Amphiphilic polymer as well as preparation method and application thereof

Abstract

The invention discloses an amphiphilic polymer, relates to the technical field of reservoir fracturing and extraction integrated transformation in the petroleum industry, and in particular relates to an amphiphilic polymer as well as a preparation method and application thereof. The preparation raw materials of the amphiphilic polymer comprise acrylamide or a derivative thereof, a hydrophobic monomer, a cationic monomer, an amphoteric active monomer and an initiator. The hydrophobic monomer is prepared from the following raw materials: chlorinated olefin, N-dimethylalkylamine or N, N-dimethylalkylamine; the preparation raw materials of the cationic monomer comprise amino amide containing double bonds and alkyl bromide; the preparation raw materials of the amphoteric active monomer comprise long-chain fatty acid, amine or alcohol amine; the amphiphilic polymer and the fracturing fluid have a synergistic effect, and the properties of oil and gas replacement, extraction efficiency and the like can be improved.

Description

Technical Field

[0001] The invention relates to the technical field of integrated transformation of reservoir fracturing and extraction in the petroleum industry, and in particular to an amphiphilic polymer and a preparation method and application thereof. Background Art

[0002] During oilfield development, the interfaces of the reservoir include three interfaces: displacement fluid-crude oil, displacement fluid-rock, and crude oil-rock. The properties of the reservoir interface have a great influence on the recovery rate of the reservoir. At present, it is generally believed that changing the wettability of the reservoir can also significantly improve the recovery rate of the reservoir. Wettability is a basic parameter of reservoir physical properties and has a great influence on crude oil recovery. Therefore, how to effectively change the wettability of the reservoir to improve the recovery rate becomes crucial. The change in wettability induced by surfactants has a great influence on the relative permeability of the oil-water phase, the distribution of residual oil, the law of oil-water seepage, and the water drive recovery rate.

[0003] Hu Jun, Jin Cheng, Shi Leiting, et al. Surfactant polymer oil displacement agent for medium and low permeability oil reservoirs [J]. Fine Chemicals: 1-15. A low molecular weight surfactant polymer (PAS) was prepared by aqueous solution free radical polymerization using surfactant monomers N-(hexadecyl)-N-(sulfo)acrylamide and acrylamide as raw materials. It has good viscosity enhancement, emulsification and oil displacement properties, can be used in the fracturing and oil displacement process of medium and low permeability tight oil reservoirs, improve the production efficiency of medium and low permeability tight oil reservoirs, and has good practical application value.

[0004] Chinese patent CN116254101A discloses a polymer-surfactant flooding composition and its preparation method and application method, including a polymer and a surfactant. The polymer-surfactant flooding composition has high interfacial activity and can reach 10 under alkali-free and high mineralization conditions. -3 The advantage of ultra-low interfacial tension of mN / m can improve the oil recovery rate.

[0005] Wang Huan, Liu Jie, Zhang Yusong, et al. Study on the Characterization of an Amphiphilic Polymer [J]. Contemporary Chemical Industry, 2023, 52(02): 302-306. This prior art successfully prepared a new type of oil displacement agent, hydrophilic and lipophilic functional amphiphilic polymer, which can be used as a polymer flooding agent by changing the molecular structure design and grafting a special lipophilic functional monomer group. The amphiphilic polymer has obvious high-efficiency viscosity increasing, dispersibility and emulsification, easy demulsification, deep profile control, etc. It can effectively prevent the increase of divalent iron ion content in the reinjection water after carbon dioxide injection from causing the viscosity reduction effect of polymer injection during the third recovery; it has obvious water reduction and oil increase effect. The use of this product after polymer flooding can increase the recovery rate by more than 10%. It can be applied to polymer flooding, binary system and ordinary heavy oil blocks, with good application prospects and wide promotion significance.

[0006] Gong Jun, Wei Min, Li Bingxian, Hao Minghui, Ye Junhong. Preparation and application of surfactant oil displacement agent suitable for high-temperature and high-salinity carbonate reservoirs [J]. Chemical Research and Application, 2023, 35(02): 470-476. The existing technology uses long-chain alkyl tertiary amine (carbon chain length is 10), epichlorohydrin and chlorosulfonic acid as the main synthetic raw materials to develop a new zwitterionic Gemini surfactant oil displacement agent (GFSS-3) suitable for high-temperature and high-salinity carbonate reservoirs. The oil displacement agent has good interfacial activity, temperature and salt resistance, wetting reversal performance and anti-adsorption performance; when its mass concentration is 0.2%, at a temperature of 120°C and a mineralization of 25.35×10 4 After aging for 30 days at 400 mg / L, the oil-water interfacial tension value can still reach 8.9×10 -3 mN / m; it can effectively improve the surface wettability of carbonate rocks; after adsorption in core powder for 5 times, the oil-water interfacial tension value can still reach 9.2×10 -3 mN / m; GFSS-3 also has a good oil displacement effect and can further increase the recovery rate after water flooding by more than 15%.

[0007] At present, under the condition of certain reservoir properties and fracturing technology, in order to further improve the recovery rate of ultra-low and ultra-low permeability reservoirs and shale reservoirs, it is necessary to use fracturing fluid to supplement energy, improve seepage, prevent scaling, and improve water injection efficiency. Furthermore, it is necessary to work on fluid dynamics to improve oil seepage efficiency, improve oil and water migration capacity, and allow crude oil to fully enter the main fracture channel to improve single well productivity and achieve the purpose of increasing production. In other words, an important factor that determines the development efficiency of ultra-low and ultra-low permeability reservoirs such as shale oil is the oil and water permeability, which plays a decisive role in oil well productivity.

[0008] Therefore, it is urgent to carry out research on key materials for improving oil recovery by using high-efficiency amphiphilic polymers, and to cooperate with fracturing fluids to improve oil and gas replacement and recovery efficiency, and to make full use of the effect of fracturing fluids in the formation to achieve economical and efficient development of shale oil reservoirs. At the same time, it can be promoted and used in fracturing and recovery of tight oil and gas and coalbed methane, and has good application prospects. Summary of the invention

[0009] The present invention aims to solve the problems in the prior art that the recovery rate of ultra-low and ultra-low permeability oil reservoirs and shale oil reservoirs is low, and the oil-water absorption capacity of the existing fracturing fluid used for the recovery of ultra-low and ultra-low permeability oil reservoirs and shale oil reservoirs is poor. The present invention provides an amphiphilic polymer, which has a synergistic effect with the fracturing fluid and can improve the performance of oil and gas replacement and recovery efficiency.

[0010] In order to solve the above technical problems, the first aspect of the present invention provides an amphiphilic polymer, which is a polymerization product of four monomers: acrylamide or its derivatives, a hydrophobic monomer, a cationic monomer, and an amphoteric active monomer; the raw materials for preparing the hydrophobic monomer include chlorinated olefins, N-dimethylalkylamine or N,N-dimethylalkylamine; the raw materials for preparing the cationic monomer include aminoamides containing double bonds and brominated alkanes; the raw materials for preparing the amphoteric active monomer include long-chain fatty acids, amines or alcoholamines.

[0011] According to some embodiments of the present invention, the mass ratio of acrylamide or its derivative, hydrophobic monomer, cationic monomer and amphoteric active monomer is 1: (0.5-0.8): (0.2-0.5): (1.2-1.8), preferably 1: 0.7: 0.3: 1.5.

[0012] According to some embodiments of the present invention, the molar ratio of N-dimethylalkylamine or N,N-dimethylalkylamine to chlorinated olefin is 1:(0.8-1.5), preferably 1:1.2.

[0013] According to some embodiments of the present invention, the molar ratio of the aminoamide containing a double bond to the brominated alkane is 1:(0.6-1.2), preferably 1:0.8.

[0014] According to some embodiments of the present invention, the molar ratio of the long-chain fatty acid to the amine or alcoholamine is 1:(0.3-0.8), preferably 1:0.5.

[0015] According to some embodiments of the present invention, the acrylamide derivative is selected from alkyl acrylamide; preferably, the alkyl acrylamide is selected from at least one of octadecyl acrylamide, N-dodecyl acrylamide and N,N-tetradecyl acrylamide.

[0016] According to some embodiments of the present invention, the chlorinated olefin is selected from at least one of 4-chloro-1-butene, 1,4-dichloro-2-butene, and allyl chloride.

[0017] According to some embodiments of the present invention, the N,N-dimethylalkylamine is selected from at least one of N,N-dimethyldodecylamine, N,N-dimethyltetradecylamine, N,N-dimethylhexadecylamine, and N,N-dimethyloctadecylamine; the N-dimethylalkylamine is selected from at least one of N-dimethyldodecylamine, N-dimethyltetradecylamine, N-dimethylhexadecylamine, and N-dimethyloctadecylamine.

[0018] According to some embodiments of the present invention, the double bond-containing aminoamide is selected from at least one of dimethylaminopropyl methacrylamide, dimethylaminoethyl methacrylate, and N-(dimethylaminopropyl) methacrylamide.

[0019] According to some embodiments of the present invention, the brominated alkane is selected from at least one of dodecane bromide, tetradecane bromide, hexadecane bromide, octadecane bromide, and eicosane bromide.

[0020] According to some embodiments of the present invention, the long-chain fatty acid is selected from C12 to C18 fatty acids; preferably, the C12 to C18 fatty acids are selected from at least one of dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), and octadecanoic acid (stearic acid).

[0021] According to some embodiments of the present invention, the amine is selected from at least one of triethylamine and trimethylamine; the alcoholamine is selected from at least one of triethanolamine, dimethylethanolamine and methyldiethanolamine.

[0022] According to some embodiments of the present invention, the method for preparing the hydrophobic monomer comprises: preparing a chlorinated olefin solution, an N-dimethylalkylamine solution or an N,N-dimethylalkylamine solution respectively, adding the N-dimethylalkylamine solution or the N,N-dimethylalkylamine solution dropwise to the chlorinated olefin solution, and reacting to obtain a hydrophobic monomer;

[0023] Preferably, an equal amount of solvent I is added to the chlorinated olefin solution, N-dimethylalkylamine solution or N,N-dimethylalkylamine solution; the solvent I is selected from at least one of anhydrous ethanol, acetone, carbon tetrachloride, ether and chloroform; further preferably, the molar concentration of the chlorinated olefin solution is 8 mol / L to 15 mol / L, preferably 10 mol / L; further preferably, the speed of adding I is 2 seconds / drop to 5 seconds / drop, preferably 3 seconds / drop; further preferably, the conditions of the reaction I include: reaction temperature of 45°C to 65°C, preferably 55°C, reaction time of 4h to 8h, preferably 6h; stirring rate of 200r / min to 400r / min.

[0024] In the preparation process of the hydrophobic monomer of the present invention, after the reaction I is completed, it is naturally cooled to room temperature, and then unreacted chloroolefin, N-dimethylalkylamine or N,N-dimethylalkylamine is washed with excess acetone, and after suction filtration, the filter cake is vacuum dried at room temperature to obtain the hydrophobic monomer.

[0025] In the preparation process of the hydrophobic monomer of the present invention, the path of reaction I is as follows:

[0026]

[0027] According to some embodiments of the present invention, the method for preparing the cationic monomer comprises: preparing an aminoamide solution containing a double bond and a brominated alkane solution respectively, and adding the brominated alkane solution dropwise II to the aminoamide solution containing a double bond under an inactive atmosphere I, and performing a reaction II to obtain the cationic monomer;

[0028] Preferably, an equal amount of solvent II is added to the aminoamide solution containing double bonds and the bromoalkane solution; the solvent II is selected from at least one of anhydrous acetone, ethanol, carbon tetrachloride, ether, and chloroform; further preferably, the molar concentration of the aminoamide solution containing double bonds is 4 mol / L to 10 mol / L, preferably 6 mol / L; further preferably, the speed of adding II is 2 seconds / drop to 5 seconds / drop, preferably 3 seconds / drop; further preferably, the conditions of the reaction II include: the reaction temperature is 20°C to 40°C, preferably 30°C, the reaction time is 18h to 24h, preferably 20h; the stirring rate is 200r / min to 400r / min; the inactive atmosphere I is selected from nitrogen or carbon dioxide.

[0029] In the preparation process of the cationic monomer of the present invention, after reaction II is completed, the reaction mixture is placed in a refrigerator (2°C to 8°C) for 3h to 5h. After a light yellow solid is precipitated, the solid is washed with acetone 2 to 3 times to remove unreacted aminoamide and brominated alkane containing double bonds, and then filtered and vacuum dried at room temperature for 12h to 20h, preferably 16h, to obtain a cationic monomer.

[0030] In the preparation process of the hydrophobic monomer of the present invention, the path of reaction II is as follows:

[0031]

[0032] According to some embodiments of the present invention, the method for preparing the amphoteric active monomer comprises:

[0033] a. Prepare a long-chain fatty acid solution with a molar concentration of 2 mol / L to 5 mol / L, preferably 3 mol / L, then add triethylamine, heat to the reaction temperature, add bromine as a brominating agent, then dropwise add III chlorosulfonic acid solution, and react III to obtain an amphoteric active monomer;

[0034] b. preparing an allylamine solution with a molar concentration of 3 mol / L to 8 mol / L, preferably 5 mol / L, and then adding the amphoteric active monomer precursor prepared in step a to react IV in the presence of a catalyst to obtain an amphoteric active monomer;

[0035] Preferably, in step a, the molar ratio of the long-chain fatty acid to bromine is 1:(0.1-0.5), preferably 1:0.3; the molar ratio of the long-chain fatty acid to chlorosulfonic acid is 1:(0.1-0.3), preferably 1:0.2; in the chlorosulfonic acid solution, the ratio of chlorosulfonic acid to solvent III is 0.2-0.5 mol:25 mL, preferably 0.3 mol:25 mL; further preferably, in the long-chain fatty acid solution and the chlorosulfonic acid solution, the solvent III is the same and is selected from at least one of chloroform, acetone, ethanol, ether, and N,N-dimethylformamide; further preferably, the speed of adding III is 3 seconds / drop to 8 seconds / drop, preferably 5 seconds / drop; further preferably, the conditions of the reaction III include: the reaction temperature is 75°C to 95°C, preferably 80°C, the reaction time is 2h to 5h, preferably 3h; the stirring rate is 200r / min to 400r / min.

[0036] In the preparation process of the amphoteric active monomer precursor of the present invention, after reaction III is completed, the reaction mixture is naturally cooled to room temperature, and then unreacted long-chain fatty acids, triethylamine and bromine are washed away with excess chloroform. After filtration, the reaction mixture is vacuum dried at room temperature to obtain the amphoteric active monomer precursor.

[0037] In the preparation process of the amphoteric active monomer precursor of the present invention, the path of reaction III is as follows:

[0038]

[0039] Preferably, in step b, the molar ratio of the amphoteric active monomer precursor to allylamine is 1:(0.8-1.2), preferably 1:1; the catalyst is N-methylmorpholine and 2-(7-azobenzotriazole)-N,N,N',N'-tetramethyluronium hexafluorophosphate; further preferably, the molar ratio of N-methylmorpholine to allylamine is 1:(0.02-0.08), preferably 1:0.05; the molar ratio of 2-(7-azobenzotriazole)-N,N,N',N'-tetramethyluronium hexafluorophosphate to allylamine is 1:(0.2-0.3), preferably 1:0.25; further preferably, the conditions of reaction IV include: reaction temperature of 50°C to 60°C, preferably 55°C, reaction time of 2h to 5h, preferably 3h; stirring rate of 200r / min to 400r / min.

[0040] In the preparation process of the amphoteric active monomer of the present invention, after reaction IV is completed, the mixture is naturally cooled to room temperature, washed with ethanol 2 to 3 times, filtered and vacuum dried at room temperature to obtain the amphoteric active monomer.

[0041] In the preparation process of the amphoteric active monomer of the present invention, the path of reaction IV is as follows:

[0042]

[0043] The second aspect of the present invention provides a method for preparing the above-mentioned amphiphilic polymer, comprising the following steps:

[0044] 1) preparing a solution containing four monomers;

[0045] 2) In the presence of an inert atmosphere II and an initiator, a reducing agent is added to polymerize the solution containing the four monomers obtained in step 1) to obtain the amphiphilic polymer.

[0046] According to some embodiments of the present invention, in step 1), the solvent IV in the solution containing four monomers is distilled water.

[0047] According to some embodiments of the present invention, in step 1), the mass fraction of the four monomers in the solution containing the four monomers is 25% to 40%, preferably 30%.

[0048] According to some embodiments of the present invention, in step 1), the pH value of the solution containing the four monomers is adjusted to 6.0-7.0; wherein the pH adjuster used is acrylic acid or sodium hydroxide.

[0049] According to some embodiments of the present invention, in step 2), the inert atmosphere II is selected from nitrogen or carbon dioxide.

[0050] According to some embodiments of the present invention, in step 2), the mass of the initiator is 0.2% to 0.5%, preferably 0.3%, of the total mass of the four monomers.

[0051] According to some embodiments of the present invention, in step 2), the initiator is selected from at least one of ammonium persulfate, potassium persulfate, and benzoyl peroxide.

[0052] According to some embodiments of the present invention, in step 2), before adding the reducing agent, the solution containing the four monomers is heated to 20°C to 30°C, preferably to 25°C; preferably, the amount of the reducing agent added is 0.1% to 0.3% of the total mass of the acrylamide or its derivative, the hydrophobic monomer, the cationic monomer and the amphoteric active monomer; further preferably, the reducing agent is selected from sodium bisulfite.

[0053] According to some embodiments of the present invention, after the polymerization reaction, the temperature is kept at 40° C. to 60° C. for 1 h to 3 h, preferably, at 50° C. for 2 h.

[0054] According to some embodiments of the present invention, the amphiphilic polymer also includes purification; the purification process is: after the insulation is completed, the heating is stopped, and a crude product is obtained after filtration; the crude product is then transferred to a single-necked flask, anhydrous ethanol is added, shaken, the unreacted raw materials are dissolved in anhydrous ethanol, and then filtered to obtain a precipitate; after repeating the washing 2 to 3 times, a product with higher purity is obtained; finally, the product is transferred to a watch glass, and vacuum dried at a temperature of 40°C to 50°C for 5h to 8h to obtain the amphiphilic polymer product.

[0055] In the preparation process of the amphiphilic polymer of the present invention, the polymerization reaction path is as follows:

[0056]

[0057] The third aspect of the present invention provides a fracturing fluid, comprising the above-mentioned amphiphilic polymer; preferably, in the fracturing fluid, based on 100% water, the amount of the amphiphilic polymer added is 0.1 wt% to 0.7 wt%.

[0058] A fourth aspect of the present invention provides a use of the above-mentioned amphiphilic polymer in fracturing fluid.

[0059] Beneficial effects:

[0060] The invention uses acrylamide or its derivatives, hydrophobic monomers, cationic monomers, amphoteric active monomers and initiators to prepare amphiphilic polymers, wherein acrylamide is low in price and suitable for the main body, the hydrophobic monomer provides hydrophobic properties, the cationic monomer can provide surface activity, reduce surface tension, and improve the recovery effect, and the amphoteric active monomer provides emulsification ability and strengthens the oil stripping effect; the amphiphilic polymer cooperates with the fracturing fluid, can be adsorbed on the rock surface, improves the wettability of the rock surface, and promotes the desorption and stripping of crude oil from the rock surface (cationic monomer); in addition, the surfactant has amphiphilic properties, can form an adsorption film on the surface of the oil droplet, promotes the oil-water emulsification effect (amphiphilic monomer), enables the oil to be discharged with the flowback fluid, can significantly reduce the surface tension and interfacial tension of the fracturing fluid, and improves the imbibition recovery rate of the fracturing fluid. DETAILED DESCRIPTION

[0061] The present invention will be further described below in conjunction with the embodiments, but the present invention is not limited by these embodiments.

[0062] The three-necked flask, the single-necked flask, the feeding funnel and the heat-collecting magnetic heating and stirring water bath pot in the present invention are all common commercially available products.

[0063] The N-dimethyloctadecylamine in the present invention was purchased from Aladdin Biochemical Technology Co., Ltd. and was analytically pure.

[0064] The N-dimethyldodecylamine in the present invention was purchased from Aladdin Biochemical Technology Co., Ltd. and was analytically pure.

[0065] The dodecane bromide in the present invention was purchased from Aladdin Biochemical Technology Co., Ltd. and was analytically pure.

[0066] The hexadecane bromide in the present invention was purchased from Aladdin Biochemical Technology Co., Ltd. and was analytically pure.

[0067] The octadecane bromide in the present invention was purchased from Aladdin Biochemical Technology Co., Ltd. and was analytically pure.

[0068] The dimethylaminopropyl methacrylamide in the present invention was purchased from Aladdin Biochemical Technology Co., Ltd. and was analytically pure.

[0069] The hexadecanoic acid in the present invention was purchased from Aladdin Biochemical Technology Co., Ltd. and was analytically pure.

[0070] The dodecanoic acid in the present invention was purchased from Aladdin Biochemical Technology Co., Ltd. and was analytically pure.

[0071] The octadecanoic acid in the present invention was purchased from Aladdin Biochemical Technology Co., Ltd. and was analytically pure.

[0072] The N-methylmorpholine in the present invention was purchased from Aladdin Biochemical Technology Co., Ltd. and was analytically pure.

[0073] In the present invention, 2-(7-azobenzotriazole)-N,N,N',N'-tetramethyluronium hexafluorophosphate was purchased from Aladdin Biochemical Technology Co., Ltd. and was analytically pure.

[0074] The alkyl acrylamide in the present invention was purchased from Aladdin Biochemical Technology Co., Ltd. and was analytically pure.

[0075] Example 1

[0076] The preparation of the hydrophobic monomer in this embodiment is as follows:

[0077] 4-chloro-1-butene and 200 mL of ethanol were added to a three-necked flask 1 to prepare a 4-chloro-1-butene solution with a molar concentration of 10 mol / L; then the three-necked flask 1 was installed in a heat-collecting magnetic heating stirring water bath, stirred at a rate of 300 r / min, and heated to a set temperature of 55° C.; N-dimethylalkylamine was dissolved in an equal amount of ethanol to obtain an N-dimethylalkylamine solution, and after the temperature of the 4-chloro-1-butene solution in the three-necked flask 1 reached the set temperature of 55° C., the N-dimethylalkylamine solution was added dropwise to the three-necked flask 1 using a feeding funnel, and the dropping speed was controlled at 3 seconds / drop; after the dropwise addition was completed, the product solution 1 was reacted within the set temperature range for 6 hours to obtain a product solution 1; and after the reaction was completed, the product solution 1 was naturally cooled to 25° C., and then the unreacted monomer was washed with excess acetone, and after suction filtration, it was vacuum dried at room temperature to obtain a hydrophobic monomer.

[0078] In the preparation process of the hydrophobic monomer, the N-dimethylalkylamine is selected from N-dimethyloctadecylamine, and the molar ratio of N-dimethylalkylamine to 4-chloro-1-butene is 1:1.2.

[0079] The preparation of the cationic monomer in this embodiment is as follows:

[0080] Add dimethylaminopropyl methacrylamide and 500mL acetone to three-necked flask 2 to prepare a dimethylaminopropyl methacrylamide solution with a molar concentration of 6 mol / L; then wrap the three-necked flask 2 with light-proof tin foil, install it in a heat-collecting magnetic heating stirring water bath, introduce nitrogen protection, stir at a rate of 300r / min and heat to a set temperature of 30°C; take another bromoalkane and dissolve it in an equal amount of acetone to obtain a bromoalkane solution; wait for the dimethylaminopropyl methacrylamide in the three-necked flask 2 to After the solution temperature reaches the set temperature of 30°C, the brominated alkane solution is added dropwise into the three-necked flask 2 using a feeding funnel, and the dropping speed is controlled at 3 seconds / drop; after the dropwise addition is completed, the product solution 2 is obtained after reacting in the set temperature range for 20 hours, and after the reaction is completed, the three-necked flask 2 containing the product solution 2 is placed in a refrigerator at a temperature of 6°C for 4 hours. After a light yellow solid is precipitated, it is washed with acetone for 2 to 3 times to remove unreacted monomers, and filtered, and vacuum dried at room temperature for 16 hours to obtain a cationic monomer.

[0081] In the preparation process of the cationic monomer, the brominated alkane is selected from dodecane bromide; the molar ratio of the dimethylaminopropyl methacrylamide to dodecane bromide is 1:0.8.

[0082] The preparation of the amphoteric active monomer in this embodiment is as follows:

[0083] a. Add long-chain fatty acids and 500 mL of chloroform to a three-necked flask 3 to prepare a long-chain fatty acid solution with a molar concentration of 3 mol / L. After adding triethylamine, install the three-necked flask 3 in a heat-collecting magnetic heating stirring water bath, stir and heat to a set temperature of 80°C at a rate of 200 r / min, and after the temperature of the long-chain fatty acid solution in the three-necked flask 3 reaches 80°C, add bromine and stir evenly; separately take chlorosulfonic acid, dissolve it in chloroform (wherein, 0.3 mol of chlorosulfonic acid is dissolved in 25 mL of chloroform) to obtain a chlorosulfonic acid solution, and then use a feeding funnel to dropwise add the chlorosulfonic acid solution to the three-necked flask 3, and the dropping speed is controlled at 5 seconds / drop; after the dropwise addition is completed, react within the set temperature range for 3 h to obtain a product solution 3, and after the reaction is completed, the product solution 3 is naturally cooled to room temperature, and then the unreacted monomer and bromine are washed away with excess chloroform, and after suction filtration, vacuum drying is performed at room temperature to obtain an amphoteric active monomer precursor.

[0084] b. Add allylamine and 100 mL of ethanol to a three-necked flask 4 to prepare an allylamine solution with a molar concentration of 5 mol / L, and then add the amphoteric active monomer precursor obtained in step a; then add N-methylmorpholine (NMM) and 2-(7-azobenzotriazole)-N,N,N',N'-tetramethyluronium hexafluorophosphate (HATU) as catalysts; then install the three-necked flask 4 in a heat-collecting magnetic heating stirring water bath, stir and heat to a set temperature of 55° C. at a rate of 200 r / min, and react within the target temperature range for 3 hours to obtain a product solution 4. Finally, after the reaction is completed, the product solution 4 is naturally cooled to room temperature, washed with ethanol 2 to 3 times, filtered, and vacuum dried at room temperature to obtain an amphoteric active monomer.

[0085] In the preparation process of the above-mentioned amphoteric active monomer, the long-chain fatty acid is selected from hexadecanoic acid; the molar ratio of the long-chain fatty acid to triethylamine is 1:0.5; the molar ratio of the long-chain fatty acid to bromine is 1:0.3; the molar ratio of the long-chain fatty acid to chlorosulfonic acid is 1:0.2; the molar ratio of the amphoteric active monomer precursor to allylamine is 1:1; the molar ratio of N-methylmorpholine to allylamine is 1:0.05; the molar ratio of 2-(7-azobenzotriazole)-N,N,N',N'-tetramethyluronium hexafluorophosphate to allylamine is 1:0.25.

[0086] This embodiment further provides an amphiphilic polymer.

[0087] The preparation method is as follows:

[0088] Add distilled water and alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer into a three-necked flask 5 to prepare a solution with a mass fraction of 30% of alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer; then install the three-necked flask 5 in a heat-collecting magnetic heating stirring water bath, introduce nitrogen for protection, adjust the pH value of the solution (colorimetric card) to between 6.0 and 7.0 with sodium hydroxide, add ammonium persulfate, stir at a rate of 200 r / min and heat to a set temperature of 25° C., then turn off the heating. , sodium bisulfite is added to initiate the polymerization reaction. When the reaction temperature no longer continues to rise, the polymerization reaction is completed, and the heating is turned on again to maintain the temperature at 50°C. After keeping warm for 2 hours, the heating is stopped and the crude product is obtained by filtration. The crude product is then transferred to a single-necked flask, anhydrous ethanol is added, shaken to dissolve the unreacted raw materials in anhydrous ethanol, and then filtered to obtain a precipitate. After repeated washing 2 to 3 times, a product with higher purity is obtained. Finally, the product is transferred to a watch glass and vacuum dried at 45°C for 6 hours to obtain the amphiphilic polymer.

[0089] In the above, the mass ratio of alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer is 1:0.7:0.3:1.5; the mass of the ammonium persulfate is 0.3% of the total mass of the alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer; the mass of the sodium bisulfite is 0.2% of the total mass of the alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer.

[0090] Example 2

[0091] The preparation of the hydrophobic monomer in this embodiment is as follows:

[0092] Different from Example 1, during the preparation of the hydrophobic monomer, the N-dimethylalkylamine is selected from N-dimethyloctadecylamine.

[0093] The preparation of the cationic monomer in this embodiment is as follows:

[0094] Different from Example 1, during the preparation of the cationic monomer, the brominated alkane is selected from hexadecane bromide.

[0095] The preparation of the amphoteric active monomer in this embodiment is as follows:

[0096] Different from Example 1, during the preparation of the amphoteric active monomer, the long-chain fatty acid is selected from hexadecanoic acid.

[0097] This embodiment further provides an amphiphilic polymer.

[0098] The preparation method is as follows:

[0099] Add distilled water and alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer into a three-necked flask 5 to prepare a solution with a mass fraction of 30% of alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer; then install the three-necked flask 5 in a heat-collecting magnetic heating stirring water bath, introduce nitrogen for protection, adjust the pH value of the solution (colorimetric card) to between 6.0 and 7.0 with sodium hydroxide, add ammonium persulfate, stir at a rate of 200 r / min and heat to a set temperature of 25° C., then turn off the heating. , sodium bisulfite is added to initiate the polymerization reaction. When the reaction temperature no longer continues to rise, the polymerization reaction is completed, and the heating is turned on again to maintain the temperature at 50°C. After keeping warm for 2 hours, the heating is stopped and the crude product is obtained by filtration. The crude product is then transferred to a single-necked flask, anhydrous ethanol is added, shaken to dissolve the unreacted raw materials in anhydrous ethanol, and then filtered to obtain a precipitate. After repeated washing 2 to 3 times, a product with higher purity is obtained. Finally, the product is transferred to a watch glass and vacuum dried at 45°C for 6 hours to obtain the amphiphilic polymer.

[0100] In the above, the mass ratio of alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer is 1:0.7:0.3:1.5; the mass of the ammonium persulfate is 0.3% of the total mass of the alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer; the mass of the sodium bisulfite is 0.2% of the total mass of the alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer.

[0101] Example 3

[0102] The preparation of the hydrophobic monomer in this embodiment is as follows:

[0103] Different from Example 1, during the preparation of the hydrophobic monomer, the N-dimethylalkylamine is selected from N-dimethyloctadecylamine.

[0104] The preparation of the cationic monomer in this embodiment is as follows:

[0105] The difference from Example 1 is that during the preparation of the cationic monomer, the brominated alkane is selected from brominated dodecane.

[0106] The preparation of the amphoteric active monomer in this embodiment is as follows:

[0107] Different from Example 1, during the preparation of the amphoteric active monomer, the long-chain fatty acid is selected from dodecanoic acid.

[0108] This embodiment further provides an amphiphilic polymer.

[0109] The preparation method is as follows:

[0110] Add distilled water and alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer into a three-necked flask 5 to prepare a solution with a mass fraction of 30% of alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer; then install the three-necked flask 5 in a heat-collecting magnetic heating stirring water bath, introduce nitrogen for protection, adjust the pH value of the solution (colorimetric card) to between 6.0 and 7.0 with acrylic acid, add ammonium persulfate, stir at a rate of 200 r / min and heat to a set temperature of 25° C., then turn off the heating, Sodium bisulfite is added to initiate the polymerization reaction. When the reaction temperature no longer continues to rise, the polymerization reaction is completed, and the heating is turned on again to maintain the temperature at 50°C. After keeping warm for 2 hours, the heating is stopped and a crude product is obtained by filtration. The crude product is then transferred to a single-necked flask, anhydrous ethanol is added, shaken to dissolve the unreacted raw materials in the anhydrous ethanol, and then filtered to obtain a precipitate. After repeated washing 2 to 3 times, a product with higher purity is obtained. Finally, the product is transferred to a watch glass and vacuum dried at a temperature of 45°C for 6 hours to obtain the amphiphilic polymer.

[0111] In the above, the mass ratio of alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer is 1:0.7:0.3:1.5; the mass of the ammonium persulfate is 0.3% of the total mass of the alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer; the mass of the sodium bisulfite is 0.2% of the total mass of the alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer.

[0112] Example 4

[0113] The preparation of the hydrophobic monomer in this embodiment is as follows:

[0114] Different from Example 1, during the preparation of the hydrophobic monomer, the N-dimethylalkylamine is selected from N-dimethyldodecylamine.

[0115] The preparation of the cationic monomer in this embodiment is as follows:

[0116] The difference from Example 1 is that during the preparation of the cationic monomer, the brominated alkane is selected from brominated dodecane.

[0117] The preparation of the amphoteric active monomer in this embodiment is as follows:

[0118] Different from Example 1, during the preparation of the amphoteric active monomer, the long-chain fatty acid is selected from hexadecanoic acid.

[0119] This embodiment further provides an amphiphilic polymer.

[0120] The preparation method is as follows:

[0121] Add distilled water and alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer into a three-necked flask 5 to prepare a solution with a mass fraction of 30% of alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer; then install the three-necked flask 5 in a heat-collecting magnetic heating stirring water bath, introduce nitrogen for protection, adjust the pH value of the solution (colorimetric card) to between 6.0 and 7.0 with sodium hydroxide, add ammonium persulfate, stir at a rate of 200 r / min and heat to a set temperature of 25° C., then turn off the heating. , sodium bisulfite is added to initiate the polymerization reaction. When the reaction temperature no longer continues to rise, the polymerization reaction is completed, and the heating is turned on again to maintain the temperature at 50°C. After keeping warm for 2 hours, the heating is stopped and the crude product is obtained by filtration. The crude product is then transferred to a single-necked flask, anhydrous ethanol is added, shaken to dissolve the unreacted raw materials in anhydrous ethanol, and then filtered to obtain a precipitate. After repeated washing 2 to 3 times, a product with higher purity is obtained. Finally, the product is transferred to a watch glass and vacuum dried at 45°C for 6 hours to obtain the amphiphilic polymer.

[0122] In the above, the mass ratio of alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer is 1:0.7:0.3:1.5; the mass of the ammonium persulfate is 0.3% of the total mass of the alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer; the mass of the sodium bisulfite is 0.2% of the total mass of the alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer.

[0123] Example 5

[0124] The preparation of the hydrophobic monomer in this embodiment is as follows:

[0125] Same as Example 1.

[0126] The preparation of the cationic monomer in this embodiment is as follows:

[0127] Same as Example 1.

[0128] The preparation of the amphoteric active monomer in this embodiment is as follows:

[0129] Same as Example 1.

[0130] This embodiment further provides an amphiphilic polymer.

[0131] The preparation method is as follows:

[0132] Add distilled water and alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer into a three-necked flask 5 to prepare a solution with a mass fraction of 30% of alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer; then install the three-necked flask 5 in a heat-collecting magnetic heating stirring water bath, introduce nitrogen for protection, adjust the pH value of the solution (colorimetric card) to between 6.0 and 7.0 with sodium hydroxide, add ammonium persulfate, stir at a rate of 200 r / min and heat to a set temperature of 25° C., then turn off the heating. , sodium bisulfite is added to initiate the polymerization reaction. When the reaction temperature no longer continues to rise, the polymerization reaction is completed, and the heating is turned on again to maintain the temperature at 50°C. After keeping warm for 2 hours, the heating is stopped and the crude product is obtained by filtration. The crude product is then transferred to a single-necked flask, anhydrous ethanol is added, shaken to dissolve the unreacted raw materials in anhydrous ethanol, and then filtered to obtain a precipitate. After repeated washing 2 to 3 times, a product with higher purity is obtained. Finally, the product is transferred to a watch glass and vacuum dried at 45°C for 6 hours to obtain the amphiphilic polymer.

[0133] In the above, the mass ratio of alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer is 1:0.5:0.5:1.5; the mass of the ammonium persulfate is 0.3% of the total mass of the alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer; the mass of the sodium bisulfite is 0.2% of the total mass of the alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer.

[0134] Example 6

[0135] The preparation of the hydrophobic monomer in this embodiment is as follows:

[0136] Different from Example 1, during the preparation of the hydrophobic monomer, the N-dimethylalkylamine is selected from N-dimethyldodecylamine.

[0137] The preparation of the cationic monomer in this embodiment is as follows:

[0138] The difference from Example 1 is that during the preparation of the cationic monomer, the brominated alkane is selected from brominated dodecane.

[0139] The preparation of the amphoteric active monomer in this embodiment is as follows:

[0140] Different from Example 1, during the preparation of the amphoteric active monomer, the long-chain fatty acid is selected from dodecanoic acid.

[0141] This embodiment further provides an amphiphilic polymer.

[0142] The preparation method is as follows:

[0143] Add distilled water and alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer into a three-necked flask 5 to prepare a solution with a mass fraction of 30% of alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer; then install the three-necked flask 5 in a heat-collecting magnetic heating stirring water bath, introduce nitrogen for protection, adjust the pH value of the solution (colorimetric card) to between 6.0 and 7.0 with acrylic acid, add ammonium persulfate, stir at a rate of 200 r / min and heat to a set temperature of 25° C., then turn off the heating, Sodium bisulfite is added to initiate the polymerization reaction. When the reaction temperature no longer continues to rise, the polymerization reaction is completed, and the heating is turned on again to maintain the temperature at 50°C. After keeping warm for 2 hours, the heating is stopped and a crude product is obtained by filtration. The crude product is then transferred to a single-necked flask, anhydrous ethanol is added, shaken to dissolve the unreacted raw materials in the anhydrous ethanol, and then filtered to obtain a precipitate. After repeated washing 2 to 3 times, a product with higher purity is obtained. Finally, the product is transferred to a watch glass and vacuum dried at a temperature of 45°C for 6 hours to obtain the amphiphilic polymer.

[0144] In the above, the mass ratio of alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer is 1:0.7:0.3:1.5; the mass of the ammonium persulfate is 0.3% of the total mass of the alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer; the mass of the sodium bisulfite is 0.2% of the total mass of the alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer.

[0145] Example 7

[0146] The preparation of the hydrophobic monomer in this embodiment is as follows:

[0147] Different from Example 1, during the preparation of the hydrophobic monomer, the N-dimethylalkylamine is selected from N-dimethyloctadecylamine.

[0148] The preparation of the cationic monomer in this embodiment is as follows:

[0149] The difference from Example 1 is that during the preparation of the cationic monomer, the brominated alkane is selected from brominated octadecane.

[0150] The preparation of the amphoteric active monomer in this embodiment is as follows:

[0151] Different from Example 1, during the preparation of the amphoteric active monomer, the long-chain fatty acid is selected from octadecanoic acid.

[0152] This embodiment further provides an amphiphilic polymer.

[0153] The preparation method is as follows:

[0154] Add distilled water and alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer into a three-necked flask 5 to prepare a solution with a mass fraction of 30% of alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer; then install the three-necked flask 5 in a heat-collecting magnetic heating stirring water bath, introduce nitrogen for protection, adjust the pH value of the solution (colorimetric card) to between 6.0 and 7.0 with acrylic acid, add ammonium persulfate, stir at a rate of 200 r / min and heat to a set temperature of 25° C., then turn off the heating, Sodium bisulfite is added to initiate the polymerization reaction. When the reaction temperature no longer continues to rise, the polymerization reaction is completed, and the heating is turned on again to maintain the temperature at 50°C. After keeping warm for 2 hours, the heating is stopped and a crude product is obtained by filtration. The crude product is then transferred to a single-necked flask, anhydrous ethanol is added, shaken to dissolve the unreacted raw materials in the anhydrous ethanol, and then filtered to obtain a precipitate. After repeated washing 2 to 3 times, a product with higher purity is obtained. Finally, the product is transferred to a watch glass and vacuum dried at a temperature of 45°C for 6 hours to obtain the amphiphilic polymer.

[0155] In the above, the mass ratio of alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer is 1:0.7:0.3:1.5; the mass of the ammonium persulfate is 0.3% of the total mass of the alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer; the mass of the sodium bisulfite is 0.2% of the total mass of the alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer.

[0156] Example 8

[0157] The preparation of the hydrophobic monomer in this embodiment is as follows:

[0158] Same as Example 1.

[0159] The preparation of the cationic monomer in this embodiment is as follows:

[0160] Same as Example 1.

[0161] The preparation of the amphoteric active monomer in this embodiment is as follows:

[0162] Same as Example 1.

[0163] This embodiment further provides an amphiphilic polymer.

[0164] The preparation method is as follows:

[0165] Add distilled water and alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer into a three-necked flask 5 to prepare a solution with a mass fraction of 25% of alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer; then install the three-necked flask 5 in a heat-collecting magnetic heating stirring water bath, introduce nitrogen for protection, adjust the pH value of the solution (colorimetric card) to between 6.0 and 7.0 with acrylic acid, add ammonium persulfate, stir at a rate of 200 r / min and heat to a set temperature of 25° C., then turn off the heating, Sodium bisulfite is added to initiate the polymerization reaction. When the reaction temperature no longer continues to rise, the polymerization reaction is completed, and the heating is turned on again to maintain the temperature at 40°C. After keeping warm for 2 hours, the heating is stopped and a crude product is obtained by suction filtration. The crude product is then transferred to a single-necked flask, anhydrous ethanol is added, shaken to dissolve the unreacted raw materials in the anhydrous ethanol, and then filtered to obtain a precipitate. After repeated washing 2 to 3 times, a product with higher purity is obtained. Finally, the product is transferred to a watch glass and vacuum dried at a temperature of 45°C for 6 hours to obtain the amphiphilic polymer.

[0166] In the above, the mass ratio of alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer is 1:0.7:0.3:1.5; the mass of the ammonium persulfate is 0.3% of the total mass of the alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer; the mass of the sodium bisulfite is 0.2% of the total mass of the alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer.

[0167] Example 9

[0168] The preparation of the hydrophobic monomer in this embodiment is as follows:

[0169] Same as Example 1.

[0170] The preparation of the cationic monomer in this embodiment is as follows:

[0171] Same as Example 1.

[0172] The preparation of the amphoteric active monomer in this embodiment is as follows:

[0173] Same as Example 1.

[0174] This embodiment further provides an amphiphilic polymer.

[0175] The preparation method is as follows:

[0176] Add distilled water and alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer into a three-necked flask 5 to prepare a solution with a mass fraction of 40% of alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer; then install the three-necked flask 5 in a heat-collecting magnetic heating stirring water bath, introduce nitrogen for protection, adjust the pH value of the solution (colorimetric card) to between 6.0 and 7.0 with sodium hydroxide, add ammonium persulfate, stir at a rate of 200 r / min and heat to a set temperature of 25° C., then turn off the heating. , sodium bisulfite is added to initiate the polymerization reaction. When the reaction temperature no longer continues to rise, the polymerization reaction is completed, and the heating is turned on again to maintain the temperature at 60°C. After keeping warm for 2 hours, the heating is stopped and the crude product is obtained by filtration. The crude product is then transferred to a single-necked flask, anhydrous ethanol is added, shaken to dissolve the unreacted raw materials in anhydrous ethanol, and then filtered to obtain a precipitate. After repeated washing 2 to 3 times, a product with higher purity is obtained. Finally, the product is transferred to a watch glass and vacuum dried at 45°C for 6 hours to obtain the amphiphilic polymer.

[0177] In the above, the mass ratio of alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer is 1:0.7:0.3:1.5; the mass of the ammonium persulfate is 0.3% of the total mass of the alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer; the mass of the sodium bisulfite is 0.2% of the total mass of the alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer.

[0178] Example 10

[0179] The preparation of the hydrophobic monomer in this embodiment is as follows:

[0180] Same as Example 1.

[0181] The preparation of the cationic monomer in this embodiment is as follows:

[0182] Same as Example 1.

[0183] The preparation of the amphoteric active monomer in this embodiment is as follows:

[0184] Same as Example 1.

[0185] This embodiment further provides an amphiphilic polymer.

[0186] The preparation method is as follows:

[0187] Add distilled water and alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer into a three-necked flask 5 to prepare a solution with a mass fraction of 30% of alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer; then install the three-necked flask 5 in a heat-collecting magnetic heating stirring water bath, introduce nitrogen for protection, adjust the pH value of the solution (colorimetric card) to between 6.0 and 7.0 with sodium hydroxide, add ammonium persulfate, stir at a rate of 200 r / min and heat to a set temperature of 25° C., then turn off the heating. , sodium bisulfite is added to initiate the polymerization reaction. When the reaction temperature no longer continues to rise, the polymerization reaction is completed, and the heating is turned on again to maintain the temperature at 50°C. After keeping warm for 2 hours, the heating is stopped and the crude product is obtained by filtration. The crude product is then transferred to a single-necked flask, anhydrous ethanol is added, shaken to dissolve the unreacted raw materials in anhydrous ethanol, and then filtered to obtain a precipitate. After repeated washing 2 to 3 times, a product with higher purity is obtained. Finally, the product is transferred to a watch glass and vacuum dried at 45°C for 6 hours to obtain the amphiphilic polymer.

[0188] In the above, the mass ratio of alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer is 1:0.7:0.3:1.0; the mass of the ammonium persulfate is 0.3% of the total mass of the alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer; the mass of the sodium bisulfite is 0.2% of the total mass of the alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer.

[0189] Comparative Example 1

[0190] The method described in Example 1 was followed, except that no hydrophobic monomer was added when preparing the amphiphilic polymer.

[0191] Comparative Example 2

[0192] The method described in Example 1 was followed, except that no cationic monomer was added when preparing the amphiphilic polymer.

[0193] Comparative Example 3

[0194] The method described in Example 1 was followed, except that no amphoteric active monomer was added when preparing the amphiphilic polymer.

[0195] Comparative Example 4

[0196] The method described in Example 1 is followed, except that when preparing the amphiphilic polymer, distilled water and alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer are added to the three-necked flask 5 to obtain a solution with a mass fraction of 60% of alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer.

[0197] In order to further illustrate the progress of the present invention, the specific types and proportions of the raw materials alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer for preparing the amphiphilic polymers described in Examples 1-10 of the present invention and Comparative Examples 1-4, as well as the mass fractions of alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer in the alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer solutions, and the insulation temperature are statistically shown in the following Table 1;

[0198] Table 1

[0199]

[0200]

[0201] In Table 1 above, the total amount of monomers is the mass fraction of alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer in the alkyl acrylamide, hydrophobic monomer, cationic monomer and amphoteric active monomer solution; in the alkyl acrylamide column, "C12" or "C18" represents the alkyl carbon number of the alkyl acrylamide; in the hydrophobic monomer column, "C12", "C16" or "C18" represents the alkyl carbon number of N-dimethylalkylamine; in the cationic monomer column, "C12", "C16" or "C18" represents the carbon number of the long-chain fatty acid.

[0202] Test Case

[0203] The amphiphilic polymers prepared in Examples 1-10 of the present invention and Comparative Examples 1-4 were applied to fracturing fluids for extraction, and the surface tension and interfacial tension of the fracturing fluid containing the amphiphilic polymer of the present invention were measured according to the "SY / T5370 Surface and interfacial tension determination method", and the imbibition extraction rate of the fracturing fluid containing the amphiphilic polymer of the present invention was measured according to the "Q_SLCG0403-2021 Imbibition Extraction Agent for Fracturing Fluid", and the measurement results are statistically shown in Table 2;

[0204] Wherein, the fracturing fluid is prepared as follows: based on 100% water, the added amount of the drag reducing agent is 0.3wt%, the added amount of the clay stabilizer is 0.1wt%, the added amount of the drainage agent is 0.1wt%, and the added amount of the amphiphilic polymer described in the present invention is 0.2wt%; wherein, the drag reducing agent is a drag reducing agent for fracturing, liquid, numbered Q / SLCG0089, purchased from Beijing Hongyi Enze Energy Technology Co., Ltd.; the clay stabilizer product number is acid fracturing / clay stabilizer, liquid, numbered Q / SHCG125, purchased from Beijing Hongyi Enze Energy Technology Co., Ltd.; the drainage agent is purchased from the Petroleum Engineering Research Institute of China Petrochemical Corporation, industrial grade (preparation method such as Example 1 of CN108239532B); other components are commonly used components of fracturing fluid and are not limited.

[0205] Table 2

[0206]

[0207] In Table 2, the blank group is a fracturing fluid without adding the amphiphilic polymer of the present invention; the pure water group is a fracturing fluid containing only water;

[0208] It can be seen from the data in Table 2 that, compared with the pure water group, although the blank group added a drag reducer, a clay stabilizer and a drainage agent to reduce the surface tension and interfacial tension of the fracturing fluid, the imbibition recovery rate did not improve at all; while compared with the blank group, the comparative examples 1-4 respectively added the amphiphilic polymers prepared in comparative examples 1-4, which reduced the surface tension and interfacial tension of the fracturing fluid to a certain extent, and improved the imbibition recovery rate of the fracturing fluid; in Examples 1-10, compared with the blank group and comparative examples 1-4, the amphiphilic polymers prepared in Examples 1-10 were respectively added, which significantly reduced the surface tension and interfacial tension of the fracturing fluid, and improved the imbibition recovery rate of the fracturing fluid, indicating that the amphiphilic polymers described in the present invention can improve the imbibition recovery rate of the fracturing fluid.

[0209] It should be noted that the embodiments described above are only used to explain the present invention and do not constitute any limitation to the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory words, rather than restrictive words. The present invention may be modified as specified within the scope of the claims of the present invention, and the present invention may 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. An amphiphilic polymer, characterized in that The amphiphilic polymer is a polymerization product of four monomers, namely, acrylamide or its derivatives, a hydrophobic monomer, a cationic monomer, and an amphoteric active monomer; the hydrophobic monomer is prepared from raw materials including chlorinated olefins, N-dimethylalkylamine or N,N-dimethylalkylamine; the cationic monomer is prepared from raw materials including aminoamide containing double bonds and brominated alkanes; and the amphoteric active monomer is prepared from raw materials including long-chain fatty acids, amines or alcoholamines.

2. The amphiphilic polymer according to claim 1, characterized in that The mass ratio of acrylamide or its derivative, hydrophobic monomer, cationic monomer and amphoteric active monomer is 1: (0.5-0.8): (0.2-0.5): (1.2-1.8); and / or, the molar ratio of N-dimethylalkylamine or N,N-dimethylalkylamine to chlorinated olefin is 1:(0.8-1.5); and / or, the molar ratio of the aminoamide containing a double bond to the brominated alkane is 1:(0.6-1.2); And / or, the molar ratio of the long-chain fatty acid to the amine or alcoholamine is 1:(0.3-0.8).

3. The amphiphilic polymer according to claim 1 or 2, characterized in that The acrylamide derivative is selected from alkyl acrylamide; preferably, the alkyl acrylamide is selected from at least one of octadecyl acrylamide, N-dodecyl acrylamide, and N,N-tetradecyl acrylamide; And / or, the chlorinated olefin is selected from at least one of 4-chloro-1-butene, 1,4-dichloro-2-butene, and allyl chloride; And / or, the N,N-dimethylalkylamine is selected from at least one of N,N-dimethyldodecylamine, N,N-dimethyltetradecylamine, N,N-dimethylhexadecylamine and N,N-dimethyloctadecylamine; the N-dimethylalkylamine is selected from at least one of N-dimethyldodecylamine, N-dimethyltetradecylamine, N-dimethylhexadecylamine and N-dimethyloctadecylamine; And / or, the aminoamide containing a double bond is selected from at least one of dimethylaminopropyl methacrylamide, dimethylaminoethyl methacrylate, and N-(dimethylaminopropyl) methacrylamide; And / or, the brominated alkane is at least one selected from dodecane bromide, tetradecane bromide, hexadecane bromide, octadecane bromide, and eicosane bromide; And / or, the long-chain fatty acid is selected from C12-C18 fatty acids; preferably, the C12-C18 fatty acid is selected from at least one of lauric acid, myristic acid, palmitic acid and stearic acid; And / or, the amine is selected from at least one of triethylamine and trimethylamine; the alcoholamine is selected from at least one of triethanolamine, dimethylethanolamine and methyldiethanolamine.

4. The amphiphilic polymer according to claim 3, characterized in that The preparation method of the hydrophobic monomer comprises: preparing a chlorinated olefin solution, an N-dimethylalkylamine solution or an N,N-dimethylalkylamine solution respectively, adding the N-dimethylalkylamine solution or the N,N-dimethylalkylamine solution dropwise to the chlorinated olefin solution, and reacting to obtain the hydrophobic monomer; Preferably, an equal amount of solvent I is added to the chlorinated olefin solution, N-dimethylalkylamine solution or N,N-dimethylalkylamine solution; the solvent I is selected from at least one of anhydrous ethanol, acetone, carbon tetrachloride, ether and chloroform; further preferably, the molar concentration of the chlorinated olefin solution is 8 mol / L to 15 mol / L, preferably 10 mol / L; further preferably, the speed of adding I is 2 seconds / drop to 5 seconds / drop, preferably 3 seconds / drop; further preferably, the conditions of the reaction I include: reaction temperature of 45°C to 65°C, preferably 55°C, reaction time of 4h to 8h, preferably 6h; stirring rate of 200r / min to 400r / min; And / or, the preparation method of the cationic monomer comprises: preparing an aminoamide solution containing a double bond and a brominated alkane solution respectively, and dripping the brominated alkane solution II into the aminoamide solution containing a double bond under an inactive atmosphere I, and reacting II to obtain the cationic monomer; Preferably, an equal amount of solvent II is added to the aminoamide solution containing double bonds and the bromoalkane solution; the solvent II is selected from at least one of anhydrous acetone, ethanol, carbon tetrachloride, ether, and chloroform; further preferably, the molar concentration of the aminoamide solution containing double bonds is 4 mol / L to 10 mol / L, preferably 6 mol / L; further preferably, the speed of adding II is 2 seconds / drop to 5 seconds / drop, preferably 3 seconds / drop; further preferably, the conditions of the reaction II include: the reaction temperature is 20°C to 40°C, preferably 30°C, the reaction time is 18h to 24h, preferably 20h; the stirring rate is 200r / min to 400r / min; the inactive atmosphere I is selected from nitrogen or carbon dioxide; And / or, the preparation method of the amphoteric active monomer comprises: a. Prepare a long-chain fatty acid solution with a molar concentration of 2 mol / L to 5 mol / L, preferably 3 mol / L, then add triethylamine, heat to the reaction temperature, add bromine, and then dropwise add III chlorosulfonic acid solution, react III to obtain an amphoteric active monomer precursor; b. preparing an allylamine solution with a molar concentration of 3 mol / L to 8 mol / L, preferably 5 mol / L, and then adding the amphoteric active monomer precursor prepared in step a to react IV in the presence of a catalyst to obtain an amphoteric active monomer; Preferably, in step a, the molar ratio of the long-chain fatty acid to bromine is 1:(0.1-0.5), preferably 1:0.3; the molar ratio of the long-chain fatty acid to chlorosulfonic acid is 1:(0.1-0.3), preferably 1:0.2; in the chlorosulfonic acid solution, the ratio of chlorosulfonic acid to solvent III is 0.2-0.5 mol:25 mL; further preferably, in the long-chain fatty acid solution and the chlorosulfonic acid solution, the solvent III is the same and is selected from at least one of chloroform, acetone, ethanol, ether, and N,N-dimethylformamide; further preferably, the speed of adding III is 3 seconds / drop to 8 seconds / drop, preferably 5 seconds / drop; further preferably, the conditions of the reaction III include: the reaction temperature is 75°C to 95°C, preferably 80°C, the reaction time is 2h to 5h, preferably 3h; the stirring rate is 200r / min to 400r / min; Preferably, in step b, the molar ratio of the amphoteric active monomer precursor to allylamine is 1:(0.8-1.2), preferably 1:1; the catalyst is N-methylmorpholine and 2-(7-azobenzotriazole)-N,N,N',N'-tetramethyluronium hexafluorophosphate; further preferably, the molar ratio of N-methylmorpholine to allylamine is 1:(0.02-0.08), preferably 1:0.05; the molar ratio of 2-(7-azobenzotriazole)-N,N,N',N'-tetramethyluronium hexafluorophosphate to allylamine is 1:(0.2-0.3), preferably 1:0.25; further preferably, the conditions of reaction IV include: reaction temperature of 50°C to 60°C, preferably 55°C, reaction time of 2h to 5h, preferably 3h; stirring rate of 200r / min to 400r / min.

5. A method for preparing an amphiphilic polymer as claimed in any one of claims 1 to 4, characterized in that: The steps include: 1) preparing a solution containing four monomers; 2) In the presence of an inert atmosphere II and an initiator, a reducing agent is added to polymerize the solution containing the four monomers obtained in step 1) to obtain the amphiphilic polymer.

6. The preparation method according to claim 5, characterized in that: In step 1), the solvent IV in the solution containing four monomers is distilled water; And / or, the mass fraction of the four monomers in the solution containing the four monomers is 25% to 40%, preferably 30%; And / or, the pH value of the solution containing the four monomers is adjusted to 6.0-7.

0.

7. The preparation method according to claim 5 or 6, characterized in that: In step 2), the inert atmosphere II is selected from nitrogen or carbon dioxide; and / or, the mass of the initiator is 0.2% to 0.5% of the total mass of the four monomers; And / or, the initiator is selected from at least one of ammonium persulfate, potassium persulfate and benzoyl peroxide; And / or, before adding the reducing agent, the solution containing the four monomers is heated to 20°C to 30°C, preferably to 25°C; preferably, the amount of the reducing agent added is 0.1% to 0.3%; further preferably, the reducing agent is selected from sodium bisulfite.

8. The preparation method according to any one of claims 5 to 7, characterized in that: After the polymerization reaction, the mixture is kept at a temperature of 40° C. to 60° C. for 1 to 3 hours, preferably at a temperature of 50° C. for 2 hours.

9. A fracturing fluid, characterized in that: The fracturing fluid comprises the amphiphilic polymer described in any one of claims 1 to 4 or the amphiphilic polymer prepared by the preparation method described in any one of claims 5 to 9; preferably, in the fracturing fluid, based on 100% water, the addition amount of the amphiphilic polymer is 0.1 wt% to 0.7 wt%.

10. Use of the amphiphilic polymer according to any one of claims 1 to 4 or the amphiphilic polymer prepared by the preparation method according to any one of claims 5 to 9 in fracturing fluid.

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