CN110746551B - Copolymer containing double-polyoxyethylene-ether branched chain structure and preparation and application thereof - Google Patents
Copolymer containing double-polyoxyethylene-ether branched chain structure and preparation and application thereof Download PDFInfo
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Abstract
The invention provides a copolymer containing a double-polyoxyethylene-ether branched chain structure, and preparation and application thereof. The copolymer containing the double-polyoxyethylene-ether branched chain structure is prepared by copolymerization of a double-polyoxyethylene-ether macromonomer, a long-chain alkyl ester monomer, acrylamide and other monomers. The copolymer molecular structure contains various functional groups such as a polyoxyethylene ether long-chain branch, an alkyl ester branch, a sulfonic group and the like, has amphiphilic performance, can efficiently emulsify and disperse crude oil to reduce the viscosity of the crude oil, and can be used for oil extraction processes such as heavy oil exploitation, transportation, enhanced water flooding, polymer flooding, compound flooding and the like. The copolymer of the invention has unique molecular structure design, excellent performance and high application value.
Description
Technical Field
The invention relates to the field of petrochemical industry, in particular to a copolymer containing a double-polyoxyethylene-ether branched chain structure, and preparation and application thereof, and especially relates to a copolymer containing a double-polyoxyethylene-ether branched chain structure, which is suitable for oil extraction processes such as heavy oil exploitation, transportation, enhanced water flooding, polymer flooding, compound flooding and the like.
Background
China's thick oil resources are abundant, accounting for about 30% of the total oil reserves, and China's thick oil producing areas mainly include oil fields such as Liaohe, Xinjiang, Shengli and Henan. The thickened oil becomes an important unconventional energy source in the 21 st century, and has great significance for guaranteeing the energy safety of China. However, the viscous oil has high viscosity and poor fluidity, so that the viscous oil is difficult to recover. The thick oil development mode mainly comprises steam huff and puff, steam flooding and water injection oil extraction. The prior viscosity reduction method in thickened oil recovery mainly comprises heating, thin oil doping, thickened oil modification viscosity reduction and chemical viscosity reduction. Both the dilution method and the heating method need to consume a large amount of resources and heat energy, and the reaction conditions for modification are harsh. The chemical viscosity reduction can be used for production processes of oil layer exploitation, shaft viscosity reduction, pipeline transportation and the like, and has the characteristics of low cost and easiness in implementation.
The common chemical viscosity reducer mainly comprises a solvent, an oil-soluble pour point depressant, alkali, a surfactant and the like, and the viscosity reduction mechanism mainly comprises emulsification viscosity reduction, demulsification viscosity reduction and adsorption viscosity reduction. The viscosity reduction of the emulsification is to mix viscosity reducer solution with thickened oil to ensure that the high-viscosity thickened oil is dispersed in water in an oil drop form to form low-viscosity oil-in-water emulsion, thereby reducing the flow resistance of crude oil. The injection of surfactant solution into the well bore has been studied abroad to reduce the viscosity of highly viscous crude oil and improve the oil recovery, and the viscosity reducing agent selected comprises alkylphenol ethoxylates, polyoxyethylene type rosin surfactant and the like.
The development of the efficient thick oil emulsifying viscosity reducer has important significance for improving the recovery ratio of thick oil. Currently, the majority of domestic research is low molecular surfactants and complex systems, such as cocoyl propyl sulfobetaine, lauryl sulfobetaine, sodium lauryl sulfate and sodium lauryl sulfate. The low molecular weight emulsifier has certain emulsification effect indoors, but the effect in a stratum porous medium is not ideal, and the low molecular weight emulsifier is easy to invert into water-in-oil type emulsion with high viscosity. The currently researched acrylamide polymers mostly improve the tackifying performance by increasing hydrophobic monomers, but have low surface activity and are difficult to emulsify crude oil into an oil-in-water emulsion.
The invention relates to a copolymer containing a double-polyoxyethylene-ether branched chain structure. Functional groups such as a polyoxyethylene ether branched chain and the like are introduced into a polyacrylamide skeleton, so that the emulsification and viscosity reduction effects of the copolymer on the thickened oil are greatly improved, the flow resistance of crude oil in an oil reservoir porous medium is reduced, the effects of blockage removal, cleaning and the like are realized, and the thickened oil development effect is remarkably improved.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a copolymer containing a double polyoxyethylene ether branched chain structure, which can emulsify and disperse thickened oil to form an oil-in-water emulsion with low viscosity and is suitable for oil extraction processes such as thickened oil exploitation, transportation, enhanced water flooding, polymer flooding, compound flooding and the like, and production processes such as oil-containing sludge treatment and the like.
In order to achieve the above object, in one aspect, the present invention provides a copolymer containing a branched structure of a polyoxyethylene ether, wherein the copolymer containing a branched structure of a polyoxyethylene ether contains a structural unit a represented by formula (1), a structural unit B represented by formula (2), a long-chain alkyl ester structural unit C represented by formula (3), and a branched structural unit D of a polyoxyethylene ether represented by formula (4); and based on 100% of the total mass of structural units A, B, C and D in the copolymer containing the double-polyoxyethylene-ether branched chain structure, the content of the structural unit A is 11.0-97.0 wt%, the content of the structural unit B is 0.3-32.0 wt%, the content of the structural unit C is 0.2-19.0 wt%, and the content of the structural unit D is 0.2-56.0 wt%:
wherein the content of the first and second substances,
R1is NH2And one of ONa and OK, R2Is H or CH3；
x is 5-20, m is 1-5, and n is 5-60.
According to some embodiments of the present invention, wherein the relative molecular weight (viscosity average molecular weight) of the copolymer containing a branched structure of a polyoxyethylene ether is 180 to 1800 ten thousand.
On the other hand, the invention also provides a preparation method of the copolymer containing the double-polyoxyethylene-ether branched chain structure, wherein the preparation method comprises the step of carrying out polymerization reaction on a monomer mixture to obtain the copolymer containing the double-polyoxyethylene-ether branched chain structure, wherein the monomer mixture contains a monomer E shown in a formula (4), a monomer F shown in a formula (5), a long-chain alkyl ester monomer G shown in a formula (6) and a double-polyoxyethylene-ether macromonomer H shown in a formula (7). Based on 100% of the total mass of the mixture of the monomers (i.e., the monomer E shown in the formula (4), the monomer F shown in the formula (5), the long-chain alkyl ester monomer G shown in the formula (6) and the polyoxyethylene ether macromonomer H shown in the formula (7)), the content of the monomer E is 11.0-97.0 wt%, the content of the monomer F is 0.3-32.0 wt%, the content of the monomer G is 0.2-19.0 wt%, and the content of the monomer H is 0.2-56.0 wt%; the relative molecular mass of the copolymer obtained by the solution polymerization reaction is 180-1800 ten thousand,
wherein the content of the first and second substances,
R1is NH2And one of ONa and OK, R2Is H or CH3；
x is 5-20, m is 1-5, and n is 5-60.
According to some embodiments of the present invention, the method comprises polymerizing the monomer mixture in the presence of an aqueous medium, an initiator, and a polymerization assistant to obtain the copolymer containing the branched structure of the polyoxyethylene ether.
According to some embodiments of the invention, wherein the ratio of the mass of the monomer mixture to the total mass of the reaction system is (0.10 to 0.35): 1.
the reaction system comprises a monomer mixture, an aqueous medium, an initiator and a polymerization auxiliary agent; the total mass of the reaction system refers to the total mass including the monomer mixture, the aqueous medium, the initiator and the polymerization auxiliary agent.
According to some embodiments of the invention, wherein the initiator is selected from the group consisting of a redox initiator, a catalyst, and a mixture of one or more of azo-type initiators; when the initiators are respectively present, the initiators are respectively and independently used according to the total mass of the reaction system of 100 percent: 0.0010-0.0800% of redox agent, 0.0010-0.0400% of azo initiator and 0.0010-0.0600% of catalyst.
It is to be understood that the terms "present in each case" in the context of the invention mean that the particular constituents thereof are present in each case independently of one another. For example, the "presence of each initiator" means that one or more of a redox initiator, a catalyst and an azo-based initiator are present as the initiator, and for example, when a redox agent is present, it is used in an amount of 0.0010 to 0.0800%, and when an azo-based initiator is present, it is used in an amount of 0.0010 to 0.0400%. When the above components are present independently of each other, the amount ranges do not vary with the presence or absence of other components.
According to some embodiments of the invention, the redox initiator comprises an oxidizing agent and a reducing agent, wherein the molar ratio of the oxidizing agent to the reducing agent is (0.3-3.0): 1.
according to some embodiments of the invention, wherein the oxidizing agent is selected from at least one of potassium persulfate, ammonium persulfate, and sodium persulfate; the reducing agent is at least one selected from sodium bisulfite, sodium sulfite, sodium formaldehyde sulfoxylate and sodium thiosulfate.
According to some embodiments of the invention, the catalyst is selected from at least one of tetramethylethylenediamine, tetramethylbutanediamine, tetramethylpropanediamine, morpholine, and piperidine.
According to some embodiments of the present invention, the azo initiator is at least one selected from the group consisting of azobisisobutyronitrile, azobisisoheptonitrile, 2-azobisisobutylamidine dihydrochloride, and azobisisobutylamidine hydrochloride (V-50).
According to some embodiments of the present invention, wherein the polymerization auxiliary agent is selected from at least one of an alkaline agent, a metal masking agent, a chain transfer agent, and other auxiliary agents; when the polymerization auxiliary agents are respectively present, the dosage of the polymerization auxiliary agents is 100 percent of the total mass of the reaction system, and the dosage is respectively and independently: 0.00-6.0% of alkaline agent, 0.0010-0.0700% of metal shielding agent, 0.0010-0.0800% of chain transfer agent and 0.0010-2.0000% of other auxiliary agents.
According to some embodiments of the invention, wherein the alkaline agent is selected from the group consisting of a mixture of one or more of sodium hydroxide, sodium carbonate and sodium bicarbonate; the metal masking agent is selected from one or more of disodium ethylene diamine tetraacetate, tetrasodium ethylene diamine tetraacetate and sodium citrate; the chain transfer agent is one or a mixture of sodium formate, sodium hypophosphite and isopropanol; the other auxiliary agent is selected from one or a mixture of two of urea and lauryl sodium sulfate.
According to some embodiments of the present invention, the polymerization reaction comprises reacting at 3-20 ℃ for 1-10h, and then aging at 60-80 ℃ for 1-5h to obtain the copolymer containing the branched structure of the bis-polyoxyethylene ether.
According to some specific embodiments of the invention, the monomer mixture is subjected to a polymerization reaction in the presence of an aqueous medium, an initiator and a polymerization assistant to obtain the copolymer containing the branched-chain structure of the polyoxyethylene ether, and the method comprises the steps of adding the polymerization assistant to a solution of the monomer mixture and the aqueous medium at 3-20 ℃, introducing nitrogen for 20-40 min, then adding the initiator, continuously introducing nitrogen for 5-10 min, reacting for 1-10 hours after sealing, and then heating to 60-80 ℃ to cure for 1-5 hours to obtain the copolymer containing the branched-chain structure of the polyoxyethylene ether.
According to some embodiments of the present invention, the method comprises aging at 60-80 ℃ for 1-5h to obtain a gel product, and then granulating, drying, pulverizing and sieving the gel product to obtain solid particles of the copolymer containing the branched chain structure of the polyoxyethylene ether.
In another aspect, the invention further provides an application of the copolymer containing the double-polyoxyethylene-ether branched chain structure in oil recovery processes such as heavy oil recovery, transportation, enhanced water flooding, polymer flooding, compound flooding and the like, and an application in the aspect of oily sewage sludge treatment.
The embodiments of the present invention may be combined with each other arbitrarily without contradiction.
In conclusion, the invention provides a copolymer containing a double-polyoxyethylene-ether branched chain structure, and preparation and application thereof. The copolymer molecule is introduced with nonionic polyoxyethylene ether branched chain, anionic side chain and long-chain alkyl ester side chain, so that the copolymer has the following advantages:
the copolymer structural unit of the invention contains two double polyoxyethylene ether branched chains, and due to the hydrophilic and oleophilic properties of the polyoxyethylene ether chain, the wetting, adsorption, wrapping and winding effects of copolymer molecules on the surface of crude oil are stronger than those of single polyoxyethylene ether branched chains, and the combination of the copolymer molecules on the surface of the crude oil is firmer, the coverage surface is larger, and the space effect is stronger, so that the thickened oil can be more effectively dispersed and emulsified to form fine and stable oil-in-water emulsion, and the thickened oil viscosity reducing effect is achieved. On the other hand, the polyoxyethylene branched chain is connected with the main chain through a benzene ring, the benzene ring can be anchored in the thickened oil, the branched chain can better permeate into a planar stacking aggregate of colloid and asphaltene, and the affinity degree and the dispersing capacity of the polyoxyethylene branched chain and the thickened oil are improved. Moreover, the active macromonomer of the invention does not contain ester bonds, and after the active macromonomer is polymerized on a copolymer molecular chain, the active macromonomer can not be hydrolyzed to cause chain scission of a branched chain from the main chain of the copolymer molecular, thereby being obviously superior to the copolymer prepared by the ester type polyether active monomer. In addition, the polyoxyethylene ether macromonomer and other surface active monomers participating in polymerization can cooperatively form micelles, so that the polymerization capability of the water-insoluble ester monomer is improved, the addition of other cosolvents and subsequent purification steps are reduced, and the quality of a copolymerization product is improved.
The long alkyl ester side chain structural unit in the copolymer molecule contains a polar ester group and a non-polar long alkyl chain, so that the aggregate structures such as asphaltene and wax crystals in the crude oil can be disassembled, the viscosity of the crude oil is reduced, and the fluidity of the crude oil is improved. The long alkyl chain can participate in the crystallization process of paraffin molecules in the crude oil, and the alkyl chain with proper length can form eutectic when the wax begins to crystallize, so that the crystal orientation, size and distribution of wax crystals are changed, and the flowability of the crude oil is improved; the long carbon chain can also break up the stacking and gathering structure of colloid and asphaltene in the thick oil; the polar ester group can form hydrogen bond with colloid and asphaltene in the thick oil, and can cover the surface of wax crystal, inhibit the growth of wax crystal molecules and improve the fluidity of crude oil. Meanwhile, a part of hydrophobic alkyl chain extends in water to form an association structure, so that the viscosity of a water phase is increased, the space resistance among oil drops is increased, and the dispersion and the stability of an oil phase are promoted. The alkyl sulfonate chain on the side group contains a sulfonate with high hydration and high polarity, so that the solubility and the salt resistance of the copolymer can be improved, the molecular weight can be increased, and the adverse effects of molecular weight reduction, poor water solubility and the like caused by long chain of the side group can be overcome. In addition, the sulfonate increases the electronegativity and electrostatic repulsion of oil drops, promotes the oil drops to be dispersed in water, and contributes to improving the stability of the O/W emulsion.
Due to the synergistic effect of the nonionic polyoxyethylene ether branched chain and the alkyl ester long chain, anionic sulfonate chain and other structural units in the copolymer molecule, the affinity degree, the coverage area and the space effect of the copolymer molecule on the surface of crude oil are greatly improved, thick oil can be more effectively dispersed to form an oil-in-water emulsion, and the viscosity and pour point reducing effect of the thick oil is fully exerted.
Drawings
FIG. 1 is an infrared spectrum of a branched copolymer containing a polyoxyethylene ether in example 1, example 2, and example 3;
FIG. 2 wet spreading of a solution containing a branched copolymer of polyoxyethylene ether (example 1) on a thick oil surface;
FIG. 3 viscosity of aqueous phase containing branched copolymer of bis (oxyethylene) ether (example 2) at different concentrations.
Detailed Description
The following detailed description is provided for the purpose of illustrating the embodiments and the advantageous effects thereof, and is not intended to limit the scope of the present disclosure.
Example 1
This example provides a copolymer containing a polyoxyethylene ether branch, which is prepared by the following steps:
28.43g of monomer E (R) were weighed1Is NH2I.e., acrylamide), 2.38G of monomer F, 0.56G of monomer G (R)2Adding 104.2g of deionized water into a dissolver, stirring and dissolving, then adding 4.02g of sodium carbonate, stirring and dissolving, adjusting the temperature to 15 ℃, transferring the solution into a reactor, adding 2.2g of disodium ethylenediamine tetraacetic acid with the concentration of 3.0%, 1.26g of sodium formate with the concentration of 6.0%, 2.2g of sodium bisulfite with the concentration of 1.5% and other polymerization aids, introducing nitrogen for 30min, adding 4.6g of potassium persulfate with the concentration of 0.7%, 3.1g of 2, 2-azo-diisobutylaminidine hydrochloride with the concentration of 0.25%, continuously introducing nitrogen for 10min, sealing the reactor, completing the reaction after 4H, heating the rubber block to 80 ℃, curing for 2H, and obtaining the polymer rubber block.
And taking out the obtained polymer gel block, and granulating, drying, crushing and screening to obtain the copolymer containing the polyoxyethylene ether branched chain, wherein the molecular weight of the polymer is 1262.0 ten thousand.
The synthesized polymer was isolated, purified, and then analyzed by infrared spectroscopy using the tabletting method, the results of which are shown in FIG. 1. Wherein the wave number is 3429cm-1Absorption peak is-NH2Absorption; wave number 2941cm-1The absorption peak is methylene-CH2-antisymmetric telescopic vibration of; wave number 1665cm-1The absorption peak is the stretching vibration absorption of carbonyl C ═ O; wave number 1042cm-1The absorption peak in the vicinity of 621cm, which is the asymmetric stretching vibration of the polyoxyethylene C-O-C bond-1The nearby absorption peak is the swing vibration of the polyoxyethylene plane; wave number of 1117cm-1Strong absorption peak of (2) and 1042cm-1The nearby middle-strong narrow peak is sulfonate radical absorption. And (4) according to the judgment of absorption peaks such as oxyethylene, alkyl, sulfonic acid and the like on a spectrogram, the monomer participates in polymerization to obtain a target product.
Example 2
This example provides a multipolymer with long chain side groups, which is prepared by the same procedure as in example 1, and the molecular weight of the obtained polymer is 830.2 ten thousand.
25.2g of monomer E (R) are weighed out1Is NH2I.e., acrylamide), 3.32G of monomer F, 1.08G of monomer G (R)2Adding 103.8g of deionized water into a dissolver, stirring and dissolving, then adding 4.08g of sodium carbonate, stirring and dissolving, adjusting the temperature to 15 ℃, transferring the solution into a reactor, adding 3.08g of disodium ethylenediamine tetraacetic acid with the concentration of 3.0%, 1.48g of sodium hypophosphite with the concentration of 6.0%, 3.6g of sodium bisulfite with the concentration of 1.5% and other polymerization aids, introducing nitrogen for 30min, adding 5.72g of ammonium persulfate with the concentration of 0.7%, 4.78g of 2, 2-azo-diisobutylaminidine hydrochloride with the concentration of 0.25%, continuing introducing nitrogen for 10min, sealing the reactor, completing the reaction after 4H, heating the rubber block to 80 ℃, curing for 2H, and obtaining the polymer rubber block.
And taking out the obtained polymer gel block, and granulating, drying, crushing and screening to obtain the copolymer containing the polyoxyethylene ether branched chain, wherein the molecular weight of the polymer is 822.0 ten thousand. After the synthesized polymer is separated and purified, infrared spectrum analysis is carried out by a tabletting method, the result is shown in figure 1, and the target product is obtained by the polymerization of the monomer according to the judgment of absorption peaks of oxyethylene, alkyl, sulfonic acid, phenyl and the like on a spectrogram.
Example 3
The implementation provides a copolymer containing a double-polyoxyethylene-ether branched chain, sodium acrylate is used for replacing acrylamide, and alkali is not added in the preparation process for neutralization. 24.6g of monomer E (R) were weighed1ONa, i.e. sodium acrylate), 3.82G of monomer F, 1.20G of monomer G (R)2H, x ═ 14), 6.80g of the polyoxyethylene ether macromonomer H (m ═ 1,n-36) is put into a dissolver, 109.6g of deionized water is added and stirred for dissolution, then the temperature is adjusted to 15 ℃, the solution is transferred into a reactor, 2.86g of disodium ethylene diamine tetraacetate with the concentration of 3.0 percent, 1.8g of sodium formate with the concentration of 6.0 percent, 5.8g of polymerization aids such as sodium formaldehyde sulfoxylate with the concentration of 1.5 percent are added, nitrogen is introduced for 30min, 6.4g of potassium persulfate with the concentration of 0.7 percent and 5.9g of 2, 2-azo-diisobutyl amidine dihydrochloride with the concentration of 0.25 percent are added, the reactor is sealed after nitrogen is continuously introduced for 10min, the reaction is completed after 4h, the gel block is heated to 80 ℃ for curing for 2h, and the polymer gel block is obtained. And taking out the obtained polymer gel block, and granulating, drying, crushing and screening to obtain the copolymer containing the polyoxyethylene ether branched chain, wherein the molecular weight of the polymer is 432.0 ten thousand. After the synthesized polymer is separated and purified, infrared spectrum analysis is carried out by a tabletting method, the result is shown in figure 1, and the target product is obtained by the polymerization of the monomer according to the judgment of absorption peaks of oxyethylene, alkyl, sulfonic acid, phenyl and the like on a spectrogram.
Evaluation of Performance
(1) Wetting and dispersing viscosity reducing effects
The thick oil on site is evenly coated on a quartz glass slide at room temperature, a copolymer solution with a certain concentration is dripped on the surface of the oil film by using an OCA200 video optical contact angle measuring instrument of the company Dataphy, and the change process of the contact angle value is recorded. From FIG. 2 (left to right are images of the solution contacting the oil film for 1min, 3min, and 6 min), it is seen that the copolymer solution spreads rapidly after dropping on the surface of the oil film, and the contact angle decreases, indicating that the copolymer solution has good wettability to the thick oil, which also proves that the affinity of the copolymer to the surface of the thick oil is strong.
Preparing a proper amount of the copolymer into 0.1% solution by using oilfield field sewage, mixing the solution with oilfield dehydrated crude oil (the viscosity is 961.6mPa.s at 50 ℃) according to the oil-water ratio of 4:6 (volume ratio, v/v), placing the mixture into a glass tube with a plug, and performing low-speed (the shear rate is 10-20S) at 50 DEG C-1) Oscillating and shearing for 20min, observing and recording the volume change of the water phase, calculating the water content change of the emulsion at different time (see table 1, the water content in the emulsion is 60% when the emulsion is completely emulsified), and measuring the viscosity of the emulsion at 50 ℃ by using an MCR301 rheometer after the oil-water system is completely emulsified.
From the experimental results, the oil displacement polymer sample has low emulsification speed and the viscosity reduction rate is lower than 40% under the low shear condition. The branched copolymer containing the polyoxyethylene has high emulsification speed, forms an oil-in-water emulsion, and has the viscosity reduction rate of the thickened oil of more than 93 percent (the viscosity of the thickened oil is 962.1 mPa.s).
TABLE 1 viscous oil emulsification viscosity reduction Effect of the inventive copolymer
(2) Thickening effect and oil displacement effect of solution
The polymer type prepared in example 2 was formulated into an aqueous solution (degree of mineralization: 1200mg/L) having a concentration of 400 to 1600mg/L, and the apparent viscosity at 25 ℃ was measured using LVDV type II viscometer manufactured by Brookfield corporation, and the results are shown in FIG. 3. It can be seen that as the polymer concentration increases, the solution viscosity value increases. When the concentration of the polymer is 1200-1600 mg/L, the viscosity value of the solution is about 25.0-38.0 mPa.s, which shows that the polymer solution has strong thickening effect.
And (3) carrying out core oil displacement effect test by using thickened oil of Liaohe oil field and on-site sewage. The viscosity of the thickened oil at 50 ℃ is 961.6mPa.s, the mineralization degree of sewage is 1200mg/L, the artificial rock core is 25mm multiplied by 300mm, and the air permeability is 750 mD. The oil displacement experiment comprises the steps of firstly, saturating a thick oil in a rock core at 50 ℃, and calculating the saturated oil quantity and the initial oil saturation; then water flooding the rock core until the water content of the flooding fluid reaches 98%, and calculating the water flooding recovery ratio; and displacing the core by using the polymer aqueous solution until the water content of the displacement fluid reaches 98%, and calculating to obtain that the recovery ratio can be improved by more than 10% on the basis of water displacement.
Claims (16)
1. A copolymer containing a double-polyoxyethylene-ether branched chain structure comprises a structural unit A shown in a formula (1), a structural unit B shown in a formula (2), a long-chain alkyl ester structural unit C shown in a formula (3) and a double-polyoxyethylene-ether branched chain structural unit D shown in a formula (4); and based on 100% of the total mass of structural units A, B, C and D in the copolymer containing the double-polyoxyethylene-ether branched chain structure, the content of the structural unit A is 11.0-97.0 wt%, the content of the structural unit B is 0.3-32.0 wt%, the content of the structural unit C is 0.2-19.0 wt%, and the content of the structural unit D is 0.2-56.0 wt%:
wherein the content of the first and second substances,
R1is NH2And one of ONa and OK, R2Is H or CH3；
x is 5-20, m is 1-5, and n is 5-60.
2. The copolymer containing a branched bis-oxyethylene ether structure as claimed in claim 1, wherein the copolymer containing a branched bis-oxyethylene ether structure has a relative molecular weight of 180 to 1800 ten thousand.
3. The preparation method of the copolymer containing the branched-chain structure of the polyoxyethylene ether as claimed in any one of claims 1 to 2, wherein the method comprises the step of carrying out polymerization reaction on a monomer mixture to obtain the copolymer containing the branched-chain structure of the polyoxyethylene ether, wherein the monomer mixture contains a monomer E shown in a formula (5), a monomer F shown in a formula (6), a long-chain alkyl ester monomer G shown in a formula (7) and a polyoxyethylene ether macromonomer H shown in a formula (8); based on the total mass of the monomer mixture being 100%, the content of the monomer E is 11.0-97.0 wt%, the content of the monomer F is 0.3-32.0 wt%, the content of the monomer G is 0.2-19.0 wt%, and the content of the monomer H is 0.2-56.0 wt%; the relative molecular mass of the copolymer obtained by the polymerization reaction is 180-1800 ten thousand,
wherein the content of the first and second substances,
R1is NH2And one of ONa and OK, R2Is H or CH3；
x is 5-20, m is 1-5, and n is 5-60.
4. The preparation method of claim 3, wherein the method comprises polymerizing the monomer mixture in the presence of an aqueous medium, an initiator and a polymerization assistant to obtain the copolymer containing the branched structure of the polyoxyethylene ether.
5. The production method according to claim 4, wherein the ratio of the mass of the monomer mixture to the total mass of the reaction system is (0.10 to 0.35): 1.
6. the production method according to claim 4, wherein the initiator is selected from a mixture of one or more of a redox initiator, a catalyst and an azo-based initiator; when the initiators are respectively present, the initiators are respectively and independently used according to the total mass of the reaction system of 100 percent: 0.0010-0.0800% of redox agent, 0.0010-0.0400% of azo initiator and 0.0010-0.0600% of catalyst.
7. The production method according to claim 6, wherein the redox initiator comprises an oxidizing agent and a reducing agent in a molar ratio of (0.3-3.0): 1.
8. the production method according to claim 6, wherein the oxidizing agent is selected from at least one of potassium persulfate, ammonium persulfate, and sodium persulfate; the reducing agent is at least one selected from sodium bisulfite, sodium sulfite, sodium formaldehyde sulfoxylate and sodium thiosulfate.
9. The production method according to claim 6, wherein the catalyst is selected from at least one of tetramethylethylenediamine, tetramethylbutanediamine, tetramethylpropanediamine, morpholine, and piperidine.
10. The production method according to claim 6, wherein the azo-based initiator is selected from at least one of azobisisobutyronitrile, azobisisoheptonitrile, 2-azobisisobutylamidine dihydrochloride, and azobisisobutylamidine hydrochloride.
11. The production method according to claim 4, wherein the polymerization auxiliary agent is selected from at least one of an alkali agent, a metal masking agent, a chain transfer agent, and other auxiliary agents; when the polymerization auxiliary agents are respectively present, the dosage of the polymerization auxiliary agents is 100 percent of the total mass of the reaction system, and the dosage is respectively and independently: 0.00-6.0% of alkaline agent, 0.0010-0.0700% of metal shielding agent, 0.0010-0.0800% of chain transfer agent and 0.0010-2.0000% of other auxiliary agents.
12. The preparation method according to claim 11, wherein the alkaline agent is selected from a mixture of one or more of sodium hydroxide, sodium carbonate and sodium bicarbonate; the metal masking agent is selected from one or more of disodium ethylene diamine tetraacetate, tetrasodium ethylene diamine tetraacetate and sodium citrate; the chain transfer agent is one or a mixture of sodium formate, sodium hypophosphite and isopropanol; the other auxiliary agent is selected from one or a mixture of two of urea, sodium dodecyl sulfate and polyoxyethylene ether laurate.
13. The preparation method of any one of claims 3 to 12, wherein the polymerization reaction comprises reacting at 3-20 ℃ for 1-10h, and then curing at 60-80 ℃ for 1-5h to obtain the copolymer containing the branched structure of the polyoxyethylene ether.
14. The preparation method of claim 13, wherein the monomer mixture is subjected to a polymerization reaction in the presence of an aqueous medium, an initiator and a polymerization assistant to obtain the copolymer containing the branched-chain structure of the polyoxyethylene ether, and the method comprises the steps of adding the polymerization assistant to a solution of the monomer mixture and the aqueous medium at 3-20 ℃, introducing nitrogen for 20-40 min, then adding the initiator, continuously introducing nitrogen for 5-10 min, reacting for 1-10 hours after sealing, and then heating to 60-80 ℃ to cure for 1-5 hours to obtain the copolymer containing the branched-chain structure of the polyoxyethylene ether.
15. The preparation method of claim 13, wherein the method comprises aging at 60-80 ℃ for 1-5h to obtain a gel product, and then granulating, drying, pulverizing and sieving the gel product to obtain the solid granular copolymer containing the branched structure of the polyoxyethylene ether.
16. The use of the copolymer containing a branched polyoxyethylene ether chain structure according to any one of claims 1 to 2 in the processes of heavy oil recovery, transportation, and enhanced water flooding, polymer flooding and compound flooding oil recovery, and in the aspect of oily sewage sludge treatment.
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