CN111607029B - Supermolecule oil displacement agent and preparation method thereof - Google Patents
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
Abstract
The invention discloses a supermolecule oil-displacing agent and a preparation method thereof, wherein a functional supermolecule oil-displacing agent is synthesized by using hydrophilic monomers containing ether bonds, quaternary ammonium salt cationic monomers and the like, a phase-transfer agent and a solvent. According to the invention, the hydrophilic group in the molecular structure of the functional supramolecular oil-displacing agent is utilized to make the rock more hydrophilic, so that the interaction between crude oil and the rock is reduced, and the oil reservoir wettability is improved; the interface activity of the zwitterionic polymer molecules is utilized to increase the interaction between the crude oil and water molecules and improve the solubilizing capability of the crude oil; by using the cation and the benzene ring group, the interaction between colloid asphaltene molecules in crude oil can be particularly reduced, the pour point and the viscosity can be reduced, the seepage resistance can be reduced, the technical problems of low efficiency and the like of the conventional polymer oil displacement agent are solved, compared with the conventional polymer oil displacement agent, the use of the functional supramolecular oil displacement agent can improve the crude oil recovery ratio by 5-10 percent, and the tertiary oil recovery benefit of an oil field is improved.
Description
Technical Field
The invention relates to the technical field of oil exploitation, in particular to a supramolecular oil displacement agent and a preparation method thereof.
Background
Energy is the material basis of human activities and is a precondition for national economic development. Petroleum has wide application in the fields of daily life, industry, agriculture, military and the like, and the petroleum industry is required to provide more petroleum products. Since 2010, most oil fields in China are in an uninterrupted exploitation state for a long time, nearly all domestic oil fields are in a high and ultrahigh water cut period, but the polymer flooding technology can be used for continuous development. More oil and gas resources are obtained, the recovery ratio of crude oil is improved, and the method is a core problem of development of the petroleum field all over the world. The tertiary oil recovery technology is the most effective means for improving the oil recovery efficiency, through more than 20 years of research and practice, the technology, scale and the like of Chinese chemical flooding are ranked in the front of the world, the polymer flooding can improve the recovery efficiency by 10 percent, and the polymer flooding becomes a key technology for improving the recovery efficiency.
In recent years, oil displacement agents with obvious effects obtained in tertiary oil recovery popularized in various large oil fields in China mainly comprise two categories of polymers and surfactants. The polymer mainly utilizes the strong tackifying capability of a water-soluble polymer to increase the viscosity of a displacement phase in an oil reservoir, improve the fluidity ratio and adjust the formation permeability so as to achieve the aim of improving the recovery ratio. The surfactant mainly utilizes the capability of reducing the surface tension of an aqueous solution of the surfactant and achieves the purpose of improving the recovery ratio by reducing the interfacial tension of oil and water. Therefore, the development of a compound having both the functions of a surfactant and a polymer is an important concept for molecular design of a high molecular surfactant.
The high molecular surfactant is a novel chemical oil-displacing agent with single component, is derived from the design ideas of polymer flooding and surfactant flooding of tertiary oil recovery, takes a flexible polyacrylamide hydrocarbon chain as a framework, and introduces a plurality of functional groups with surface active functions. The macromolecular surfactant mainly comprises three molecular structural components, namely, a hydrophilic main chain containing a hydrophobic side group, a hydrophobic main chain containing a hydrophilic side group, and a hydrophilic block and a hydrophobic block. The current high molecular surfactant applied to tertiary oil recovery is mainly formed by taking a hydrophilic polyacrylamide molecular chain as a main component and copolymerizing a hydrophilic monomer with the surfactant, wherein the molecular structure of the surfactant is mainly alkyl, sulfonic group and functional group with surface activity, and the surfactant is mainly a rigid group capable of improving the stability of polyacrylamide, such as benzene ring, pyrrole, thiophene and the like.
The research on the aspect of tertiary oil recovery technology related to the polymer surfactant can be traced back to 1989, Youssef, Tahany and the like mainly research a class of polyepitometer agent with a cyclic main chain using phenol as a raw material, and the literature carries out systematic research on the class of polymer surfactant, and the surfactant is considered to have important application potential in the tertiary oil recovery technology, the dependency of the polyepitometer agent on the carbon number of an equivalent alkane is the same as that of a monomer, the response of the polyepitometer agent on an external polyelectrolyte is the same as that of a negative nonionic surfactant, and the interfacial tension can be minimized when the carbon number of the equivalent alkane is less than 5 and is less than 10-3mN/m. Liqiang and the like take polymer surfactants of Daqing refining and Shanghai Haibo as research objects, molecular coil sizes and microscopic aggregation structures of 4 polymer surfactants are respectively researched, and influences of solution concentration, water for liquid preparation and the like on seepage characteristics are investigated through a core flow experiment. The research finds that the high molecular surfactant molecules are characterized by cross-linking reaction to different degrees and present a sheet-network aggregation structure, which is different from the conventional polymers. With Na+In contrast, Ca2+And Mg2+The influence on the solution resistance coefficient and the residual resistance coefficient of the macromolecular surfactant is large, and the macromolecular surfactant is easier to generate intramolecular cross-linking reaction. The intramolecular cross-linking reaction is expected to enable the macromolecular surfactant to be more suitable for the oil deposit environment with high mineralization and play a better role in the heterogeneous oil deposit. The TBF type polymer surfactant produced in Shanghai Meiya has initial popularization and application in Daqing oil fields, Shengli oil fields and Hasekstein KBM oil fields, and reportedly, in field experiments of island oil fields, the accumulated oil production in a handling period is increased from 366t to 1207t, the oil yield is increased by 2.3 times, and the average ton of the surfactant is increased by 56 t. The TBF solution has the effects of greatly reducing the viscosity of crude oil and improving the phase permeability of the crude oil on the thick oil of the stratum, and meanwhile, a mixed system formed by the TBF solution and the crude oil has a certain displacement effect on the residual oil at the front end. FSX type high surface active agent in thin layer in londong developed by Shengli oil field oil extraction institute3 wells are implemented in a thickened oil block on site, a good yield increasing effect is achieved, the water content is reduced to 84% at the lowest, the oil yield is 6.70t/d at the highest, and the daily liquid yield is 40.0m on average3And d, the cumulative oil increment is more than 800 t. In a field test of Daqing oil fields, the water content of an oil well comprehensively containing 97.9% of high molecular surfactant in an oil reservoir after polymer flooding is reduced to 88.2%, the maximum daily oil increase is 21.8t, the oil recovery rate is increased by 10.8%, and an excellent effect is achieved.
At present, the high molecular surfactant for tertiary oil recovery is derived from polyacrylamide and a surfactant which are traditional oil-displacing agents, and the main body of the high molecular surfactant is a structural unit of the polyacrylamide, so that the high molecular surfactant has the tackifying capability of the polyacrylamide and inherits the poorer thermal stability performance. The synthesis of the high-molecular surfactant is mainly obtained by copolymerizing acrylamide and a surfactant monomer, and the polymerization efficiency of the surfactant structural unit is limited due to the polymerization activity difference between the comonomers. Therefore, the development of the high molecular surface active agent with better polyvinyl alcohol type thermal stability on the basis of the non-polyacrylamide skeleton becomes an important direction of the current technical development.
CN 201710415273.6 discloses a betaine type zwitterionic polymer oil-displacing agent and a synthesis method thereof, wherein the zwitterionic copolymer is obtained by taking 80 parts of acrylamide, 18 parts of acrylic acid, 1 part of 3- (3-methacrylamide propyl dimethylamino) propyl-1-sulfonate and 0.3 part of N-allyl-2-phenoxyacetamide as monomers through polymerization reaction. The polymer is based on acrylamide and the like, and can resist temperature lower than 80 ℃; the sulfonic betaine is introduced into the polymer branched chain, the part of quaternary ammonium salt cations is low, the self-assembly capability of molecules is poor, and the shearing thickening capability is weak; the polymer has no hydroxyl hydrophilic branched chain, has relatively poor water solubility, and improves poor oil reservoir wetting ability; benzene rings are on the larger branched chains, the fraction is low, the molecular rigidity is weak, and the surface performance is poor.
Disclosure of Invention
Aiming at the technical problems, the invention provides a supramolecular oil-displacing agent and a preparation method thereof, which can reduce the interaction between crude oil and rock and improve the wettability of an oil reservoir; the interaction between the crude oil and water molecules is increased, and the solubilizing capability of the crude oil is improved; the interaction between crude oil molecules is reduced, the pour point and the viscosity are reduced, and the seepage resistance is reduced; the temperature resistance is improved, the technical problems of low efficiency, low temperature resistance and the like of the conventional polymer oil displacement agent are solved, and the tertiary oil recovery benefit is improved.
The invention provides a preparation method of a supramolecular oil-displacing agent, which comprises the following steps:
(1) accurately weighing reactants, a phase transfer agent and a solvent, wherein the reactants are an ether bond-containing hydrophilic unsaturated monomer, a quaternary ammonium salt-containing cationic unsaturated monomer, a carboxylate radical-containing anionic unsaturated monomer and a benzene ring-containing hydrophobic unsaturated monomer, and the molar ratio of the reactants is as follows: n (hydrophilic unsaturated monomer containing ether bond): n (quaternary ammonium salt cation-containing unsaturated monomer): n (carboxylate anion containing unsaturated monomer): n (benzene ring-containing hydrophobic unsaturated monomer) ═ 3-6): (1-3): (6-12): 1; the mass ratio of the phase transfer agent to the reaction mass is w (phase transfer agent): w (reactant) ═ 0.01 to 0.02): 1; the mass ratio of the solvent to the reactant and the phase transfer agent is w (solvent): w (reactant + phase transfer agent) ═ 1.0 to 1.5: 1;
(2) firstly, adding reactants, a phase transfer agent and 70% of solvent in parts by mole into a reaction vessel, and uniformly stirring; dissolving an initiator into the rest 30% of solvent in a ratio of the initiator to the reactant of (0.06-0.10): 1 to prepare an initiator solution;
(3) and (3) placing the initiator solution obtained in the step (2) in a constant-pressure dropping funnel, introducing nitrogen to replace gas, heating to 75-85 ℃, slowly dropwise adding the initiator solution into the reaction container for 1-2 hours, continuously reacting for 3-5 hours at 75-85 ℃ after dropwise adding, cooling to 35-45 ℃, and adjusting the pH value to 6-7 by using a proper amount of pH regulator to obtain the supramolecular oil-displacing agent.
As a preferred embodiment of the present invention, the hydrophilic unsaturated monomer containing an ether bond includes ethylene glycol monoallyl ether, glycerol allyl ether, allyl polyoxyethylene methyl ether, and allyl polyoxyethylene ether.
As a preferred embodiment of the present invention, the quaternary ammonium salt-containing cationic unsaturated monomer includes trimethyl allyl ammonium chloride, methacryloyloxyethyl trimethyl ammonium chloride, and dimethyl diallyl ammonium chloride.
As a preferred embodiment of the present invention, the carboxylate anion containing unsaturated monomer includes acrylic acid and methacrylic acid.
As a preferred embodiment of the present invention, the hydrophobic unsaturated monomer having a benzene ring includes vinyltoluene, styrene and 1-allylnaphthalene.
As a preferred embodiment of the present invention, the phase transfer agent includes sodium dodecylbenzenesulfonate and alkylphenol ethoxylate-10 (OP-10).
As a preferred embodiment of the present invention, the initiator includes sodium persulfate, potassium persulfate, and ammonium persulfate.
As a preferred embodiment of the present invention, the pH adjusting agent includes sodium hydroxide and potassium hydroxide; the solvent is deionized water.
The invention provides a supermolecule oil displacement agent prepared by the method, and the general formula of the reaction equation is as follows:
wherein, R1: a polyhydroxy alkyl ether in a polyhydroxy alkyl group,
r2: 3-methyl-methylene ammonium chloride or hydrogenoyloxyethyl-trimethyl ammonium chloride,
r3 is a carboxyl group, and R3 is a carboxyl group,
r4 is phenyl or p-alkylphenyl,
a:b:c:d＝(3～6)：(1～3)：(6～12)：1，
in a preferred embodiment of the present invention, the multifunctional supramolecular thickener has an average relative molecular weight of 300 to 600 ten thousand.
The invention has the beneficial effects that:
the invention can improve the oil reservoir wettability, improve the crude oil solubilizing capability, reduce the seepage resistance, improve the temperature resistance of the oil displacement agent, and solve the technical problems of low efficiency, low temperature resistance and the like of the conventional polymer oil displacement agent. Compared with the conventional polymer oil-displacing agent, the temperature resistance of the functional supermolecule oil-displacing agent is improved to 105 ℃, and the crude oil recovery ratio can be improved by 5-10 percent.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without any creative effort belong to the protection scope of the embodiments of the present invention.
Example 1
Adding appropriate amount of reactants of ethylene glycol monoallyl ether (AEO), trimethyl allyl ammonium chloride (TMAAC), methacrylic acid (MAA), p-methylstyrene (PMS), phase transfer agent sodium dodecyl benzene sulfonate and solvent deionized water into a four-neck flask provided with a stirrer, a constant-pressure dropping funnel, a thermometer and a condenser, wherein the molar ratio of the reactants is n (ethylene glycol monoallyl ether): n (trimethylallylammonium chloride): n (methacrylic acid): n (p-methylstyrene) ═ 3: 1: 6: 1; the mass ratio of the phase transfer agent sodium dodecyl benzene sulfonate to the reactant is w (sodium dodecyl benzene sulfonate): w (reactant) ═ 0.02: 1, the mass ratio of the solvent deionized water to the reactants and the phase transfer agent is w (deionized water): w (reactant + phase transfer agent) 1:1, adding 70% of deionized water in molar parts into a four-neck flask, and uniformly stirring. The mass of the initiator ammonium persulfate and the reaction mass are w (ammonium persulfate): w (reactant) ═ 0.07: dissolving ammonium persulfate in the rest 30 mol% of deionized water, placing the mixture in a constant-pressure dropping funnel, introducing nitrogen to replace air, heating the mixture to 75 ℃, slowly dropping an ammonium persulfate solution for 1 hour, continuing to react for 3 hours at the temperature of 75 ℃ after dropping is finished, cooling the mixture to 40 ℃, and adjusting the pH value to 6.5 by using a proper amount of sodium hydroxide to obtain a light brown oil displacement agent, namely, a solution of ethylene glycol monoallyl ether-trimethyl allyl ammonium chloride-methacrylic acid-vinyl toluene copolymer (AEO-TMAAC-NaMA-PMS copolymer).
Wherein, the molar ratio of reactants is as follows: a, b, c, d-3: 1: 6: 1.
the average relative molecular weight was 600 ten thousand.
Example 2
Adding proper amounts of reactants of glycerol allyl ether (AG), methacryloyloxyethyl trimethyl ammonium chloride (DMC), Acrylic Acid (AA), styrene (St), phase transfer agent of nonylphenol polyoxyethylene ether and solvent deionized water into a four-neck flask provided with a stirrer, a constant-pressure dropping funnel, a thermometer and a condenser, wherein the molar ratio of the reactants is n (glycerol allyl ether): n (methacryloyloxyethyl trimethyl ammonium chloride): n (acrylic acid): n (styrene) ═ 4: 2: 8: 1; the mass ratio of the phase transfer agent nonylphenol polyoxyethylene ether-10 (OP-10) to the reaction mass is w (nonylphenol polyoxyethylene ether-10): w (reactant) ═ 0.01: 1, the mass ratio of the solvent deionized water to the reactants and the phase transfer agent is w (deionized water): w (reactant + phase transfer agent) ═ 1.5: 1, adding 70% of deionized water in molar parts into a four-neck flask, and uniformly stirring. The mass of initiator sodium persulfate and reactant is w (sodium persulfate): w (reactant) ═ 0.08: dissolving sodium persulfate in the rest 30 mol% of deionized water, placing the solution in a constant-pressure dropping funnel, introducing nitrogen to replace air, heating the solution to 85 ℃, slowly dropwise adding the sodium persulfate solution for 1.5 hours, continuously reacting for 4 hours at 85 ℃ after dropwise adding, cooling the solution to 40 ℃, and adjusting the pH value to 6.5 by using a proper amount of sodium hydroxide to obtain a light brown oil displacement agent, namely, glycerol allyl ether-methacryloyloxyethyl trimethylammonium chloride-acrylic acid-styrene copolymer (AG-DMC-NaAA-St copolymer) solution.
Molar ratio of reactants: a, b, c, d-4: 2: 8: 1.
average relative molecular weight: 500 ten thousand.
Example 3
A four-neck flask provided with a stirrer, a constant pressure dropping funnel, a thermometer and a condenser is added with proper amounts of reactants of allyl polyoxyethylene methyl ether (HPEG) (n ═ 60), dimethyl diallyl ammonium chloride (DMDAAC), Acrylic Acid (AA), styrene (St), nonylphenol polyoxyethylene ether and solvent deionized water, wherein the molar ratio of the reactants is n (allyl polyoxyethylene methyl ether (n ═ 60)): n (dimethyldiallylammonium chloride): n (acrylic acid): n (styrene) ═ 6: 3: 12: 1; the mass ratio of the phase transfer agent alkylphenol polyoxyethylene ether-10 (OP-10) to the reactant is w (alkylphenol polyoxyethylene ether-10): w (reactant) ═ 0.02: 1, the mass ratio of the solvent deionized water to the reactants and the phase transfer agent is w (deionized water): w (reactant + phase transfer agent) ═ 1.5: 1, adding 70% of deionized water in molar parts into a four-neck flask, and uniformly stirring. The mass of the initiator ammonium persulfate and the reaction mass are w (ammonium persulfate): and w (reactant) is 0.1:1, dissolving ammonium persulfate in the rest 30 mol% of deionized water, placing the mixture in a constant-pressure dropping funnel, introducing nitrogen to replace air, heating to 85 ℃, slowly dropwise adding an ammonium persulfate solution for 2 hours, continuing to react for 5 hours at 85 ℃ after the dropwise adding is finished, cooling to 40 ℃, and adjusting the pH value to 6.5 by using a proper amount of potassium hydroxide to obtain a light brown oil displacement agent allyl polyoxyethylene methyl ether-dimethyl diallyl ammonium chloride-acrylic acid-styrene copolymer (HPEG-DMDAAC-NaAA-St copolymer) solution.
Molar ratio of reactants: a, b, c, d-6: 3: 12: 1.
the average relative molecular weight was 300 ten thousand.
Example 4
In this embodiment, the supramolecular oil-displacing agent in example 1 is used to prepare an oil-displacing injection liquid for the intermediate-permeability oil reservoir, wherein the mass concentration of the supramolecular oil-displacing agent effective polymer AEO-TMAAC-NaMA-PMS is 49.0%, and the oil-displacing injection liquid for the intermediate-permeability oil reservoir is prepared according to the following mass concentration ratios: ultra-minuteThe mass concentration of the sub oil-displacing agent is 0.612 percent (the effective mass concentration is 0.3 percent), and the balance is water. An SN oil field S7 well group adopts the supermolecule oil displacement agent in the embodiment 1 to carry out an oil displacement field test, the injection well section is (2211-2235) m, the formation temperature is 87 ℃, the porosity is electrically measured and explained to be 16.5 percent, and the permeability is 92.5 multiplied by 10-3μm2. 720t of supermolecule oil displacement agent is injected in a cumulative way, and 23.1 multiplied by 10 of solution is injected4m3The oil increasing and water reducing are realized, the gradual decrease is effectively controlled, the daily oil yield of an effective well group is increased to 20.4t from 12.2t, the maximum daily oil yield is 39.8t, the cumulative oil increasing is 3.6 ten thousand tons, the oil increasing is 50.2 tons/ton per ton of ton agent, the maximum comprehensive water content is reduced by 17 percentage points, and the recovery ratio is improved by 7.0 percent.
Example 5
In this embodiment, a medium-permeability reservoir flooding injection liquid prepared by using the supramolecular oil-displacing agent synthesized in example 2 is used, wherein the mass concentration of the supramolecular oil-displacing agent effective polymer AG-DMC-NaAA-St is 39.6%, and the medium-permeability reservoir flooding injection liquid is prepared according to the following mass concentration ratios: the supermolecule oil displacement agent has the mass concentration of 0.758% (the effective mass concentration is 0.3%), and the balance is water. The injection well section of the ZW oil field Z35 well group is (2212-2230) m, the formation temperature is 97 ℃, the porosity is electrically measured and explained to be 20%, and the permeability is 97 multiplied by 10-3μm2. Injecting supermolecule oil displacement agent 180t in a cumulative mode, and injecting solution 2.6 multiplied by 104m3The oil increasing and water reducing are realized, the gradual decrease is effectively controlled, the daily oil production of the effective well group is increased from 15.2t to 20.7t, the cumulative oil increasing is 0.86 ten thousand tons, the oil increasing is 48 tons/ton per ton of the agent, and the recovery ratio is improved by 9.4 percent.
Example 6
In this embodiment, the supramolecular oil-displacing agent synthesized in example 3 is used to prepare an oil-displacing injection liquid for the intermediate-permeability oil reservoir, wherein the mass concentration of the supramolecular oil-displacing agent effective polymer HPEG-DMDAAC-NaAA-St is 39.2%, and the oil-displacing injection liquid for the intermediate-permeability oil reservoir is prepared according to the following mass concentration ratios: the supermolecule oil displacement agent has the mass concentration of 0.765% (the effective mass concentration is 0.3%) and the balance of water. The oleophylic rock core is displaced by the prepared middle-permeability reservoir flooding injection liquid, so that the flooding efficiency is improved by 13.6 percent compared with that of water flooding; measuring a contact angle by using an OCA optical contact angle measuring instrument, reducing the core contact angle from 132.1 degrees before displacement to 60.2 degrees, and converting the oil humidity into water humidity of the core; all with TX500CThe measuring range interfacial tension measuring instrument measures the interfacial tension between the solution of the formula and the WZ crude oil in the oil field at the temperature of 60 ℃ and the rotating speed of 5000r/min, the interfacial tension is 0.007mN/m, and the measuring range interfacial tension measuring instrument has better interfacial performance. The sample is put into a 20ml ampoule bottle and placed in a 105 ℃ oven, and the interfacial tension of the sample is respectively tested for 5 days, 15 days, 30 days and 45 days, wherein the interfacial tension is 10-3～10-2mN/m。
Finally, it should be noted that: the above embodiments are only used for illustrating the technical solutions of the embodiments of the present invention, and are not limited thereto; although embodiments of the present invention have been described in detail with reference to the foregoing embodiments, those skilled in the art will understand that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (4)
1. The preparation method of the supramolecular oil-displacing agent is characterized by comprising the following steps:
(1) accurately weighing reactants, a phase transfer agent and a solvent, wherein the reactants are an ether bond-containing hydrophilic unsaturated monomer, a quaternary ammonium salt-containing cationic unsaturated monomer, a carboxylate radical-containing anionic unsaturated monomer and a benzene ring-containing hydrophobic unsaturated monomer, and the molar ratio of the reactants is as follows: n (hydrophilic unsaturated monomer containing ether bond): n (quaternary ammonium salt cation-containing unsaturated monomer): n (carboxylate anion containing unsaturated monomer): n (benzene ring-containing hydrophobic unsaturated monomer) = (3-6): (1-3): (6-12): 1; the mass ratio of the phase transfer agent to the reaction mass is w (phase transfer agent): w (reactant) = (0.01-0.02): 1; the mass ratio of the solvent to the reactant and the phase transfer agent is w (solvent): w (reactant + phase transfer agent) = (1.0-1.5): 1;
(2) firstly, adding reactants, a phase transfer agent and 70% of solvent in parts by mole into a reaction vessel, and uniformly stirring; dissolving an initiator into the rest 30% of solvent in a ratio of the initiator to the reactant of (0.06-0.10): 1 to prepare an initiator solution;
(3) placing the initiator solution obtained in the step (2) in a constant-pressure dropping funnel, introducing nitrogen to replace gas, heating to 75-85 ℃, slowly dropwise adding the initiator solution into a reaction container for 1-2 hours, continuously reacting for 3-5 hours at 75-85 ℃ after dropwise adding, cooling to 35-45 ℃, and adjusting the pH value to 6-7 by using a proper amount of pH regulator to obtain the supermolecule oil displacement agent;
the hydrophilic unsaturated monomer containing ether bond comprises ethylene glycol monoallyl ether, glycerol allyl ether, allyl polyoxyethylene methyl ether and allyl polyoxyethylene ether;
the quaternary ammonium salt-containing cationic unsaturated monomer comprises trimethyl allyl ammonium chloride, methacryloyloxyethyl trimethyl ammonium chloride and dimethyl diallyl ammonium chloride;
the carboxylate anion-containing unsaturated monomer includes acrylic acid and methacrylic acid;
the hydrophobic unsaturated monomer containing benzene ring comprises vinyl toluene, styrene and 1-allyl naphthalene.
2. The method of claim 1, wherein the phase transfer agent comprises sodium dodecylbenzenesulfonate and alkylphenol ethoxylate-10 (OP-10).
3. The production method according to claim 1, wherein the initiator comprises sodium persulfate, potassium persulfate, and ammonium persulfate.
4. The production method according to claim 1, wherein the pH adjuster includes sodium hydroxide and potassium hydroxide; the solvent is deionized water.
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