Polymer gel deep profile control agent, its preparation method and application
By crosslinking ketone carbonyl structural units with crosslinking agents, a polymer gel deep profile control agent free of harmful substances was prepared, solving the environmental pollution problem of existing gel profile control agents and achieving efficient plugging and environmentally friendly oilfield development results.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- CHINA PETROLEUM & CHEMICAL CORP
- Filing Date
- 2022-08-09
- Publication Date
- 2026-05-29
AI Technical Summary
Existing gel profilers often require modification to delay gel formation and ensure they can reach deep formations. However, the organic or inorganic crosslinking agents used in this process, such as formaldehyde, phenol, or potassium dichromate, can pollute the environment.
A polymer gel containing ketone carbonyl structural units is crosslinked with a crosslinking agent to form a polymer gel deep profile control agent that does not contain heavy metal ions, formaldehyde, phenol, or other substances. The slow crosslinking is achieved through the reaction of the ketone carbonyl with the active hydrogen in the crosslinking agent, ensuring that a low viscosity is maintained during the injection process and a high-strength crosslinked structure is formed in the target formation.
It achieves efficient sealing of high-permeability layers in oil fields while avoiding environmental pollution. It is simple to prepare, easy to construct, has a long gelation time, high gel strength, and improves the water injection development effect.
Smart Images
Figure QLYQS_1 
Figure QLYQS_2 
Figure QLYQS_3
Abstract
Description
Technical Field
[0001] This invention belongs to the field of oilfield development technology, and particularly relates to profile control agents, specifically, to a polymer gel deep profile control agent and its preparation method and application. Background Technology
[0002] For old oilfields that have been developed with long-term water injection, their heterogeneity will continuously increase, and problems such as water flooding and water channeling will gradually become more prominent. This leads to water injection protruding and fingering along high-permeability layers or fractures between injection wells and production wells, resulting in decreased oil production and increased water cut. To adjust and improve the heterogeneity of the reservoir formation, profile control agents can be injected into the injection wells to plug high-permeability layers. Polymer gels are an important type of deep profile control agent. They are colloids with certain strength and fluidity formed by intermolecular cross-linking of low-concentration polymers with a small amount of cross-linking agent. The system needs to have the characteristic of slow cross-linking to ensure that the system can maintain a low viscosity state for a long time during the injection process, making it easy to pump to the target formation; after reaching the target formation, it must also have high strength to achieve an efficient plugging effect.
[0003] CN114075941A provides a method for extending the effective period of deep profile control in light oil injection wells, which includes (1) analyzing and determining the dominant channel type of the injection well by combining the injection situation, water absorption profile, whether there is an obvious injection-production correspondence between the injection well and the surrounding oil wells, and the production situation of the oil wells. The dominant channel type of the injection well includes the heterogeneous mobilization type and the water channeling type; (2) for the injection well with the dominant channel type being the heterogeneous mobilization type, the method includes sequentially injecting a pre-profile control plug and a post-blocking plug into the formation, wherein the pre-profile control plug is an organic gel profile control agent, and the post-blocking plug is a high-viscosity gel-type plugging agent; for the injection well with the dominant channel type being the water channeling type, the method includes clamping a packer above and below the target profile control layer, connected in the middle by an injection valve, and after the packer is set, accurately injecting the profile control agent into the target layer through the injection valve; wherein the profile control agent is a mineral polymer permanent plugging agent. Based on the total weight of the raw materials used to prepare the organic gel profile modifier as 100%, the raw material composition of the organic gel profile modifier includes 0.5-1 wt% polyacrylamide, 0.1-0.15 wt% formaldehyde, 0.015-0.02 wt% oxalic acid, 0.03 wt% NH4Cl, 0.02 wt% resorcinol, and the balance being water.
[0004] CN108504341A discloses a gelled membrane-coated profile control agent, comprising a polymer, a crosslinking agent, clay, and water; it features convenient injection, broad applicability, low cost, and excellent sealing effect. The gel plug is made by uniformly dispersing a comb-type polyacrylamide polymer and a crosslinking agent in water, wherein the comb-type polyacrylamide polymer has a mass percentage of 0.4%-1.5%; the crosslinking agent includes phenolic resin prepolymer or inorganic chromium; the phenolic resin prepolymer has a mass percentage of 0.4%-1.5%; the inorganic chromium is composed of a mixture of sodium dichromate and sodium sulfite, wherein the mass ratio of sodium dichromate to sodium sulfite is 1:2, and the mass percentage of sodium dichromate is 0.1%-0.3%.
[0005] CN106634908A discloses a high-temperature resistant interpenetrating network composite gel profile modifier, characterized in that the profile modifier is composed of the following components: (a) water glass; (b) crosslinking agent I, which is a hydrolyzable ester compound; (c) crosslinking agent II, which is selected from phenolic resin crosslinking agents, chromium lactate, aluminum citrate or zirconium citrate compounds; (d) polymer, which is selected from hydrolyzable polyacrylamide, xanthan gum or cellulose; (e) auxiliary agent I, which is selected from sodium bentonite, calcium bentonite or nano-sized silica; (f) auxiliary agent II, which is selected from diatomaceous earth or silicate; and (g) water.
[0006] However, as mentioned above, common gel systems include aluminum citrate gel, organochromium gel, organozirconium gel, and phenolic gel. These often require modification to delay gel formation and ensure the gel can reach deep formations. However, the organic crosslinking agents used, such as formaldehyde and phenol, or the inorganic crosslinking agents, such as potassium dichromate and aluminum citrate, can all cause varying degrees of environmental pollution. Summary of the Invention
[0007] To overcome the problems existing in the prior art, this invention provides a polymer gel deep profile control agent, its preparation method, and its application. The polymer gel deep profile control agent comprises a gelling polymer, a crosslinking agent, and water. The gelling polymer contains ketone carbonyl structural units, and the crosslinking agent contains at least two active hydrogen atoms. In this invention, the ketone carbonyl group in the gelling polymer reacts with the active hydrogen atoms in the crosslinking agent to achieve crosslinking of the gelling polymer. The polymer gel deep profile control agent does not contain heavy metal ions, formaldehyde, phenol, or other substances, making it an environmentally friendly water-blocking and profile control agent.
[0008] One objective of this invention is to provide a polymer gel deep profile modifier comprising a gelling polymer, a crosslinking agent, and water, wherein the gelling polymer contains a ketone carbonyl structural unit, and the crosslinking agent contains at least two active hydrogen atoms (e.g., two or more).
[0009] In a preferred embodiment, the side chain of the ketone carbonyl structural unit contains a ketone carbonyl group, and preferably, the structure of the ketone carbonyl structural unit is as shown in formula (I):
[0010]
[0011] In formula (I), R1 is a side group containing a ketone carbonyl group, and R2, R3, and R4 are each independently selected from hydrogen, alkyl, or substituted alkyl groups.
[0012] In a further preferred embodiment, in formula (I), R1 is a side group containing a ketone carbonyl group, and R2, R3, and R4 are each independently selected from hydrogen, C1-C10 alkyl groups, or C1-C10 substituted alkyl groups.
[0013] In a preferred embodiment, the gelling polymer further contains acrylamide structural units, optional anionic structural units, and optional cationic structural units.
[0014] In a further preferred embodiment, the side chain of the acrylamide structural unit contains an acrylamide group, and / or the side chain of the anionic structural unit contains an anionic group (preferably a carboxylic acid anionic group or a sulfonic acid anionic group), and / or the side chain of the cationic structural unit contains a cationic group (preferably a quaternary ammonium salt group).
[0015] In a further preferred embodiment, the acrylamide structural unit has the structure shown in formula (II), and / or the anionic structural unit has the structure shown in formula (III), and / or the cationic structural unit has the structure shown in formula (IV):
[0016]
[0017]
[0018] In equation (II), R5 is selected from -R 1 -CONH2, R 1 R6, R7, and R8 are each independently selected from hydrogen, alkyl, substituted alkyl, aromatic, or substituted aromatic groups; in formula (III), R9 is selected from -(CONH). n -R 2 -COOM or -(CONH) n -R 2 -SO3M, n is 0 or 1, R 2 Selected from hydrogen, alkylene, substituted alkylene, aromatic or substituted aromatic, M selected from hydrogen or alkali metal, R 10 R 11 R 12Each is independently selected from hydrogen, alkyl, or substituted alkyl; in formula (IV), R 13 Selected from -R 3 -(CONH) m -R 4 -N(R 5 R 6 R 7 )·X or -(CONH) m -R 4 -N(R 5 R 6 R 7 )·X,R 3 R 4 Each is independently selected from alkylene, substituted alkylene, aromaticene, or substituted aromaticene, R 5 R 6 R 7 Each is independently selected from alkyl, substituted alkyl, aryl, or substituted aryl groups, where X is an anion, m = 0 or 1, and R... 14 R 15 R 16 Each is independently selected from hydrogen, alkyl, or substituted alkyl.
[0019] Preferably:
[0020] In equation (II), R5 is selected from -R 1 -CONH2, R 1 The components are selected from hydrogen, C1-C10 alkyl groups, C1-C10 substituted alkyl groups, C6-C10 aryl groups, or C6-C10 substituted aryl groups; R6, R7, and R8 are each independently selected from hydrogen, C1-C10 alkyl groups, or C1-C10 substituted alkyl groups; and / or,
[0021] In equation (III), R9 is selected from -(CONH). n -R 2 -COOM or -(CONH) n -R 2 -SO3M, n is 0 or 1, R 2 Selected from hydrogen, C1-C10 alkylene, C1-C10 substituted alkylene, C6-C10 aromaticity, or C6-C10 substituted aromaticity, R 10 R 11 R 12 Each is independently selected from hydrogen, C1-C10 alkyl groups, or C1-C10 substituted alkyl groups, M is selected from hydrogen or alkali metal, and R... 10 R 11 R 12 Each is independently selected from hydrogen, C1-C10 alkyl groups, or C1-C10 substituted alkyl groups; and / or,
[0022] In equation (IV), R 13 Selected from -R 3 -(CONH) m -R 4 -N(R 5 R 6 R 7 )·X or -(CONH) m -R 4 -N(R 5 R 6 R 7 )·X,R 3 R 4 Each is independently selected from C1-C10 alkylene groups, C1-C10 substituted alkylene groups, C6-C10 aromatic demerses, or C6-C10 substituted aromatic demerses, R 5 R 6 R 7 Each is independently selected from C1-C10 alkyl, C1-C10 substituted alkyl, C6-C10 aryl, or C6-C10 substituted aryl, where X is a halide ion (e.g., chloride, bromide, or iodide), m = 0 or 1, and R 14 R 15 R 16 Each is independently selected from hydrogen, C1-C10 alkyl groups, or C1-C10 substituted alkyl groups.
[0023] In a preferred embodiment, the ketone carbonyl structural unit is formed by polymerization of a ketone carbonyl-containing monomer. Preferably, the ketone carbonyl-containing monomer is selected from at least one of diacetone acrylamide, (meth)acrylaldehyde, methyl vinyl ketone, (meth)acrylate acetoacetoxyethyl ester, and (meth)acrylate acetoacetamidoethyl ester.
[0024] In a preferred embodiment, the acrylamide structural unit is formed by polymerization of acrylamide monomers. Preferably, the acrylamide monomers are selected from at least one of acrylamide, methacrylamide, N-isopropylacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, and N-hydroxymethylacrylamide.
[0025] In a preferred embodiment, the anionic structural unit is formed by polymerization of a monomer containing anionic groups. Preferably, the monomer containing anionic groups is selected from at least one of acrylic acid, methacrylic acid, sodium vinyl sulfonate, p-vinylbenzenesulfonic acid, sodium allyl sulfonate, and sodium 2-acrylamido-2-methylpropanesulfonate.
[0026] In a preferred embodiment, the cationic structural unit is formed by polymerization of a monomer containing a cationic group. Preferably, the monomer containing a cationic group is selected from at least one of methacryloyloxyethyltrimethylammonium chloride, 2-acrylamido-2-methylpropyltrimethylammonium chloride, dimethylethylallylammonium chloride, dimethyldiallylammonium chloride, acryloyloxyethyltrimethylammonium chloride, acryloyloxyethyldimethylbenzylammonium chloride, and methacryloyloxyethyldimethylbenzylammonium chloride.
[0027] In a preferred embodiment, the weight ratio of the acrylamide structural unit, anionic structural unit, cationic structural unit, and ketone carbonyl structural unit in the gelling polymer is (3-50):(0-30):(0-20):(1-10).
[0028] In a further preferred embodiment, in the gelling polymer, the weight ratio of the acrylamide structural unit, the anionic structural unit, the cationic structural unit, and the ketone carbonyl structural unit is (10-45):(2-15):(0-10):(2-8), preferably (25-40):(4-10):(0-5):(2-6).
[0029] In a further preferred embodiment, in the gelling polymer, the weight ratio of the acrylamide structural unit, the anionic structural unit, the cationic structural unit, and the ketone carbonyl structural unit is 30:(0-30):(0-20):(1-10), preferably 30:(2-15):(0-10):(2-8), and more preferably 30:(4-10):(0-5):(2-6).
[0030] For example, in the gelling polymer, the weight ratio of the acrylamide structural unit to the anionic structural unit is 30:1, 30:2, 30:4, 30:6, 30:8, 30:10, 30:12, 30:14, 30:16, 30:18, or 30:20; the weight ratio of the acrylamide structural unit to the cationic structural unit is 30:1, 30:2, 30:4, 30:6, 30:8, 30:10, 30:12, 30:14, 30:16, 30:18, or 30:20; and the weight ratio of the acrylamide structural unit to the ketone carbonyl structural unit is 30:1, 30:2, 30:4, 30:6, 30:8, or 30:10.
[0031] In a preferred embodiment, the molecular weight (e.g., viscosity-average molecular weight) of the gelling polymer is 1 million to 20 million, preferably 2 million to 10 million, for example 1 million, 2 million, 5 million, 8 million, 10 million, 12 million, 15 million, 18 million or 20 million.
[0032] In a preferred embodiment, the crosslinking agent is selected from compounds containing at least two active hydrogen atoms.
[0033] In a further preferred embodiment, the crosslinking agent is selected from at least one of dicarboxylic acid hydrazide, polycarboxylic acid hydrazide, N-aminopolyacrylamide, diamine, and polyamine.
[0034] In a further preferred embodiment, the dicarboxylic acid hydrazide is selected from at least one of dicarboxylic acid hydrazide carbonate, dicarboxylic acid hydrazide oxalate, dicarboxylic acid hydrazide succinate, and dicarboxylic acid hydrazide adipic acid; and / or, the polycarboxylic acid hydrazide is selected from N[(CH2)] p CONHNH2]3 and / or (H2NHNCO(CH2)) q )2NCH2CH2N((CH2) p CONHNH2)2, wherein p = 1 to 10, q = 1 to 10; and / or, the N-aminopolyacrylamide has a degree of polymerization of less than 100, preferably containing 5 to 15 mol% of hydrazide groups; and / or, the diamine is selected from at least one of 1,6-hexanediamine, 1,12-dodecanediamine, 1,5-pentanediamine, ethylenediamine, 1,3-pentanediamine, and phenylenediamine; and / or, the polyamine is selected from diethylenetriamine.
[0035] In a preferred embodiment, the polymer gel deep profile modifier comprises 0.1 to 1 part by weight of the gelling polymer, 0.02 to 1 part by weight of the crosslinking agent, and 98 to 99.88 parts by weight of water.
[0036] In a further preferred embodiment, in the polymer gel deep profile modifier, the gelling polymer is 0.3 to 0.8 parts by weight, the crosslinking agent is 0.05 to 0.5 parts by weight, and the water is 98 to 99.65 parts by weight.
[0037] For example, in the polymer gel deep profile modifier, the gelling polymer is 0.1 parts by weight, 0.2 parts by weight, 0.4 parts by weight, 0.6 parts by weight, 0.8 parts by weight, or 1 part by weight; the crosslinking agent is 0.02 parts by weight, 0.04 parts by weight, 0.06 parts by weight, 0.08 parts by weight, 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.4 parts by weight, 0.5 parts by weight, 0.6 parts by weight, 0.7 parts by weight, 0.8 parts by weight, 0.9 parts by weight, or 1 part by weight; and water is 98 parts by weight, 98.2 parts by weight, 98.4 parts by weight, 98.6 parts by weight, 98.8 parts by weight, 99 parts by weight, 99.2 parts by weight, 99.4 parts by weight, 99.6 parts by weight, 99.8 parts by weight, or 99.88 parts by weight.
[0038] In a further preferred embodiment, the weight parts of the gelling polymer, crosslinking agent, and water are based on a total amount of 95 to 100 parts by weight (preferably 99 to 100 parts by weight) of the polymer gel deep profile modifier, for example, based on a total amount of 95, 96, 97, 98, 99, or 100 parts by weight of the polymer gel deep profile modifier.
[0039] In this invention, the ketone carbonyl structural unit of the gelling polymer can react with the active hydrogen of the crosslinking agent to form hydrazones or imines, thereby achieving crosslinking of the gelling polymer. In this invention, the crosslinking rate increases with increasing temperature, giving the profile control agent a slow crosslinking characteristic. This ensures that the profile control agent maintains a low viscosity state for a long time during injection, making it easy to pump to the target formation. Upon reaching the target formation, it forms a crosslinked structure with high strength, achieving efficient sealing.
[0040] In a preferred embodiment, the crosslinking time of the polymer gel deep profile modifier is 1 to 7 days.
[0041] The second objective of this invention is to provide a method for preparing a polymer gel deep profile control agent, preferably used to prepare the polymer gel deep profile control agent described in the first objective of this invention, wherein the preparation method includes: (1) polymerizing an acrylamide monomer, a ketone carbonyl monomer, an optional anionic monomer, and an optional cationic monomer to obtain a gelling polymer; (2) mixing the gelling polymer with a crosslinking agent and water to obtain the polymer gel deep profile control agent.
[0042] In a preferred embodiment, the ketone-carbonyl-containing monomer contains polymerizable double bonds and ketone carbonyl groups.
[0043] In a further preferred embodiment, the ketone carbonyl monomer is selected from at least one of the compounds shown in formula (i):
[0044]
[0045] In formula (i), R1 is a side group containing a ketone carbonyl group, and R2, R3, and R4 are each independently selected from hydrogen, alkyl, or substituted alkyl groups;
[0046] Preferably, R1 is a side group containing a ketone carbonyl group, and R2, R3, and R4 are each independently selected from hydrogen, C1-C10 alkyl groups, or C1-C10 substituted alkyl groups.
[0047] In a further preferred embodiment, the ketone-carbonyl monomer is selected from at least one of diacetone acrylamide, (meth)acrylaldehyde, methyl vinyl ketone, (meth)acrylate acetoacetoxyethyl ester, and (meth)acrylate acetoacetamidoethyl ester.
[0048] In a preferred embodiment, the acrylamide monomer contains polymerizable double bonds and amide groups.
[0049] In a further preferred embodiment, the acrylamide monomer is selected from at least one of the compounds shown in formula (ii):
[0050]
[0051] In equation (ii), R5 is selected from -R 1 -CONH2, R 1 R6, R7, and R8 are each independently selected from hydrogen, alkyl, substituted alkyl, aromatic, or substituted aromatic groups;
[0052] Preferably, R5 is selected from -R 1 -CONH2, R 1 R6, R7, and R8 are each independently selected from hydrogen, C1-C10 alkyl, C1-C10 substituted alkyl, C6-C10 aromatic or C6-C10 substituted aromatic, and R8 are each independently selected from hydrogen, C1-C10 alkyl or C1-C10 substituted alkyl.
[0053] In a further preferred embodiment, the acrylamide monomer is selected from at least one of acrylamide, methacrylamide, N-isopropylacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, and N-hydroxymethylacrylamide.
[0054] In a preferred embodiment, the monomer containing anionic groups contains polymerizable double bonds and anionic groups, preferably containing polymerizable double bonds and carboxylic acid anionic groups or sulfonic acid anionic groups.
[0055] In a further preferred embodiment, the monomer containing the anionic group is selected from at least one of the compounds shown in formula (iii):
[0056]
[0057] In equation (iii), R9 is selected from -(CONH). n -R 2 -COOM or -(CONH) n -R 2 -SO3M, n is 0 or 1, R 2 Selected from hydrogen, alkylene, substituted alkylene, aromatic or substituted aromatic, M selected from hydrogen or alkali metal, R 10 R 11 R 12 Each is independently selected from hydrogen, alkyl, or substituted alkyl;
[0058] Preferably, R9 is selected from -(CONH) n -R 2 -COOM or -(CONH) n -R 2 -SO3M, n is 0 or 1, R 2 Selected from hydrogen, C1-C10 alkylene, C1-C10 substituted alkylene, C6-C10 aromaticity, or C6-C10 substituted aromaticity, R 10 R 11 R 12 Each element is independently selected from hydrogen, C1-C10 alkyl groups, or C1-C10 substituted alkyl groups, M is selected from hydrogen or an alkali metal, preferably, the alkali metal is selected from sodium and / or potassium, R 10 R 11 R 12 Each is independently selected from hydrogen, C1-C10 alkyl groups, or C1-C10 substituted alkyl groups.
[0059] In a further preferred embodiment, the monomer containing anionic groups is selected from at least one of acrylic acid, methacrylic acid, sodium vinyl sulfonate, p-vinylbenzenesulfonic acid, sodium allyl sulfonate, and sodium 2-acrylamido-2-methylpropanesulfonate.
[0060] In a preferred embodiment, the monomer containing cationic groups contains polymerizable double bonds and cationic groups, and preferably contains polymerizable double bonds and quaternary ammonium salt groups.
[0061] In a further preferred embodiment, the monomer containing the cationic group is selected from at least one of the compounds shown in formula (iv):
[0062]
[0063] In equation (iv), R 13 Selected from -R 3 -(CONH) m -R 4 -N(R 5 R 6 R 7 )·X or -(CONH) m -R 4 -N(R 5 R 6 R 7 )·X,R 3 R 4 Each is independently selected from alkylene, substituted alkylene, or aromatic or substituted aromatic, R 5 R 6 R 7Each is independently selected from alkyl, substituted alkyl, aryl, or substituted aryl groups, where X is an anion, m = 0 or 1, and R... 14 R 15 R 16 Each is independently selected from hydrogen, alkyl, or substituted alkyl;
[0064] Preferably, R 13 Selected from -R 3 -(CONH) m -R 4 -N(R 5 R 6 R 7 )·X or -(CONH) m -R 4 -N(R 5 R 6 R 7 )·X,R 3 R 4 Each is independently selected from C1-C10 alkylene groups, C1-C10 substituted alkylene groups, C6-C10 aromatic demerses, or C6-C10 substituted aromatic demerses, R 5 R 6 R 7 Each is independently selected from C1-C10 alkyl, C1-C10 substituted alkyl, C6-C10 aryl, or C6-C10 substituted aryl, X is selected from halide ions (e.g., chloride, bromide, or iodide ions), m = 0 or 1, R 14 R 15 R 16 Each is independently selected from hydrogen, C1-C10 alkyl groups, or C1-C10 substituted alkyl groups.
[0065] In a further preferred embodiment, the monomer containing a cationic group is selected from at least one of methacryloyloxyethyltrimethylammonium chloride, 2-acrylamido-2-methylpropyltrimethylammonium chloride, dimethylethylallylammonium chloride, dimethyldiallylammonium chloride, acryloyloxyethyltrimethylammonium chloride, acryloyloxyethyldimethylbenzylammonium chloride, and methacryloyloxyethyldimethylbenzylammonium chloride.
[0066] In a preferred embodiment, in step (1), the weight ratio of the acrylamide monomer, the anionic monomer, the cationic monomer, and the ketone carbonyl monomer is (3-50):(0-30):(0-20):(2-5).
[0067] In a further preferred embodiment, in step (1), the weight ratio of the acrylamide monomer, the monomer containing anionic groups, the monomer containing cationic groups, and the monomer containing ketone carbonyl groups is (10-45):(2-15):(0-10):(2-5), preferably (25-40):(5-10):(0-5):(2-5).
[0068] In a further preferred embodiment, in step (1), the weight ratio of the acrylamide monomer, the monomer containing anionic groups, the monomer containing cationic groups, and the monomer containing ketone carbonyl groups is 30:(0-30):(0-20):(1-10), preferably 30:(2-15):(0-10):(2-8), and more preferably 30:(4-10):(0-5):(2-6).
[0069] For example, in the gelling polymer, the weight ratio of the acrylamide monomer to the monomer containing anionic groups is 30:1, 30:2, 30:4, 30:6, 30:8, 30:10, 30:12, 30:14, 30:16, 30:18, or 30:20; the weight ratio of the acrylamide monomer to the monomer containing cationic groups is 30:1, 30:2, 30:4, 30:6, 30:8, 30:10, 30:12, 30:14, 30:16, 30:18, or 30:20; and the weight ratio of the acrylamide monomer to the monomer containing ketone carbonyl groups is 30:1, 30:2, 30:4, 30:6, 30:8, or 30:10.
[0070] In a preferred embodiment, the polymerization in step (1) is carried out in water, wherein the weight ratio of water to acrylamide monomer is (5-50):(3-50), preferably (20-50):(10-45), and more preferably (30-50):(25-40).
[0071] In a further preferred embodiment, the weight ratio of water to acrylamide monomer is 30:(3-50), preferably 30:(10-45), and more preferably 30:(25-40).
[0072] In a preferred embodiment, the polymerization temperature in step (1) is 20–80°C and the time is 3–8 hours.
[0073] For example, the polymerization temperature in step (1) is 20°C, 30°C, 40°C, 50°C, 60°C, 70°C or 80°C, and the time is 3h, 4h, 5h, 6h, 7h or 8h.
[0074] In a preferred embodiment, the polymerization in step (1) is carried out in the presence of an initiator.
[0075] In a further preferred embodiment, the initiator is selected from at least one of oxidant-reducant initiation systems and / or azo initiators.
[0076] In a further preferred embodiment, the oxidant is selected from at least one of potassium persulfate, sodium persulfate, ammonium persulfate, benzoyl peroxide, and tert-butyl hydroperoxide; and / or, the reducing agent is selected from at least one of sodium sulfite, potassium sulfite, sodium bisulfite, sodium thiosulfate, ferrous chloride, and ferrous ammonium sulfate; and / or, the azo compound is selected from at least one of azobisisobutylamidine hydrochloride, 2,2'-azo[2-(2-imidazolin-2-yl)propane] dihydrochloride, 4,4'-azobis(4-cyanopentanoic acid), and azobis(2,5-dimethyl-6-carboxy)hexanonitrile.
[0077] In a further preferred embodiment, based on 100 wt% of all monomers in step (1), the amount of the initiator is 0.05 to 3 wt%, preferably 0.05 to 1 wt%, more preferably 0.05 to 0.5 wt%, for example 0.05 wt%, 0.1 wt%, 0.15 wt%, 0.2 wt%, 0.25 wt%, or 3 wt%.
[0078] In a preferred embodiment, the polymerization in step (1) is performed as follows:
[0079] (1.1) Mix acrylamide monomers, ketone carbonyl monomers, optional anionic monomers, optional cationic monomers, and water to obtain a monomer aqueous solution, and adjust the pH to 7-8.
[0080] (1.2) Initiator is added under a protective atmosphere to initiate polymerization. After polymerization, the polymer product is taken out, granulated, dried and crushed to obtain gelled polymer powder.
[0081] In a preferred embodiment, the crosslinking agent is selected from compounds containing at least two active hydrogen atoms.
[0082] In a further preferred embodiment, the crosslinking agent is selected from at least one of dicarboxylic acid hydrazide, polycarboxylic acid hydrazide, N-aminopolyacrylamide, diamine, and polyamine.
[0083] In a further preferred embodiment, the dicarboxylic acid hydrazide is selected from at least one of dicarboxylic acid hydrazide carbonate, dicarboxylic acid hydrazide oxalate, dicarboxylic acid hydrazide succinate, and dicarboxylic acid hydrazide adipic acid; and / or, the polycarboxylic acid hydrazide is selected from N[(CH2)] p CONHNH2]3 and / or (H2NHNCO(CH2)) q )2NCH2CH2N((CH2) pCONHNH2)2, wherein p = 1 to 10, q = 1 to 10; and / or, the N-aminopolyacrylamide has a degree of polymerization of less than 100, preferably containing 5 to 15 mol% of hydrazide groups; and / or, the diamine is selected from at least one of 1,6-hexanediamine, 1,12-dodecanediamine, 1,5-pentanediamine, ethylenediamine, 1,3-pentanediamine, and phenylenediamine; and / or, the polyamine is selected from diethylenetriamine.
[0084] In a preferred embodiment, in step (2), the amount of the gelling polymer is 0.1 to 1 part by weight, the amount of the crosslinking agent is 0.02 to 1 part by weight, and the amount of water is 98 to 99.88 parts by weight.
[0085] Preferably, the water is deionized water or recycled water.
[0086] In a further preferred embodiment, the amount of the gelling polymer is 0.3 to 0.8 parts by weight, the amount of the crosslinking agent is 0.05 to 0.5 parts by weight, and the amount of water is 98 to 99.65 parts by weight.
[0087] For example, the amount of the gelling polymer is 0.1 parts by weight, 0.2 parts by weight, 0.4 parts by weight, 0.6 parts by weight, 0.8 parts by weight, or 1 part by weight; the amount of the crosslinking agent is 0.02 parts by weight, 0.04 parts by weight, 0.06 parts by weight, 0.08 parts by weight, 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.4 parts by weight, 0.5 parts by weight, 0.6 parts by weight, 0.7 parts by weight, 0.8 parts by weight, 0.9 parts by weight, or 1 part by weight; and the amount of water is 98 parts by weight, 98.2 parts by weight, 98.4 parts by weight, 98.6 parts by weight, 98.8 parts by weight, 99 parts by weight, 99.2 parts by weight, 99.4 parts by weight, 99.6 parts by weight, 99.8 parts by weight, or 99.88 parts by weight.
[0088] In a further preferred embodiment, the amounts of the gelling polymer, crosslinking agent, and water are based on a total weight of 95 to 100 parts by weight (preferably 99 to 100 parts by weight) of the polymer gel deep profile modifier, for example, based on a total weight of 95, 96, 97, 98, 99, or 100 parts by weight of the polymer gel deep profile modifier.
[0089] In a preferred embodiment, in step (2), the gelling polymer is first mixed with water, and after it is fully dissolved, a polymer solution is obtained. Then, the crosslinking agent is added, and the polymer gel deep profile modifier is obtained by stirring.
[0090] In a further preferred embodiment, the pH value of the polymer solution is 5-6.
[0091] The third objective of this invention is to provide the application of the polymer gel deep profile control agent described in the first objective of this invention or the polymer gel deep profile control agent obtained by the preparation method described in the second objective of this invention in the field of oilfield development, especially its application as a deep profile control agent in the field of oilfield development.
[0092] In a preferred embodiment, the crosslinking time of the polymer gel deep profile modifier is 1 to 7 days.
[0093] The endpoints and any values of the ranges disclosed in this invention are not limited to the precise ranges or values; these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, the endpoint values of the various ranges, the endpoint values of the various ranges and individual point values, and individual point values can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein. In the following, various technical solutions can, in principle, be combined with each other to obtain new technical solutions, which should also be considered as specifically disclosed herein.
[0094] Compared with the prior art, the present invention has the following beneficial effects:
[0095] (1) It is simple to prepare, has stable performance, is easy to apply, has a long gelation time, and has high gel strength after gelation. This allows the polymer gel to penetrate deep into the reservoir, block high-permeability layers, and improve the water injection development effect. In addition, the gel system after gelation does not contain heavy metal ions, making it an environmentally friendly water shut-off and profile control agent.
[0096] (2) The polymer gel deep profile control agent of the present invention does not contain heavy metal ions, formaldehyde, phenol and other substances, and is an environmentally friendly water-blocking profile control agent. Attached Figure Description
[0097] Figure 1 The nuclear magnetic resonance spectrum of the gelling polymer powder prepared in Example 1 is shown.
[0098] Figure 2 The NMR spectrum of the gelling polymer powder prepared in Example 2 is shown.
[0099] Figure 3 The nuclear magnetic resonance spectrum of the gelling polymer powder prepared in Example 3 is shown.
[0100] Figure 4 The NMR spectrum of the gelling polymer powder prepared in Example 4 is shown.
[0101] Figure 5 The oscillation test results of Experiment Example 1 are shown;
[0102] Figure 6 The results of the moisture content test in Experiment Example 2 are shown;
[0103] Figure 7 The viscosity test results of Experiment Example 3 are shown. Detailed Implementation
[0104] The present invention will now be described in detail with reference to specific embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention are still within the scope of protection of the present invention.
[0105] It should also be noted that the various specific technical features described in the following embodiments can be combined in any suitable manner without contradiction. To avoid unnecessary repetition, the various possible combinations will not be described separately in this invention.
[0106] Furthermore, various embodiments of the present invention can be combined in any way, as long as they do not violate the spirit of the present invention. The resulting technical solutions are part of the original disclosure of this specification and also fall within the protection scope of the present invention.
[0107] Unless otherwise specified, the raw materials used in the examples and comparative examples are all disclosed in the prior art, such as those that can be directly purchased or prepared according to the preparation methods disclosed in the prior art.
[0108]
Example 1
[0109] 30 parts acrylamide, 5 parts 2-acrylamido-dimethylpropanesulfonic acid, 5 parts methacryloyloxyethyltrimethylammonium chloride, and 2 parts diacetone acrylamide were dissolved in 45 parts water, and the pH was adjusted to 7. After purging with nitrogen for 30 min to remove oxygen, 0.05 wt% potassium bisulfite and 0.05 wt% sodium persulfate were added to initiate polymerization at room temperature. The maximum temperature during the reaction was controlled at 55℃. After reacting for 4 h, the polymer product was removed, granulated, dried, and pulverized to obtain a gelled polymer powder with a molecular weight of 7 million.
[0110] The obtained gelling polymer powder was subjected to NMR analysis, and the results are as follows: Figure 1 As shown.
[0111] 0.3g of the gelling polymer was added to 98.7g of water and dissolved completely to obtain a polymer solution. Then, 0.05g of succinic dihydrazide (1g of a 0.05% aqueous solution) was added and stirred thoroughly to obtain a polymer gel deep profile modifier. The pH of the polymer gel deep profile modifier was adjusted to 5.8, and cross-linking was initiated at 25°C to achieve the gelation process, which took 7 days.
[0112]
Example 2
[0113] 40 parts acrylamide, 8 parts acrylic acid, and 3 parts methyl vinyl ketone were dissolved in 45 parts water, and the pH was adjusted to 8. After purging with nitrogen for 30 minutes to remove oxygen, sodium thiosulfate (0.1 wt% of total monomer weight) and ammonium persulfate (0.1 wt% of total monomer weight) were added, and polymerization was initiated at room temperature. The maximum temperature during the reaction was controlled at 60°C. After 6 hours of reaction, a white gel-like product was obtained, which was pelleted, dried, and pulverized to obtain a gelled polymer powder with a molecular weight of 6.51 million.
[0114] The obtained gelling polymer powder was subjected to NMR analysis, and the results are as follows: Figure 2 As shown.
[0115] 0.5g of the gelling polymer was added to 98.5g of water and dissolved completely to obtain a polymer solution. Then, 0.05g of adipic acid dihydrazide (1g of a 0.05% aqueous solution) was added and stirred thoroughly to obtain a polymer gel deep profile modifier. The pH of the polymer gel deep profile modifier was adjusted to 6.0, and cross-linking was carried out at 65℃ to achieve the gelation process, which took 3 days.
[0116]
Example 3
[0117] 25 parts acrylamide, 5 parts 2-acrylamido-dimethylpropanesulfonic acid, and 5 parts methacrolein were dissolved in 40 parts water, and the pH was adjusted to 7. After purging with nitrogen for 30 minutes to remove oxygen, potassium persulfate (0.05% by weight of all monomers), sodium bisulfite (0.09% by weight of all monomers), and azobisisobutylamidine hydrochloride (0.06% by weight of all monomers) were added. Polymerization was initiated at room temperature, with the maximum temperature controlled at 52°C during the reaction. After 8 hours of reaction, a white gel-like product was obtained, which was granulated, dried, and pulverized to obtain a gelled polymer powder with a molecular weight of 9.3 million.
[0118] The obtained gelling polymer powder was subjected to NMR analysis, and the results are as follows: Figure 3 As shown.
[0119] 0.6 g of the gelling polymer was added to 98.4 g of water and dissolved completely to obtain a polymer solution. Then, 0.3 g of hexamethylenediamine (1 g of a 0.3% aqueous solution) was added and stirred thoroughly to obtain a polymer gel deep profile modifier. The pH of the polymer gel deep profile modifier was adjusted to 5.5, and cross-linking was carried out at 75°C to achieve the gelation process, which took 1 day.
[0120]
Example 4
[0121] 35 parts acrylamide, 5 parts methacrylic acid, and 4 parts acetyl acetoxyethyl methacrylate were dissolved in 40 parts water, and the pH was adjusted to 7. After purging with nitrogen for 30 min, 0.05 wt% azobisisobutylamidine hydrochloride was added, and polymerization was initiated at 50 °C. The maximum temperature during the reaction was controlled at 74 °C. After 4 h of reaction, a white gel-like product was obtained, which was pelleted, dried, and pulverized to obtain a gelled polymer powder with a molecular weight of 3.3 million.
[0122] The obtained gelling polymer powder was subjected to NMR analysis, and the results are as follows: Figure 4 As shown.
[0123] 0.8 g of the gelling polymer was added to 98.2 g of water and dissolved completely to obtain a polymer solution. Then, 0.1 g of adipic acid dihydrazide (1 g of a 0.1% aqueous solution) was added and stirred thoroughly to obtain a polymer gel deep profile modifier. The pH of the polymer gel deep profile modifier was adjusted to 5.5, and cross-linking was carried out at 75°C to achieve the gelation process, which took 3 days.
[0124]
Experiment Example 1
[0125] The viscosities of the polymer gel deep profile modifiers obtained in Examples 1-4 before and after gelation were compared. Oscillation tests were performed using a Thermofisher Haake MarsIII rotational rheometer and a PP35ER at the gelation temperature. The results are as follows: Figure 5 As shown.
[0126] As can be seen, the elastic modulus increases significantly after gelation while the phase difference decreases. The phase difference was greater than 45° before gelation, but less than 45° after gelation, indicating that the gelation was good. The test sample changed from a solution to a gel after gelation, and has a three-dimensional bulk network structure, exhibiting the characteristics of an elastomer.
[0127]
Experiment Example 2
[0128] Using a small core with a permeability of 1500 mD, a length of 5 cm, and a cross-sectional diameter of 2.5 cm, oil displacement experiments were conducted after saturation with oil at the gelation temperature. Water flooding was first performed until the recovery rate stabilized, followed by injection of a profile control agent and then water flooding again. The water content of the produced fluid before and after the injection of the profile control agent was compared. The results are as follows: Figure 6 As shown.
[0129] As can be seen, the polymer gel deep profile control agents obtained in Examples 1-4 formed large channels before injection, resulting in significant water channeling and a very high water content in the produced fluid, approaching 100%. After injection of the polymer gel deep profile control agents obtained in Examples 1-4, the large channels of the profile control agent were effectively blocked, forcing subsequent water drive to change direction, increasing the recovery rate, and decreasing the water content in the produced fluid.
[0130]
Experiment Example 3
[0131] The polymer gel deep profile modifiers obtained in Examples 1-4 were gelled and aged at the gelation temperature. They were removed after 1, 3, 7, 15, and 30 days, and their viscosity was tested using a Thermofisher Haake Mars III rotational rheometer and a PP35ER. The results are as follows: Figure 7 As shown.
[0132] Depend on Figure 7 As can be seen, the gel viscosity remained basically stable within the 30-day aging period.
[0133] The present invention has been described in detail above with reference to specific embodiments and exemplary examples; however, these descriptions should not be construed as limiting the present invention. Those skilled in the art will understand that various equivalent substitutions, modifications, or improvements can be made to the technical solutions and embodiments of the present invention without departing from the spirit and scope of the invention, and all such modifications and improvements fall within the scope of the present invention. The scope of protection of the present invention is defined by the appended claims.
Claims
1. A polymer gel deep profile modifier, comprising a gelling polymer, a crosslinking agent, and water, wherein, The gelling polymer contains a ketone carbonyl structural unit, and the crosslinking agent contains at least two active hydrogen atoms; the gelling polymer further contains an acrylamide structural unit, optional anionic structural unit, and optional cationic structural unit; in the gelling polymer, the weight ratio of the acrylamide structural unit, anionic structural unit, cationic structural unit, and ketone carbonyl structural unit is 30:(0~30):(0~20):(1~6), and the molecular weight of the gelling polymer is 100~2000 million.
2. The polymer gel deep profile control agent according to claim 1, characterized in that, The side chain of the ketone carbonyl structural unit contains a ketone carbonyl group, and the structure of the ketone carbonyl structural unit is shown in formula (I): Equation (I); In formula (I): R1 is a side group containing a ketone carbonyl group; R2, R3, and R4 are each independently selected from hydrogen, alkyl, or substituted alkyl groups.
3. The polymer gel deep profile control agent according to claim 2, characterized in that, R2, R3, and R4 are each independently selected from hydrogen, C1-C10 alkyl groups, or C1-C10 substituted alkyl groups.
4. The polymer gel deep profile control agent according to claim 1, characterized in that, The structure of the acrylamide structural unit is shown in formula (II), where R5 is selected from -R 1 -CONH2, R 1 R6, R7, and R8 are each independently selected from hydrogen, alkyl, substituted alkyl, aromatic, or substituted aromatic groups; Equation (II).
5. The polymer gel deep profile control agent according to claim 1, characterized in that, The structure of the anionic structural unit is shown in formula (III), where R9 is selected from -(CONH). n -R 2 -COOM or -(CONH) n -R 2 -SO3M, n is 0 or 1, R 2 Selected from hydrogen, alkylene, substituted alkylene, aromatic or substituted aromatic, M selected from hydrogen or alkali metal, R 10 R 11 R 12 Each is independently selected from hydrogen, alkyl, or substituted alkyl; Equation (III).
6. The polymer gel deep profile control agent according to claim 1, characterized in that, The structure of the cation structural unit is shown in formula (IV), where R 13 Selected from -R 3 -(CONH) m -R 4 -N(R 5 R 6 R 7 )·X or -(CONH) m -R 4 -N(R 5 R 6 R 7 )·X,R 3 R 4 Each is independently selected from alkylene, substituted alkylene, aromaticene, or substituted aromaticene, R 5 R 6 R 7 Each is independently selected from alkyl, substituted alkyl, aryl, or substituted aryl groups, where X is an anion, m = 0 or 1, and R... 14 R 15 R 16 Each is independently selected from hydrogen, alkyl, or substituted alkyl; Formula (IV).
7. The polymer gel deep profile control agent according to claim 1, characterized in that, The ketone carbonyl structural unit is formed by the polymerization of monomers containing a ketone carbonyl group; and / or, The acrylamide structural unit is formed by the polymerization of acrylamide monomers; and / or, The anionic structural unit is formed by the polymerization of monomers containing anionic groups; and / or, The cationic structural unit is formed by the polymerization of monomers containing cationic groups.
8. The polymer gel deep profile control agent according to claim 7, characterized in that, The ketone-carbonyl monomer is selected from at least one of diacetone acrylamide, (meth)acrylaldehyde, methyl vinyl ketone, (meth)acrylate acetoacetoxyethyl ester, and (meth)acrylate acetoacetamidoethyl ester; and / or, The acrylamide monomer is selected from at least one of acrylamide, methacrylamide, N-isopropylacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, and N-hydroxymethylacrylamide; and / or, The monomer containing the anionic group is selected from at least one of acrylic acid, methacrylic acid, sodium vinyl sulfonate, p-vinylbenzenesulfonic acid, sodium allyl sulfonate, and sodium 2-acrylamido-2-methylpropanesulfonate; and / or, The monomer containing the cationic group is selected from at least one of methacryloyloxyethyltrimethylammonium chloride, 2-acrylamido-2-methylpropyltrimethylammonium chloride, dimethylethylallylammonium chloride, dimethyldiallylammonium chloride, acryloyloxyethyltrimethylammonium chloride, acryloyloxyethyldimethylbenzylammonium chloride, and methacryloyloxyethyldimethylbenzylammonium chloride.
9. The polymer gel deep profile control agent according to claim 1, characterized in that, In the gelling polymer, the weight ratio of the acrylamide structural unit, anionic structural unit, cationic structural unit, and ketone carbonyl structural unit is 30:(2~15):(0~10):(2~6).
10. The polymer gel deep profile control agent according to claim 1, characterized in that, The crosslinking agent is selected from at least one of dibasic acid hydrazide, polybasic acid hydrazide, N-amino polyacrylamide, diamine, and polyamine.
11. The polymer gel deep profile control agent according to claim 10, characterized in that, The dicarboxylic acid hydrazide is selected from at least one of dicarboxylic acid hydrazide, dicarboxylic acid hydrazide, dicarboxylic acid hydrazide, and dicarboxylic acid hydrazide; and / or, the polycarboxylic acid hydrazide is selected from N[(CH2)] p CONHNH2]3 and / or (H2NHNCO(CH2)) q )2NCH2CH2N((CH2) p CONHNH2)2, wherein p=1~10, q=1~10; and / or, the degree of polymerization of the N-aminopolyacrylamide is less than 100; and / or, the diamine is selected from at least one of 1,6-hexanediamine, 1,12-dodecanediamine, 1,5-pentanediamine, ethylenediamine, 1,3-pentanediamine, and phenylenediamine; and / or, the polyamine is selected from diethylenetriamine.
12. The polymer gel deep profile control agent according to claim 11, characterized in that, The N-aminopolyacrylamide contains 5-15 mol% hydrazide groups.
13. The polymer gel deep profile control agent according to any one of claims 1 to 12, characterized in that, In the polymer gel deep profile modifier, the gelling polymer is 0.1 to 1 part by weight, the crosslinking agent is 0.02 to 1 part by weight, and the water is 98 to 99.88 parts by weight.
14. The polymer gel deep profile control agent according to claim 13, characterized in that, The gelling polymer is 0.3 to 0.8 parts by weight, the crosslinking agent is 0.05 to 0.5 parts by weight, and the water is 98 to 99.65 parts by weight.
15. A method for preparing a polymer gel deep profile control agent, used to prepare the polymer gel deep profile control agent according to any one of claims 1 to 14, wherein, The preparation method includes: (1) polymerizing acrylamide monomers, ketone carbonyl monomers, optional anionic monomers, and optional cationic monomers to obtain a gelling polymer; (2) mixing the gelling polymer with a crosslinking agent and water to obtain the polymer gel deep profile modifier; in step (1), the weight ratio of the acrylamide monomers, anionic monomers, cationic monomers, and ketone carbonyl monomers is 30:(0~30):(0~20):(1~6).
16. The preparation method according to claim 15, characterized in that, The monomer containing a ketone carbonyl group contains a polymerizable double bond and a ketone carbonyl group; And / or, The acrylamide monomers contain polymerizable double bonds and amide groups; And / or, The monomer containing anionic groups contains polymerizable double bonds and anionic groups; And / or, The monomer containing cationic groups contains polymerizable double bonds and cationic groups.
17. The preparation method according to claim 16, characterized in that, The ketone carbonyl monomer is selected from at least one of the compounds shown in formula (i): Equation (i) In formula (i), R1 is a side group containing a ketone carbonyl group, and R2, R3, and R4 are each independently selected from hydrogen, alkyl, or substituted alkyl groups; And / or, The acrylamide monomer is selected from at least one of the compounds shown in formula (ii): Formula (ii) In equation (ii), R5 is selected from -R 1 -CONH2, R 1 R6, R7, and R8 are each independently selected from hydrogen, alkyl, substituted alkyl, aromatic, or substituted aromatic groups; And / or, The monomer containing the anionic group is selected from at least one of the compounds shown in formula (iii): Equation (iii) In equation (iii), R9 is selected from -(CONH). n -R 2 -COOM or -(CONH) n -R 2 -SO3M, n is 0 or 1, R 2 Selected from hydrogen, alkylene, substituted alkylene, aromaticylene, or substituted aromaticylene, M is selected from hydrogen or an alkali metal, R 10 R 11 R 12 Each is independently selected from hydrogen, alkyl, or substituted alkyl; And / or, The monomer containing the cationic group is selected from at least one of the compounds shown in formula (iv): Formula (iv) In equation (iv), R 13 Selected from -R 3 -(CONH) m -R 4 -N(R 5 R 6 R 7 )·X or -(CONH) m -R 4 -N(R 5 R 6 R 7 )·X,R 3 R 4 Each is independently selected from alkylene, substituted alkylene, or aromatic or substituted aromatic, R 5 R 6 R 7 Each is independently selected from alkyl, substituted alkyl, aryl, or substituted aryl groups, where X is an anion, m = 0 or 1, and R... 14 R 15 R 16 Each is independently selected from hydrogen, alkyl, or substituted alkyl.
18. The preparation method according to claim 17, characterized in that, In formula (i), R2, R3, and R4 are each independently selected from hydrogen, C1-C10 alkyl groups, or C1-C10 substituted alkyl groups.
19. The preparation method according to claim 15, characterized in that, The ketone-carbonyl monomer is selected from at least one of diacetone acrylamide, (meth)acrylaldehyde, methyl vinyl ketone, (meth)acrylate acetoacetoxyethyl ester, and (meth)acrylate acetoacetamidoethyl ester; and / or, The acrylamide monomer is selected from at least one of acrylamide, methacrylamide, N-isopropylacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, and N-hydroxymethylacrylamide; and / or, The monomer containing the anionic group is selected from at least one of acrylic acid, methacrylic acid, sodium vinyl sulfonate, p-vinylbenzenesulfonic acid, sodium allyl sulfonate, and sodium 2-acrylamido-2-methylpropanesulfonate; and / or, The monomer containing the cationic group is selected from at least one of methacryloyloxyethyltrimethylammonium chloride, 2-acrylamido-2-methylpropyltrimethylammonium chloride, dimethylethylallylammonium chloride, dimethyldiallylammonium chloride, acryloyloxyethyltrimethylammonium chloride, acryloyloxyethyldimethylbenzylammonium chloride, and methacryloyloxyethyldimethylbenzylammonium chloride.
20. The preparation method according to claim 15, characterized in that, In step (1), the weight ratio of the acrylamide monomer, the anionic monomer, the cationic monomer, and the ketone carbonyl monomer is 30:(2~15):(0~10):(2~5); and / or, The polymerization in step (1) is carried out in water, wherein the weight ratio of water to acrylamide monomer is (5~50):(3~50); and / or, The polymerization described in step (1) is carried out in the presence of an initiator.
21. The preparation method according to claim 20, characterized in that, The polymerization described in step (1) is carried out in water, wherein the weight ratio of water to acrylamide monomer is (20~50):(10~45); and / or, The initiator is selected from at least one of oxidant-reducant initiation systems and / or azo initiators.
22. The preparation method according to any one of claims 15 to 21, characterized in that, The crosslinking agent is selected from at least one of dibasic acid hydrazide, polybasic acid hydrazide, N-amino polyacrylamide, diamine, and polyamine.
23. The preparation method according to claim 22, characterized in that, The dicarboxylic acid hydrazide is selected from at least one of dicarboxylic acid hydrazide, dicarboxylic acid hydrazide, dicarboxylic acid hydrazide, and dicarboxylic acid hydrazide; and / or, the polycarboxylic acid hydrazide is selected from N[(CH2)] p CONHNH2]3 and / or (H2NHNCO(CH2)) q )2NCH2CH2N((CH2) p CONHNH2)2, wherein p=1~10, q=1~10; and / or, the degree of polymerization of the N-aminopolyacrylamide is less than 100; and / or, the diamine is selected from at least one of 1,6-hexanediamine, 1,12-dodecanediamine, 1,5-pentanediamine, ethylenediamine, 1,3-pentanediamine, and phenylenediamine; and / or, the polyamine is selected from diethylenetriamine.
24. The preparation method according to claim 23, characterized in that, The N-aminopolyacrylamide contains 5-15 mol% hydrazide groups.
25. The preparation method according to claim 22, characterized in that, In step (2), the amount of the gelling polymer is 0.1 to 1 part by weight, the amount of the crosslinking agent is 0.02 to 1 part by weight, and the amount of water is 98 to 99.88 parts by weight.
26. The application of the polymer gel deep profile control agent according to any one of claims 1 to 14 or the polymer gel deep profile control agent obtained by the preparation method according to any one of claims 15 to 25 in the field of oilfield development.
27. The application according to claim 26, characterized in that, Its application as a deep profile control agent in the field of oilfield development.