Surfactant as well as preparation method and application thereof

Abstract

The invention relates to the technical field of petroleum additives, in particular to a surfactant as well as a preparation method and application thereof. The structure of the surfactant is # imgabs0 #, and in the formula, T is selected from bicycloalkane or polycycloalkane; r and R0 are the same or different and are independently selected from H or C1-C6 alkyl groups; r1, R2, R3, R4 and R5 are the same or different and are respectively and independently selected from H and substituted or unsubstituted sulfonic acid groups; t is a natural number from 0 to 9; the surfactant takes a bicyclic or polycyclic naphthenic base group as a hydrophobic group, a hydrophobic association polymer can be prepared through a soap-free emulsion polymerization method, the molecular weight is adjustable and controllable, the hydrophobic association effect is outstanding, the post-treatment process is simple, and industrial production is facilitated.

Description

Technical Field

[0001] The present invention relates to the technical field of petroleum additives, and particularly relates to a surfactant, a preparation method thereof and an application thereof. Background Art

[0002] Hydrophobically associating polymers refer to water-soluble polymers in which a small amount of hydrophobic groups are introduced into the hydrophilic macromolecular chains of the polymers. In an aqueous solution, the hydrophobic groups on the molecular chains of hydrophobically associating polymers aggregate with each other, and their behavior is similar to the clustering of organic small molecules, except that this clustering is restricted by the molecular chains dissolved in water, and this aggregation is called hydrophobic association. Compared with water-soluble polymers, hydrophobically associating polymers have special rheological properties. In a dilute solution, the concentration of the polymer is less than the critical association concentration, and the molecular chains in the solution are mainly intramolecularly associated, and the macromolecular chains curl up, and the hydrodynamic system decreases; when the concentration of the polymer is higher than the critical association concentration, the molecular chains in the solution are mainly intermolecularly associated, and the macromolecular chains stretch, forming a physical crosslinked network structure inside the solution, the hydrodynamic volume increases, and the solution viscosity increases sharply. Generally, the increase of the temperature of the solution salinity promotes the hydrophobic association, and the shear action can destroy the crosslinked network structure formed inside the solution due to the hydrophobic association, resulting in the decrease of the solution viscosity, but after the shear action disappears, the crosslinked network structure inside the solution will be formed again and the viscosity will recover. In the field of drilling fluids, hydrophobically associating polymers can be used as viscosifiers, filtration loss reducers, and coating agents.

[0003] At present, there are mainly two ways to prepare hydrophobically associating polymers: one is the copolymerization method of water-soluble monomers and hydrophobic monomers, and the other is the emulsion polymerization method with the participation of surfactants. When using the copolymerization method, if water is used as the solvent, due to the poor water solubility of hydrophobic monomers, the copolymerization reaction in aqueous solution is essentially a heterogeneous reaction process, and the synthesized product is a copolymer with a low content of hydrophobic monomer units, and does not have significant hydrophobic association behavior. Using organic solvents or mixed solvents instead of water as the solvent can effectively solve the problem of immiscibility between hydrophobic monomers and hydrophilic monomers, but as the polymerization reaction proceeds, the polymer product will continuously precipitate from the solvent, resulting in a low molecular weight of the product. In addition, most of these products are random copolymers, that is, no hydrophobic blocks are formed in the molecular chain, resulting in insignificant hydrophobic association effects. To effectively utilize the performance characteristics of hydrophobically associating polymers, the micellar polymerization method emerged, that is, by adding surfactants in water, making hydrophobic monomers dissolve in the micelles formed by surfactants, and then copolymerizing with hydrophilic monomers dissolved in water. However, this preparation method has the technical defect of complex post-treatment process. Against this background, the soap-free emulsion polymerization method is widely recommended because of its high introduction degree of hydrophobic monomers, long hydrophobic blocks, significant product association effects, and simple post-treatment process. However, the hydrophobic monomers used in this polymerization method must have certain surface activity in addition to polymerizable reaction groups (generally referring to double bonds). Generally, reactive surfactants can be divided into cationic, anionic, non-ionic, and zwitterionic types, with cationic surfactants being the most common. For example, as early as 1996, the article "Study on Soap-Free Cationic Emulsion of Styrene-Butyl Acrylate-(Dimethylbutyl) Methacryloyloxyethyl Ammonium Bromide" published in the journal "Journal of Hubei University (Natural Science Edition)" reported the preparation of hydrophobically associating polymers using reactive surfactants. Chinese patent document CN103342778B reported a cationic hydrophobic monomer DMABA, which is also a cationic reactive surfactant, and used this agent to carry out soap-free emulsion polymerization with acrylamide (AM) and acrylic acid (AA) to obtain a class of hydrophobically associating amphoteric flocculants with excellent salt tolerance. Chinese patent document CN103275270B introduced a fluorocarbon / hydrocarbon mixed cationic surfactant, and used this monomer to carry out soap-free polymerization reaction with AM to obtain a hydrophobically associating polymer with excellent temperature resistance, viscosity increase, and shear resistance. Of course, there are also reports on other types of reactive surfactants. For example, Chinese patent document CN104140507B introduced a non-ionic reactive surfactant - dodecyl polyoxyethylene ether methacrylate, and used this monomer to carry out soap-free emulsion polymerization with AM and methacryloyloxyethyl-N,N-dimethylpropylsulfonate to obtain a class of hydrophobically associating polymers with excellent salt tolerance.

[0004] Currently, the hydrophobic groups of reactive surfactants mainly consist of long hydrocarbon chains and long fluorocarbon chains. There are also occasional literature reports on using benzene rings as hydrophobic groups, but there are few related studies on using bicyclic or polycyclic cycloalkyl groups with larger non-polar regions and stronger rigidity as hydrophobic groups. Summary of the Invention

[0005] In view of the problems in the prior art, the present invention provides a reactive surfactant. Using this surfactant, a hydrophobically associating polymer is prepared based on the soap-free emulsion polymerization method. In particular, a hydrophobically associating polymer type treatment agent for drilling fluids can be prepared using this type of surfactant, including viscosifiers, filtration loss reducers, coating agents, etc.

[0006] The present invention provides a reactive surfactant with a bicyclic or polycyclic cycloalkyl alkyl structure as the hydrophobic group, and this surfactant can be used to carry out polymerization reactions with conventional water-soluble monomers or hydrophobic monomers, thereby obtaining polymer products with significant hydrophobically associating effects.

[0007] To solve the above technical problems, in the first aspect, the present invention provides a surfactant having the structure shown in formula (I):

[0008]

[0009] In formula (I), T is selected from bicyclic alkanes or polycyclic alkanes; R and R0 are the same or different and are each independently selected from H or C1-C6 alkyl; R1, R2, R3, R4, and R5 are the same or different and are each independently selected from H, substituted or unsubstituted sulfonic acid groups;

[0010] t is a natural number from 0 to 9.

[0011] According to some embodiments of the present invention, in formula (I), T is selected from

[0012] R and R0 are the same or different and are each independently selected from H, -CH3, -C2H5, -CH2CH2CH3, or -CH(CH3)2; R1, R2, R3, R4, and R5 are the same or different and are each independently selected from H, -SO3H, -SO3Na, or -SO3K;

[0013] t is 0, 1, or 2.

[0014] According to specific embodiments of the present invention, the surfactant is selected from the following compounds:

[0015]

[0016]

[0017]

[0018]

[0019] The second aspect of the present invention provides a method for preparing the above surfactant, which includes carrying out a synthesis reaction on the cycloalkyl compound represented by formula (II) and the phenylsulfonic acid compound represented by formula (III) in the presence of a catalyst to obtain a surfactant having the structure represented by formula (I);

[0020]

[0021] According to some embodiments of the present invention, the catalyst is selected from at least one of low-valent titanium reagents, low-valent tungsten reagents, low-valent molybdenum reagents, low-valent zirconium reagents, low-valent vanadium reagents, and low-valent niobium reagents; preferably, the catalyst is selected from low-valent titanium reagents; further preferably, the molar ratio of the cycloalkyl compound represented by formula (II) to titanium in the low-valent titanium reagent is 1:(1-6), such as 1:1.67, 1:2.5, 1:2.9, 1:4, 1:5, 1:6.

[0022] The low-valent titanium reagents, low-valent tungsten reagents, low-valent molybdenum reagents, low-valent zirconium reagents, low-valent vanadium reagents, and low-valent niobium reagents selected as the catalysts in the present invention can be substances obtained by methods well known in the art, taking the preparation of low-valent titanium reagents as an example.

[0023] According to a preferred embodiment of the present invention, the catalyst is a low-valent titanium reagent.

[0024] According to a preferred embodiment of the present invention, for example, the preparation method of the low-valent titanium reagent includes: dissolving a titanium-containing reagent and a reducing agent in a solvent (hereinafter referred to as solvent A) and carrying out a reduction reaction.

[0025] Preferably, the preparation method of the low-valent titanium reagent further includes: the reduction reaction is carried out under a protective atmosphere, wherein the protective atmosphere is nitrogen and / or argon.

[0026] According to the present invention, the titanium-containing reagent is selected from at least one of TiCl3 and TiCl4; the reducing agent is selected from at least one of K, Li, Na, Zn+CuCl, LiAlH4, Mg, Mg+Hg, Li+Hg, and chlorosilane. The valence state of the low-valent titanium reagent 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.

[0027] According to the present invention, solvent A is tetrahydrofuran (THF) and / or dimethyl ether (DME).

[0028] According to a preferred embodiment of the present invention, the titanium-containing reagent is TiCl4; the reducing agent is Zn and CuCl; the solvent A is one of THF and DME.

[0029] Preferably, the concentration of TiCl4 in the solvent A is 0.2 - 0.5 mmol / mL, such as 0.2 mmol / mL, 0.3 mmol / mL, 0.35 mmol / mL, 0.4 mmol / mL, 0.42 mmol / mL, 0.5 mmol / mL, the concentration of Zn in the solvent A is 0.3 - 0.6 mmol / mL, such as 0.3 mmol / mL, 0.36 mmol / mL, 0.4 mmol / mL, 0.5 mmol / mL, 0.6 mmol / mL, and the concentration of CuCl in the solvent A is 0.04 - 0.08 mmol / mL, such as 0.04 mmol / mL, 0.05 mmol / mL, 0.06 mmol / mL, 0.07 mmol / mL, 0.075 mmol / mL, 0.08 mmol / mL.

[0030] According to a specific embodiment of the present invention, the preparation method of the low-valent titanium reagent further specifically includes: adding activated Zn, CuCl and the solvent A into a reactor, then cooling and stirring, and then adding TiCl4, and performing the reduction reaction in a reflux manner to obtain the low-valent titanium reagent.

[0031] According to a preferred embodiment of the present invention, when the solvent A is THF, the reflux temperature is 68 - 78 °C, and it is necessary to cool again after reflux; when the solvent A is DME, no heating is required for reflux, that is, reflux is carried out at the cooling temperature in the previous step.

[0032] Preferably, the particle size of the Zn is greater than 400 mesh, more preferably 400 - 800 mesh, such as 400 mesh, 500 mesh, 600 mesh, 700 mesh, 800 mesh.

[0033] Preferably, the cooling temperature is -10 - 0 °C, such as -10 °C, -5 °C, -4 °C, -2 °C, 0 °C, and the reflux time is 2 - 5 h, such as 2 h, 2.5 h, 3 h, 3.5 h, 4 h, 4.5 h, 5 h.

[0034] According to some embodiments of the present invention, the molar ratio of the cycloalkyl compound represented by the formula (II) to the phenylsulfonic acid compound represented by the formula (III) is 1:(1.2 - 1.5), such as 1:1.2, 1:1.25, 1:1.3, 1:1.4, 1:1.429, 1:1.5.

[0035] According to some embodiments of the present invention, the conditions of the synthesis reaction include: the temperature is -10 to 78 °C, the time is 2 to 10 h, preferably 5 to 8 h.

[0036] According to some embodiments of the present invention, before the synthesis reaction, it further includes dissolving the cycloalkyl compound shown in formula (II) and the phenylsulfonic acid compound shown in formula (III) in a solvent (hereinafter referred to as solvent B); preferably, the solvent B is selected from at least one of THF and DME; further preferably, the concentration of the cycloalkyl compound shown in formula (II) in the solvent B is 0.2 to 0.8 mmol / mL.

[0037] In the present invention, when the solvent B is THF, the temperature of the synthesis reaction is 68 to 78 °C, such as 68 °C, 70 °C, 72 °C, 78 °C; when the solvent B is DME, the temperature of the synthesis reaction is -10 to 0 °C.

[0038] The preparation method of the surfactant provided in the present invention may further include quenching the reaction after the synthesis reaction proceeds to a certain extent. Since there are excess reactants in the synthesis reaction, when the reaction proceeds to a certain extent and the target product has been obtained, if the excess reactants continue to exist, they will further react to form undesired products. The principle of the quenching reaction is to react with another compound that is more likely to react with the excess compound, thereby removing it from the system.

[0039] In order to avoid impurities in the target product, the present invention preferably quenches the reaction after the synthesis reaction proceeds to a certain extent, that is, after the cycloalkyl compound reacts completely (after the synthesis reaction proceeds for 2 to 10 h, preferably 5 to 8 h).

[0040] The quenching reaction involved in the present invention is specifically to cool the system after the synthesis reaction is completed and then add a quenching reagent, add water for the first time and then add a 10 wt% NaOH solution, and then add water again.

[0041] The present invention has no particular limitation on the quenching reagent, and conventional quenching reagents can be selected, such as alkali metal cyanides, amides, boranes, K2CO3, LiAlH4, and NaBH. However, considering the stability of the product and the ease of treatment, the present invention preferably uses LiAlH4 as the quenching reagent.

[0042] According to the preferred embodiment of the present invention, the molar amount of LiAlH4 is 0.05% to 0.12% of the molar amount of the cycloalkyl compound.

[0043] According to a preferred embodiment of the present invention, the volume ratio of the first addition of water to the volume of solvent B is 1:(50 - 100), such as 1:50, 1:60, 1:62.5, 1:64, 1:70, 1:75, 1:80, 1:100, and the dropping rate is controlled at 2.0 - 4.0 mL / min, such as 2.0 mL / min, 2.5 mL / min, 3.0 mL / min, 3.5 mL / min, 4.0 mL / min.

[0044] According to a preferred embodiment of the present invention, the volume of the 10 wt% NaOH solution is the same as the volume of the first addition of water, and there is no limit to the addition rate. It can be added all at once or drop by drop.

[0045] According to a preferred embodiment of the present invention, the mass of the water added again is 3 times the mass of the water added for the first time, and there is no limit to the addition rate. It can be added all at once or drop by drop.

[0046] In order to obtain the purified product of the surfactant, the preparation method of the surfactant provided by the present invention may further include: after quenching the reaction, adding a desiccant to the system, filtering, rinsing, collecting the filtrate, and performing vacuum distillation to remove the solvent and the rinsing reagent to obtain the crude product of the surfactant; finally, performing recrystallization on the crude product to remove unreacted raw materials, by-products, and residual catalysts.

[0047] According to a preferred embodiment of the present invention, the present invention uses a desiccant for drying, and after filtering, performs vacuum distillation to remove the solvent to obtain a light yellow crude product.

[0048] According to a preferred embodiment of the present invention, the desiccant is preferably an inorganic neutral desiccant, such as one or more of MgSO4, Na2SO4, CaSO4, and CaCl2.

[0049] The present invention has no limitation on the filtration method, as long as it can filter out low-valent titanium. Conventional filter aids can be added, such as alumina filter aid, diatomaceous earth filter aid, charcoal powder filter aid, activated carbon filter aid, and perlite filter aid.

[0050] According to a preferred embodiment of the present invention, diatomaceous earth filtration is used.

[0051] In order to collect as much target product as possible, the present invention also preferably performs rinsing after filtering and collecting the filtrate. The rinsing solvent can be selected from conventional rinsing reagents. Preferably, it is rinsed with CH2Cl2. After rinsing, the rinsing liquid is mixed with the filtrate to obtain a mixed liquid, which is the crude product of the surfactant.

[0052] In order to obtain a surfactant with higher purity, the preparation method of the surfactant provided by the present invention further includes a deep purification operation, that is, recrystallization of the crude product of the surfactant.

[0053] According to a preferred embodiment of the present invention, after vacuum distillation, methanol or ethanol is added to the crude product of the surfactant, and after stirring evenly, the temperature is lowered, and then light yellow solids will precipitate. After filtration and rinsing with methanol or ethanol, the recrystallized surfactant is obtained.

[0054] The third aspect of the present invention provides an application of the above surfactant in the preparation of oilfield auxiliaries, preferably for the preparation of polymer treatment agents for drilling fluids, and more preferably for the preparation of hydrophobically associating polymer treatment agents.

[0055] The fourth aspect of the present invention provides a copolymer, and the comonomers of the copolymer include the above surfactant.

[0056] The present invention has no particular limitation on the type of the copolymer, and the copolymer is obtained by polymerizing the surfactant of the present invention alone or copolymerizing with other monomers.

[0057] Preferably, the other monomers may be selected from, but not limited to, one or more of acrylamide (AM), N-isopropylacrylamide (NIPAM), N,N'-methylenebisacrylamide (MBAA), N-vinylpyrrolidone (NVP), acrylic acid (AA), sodium acrylate (AAS), acrylonitrile (AN), sodium styrenesulfonate (SSS), 2-acrylamido-2-methylpropanesulfonic acid (AMPS), dimethyldiallylammonium chloride (DMDAAC), ethyl p-acetylbenzoate, dodecyl acrylate, and γ-methacryloxypropyltrimethoxysilane (KH570).

[0058] The present invention has no particular limitation on the polymerization method of the polymer. However, in combination with the preparation method of the surfactant, any one of bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, inverse emulsion polymerization, melt polymerization, and interfacial polymerization can be used.

[0059] According to a specific embodiment of the present invention, solution polymerization is preferably used. The present invention lists specific operations in the text, and those skilled in the art should not understand it as a limitation of the present invention.

[0060] The fifth aspect of the present invention provides an application of the above copolymer as a viscosifier, a fluid loss reducer, or a coating agent.

[0061] The sixth aspect of the present invention provides a drilling fluid, and the drilling fluid includes the above copolymer.

[0062] In the present invention, there is no particular limitation on the above-mentioned drilling fluid, and various drilling fluid systems known in the art can be used, such as bentonite drilling fluid system, potassium amine-based drilling fluid system, polymer strong inhibition drilling fluid system, polyalcohol drilling fluid system, sulfonated drilling fluid system, polysulfonated drilling fluid system, brine drilling fluid system, composite salt drilling fluid system, seawater drilling fluid system, calcium chloride drilling fluid system, solids-free drilling fluid system, oil-in-water drilling fluid system, and silicate drilling fluid system.

[0063] According to the specific embodiments of the present invention, the drilling fluid of the present invention can be bentonite drilling fluid or brine drilling fluid.

[0064] Preferably, additives are further contained in the water-based drilling fluid.

[0065] Preferably, the additives include bentonite and Na2CO3.

[0066] In the present invention, 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, based on the total amount of the drilling fluid, the content of the copolymer can be 0.2 wt% to 2.0 wt%.

[0067] In the present invention, there is no particular limitation on the preparation method of the drilling fluid, and the preparation methods well-known to those skilled in the art can be used. The present invention will not elaborate here. Specific operations are listed in the text, and those skilled in the art should not understand it as a limitation to the present invention.

[0068] Beneficial effects:

[0069] The present invention provides a surfactant, a polymer, and their preparation methods and applications. The surfactant uses a bicyclic or polycyclic cycloalkyl group as the hydrophobic group, and a hydrophobically associating polymer can be prepared by a soap-free emulsion polymerization method. The molecular weight can be adjusted and controlled, the hydrophobically associating effect is prominent, and the post-treatment process is simple, which is conducive to industrial production.

[0070] In the molecular structure of the surfactant of the present invention, the three-dimensional alkyl structure has high rigidity, which can increase the spatial volume and steric hindrance of the polymer molecular chain, reduce the thermal motion degree of the polymer molecules under high-temperature conditions, and is beneficial to improving the temperature resistance of the polymer molecules.

[0071] In the surfactant of the present invention, the P-π conjugation effect between the alkenyl group and the benzene ring disperses the electron cloud on the molecular double bond, makes the bond length tend to be averaged, increases the molecular refractive index, reduces the internal energy, makes the double bond easier to be opened, and increases the polymerization reaction activity. Description of the drawings

[0072] Figure 1 For the surfactant prepared in Example 1 of the present invention 1 1H NMR spectrum.

[0073] Figure 2 1H NMR spectrum of the surfactant prepared in Example 2 of the present invention 1 1H NMR spectrum

[0074] Figure 3 1H NMR spectrum of the surfactant prepared in Example 3 of the present invention 1 1H NMR spectrum

[0075] Figure 4 1H NMR spectrum of the surfactant prepared in Example 4 of the present invention 1 1H NMR spectrum

[0076] Figure 5 1H NMR spectrum of the surfactant prepared in Example 5 of the present invention 1 1H NMR spectrum

[0077] Figure 6 1H NMR spectrum of the surfactant prepared in Example 6 of the present invention 1 1H NMR spectrum Detailed implementation manners

[0078] The present invention will be further described below in conjunction with embodiments. However, the present invention is not limited by these embodiments.

[0079] Unless otherwise specified, the reactors, vacuum drying ovens, aging tanks, and Soxhlet extractors used in the embodiments of the present invention are all ordinary commercially available products.

[0080] Unless otherwise specified, the activated Zn powder, CuCl, DME, THF, TiCl4, 1-adamantanecarbaldehyde, 2-adamantanecarbaldehyde, 2-acetyladamantane, 1-acetyladamantane, norbornane-2-ethanone, norbornane-7-n-butyl ketone, 3-naphthalenecarbaldehyde, 2-propionylnaphthalane, 1-aldehydospiro[4,4]nonane, 5-propionylspiro[3,4]octane, 5-aldehydospiro[2,4]heptane, sodium benzenesulfonate-4-sulfonate, sodium benzenesulfonate-2,4,6-trisulfonate, potassium benzenesulfonate-3-sulfonate, potassium 1-methylpropionylbenzene-4-sulfonate, sodium 1-ethylacetylbenzene-4-sulfonate, 1-acetylbenzene-3,5-disulfonic acid, potassium 1-isobutyrylbenzene-2-sulfonate, 1-ethylacetylbenzene-3,5-disulfonic acid, sodium 1-methylpropionylbenzene-3-sulfonate, 1-acetylbenzene-2,4,6-trisulfonic acid, sodium benzenesulfonate-2-sulfonate, potassium benzenesulfonate-2,4-disulfonate, LiAlH4, 10wt% NaOH solution, anhydrous Na2SO4, MgSO4, CaCl2, CaSO4, CH2Cl2, methanol, ethanol, benzaldehyde, cyclohexanecarbaldehyde, lauraldehyde, sodium 1-acetylbenzene-4-sulfonate, sodium 1-butylacetylbenzene-4-sulfonate, sodium ethanesulfonate used in the embodiments of the present invention are all ordinary commercially available products.

[0081] In the embodiments of the present invention, sodium octadecyl sulfate and cetyltrimethylammonium bromide used are all ordinary commercially available products without special instructions.

[0082] The automatic surface tension measuring instrument used in the test examples of the present invention was purchased from Beijing Jinyang Wanda Technology Co., Ltd., model JY - BZY - 2.

[0083] In the embodiments of the present invention, without special instructions, the room temperature is 25 °C.

[0084] In the embodiments of the present invention, the yield calculation formula of the surfactant is: Wherein, R - the yield of the surfactant; H0 - the theoretical mass of the surfactant; H1 - the measured mass of the surfactant (the mass of the surfactant after recrystallization).

[0085] In the embodiments of the present invention, when performing NMR characterization on the prepared surfactant, specifically, the purified surfactant is dissolved in (CD3)2SO to prepare a 20% solution, which is introduced into a φ5 * 180 mm glass tube, and the height of the solution in the glass tube is 4 mm. The glass tube is capped and sealed with a wax film; then the glass tube is inserted into the rotor of a nuclear magnetic resonance spectrometer (model AVANCE III HD400MHz, purchased from Bruker, Switzerland), and then the rotor is placed in a depth - fixed measuring cylinder, and the rotor is in close contact with the mouth of the measuring cylinder; the experimental chamber is closed, and the nuclear magnetic resonance spectrometer is started for measurement.

[0086] Example 1

[0087] This example provides a surfactant.

[0088] (1) Preparation of the catalyst

[0089] 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 are added to a reactor, the temperature is controlled to - 5 °C, stirred, and 75.8716 g (400 mmol) of TiCl4 is added, and refluxed for 3 h at - 5 °C to obtain a low - valent titanium reagent, which is the catalyst.

[0090] (2) Preparation of the surfactant

[0091] 16.4248 g (100 mmol) of 1 - adamantanecarbaldehyde (T is 29.1428 g (140 mmol) of sodium benzaldehyde-4-sulfonate (R0, R1, R2, R4, and R5 are H, R3 is NaSO3, t = 0) (denoted as Y1) is dissolved in 250 mL of DME, mixed with the low-valent titanium reagent prepared in the above step (1), and refluxed at -5 °C for 7.5 h.

[0092] Then, 0.003 g (0.08 mmol) of LiAlH4 is added, 4 mL of water is added dropwise at a rate of 2.5 mL / min, 4 mL of 10 wt% NaOH solution is added, and then 12 mL of water is added again. An appropriate amount of anhydrous Na2SO4 is added to the above system (the amount of anhydrous Na2SO4 added as a desiccant is the sum of the amounts of water and NaOH solution added to quench the reaction. In this example, the amount of anhydrous Na2SO4 added is 4 + 4 + 12 = 20 g). After filtration through diatomaceous earth, the filtrate is collected, and then rinsed with CH2Cl2, and the filtrate is collected. The filtrate is distilled under reduced pressure to remove DME and CH2Cl2, obtaining 26.14 g of a pale yellow solid (denoted as M1).

[0093] 200 mL of methanol is added to the above pale yellow solid M1, and after stirring evenly, the temperature is lowered to -24 °C, and a pale yellow solid (denoted as M2) precipitates. After filtration, the pale yellow solid M2 is rinsed with methanol to obtain the purified surfactant (denoted as S1), with a yield of 52.28%.

[0094] The reaction path in the above step (2) is as follows:

[0095]

[0096] The surfactant S1 obtained in Example 1 is characterized by NMR [(CD3)2SO, 25 °C], and the nuclear magnetic resonance spectrum ( 1 1H NMR) is as Figure 1 ; According to 1 the 1H NMR analysis results, it is consistent with the molecular structure of the target product.

[0097] Example 2

[0098] This example provides a surfactant.

[0099] (1) Preparation of the catalyst

[0100] Under nitrogen protection, 26.152 g (400 mmol) of 800-mesh activated Zn powder, 4.95 g (50 mmol) of CuCl, and 1000 mL of THF are added to the reactor, cooled to -5 °C, stirred, 56.9037 g (300 mmol) of TiCl4 is added, and the temperature is raised to 72 °C and refluxed for 3 h, and then cooled to -5 °C again to obtain the low-valent titanium reagent, which is the catalyst.

[0101] (2) Preparation of surfactant

[0102] Add 19.7098 g (120 mmol) of 2-adamantanecarboxaldehyde (T is R is H) and 61.836 g (150 mmol) of sodium benzenesulfonate-2,4,6-trisulfonate (R0, R2 and R4 are H, R1, R3 and R5 are NaSO3, t = 0) (denoted as Y2) to 400 mL of THF, and mix them into the low-valent titanium reagent prepared in the above step (1). Heat the mixture to 72 °C under stirring conditions and reflux for 6 h.

[0103] Then add 0.0027 g (0.072 mmol) of LiAlH4, dropwise add 5 mL of water at a constant dropping rate of 3 mL / min, then add 5 mL of 10 wt% NaOH solution, and then add 15 mL of water again. Add sufficient MgSO4 to the above system, filter through diatomaceous earth, collect the filtrate, and then rinse with CH2Cl2 and collect the filtrate. Distill the filtrate under reduced pressure to remove THF and CH2Cl2, and 42.19 g of a pale yellow solid (denoted as M1) is obtained.

[0104] Add 200 mL of ethanol to the above pale yellow solid M1, stir evenly and cool to -32 °C, then a pale yellow solid (denoted as M2) precipitates. Filter and rinse the pale yellow solid M2 with ethanol to obtain the purified surfactant (denoted as S2) with a yield of 48.77%.

[0105] The reaction path in the above step (2) is as follows:

[0106]

[0107] Perform NMR characterization [(CD3)2SO, 25 °C] on the surfactant S2 obtained in Example 2. The nuclear magnetic resonance spectrum 1 (1H NMR) is as Figure 2 ; According to 1 the 1H NMR analysis results, it is consistent with the molecular structure of the target product.

[0108] Example 3

[0109] This example provides a surfactant.

[0110] (1) Preparation of catalyst

[0111] Under argon protection, 39.228 g (600 mmol) of 400-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. Then, 94.8395 g (500 mmol) of TiCl4 was added, and the mixture was refluxed at 0 °C for 2 h to obtain a low-valent titanium reagent, which was the catalyst.

[0112] (2) Preparation of surfactant

[0113] 17.8275 g (100 mmol) of 2-acetyladamantane (T is R is CH3) and 33.6407 g (150 mmol) of potassium benzaldehyde-3-sulfonate (R0, R1, R3, R4, and R5 are H, R2 is KSO3, t = 0) (denoted as Y3) were dissolved in 200 mL of DME, mixed into the low-valent titanium reagent prepared in the above step (1), and continued to reflux at 0 °C for 5 h.

[0114] Then, 0.0038 g (0.1 mmol) of LiAlH4 was added, 4 mL of water was added dropwise at a constant rate of 2 mL / min, 4 mL of 10 wt% NaOH solution was added, and then 12 mL of water was added again. Sufficient 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. The filtrate was distilled under reduced pressure to remove DME and CH2Cl2, and 27.13 g of a pale yellow solid (denoted as solid M1) was obtained.

[0115] 120 mL of ethanol was added to the above pale yellow solid M1, and after stirring evenly, the temperature was lowered to -24 °C, and a pale yellow solid (denoted as M2) precipitated. After filtration and rinsing the pale yellow solid M2 with ethanol, the purified surfactant (denoted as S3) was obtained, with a yield of 51.08%.

[0116] The reaction path in the above step (2) is as follows:

[0117]

[0118] The surfactant S3 obtained in Example 3 was characterized by NMR [(CD3)2SO, 25 °C], and the nuclear magnetic resonance spectrum 1 HNMR) was as Figure 3 ; According to 1 the H NMR analysis results, it was consistent with the molecular structure of the target product.

[0119] Example 4

[0120] This example provides a surfactant.

[0121] (1) Preparation of catalyst

[0122] Under argon protection, 19.614 g (300 mmol) of 500-mesh activated Zn powder, 7.92 g (80 mmol) of CuCl and 1000 mL of THF were added to a reactor, cooled to 0 °C, stirred, and 37.9358 g (200 mmol) of TiCl4 was added. The temperature was raised to 78 °C and refluxed for 2 h, and then cooled to 0 °C again to obtain a low-valent titanium reagent, which was the catalyst.

[0123] (2) Preparation of surfactant

[0124] 16.4248 g (100 mmol) of 1-adamantanecarbaldehyde (T is R is H) and 31.9623 g (120 mmol) of potassium 1-methylpropanoylbenzene-4-sulfonate (R0 is CH2CH3, R1, R2, R4 and R5 are H, R1, R3 are KSO3, t = 1) (denoted as Y4) in 500 mL of THF were mixed into the low-valent titanium reagent prepared in the above step (1), and the temperature was raised to 78 °C under stirring and refluxed for 5 h.

[0125] Then 0.0019 g (0.05 mmol) of LiAlH4 was added, 5 mL of water was added dropwise at a constant rate of 2.5 mL / min, 5 mL of 10 wt% NaOH solution was added, and then 15 mL of water was added again. Sufficient 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. The filtrate was distilled under reduced pressure to remove THF and CH2Cl2, and 31.16 g of a pale yellow solid (denoted as M1) was obtained.

[0126] 100 mL of methanol was added to the above pale yellow solid M1, and after stirring evenly, the temperature was lowered to -18 °C, and a pale yellow solid (denoted as M2) precipitated. After filtration and rinsing the pale yellow solid M2 with methanol, the purified surfactant (denoted as S4) was obtained, with a yield of 44.69%.

[0127] The reaction path in the above step (2) is as follows:

[0128]

[0129] The surfactant S4 obtained in Example 4 was characterized by NMR [(CD3)2SO, 25 °C], and the nuclear magnetic resonance spectrum ( 1 1H NMR) was as Figure 4 ; According to 1 the 1H NMR analysis results, it was consistent with the molecular structure of the target product.

[0130] Example 5

[0131] This example provides a surfactant.

[0132] (1) Preparation of catalyst

[0133] Under argon protection, 26.152 g (400 mmol) of 600-mesh activated Zn powder, 7.425 g (75 mmol) of CuCl and 1000 mL of DME were added to a reactor. The temperature was controlled to -10 °C, and the mixture was stirred. Then 66.3877 g (350 mmol) of TiCl4 was added, and the mixture was refluxed at -10 °C for 5 h to obtain a low-valent titanium reagent, which was the catalyst.

[0134] (2) Preparation of surfactant

[0135] 33.393 g (120 mmol) of 1-acetyladamantane (T is R is CH3) and 39.0396 g (156 mmol) of sodium 1-ethylacetylbenzene-4-sulfonate (R0 is CH3, R1, R2, R4 and R5 are H, R3 is NaSO3, t = 2) (denoted as Y5) were dissolved in 360 mL of DME and mixed into the low-valent titanium reagent prepared in the above step (1). The mixture was continuously refluxed at -10 °C for 5 h.

[0136] Then 0.0034 g (0.09 mmol) of LiAlH4 was added, and 6 mL of water was added dropwise at a constant rate of 3 mL / min. Then 6 mL of 10 wt% NaOH solution was added, and then 18 mL of water was added again. Sufficient Na2SO4 was added to the above system, and the mixture was filtered through diatomaceous earth. The filtrate was collected, and then rinsed with CH2Cl2, and the filtrate was collected again. The filtrate was distilled under reduced pressure to remove DME and CH2Cl2, and 36.51 g of a pale yellow solid (denoted as M1) was obtained.

[0137] 120 mL of methanol was added to the above pale yellow solid M1, and the mixture was stirred evenly and then cooled to -18 °C. Then a pale yellow solid (denoted as M2) precipitated out. The pale yellow solid M2 was filtered and rinsed with toluene to obtain a purified surfactant (denoted as S5), and the yield was 50.84%.

[0138] The reaction path in the above step (2) is as follows:

[0139]

[0140] The surfactant S5 obtained in Example 5 was characterized by NMR [(CD3)2SO, 25 °C], and the nuclear magnetic resonance spectrum ( 1 1H NMR) was as Figure 5 ; According to the 1 1H NMR analysis results, it was consistent with the molecular structure of the target product.

[0141] Example 6

[0142] This embodiment provides a surfactant.

[0143] (1) Preparation of catalyst

[0144] Under nitrogen protection, 39.228 g (600 mmol) of 400-mesh activated Zn powder, 6.93 g (70 mmol) of CuCl and 1000 mL of THF were added to a reactor, cooled to 0 °C and stirred. Then 79.6652 g (420 mmol) of TiCl4 was added, and the temperature was raised to 68 °C and refluxed for 5 h. Then it was cooled to 0 °C again to obtain a low-valent titanium reagent, which was the catalyst.

[0145] (2) Preparation of surfactant

[0146] 12.4793 g (70 mmol) of 2-acetyladamantane (T is R is CH3) and 28.0265 g (100 mmol) of 1-acetylbenzene-3,5-disulfonic acid (R0 is CH3, R1, R2, R4 and R5 are H, R3 is NaSO3, t = 0) (denoted as Y6) in 280 mL of THF were mixed into the low-valent titanium reagent prepared in the above step (1), and the temperature was raised to 68 °C under stirring and refluxed for 8 h.

[0147] Then 0.0016 g (0.042 mmol) of LiAlH4 was added, 4 mL of water was added dropwise at a constant rate of 2.5 mL / min, 4 mL of 10 wt% NaOH solution was added, and then 12 mL of water was added again. Sufficient anhydrous 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. The filtrate was distilled under reduced pressure to remove THF and CH2Cl2, and 23.27 g of a pale yellow solid (denoted as M1) was obtained.

[0148] 80 mL of ethanol was added to the above pale yellow solid M1, and after stirring evenly, the temperature was lowered to -24 °C, and a pale yellow solid (denoted as M2) precipitated. After filtration and rinsing the pale yellow solid M2 with ethanol, the purified surfactant (denoted as S6) was obtained, and the yield was 45.91%.

[0149] The reaction path in the above step (2) is as follows:

[0150]

[0151] The surfactant S6 obtained in Example 6 was characterized by NMR [(CD3)2SO, 25 °C], and the nuclear magnetic resonance spectrum 1 HNMR) was as Figure 6 ; According to 1 the H NMR analysis results, it was consistent with the molecular structure of the target product.

[0152] Example 7

[0153] This example provides a surfactant.

[0154] (1) Preparation of catalyst

[0155] Under nitrogen protection, 26.152 g (400 mmol) of 800-mesh activated Zn powder, 5.94 g (60 mmol) of CuCl and 1000 mL of DME were added to a reactor. The temperature was controlled to -2 °C, and the mixture was stirred. Then 75.8716 g (400 mmol) of TiCl4 was added, and the mixture was refluxed at -2 °C for 4 h to obtain a low-valent titanium reagent, which is the catalyst.

[0156] (2) Preparation of surfactant

[0157] 13.821 g (100 mmol) of norbornane-2-ethanone (T is R is CH3) and 39.9528 g (150 mmol) of 1-isobutyrylbenzene-2-sulfonate potassium (R0 is CH(CH3)2, R1, R3, R4 and R5 are H, R2 is KSO3, t = 0) (denoted as Y7) were dissolved in 450 mL of DME, and then mixed into the low-valent titanium reagent prepared in the above step (1). The mixture was continuously refluxed at -2 °C for 6 h.

[0158] Then 0.0043 g (0.1125 mmol) of LiAlH4 was added, and 6 mL of water was added dropwise at a constant rate of 3 mL / min. Then 6 mL of 10 wt% NaOH solution was added, and then 18 mL of water was added again. An appropriate amount of CaSO4 was added to the above system, and the mixture was filtered through diatomaceous earth. The filtrate was collected, and then rinsed with CH2Cl2, and the filtrate was collected again. The filtrate was distilled under reduced pressure to remove DME and CH2Cl2, and 28.22 g of a pale yellow solid (denoted as M1) was obtained.

[0159] 160 mL of ethanol was added to the above pale yellow solid M1. After stirring evenly, the temperature was lowered to -12 °C, and a pale yellow solid (denoted as M2) precipitated. The pale yellow solid M2 was filtered and rinsed with ethanol to obtain a purified surfactant (denoted as S7), and the yield was 41.75%.

[0160] The reaction path in the above step (2) is as follows:

[0161]

[0162] Example 8

[0163] This example provides a surfactant.

[0164] (1) Preparation of catalyst

[0165] Under argon protection, 23.5368 g (360 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 -4 °C, stirred, and 37.9358 g (200 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 reagent, which was the catalyst.

[0166] (2) Preparation of surfactant

[0167] 19.9517 g (120 mmol) of norbornane-7-n-butyl ketone (T is R is CH2CH2CH3) and 29.789 g (160 mmol) of benzaldehyde-4-sulfonic acid (R0, R1, R2, R4 and R5 are H, R3 is HSO3, t = 0) (denoted as Y8) in 320 mL of THF were mixed into the low-valent titanium reagent prepared in the above step (1), and the temperature was raised to 70 °C under stirring and refluxed for 8 h.

[0168] Then 0.0027 g (0.072 mmol) of LiAlH4 was added, 5 mL of water was added dropwise at a constant rate of 2.5 mL / min, 5 mL of 10 wt% NaOH solution was added, and then 15 mL 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. The filtrate was distilled under reduced pressure to remove THF and CH2Cl2, and 27.05 g of a pale yellow solid (denoted as M1) was obtained.

[0169] 100 mL of methanol was added to the above pale yellow solid M1, and after stirring evenly, the temperature was lowered to -16 °C, and a pale yellow solid (denoted as M2) precipitated. After filtration and rinsing the pale yellow solid M2 with methanol, the purified surfactant (denoted as S8) was obtained, and the yield was 46.17%.

[0170] The reaction path in the above step (2) is as follows:

[0171]

[0172] Example 9

[0173] This example provides a surfactant.

[0174] According to the method of Example 1, the difference is that 1-adamantanecarbaldehyde was replaced with 3-naphthalenecarbaldehyde in the same molar amount, and sodium benzaldehyde-4-sulfonate was replaced with 1-ethylacetylbenzene-3,5-disulfonic acid (denoted as Y9) in the same molar amount. Other conditions were the same as those in Example 1, and the target product was denoted as S9, and the yield was 42.94%.

[0175] Example 10

[0176] This example provides a surfactant.

[0177] According to the method of Example 2, the difference is that 2-adamantanecarboxaldehyde is replaced with 2-propionylnaphthalane in the same molar amount, and sodium benzenesulfonate-2,4,6-trisulfonate is replaced with sodium 1-methylpropanoylbenzene-3-sulfonate (denoted as Y10) in the same molar amount. Other conditions are the same as those in Example 1, and the target product is denoted as S10, with a yield of 44.51%.

[0178] Example 11

[0179] This example provides a surfactant.

[0180] According to the method of Example 1, the difference is that 1-adamantanecarboxaldehyde is replaced with 1-formylspiro[4.4]nonane in the same molar amount, and sodium benzenesulfonate-4-sulfonate is replaced with sodium 1-acetylbenzene-2,4,6-trisulfonate (denoted as Y11) in the same molar amount. The target product is denoted as S11, with a yield of 40.75%.

[0181] Example 12

[0182] This example provides a surfactant.

[0183] According to the method of Example 2, the difference is that 2-adamantanecarboxaldehyde is replaced with 5-propionylspiro[3.4]octane in the same molar amount, and sodium benzenesulfonate-2,4,6-trisulfonate is replaced with sodium benzenesulfonate-2-sulfonate (denoted as Y12) in the same molar amount. The target product is denoted as S12, with a yield of 42.76%.

[0184] Example 13

[0185] This example provides a surfactant.

[0186] According to the method of Example 2, the difference is that 2-adamantanecarboxaldehyde is replaced with 5-formylspiro[2.4]heptane in the same molar amount, and sodium benzenesulfonate-2,4,6-trisulfonate is replaced with potassium benzenesulfonate-2,4-disulfonate (denoted as Y13) in the same molar amount. Other conditions are the same as those in Example 2, and the target product is denoted as S13, with a yield of 41.71%.

[0187] Comparative Example 1

[0188] This comparative example provides a surfactant.

[0189] According to the method of Example 1, the difference is that 1-adamantanecarboxaldehyde is replaced with benzaldehyde in the same molar amount. Other conditions are the same as those in Example 1, and the target product is denoted as SY1, with a yield of 57.91%.

[0190] Comparative Example 2

[0191] This comparative example provides a surfactant.

[0192] According to the method of Example 1, except that 1-adamantanecarboxaldehyde was replaced with cyclohexylcarboxaldehyde in an equimolar amount, and other conditions were the same as those in Example 1, the target product was designated as SY2, and the yield was 48.63%.

[0193] Comparative Example 3

[0194] This comparative example provides a surfactant.

[0195] According to the method of Example 1, except that 1-adamantanecarboxaldehyde was replaced with lauryl aldehyde in an equimolar amount, and other conditions were the same as those in Example 1, the target product was designated as SY3, and the yield was 52.68%.

[0196] Comparative Example 4

[0197] This comparative example provides a surfactant.

[0198] According to the method of Example 5, except that sodium 1-ethylacetylbenzene-4-sulfonate was replaced with sodium 1-acetylbenzene-4-sulfonate in an equimolar amount, and other conditions were the same as those in Example 5, the target product was designated as SY4, and the yield was 47.36%.

[0199] Comparative Example 5

[0200] This comparative example provides a surfactant.

[0201] According to the method of Example 5, except that sodium 1-ethylacetylbenzene-4-sulfonate was replaced with sodium 1-butylacetylbenzene-4-sulfonate in an equimolar amount, and other conditions were the same as those in Example 5, the target product was designated as SY5, and the yield was 42.67%.

[0202] Comparative Example 6

[0203] This comparative example provides a surfactant.

[0204] According to the method of Example 5, except that sodium 1-ethylacetylbenzene-4-sulfonate was replaced with sodium ethanesulfonate in an equimolar amount, and other conditions were the same as those in Example 5, the target product was designated as SY6, and the yield was 40.53%.

[0205] Test Example 1

[0206] Surface activity evaluation: Quantitatively dissolve the surfactants S1-S13 prepared in Examples 1-13 of the present invention, the surfactants SY1-SY6 prepared in Comparative Examples 1-6, commercially available sodium octadecyl sulfate, and cetyltrimethylammonium bromide in deionized water respectively to prepare a series of solutions with different concentrations (0.1 mol / L, 0.01 mol / L, 0.001 mol / L, 0.0001 mol / L, and 0.00001 mol / L). At room temperature, using the platinum ring method, measure their surface tension (γ) with the help of a fully automatic surface tension measuring instrument, measure it 3 times in parallel, and take the average value; draw a γ-lgC curve graph, and the concentration corresponding to the turning point of the data curve is the critical micelle concentration (CMC). The measurement results are shown in Table 1.

[0207] Table 1 Surface activity measurement results

[0208] Test sample CMC (mmol / L) <![CDATA[γ cmc (mN·m -1 )]]> S1 0.771 31.25 S2 0.766 31.00 S3 0.770 31.17 S4 0.751 30.00 S5 0.762 30.65 S6 0.784 31.83 S7 0.655 30.00 S8 0.666 30.14 S9 0.719 32.07 S10 0.725 31.28 S11 0.613 31.83 S12 0.620 29.31 S13 0.608 29.20 SY1 0.810 36.16 SY2 0.821 36.91 SY3 0.857 38.75 SY4 0.752 31.14 SY5 0.739 31.00 SY6 0.904 37.29 Sodium octadecyl sulfate 1.114 41.95 Cetyl trimethyl ammonium bromide 0.992 40.76

[0209] As can be seen from Table 1, the γ values of the surfactants S1-S13 prepared in Examples 1-13 of the present invention and the surfactants SY1-SY6 prepared in Comparative Examples 1-6 cmc are all relatively small, and the surface tension is significantly lower than that of conventional surfactants (commercially available sodium octadecyl sulfate and cetyltrimethylammonium bromide). cmc Compared with the surfactants SY1-SY3 prepared in Comparative Examples 1-3 of the present invention, the surfactants S1-S13 prepared in Examples 1-13 of the present invention have a lower CMC, indicating that the hydrophobic groups in the molecules of the surfactants S1-S13 prepared in Examples 1-13 of the present invention have stronger hydrophobicity and stronger surface activity.

[0210] Test Example 2

[0211] Determination of reactivity ratios: Add 500 mL of water, 28.43 g (0.4 mol) of acrylamide (AM), and 6.81 g (0.02 mol) of the surfactant S1 prepared in Example 1 of the present invention to a reactor equipped with a mechanical stirring device, stir well to obtain a light yellow clear and transparent solution, pass N2 for 30 min, heat up to 45 °C, and add 0.4 g of (NH4)2S2O8. After about 3 min, it is found that the reaction solution begins to become turbid, and after about 30 min, it is found that the reaction solution begins to become viscous, and the longer the reaction time, the higher the viscosity, and at the same time, a small amount of foam is generated. After the reaction proceeds for 4 h, put the reaction system into 1000 mL of absolute ethanol, wash the product with acetone 3 times successively, and then use a Soxhlet extractor to extract the product with an ice acetic acid-ethylene glycol mixed solvent with a volume ratio of 3:2 for 24 h, and vacuum dry it to constant weight at 25 °C, crush and encapsulate it. The target product is denoted as C1.

[0212] According to the method of Test Example 2, the difference is that S1 is replaced with SY4 of the same molar amount, and other conditions are the same as those in Test Example 2. The target product is denoted as C2.

[0213] According to the method of Test Example 2, the difference is that S1 is replaced with SY5 of the same molar amount, and other conditions are the same as those in Test Example 2. The target product is denoted as C3.

[0214] According to the method of Test Example 2, the difference is that S1 is replaced with SY6 of the same molar amount, and other conditions are the same as those in Test Example 2. The target product is denoted as C4.

[0215] Using (CD3)2SO as the solvent, the 1H nuclear magnetic resonance spectra ( 1 1H NMR) of C1 - C4 were measured. In 1 1H NMR, according to the ratio of the proton peak area on the amide group in the AM structural unit to the proton peak area on the benzene ring in the structural units of S1, SY4, SY5, and SY6 respectively, the ratio of the two unit structures in the polymers (C1 - C4) was indirectly calculated. The reactivity ratios of each group of monomers were calculated using the forward and reverse Fineman - Ross method. Among them, the test method for the reactivity ratios refers to

Li Qiulian, Ding Yaqin, Zhou Jinlan, etc. Design and Practice of the Experiment for Determining the Reactivity Ratios of Copolymerization Monomers [J]. Polymer Bulletin, 2019, 11, 69 - 72.

[0216] Table 2 Test Results of Monomer Reactivity Ratios

[0217]

[0218]

[0219] It can be seen from the results in Table 2 that the reactivity ratio of SY4 is the highest, followed by the reactivity ratios of S1, SY5, and SY6 respectively, indicating that the stronger the conjugation effect, the higher the reactivity ratio.

[0220] Test Example 3

[0221] Thermal resistance test: 50.55 g (0.5 mol) of N - hydroxymethylacrylamide, 21.62 g (0.15 mol) of sodium allylsulfonate, 12.91 g (0.15 mol) of methacrylic acid, 10.21 g (0.03 mol) of the surfactant S1 prepared in Example 1 of the present invention, and 500 mL of distilled water were successively added to the reactor, stirred well, and nitrogen was introduced for 30 min to remove the dissolved oxygen in the reaction system. The water bath was heated to the predetermined temperature of 50 °C, 1.25 g of (NH4)2S2O8 was added, and the reaction was carried out for 4 h under continuous stirring to obtain a light - yellow transparent colloidal crude product. The crude product was precipitated and purified with absolute ethanol and dried to a constant weight in a vacuum drying oven at 30 °C to obtain a viscosifier for solid - free drilling fluid, denoted as Z0.

[0222] According to the method of Test Example 3, the difference is that S1 is replaced with SY1 of the same molar amount, and other conditions are the same as those in Test Example 3. The target product is denoted as Z1.

[0223] According to the method of Test Example 3, the difference is that S1 is replaced with SY2 of the same molar amount, and other conditions are the same as those in Test Example 3. The target product is denoted as Z2.

[0224] According to the method of Test Example 3, the difference is that S1 is replaced with SY3 of the same molar amount, and other conditions are the same as those in Test Example 3. The target product is denoted as Z3.

[0225] Dissolve Z0 to Z3 in water respectively to prepare a solution with a mass percentage concentration of 2.0%. Add iron ore powder to simulate the cuttings entering the solids-free drilling fluid in the formation, and adjust the density to 2.00 g / cm 3 , put it into an aging tank, age for 16 h at different temperatures, cool to room temperature, put it into a graduated cylinder and let it stand for 12 h. Select the drilling fluid above the upper one-fifth and below the lower one-fifth, and measure their densities ρ 上层 , ρ 下层 , and calculate the density difference △ρ. The experimental results are shown in Table 3.

[0226] Table 3 Influence of thickeners Z0 to Z3 on the suspension stability of iron ore powder

[0227]

[0228] It can be seen from the results in Table 3 that at the same aging temperature, the △ρ of Z0 is the smallest, indicating excellent suspension stability; when the aging temperature is increased from 140 °C to 160 °C, the △ρ of Z0 is still the smallest, indicating that Z0 has better temperature resistance compared to Z1 to Z3.

[0229] It should be noted that the above-described embodiments are only used to explain the present invention and do not constitute any limitation to the present invention. The present invention has been described by referring to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory words rather than limiting words. Modifications can be made to the present invention within the scope of the claims of the present invention as stipulated, and the present invention can be revised without departing from the scope and spirit of the present invention. Although the present invention described therein relates to specific methods, materials and embodiments, it does not mean that the present invention is limited to the specific examples disclosed therein. On the contrary, the present invention can be extended to all other methods and applications with the same functions.

Claims

1. A surfactant, characterized in that, The surfactant has the structure shown in formula (I): In formula (I), T is selected from bicycloalkanes or polycycloalkanes; R and R0 are the same or different and are each independently selected from H or C1-C6 alkyl; R1, R2, R3, R4, and R5 are the same or different and are each independently selected from H, substituted or unsubstituted sulfonic acid groups; t is a natural number from 0 to 9.

2. The surfactant according to claim 1, characterized in that, In formula (I), T is selected from R and R0 are the same or different and are each independently selected from H, -CH3, -C2H5, -CH2CH2CH3, or -CH(CH3)2; R1, R2, R3, R4, and R5 are the same or different and are each independently selected from H, -SO3H, -SO3Na, or -SO3K; t is 0, 1, or 2.

3. A method for preparing the surfactant according to claim 1 or 2, characterized in that, It includes carrying out a synthesis reaction on the cycloalkyl compound shown in formula (II) and the phenylsulfonic acid compound shown in formula (III) in the presence of a catalyst to obtain a surfactant having the structure shown in formula (I); 4. The preparation method according to claim 3, characterized in that, The catalyst is selected from at least one of low-valent titanium reagents, low-valent tungsten reagents, low-valent molybdenum reagents, low-valent zirconium reagents, low-valent vanadium reagents, and low-valent niobium reagents; preferably, the catalyst is selected from low-valent titanium reagents; further preferably, the molar ratio of the cycloalkyl compound shown in formula (II) to titanium in the low-valent titanium reagent is 1:(1-6); and / or, the molar ratio of the cycloalkyl compound shown in formula (II) to the phenylsulfonic acid compound shown in formula (III) is 1:(1.2-1.5).

5. The preparation method according to claim 3 or 4, characterized in that, The conditions of the synthesis reaction include: the temperature is -10 to 78 °C, and the time is 2 to 10 h, preferably 5 to 8 h.

6. The preparation method according to any one of claims 3-5, characterized in that, Before the synthesis reaction, it also includes dissolving the cycloalkyl compound shown in formula (II) and the phenylsulfonic acid compound shown in formula (III) in a solvent; preferably, the solvent is selected from at least one of tetrahydrofuran and dimethyl ether; further preferably, the concentration of the cycloalkyl compound shown in formula (II) in the solvent is 0.2 to 0.8 mmol / mL.

7. Use of the surfactant according to claim 1 or 2 or the surfactant prepared by the preparation method according to any one of claims 3-6 in the preparation of oilfield additives, preferably for the preparation of polymer treatment agents for drilling fluids, and further preferably for the preparation of hydrophobically associating polymer treatment agents.

8. A copolymer, characterized in that, The comonomer of the copolymer includes the surfactant according to claim 1 or 2 or the surfactant prepared by the preparation method according to any one of claims 3-6.

9. Use of the copolymer according to claim 8 as a viscosifier, a fluid loss reducer, or a coating agent.

10. A drilling fluid, characterized in that, The drilling fluid includes the copolymer according to claim 8.

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