ZB / TE13004-90: Drilling Fluid Testing Procedure.

[0151] Drilling fluids 1-18 (each drilling fluid 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 150℃ for 16h. The high-temperature and high-pressure fluid loss (FL) of the drilling fluid was measured using a high-temperature and high-pressure fluid loss instrument. HTHP ), the test results are shown in Table 1.

[0152] Table 1 FL of different experimental pulps HTHP (mL)

[0153]

[0154] As can be seen from Table 1, the filtrate reducer obtained by using the sulfonic acid monomer of the present invention prepared in Examples 1-13 as raw materials has 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 the sulfonic acid monomer prepared in Example 1-13 has completed the polymerization reaction with AM and NVP within 0.5h, indicating that the monomer has good reactivity and rapid polymerization ability. Compared with the fluid loss reducer prepared in Example 1-13 using the sulfonic acid monomer of the present invention as the raw material, the drilling fluid 14 contains the fluid loss reducer obtained from sodium isoprene sulfonate as the raw material. When the polymerization reaction time of this monomer is also about 0.5h, its FL HTHP In comparison, when AMPS, AOPS, SSS and SMAS are used as sulfonic acid monomers and further copolymerized to obtain a fluid loss reducer, its FL HTHP The value of gradually decreases, indicating that within a longer polymerization reaction time, AMPS, AOPS, SSS and SMAS have not completed the polymerization reaction with AM and NVP. The above test results show that the sulfonic acid monomers of the present invention prepared in Examples 1-13 have higher polymerization reaction activity, and the filtration loss reducer obtained by further copolymerization has better filtration loss reduction effect than the filtration loss reducer obtained by using sodium isoprene sulfonate as raw material. In addition, the sulfonic acid monomers prepared in Examples 9-10 have the same structure as the sulfonic acid monomers prepared in Example 8, and the yield of the sulfonic acid monomers is reduced. Therefore, the FL value of the filtration loss reducer obtained by further copolymerization using the sulfonic acid monomers prepared in Examples 9-10 as raw materials is the same as that of the filtration loss reducer obtained by further copolymerization using the sulfonic acid monomers prepared in Example 8. HTHP Similarly, the sulfonic acid monomers prepared in Examples 11-13 have the same structure as the sulfonic acid monomers prepared in Example 6, and the yield of the sulfonic acid monomers is reduced. Therefore, the FL of the fluid loss reducer obtained by further copolymerization using the sulfonic acid monomers prepared in Examples 11-13 as raw materials is the same as that of the fluid loss reducer obtained by further copolymerization using the sulfonic acid monomers prepared in Example 6 as raw materials. HTHP same.

[0155] Test Example 2 Evaluation of Salt Resistance of Fluid Loss Control Products

[0156] 1. Preparation of drilling fluid

[0157] Saltwater-based slurry: Add 400 mL of tap water to a high-stirring beaker. While stirring continuously, quantitatively add 40 g of NaCl, 16.0 g of calcium bentonite, and 0.8 g of Na2CO3. Stir for 20 minutes, stopping at least twice to scrape off any bentonite adhering to the container walls. Cure in a sealed container for 24 hours.

[0158] 8 g of the copolymers obtained in Preparation Examples 1-18 with different set copolymerization reaction times were respectively weighed as fluid loss reducers, and then added to the above 400 mL of salt water-based slurry, stirred thoroughly, and cured under sealed conditions for 24 hours to obtain drilling fluids 19-36, respectively. Each drilling fluid contains a copolymer obtained with a different copolymerization reaction time, as shown in Table 2.

[0159] 2. Test method:

[0160] Adopt ZB / TE13004-90: Drilling Fluid Testing Procedure.

[0161] Drilling fluids 19-36 (each drilling fluid 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 150℃ for 16h. The high-temperature and high-pressure fluid loss (FL) of the drilling fluid was measured using a high-temperature and high-pressure fluid loss instrument. HTHP ), the test results are shown in Table 2.

[0162] Table 2 FL of different experimental pulps HTHP (mL)

[0163]

[0164] As can be seen from Table 2, the fluid loss reducer obtained by using the sulfonic acid monomer of the present invention prepared in Examples 1-13 as raw materials has a FL of 0.5h after the copolymerization time reaches 0.5h. 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 the sulfonic acid monomer prepared in Example 1-13 has completed the polymerization reaction with AM and NVP within 0.5h, indicating that the monomer has good reactivity and rapid polymerization ability. Compared with the fluid loss reducer prepared in Example 1-13 using the sulfonic acid monomer of the present invention as the raw material, the drilling fluid 32 contains the fluid loss reducer obtained from sodium isoprene sulfonate as the raw material. When the polymerization reaction time of this monomer is also about 0.5h, its FL HTHPIn comparison, when AMPS, AOPS, SSS and SMAS are used as sulfonic acid monomers and further copolymerized to obtain a fluid loss reducer, its FL HTHP The value of gradually decreases, indicating that AMPS, AOPS, SSS, and SMAS have not completed the polymerization reaction with AM and NVP over a longer polymerization time. This is consistent with the performance change trend of different fluid loss additives measured in freshwater-based slurry.

[0165] Comparing the test results of the fluid loss agent in fresh water-based slurry, the fluid loss agent obtained by further copolymerizing the sulfonic acid monomer prepared by Examples 1-13 of the present invention and sodium isoprene sulfonate as raw materials has a FL value of 0.05.0 in salt water-based slurry. HTHP The FL value of the slurry is slightly higher than that in fresh water slurry, but still within the controllable range, and has good salt resistance. For the filtrate reducer obtained by further copolymerization of AMPS, AOPS, SSS and SMAS as sulfonic acid monomers, when the copolymerization reaction time reaches 8h, the FL value of the slurry is slightly higher than that in fresh water slurry, but still within the controllable range, and has good salt resistance. HTHP It is still large, that is, a longer polymerization reaction time is required to complete the polymerization reaction, indicating that the reaction activity and polymerization ability of the monomer are poor.

[0166] In addition, the performance change trend is the same as that measured in fresh water-based slurry. In salt water-based slurry, the sulfonic acid monomer prepared in Examples 9-10 has the same structure as the sulfonic acid monomer prepared in Example 8, and the yield of the sulfonic acid monomer is reduced. Therefore, the FL of the fluid loss reducer obtained by further copolymerization using the sulfonic acid monomer prepared in Examples 9-10 as a raw material is lower than that of the fluid loss reducer obtained by further copolymerization using the sulfonic acid monomer prepared in Example 8 as a raw material. HTHP Similarly, the sulfonic acid monomers prepared in Examples 11-13 have the same structure as the sulfonic acid monomers prepared in Example 6, and the yield of the sulfonic acid monomers is reduced. Therefore, the FL of the fluid loss reducer obtained by further copolymerization using the sulfonic acid monomers prepared in Examples 11-13 as raw materials is the same as that of the fluid loss reducer obtained by further copolymerization using the sulfonic acid monomers prepared in Example 6 as raw materials. HTHP same.

[0167] The above test results show that the sulfonic acid monomers of the present invention prepared in Examples 1-13 have high polymerization reaction activity, and the fluid loss control agent obtained by further copolymerization thereof has better temperature and salt resistance than the fluid loss control agent obtained by further copolymerization of sodium isoprene sulfonate, and the fluid loss control effect is better than the fluid loss control effect of the fluid loss control agent obtained by further copolymerization using sodium isoprene sulfonate as a raw material.

[0168] The above combined with the attached Figure 1-2While preferred embodiments of the present invention have been described in detail, the present invention is not limited thereto. Within the technical scope of the present invention, various simple variations of the technical solution of the present invention may be made, including combining the specific technical features in any suitable manner. To avoid unnecessary repetition, the present invention will not further describe various possible combinations. However, these simple variations and combinations should also be considered as disclosed herein and fall within the scope of protection of the present invention.

Claims

1. A sulfonic acid monomer, characterized in that The sulfonic acid monomer has a structure shown in formula (I-1), Among them, R, R 1 、R 2 、R 3 Each is independently H or CH3, R0 is H, CH3, C2H5, CH(CH3)2 or C(CH3)3; at least one of R1, R2, R3, R4 and R5 is SO3H, SO3Na or SO3K, and the rest are H; t is 0, 1 or 2.

2. The sulfonic acid monomer according to claim 1, characterized in that The sulfonic acid monomer is selected from the following compounds:

3. A method for preparing a sulfonic acid monomer, characterized in that: The method comprises: in the presence of a catalyst, performing a synthesis reaction on an alkenyl compound represented by formula (II-1) and a phenyl compound represented by formula (II-2) to obtain a sulfonic acid monomer represented by formula (I-1), wherein the catalyst is selected from at least one of low-valent titanium; the preparation method of the low-valent titanium comprises: in a protective atmosphere, dissolving a titanium-containing reagent and a reducing agent in a solvent A to perform a reduction reaction; the titanium-containing reagent is selected from at least one of titanium trichloride, titanium tetrachloride and titanium powder; the reducing agent is Zn and CuCl; and the solvent A is tetrahydrofuran and / or dimethyl ether; Among them, R, R 1 、R 2 、R 3 The definitions of R0, R1, R2, R3, R4, R5 and t are the same as those in claim 1 or 2.

4. The preparation method according to claim 3, characterized in that The protective atmosphere is nitrogen and / or argon.

5. The preparation method according to claim 3, characterized in that The titanium-containing reagent is titanium tetrachloride.

6. The preparation method according to claim 5, characterized in that The concentration of titanium tetrachloride in solvent A is 0.2-0.7 mmol / mL, the concentration of Zn in solvent A is 0.3-0.8 mmol / mL, and the concentration of CuCl in solvent A is 0.02-0.06 mmol / mL.

7. The preparation method according to claim 3, characterized in that The molar ratio of the alkenyl compound to the phenyl compound in the synthesis reaction is 1:(1.2-1.6).

8. The preparation method according to claim 3, characterized in that The preparation method further comprises: before the synthesis reaction, dissolving the alkenyl compound and the phenyl compound in solvent B.

9. The preparation method according to claim 8, characterized in that The solvent B is the same as the solvent A, wherein the volume ratio of the solvent B to the solvent A is 1:(2.5-5).

10. The preparation method according to claim 8, characterized in that The concentration of the alkenyl compound in the solvent B is 0.2-0.5 mmol / mL.

11. The preparation method according to claim 3, characterized in that The temperature of the synthesis reaction is -10°C to 0°C or 66°C to 72°C; the time of the synthesis reaction is 2-8 hours.

12. The preparation method according to claim 11, characterized in that The synthesis reaction time is 3-6 hours.

13. Use of the sulfonic acid monomer according to claim 1 or 2 in oilfield additives.

14. A copolymer, characterized in that The copolymer contains structural units derived from the sulfonic acid monomer according to claim 1 or 2.

15. The copolymer according to claim 14, characterized in that The copolymer further comprises structural units derived from one or more monomers selected from the group consisting of acrylamide, N-isopropylacrylamide, vinylpyrrolidone, acrylic acid, sodium acrylate, acrylonitrile, 2-acrylamido-2-methylpropanesulfonic acid, dimethyldiallylammonium chloride, and gamma-methacryloyloxypropyltrimethoxysilane.

16. Use of the copolymer according to claim 14 or 15 as a fluid loss reducer.

17. A drilling fluid comprising the copolymer according to claim 14 or 15.

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